|HAO WANATA UT TILUS010023760B2 AT HA MAMMUT (12 ) United States Patent ( 10 ) Patent No. : US 10 , 023 ,760 B2 Yamauchi et al. ( 45 ) Date of Patent : Jul. 17 , 2018 (54 ) SEMICARBAZIDE COMPOSITION , ( 56 ) References Cited METHOD FOR PRODUCING SEMICARBAZIDE COMPOSITION , U . S . PATENT DOCUMENTS AQUEOUS POLYMER COMPOSITION AND 5 , 098 ,466 A * 3 / 1992 Anderson ...... A01N 47/ 34 COMPOSITE 504 / 235 5 ,472 ,996 A 12/ 1995 Hayashi et al . @( 71 ) Applicant: ASAHI KASEI CHEMICALS 5 ,714 ,615 A * 2 / 1998 Powers ...... A61K 31 / 44 546 / 291 CORPORATION , Tokyo ( JP ) 5 , 880 ,312 A 3 / 1999 Nakabayashi et al. 6 , 893 ,683 B15 / 2005 Hesselmans et al. (72 ) Inventors : Toyoaki Yamauchi, Tokyo ( JP ); 2001/ 0018170 A1 * 8 /2001 Oyamada ...... GO3C 1 /49809 TakayukiMiyazaki , Tokyo ( JP ) ; 430 /620 Takahiro Itamochi, Tokyo ( JP ) 2006 / 0287260 Al 12/ 2006 Manoharan et al . 2009 /0099298 AL 4 /2009 Yukawa ( 73 ) Assignee : ASAHI KASEI CHEMICALS CORPORATION , Tokyo ( JP ) FOREIGN PATENT DOCUMENTS CN 101407688 A 4 /2009 ( * ) Notice : Subject to any disclaimer, the term of this GB 2453669 A 4 / 2009 patent is extended or adjusted under 35 46 - 20053 Y1 6 / 1971 57 - 3850 A 1 / 1982 U . S . C . 154 (b ) by 321 days . 57 - 3857 A 1 / 1982 58 - 96643 A 6 / 1983 (21 ) Appl. No. : 14 /443 , 288 4 - 249587 A 9 / 1992 6 - 287457 A 10 / 1994 ( 22 ) PCT Filed : Nov . 15 , 2013 10 - 298158 A 11/ 1998 2001 - 164126 A 6 / 2001 2003 -510431 A 3 / 2003 ( 86 ) PCT No. : PCT/ JP2013/ 080908 2005- 29515 A 2 /2005 2005 - 42023 A 2 / 2005 § 371 (c )( 1 ), 2005 - 350580 A 12 / 2005 (2 ) Date : May 15 , 2015 4033518 B2 11 /2007 2008 -504840 A 2 / 2008 ( 87 ) PCT Pub . No. : WO2014 /077363 WO 96 /01252 AL 1 / 1996 PCT Pub . Date :May 22 , 2014 EEEEEEEEEEEEEES OTHER PUBLICATIONS (65 ) Prior Publication Data Supplementary European Search Report for European Application US 2015 /0291831 A1 Oct. 15 , 2015 No . 13855684 . 0 , dated Nov . 4 , 2015 . International Preliminary Report on Patentability and English trans Foreign Application Priority Data lation of the Written Opinion of the International Searching Author ( 30 ) ity ( Forms PCT/ IB /338 , PCT/ IB /373 and PCT /ISA / 237 ), dated May 2012 - 252603 28 , 2015 , for International Application No. PCT/ JP2013 /080908 . Nov. 16 , 2012 ( JP ) ...... * - - - * International Search Report ( Form PCT/ ISA / 210 ) , dated Feb . 10 , Nov . 30 , 2012 ( JP ) ...... 2012 - 263202 2014 , for International Application No . PCT / JP2013 /080908 . (51 ) Int. Cl. C09D 133/ 26 ( 2006 .01 ) * cited by examiner C07C 281 / 06 ( 2006 .01 ) Primary Examiner — Megan McCulley C08G 18 / 75 ( 2006 .01 ) (74 ) Attorney, Agent, or Firm — Birch , Stewart, Kolasch C08G 18 / 32 ( 2006 .01 ) & Birch , LLP C08F 220 / 18 ( 2006 .01 ) C09D 133/ 08 ( 2006 . 01 ) (57 ) ABSTRACT C09D 163/ 00 ( 2006 . 01 ) Provided is a semicarbazide composition comprising : a C08G 59 / 40 ( 2006 .01 ) semicarbazide compound ( A ) having an amino group and a (52 ) U .S . CI. semicarbazide group ; a semicarbazide compound ( B - 1 ) hav CPC ...... C09D 133 /26 ( 2013 . 01 ); C07C 281/ 06 ing a structure with a semicarbazide group substituted for ( 2013 .01 ); C08F 220 / 18 ( 2013 . 01 ) ; C08G the amino group of the semicarbazide compound ( A ); a 18 /3231 (2013 . 01 ) ; C08G 18 / 755 ( 2013 . 01 ) ; semicarbazide compound ( B - 2 ) as a dimer of the semicar CO8G 59/ 4014 ( 2013 . 01 ) ; C09D 133/ 08 bazide compound ( B - 1 ) ; and a semicarbazide compound ( 2013. 01 ) ; C09D 163 / 00 (2013 .01 ) ; C07C ( B - 3 ) as a trimer of the semicarbazide compound (B - 1) ; the 2601/ 14 (2017 .05 ) semicarbazide composition having an analysis area ratio ( a ) ( 58 ) Field of Classification Search of 0 . 008 % or more and 2 % or less . ??? ...... CO9D 133 / 26 See application file for complete search history . 2 Claims, 5 Drawing Sheets U . S . Patent Jul. 17 , 2018 Sheet 1 of 5 US 10 ,023 , 760 B2

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Fig.5 motwww. to MAU1 +008 009 400 200 O US 10 ,023 , 760 B2 SEMICARBAZIDE COMPOSITION , carbonyl group - containing copolymer deteriorate with time METHOD FOR PRODUCING as described above , the composition cannot exhibit adequate SEMICARBAZIDE COMPOSITION , cross - linking performance when applied to a substrate sur AQUEOUS POLYMER COMPOSITION AND face . Furthermore , use of dicarboxylic acid dihydrazide COMPOSITE 5 having low compatibility with a carbonyl group -containing copolymer as cross - linking agent causes a problem that the TECHNICAL FIELD produced coating film by application has markedly inferior water resistance . The present invention relates to a semicarbazide compo In Patent Literature 7 and 8 , at least one selected from the sition , the method for producing a semicarbazide composi - 10 group consisting of a semicarbazide derivative and a termi tion , and an aqueous polymer composition and a composite . nal- blocked product thereof obtained by a reaction between a polyisocyanate having 3 to 20 isocyanate groups and BACKGROUND ART hydrazine or a derivative thereof , or a mixture of a non In recent years , aqueous polymer compositions have 15 terminal- blocked product and a terminal -blocked product attracted attention as material for converting to a waterborne thereof; and a semicarbazide mixture including at least one system from an organic solvent system in the coating field . selected from the group consisting of the semicarbazide Waterborne paints produced from aqueous polymer compo derivative and a terminal- blocked product thereof, and at sitions , however, still have not exhibited sufficient physical least one selected from the group consisting of a hydrophilic properties such as water resistance , stain resistance , and 20 group -containing compound and a terminal- blocked product hardness in comparison with organic solvent- based paints . thereof is proposed as a cross - linking agent. The semicar In the description here, an aqueous polymer composition bazide mixture , however , includes a large amount of com indicates the polymer dissolved and /or dispersed in water . pounds with terminal amino groups as by - products , having In this field , in order to improve physical properties of a a disadvantage of yellowing easily caused by a basic sub coating film , a functional group is generally introduced in 25 stance . the polymer of aqueous polymer composition to make In Patent Literature 9, in addition to the auto -oxidation in cross - linkable , so that a coating film composed of a cross- a mixed system of an alkyd type emulsion and a styrene linked product of polymer (hereinafter referred to as cross acrylic emulsion containing large amounts of carboxylic linked coating film ) can be formed . acid , a styrene- acrylic emulsion ring -opening epoxy group is As an aqueous polymer composition to form a cross - 30 supported as a second cross - linking agent for combination linked coating film , the demand for cold -curing , a cold - use of the cross - linking reaction with dicarboxylic acid curing , one- pack type which is a mixture of a cross - linking dihydrazide. The water resistance of the coating film of agent and a polymer, capable of forming a cross - linked acrylic emulsion containing large amounts of carboxylic coating film in association with evaporation of an aqueous acid , however , is not satisfactory. medium without heating when applied is highly demanded . 35 In Patent Literature 10 , in order to improve the water In response to the demand , a hydrazone cross - linked water resistance of a coating film for exhibiting the stain resis borne polymer dispersions with use of a dehydration con tance , use of isophorone disemicarbazide as cross - linking densation reaction between a carbonyl group and a hydraz agent in a waterborne polymer dispersion formed of copo ide group have attracted attention in recent years . lymer which contains a carbonyl group having a high Tg In the description here , “ cold - curing , one -pack type ” 40 (glass transition temperature ) is disclosed . The combination indicates a paint which forms a coating film at 25° C . , having of a polymer having a high Tg and isophorone disemicar storage stability . In determination of storage stability , for bazide , however , has a disadvantage of incapability of film example , when a coating film formed from a paint applied formation even with use of a coalescing agent , due to to a substrate after storage at 50° C . for 2 weeks has water hardening in a film formation process . resistance , stain resistance , and hardness similar to those of 45 Though isophorone disemicarbazide is disclosed in Patent a coating film formed from the paint before the storage , the Literature 11 , a semicarbazide composition having a large paint is considered to have storage stability . amount of compounds having terminal amino groups is For example , a method for providing a waterborne paint obtained due to use of an excessive amount of hydrazine having both of the cold -curing ability and the storage during reaction , so that use of the semicarbazide composi stability , excellent in hardness , stain resistance , etc . , by 50 tion as cross - linking agent causes a problem that the pro adding dicarboxylic acid dihydrazide as a cross - linking duced cross - linked coating film easily causes yellowing agent to a carbonyl group - containing waterborne polymer when immersed in an aqueous alkali solution . Furthermore , dispersion , has been proposed (Patent Literature 1 to 6 ) . In the production method described in Patent Literature 11, a this method , however, dicarboxylic acid dihydrazide for use step for removing remaining hydrazine is required . as cross - linking agent is hydrolyzed during storage of a 55 waterborne paint , resulting in lowered cross - linking ability CITATION LIST ( curing properties ). In other words, the ability to form a cross - linked coating film having excellent hardness , stain Patent Literature resistance , and solvent resistance is lowered with time. Furthermore , in the above literature , a compound having low 60 Patent Literature 1 : Japanese Patent Publication No . compatibility with a carbonyl group - containing copolymer 46 - 20053 and high hydrophilic properties such as adipic acid dihy - Patent Literature 2 : Japanese Patent Application Laid -Open drazide is used as dicarboxylic acid dihydrazide , causing a No. 57 -3850 disadvantage that the produced cross- linked coating film has Patent Literature 3 : Japanese Patent Application Laid -Open markedly inferior water resistance . 65 No . 57 - 3857 Since the curing properties of a conventional waterborne Patent Literature 4 : Japanese Patent Application Laid - Open paint containing a conventional cross - linking agent and a No . 58 - 96643 US 10 ,023 ,760 B2 Patent Literature 5 : Japanese Patent Application Laid - Open No . Hei- 4 - 249587 Patent Literature 6 : Japanese Patent Application Laid - Open [Chemical Formula 1 ] No. Hei- 6 - 287457 ( 1 - 1 ) Patent Literature 7 : International Publication No . WOS NH2 96 /01252 Patent Literature 8 : Japanese Patent Application Laid -Open No . 2001 - 164126 y -NH , Patent Literature 9 : Japanese Patent Application Laid - Open 10 H3C 4 No . 2008 - 504840 H3C CHCH3, Patent Literature 10 : Japanese Patent Application Laid -Open ( 1 - 2 ) No . 2005 -350580 Patent Literature 11: Japanese Patent No. 4033518 NH 1515 HN SUMMARY OF INVENTION Technical Problem H3C NH2 20 An object of the present invention is to provide a semi H3C CH3 carbazide composition capable of improving the hardness , [Chemical Formula 2 ] the stain resistance , the alkali yellowing resistance , and the like of a waterborne coating film with a small amount of ( 2 - 1 ) addition , and a method for producing the same. Another 25 object of the present invention is to provide an aqueous NH2 polymer composition including the semicarbazide compo HN sition , and a composite having a coating film obtained from the aqueous polymer composition . An aspect of the present invention relates to the following. 30 " NH2 [ 1 ] | HgC P 1 A semicarbazide composition comprising : HzCTH3C a semicarbazide compound (A ) having an amino group (Ms and a semicarbazide group ; 35 a semicarbazide compound ( B - 1 ) having a structure with asa semicarbazide group substituted for the amino group of the semicarbazide compound ( A ); [3 ] a semicarbazide compound ( B - 2 ) as a dimer of the The semicarbazide composition according to [2 ], semicarbazide compound ( B - 1 ); and a dimer of me 40 wherein : a semicarbazide compound (B - 3) as a trimer of the the semicarbazide compound (B - 2) is a compound rep semicarbazide compound ( B - 1 ) ; resented by the following formula ( 2 - 2 ) , and the semicarbazide composition having an analysis area the semicarbazide compound ( B - 3 ) is a compound rep ratio ( a ) represented by the following expression ( a ) of 45 resented by the following formula ( 2 - 3 ): 0 .008 % or more and 2 % or less: [Expression 1 ] [Chemical Formula 3 ] ( 2 - 2 ) Analysis area ratio ( a ) = S2/ ( SA + SB- 1 + SB- 2 + SB- 3 )x100 (a ) 50 (2 - 2 ) wherein SA, SB - 1 , SB- 2 , and SB- 3 represent the peak areas of N N peaks derived from the semicarbazide compound ( A ), the ????????? semicarbazide compound ( B - 1 ) , the semicarbazide com pound ( B - 2 ) , and the semicarbazide compound ( B - 3 ) , 55 respectively , in a chromatogram obtained by high perfor mance liquid chromatography analysis of the semicarbazide [Chemical Formula 4 ] composition . (2 - 3 ) [ 2 ] 0 O accd whereinThe :semicarbazide composition according to [1 ] , " R _ N _ I _N _ N _ _ NN _ R _N N _ O _ NN _ N _ _N _R4 R* the semicarbazide compound ( A ) is a compound repre sented by the following formula (1 - 1) or the following wherein R ' , R2 , R3, and R + each independently represent formula ( 1 - 2 ) ; and 65 a monovalent group represented by the following formula the semicarbazide compound ( B - 1 ) is a compound rep - ( 2 - a ) or the following formula ( 2 - b ) , and R represents a resented by the following formula ( 2 - 1 ) . divalent group represented by the following formula ( 2 - c ) : US 10 ,023 , 760 B2 [Expression 2] [Chemical Formula 5 ] Analysis area ratio (b -1 ) = SB- 1/ ( SA + SB -1 + SB -2 + SB - 3) * ( 2 - a ) 100 (b - 1 ) Analysis area ratio (6 -2 ) = SB - 2/ (SA + SB- 1 + SB -2 + SB -3 ) * - NH2 100 ( b - 2) HNHN CNC Analysis area ratio (6 - 3) = SB - 3/ ( SA + SB - 1 + SB- 2 + SB - 3) * 100 (6 - 3 ) [ 7 ] 10 A method for producing the semicarbazide composition H3C according to any of [ 1 ] to [ 6 ], comprising a reaction step of reacting a compound ( C ) having two or more isocyanate H?c CH, groups in the molecule with hydrazine or a hydrazine [Chemical Formula 6 ] derivative in a solvent to obtain the semicarbazide compo (2 -b ) 15 sition . [ 8 ] The method according to [ 7 ] , wherein the ratio of the min number of moles of the hydrazine or hydrazine derivative to the number of moles of the isocyanate groups of the com pound ( C ) is 0 . 7 to 5 in the reaction step . , NH2 20 191 H3C NH IZ The method according to [ 7 ] or [ 8 ], wherein in the H3C CH3 reaction step , the solvent contains a water- soluble organic solvent and a [Chemical Formula 7] water - insoluble solvent ; and ( 2 - c ) 25 the amount of the water - insoluble solvent relative to the total amount of the water - soluble organic solvent and the mi water - insoluble solvent is 20 mass % or more . [ 10 ] An aqueous solution comprising the semicarbazide com 30 position according to any of [ 1 ] to [ 6 ] in an amount of 5 mass % or more . H3C — [ 11 ] HzCHyd CH3 mo An aqueous polymer composition for use as a waterborne paint or a waterborne coating material comprising: the semicarbazide composition according to any of [ 1 ] to [4 ] [6 ] ; and a polymer reactive with a semicarbazide group to form a The semicarbazide composition according to any of [ 1] to cross - linked structure . [ 3 ] , wherein the semicarbazide composition is a composition [ 12 ] produced by reacting a compound ( C ) having two or more A composite comprising a substrate and a coating film isocyanate groups in the molecule with hydrazine or a 40 formed of the aqueous polymer composition according to hydrazine derivative . [11 ]. [ 13 ] [ 5 ] An aqueous polymer composition comprising a cross The semicarbazide composition according to [ 4 ] , wherein linking agent and a waterborne polymer dispersion ; the compound ( C ) is a compound represented by the fol- 45 the cross -linking agent comprising the semicarbazide lowing formula ( 4 ) : composition according to any of [ 1 ] to [6 ]; and the waterborne polymer dispersion comprising at least one cross -linkable polymer having a glass transition tem [Chemical Formula 8] perature Tg of lower than 80° C ., selected from the group 450 consisting of a water - soluble or water -dispersible polycar NCO?CO bonyl compound having a number average molecular weight of 1000 to 100000 , and a water -soluble or water- dispersible polyepoxy compound having a number average molecular weight of 1000 to 100000 . H3C7 NCO 55 [ 14 ] v NCO The aqueous polymer composition according to [13 ], H3C CH3 wherein the waterborne polymer dispersion is produced by emulsion polymerization . [ 15 ] [6 ] 60 A coating film formed from the aqueous polymer com The semicarbazide composition according to any of [ 1 ] to position according to [ 13 ] or [ 14 ) , comprising a cross- linked [ 5 ] , wherein the analysis area ratio (b - 1 ) represented by the product of the cross- linkable polymer. following expression (b - 1 ) is 50 % ormore and 99 % or less , the analysis area ratio (b - 2 ) represented by the following Advantageous Effects of Invention expression (b - 2 ) is 0 .9 % or more and 30 % or less , and the 65 analysis area ratio ( b - 3 ) represented by the following expres The present invention provides a semicarbazide compo sion ( b - 3 ) is 0 . 01 % or more and 20 % or less : sition capable of improving the hardness , the stain resis US 10 , 023 , 760 B2 tance , the alkali yellowing resistance , and the like of a compound ( A ) is an irreversible reaction , so that a cross waterborne coating film with a small amount of addition , linked coating film including a large amount of cross- linked and a method for producing the same. The present invention structures formed by amino groups has excellent hydrolysis also provides an aqueous polymer composition including the resistance. On the other hand , the presence of a large amount semicarbazide composition , and a composite having a coat- 5 of amino groups in a cross- linked coating film causes a ing film obtained from the aqueous polymer composition . problem of easy yellowing when the coating film is immersed in an aqueous alkali solution . In the present BRIEF DESCRIPTION OF DRAWINGS embodiments , the presence of semicarbazide compound ( A ) FIG . 