HHHHHH. US00507932A United States Patent (19) 11) Patent Number: 5,079,312 Isozaki et al. (45) Date of Patent: Jan. 7, 1992

54 PROCESS FOR PREPARING loxane-containing resin which comprises copolymeriz POLYSILOXANE-CONTAINING RESIN ing a polysiloxane-type macromonomer with a vinyl 75 Inventors: Osamu Isozaki, Yokohama; Noboru monomer, characterized in that the polysiloxane-type Nakai, Hiratsuka; Koichiro Murata, macromonomer is one prepared by reacting about 70 to Kanagawa, all of Japan about 99.999 mole % of a compound (A) represented by the formula (73) Assignee: Kansai Paint Company, Limited, Amagasaki, Japan R (I) (21) Appl. No.: 522,401 22 Filed: May 11, 1990 Related U.S. Application Data wherein R1 represents aliphatic hydrocarbon group (63) Continuation of Ser. No. 15,398, Feb. 17, 1987, aban having 1 to 8 carbon atoms or phenyl group, and R2, R3 doned. and R4 each represent alkoxyl group having 1 to 4 car 30 Foreign Application Priority Data bon atoms or hydroxyl group with about 30 to about Feb. 25, 1986 JP Japan ...... 61-40923 0.001 mole % of a compound (B) represented by the formula 51) Int. C...... CO8F 283/12 52) U.S. C...... 525/479; 526/279; R (II) 528/25; 528/26; 528/32; 524/755; 524/761; / CH2=C-COO(CH2)Si-R 524/765; 524/770, 524/773; 524/858 N 58 Field of Search ...... 526/279; 525/479; R5 R8 528/25,32, 26; 524/755, 761, 765, 770,773, 858 (56) References Cited wherein R5 represents hydrogen atom or methyl group, U.S. PATENT DOCUMENTS Ré, R7 and R8 each represent hydroxyl group, alkoxyl group having to 4 carbon atoms or aliphatic hydrocar 2,486, 162 i0/1949 Hyde ...... 528/25 4,123,472 )0/1978 Getson et al. .... 525/479 bon group having 1 to 8 carbon atoms with the proviso 4,413,04 10/1983 Deubzer et al. .. 525/479 that Rs, R7 and R8 can not be aliphatic hydrocarbon 4,618,644 10/1986 Liu ...... 524/535 groups having 1 to 8 carbon atoms at the same time, and n is an integer of 1 to 6, the polysiloxane-type macromo OTHER PUBLICATIONS nomer having at least two free functional groups se Noll, Walter, Chemistry and Technology of Silicones, lected from hydroxyl groups and alkoxyl groups per Academic Press, New York, 1968, pp. 192-193. molecule, and the macromonomer having a number Primary Examiner-Melvyn I. Marquis average molecular weight of about 400 to about Assistant Examiner-R. Dean, Jr. 100,000. Attorney, Agent, or Firm-Armstrong, Nikaido, Marmelstein, Kubovcik & Murray (57) ABSTRACT The invention provides a process for preparing a polysi 13 Claims, No Drawings 5,079,312 1. 2 type macromonomer is one prepared by reacting about PROCESS FOR PREPARING 70 to about 99.999 mole % of a compound (A) repre POLYSLOXANE-CONTAINING RESIN sented by the formula This application is a continuation of application Ser. No. 015,398 filed Feb. 17, 1987, now abandoned. (I) This invention relates to a process for preparing a polysiloxane-containing resin, and more particularly to a process for preparing a vinyl polymer having multi functional polysiloxane at the side chain. 10 It is known to improve the characteristics of vinyl wherein R represents aliphatic hydrocarbon group polymer by introducing polysiloxane into the side chain having 1 to 8 carbon atoms or phenyl group, and R2, R3 thereof. and R4 each represent alkoxyl group having 1 to 4 car Known processes for introducing polysiloxane into bon atoms or hydroxyl group with about 30 to about the side chain of vinyl polymer include, for example, a 15 0.001 mole % of a compound (B) represented by the process for preparing a graft copolymer having polysi formula loxane group at the side chain by radically copolymeriz ing a polysiloxane group-containing monomer with an ethylenically unsaturated mono- or di-ene monomer -Rs (II) (Japanese Unexamined Patent Publication No. 20 CH2=C-COO(CH2)Si-R7 231720/1985). This process has, however, the following N drawbacks. None of functional groups such as alkoxyl Rs R8 group and hydroxyl group exist in the polysiloxane side chain of the polymer prepared by the process. Accord wherein R5 represents hydrogen atom or methyl group, ingly the polymer thus prepared is extremely poor in 25 Ré, R7 and R8 each represent hydroxyl group, alkoxyl crosslinking property. In addition, the polymers are group having 1 to 4 carbon atoms or aliphatic hydrocar further defective in being low, in compatibility with bon group having 1 to 8 carbon atoms with the proviso other components (other vinyl polymer and polysilox that Rs, R7 and Rs can not be aliphatic hydrocarbon ane, etc.) which have not participated in the reaction for groups having 1 to 8 carbon atoms at the same time, and producing the polysiloxane-containing vinyl polymer, 