1 is a chart showing the LC /MS analysis results of 10 in an appropriate range in a semicarbazide composition the semicarbazide composition obtained in Example 1 - 1 . enables formation of a cross- linked coating film excellent in FIG . 2 is a chart showing the LC /MS analysis results of both of the alkali yellowing resistance and the hydrolysis the semicarbazide composition obtained in Example 1 - 2 . resistance . FIG . 3 is a chart showing the LC /MS analysis results of From the viewpoint of further improvement of the prop the semicarbazide composition obtained in Example 1 - 3 . 15 erties of a cross - linked coating film made from a semicar FIG . 4 is a chart showing the LC /MS analysis results of bazide composition ( in particular, alkali yellowing resis the semicarbazide composition obtained in Comparative tance ) , the analysis area ratio ( a ) is preferably 0 .008 % or Example 1 - 1 . more and 1 % or less , more preferably 0 .01 % or more and FIG . 5 is a chart showing the LC /MS analysis results of 0 . 5 % or less. the semicarbazide composition obtained in Comparative 20 In order to have an analysis area ratio ( a ) of 0 . 008 % or Example 1 - 2 . more and 2 % or less, it is important to suppress the forma tion of semicarbazide compound ( A ) in the production step DESCRIPTION OF EMBODIMENTS of the semicarbazide composition , due to difficulty in removal of semicarbazide compound ( A ) from a conven The preferred embodiments of the present invention are 25 tional semicarbazide composition by an operation such as described in detail in the following . The present invention , extraction or separation . however , is not limited to the following embodiments . ( Semicarbazide Composition ) The semicarbazide compound ( A ) is a compound having The semicarbazide composition of the present embodi an amino group and a semicarbazide group . The semicar ments includes a semicarbazide compound having an amino 30 bazide compound ( A ) may have two or more amino groups , group and a semicarbazide group (hereinafter referred to as or may have two or more semicarbazide groups. The semi “ semicarbazide compound (A )" ), a semicarbazide com carbazide group is a group represented by the following pound having a structure with semicarbazide group substi formula (10 ) tuted for the amino group of the semicarbazide compound ( A ) (hereinafter referred to as “ semicarbazide compound 35 ( B - 1 ) " ) , a dimer of the semicarbazide compound ( B - 1 ) [Chemical Formula 9 ] (hereinafter referred to as " semicarbazide compound ( 10 ) ( B - 2 ) " ) , and a trimer of the semicarbazide compound ( B - 1 ) (hereinafter referred to as “ semicarbazide compound man HN ( B - 3 ) ” ) . - 8 – – NH, The semicarbazide composition of the present embodi 40 ments has an analysis area ratio ( a ) represented by the following expression ( a ) of 0 .008 % or more and 2 % or less . The semicarbazide compound ( B - 1 ) is a compound hav ing a structure with semicarbazide groups substituted for all [Expression 3 ] 45 the amino groups of the semicarbazide compound ( A ) . In other words, the semicarbazide compound ( B - 1 ) is a com Analysis area ratio ( a )= S2 /( SA + Sp +1 + SB -2 + SB -3 ) x100 pound having no amino group and at least two semicarba In the expression , S4 represents the peak area of the peak derived from semicarbazide compound ( A ) in a chromato gram obtained by high performance liquid chromatography 50 (h . The semicarbazide composition has an analysis area ratio analysis of the semicarbazide composition , SB -1 represents BU (b - 1 ) represented by the following expression (b - 1 ) of the peak area of the peak derived from semicarbazide preferably 50 % or more and 99 % or less . In the expression , compound ( B - 1 ) in the chromatogram , SB - 2 represents the S? , SB- 1 , SB - 2 , and SB- 3 are the same as defined above . peak area of the peak derived from semicarbazide compound ( B - 2 ) in the chromatogram , and SR - z represents the peak area 55 [ Expression 4 ] of the peak derived from semicarbazide compound ( B - 3 ) in the chromatogram . Analysis area ratio ( b - 1 ) = SB -1 / ( SA + SB - 1 + SB -2 + SB - 3) * With an analysis area ratio (a ) of 2 % or less, the alkali 100 (6 - 1) yellowing resistance of the cross - linked coating film made The semicarbazide compound ( B - 2 ) is a dimer of the from a semicarbazide composition can be remarkably 60 semicarbazide compound ( B - 1 ) . It can be said that the improved . With an analysis area ratio (a ) of 0 .008 % or more, semicarbazide compound (B -2 ) is a compound of two semi the hydrolysis resistance of the cross - linked coating film carbazi de compounds ( B - 1 ) coupled by a condensation made from a semicarbazide composition is remarkably reaction of semicarbazide groups , having a bond represented improved by the following formula (11 ) . Alternatively it can be said The cross -linking reaction of the semicarbazide group is 65 that the semicarbazide compounds ( B - 2 ) is a compound a reversible reaction in the presence of water , while the having two or more semicarbazide groups and one bond cross - linking reaction of the amino group of a semicarbazide represented by the following formula ( 11) . US 10 , 023 ,760 B2 10 (MODEL MCD - 2000 ) and the supernatant thereof is mea [ Chemical Formula 10 ] sured by LC /MS . The device configuration of the LC /MS includes an “ AGILENT, 1100 series” as LC and “ THERMO (11 ) ELECTRON , LCQ ” as MS. Each of the peaks obtained by = 5 the measurement is identified by MS, and the peak area of ZI N N each peak is obtained from the area value of the absorbance at 200 nm in the ultraviolet - visible detector in LC . fului The measurement conditions for LC /MS are shown in the following . The LC conditions are shown in the first place . The semicarbazide composition has an analysis area ratio 10 By using an LC column of Phenomenex , Kinetex 2 .6u ( b - 2 ) represented by the following expression ( b - 2 ) of C18 - XB 100A ( 2 . 1 mm LD . X50 mm ), at a column oven preferably 0 . 9 % or more and 30 % or less . In the expression , temperature of 40° C ., with two types of solutions, i .e . a SA , SB -1 , SB -2 , and SB- 3 are the same as defined above. With 0 .1 % formic acid aqueous solution (a ) and a 0 . 1 % formic an analysis area ratio (b - 2 ) in the range, the resulting coating acid containing methanol solution ( b ) as the solvents for the film can be further toughened . 15 mobile phase , the liquid composition is linearly changed [Expression 5 ] from 98 % of liquid ( a ) to 100 % of liquid ( b ) in 5 minutes , and then brought back to 98 % of liquid ( a ) again in 5 . 1 Analysis area ratio (6 - 2 ) = SB - 2/ (SA + SB - 1 + SB- 2 + SB -3 ) * minutes , so that the liquid composition with 98 % of liquid 100 (b -2 ) (a ) is maintained for 12 minutes. The flow rate of the mobile The semicarbazide compound ( B - 3 ) is a trimer of the 20 phase is set to 0 . 4 ml/min , and the sample injection volume semicarbazide compound ( B - 1 ) . It can be said that the is set to 1 ul. semicarbazide compound ( B - 3 ) is a compound of three The wavelength of the ultraviolet - visible absorption semicarbazide compounds ( B - 1 ) bonded by a condensation detector attached to LC is set to 200 nm . The wavelength of reaction of semicarbazide groups , or a compound of the the detector can be appropriately changed according to the semicarbazide compound ( B - 2 ) and the semicarbazide com - 25 substance to be handled , and a wavelength of 200 nm is pound ( B - 1 ) bonded by a condensation reaction of semicar- preferred for the semicarbazide composition obtained by the bazide groups. Alternatively it can be said that the semicar - reaction of isophorone diisocyanate with hydrazine . bazide compound (B - 2 ) is a compound having two or more The MS conditions are shown in the second place. In semicarbazide groups and two bonds represented by formula positive mode of ESI ( Electrospray Ionization ), scanning is ( 11 ) . 30 performed with a mass - to - charge ratio ( m / z ) in the range of The semicarbazide composition has an analysis area ratio 150 to 1000 . ( b - 3 ) represented by the following expression (b - 3 ) of Each of the semicarbazide compound ( A ) , the semicar preferably 0 .01 % or more and 20 % or less . In the expres bazide compound ( B - 1 ) , the semicarbazide compound ( B - 2 ) , and the semicarbazide compound ( B - 3 ) may include sionWith , S4an , analysisSB - 1, SB - area 2, and ratio SB - 3( bare - 3 ) thein thesame range as defined , the resulting above . 35 a plurality of isomers . In this case , the sum of the peak areas coating film can be further toughened . of a peak group including a plurality of isomers is assumed to be the peak area for each of the semicarbazide compound [Expression 6] ( A ) , the semicarbazide compound ( B - 1 ) , the semicarbazide compound ( B - 2 ) , and the semicarbazide compound ( B - 3 ) . Analysis area ratio ( b - 3 ) = SB- 3 /( SA + SB - 1 + SB- 2 + SB- 3 ) * 40 For example , in the following aspects , each of the com 100 ( 6- 3 ) pounds represented by formulas (1 - 1 ) , ( 1 - 2 ), ( 2 - 1 ) , ( 2 -2 ) and In a semicarbazide composition , the total content of the ( 2 - 3 ) may have a plurality of isomers. On this occasion , the semicarbazide compound ( A ) , the semicarbazide compound peak area of the semicarbazide compound ( A ) is the sum of (B -1 ), the semicarbazide compound (B -2 ), and the semicar - the peak areas of the group of compounds represented by bazide compound ( B - 3 ) is preferably 90 mass % or more , 45 formula ( 1 - 1) or ( 1 - 2 ), the peak areas of the semicarbazide more preferably 95 mass % or more , furthermore preferably compound (B - 1 ) is the sum of the peak areas of the group of 98 mass % or more , based on the total amount of the compounds represented by formula ( 2 - 1 ) , the peak area of semicarbazide composition . the semicarbazide compound ( B - 2 ) is the sum of the peak Although the semicarbazide composition may contain areas of the group of compounds represented by formula high molecular weight components , i. e . the tetramer or more 50 ( 2 - 2 ) , and the peak area of the semicarbazide compound of the semicarbazide compound ( A ) , such high molecular ( B - 3 ) is the sum of the peak areas of the group of compounds weight components are insoluble in water in many cases , so represented by formula ( 2 - 3 ) . that the content of the high molecular weight components is Even a semicarbazide composition contained in the aque preferably small. For example , the content of the high ous polymer composition of a paint or the like can be molecular weight components is preferably 1 . 0 mass % or 55 analyzed , for example , by the following method . First , the less , more preferably 0 . 5 mass % or less, furthermore paint is diluted with water , and subjected to centrifugal preferably 0 . 1 mass % or less , based on the total amount of separation for sampling the supernatant. After precipitation the semicarbazide composition . of latex by ultracentrifugation , the supernatant is passed The high performance liquid chromatography analysis of through a dialysis membrane (Molecular weight cut off : a semicarbazide composition may be performed with an 60 10000 ). Subsequently the liquid passing through the dialysis LC /MS (Liquid Chromatograph Mass Spectrometer ) by the membrane is concentrated into a concentrate , which is following method . analyzed by LC /MS so as to obtain the peak areas of the (Analysis Method ) peaks derived from the semicarbazide compounds ( A ), A semicarbazide composition is freeze -dried and then a ( B - 1 ), ( B - 2 ), and (B -3 ). In order to further detect the 10 mg/ml of aqueous solution is prepared . Subsequently, the 65 semicarbazide compound ( A ) immobilized in latex , the latex solution is centrifuged at 12000 rpm for 10 minutes with a precipitated by ultracentrifugation is re -dispersed in water . centrifugal separator made by Hsiangtai Machinery Industry The re -dispersed solution and a cation exchange polymer are US 10 ,023 , 760 B2 12 mixed for adsorption of alkali components , and the cation exchange polymer is filtered and substituted with a diluted [ Chemical Formula 15 ] KOH aqueous solution . The aqueous solution is analyzed by LC /MS for detection of the semicarbazide compound ( A ) ( 2 -a ) immobilized in latex . Subsequently , one preferred aspect of the semicarbazide NH2 composition is described in the following . In the present HN IZ aspect, the semicarbazide compound ( A ) is a compound represented by the following formula ( 1 - 1 ) or the following formula ( 1- 2 ), and the semicarbazide compound (B - 1) is a 10 compound represented by the following formula ( 2 - 1 ). H3CH3CH mm Hz? CH3 [Chemical Formula 11 ] [ Chemical Formula 16 ] (1 - 1) 15 ( 2 - b ) NH2 winan NH2 H3C N IZ 20 NH2 H3C H3CR ( 1 - 2 ) H3C CH3 [ Chemical Formula 17 ] V -NH NH2, 25 ( 2 - c ) HNZoal ? min

H3C NH2 30 H3C CH3 H3C [Chemical Formula 12 ] H3C (2 - 1) 35 The semicarbazide composition of the present aspect is FO NH2 excellent particularly in water -solubility , being suitably used HN † as a cross- linking agent for a waterborne paint, in particular . Further, the semicarbazide composition of the present aspect with an analysis area ratio ( a ) in the specific range more NH2 remarkably exhibits the effect of the present invention . H3C A semicarbazide composition can be obtained by, for HzC CHz example , reacting a compound having two or more isocya nate groups in the molecule (hereinafter referred to as Further, in the present aspect , the semicarbazide com - 45 “ isocyanate compound (C )” ) with hydrazine or a hydrazine pound ( B - 2 ) is a compound represented by the following derivative (hereinafter referred to as “ hydrazines (D )” ) . formula ( 2 - 2 ), and the semicarbazide compound ( B - 3 ) is a On this occasion , the semicarbazide compound (A ) is a compound represented by the following formula ( 2 - 3 ) . compound in which a portion of isocyanate groups of the isocyanate compound ( C ) is converted to amino groups and 50 another portion is converted into semicarbazide groups . The [Chemical Formula 13 ] semicarbazide compound ( B - 1 ) is a compound in which the ( 2 - 2 ) entire isocyanate groups of the isocyanate compound ( C ) are converted to semicarbazide groups . Examples of the isocyanate compound ( C ) include a R _ N _ O _ N _ N _ O _ N _ R ? 55 diisocyanate compound having two isocyanate groups in the molecule and a polyisocyanate compound having three or [Chemical Formula 14 ] more isocyanate groups in the molecule , (2 -3 ) Examples of the diisocyanate compound include an alky lene diisocyanate such as N - hexamethylene diisocyanate 03 _ H _ O_ _ _ # _ _ # _ D _ H _ I _ # _ # _ ! _ _ 04 60 (HDI ) ; a cycloalkylene diisocyanate such as 4, 4 ' - methylene N - C - Ñ - Ñ - Ö - N - R4 bis ( cyclohexyl) diisocyanate (hydrogenated MDI) , iso phorone diisocyanate ( IPDI) , and dimethyl cyclohexane In the formulas , R ' , R ? , R , and R4 each independently diisocyanate ( hydrogenated XDI) ; an arylene diisocyanate represent a monovalent group represented by the following such as 2 ,4 - tolylene diisocyanate , 2 ,6 -tolylene diisocyanate formula ( 2- a ) or the following formula ( 2- b ), and R $ repre - 65 and a mixture thereof ( TDIs ), diphenylmethane- 4 ,4 '- diiso sents a divalent group represented by the following formula cyanate (MDI ) , naphthalene - 1, 5 -diisocyanate (NDI ) , 3 , 3 ( 2 - c ) . dimethyl -4 , 4 - diphenylene diisocyanate ( TODI) , crude TDIS , US 10 ,023 , 760 B2 13 14 polymethylene polyphenyl diisocyanate , crude MDI, and isopropanol, 1 - butanol, 2 - butanol butyl cellosolve, propyl phenylene diisocyanate ; and an aralkylene diisocyanate such ene glycol monopropyl ether , and octyl alcohol; esters such as xylylene diisocyanate (XDI ) ; which may be used in as methyl acetate , ethyl acetate and butyl acetate ; ethers such combination . as diethyl ether, tetrahydrofuran , dioxane , dimethoxyethane , Examples of the polyisocyanate compound include trimer 5 and diethylene glycol dimethyl ether ; ketones such as to 20 -mers oligomerized from a diisocyanate compound by acetone , methyl ethyl ketone, methyl isobutyl ketone ; forming a biuret bond , a urea bond , an isocyanurate bond, a amides such as dimethylformamide and dimethylacetamide ; chlorinated solvents such as methylene chloride, chloro urethane bond , an allophanate bond , or a uretdione bond . For form , and carbon tetrachloride; and nonpolar solvents such further information on the method for producing these 10 as toluene , xylene, hexane , cyclohexane , and petroleum polyisocyanate compounds and the bonds in polyisocyanate ether . Among them , ketones cause dehydration condensation compounds , refer to , for example , “ Polyurethane Hand with a semicarbazide compound , so that hydrolysis with book ” edited by G . Oertel (Hauser Publishers , Germany, water is required after reaction . 1985) . The solvent for use in the reaction into semicarbazide is | As the isocyanate compound ( C ), diisocyanate com - 15 not necessarily a solvent which dissolves both the isocyanate pounds are preferred , and isophorone diisocyanate is par compound (C ) and the hydrazines (D ), because the reaction ticularly preferred . Isophorone diisocyanate is a compound can be performed with forced agitation in a reaction vessel . represented by the following formula ( 4 ) , and the semicar - Alternatively, a water -soluble organic solvent and a bazide composition obtained from isophorone diisocyanate water - insoluble organic solventmay be used in combination can be particularly suitably used as a cross - linking agent for 20 as the solvent, with a ratio of the amount of water - insoluble a waterborne paint or the like, with high water- solubility . organic solvent to the total amount of solvent at the end of the reaction of preferably 20 mass % or more , more pref erably 30 mass % or more , furthermore preferably 45 mass [Chemical Formula 18 ] % or more . The ratio may be 100 mass % . ( 4 ) 25 Examples of the water -soluble organic solvent include the NCO alcohols , the esters , the ethers , the ketones, and the amides described above. Examples of the water- insoluble organic solvent include the chlorinated solvents and the non -polar solvents described above . H3CH3C NCO 30 Although the reaction into semicarbazide may be per formed at any temperature , the temperature is preferably 0 HzC CH3 to 100° C . , more preferably 0 to 50° C ., from the viewpoint of sufficiently suppressing the formation of the dimer semi Examples of the hydrazines ( D ) include hydrazine and a carbazide compound ( B - 2 ) and the trimer semicarbazide hydrate thereof; a monoalkyl- substituted hydrazine com - 35 compound ( B - 3 ) as byproducts so as to increase the yield of pound such as monomethyl hydrazine , monoethyl hydra - the semicarbazide compound ( B - 1 ) . zine , and monobutyl hydrazine ; a dihydrazine compound Although the reaction into semicarbazide may be per such as ethylene - 1 , 2 -dihydrazine , propylene- 1 , 3 - dihydra - formed by any method for mixing the isocyanate compound zine , and butylene - 1 , 4 - dihydrazine ; a dicarboxylic acid ( C ) and the hydrazines ( D ) , a reaction method of adding the dihydrazide such as oxalic acid dihydrazide , malonic acid 40 isocyanate compound ( C ) or the solution thereof into the dihydrazide , succinic acid dihydrazide , glutaric acid dihy - hydrazines ( D ) or the solution thereof; a reaction method of drazide , adipic acid dihydrazide , sebacic acid dihydrazide, simultaneously adding the isocyanate compound ( C ) or the maleic acid dihydrazide , fumaric acid dihydrazide, itaconic solution thereof and the hydrazines (D ) or the solution acid dihydrazide, isophthalic acid dihydrazide, and phthalic thereof into a solvent; or a reaction method of simultane acid dihydrazide ; a reaction product of hydrazine and a 45 ously adding the isocyanate compound ( C ) or the solution compound having two or more carboxyl groups such as a thereof into the hydrazines ( D ) or the solution thereof are tricarboxylic acid trihydrazide such as trimellitic trihydraz- preferred from the viewpoint of further suppressing side ide , and a mixture thereof. reactions. In the reaction of the isocyanate compound ( C ) with the After the reaction into semicarbazide , the semicarbazide hydrazines (D ) (hereinafter referred to as “ reaction into 50 composition having an analyzed area ratio ( a ) in the range semicarbazide ” in some cases ) , the ratio of the amount used can be obtained through , for example , extraction operation X , (mol ) ofthe hydrazines (D ) to the total number Xc (mol ) or the like from the reaction liquid of the isocyanate groups of the isocyanate compound (C ), Examples of the extraction operation include distillation , i. e . X / Xc, is preferably 0 .7 to 2 .50 , more preferably 0 .75 to crystallization , and column chromatography . Among them , 1 . 19 , furthermore preferably 0 . 80 to 0 . 99 . As the ratio 55 an extraction operation requiring no heating ( e . g . crystalli X Xc increases, the basicity of the reaction system is zation , column chromatography, extraction with water from enhanced , so that isocyanate groups tend to be easily con - suspension in organic solvent) is preferred to avoid yellow verted to amino groups . With a ratio X Xc in the range , a ing by heating. sufficient reaction rate can be obtained , and the conversion The solvent for use in crystallization is not particularly of isocyanate groups to amino groups can be sufficiently 60 limited as long as the solvent is nonreactive with the suppressed . With a ratio X Xc in the range , the hydrazines semicarbazide composition , and examples thereof include ( D ) hardly remain unreacted , resulting in another advantage alcohols such as methanol, ethanol, isopropanol, 1 -butanol , that the operation to remove the unreacted hydrazines ( D ) is 2 -butanol butyl cello solve, and propylene glycol monopro unnecessary after the reaction . pyl ether ; esters such as methyl acetate , ethyl acetate and The reaction into semicarbazide may be performed using 65 butyl acetate ; ethers such as diethyl ether, tetrahydrofuran , a suitable solvent, on an as needed basis . Examples of the dioxane, dimethoxyethane , diethylene glycol dimethyl solvent include water ; alcohols such as methanol, ethanol, ether; and amides such as dimethylformamide and dimethy US 10 , 023 , 760 B2 15 16 lacetamide . Among them , ethers are preferred , with the and Japanese Patent No. 3212857 ) . Among them , the com solubility of the semicarbazide compound ( B - 1 ) being bination use with adipic acid dihydrazide having water greatly different depending on temperature ; and dioxane , solubility is particularly preferred . The molar ratio between tetrahydrofuran , and dimethoxyethane are more preferred . the semicarbazide composition and a compound for combi In the method of extraction with water from suspension in 5 nation use is preferably in the range of 100 / 0 to 0 . 1 /99 . 9 , organic solvent, an organic solvent hardly dissolving the more preferably in the range of 90 / 10 to 10 / 90 . With the semicarbazide compound ( B - 1 ) can be used , and examples combination use of the semicarbazide composition and of the organic solvent for suitable use include non - polar another compound in coating film formation of an aqueous solvents such as toluene , xylene, hexane , cyclohexane , and polymer composition , an excellent coating film having both petroleum ether. 10 of rigidity and flexibility , or having flexibility , stain resis Alternatively , a semicarbazide composition may be suit - tance , hardness , etc ., all together can be obtained . ably obtained by reacting the isocyanate compound ( C ) and The semicarbazide composition may be added to an the hydrazines ( D ) with forced agitation , suspending water aqueous polymer composition , for example , in an aqueous after completion of the reaction , and then extracting the solution form diluted with water . Examples of the aqueous semicarbazide composition with water . 15 solutions include an aqueous solution containing 5 mass % The semicarbazide composition obtained by the extrac or more ( preferably 25 mass % or more, more preferably 40 tion operation may be directly used or may be diluted with mass % or more ) of the semicarbazide composition . The a solvent for use. Though examples of the diluting solvent semicarbazide composition concentration maybe 95 mass % include water ; alcohols such as methanol, ethanol, isopro - or less , preferably 80 mass % or less . Alternatively , the panol, and butanol; and a coalescing agent such as butyl 20 semicarbazide composition in a solid form may be directly cellosolve , CS - 12 (made by JNC Corporation ), and butyl added to an aqueous polymer composition without dilution carbitol; water is preferred to reduce volatile organic sol- with water or the like. vent . (Aqueous Polymer Composition ) The semicarbazide composition can be suitably used as a The aqueous polymer composition of the present embodi cross - linking agent for a polymer capable of forming a 25 ment contains the semicarbazide composition described cross - linked structure by reacting with semicarbazide above and a polymer which can form a cross - linked struc groups . More specifically , the semicarbazide composition ture by reacting with semicarbazide groups (hereinafter can be suitably used as a cross- linking agent to be added to referred to as “ polymer ( E ) ” ) . According to the aqueous an aqueous polymer composition containing a polymer polymer composition of the present embodiment, a coating capable of forming a cross- linked structure by reacting with 30 film having excellent hardness , stain resistance and alkali semicarbazide groups. yellowing resistance can be formed , so that the aqueous The semicarbazide composition can be used in combina - polymer composition can be suitably used as a waterborne tion with another compound having two or more hydrazide paint or a waterborne coating material. groups or semicarbazide groups . Examples of the compound The polymer ( E ) is not particularly limited as long as a include a saturated aliphatic carboxylic acid dihydrazide 35 cross -linked structure can be formed with a reaction with having 2 to 18 carbon atoms such as oxalic acid dihydrazide , semicarbazide groups, and examples of the polymer ( E ) malonic acid dihydrazide, glutaric acid dihydrazide, suc include a compound having a plurality of carbonyl groups cinic acid dihydrazide , adipic acid dihydrazide , and sebacic (hereinafter referred to as “ polycarbonyl compounds” , a acid dihydrazide ; a monoolefinic unsaturated dicarboxylic compound having a plurality of epoxy groups (hereinafter acid dihydrazide such as maleic acid dihydrazide , fumaric 40 referred to as “ polyepoxy compound” ), and the like . acid dihydrazide , and itaconic acid dihydrazide ; an acid The polymer ( E ) is preferably obtained as a waterborne dihydrazide compound such as phthalic acid dihydrazide, polymer dispersion by emulsion polymerization or the like . terephthalic acid dihydrazide, isophthalic acid dihydrazide , The waterborne polymer dispersion is a liquid composition pyromellitic acid dihydrazide , pyromellitic acid trihydraz with the polymer ( E ) dispersed in water, and a suitable ide , and pyromellitic acid tetrahydrazide ; nitrilotrihydrazide , 45 aqueous polymer composition can be obtained by adding the citric acid trihydrazide , 1 , 2 , 4 -benzene trihydrazide , ethyl- semicarbazide composition to the waterborne polymer dis enediamine tetraacetic acid tetrahydrazide , 1 , 4 ,5 , 8 -naph persion . thoic acid tetrahydrazide , polyhydrazide produced by react Among the polymers ( E ), a polycarbonyl compound is ing a low polymer having a carboxylic acid lower alkyl ester particularly preferred , because when combined with a semi group with hydrazine or a hydrazine hydrate (refer to 50 carbazide composition , excellent storage stability of an Japanese Patent Publication No. 52 - 22878 ) ; carbonate dihy - aqueous polymer composition can be achieved and a coating drazide and bis semicarbazide ; polyfunctional semicarbaz film excellent in weather resistance , water resistance , stain ide obtained by reacting a polyisocyanate compound having resistance , hardness, etc . can be produced at relatively low an allophanate group obtained by allophanatization reaction temperature . after or in parallel with urethanization reaction between 55 Examples of the polycarbonyl compound include a car alcohols and diisocyanate such as hexamethylene diisocya - bonyl group -containing copolymer, carbonyl group - contain nate and isophorone diisocyanate with a hydrazine com - ing polyurethanes made from raw material mono - or poly pound or the dihydrazide exemplified above , an aqueous alcohol having a carbonyl group such as hydroxyacetone polyfunctional semicarbazides obtained by reacting an iso - described in Japanese Patent Application Laid - Open No. cyanate group in a reaction product between the polyiso - 60 Hei - 2 - 238015 , acetoacetylated polyvinyl alcohol, a polyvi cyanate compound and an active hydrogen compound con - nyl alcohol polymer having a di acetone group in a side taining a hydrophilic group of polyether polyols and chain described in Japanese Patent Application Laid - Open polyethylene glycol monoalkyl ethers with the exemplified No . Hei - 9 -324095 , acetoacetylated hydroxyalkyl cellulose , dihydrazide , or a mixture of the polyfunctional semicarba - and a combination thereof. zide and an aqueous polyfunctional semicarbazide (refer to 65 Among these polycarbonyl compounds , a carbonyl group Japanese Patent Application Laid - Open No, Hei - 8 - 151358 , containing copolymer produced by copolymerization of a Japanese Patent Application Laid -Open No. Hei 8 - 245878 , carbonyl group - containing ethylenically unsaturated mono US 10 , 023 , 760 B2 17 18 mer ( a ) and an ethylenically unsaturated monomer ( B ) having an epoxy group include glycidyl( meth ) acrylate , 2 , 3 copolymerizable with the carbonyl group - containing ethyl - cyclohexene oxide( meth )acrylate , and allyl glycidyl ether . enically unsaturated monomer ( a ) is preferred , and a car - Specific examples other than the above include : olefins bonyl group - containing copolymer produced by copolymer such as ethylene , propylene , and isobutylene ; dienes such as ization of 0 . 1 to 30 mass % of a carbonyl group containing 5 butadiene; halo -olefins such as vinyl chloride and vinylidene chloride ; carboxylic acid vinyl esters such as vinyl acetate , ethylenically unsaturated monomer ( a ) and 70 to 99. 9 mass vinyl propionate , vinyl n -butyrate , vinyl benzoate , p -t - butyl % of an ethylenically unsaturated monomer ( B ) copolymer vinylbenzoate , vinyl pivalate , vinyl 2 - ethyl hexanoate , vinyl izable with the carbonyl group - containing ethylenically versatate , and vinyl laurate ; carboxylic acid isopropenyl unsaturated monomer (a ) is more preferred . 10 esters such as isopropenyl acetate and isopropenyl propi Examples of the carbonyl group - containing ethylenically onate ; vinyl ethers such as ethyl vinyl ether, isobutyl vinyl unsaturated monomer ( a ) include diacetone acrylamide , ether and cyclohexyl vinyl ether ; aromatic vinyl compounds diacetone methacrylamide , acrolein , vinyl methyl ketone, such as styrene and vinyl toluene ; allyl esters such as allyl acetoacetoxyethylmethacrylate , acetoacetoxyethyl acrylate , acetate and allyl benzoate ; allyl ethers such as allyl ethyl and formylstyrol, and a combination thereof. 15 ether and allyl phenyl ether ; y - (meth )acryloxy propylt Examples of the ethylenically unsaturated monomer (B ) rimethoxysilane , 4 - meth ) acryloyloxy - 2 , 2 , 6 , 6 - tetramethyl copolymerizable with the carbonyl group -containing ethyl piperidine, 4 - (meth ) acryloyloxy - 1 , 2 , 2 ,6 , 6 -pentamethylpip enically unsaturated monomer ( a ) include an acrylic acid eridine, perfluoromethyl( meth ) acrylate , perfluoropropyl ester , a methacrylic acid ester , ethylenically unsaturated (meth )acrylate , perfluoropropylomethyl (meth )acrylate , monomers having a carboxyl group , ethylenically unsatu - 20 vinylpyrrolidone, trimethylolpropane tri (meth )acrylate , and rated monomers having an epoxy group , an acrylamide allyl( methacrylate , and combinations thereof. monomer, a methacrylamide monomer, and vinyl cyanides ; The polycarbonyl compound is preferably obtained by and examples of the meth )acrylic acid ester include a suspension polymerization , emulsion polymerization , or (meth ) acrylic acid alkyl ester with an alkyl portion having 1 solution polymerization , and more preferably obtained from to 18 carbon atoms, a (methacrylic acid hydroxyalkyl ester 25 a carbonyl group - containing waterborne polymer dispersion with an alkyl portion having 1 to 18 carbon atoms, a ( aqueous polymer emulsion ) by emulsion polymerization . A (poly ) oxy -ethylene (meth ) acrylate having 1 to 100 ethylene particularly suitable aqueous polymer composition can be oxide groups, a (poly )oxypropylene ( meth )acrylate having 1 obtained by preparing a polycarbonyl compound in a water to 100 propylene oxide groups, and ( polyoxyethylene borne polymer dispersion form and adding a semicarbazide di( meth )acrylate having 1 to 100 ethylene oxide groups. 30 composition to the waterborne polymer dispersion . Specific examples of the acrylic acid ester and the meth - The waterborne polymer dispersion is preferably a car acrylic acid ester include methyl( meth )acrylate , ethyl( meth ) bonyl group - containing acrylic copolymer dispersion with acrylate , n -butyl (meth ) acrylate , iso - butyl (meth ) acrylate use of acrylic monomers . Preferably the polycarbonyl com tert -butyl ( meth )acrylate , 2 - ethylhexyl( meth ) acrylate , pound is obtained as waterborne polymer dispersion by methyl cyclohexyl (methacrylate , cyclohexyl (meth ) acry - 35 copolymerizing a carbonyl group - containing ethylenically late , dodecyl (meth )acrylate , stearyl( methacrylate , and ada unsaturated monomer ( a ) and an ethylenically unsaturated mantyl(meth )acrylate . monomer ( B ) under presence of an anion - type ethylenically Specific examples of the (methacrylic acid hydroxyalkyl unsaturated monomer ( Y ) selected from the group consisting ester include 2 -hydroxyethyl ( methacrylate , 2 -hydroxypro of, for example , an ethylenically unsaturated monomer pyl( meth ) acrylate , 2 -hydroxycyclohexyl ( meth ) acrylate , and 40 having a sulfonic acid group or a sulfonate group , an dodecyl( meth )acrylate . ethylenically unsaturated monomer having a sulfonic acid Specific examples of the (poly ) oxyethylene( methacry - ester group , and a mixture thereof. late include ethylene glycol( meth ) acrylate , ethylene glycol Emulsion polymerization to produce the polymer ( E ) methoxy (methacrylate , diethylene glycol( meth ) acrylate , (polycarbonyl compound , in particular ) can be performed in diethylene glycol methoxy( meth )acrylate , tetraethylene gly - 45 an aqueousmedium using a surfactant. As the surfactant for col( meth )acrylate , and tetraethylene glycol methoxy (meth ) use in the emulsion polymerization , a so - called reactive acrylate . surfactant having an ethylenic double bond group in the Specific examples of the (poly )oxypropylene (meth )acry chemical structural formula of the surfactant having a hydro late include propylene glycol( meth ) acrylate , propylene gly philic group and a lipophilic group , so as to impart high col methoxy (methacrylate , dipropylene glycol( meth ) acry - 50 water resistance to a coating film . late, dipropylene glycolm ethoxy (meth )acrylate , Among the reactive surfactants , examples of the anionic tetrapropylene glycol( meth )acrylate , and tetrapropylene gly - surfactant include an ethylenically unsaturated monomer col methoxy (meth )acrylate . having a sulfonic acid group , a sulfonate group , a sulfonic Specific examples of the (poly ) oxyethylene di( meth )acry - acid ester group , or a salt thereof; and a compound having late include ethylene glycol di( meth )acrylate , diethylene 55 a sulfonic acid group , an ammonium salt of sulfonic acid glycol di (meth )acrylate , diethylene glycol methoxy (meth ) group (ammonium sulfonate group ), or a group as alkali acrylate , and tetraethylene glycol di( meth Jacrylate . metal salt of sulfonic acid group ( alkali metal sulfonate Specific examples of the ethylenically unsaturated mono group ) can be suitably used . Specific examples include alkyl mers having a carboxyl group include acrylic acid , meth - allyl sulfosuccinate (e . g . trade name : ELEMINOL JS - 2 and acrylic acid , itaconic acid , fumaric acid , maleic acid , a half 60 JS - 5 , made by Sanyo Chemical Industries , Ltd . ; and trade ester ofmaleic acid , and crotonic acid . name: LAIEMUL S - 120 , S - 180A , and S - 180 , made by Kao Examples of the (methacrylamide monomers include Corporation ), polyoxyethylene alkyl propenyl phenyl ether (meth ) acrylamide, N - isobutyl( meth )acrylamide , N - diethyl sulfate ( e . g . trade name: Aqualon HS - 10 , made by Dai- ichi (meth ) acrylamide , N -methylol ( meth ) acrylamide , N - bu Kogyo Seiyaku Co ., Ltd . ) , a - [ 1 - [ (allyloxy )methyl ] - 2 - ( phe toxymethyl (meth )acrylamide , and vinyl pyrrolidone; 65 nylphenoxy )ethyl ]- w -polyoxyethylene sulfate ( e. g trade examples of the vinyl cyanide include (methacrylonitrile ; name: ADEKARIA SOAP SE - 1025A , made by Adeka Cor and examples of the ethylenically unsaturated monomers poration ), an ammonium salt of a -sulfo - -( 1 - alkoxy ) US 10 , 023 , 760 B2 19 20 methyl) - 2 - ( 2 - propenyloxy ) ethoxy) -poly ( oxy - 1 - 2 - eth under high pressure corresponding to the properties of the anediyl) ( e . g . trade name: SR - 1025 , made by Adeka monomer such as vapor pressure at the polymerization Corporation ) , and ammonium = a - sulfonate - w - 1 - ( allyloxym - temperature . When acceleration of the polymerization rate ethyl) alkyloxy polyoxyethylene ( e . g . trade name: AQUA or polymerization at a low temperature of 70° C . or lower is LON KH - 10 , made by Dai - ichi Kogyo Seiyaku Co . , Ltd .) . 