30 n is an integer of 1 to 6, the polysiloxane-type macromo with the result that the liquid reaction product tends to become turbid. If reaction ratio is enhanced to prevent nomer having at least two free functional groups se the reaction product from getting turbid, the reaction lected from hydroxyl groups and alkoxyl groups per product is prone to gelation. molecule, and the macromonomer having a number Another example of processes for preparing a polysi 35 average molecular weight of about 400 to about loxane-containing resin is a process for preparing a graft 100,000. copolymer by radically copolymerizing a radically According to the process of this invention, a polysi polymerizable mononer with an acryl-modified sili loxane side chain with at least two free functional cone which is a condensation product of silicone and groups can be introduced into a vinyl polymer by copo acrylic compound (Japanese Unexamined Patent Publi lymerizing a vinyl monomer with a polysiloxane-type cation No. 167606/1983). This process can introduce alkoxyl, hydroxyl or like functional group into the poly macromonomer which is prepared by reacting the com siloxane side chain of the vinyl polymer but two non pound (A) and the compound (B) and which has at least functional groups such as alkyl group and phenyl group two free functional groups selected from hydroxyl exist as bonded to Si having the functional group at 45 groups and alkoxyl groups. tached thereto so that the reactivity of the functional In the vinyl polymer thus prepared, the functional group is insufficient from a viewpoint of chemical struc groups at the side chain are high in reactivity and at ture. Accordingly this process gives a polysiloxane-con least two such reactive functional groups are present. taining resin unsatisfactory in crosslinking property and Therefore, the polymer is improved in crosslinking in compatibility with other components. It is an object of the present invention to provide a property and compatibility with other resins and the process for preparing a polysiloxane-containing vinyl like. Furthermore, the polymer has the siloxane bond polymer having an improved crosslinking property. containing side chain which serves to improve the prop It is another object of the invention to provide a erties of the polymer including water repellency, water process for preparing a polysiloxane-containing vinyl 55 resistance, chemical resistance, weatherability, heat polymer having a high compatibility with other organic resistance, stain resistance, mar resistance and the like. resins and the like. The polysiloxane-type macromonomer to be used in It is a further object of the invention to provide a this invention can be prepared by reacting a compound process for preparing a polysiloxane-containing vinyl (A) represented by the formula polymer which is outstanding in water repellency, water resistance, chemical resistance, weatherability, mar resistance, heat resistance, stain resistance, etc. (I) Other objects and features of the invention will be come apparent from the following description. This invention provides a process for preparing a 65 polysiloxane-containing resin which comprises copoly merizing a polysiloxane-type macromonomer with a wherein R, R2, R3 and R4 are as defined above with a vinyl monomer, characterized in that the polysiloxane compound (B) represented by the formula 5,079,312 3 4. 99.9 mole %, more preferably about 95 to about 99 mole R6 (II) %, of the compound (A) and about 30 to about 0.001 / mole %, preferably about 10 to about 0.1 mole %, more CH=C-COO(CH)Si-R7 N preferably about 5 to about 1 mole %, of the compound R5 R8 (B), based on the combined amount of compounds (A) and (B). Use of less than 70 mole % of the compound wherein R5, R6, R7, R8 and n are as defined above. The (A) is undesirable since gelation tends to occur during macromonomer thus prepared has the main skeleton copolymerization reaction. Use of over 99.999 mole % composed of siloxane bond. To Si in the main skeleton of the compound (A) increases the amount of un is attached directly or indirectly groups such as hy 10 copolymerizable polysiloxane, thereby rendering turbid droxyl group, alkoxyl group, aliphatic hydrocarbon the resin liquid prepared by copolymerization of the group, phenyl group, and group having polymerizable macromonomer and vinyl monomer. unsaturated bond. When the compounds (A) and (B) are subjected to In the compound (A), R represents aliphatic hydro reaction, there arises condensation of hydroxyl groups carbon group having 1 to 8 carbon atoms or phenyl 15 with the separation of water which hydroxyl groups are group, and