5 desired , use of a reducing agent such as sodium bisulfite , Specific examples of the compound having aryl groups ferrous chloride , ascorbate , and Rongalite , in combination partially substituted with sulfonate groups include an ammo - with a radical polymerization initiator is advantageous . nium salt , a sodium salt , and a potassium salt of p -styrene Further, a chain transfer agent such as dodecyl mercaptan sulfonic acid . Examples of the vinyl sulfonate compound may be optionally added for regulation of the molecular having a vinyl group to which the group of ammonium salt , 10 weight . sodium salt , or potassium salt of a sulfonic acid group is Since the aqueous polymer composition containing a bonded include alkyl sulfonic acid (methacrylate such as polycarbonyl compound as the polymer (E ) has long - term 2 -sulfoethyl acrylate , and an ammonium salt, sodium salt, storage stability , preferably the pH is adjusted to within the and potassium salt of methyl propane sulfonic acid (meth ) range of 5 to 10 . For the pH adjustment, ammonia , sodium acrylamide, allyl sulfonic acid , etc . 15 hydroxide , potassium hydroxide , amines such as dimethyl Examples of the nonionic surfactant include a - [ 1 - [ ( ally amino ethanol, acids such as hydrochloric acid , sulfuric loxy )methyl ) - 2 - (phenylphenoxy ) ethyl] - w -hydroxy -poly acid , acetic acid , and lactic acid may be added to the aqueous oxyethylene ( e. g . trade name: ADEKARIA SOAP NE - 20 , polymer composition . NE -30 , NE -40 , ER - 10 , ER - 20 , ER - 30 , and ER -40 , made by Examples of the polyepoxy compound as the polymer (E ) Adeka Corporation ), and polyoxyethylene alkyl propenyl- 20 include an epoxy group -containing copolymer produced by phenyl ether ( e .g . trade name: AQUALON RN - 10 , RN - 20 , copolymerization of epoxy group -containing ethylenically RN - 30 , and RN - 50 , made by Dai - ichi Kogyo Seiyaku Co ., unsaturated monomers such as glycidyl( meth )acrylate with Ltd .) . other unsaturated monomers by bulk polymerization , sus In emulsion polymerization , a conventional surfactant pension polymerization , emulsion polymerization , solution may be used other than the reactive surfactant having an 25 polymerization , or the like ; a bisphenol A - type epoxy resin ; ethylenic double bond group in the chemical structural a bisphenol F - type epoxy resin ; an alicyclic epoxy resin ; a formula of the surfactant having a hydrophilic group and a glycidyl ester type epoxy resin ; a glycidyl amine epoxy lipophilic group . Examples of such a surfactant include an resin ; a hydantoin epoxy resin ; and triglycidylisocyanurate ; anion - type surfactant such as a fatty acid soap , alkyl sul - which may be used in combination . Preferably these poly fonate , alkylbenzene sulfonate , alkyl sulfosuccinate , poly - 30 epoxy compounds are dispersed in water for use in a oxyethylene alkyl sulfate , and polyoxyethylene alkyl aryl waterborne polymer dispersion form . sulfate ; and a nonreactive nonionic surfactant such as poly - Examples of the waterborne polymer dispersion of a oxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyepoxy compound dispersed in water include an epoxy polyoxyethylene sorbitan fatty acid ester , and an oxyethyl group -containing acrylic copolymer aqueous dispersion . ene oxypropylene block copolymer . 35 The epoxy group -containing acrylic copolymer aqueous Each of the surfactants may be used alone , or two or more dispersion can be produced , for example , by the same way thereofmay be used in combination , and the amount thereof as in the production of the carbonyl group containing water used may be typically 0 .05 mass % to 10 mass % , preferably borne polymer dispersion except for the type of monomers 0 . 1 mass % to 5 mass % relative to the total mass of the for use . As the epoxy group containing ethylenically unsatu radical polymerizable monomers to produce the polymer 40 rated monomer, glycidyl( meth )acrylate can be suitably used . ( E ) . With an amount of the surfactant used of 0 . 05 mass % As the polymer ( E ) , a polyepoxy compound having a part or more , the polymerization stability is high with less of or the entire of epoxy groups ring - opened with addition occurrence of aggregates in emulsion polymerization , and of water can be used . Such a compound can be obtained by with an amount used of 10 mass % or less , the water heating a polyepoxy compound - containing waterborne poly resistance of a coating film obtained from the aqueous 45 mer dispersion or an aqueous polymer composition . polymer composition including the polymer ( E ) produced by The aqueous polymer composition has a mass ratio of the emulsion polymerization can be further improved . A reac - semicarbazide composition content C , to the polymer ( E ) tive surfactant is preferred from the viewpoint of further content C2, i. e . C1/ C2, in the range of preferably 0 . 1 /99 . 9 to improvement in water resistance and weather resistance of a 90 / 10 . Within the range , the aqueous polymer composition coating film . 50 can have both cold curing ability and storage stability , and In emulsion polymerization , a compound able to cause a coating film produced from the aqueous polymer compo addition polymerization of radically polymerizable unsatu - sition is excellent in water resistance , stain resistance , hard rated monomers by radical decomposition with heating or ness , etc . With a ratio C / C , of less than 0 . 1 /99 . 9 , the effect reducing material can be used as radical polymerization of cross - linking cannot be achieved due to lowered cross initiator . 55 linking density , which is undesirable . With a ratio C , / C , of As the radical polymerization initiator, a water - soluble or more than 90 / 10 , the coating film to be produced is oil -soluble persulfate salt, peroxide , an azobis compound extremely brittle, which is undesirable . and the like can be used . Examples thereof include potas - The aqueous polymer composition can be suitably used as sium persulfate , sodium persulfate , ammonium persulfate , a waterborne paint or a waterborne coating material . A hydrogen peroxide , t - butyl hydroperoxide , t -butyl peroxy - 60 component other than the semicarbazide composition and benzoate, 2 , 2 -azobis ( isobutyronitrile ), 2 , 2 -azobis ( 2 - di the polymer ( E ) may be added to the aqueous polymer aminopropane) hydrochloride , and 2 ,2 - azobis ( 2 , 4 - dimethyl- composition , corresponding to the application . valeronitrile ); and the amount used can be 0 . 1 to 1 mass % The aqueous polymer composition may contain , for relative to the ethylenically unsaturated monomer . example , a known ultraviolet absorber such as benzophe Although the emulsion polymerization is preferably per - 65 none , benzotriazole , or triazin , and a known photostabilizer formed typically at a polymerization temperature of 65 to such as hindered phenol or hindered amine . Further , com 90° C . under normal pressure, it may be also performed ponents commonly added to a waterborne paint or the like , US 10 ,023 , 760 B2 such as a pigment, a filler , a dispersant, a wetting agent, a allophanate group obtained by allophanatization reaction thickener, a rheology control agent, a defoamer, a plasticizer , after or in parallel with urethanization reaction between a coalescing agent , a rust inhibitor , a dye , and a preservative , alcohols and diisocyanate such as hexamethylene diisocya can be selected and formulated in combination so as to be nate and isophorone diisocyanate with a hydrazine com added to the aqueous polymer composition on an as needed 5 pound or the dihydrazide exemplified above , an aqueous basis . polyfunctional semicarbazide obtained by reacting an iso [Description of a Preferred Aspect of the Aqueous Poly cyanate group in a reaction product between the polyiso mer Composition ] cyanate compound and an active hydrogen compound con One preferred aspect of the aqueous polymer composition taining a hydrophilic group of polyether polyols and of the present embodiment is described in the following . The 10 polyethylene glycolmonoalkyl ethers with the exemplified aqueous polymer composition in the present aspect is an dihydrazide , or a mixture of the polyfunctional semicarba aqueous polymer composition including a cross - linking zide and an aqueous polyfunctional semicarbazide (refer to agent and a waterborne polymer dispersion which are Japanese Patent Application Laid -Open No . Hei - 8 - 151358 , blended . In the present aspect , the cross - linking agent con Japanese Patent Application Laid -Open No . Hei 8 - 245878 , tains the semicarbazide composition described above . The 15 and Japanese Patent No. 3212857 ) . Among them , the com waterborne polymer dispersion includes at least one cross - bination use with adipic acid dihydrazide having water linkable polymer having a glass transition temperature Tg of solubility is particularly preferred . The molar ratio between lower than 80° C ., selected from the group consisting of a the semicarbazide composition and a compound for combi water- soluble or water -dispersible polycarbonyl compound nation use is preferably in the range of 100 / 0 to 0 . 1 /99 . 9 , having a number average molecular weight of 1000 to 20 more preferably in the range of 90 / 10 to 10 / 90 . With the 100000 , and a water - soluble or water- dispersible polyepoxy combination use of the semicarbazide composition and compound having a number average molecular weight of another compound in coating film formation of an aqueous 1000 to 100000 . polymer composition , an excellent coating film having both < Cross -Linking Agent > of rigidity and flexibility , or having flexibility, stain resis The cross - linking agent contains the semicarbazide com - 25 tance , hardness , etc ., all together can be obtained . position described above . The semicarbazide composition is The amount of the cross - linking agent blended is con nonreactive with an aldo group , a keto group , an epoxy trolled to have a ratio M , /M2 , i. e . the total amount M , of group , etc . , of a cross - linkable polymer in the presence of semicarbazide groups and hydrazine groups in a cross water in the aqueous polymer composition , and reactive linking agent to the total amount M , of cross - linkable groups with these groups when water disappears , capable of being 30 contained in the polymer component in an waterborne suitably used as a cross -linking agent for a one - pack type polymer dispersion , of preferably in the range of 0 .01 to 10 , waterborne paint or a waterborne coating material . more preferably in the range of 0 .05 to 5, furthermore The semicarbazide composition can be used as a cross preferably in the range of 0 . 1 to 2 . linking agent, for example , in an aqueous solution form < Waterborne Polymer Dispersion > diluted with water. Examples of the aqueous solution 35 In the present aspect , the waterborne polymer dispersion include an aqueous solution containing the semicarbazide is a liquid composition containing an aqueous dispersion composition in an amount of 5 mass % or more (preferably medium and a polymer component dispersed in the aqueous 25 mass % or more , more preferably 40 mass % or more ) . dispersion medium , and the polymer component contains at The concentration of the semicarbazide composition in the least one cross - linkable polymer selected from the group aqueous solution may be 95 mass % or less , preferably 80 40 consisting of a water - soluble or water- dispersible polycar mass % or less . Alternatively , the solid semicarbazide com - bonyl compound having a number average molecular weight position can be directly used as a cross - linking agent without of 1000 to 100000 , and a water -soluble or water -dispersible dilution with water or the like . ?????????polyepoxy compound having a number average molecular As the cross - linking agent, a cross- linking agent other w eight of 1000 to 100000 . than the semicarbazide composition may also be used in 45 The term “ water- soluble or water- dispersible ” includes combination . As such a cross - linking agent, for example , a being dissolved in water or being dispersed in water to form compound having two or more hydrazide groups or semi- an emulsion partially dissolved in water. carbazide groups is suitable , and specific examples thereof The aqueous dispersion medium contains at least water, include a saturated aliphatic carboxylic acid dihydrazide and contains a water - soluble organic solvent in some cases . having 2 to 18 carbon atoms such as oxalic acid dihydrazide , 50 The water content in the aqueous dispersion medium is malonic acid dihydrazide , glutaric acid dihydrazide , suc preferably 5 mass % or more , more preferably 50 mass % or cinic acid dihydrazide , adipic acid dihydrazide and sebacic more. acid dihydrazide ; mono - olefinic unsaturated dicarboxylic The polymer component content in a waterborne polymer acid dihydrazide such as maleic acid dihydrazide , fumaric dispersion is preferably 1 to 70 mass % , more preferably 5 acid dihydrazide, itaconic acid dihydrazide; an acid dihy - 55 to 67 mass % , relative to the total amount of the waterborne drazide compound such as phthalic acid dihydrazide , polymer dispersion . terephthalic acid dihydrazide , isophthalic acid dihydrazide , (Water - Soluble or Water Dispersible Polycarbonyl Com pyromellitic acid dihydrazide , pyromellitic acid trihydraz pound) ide , pyromellitic acid tetrahydrazide ; nitrilotrihydrazide , cit The water- soluble or water -dispersible polycarbonyl ric acid trihydrazide, 1, 2 ,4 -benzene trihydrazide, ethylene - 60 compound (hereinafter referred to simply as “ polycarbonyl diamine tetraacetic acid tetrahydrazide, 1 , 4 , 5 , 8 - naphthoic compound ” ) is a compound having at least two or more of acid tetrahydrazide , polyhydrazide produced by reacting a aldo groups or keto groups. Examples of the polycarbonyl low polymer having carboxylic acid lower alkyl ester group compound include a conventionally known polycarbonyl with hydrazine or hydrazine hydrate ( refer to Japanese compound such as polyurethane , polyester, poly (methacry Patent Publication No . 52 - 22878 ); carbonate dihydrazide 65 late , polyvinyl acetate , polybutadiene , polyvinyl chloride , and bis semicarbazide; polyfunctional semicarbazide chlorinated polypropylene, polyethylene, polystyrene , a obtained by reacting a polyisocyanate compound having an polystyrene - (meth )acrylate copolymer , a rosin derivative , a US 10 ,023 , 760 B2 23 styrene -maleic anhydride copolymer and an alcohol adduct intrusion of water into the fused part of emulsion particles , thereof, and a cellulose polymer , and one or a plurality of the fused part of emulsion particles of the present invention these may be used . is hydrophobized by the cross - linking reaction of the semi The polycarbonyl compound can be obtained by copoly - carbazide composition . In the present embodiment, there merization or addition polymerization of a monomer having 5 fore , whitening of the coating film when immersed in water at least one aldo group or keto group in the molecule with can be sufficiently suppressed even for the polycarbonyl other monomer . It is presumed that the aldo group and the compound having high solubility in water with an acid value keto group are involved in the cross - linking reaction asa of 20 mg KOH / g or more . carbonyl group after polymerization reaction . Examples of the nonionic polycarbonyl compound Specific examples of the monomer having at least one 10 include the compound of a water- soluble polymer having a aldo group or keto group in the molecule include acetone hydroxyl group and a derivative thereof such as cellulose , dicarboxylic acid , dihydroxyacetone, monohydroxyacetone , methyl cellulose (MC ) , carboxymethyl cellulose (CMC ) , and dihydroxybenzaldehyde, and a polycarbonyl compound polyvinyl alcohol (PVA ) , polyethylene glycol ( PEG ), or can be obtained by addition polymerization of a single one polypropylene glycol (PPG ), which are modified with thereof or a plurality thereof in combination . 15 diketene, pyruvic acid , levulinic acid , acetoacetic acid , trim Specific examples of the ethylenically unsaturated mono - ethyl pyruvate , propionyl acetate , benzoyl formate, phe mer having at least one aldo group or keto group in the nylpyruvate , ketocapric acid , ketoundecanoic acid , ketoste molecule include acrolein , diacetone acrylamide , diacetone a ric acid , ketoheneicosenoic acid , benzoyl acetate , benzoyl methacrylamide, formylstyrol , vinyl methyl ketone, vinyl propionate , ketogluconic acid , ketomalonic acid , acetone ethyl ketone , vinyl isobutylketone , acryloxyalkyl propanals , 20 dicarboxylic acid , 2 -ketoglutaric acid , acetone diacetic acid , methacryloxyalkyl propanals , diacetone acrylate , diacetone acetone propionic acid , or a derivative thereof. These com methacrylate , acetonyl acrylate, 2 - hydroxypropyl acrylate pounds are produced typically by addition reaction in a acetyl acetate , and butanedio - 1 , 4 -acrylate acetyl acetate , and solution or in a fused state under presence or absence of acid , a polycarbonyl compound can be obtained by polymerizing alkali , etc ., with adjustment of the amount ofmodification to one or more thereof with an ethylenically unsaturated mono - 25 the extent that the solubility in water can be maintained , mer mixture containing an ethylenically unsaturated mono - while removing the hydroxyl compounds as by - product . mer other than these . An ethylenically unsaturated monomer In the case of a cationic polycarbonyl compound , the having a carbonyl group belonging to a carboxylic acid or an monomer mixture for use in polymerization contains an ester , however, is excluded from the ethylenically unsatu ethylenically unsaturated monomer having a cationic group . rated monomer having at least one aldo group or keto group 30 Examples of the ethylenically unsaturated monomer hav in the molecule . ing a cationic group include dimethylaminoethyl( meth )acry Preferably the monomer mixture for obtaining the poly - late and salt , diethylaminoethylmeth )acrylate and salt , dim carbonyl compound includes 0 . 5 wt. % or more of an ethylaminopropyl( methacrylate and salt , ethylenically unsaturated monomer having at least one aldo dimethylaminomethylmethacrylamide and salt , dimethyl group or keto group in the molecule . With a content of the 35 aminoethyl( methacrylamide and salt , dimethylaminopropyl ethylenically unsaturated monomer having an aldo group or (methacrylamide and salt, vinyl pyridine , halide salt of keto group in a monomer mixture of 0 . 5 wt. % or more, dimethylamino methyl( meth ) acrylamide epichlorohydrin sufficient performance of a coating film can be achieved with adduct, halide salt and alkylsulfonate of dimethylaminopro increased cross- linking points . More preferably, the content pyl( meth ) acrylamide epichlorohydrin adduct, halide salt of is 0 . 5 wt. % or more and 20 wt. % or less . 40 dimethylaminomethyl( meth )acrylate epichlorohydrin The polycarbonyl compound may be any of anionic , adduct , halide salt and alkylsulfonate of dimethylaminopro cationic , nonionic , and amphoteric . Among them , being pyl( meth ) acrylate epichlorohydrin adduct. anionic is preferred , and being anionic due to inclusion of The amount of the ethylenically unsaturated monomer carboxylic acid groups is particularly preferred from the having a cationic group for use in a monomer mixture is viewpoint of enhancing the solubility in water . 45 preferably 0 . 5 wt. % to 30 wt. % , more preferably 1 wt. % A polycarbonyl compound having a carboxylic acid group to 20 wt. % . The polycarbonyl compound having better has an acid value . In order to allow a polycarbonyl com - solubility in water can be thus obtained . pound to retain a carboxylic acid group , an ethylenically . The polycarbonyl compound has a number average unsaturated carboxylic acid monomer is mixed with the molecular weight of 1000 to 100000 , preferably 1000 to monomer mixture for use in polymerization . Examples of 50 50000 , more preferably 4000 to 50000 . It is presumed that the ethylenically unsaturated carboxylic acid monomer due to having a water -soluble component with a relatively include acrylic acid , methacrylic acid , itaconic acid , fumaric low molecular weight, the aqueous polymer composition acid , maleic acid , maleic anhydride , and a half -ester of can be handled as an aqueous dispersion or an aqueous itaconic acid , fumaric acid , or maleic acid . solution with low viscosity , so that a coating film can be The acid value of the polycarbonyl compound is prefer - 55 easily formed by fusion of emulsion particles , and the ably 20 mg KOH / g or more , more preferably 25 mg KOH / g cross - linking reaction with a semicarbazide composition can or more, furthermore preferably 25 mg KOH / g or more and be rapidly caused . 350 mg KOH / g or less . With an acid value of 20 mg KOH / g (Water -Soluble or Water- Dispersible Polyepoxy Com or more , the polycarbonyl compound has increased solubil - pound ) ity in water , so that the fusion between emulsion particles 60 A water -soluble or water - dispersible polyepoxy com and the mutual diffusion ofmolecules can be facilitated . The pound (hereinafter referred to simply as “ polyepoxy com acid value is expressed by the solid weight ofKOH used for pound” ) is a compound having two or more epoxy groups or neutralization relative to the gram -weight of dry polymer . ring - opened epoxy group . The coating film obtained from the aqueous polymer The ring - opened epoxy group is a group produced by composition hardly causes whitening of the coating film 65 ring -opening reaction of an epoxy group , which can be when immersed in water. Though a cause for whitening of represented by — X — C — C ( OH ) . In the formula , X the coating film when immersed in water is presumed to be represents an oxygen atom or a nitrogen atom . Examples of US 10 , 023 , 760 B2 25 26 the ring - opened epoxy group include a ring - opened glycidyl the mutual diffusion of molecules can be facilitated . The group . The ring - opened glycidyl group is a group produced acid value is expressed by the solid weight of KOH used for by ring- opening reaction of a glycidyl group , which can be neutralization relative to the gram -weight of dry polymer . represented by - X - CH2- C ( OH ) - CH2 Examples The coating film obtained from the aqueous polymer of the ring - opening reaction include the reaction between an 5 composition hardly causes whitening of the coating film epoxy group and a carboxyl group, and a reaction between when immersed in water . Though a cause for whitening of an epoxy group and an amino group . the coating film when immersed in water is presumed to be The polyepoxy compound can be obtained by changing an intrusion of water into the fused part of emulsion particles , ethylenically unsaturated monomer having at least one aldo the fused part of emulsion particles of the present invention group or keto group in the molecule into an ethylenically 10 is hydrophobized by the cross - linking reaction of the semi unsaturated monomer having at least one epoxy group in the carbazide composition . In the present aspect, therefore , molecule , in the production process of the polycarbonyl whitening of the coating film when immersed in water can compound . More specifically , the polyepoxy compound can be sufficiently suppressed even for the polyepoxy compound be obtained by copolymerizing an ethylenically unsaturated having high solubility in water with an acid value of 20 mg monomer having at least one epoxy group in the molecule 15 KOH / g or more . with other monomer . As described above , a monomer having at least one aldo Further, the polyepoxy compound having two or more group or keto group in the molecule or a monomer having ring -opened epoxy groups may be obtained , for example , by at least one epoxy group and other monomer component can reacting a compound having two or more carboxyl groups or be copolymerized to produce a polycarbonyl compound or a amino groups with two or more equivalents of a compound 20 polyepoxy compound , and examples of the other monomer having at least one epoxy groups under presence of a component for use include acrylic acid ester, methacrylic catalyst . Alternatively the polyepoxy compound having two acid ester, an acrylamide monomer , a methacrylamide or more ring - opened epoxy groups may be obtained by monomer , and vinyl cyanides . reacting a compound having two or more epoxy groups withwith Examples of the (meth )acrylic acid ester include a (meth ) two or more equivalents of a compound having at least one 25 acrylic acid alkyl ester with an alkyl portion having 1 to 18 carboxyl group or amino groups under presence of a cata - carbon atoms, a (meth ) acrylic acid hydroxyalkyl ester with lyst. On this occasion , a catalyst for use as curing catalyst an alkyl portion having 1 to 18 carbon atoms, a (poly ) such as a tertiary amine and a quaternary ammonium salt can oxyethylene (meth )acrylate having 1 to 100 ethylene oxide be used as the catalyst ; more specifically , tetra -n -butyl groups, a ( poly ) oxypropylene( meth )acrylate having 1 to 100 ammonium hydroxide, methyltributyl ammonium hydrox - 30 propylene oxide groups, and ( poly )oxyethylene di( meth ) ide , benzyltriethyl ammonium hydroxide , and the like can be acrylate having 1 to 100 ethylene oxide groups . used . Specific examples of the methacrylic acid esters include Examples of the ethylenically unsaturated monomer hav - methyl( meth )acrylate , ethyl( meth )acrylate , n -butyl ( meth ) ing one or more epoxy groups include glycidyl( meth ) acry - acrylate , iso -butyl ( meth ) acrylate tert- butyl ( meth ) acrylate , late , allyl glycidyl ether, glycidyl cinnamate , glycidyl cro - 35 2 - ethylhexyl( meth ) acrylate , cyclohexyl( methacrylate , tonate , glycidyl itaconate , glycidyl, glycidyl norbomenyl methylcyclohexyl( meth )acrylate , dodecyl (meth )acrylate , ester , and glycidyl norbomenyl ether . isobornyl( meth )acrylate , stearyl( meth )acrylate , and ada A compound having an epoxy group can be used as the mantyl( meth )acrylate . compound having at least one epoxy group in the molecule Specific examples of the (methacrylic acid hydroxyalkyl for producing a polyepoxy compound having a ring -opened 40 ester include 2 -hydroxyethyl ( meth )acrylate , 2 -hydroxypro epoxy group without specific limitations, and specific pyl( meth )acrylate , 2 -hydroxycyclohexyl (meth )acrylate , and examples thereof include a reaction product of a compound dodecyl( methacrylate . having at least one carboxyl group and epichlorohydrin , and Specific examples of the (poly )oxyethylene (meth )acry the like . late include ethylene glycol( meth ) acrylate , ethylene glycol The polyepoxy compound has a number average molecu - 45 methoxy (methacrylate , diethylene glycol( methacrylate , lar weight of, preferably 1000 to 100000 , more preferably diethylene glycol methoxy (meth ) acrylate , tetraethylene gly 1000 to 50000 , furthermore preferably 4000 to 50000 . col (methacrylate , and tetraethylene glycol methoxy (meth ) The polyepoxy compound may be any of anionic , cat- acrylate. ionic , nonionic , and amphoteric . Among them , being anionic Specific examples of the (poly ) oxypropylene (meth ) acry is preferred , and being anionic due to inclusion of a carbox - 50 late include propylene glycol (meth ) acrylate , propylene gly ylic acid group is particularly preferred from the viewpoint col methoxy (meth )acrylate , dipropylene glycol( meth )acry of enhancing the solubility in water . late , dipropylene glycol methoxy (methacrylate , A polyepoxy compound having a carboxylic acid group tetrapropylene glycol( meth )acrylate , and tetrapropylene gly has an acid value. In order to allow a polyepoxy compound col methoxy (meth ) acrylate . to retain a carboxylic acid group , an ethylenically unsatu - 55 Specific examples of the (poly ) oxyethylene di( methacry rated carboxylic acid monomer is mixed with the monomer late include ethylene glycol di( meth ) acrylate , diethylene mixture for use in polymerization . Examples of the ethyl- glycol di( methacrylate , diethylene glycol methoxy (meth ) enically unsaturated carboxylic acid monomer include acrylate , and tetraethylene glycol di( meth )acrylate . acrylic acid , methacrylic acid , itaconic acid , fumaric acid , Examples of the (methacrylamide monomers include maleic acid , maleic anhydride , and a half ester of itaconic 60 (meth )acrylamide , N - isobutyl( meth )acrylamide , N -dimethyl acid , fumaric acid , or maleic acid . (meth ) acrylamide, N - diethyl( meth ) acrylamide, N -methylol The acid value of the polyepoxy compound is preferably (meth ) acrylamide, and N -butoxymethyl ( meth ) acrylamide , 20 mg KOH / g or more, more preferably 25 mg KOH / g or and examples of the vinyl cyanides include (meth )acryloni more , furthermore preferably 25 mg KOH / g or more and trile . 350 mg KOH / g or less . With an acid value of 20 mg KOH / g 65 Specific examples other than the above include: olefins or more , the polyepoxy compound has increased solubility such as ethylene , propylene , and isobutylene ; dienes such as in water, so that the fusion between emulsion particles and butadiene; halo -olefins such as vinyl chloride and vinylidene US 10 ,023 ,760 B2 27 28 chloride; carboxylic acid vinyl esters such as vinyl acetate , Among the reactive surfactants, examples of the anionic vinyl propionate , vinyl n - butyrate , vinyl benzoate , p -t -butyl surfactant include an ethylenically unsaturated monomer vinyl benzoate , vinyl pivalate, vinyl 2 -ethyl hexanoate , vinyl having a sulfonic acid group , a sulfonate group , a sulfonic versatate , and vinyl laurate ; carboxylic acid isopropenyl acid ester group , or a salt thereof; and a compound having esters such as isopropenyl acetate and isopropenyl propi- 5 a sulfonic acid group , an ammonium salt of sulfonic acid onate ; vinyl ethers such as ethyl vinyl ether , isobutyl vinyl group (ammonium sulfonate group ) , or a group as alkali ether and cyclohexyl vinyl ether; aromatic vinyl compounds metal salt of sulfonic acid group (alkali metal sulfonate group ) can be suitably used . such as styrene and vinyl toluene ; allyl esters such as allyl Specific examples include allyl sulfonic acid , p -styrene acetate and allyl benzoate ; allyl ethers such as allyl ethyl 10 sulfonic acid , alkyl allyl sulfosuccinate ( e . g . trade name: ether, allyl glycidyl ether, and allyl phenyl ether ; y - (meth ) ELEMINOL JS - 2 and JS - 5 , made by Sanyo Chemical acryloxy propyltrimethoxysilane , vinyl methyl diethoxysi Industries , Ltd .; and trade name: LATEMUL S - 120 , lane, vinyl methyl dimethoxysilane , vinyl dimethyl ethox S - 180A , and S - 180 , made by Kao Corporation ), polyoxy ysilane, vinyl dimethyl methoxysilane, vinyl ethylene alkyl propenyl phenyl ether sulfate ( e . g . trade trimethoxysilane, vinyl triethoxysilane, 4 - (meth ) acryloy 15 name: Aqualon HS- 10 , made by Dai - ichi Kogyo Seiyaku loxy -2 ,2 , 6 ,6 - tetramethylpiperidine , 4 - meth )acryloyloxy - 1, Co ., Ltd .) , a - [ 1 - [ ( allyloxy )methyl ) - 2 - (phenylphenoxy ) 2 ,2 , 6 ,6 -pentamethylpiperidine , perfluoromethyl( meth ) acry ethyl ] - w - polyoxyethylene sulfate ( e . g . trade name: late , perfluoropropyl( meth ) acrylate , ADEKARIA SOAP SE - 1025A , made by Adeka Corpora perfluoropropylomethyl(meth )acrylate , vinylpyrrolidone , tion ), an ammonium salt of a - sulfo -w -( 1 -( alkoxy )methyl ) trimethylolpropane tri (meth ) acrylate , 2 , 3 - cyclohexene ,20 2 -( 2 - propenyloxy ) ethoxy )- poly (oxy - 1 - 2 -ethanediyl ) (e . g . oxide (meth ) acrylate , allyl (methacrylate , acid phosphoxy trade name: SR - 1025 , made by Adeka Corporation ) , and ethyl methacrylate , 3 -chloro -2 -acid phosphoxypropyl meth ammonium = a - sulfonate - w - 1 -( allyloxymethyl) alkyloxy acrylate , methylpropane sulfonic acid acrylamide, and divi polyoxyethylene (e .g . trade name : AQUALON KH - 10 , nylbenzene , and combinations thereof. made by Dai- ichi Kogyo Seiyaku Co ., Ltd . ) . The cross- linkable polymer has a glass transition tem Among the reactive surfactants, examples of the nonionic perature Tg of lower than 80° C ., preferably 65° C . or lower , surfactant include a - [ 1 - [ ( allyloxy )methyl ) - 2 - ( phenylphe more preferably 50° C . or lower. With a glass transition noxy ) ethyl) - w -hydroxy -polyoxyet hylene ( e . g . trade name: temperature of 80° C . or higher , the aqueous polymer ADEKARIA SOAP NE - 20 , NE - 30 , and NE -40 , made by composition tends to have poor coating film formation Adeka Corporation ), and polyoxyethylene alkyl propenyl properties . 30 phenyl ether ( e . g . trade name: AQUALON RN - 10 , RN - 20 , The Tg of the cross -linkable polymer may be calculated RN - 30 , and RN - 50 , made by Dai- ichi Kogyo Seiyaku Co . , by applying the following Fox equation to the monomers Ltd .) . constituting the polymer. In emulsion polymerization or mini- emulsion polymer ization for producing the cross- linkable polymer in the 1/ Tg = a [/ Tg1 + az /Tg2 + . . . + ar /Ten ; Fox equationan !: 35 present aspect, a conventional surfactant may be used other wherein a , a , , . . . a ,, represent the mass fractions of the than the reactive surfactant having an ethylenic double bond respective monomers , and Tg , Tg , . . . Tg , represent Tg of group in the chemical structural formula of the surfactant homopolymers of the respective monomers . The Tg of the having a hydrophilic group and a lipophilic group . Examples homopolymer of each monomer for use in calculation is of such a surfactant include an anion - type surfactant such as described , for example , in Polymer Handbook ( John Wiley 40 a fatty acid soap , alkyl sulfonate , alkylbenzene sulfonate , & Sons ) , Introduction to Synthetic Polymer for Paint. alkyl sulfosuccinate, polyoxyethylene alkyl sulfate , and The cross - linkable polymer is obtained preferably by polyoxyethylene alkyl aryl sulfate ; and a nonreactive non emulsion polymerization , mini- emulsion polymerization or ionic surfactant such as polyoxyethylene alkyl ether, poly solution polymerization . oxyethylene alkyl aryl ether , polyoxyethylene sorbitan fatty The solution polymerization may be performed by a 45 acid ester , and an oxyethylene oxypropylene block copoly conventional method , and examples of the organic solvent mer. for use include toluene , xylene, cyclohexane , ethyl acetate , The amount of the surfactant for use is preferably 0 .05 to butyl acetate , CS - 12 (made by JNC Corporation ) , ethylene 20 wt. % relative to the total mass of the monomers for glycol monobutyl ether, ethylene glycol mono - 2 - ethylhexyl producing a cross - linkable polymer . The surfactant may ether, ethylene glycol monoethyl ether, ethylene glycol 50 contain a plurality of surfactants for use in combination , and monobutyl ether acetate , ethylene glycol mono - 2 - ethylhexyl emulsion polymerization can be performed according to the ether acetate , ethylene glycol monoethyl ether acetate , dieth - conventional conditions without specific limitations. ylene glycol monobutyl ether , diethylene glycolmonobutyl In the polymerization reaction for producing the cross ether acetate , propylene glycolmonoethyl ether , propylene linkable polymer , a radical polymerization initiator can be glycol monopropyl ether, propylene glycolmonobutyl ether, 55 used . A compound to cause radical polymerization of eth dipropylene glycol monoethyl ether , dipropylene glycol ylenically unsaturated monomers by radical decomposition monopropyl ether, dipropylene glycol monobutyl ether , ben - with heating or reducing material can be used as radical zyl alcohol, dimethyl glutarate , and isopropyl glutarate . polymerization initiator. Emulsion polymerization and mini- emulsion polymeriza - Among the radical polymerization initiators , a water tion can be performed using a surfactant, and an anionic 60 soluble