R2, R3 and R4 each represent alkoxyl group present in the compound (A) and/or (B) or are pro having 1 to 4 carbon atoms or hydroxyl group. R2, R3 duced by hydrolysis of alkoxyl present in the compound and R4 may be the same or, any or all of the groups may (A) and/or (B). Depending on the reaction conditions, be different. condensation with the separation of alcohol may par Examples of alkoxyl groups having 1 to 4 carbon tially occur instead. atoms in the compound (A) are straight chain or Although feasible in the absence of a solvent, the branched chain alkoxyl groups such as methoxy, eth reaction of the compounds (A) and (B) is performed oxy, propoxy, butoxy and the like. Examples of ali preferably in the presence of water or an organic sol phatic hydrocarbon groups having 1 to 8 carbon atoms vent capable of dissolving the compounds (A) and (B). in the compound (A) are straight chain or branched 25 chain aliphatic hydrocarbon groups such as methyl, Examples of useful organic solvents are hydrocarbon ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the type solvents such as heptane, toluene, xylene, octane, like. mineral spirit and the like; ester-type solvents such as Examples of preferred groups represented by R in ethyl acetate, n-butyl acetate, isobutyl acetate, methyl the compound (A) are methyl, phenyl and the like. 30 cellosolve acetate, butylcarbitol acetate and the like; Examples of preferred groups represented by R2, R3 ketone-type solvents such as methyl ethyl ketone, and R4 in the compound (A) are methoxy, ethoxy, methyl isobutyl ketone, diisobutyl ketone and the like; propoxy, butoxy, hydroxyl and the like. Examples of alcohol-type solvents such as, ethanol, isopropanol, n useful compounds (A) are methyltrimethoxysilane, phe butanol, sec.-butanol, isobutanol and the like; and ether nyltrimethoxysilane, butyltrimethoxysilane, methyltrie 35 type solvents such as n-butyl ether, dioxane, ethylene thoxysilane, methyltributoxysilane, phenyltrisilanol, glycol monomethyl ether, ethylene glycol monoethyl methyltrisilanol and the like. Of these examples, methyl ether and the like. These solvents can be used singly or trimethoxysilane, phenyltrimethoxysilane, phenyl at least two of them are usable in mixture. trisilanol and the like are more preferable. These com When a solvent is used, it is suitable that the concen pounds can be used singly or at least two of them are tration of compounds (A) and (B) as combined be about usable in mixture. 5% by weight or more. In the compound (B), R5 represents hydrogen atom The reaction of the compounds (A) and (B) is carried or methyl group, Ré, R7 and Rs each represent hydroxyl out at a temperature of about 20 to about 180° C., group, alkoxyl group having 1 to 4 carbon atoms or preferably about 50 to about 120° C. and is completed aliphatic hydrocarbon group having 1 to 8 carbon 45 in about 1 to about 40 hours. atoms, and n is an integer of 1 to 6. Re, R7 and R8 may When required, a polymerization inhibitor can be be the same or different although all of these groups are used for the reaction. The polymerization inhibitor is not aliphatic hydrocarbon group having 1 to 8 carbon effective in inhibiting the polymerization of unsaturated atoms at the same time. bond contained in the compound (B) during the reac Usable as the aliphatic hydrocarbon groups having 1 tion of the compounds (A) and (B). Examples of useful to 8 carbon atoms and alkoxyl groups having 1 to 4 polymerization inhibitors are hydroquinone, hydroqui carbon atoms in the compound (B) are those exempli none monomethyl ether, etc. fied above for the compound (A). In preparation of polysiloxane-type macromonomer, It is preferred to use methoxy, ethoxy and hydroxyl the reaction system comprising the compounds (A) and as the groups Re, R7 and Rs. Preferred integer range of 55 (B) may contain tetraalkoxysilane, dialkyldialkoxysilane n is 2 to 4. Examples of useful compounds (B) are y or the like in an amount of about 20% by weight or less methacryloxypropyltrimethoxysilane, y-methacryloxy based on the compounds (A) and (B). propyltriethoxysilane, y-acryloxypropyltrimethoxysi When the groups R2, R3, R, R6, R7 and Rs are all lane, y-methacryloxybutyltriethoxysilane, y-acryloxy hydroxyl in the condensation reaction of the corn propyltrisilanol, etc. Of these examples, more preferable 60 pounds (A) and (B), the reaction is preferably con are y-methacryloxypropyltrimethoxysilane, y-metha ducted with heating and stirring in an organic solvent. cryloxypropyltriethoxysilane, Ty-acryloxypropyl When the compound (A) and/or (B) has alkoxyl trisilanol, etc. These compounds can be used singly or at