persulfate salt, a peroxide , an azobis compound and surfactant or a nonionic surfactant is used as the surfactant the like can be used as the water - soluble initiator, and in production of an anionic cross - linkable polymer . examples thereof include potassium persulfate , sodium per A reactive surfactant having an ethylenic double bond sulfate , ammonium persulfate , hydrogen peroxide, t -butyl group in the chemical structural formula of the surfactant hydroperoxide, and 2 , 2 - azobis ( 2 - diaminopropane hydro having a hydrophilic group and a lipophilic group may be 65 chloride. Among the radical polymerization initiators , used as the surfactant so as to impart high water resistance examples of the oil -soluble initiator include t -butyl peroxy to a coating film . benzoate , 2 ,2 -azobis ( isobutyronitrile ), and 2 , 2 -azobis ( 2 ,4 US 10 ,023 , 760 B2 29 30 dimethylvaleronitrile ). When the polymerization reaction second polymer is preferably 50000 to 2000000 , more for producing the cross - linkable polymer is performed by preferably 100000 to 1000000 . emulsion polymerization , use of a water - soluble initiator is In the above aspect, the mass ratio of the content Y of the preferred , while when performed by solution polymerization cross - linkable polymer to the content Y2 of the second or mini- emulsion polymerization , use of an oil- soluble ini- 5 polymer in the polymer component of a waterborne polymer tiator is preferred . dispersion , i. e . Y , /Y2 , is preferably 1 /99 to 90 / 10 , more The radical polymerization initiator is blended typically in preferably 5 / 95 to 60 /40 , furthermore preferably 5 / 95 to an amount of 0 .1 to 10 mass % relative to the total of the 40 /60 . With a ratio of content Y of the cross - linkable entire monomers . When acceleration of the polymerization polymer of 1 or more , a coating film excellent in stain rate or the polymerization at low temperature is desired , a 10 resistance can be produced , while with a ratio of content Y reducing agent such as sodium bisulfite , ferrous chloride , of 90 or less , a coating film further excellent in water ascorbate, and Rongalite , may be used in combination with resistance can be produced . In other words, with a ratio a radical polymerization initiator. Y / Y , in the range , both of further excellent water resistance In the case of a monomer having an anion group for and stain resistance can be achieved . producing the cross - linkable polymer , an alkali may be 15 The Tg of the polymer component of a waterborne added to the reaction system for neutralization or solubili - polymer dispersion is preferably 60° C . or lower ( - 65° C . or zation of the anion group in polymerization with a water - higher ) , more preferably 50° C . or lower , furthermore pref soluble polymerization initiator; while in the case of a erably 40° C . or lower . The aqueous polymer composition monomer having a cation group for producing the cross - thus has excellent film forming properties ; and the flexibility linkable polymer , an acid may be added to the reaction 20 and the stain resistance of a coating film are improved in system for neutralization or solubilization in polymerization with a water- soluble polymerization initiator. The waterborne polymer dispersion containing two or In polymerization of the cross - linkable polymer , a chain more polymers as polymer components may contain emul transfer agent may be further added in the polymerization sion particles composed of respective polymers , or may process for regulation of the molecular weight after polym - 25 contain multi - component emulsion particles formed of two erization . The amount of the chain transfer agent added may or more polymers . be, for example , 0 . 1 to 5 mass % relative to the total of the Herein , a waterborne polymer dispersion containing two entire monomers . With an amount of the chain transfer agent polymers can be obtained , for example , by the following less than 0 .1 mass % , the increased viscosity of the aqueous method . polymer composition may cause difficulty in handling in 30 (Method 1 ) some cases, while with an amount of more than 5 mass % , The method includes separately polymerizing a polymer the coating film may have insufficient water resistance in (a ) and a polymer (b ) so as to prepare a polymer ( a ) emulsion some cases . Examples of the chain transfer agent include and a polymer ( b ) emulsion , respectively , which are mixed mercaptans such as butyl mercaptan , n - dodecyl mercaptan to obtain a waterborne polymer dispersion . In this method , and t - dodecyl mercaptan ; alcohols such as methanol and 35 a simple mixture of emulsion particles formed of the poly isopropyl alcohol; a -methylstyrene dimer ; and carbon tet- mer (a ) and emulsion particles formed of the polymer (b ) is rachloride . produced . The waterborne polymer dispersion may contain two or (Method 2 ) more of the cross - linkable polymers. The waterborne poly - The method includes performing emulsion polymeriza mer dispersion may further contain a water - dispersible poly - 40 tion or mini -emulsion polymerization ofmonomers so as to mer and / or a water- soluble polymer other than the cross - obtain a polymer (b ) in an aqueous medium containing a linkable polymer. polymer (a ), thereby obtaining a waterborne polymer dis In one aspect , for example, the waterborne polymer persion . In this method , a waterborne polymer dispersion dispersion may contain a first polymer as cross - linkable containing multilayered emulsion particles having a central polymer having an acid value of 20 mgKOH / g or more , and 45 core of the polymer ( a ) of which the circumference is formed a second polymer having an acid value lower than that of the of the polymerized polymer ( b ) . cross - linkable polymer. In the method 2 , the polymer ( a ) may be dispersed in an Herein , though not required to have a cross- linkable aqueous medium to form an emulsion , or may be dissolved group ( aldo group , keto group , or epoxy group ) , the second in an aqueous medium . The polymer (a )may be obtained in polymer preferably has a cross- linkable group , more pref- 50 a dispersed form in an aqueousmedium by emulsion polym erably has the same type of cross - linkable group as that of erization or mini- emulsion polymerization , or may be dis the cross - linkable polymer , from the viewpoint of further persed or dissolved in an aqueousmedium after synthesis by improving the properties of the coating film . solution polymerization . The acid value of the second polymer is preferably less In the method 2 , when one of the polymer (a ) and the than 25 mg KOH / g , more preferably less than 20 mg 55 polymer (b ) is anionic , another is preferably anionic or KOH / g , furthermore preferably less than 18 mg KOH / g nonionic ; while when one is cationic , another is preferably The acid value of the polymer component of the water - cationic or nonionic . borne polymer dispersion is preferably 1 to 250 mg KOH / g (Method 3 ) more preferably 5 to 200 mg KOH / g , furthermore preferably The method includes the successive steps of: preparing a 5 to 100 mg KOH / g . In the above aspect , the acid value and 60 polymer ( a ) by polymerization in a first stage ; performing the content ratio of the cross -linkable polymer and the emulsion polymerization or mini - emulsion polymerization second polymer are prepared such that the acid value of the ofmonomers under presence of the produced polymer ( a ) in polymer component is controlled within the range . a second stage to obtain a polymer (b ) ; and performing a In the above aspect, preferably the number average second polymerization of the polymer ( a ) in a third stage molecular weight of the second polymer is greater than the 65 after solubilizing treatment as needed . On this occasion , the number average molecular weight of the cross - linkable monomer composition for the first polymerization of the polymer. The number average molecular weight of the polymer ( a ) and the monomer composition for the second US 10 ,023 , 760 B2 31 32 polymerization of the polymer (a ) may be different, so that Addition of the alkaline component or the acid component a waterborne polymer dispersion contains three types of may be performed prior to polymerization , during polym polymers . erization , or after polymerization . The organic solvent In the above aspect, in the method 3 for producing a usable in solubilization treatment may be auxiliarily used waterborne polymer dispersion , the case having the polymer 5 when water - solubility is insufficiently achieved with addi ( a ) as the second polymer and the polymer ( b ) as the tion of the alkali component or the acid component only, or cross - linkable polymer is particularly preferred . On this may be used alone for solubilization . occasion the cross - linkable polymer and the second polymer In the present embodiment of the production method , in are more preferably anionic . order to allow the second polymer to retain a carboxylic acid One embodiment of the method for producing the water- 10 group , an ethylenically unsaturated carboxylic acid mono borne polymer dispersion in the above aspect is shown in the mer may be used as a part of monomers for use in polym following erization . Examples of the ethylenically unsaturated carbox In the present embodiment, the second polymer can be ylic acid unit include acrylic acid , methacrylic acid , itaconic obtained by emulsion polymerization using an emulsifier . In acid , fumaric acid , maleic acid , maleic anhydride , itaconic production of the second polymer of anionic polymer, an 15 anhydride , fumaric acid , and a half -ester of maleic acid . The anionic surfactant and /or a nonionic surfactant is used as second polymer containing a carboxylic acid group is also emulsifier. More specifically , the surfactants described for useful in formation of a ring - opened epoxy group from an use in emulsion polymerization to obtain the cross- linkable epoxy group . polymer can be used in the same way. The same monomers as those for use in obtaining the In production of the second polymer of cationic polymer, 20 cross - linkable polymer may be used for obtaining the second a cationic surfactant and / or a nonionic surfactant is used as polymer, and examples thereof include ethylenically unsatu emulsifier . More specifically , the surfactants described for rated monomers having at least one aldo group or keto group use in emulsion polymerization to obtain the cross - linkable in the molecule , other ethylenically unsaturated monomers , polymer can be used in the same way. ethylenically unsaturated monomers for introducing a cat The amount of the emulsifier (surfactant ) for use is 25 ionic group , etc . Although an ethylenically unsaturated preferably 0 .05 to 25 mass % relative to the total mass of the monomer having an aldo group or keto group may not be monomers for producing a second polymer . Emulsion necessarily used in production of the second polymer , the polymerization can be performed according to the conven use in an amount of preferably 0 . 5 mass % or more , more tional conditions without specific limitations. preferably 0 . 5 mass % or more and 20 mass % or less , In polymerization of the second polymer , a chain transfer 30 relative to the total of monomers is performed from the agent may be added in the polymerization process for viewpoint of further improving the performance of a coating regulation of themolecular weight after polymerization . The film with increased cross - linking points . amount of the chain transfer agent added may be , for In the method 3 for producing a waterborne polymer example, 0 . 1 to 5 mass % relative to the total of the entire dispersion in the above aspect , the case having the polymer monomers . With an amount of the chain transfer agent less 35 ( a ) of a second polymer and the polymer ( b ) of a cross than 0 . 1 mass % , the increased viscosity of the aqueous linkable polymer is particularly preferred as described polymer composition may cause difficulty in handling in above . A specific aspect thereof is exemplified in the fol some cases , while with an amount of more than 5 mass % , lowing . the coating film may have insufficient water resistance in In this aspect, first , a monomer mixture including 0 to 3 some cases . Examples of the chain transfer agent include 40 wt. % of an ethylenically unsaturated carboxylic acid mono mercaptans such as butyl mercaptan , n - dodecyl mercaptan mer , 0 to 20 wt. % of an ethylenically unsaturated monomer and t - dodecyl mercaptan ; alcohols such as methanol and having an aldo group or keto group , and 77 to 99 . 5 wt. % of isopropyl alcohol; a -methylstyrene dimer ; and carbon tet - other monomers is emulsion -polymerized in a first stage so rachloride . as to obtain an emulsion of the second polymer (which was An alkali component may be added to an anionic second 45 polymerized in the first time ). Subsequently , a monomer polymer, while an acid component may be added to a mixture including 3 to 50 wt. % of an ethylenically unsatu cationic second polymer . The dispersion stability of the rated carboxylic acid monomer , 0 . 5 to 20 wt. % of an aqueous polymer composition can be thus improved . The ethylenically unsaturated monomer having an aldo group or amount of the alkali component or the acid component keto group , and 30 to 97 wt. % of other monomers is added is preferably controlled such that the waterborne 50 emulsion -polymerized under presence of the first - time sec polymer dispersion has a pH in the range of 3 to 10 . The ond polymer in a second stage so as to obtain an emulsion dispersion stability can be thus further improved . including the first - time second polymer and a cross - linkable Although a conventional alkali such as sodium hydroxide , polymer . After addition of an alkali component to the potassium hydroxide , and ammonia may be used as the emulsion , a monomer mixture including 0 to 3 wt. % of an alkali component without particular limitations , preferred 55 ethylenically unsaturated carboxylic acid monomer, 0 to 20 examples include monoethanolamine , N , N -dimethyl etha wt. % of an ethylenically unsaturated monomer having an nolamine , N , N - diethyl ethanolamine , diethanolamine , N - n - aldo group or keto group , and 77 to 99 . 5 wt. % of other butyl diethanolamine , triisopropanolamine , and morpho monomers is emulsion -polymerized in the emulsion in the lines such as morpholine and 4 - morpholinoethanol, subsequent third stage so as to obtain the second polymer particularly from the viewpoint of improving the water 60 (which was polymerized in the second time) . An emulsion resistance of a coating film after drying . Among them , containing the second polymer ( first - time ) , the cross - link ammonia is particularly preferred as a volatile alkali com - able polymer, and the second polymer (second - time) can be ponent. thus obtained through the three stages. On the other hand , examples of the acid component Although polymerization is performed through three include hydrochloric acid , sulfuric acid , nitric acid , meth - 65 stages in the above aspect, further multi -stage polymeriza anesulfonic acid , p - toluenesulfonic acid , acetic acid , lactic tion may be performed in the present invention , correspond acid , and hydroxyacetic acid . ing to the purpose. Through multi- stage polymerization , a US 10 ,023 ,760 B2 33 34 coating film obtained from the aqueous polymer composi tylphenyl) benzotriazole , 2 - ( 2 -hydroxy - 3 , 5 -bis ( a , a ' tion tends to have further improved performance for pre dimethylbenzyl) phenyl] benzotriazole ) , a condensate of venting whitening when immersed in water. methyl- 3 - ( 3 - tert- butyl - 5 - ( 2H -benzotriazol - 2 -yl ) - 4 -hydroxy < Aqueous Polymer Composition > phenyl ] propionate and polyethylene glycol (molecular The aqueous polymer composition of the present aspect is 5 weight: 300 ) (made by BASF Japan Ltd ., product name: a composition obtained by blending a cross- linking agent TINUVIN 1130 ) , isooctyl- 3 - (3 - (2H -benzotriazol - 2 -yl ) - 5 and a waterborne polymer dispersion . The aqueous polymertert -butyl - 4 -hydroxyphenyl ] prop ionate (made by BASF composition may include a component other than the cross Japan Ltd . , product name: TINUVIN 384 ) , 2 - ( 3 - dodecyl- 5 linking agent and the waterborne polymer dispersion . methyl- 2 -hydroxyphenyl ) benzotriazole (made by BASF In order to improve the long -term storage stability , the pH 10 Japan Ltd . , product name: TINUVIN 571 ), 2 -( 2 -hydroxy of the aqueous polymer composition is preferably in the 3 '- tert - butyl- 5 -methylphenyl ) - 5 - chlorobenzotriazole 2 - ( 2 range of 5 to 10 . As a pH adjusting agent to adjust the pH hydroxy - 3 ', 5 - di- tert - amylphenyl) benzotriazole , 2 - ( 2 ' - hy in the range , for example , ammonia , sodium hydroxide , droxy - 4 ' -octoxyphenyl ) benzotriazole , 2 - [ 2 -hydroxy - 3 ' - ( 3 " , potassium hydroxide, and amines such as dimethylamin 4 " , 5 " , 6 " -tetrahydrophthalimide methyl) - 5 '- methylphenyl ] oethanol may be used . 15 benzotriazole , 2, 2 -methylenebis [ 4 -( 1 , 1, 3 ,3 The mass ratio of the dispersoid (solid content) to the tetramethylbutyl )- 6 -( 2H -benzotriazol - 2 - yl) phenol] , and dispersion medium (aqueous medium ) in the aqueous poly 2 - (2H -benzotriazol - 2 -yl ) - 4 ,6 -bis ( 1- methyl - 1 -phenylethyl ) mer composition is preferably 70 /30 or less, more preferably phenol (made by BASF Japan Ltd ., product name: TINU 30 /70 or more and 65 /35 or less . VIN 900 ) . Examples of the aqueous medium for dispersing and /or 20 Further, examples of the radically polymerizable benzo dissolving the cross - linkable polymer and the like in the triazole ultraviolet absorber include 2 -( 2 -hydroxy - 5 '- meth aqueous polymer composition include water and a mixed acryloxyethylphenyl) - 2H -benzotriazole (manufactured by solvent of water and alcohols . Otsuka Chemical Co ., Ltd . , product name: RUVA -93 ), 2 - ( 2 The aqueous polymer composition may include compo hydroxy -5 '- methacryloxyethyl - 3 - tert- butylphenyl ) - 2H -ben nents to be typically blended in a waterborne paint or the 25 zotriazole , 2 - ( 2 - hydroxy - 5 -methacryloxypropyl - 3 -tert -bu like , such as a coalescing agent , a thickener , a defoamer , a tyl- phenyl ) - 5 - chloro - 2H -benzotriazole , and 3 -methacryloyl pigment, a dispersant, a dye , and a preservative ; and com - 2 -hydroxypropyl - 3 - [ 3 '- ( 2 " -benzotriazolyl ) - 4 -hydroxy - 5 ponents other than the above such as an ultraviolet absorber , tert -butyl ] phenylpropionate (made by BASF Japan Ltd . , an optical stabilizer, and inorganic colloidal particles may be product name: CGL - 104 ) . optionally blended . 