group to be attached to Si, hydrolysis is preferably done least two of them are usable in mixture. before condensation. Generally hydrolysis and conden The siloxane-type macromonomer to be used in the 65 sation can be continuously carried out with heating and invention can be prepared by mixing and reacting the stirring in the presence of water and a catalyst. The compounds (A) and (B). The reaction employs about 70 annount of water to be used for the reactions is not to about 99.999 mole %, preferably about 90 to about specifically limited, but is preferably about 0.1 mole or 5,079,312 5 6 more per mole of alkoxyl group. Use of less than 0.1 compounds having one polymerizable unsaturated bond mole of water is likely to hinder the smooth progress of per molecule. Examples thereof are esters of acrylic reaction. It is most preferred to use water as a solvent in acid or methacrylic acid with monohydric alcohol hav large excess. When water and a water-soluble organic ing 1 to 22 carbon atoms such as methyl acrylate, solvent are conjointly used, the reaction system is ren 5 methyl methacrylate, ethyl acrylate, ethyl methacry dered uniform where the condensation produces alco late, propyl acrylate, propyl methacrylate, butyl acry hol sparingly soluble in water. Preferred water-soluble late, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethyl organic solvents include those of alcohol-, ester-, ether hexyl methacrylate, lauryl acrylate, lauryl methacry and ketone-type as exemplified above. late, stearyl acrylate, stearyl methacrylate and the like; Usable as the catalyst for the hydrolysis reaction are 10 carboxyl group-containing vinyl monomers such as acid catalysts and alkali catalysts. Specific examples acrylic acid, methacrylic acid, maleic anhydride and the thereof are acid catalysts such as hydrochloric acid, like; hydroxyl group-containing vinyl monomers such sulfuric acid, phosphoric acid, formic acid, acetic acid, as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacry propionic acid, acrylic acid, methacrylic acid and the late, hydroxypropyl acrylate, hydroxypropyl methac like and alkali catalysts such as sodium hydroxide, tri 15 rylate and the like; glycidyl group-containing vinyl ethylamine, ammonia and the like. The amount of the monomers such as glycidyl acrylate, glycidyl methacry catalyst is about 0.0001 to about 5% by weight, prefera late and the like; amide-type vinyl monomers such as bly about 0.01 to about 0.1% by weight, based on the acrylamide, methacrylamide, N-methylolacrylamide, combined amount of the compounds (A) and (B). N-methylolmethacrylamide and the like; amine-type The polysiloxane-type macromonomer to be used in 20 the invention has a number-average molecular weight vinyl monomers such as dimethylaminoethyl methacry of about 400 to about 100,000, preferably about 1,000 to late, 2-diethylaminoethyl methacrylate, te?t about 20,000. Use of the polysiloxane-type macromo butylaminoethyl methacrylate and the like; and other nomer with a number-average molecular weight of less vinyl monomers such as styrene, vinyltoluene, acryloni than about 400 is undesirable since it tends to gel the 25 trile, methacrylonitrile, a-methyl styrene, vinyl acetate reaction mixture during copolymerization. Use of the and the like. polysiloxane-type macromonomer with a number-aver The copolymerization of the polysiloxane-type mac age molecular weight of more than about 100,000 tends romononer with the vinyl monomer in the invention to deteriorate the compatibility, hence undesirable. can be carried out in the same manner as the usual pro The main skeleton of polysiloxane-type macromo 30 cess for synthesizing acrylic resin or vinyl resin, for nomer produced by the reaction of the compounds (A) example, by dissolving or dispersing the two compo and (B) is composed of siloxane bond, and generally has nents in an organic solvent and heating the solution a linear or ladder-like structure or a structure compris with stirring to about 60 to about 180 C. in the presence ing a combination of linear and ladder-like portions. Of of a radical polymerization initiator. The reaction is these, the ladder-like structure and the structure having 35 usually completed in about 1 to about 10 hours. The the ladder-like portions in larger proportion than the proportions of the two components can be suitably linear portions are preferred because the macromo varied according to a particular application of the poly nomer of such structures serves to improve the water mer, but it is suitable to use about 1 to about 95% by resistance, heat resistance, light resistance and like weight, preferably about 10 to about 