30 Further, examples of the triazine ultraviolet absorber The colloidal inorganic particles effective to further include TINUV400 (product name, made by BASF Japan , improve stain resistance may be blended in an amount of Ltd .) . preferably 1 to 80 parts by mass , more preferably 2 to 15 Examples of the optical stabilizer include a hindered parts by mass relative to the total 100 parts by mass of the amine optical stabilizer and a radically polymerizable hin polymer components in a waterborne polymer dispersion . 35 dered amine optical stabilizer. With a blending ratio of colloidal inorganic particles within The hindered amine optical stabilizer preferably has low the range, the coating film to be produced is hardly whitened basicity , specifically with a base dissociation constant (pKb ) even when immersed in water. of 8 or more . More specifically , examples thereof include Further, an ultraviolet absorber or an optical stabilizer is bis ( 2 , 2 , 6 ,6 -tetramethyl - 4 - piperidyl) succinate , bis ( 2 , 2 , 6 ,6 preferably contained in the aqueous polymer composition 40 tetramethyl- piperidyl ) sebacate bis ( 1, 2 ,2 ,6 ,6 -pentamethyl - 4 for imparting high weather resistance. As a method for piperidyl ) 2 - ( 3 , 5 -di - tert- butyl - 4 -hydroxybenzyl ) - 2 - butylma containing the ultraviolet absorber or the optical stabilizer in lonate , 1 - [ 2 - [ 3 - ( 3 , 5 -di - tert - butyl- 4 - hydroxyphenyl) the aqueous polymer composition , the absorber or the sta - propynyloxyJethyl] - 4 - [ 3 -( 3 , 5 - di- tert - butyl - 4 bilizer may be mixed with a coalescing agent and the like hydroxyphenyl) propynyloxy ] - 2 , 2 ,6 , 6 prior to addition , though the presence thereof during emul- 45 tetramethylpiperidine , a mixture of bis( 1 , 2 , 2 ,6 , 6 sion polymerization for obtaining the waterborne polymer pentamethyl- 4 -piperidyl ) sebacate and methyl- 1, 2 ,2 , 6 ,6 dispersion is more suitable . The ultraviolet absorber or the pentamethyl- 4 - piperidyl- sebacate (made by BASF Japan optical stabilizer may be added in an amount of 0 . 1 mass % Ltd ., product name: TINUVIN 292 ), bis ( 1 -octoxy -2 ,2 ,6 ,6 to 5 mass % relative to the total amount of the monomers to tetramethyl- 4 -piperidyl ) sebacate , and TINUVIN 123 (prod produce the cross - linkable polymer, in production of the 50 uct name, made by BASF Japan Ltd .) . cross - linkable polymer. Examples of the radically polymerizable hindered amine Further, a radically polymerizable ultraviolet absorber photo stabilizer include 1 , 2 , 2 , 6 , 6 -pentamethyl - 4 - piperidyl having a radically polymerizable double bond in the mol- methacrylate , 1 , 2 ,2 ,6 , 6 - pentamethyl- 4 -piperidyl acrylate , ecule may be used as the ultraviolet absorber, and a radically 2 ,2 ,6 ,6 -tetramethyl -4 -piperidyl methacrylate , 2 ,2 , 6 ,6 - te polymerizable optical stabilizer having a radically polym - 55 tramethyl- 4 -piperidyl acrylate , 1 , 2 , 2 ,6 ,6 - pentamethyl- 4 erizable double bond in the molecule may be used as the iminopiperidyl methacrylate , 2 , 2 , 6 ,6 , - tetramethyl- 4 - imin optical stabilizer . Use of an ultraviolet absorber and an opiperidyl methacrylate , 4 -cyano -2 ,2 , 6 ,6 - tetramethyl- 4 optical stabilizer in combination further improves the piperidylmethacrylate , and 4 -cyano -1 , 2 ,2 ,6 , 6 - pentamethyl weather resistance of a coating film to be produced . 4 -piperidyl methacrylate . Examples of the ultraviolet absorber include a benzotri - 60 The aqueous polymer composition also may contain a azole ultraviolet absorber , a radically polymerizable benzo - polymer dispersion stabilizer such as (partially saponified ) triazole ultraviolet absorber, and a triazine ultraviolet polyvinyl alcohol, methyl cellulose , hydroxyethyl cellulose , absorber. and polyvinyl pyrrolidone ; a thickener such as polyether Examples of the benzotriazole ultraviolet absorber thickener; a plasticizer ; and a coalescing agent; which may include 2 - ( 2 ' -hydroxy - 5 ' -methylphenyl ) benzotriazole , 2 - ( 2 ' - 65 be used in combination . hydroxy - 5 '- tert - butylphenyl) benzotriazole , 2 - ( 2 - hydroxy - 3 , Further, the aqueous polymer composition may include 5 -di - tert- butylphenyl ) benzotriazole , 2 - ( 2 -hydroxy - 5 - tert - oc components to be added and blended in typical paints , US 10 ,023 , 760 B2 35 36 various coating materials and the like , such as a viscosity color, L , a , b values were measured with a color- difference adjusting agent, a pH adjusting agent, a defoamer , a pig - meter CR - 200 made by Minolta before and after the testing ment, a filler, a dispersant, a dye , a preservative, a surfactant, (before and after the immersion in a saturated calcium a heat stabilizer, an ultraviolet absorber , an antioxidant, an hydroxide solution ), and the variation in the b value before optical stabilizer , a flame retardant, an organic solvent, a 5 and after the testing was indicated by Ab value . moistening agent, a surfactant, a thickener, a plasticizer , a The validation testing of the cross - linking condition of a coalescing agent, and an anti- rust agent. These may be coating film was performed by immersing the coating film in dispersed in the aqueous polymer composition with use of a an organic solvent and measuring the insoluble portion . In kneading machine such as an attritor and a sand mill , such the specific measurement method , a coating film having a that the aqueous polymer composition has a predetermined 10 thickness of about 100 um was immersed in acetone for 24 viscosity corresponding to application . hours and dried for measurement of the rate of change in The aqueous polymer composition is applied , for mass before and after the immersion . example , onto a substrate and dried to form a coating film . The coating film contains a cross - linked product obtained by Synthesis Example 1 - 1 cross - linking cross - likable polymer with a cross- linking 15 agent. < Adjustment of Polycarbonyl Compounds > In the present aspect, since the cross- linkable polymer and A reaction vessel having a reflux condenser, a dripping the cross - linking agent have specific compositions as tank , a thermometer, and a stirrer was charged with 218 g of described above , the coating film produced therefrom is ion -exchanged water and 3 . 7 g of 25 % aqueous solution of excellent in hardness , stain resistance , water resistance , and 20 a surfactant ( trade name : ADEKARIA SOAP SE - 1025N , alkali yellowing resistance . made by ADEKA Corporation ), and after raising the tem (Composite ) perature in the reaction vessel to 80° C ., a mixture solution Acomposite in the present embodiment is described in the of 9 g ofmethacrylic acid , 4 . 5 g of styrene , 234 g of butyl following . The composite in the present embodiment acrylate , 13 . 5 g of diacetone acrylamide, 189 g of methyl includes a substrate and a coating film of the aqueous 25 methacrylate , 0 .45 g of dodecyl mercaptan , 225 g of ion polymer composition formed on at least one face of the exchanged water , 14 . 4 g of ADEKARIA SOAP SE - 1025N , substrate . 10 g of 25 % aqueous solution of polyoxyethylene nonyl Examples of the substrate material include: an non - phenyl ether ( trade name : EMULGEN 950 , made by Kao metallic inorganic material such as glass , plaster, and stone ; Corporation ) , and 1 g of ammonium persulfate was flowed a metal such as iron , stainless steel , aluminum , and copper ; 30 into the reaction vessel from a dripping tank for 3 hours . a polymer such as acryl, polystyrene, polyesters , polycar - During inflow , the temperature in the reaction vessel was bonate , and polyolefin ; synthetic rubber, natural rubber, kept at 80° C . After completion of the inflow , the tempera cotton , silk , hemp , fiber of nylon or the like ; and wood . ture in the reaction vessel was kept at 80° C . for 2 hours . A coating film may be formed by directly applying the Subsequently the content was cooled to room temperature , aqueous polymer composition to a substrate , or may be 35 to which 25 % ammonia aqueous solution was added for formed by applying a paint or a coating material on a adjusting the pH at 7 .5 . The content was then subjected to substrate and further applying the aqueous polymer compo - filtration with a 100 mesh screen so as to produce a water sition thereon . borne polymer dispersion of carbonyl group -containing Although the preferred embodiments of the present inven copolymer having a solid content of 46 . 8 % and an average tion have been described above , the present invention is not 40 particle diameter of 106 nm . limited to the above embodiments . To the waterborne polymer dispersion , 2 % CS - 12 (made by JNC Corporation ) was added , the resulting coating liquid EXAMPLES was thoroughly stirred and mixed to produce a coating film having a thickness of about 100 um , which was dried at 23° The following Examples more specifically illustrate the 45 C . for 1 week . The produced coating film was immersed in present invention , but the present invention is not limited to acetone for 24 hours and dried for measurement of the rate the Examples . of change in mass before and after the immersion . The The analysis area ratios of the semicarbazide composi- measurement results showed that the insoluble portion of the tions ( a ), (b - 1 ) , ( b - 2 ) and ( b - 3 ) were obtained according to coating film was 8 % . the method described above , with a wavelength of ultravio - 50 let- visible absorption detector of 200 nm . Since isophorone Example 1 - 1 diisocyanate includes a plurality of stereoisomers , the peak areas SA, SB- 1 , SB - 2 , and SR - 3 were obtained as the area of a (Semicarbazide Composition ) group of peaks as sum of the peaks derived from the A reaction vessel having a reflux condenser, a thermom respective isomers . 55 eter, and a stirrer was charged with 22 . 0 g of hydrazine Yellowing of the coating film with an aqueous alkaline monohydrate , 200 g of tetrahydrofuran (water - soluble solution was detected by measuring the change in color after organic solvent ) , and 60 g of water. Subsequently , a mixture immersion of the coating film in a saturated calcium hydrox - solution of 400 g of toluene (water - insoluble solvent ) and 50 ide solution for a predetermined period of time. More g of isophorone diisocyanate was added dropwise at room specifically , a white enamel paint was applied to a flexible 60 temperature over a time period of 1 hour . Subsequently , board to prepare a dried coated board , on which the aqueous stirring was performed at room temperature for 1 hour so as polymer composition was applied such that the coating to complete the reaction ( the ratio of water - soluble organic liquid have a thickness of 250 um , which was dried at room solvent excluding water at the end of reaction : 67 % ) . Sub temperature to make a measurement sample . The measure - sequently the organic solvent and water were removed under ment sample was immersed in a saturated calcium hydroxide 65 reduced pressure at a temperature of 50° C . or lower. The solution at 23° C . for 1 week and subjected to measurement produced white powder was vacuum dried at room tempera of the change in color. In measurement of the change in ture so as to produce 64 g of a semicarbazide composition . US 10 , 023 , 760 B2 37 38 The semicarbazide composition was dissolved in the same The produced aqueous rein composition had both of cold amount of water to make a 50 % aqueous solution . curing ability and storage stability . The LC /MS analysis of the semicarbazide composition The coating solution of the aqueous polymer composition reresulted in an analysis area ratio ( a ) of 0 .09 % , an analysis was applied to a thickness of about 100 um and dried at 23° area ratio ( b - 1 ) of 85 . 20 % , an analysis area ratio ( 5 - 2 ) of 5 C . for 1 week to obtain a coating film . The produced coating 11 . 53 % , and analysis area ratio ( b - 3 ) of 3 . 18 % . The molecu - film was immersed in acetone for 24 hours and dried for lar weight per semicarbazide group calculated from the measurement of the rate of change in mass before and after ratios is 167. The chromatogram obtained by the LC /MS analysis is shown in FIG . 1 . the immersion . The measurement results showed that the ( Aqueous Polymer Composition and Coating Film ) 10 insoluble portion of the coating film was 90 % . To 100 g of the carbonyl group - containing waterborne Further , a white enamel paint was applied to a flexible copolymer dispersion in the Synthesis Example 1 - 1 , 2 % board to prepare a dried coated board , on which the aqueous CS - 12 (made by JNC Corporation ) was added and then polymer composition was applied to a thickness of 250 um , thoroughly stirred and mixed . Subsequently , 2 .40 g of 50 % which was dried at room temperature for 1 week to make a aqueous solution of the semicarbazide composition ( semi- 1515 coating00 film . The produced coating film was immersed in a carbazide group relative to keto group : 0 . 9 equivalent) was saturated calcium hydroxide solution at 23° C . for 1 week , added and mixed to make an aqueous polymer composition . resulting in a low Ab value of 3 .2 . The produced aqueous polymer composition had both of cold curing ability and storage stability . Example 1 - 3 The coating solution of the aqueous polymer composition 20 was applied to a thickness of about 100 um and dried at 23° (Semicarbazide Composition ) C . for 1 week to obtain a coating film . The produced coating reaction vessel having a reflux condenser, a thermom film was immersed in acetone for 24 hours and dried for eter, and a stirrer was charged with 25 . 0 g of hydrazine measurement of the rate of change in mass before and after monohydrate , 200 g of tetrahydrofuran , and 60 g of water . the immersion . The measurement results showed that the 25 Subsequently , a mixture solution of 200 g of toluene and 50 insoluble portion of the coating film was 88 % . g of isophorone diisocyanate was added dropwise at room Further, a white enamel paint was applied to a flexible temperature over a time period of 1 hour. Subsequently , board to prepare a dried coated board , on which the aqueous stirring was performed at room temperature for 1 hour so as polymer composition was applied to a thickness of 250 um , to complete the reaction ( the ratio of water- soluble organic which was dried at room temperature for 1 week to make a 30 solvent excluding water at the end of reaction : 50 % ) . Sub coating film . The produced coating film was immersed in a sequently the organic solvent and water were removed under saturated calcium hydroxide solution at 23° C . for 1 week , reduced pressure at a temperature of 50° C . or lower. The resulting in a low Ab value of 3 . 7 . produced white powder was vacuum dried at room tempera ture so as to produce 64 g of a semicarbazide composition . Example 1 - 2 The semicarbazide composition was dissolved in the same amount of water to make a 50 % aqueous solution . (Semicarbazide Composition ) The LC /MS analysis of the semicarbazide composition A reaction vessel having a reflux condenser, a thermom - resulted in an analysis area ratio ( a ) of 0 .21 % , an analysis eter, and a stirrer was charged with 18 . 0 g of hydrazine area ratio (b - 1 ) of 89 % , an analysis area ratio ( b - 2 ) of 9 % , monohydrate , 200 g of tetrahydrofuran , and 60 g of water . 40 and analysis area ratio (b - 3 ) of 1. 8 % . The molecular weight Subsequently , a mixture solution of 700 g of toluene and 50 per semicarbazide group calculated from the ratios is 159 . g of isophorone diisocyanate was added dropwise at room The chromatogram obtained by the LC /MS analysis is temperature over a time period of 1 hour. Subsequently , shown in FIG . 3 . stirring was performed at room temperature for 1 hour so as ( Aqueous Polymer Composition and Coating Film ) to complete the reaction ( the ratio of water - soluble organic 45 To 100 g of the carbonyl group - containing waterborne solvent excluding water at the end of reaction : 78 % ) . Sub - copolymer dispersion in the Synthesis Example 1 - 1 , 2 % sequently the organic solvent and water were removed under CS - 12 (made by JNC Corporation ) was added and then reduced pressure at a temperature of 50° C . or lower. The thoroughly stirred and mixed . Subsequently , 2 .28 g of 50 % produced white powder was vacuum dried at room tempera - aqueous solution of the semicarbazide composition (semi ture so as to produce 61. 5 g of a semicarbazide composition . 50 carbazide group relative to keto group : 0 . 9 equivalent ) was The semicarbazide composition was dissolved in the same added and mixed to make an aqueous polymer composition . amount of water to make a 50 % aqueous solution . The produced aqueous rein composition had both of cold The LC /MS analysis of the semicarbazide composition curing ability and storage stability . resulted in an analysis area ratio ( a ) of 0 .01 % , an analysis The coating solution of the aqueous polymer composition area ratio ( b - 2 ) of 81 % , an analysis area ratio ( b - 2 ) of 15 % , 55 was applied to a thickness of about 100 um and dried at 23° and analysis area ratio (b - 3 ) of 4 % . The molecular weight C . for 1 week to obtain a coating film . The produced coating per semicarbazide group calculated from the ratios is 172 . film was immersed in acetone for 24 hours and dried for The chromatogram obtained by the LC /MS analysis is measurement of the rate of change in mass before and after shown in FIG . 2 . the immersion . The measurement results showed that the (Aqueous Polymer Composition and Coating Film ) 60 insoluble portion of the coating film was 86 % . To 100 g of the carbonyl group - containing waterborne Further , a white enamel paint was applied to a flexible copolymer dispersion in the Synthesis Example 1 - 1 , 2 % board to prepare a dried coated board , on which the aqueous CS - 12 (made by JNC Corporation ) was added and then polymer composition was applied to a thickness of 250 um , thoroughly stirred and mixed . Subsequently , 2 .48 g of 50 % which was dried at room temperature for 1 week to make a aqueous solution of the semicarbazide composition ( semi- 65 coating film . The produced coating film was immersed in a carbazide group relative to keto group : 0 . 9 equivalent ) was saturated calcium hydroxide solution at 23° C . for 1 week , added and mixed to make an aqueous polymer composition resulting in a low Ab value of 62 . US 10 ,023 , 760 B2 39 40 Further , a white enamel paint was applied to an alumite perature over a time period of 1 hour . Subsequently , stirring board to prepare a dried coated board , on which the aqueous was performed at room temperature for 1 hour so as to polymer composition was applied to a thickness of 100 um , complete the reaction ( the ratio of water - soluble organic which was dried at room temperature for 1 week to make a solvent excluding water at the end of reaction : 0 % ). Subse coating film . The coated board with the four sides and the 5 quently the organic solvent and water were removed under back side sealed with wax was immersed in 1 N sulfuric acid reduced pressure at a temperature of 50° C . or lower . The aqueous solution at 23° C . for 1 week , resulting in only a produced white powder was vacuum dried at room tempera small amount of blisters on the coated face. ture so as to produce 64 g of a semicarbazide composition . The semicarbazide composition was dissolved in the same Comparative Example 1 10 amount of water to make a 50 % aqueous solution . The LC /MS analysis of the semicarbazide composition ( Semicarbazide Composition ) resulted in an analysis area ratio ( a ) of 0 .000 % , i. e ., below A reaction vessel having a reflux condenser , a thermom - detection limit, an analysis area ratio ( b - 1 ) of 95 % , an eter, and a stirrer was charged with 120 . 0 g of hydrazine analysis area ratio ( b - 2 ) of 4 . 5 % , and analysis area ratio monohydrate , 200 g of tetrahydrofuran , and 1000 g of water . 15 (b -3 ) of 0 . 5 % . The molecular weight per semicarbazide Subsequently , a mixture solution of 200 g of tetrahydrofuran group calculated from the ratios was 150 . The chromato and 50 g of isophorone diisocyanate was added dropwise at gram obtained by the LC /MS analysis is shown in FIG . 5 . room temperature over a time period of 1 hour. Subse - (Aqueous Polymer Composition and Coating Film ) quently , stirring was performed at a temperature of 50° C . or To 100 g of the carbonyl group -containing waterborne lower for 1 hour so as to complete the reaction ( the ratio of 20 copolymer dispersion in the Synthesis Example 1 - 1 , 2 % water- soluble organic solvent excluding water at the end of CS - 12 (made by JNC Corporation ) was added and then reaction : 0 % ) . Subsequently the organic solvent and water thoroughly stirred and mixed . Subsequently , 2 . 15 g of 50 % were removed under reduced pressure at a temperature of aqueous solution of the semicarbazide composition ( semi 50° C . or lower . The produced white powder was vacuum carbazide group relative to keto group : 0 . 9 equivalent) was dried at room temperature so as to produce 64 g of a 25 added and mixed to make an aqueous polymer composition . semicarbazide composition . The semicarbazide composition The coating solution of the produced aqueous polymer was dissolved in the same amount of water to make a 50 % composition was applied to a thickness of about 100 um and aqueous solution . dried at 23° C . for 1 week to obtain a coating film . The The LC /MS analysis of the semicarbazide composition produced coating film was immersed in acetone for 24 hours resulted in an analysis area ratio ( a ) of 2 . 2 % , an analysis area 30 and dried for measurement of the rate of change in mass ratio ( b - 1 ) of 92 % , an analysis area ratio ( 6 - 2 ) of 5 % , and before and after the immersion . The measurement results analysis area ratio ( b - 3 ) of 1 % . The molecular weight per showed that the insoluble portion of the coating film was semicarbazide group calculated from the ratios was 154 . The 85 % . chromatogram obtained by the LC /MS analysis is shown in Further, a white enamel paint was applied to a flexible FIG . 4 . 35 board to prepare a dried coated board , on which the aqueous (Aqueous Polymer Composition and Coating) polymer composition was applied to a thickness of 250 um , To 100 g of the carbonyl group - containing waterborne which was dried at room temperature for 1 week to make a copolymer dispersion in the Synthesis Example 1 - 1 , 2 % coating film . The produced coating film was immersed in a CS - 12 (made by JNC Corporation ) was added and then saturated calcium hydroxide solution at 23° C . for 1 week , thoroughly stirred . Subsequently , 2 . 21 g of 50 % aqueous 40 resulting in a Ab value of 3 . 1 . solution of the semicarbazide composition (semicarbazide Further, a white enamel paint was applied to an alumite group relative to keto group : 0 .9 equivalent) was added and board to prepare a dried coated board , on which the aqueous mixed to make an aqueous polymer composition . polymer composition was applied to a thickness of 100 um , The coating solution of the produced aqueous polymer which was dried at room temperature for 1 week to make a composition was applied to a thickness of about 100 um and 45 coating film . The coated board with the four sides and the dried at 23° C . for 1 week to obtain a coating film . The back side sealed with wax was immersed in 1 N sulfuric acid produced coating film was immersed in acetone for 24 hours aqueous solution at 23° C . for 1 week , resulting in a large and dried for measurement of the rate of change in mass amount of blisters on the coated face . before and after the immersion . The measurement results The method formeasuring the number average molecular showed that the insoluble portion of the coating film was 50 weight is as follows . 87 % . Using gel permeation chromatography , determination was Further , a white enamel paint was applied to a flexible based on the standard polystyrene calibration curve . board to prepare a dried coated board , on which the aqueous (Equipment Used ) polymer composition was applied to a thickness of 250 um , Liquid chromatography equipment: HLC - 8020 manufac which was dried at room temperature for 1 week to make a 55 tured by Tosoh Corporation . coating film . The produced coating film was immersed in a Column : TSK gel G -5000 HXL , TSKgel G - 4000 HXL , saturated calcium hydroxide solution at 23° C . for 1 week , and TSKgel G -2000 HXL , made by Tosoh Corporation resulting in a high Ab value of 12 . 5 . Data processing equipment: SC 8010 made by Tosoh Corporation Comparative Example 2 60 Carrier : tetrahydrofuran (Semicarbazide Composition ) Production Example 2 - 1 A reaction vessel having a reflux condenser, a thermom eter, and a stirrer was charged with 200 g of hydrazine A reaction vessel having a reflux condenser, a thermom monohydrate , 200 g of tetrahydrofuran . Subsequently , a 65 eter, and a stirrer was charged with 22. 0 g of hydrazine mixture solution of 200 g of tetrahydrofuran and 50 g of monohydrate , 200 g of tetrahydrofuran , and 60 g of water . isophorone diisocyanate was added dropwise at room tem Subsequently , a mixture solution of 400 g of toluene and 50 US 10 ,023 , 760 B2 41 g of isophorone diisocyanate was added dropwise at room of ion -exchanged water and 3 . 5 g of 25 % aqueous solution temperature over a time period of 1 hour . Subsequently , of a surfactant ( trade name: AQUALON KH - 10 , made by stirring was performed at room temperature for 1 hour so as Dai- ichi Kogyo Seiyaku Co . , Ltd . ) , and after raising the to complete the reaction ( the ratio of non -water - insoluble temperature in the reaction vessel to 80° C ., a mixture organic solvent excluding water at the end of reaction : 67 % ) . 5 solution of 59 . 2 g of methylmethacrylate , 149. 6 g of butyl Subsequently the organic solvent and water were removed acrylate , 240. 0 g of butyl methacrylate , 2 . 4 g of methacrylic under reduced pressure at a temperature of 50° C . or lower. acid , 28 . 8 g of diacetone acrylamide, 0 . 24 g of n - dodecyl The produced white powder was vacuum dried at room mercaptan , 283 . 4 g of ion -exchanged water, 19 . 2 g of 25 % temperature so as to produce 64 g of a semicarbazide aqueous solution of AQUALON KH - 10 , and 84 . 0 g of 2 % composition . The semicarbazide composition was dissolved aqueous solution of ammonium persulfate was flowed into in the same amount of water to make a 50 % aqueous the reaction vessel from a dripping tank over a time period solution . of 2 hours , while keeping the temperature in the reaction The LC /MS analysis of the semicarbazide composition vessel at 80° C . during inflow . After completion of the resulted in an analysis area ratio ( a ) of 0 . 09 % , an analysis inflow , the temperature in the reaction vessel was kept at 80° area ratio (b - 1 ) of 85 .20 % , an analysis area ratio ( b - 2 ) of C . for 30 minutes for polymerization of the polymer ( the 11 . 53 % , and analysis area ratio ( b - 3 ) of 3 . 18 % . The molecu - 15 second polymer for the first time) . Subsequently, a mixture lar weight per semicarbazide group calculated from the solution of 11 . 2 g of methyl methacrylate , 67 . 2 g of butyl ratios is 167 . acrylate , 40 . 0 g of butyl methacrylate , 16 . 0 g of acrylic acid , 16 . 0 g of methacrylic acid , 9 . 6 g of diacetone acrylamide , Production Example 2 -2 : Production of Waterborne 1 .6 g of n -dodecyl mercaptan , 110 .0 g of ion -exchanged Polymer Dispersion A - 1 20 water , 3 . 2 g of 25 % aqueous solution ofAQUALON KH - 10 , and 24 . 0 g of 2 % aqueous solution of ammonium persulfate A reaction vessel having a reflux condenser , a dripping was flowed into the reaction vessel from a dripping tank over tank , a thermometer, and a stirrer was charged with 509 . 4 g a time period of 40 minutes , while keeping the temperature of ion - exchanged water and 3 . 5 g of 25 % aqueous solution in the reaction vessel at 80° C . during inflow . After comple of a surfactant AQUALON KH - 10 , and after raising the 25 tion of the inflow , the temperature in the reaction vessel was temperature in the reaction vessel to 80° C ., a mixture kept at 80° C . for 30 minutes , and then 10 . 4 g of 25 % solution of 11 .2 g of methyl methacrylate , 67. 2 g of butyl aqueous ammonia was added for polymerization of a poly acrylate , 40 . 0 g of butyl methacrylate , 16 . 0 g of acrylic acid , carbonyl compound portion having the same composition as 16 . 0 g of methacrylic acid , 9 . 6 g of diacetone acrylamide , in the Production Example 2 - 2 . 1 . 6 g of n - dodecyl mercaptan , 110 .0 g of ion - exchanged . Subsequently , a mixture solution of 67 . 2 g of methyl water, 3 . 2 g of 25 % aqueous solution of surfactant ( trade methacrylate, 83 . 2 g of butyl acrylate , 9 . 6 g of diacetone name: AQUALON KH - 10 , made by Dai - ichi Kogyo Sei - acrylamide, 0 .08 g of n -dodecyl mercaptan , 161. 9 g of yaku Co ., Ltd .) , and 36 . 0 g of 2 % aqueous solution of ion -exchanged water, 3 .2 g of 25 % aqueous solution of ammonium persulfate was flowed into the reaction vessel AQUALON KH - 10 , and 24 . 0 g of 2 % aqueous solution of from a dripping tank over a time period of 40 minutes, while ammonium persulfate was flowed into the reaction vessel keeping the temperature in the reaction vessel at 80° C . 35 from a dripping tank over a timeperiod of 40 minutes , while during inflow . After completion of the inflow , the tempera keeping the temperature in the reaction vessel at 80° C . ture in the reaction vessel was kept at 80° C . for 30 minutes, during inflow . After completion of the inflow , the tempera and the pH was adjusted to 7 with 25 % aqueous ammonia , ture in the reaction vessel was kept at 80º C . for 60 minutes so as to make a dispersion liquid of the polycarbonyl for polymerization of the polymer ( the second polymer for compound . A portion of the produced polycarbonyl com - 40 the second time ). Subsequently the content was cooled to pound was sampled for measurement of the number average room temperature , with a pH adjusted to 7 . 5 with addition of molecular weight and the acid value , resulting in a number 25 % aqueous ammonia , and then subjected to filtration with average molecular weight of 29000 and an acid value of 283 . a 100 mesh screen , so that a waterborne polymer dispersion Subsequently , under presence of the dispersion liquid of A - 2 having a solid content of 40 . 0 % and an average particle polycarbonyl compound , a mixture solution of 59 .2 g of 45 diameter of 176 nm was obtained . methyl methacrylate, 149 . 6 g of butyl acrylate , 240 . 0 g of butyl methacrylate , 2 . 4 g of methacrylic acid , 28 . 8 g of Example 2 - 1 diacetone acrylamide , 0 . 24 g of n - dodecyl mercaptan , 267. 0 g of ion -exchanged water, 10 . 4 g of 25 % aqueous solution To 100 g of the waterborne polymer dispersion ( A - 1 ) of AQUALON KH - 10 , and 72 .0 g of 2 % aqueous solution obtained by the method in Production Example 2 - 2 , 3 .85 g of ammonium persulfate was flowed into the reaction vessel 30 of 50 % aqueous solution of the semicarbazide composition from a dripping tank over a time period of 2 hours, while obtained by the method in Production Example 2 - 1 was keeping the temperature in the reaction vessel at 80° C . added , stirred and mixed , and to the mixture , 5 g of CS - 12 during inflow . After completion of the inflow , the tempera - (made by JNC Corporation ) was then added , thoroughly ture in the reaction vessel was kept at 80° C . for 60 minutes stirred , and mixed , so that a coating liquid formed of for polymerization of the polymer ( second polymer ). Sub - 55 aqueous polymer composition was obtained . The coating sequently the content was cooled to room temperature, with liquid was applied to a thickness of about 100 um at room a pH adjusted to 7 . 5 with addition of 25 % aqueous ammonia , temperature for film formation , which was dried at 23° C . for and then subjected to filtration with a 100 mesh screen , so 1 week to make a coating film . The produced coating film that a waterborne polymer dispersion A - 1 having a solid was immersed in water for 1 week for measurement of the content of 40 . 0 % and an average particle diameter of 186 nm 60 rate of change in mass before and after the immersion , was obtained . resulting in 1 . 7 times the weight with an absorption of 70 % . The coating film was transparent with only slight whitening . Production Example 2 -3 : Production of Waterborne Polymer Dispersion A - 2 Example 2 - 2 65 A reaction vessel having a reflux condenser , a dripping To 100 g of the waterborne polymer dispersion ( A - 2 ) tank , a thermometer, and a stirrer was charged with 509 .4 g obtained by the method in Production Example 2 -3 , 3. 85 g US 10 , 023 , 760 B2 43 44 of 50 % aqueous solution of the semicarbazide composition resulting in 2 .80 times the weight with an absorption of obtained by the method in Production Example 2 - 1 was 180 % . Further , the coating film was whitened . added , stirred and mixed , and to the mixture, 5 g of CS- 12 The invention claimed is : (made by JNC Corporation ) was then added , thoroughly 1. A method for producing a semicarbazide composition , stirred , and mixed , so that a coating liquid formed of: 5 wherein the composition comprises : aqueous polymer composition was obtained . The coating a semicarbazide compound ( A ) having an amino group liquid was applied to a thickness of about 100 um at room and a semicarbazide group ; temperature for film formation , which was dried at 23° C . for a semicarbazide compound ( B -1 ) having a structure with 1 week to make a coating film . The produced coating film a semicarbazide group substituted for the amino group was immersed in water for 1 week for measurement of the 10 of the semicarbazide compound ( A ) ; rate of change in mass before and after the immersion , a semicarbazide compound ( B - 2 ) as a dimer of the resulting in 1. 35 times the weight with an absorption of 35 % . semicarbazide compound ( B - 1 ) ; and The coating film was transparent with only slight blue tint. a semicarbazide compound (B - 3 ) as a trimer of the semicarbazide compound ( B - 1 ); Comparative Example 2 - 1 15 the semicarbazide composition having an analysis area To 100 g of the waterborne polymer dispersion ( A - 1 ) ratio ( a ) represented by the following expression (a ) of obtained by the method in Production Example 2 - 2 , 12. 7 g 0 .008 % or more and 2 % or less : of 8 % aqueous solution of adipic acid dihydrazide was Analysis area ratio (a ) = S4/ ( S1 + Sg- 1+ SB- 2+ SB- 3) x100 added , stirred and mixed , and to the mixture, 5 g of CS - 12 20 wherein S4, SB -1 , SB -2 , and SB -3 represent peak areas of (made by JNC Corporation ) was then added , thoroughly peaks derived from the semicarbazide compound (A ), stirred , and mixed to make a coating liquid . The coating the semicarbazide compound ( B - 1 ) , the semicarbazide liquid was applied to a thickness of about 100 um at room compound ( B - 2 ) , and the semicarbazide compound temperature for film formation , which was dried at 23° C . for ( B - 3 ) , respectively , in a chromatogram obtained by 1 week to make a coating film . The produced coating film 25 high performance liquid chromatography analysis of was immersed in water for 1 week for measurement of the the semicarbazide composition ; and rate of change in mass before and after the immersion , wherein the method comprises : resulting in 3 .65 times the weight with an absorption of a reaction step of reacting a compound (C ) having two or 265 % . Further , the coating film was remarkably whitened . more isocyanate groups in the molecule with hydrazine 30 or a hydrazine derivative in a solvent to obtain the Comparative Example 2 - 2 semicarbazide composition , wherein in the reaction To 100 g of the waterborne polymer dispersion ( A - 2 ) step , obtained by the method in Production Example 2 - 3 , 12 . 7 g the solvent contains water, a water -soluble organic sol of 8 % aqueous solution of adipic acid dihydrazide was 35 vent, and a water- insoluble solvent; and added , stirred and mixed , and to the mixture , 5 g of CS - 12 the amount of the water - insoluble solvent relative to the (made by JNC Corporation ) was then added , thoroughly total amount of the water- soluble organic solvent and stirred , and mixed to make a coating liquid . The coating the water - insoluble solvent is 30 mass % or more . liquid was applied to a thickness of about 100 um at room 2 . The method according to claim 1, wherein the ratio of temperature for film formation , which was dried at 23° C . for 40 the number of moles of the hydrazine or hydrazine deriva 1 week to make a coating film . The produced coating film 40 tive to the number of moles of the isocyanate groups of the was immersed in water for 1 week for measurement of the compound ( C ) is 0 . 7 to 5 in the reaction step . rate of change in mass before and after the immersion , * * * * *