70% by weight, of properties of the polymer to be produced. The desired 40 the polysiloxane-type macromonomer and about 99 to type of structure can be obtained by varying the pro about 5% by weight, preferably about 90 to about 30% portions of the compounds (A) and (B), the amounts of by weight, of the vinyl monomer, based on the com water and catalyst, etc. The polysiloxane-type mac bined amount of the macromonomer and the vinyl mon romonomer has the Si of siloxane bond to which are omer. Examples of useful organic solvents include those attached groups such as groups R1 to R4, group 45 of the alcohol-type, ether-type, ester-type, hydrocar bon-type and the like as exemplified above. When the hydrocarbon-type solvent is used, it is preferably com CH=-coochy. bined with other solvents to enhance the solubility. Rs Examples of radical polymerization initiators can be SO any of those usually used, such as benzoyl peroxide, groups Rs to Rs, and the like in the formulas (I) and (II). t-butylperoxy-2-ethylhexanoate and like peroxides, The macromonomer of such structure possesses at least azoisobutyronitrile, azobisdimethyl valeronitrile and 2 free functional groups such as hydroxyl groups and like azo compounds, etc. alkoxyl groups having 1 to 4 carbon atoms (the groups The polysiloxane-containing resin prepared accord R2 to R and Ré to R8) per molecule. 55 The polysiloxane-type macromonomer has polymer ing to the invention has a number-average molecular izable unsaturated bonds numbering, on an average, weight of about 3,000 to about 500,000, preferably preferably about 0.2 to about 1.9, more preferably about about 5,000 to about 100,000. 0.6 to about 1.4, most preferably about 0.9 to about 1.2, The polysiloxane-containing resin can be obtained, as per molecule. Presence of a far smaller number of poly 60 stated above, by subjecting the polysiloxane-type mac merizable unsaturated bonds is undesirable because it is romonomer and the vinyl monomer to copolymeriza likely to make turbid the liquid reaction product of the tion reaction which occurs at the polymerizable unsatu macromonomer and the vinyl monomer. Presence of a rated bond contained in the polysiloxane-type mac much larger number of polymerizable unsaturated romonomer with the result that the polysiloxane-type bonds is apt to cause gelation during the copolymeriza 65 macromonomer gets bonded to the resulting copolymer tion reaction, hence undesirable. as a pendant side chain. The side chain composed of the Useful vinyl monomers to be copolymerized with the polysiloxane-type macromonomer is of linear or ladder polysiloxane-type macromonomer are, for example, like structure in which at least two free functional 5,079,312 7 8 groups such as hydroxyl groups and alkoxyl groups are -continued bonded to Si. The vinyl polymer with such structure is given out Toluene 4,500 g standing surface characterisitics by the presence of the side chain having the siloxane bond. Moreover, the 5 These components were mixed together and reacted functional groups bonded to Si in the side chain of the at 117' C. for 3 hours for condensation. The polysilox vinyl polymer are more reactive than those bonded to ane-type macromonomer thus obtained was found to Si in conventional vinyl polymers with polysiloxane have a number-average molecular weight of 7,000 and side chain, and furthermore, at least two such reactive to possess, on an average, one vinyl group and 5 to 10 functional groups are present in the side chain of the 10 hydroxyl groups, per molecule. The macromonomer vinyl polymer of this invention. Therefore, the vinyl was mixed with the other components shown below. polymer of the invention has improved crosslinking 2-Hydroxyethyl acrylate: 100 g property and enhanced compatibility with other com Methyl methacrylate: 200 g ponents. 2-Ethylhexyl methacrylate: 600 g 15 Azoisobutyronitrile: 10 g The polysiloxane-containing resin prepared in the The mixture was added dropwise to 1,000 g of a mixture invention have the advantages of being: of butanol and xylene in equal amounts by weight at (1) sufficient in crosslinking property even when used 120° C. for copolymerization, giving a transparent co singly, polymer. The copolymer was found to have a number (2) crosslinkable on reaction with the hydroxyl group, 20 average molecular weight of about 40,000. (3) markedly compatible with other organic resins, es The copolymer was tested in the same manner as in pecially acrylic resin, Example 1 to determine the gel fraction ratio and the (4) water repellent and high in water resistance and surface tension. The former value was 65% and the chemical resistance, latter was 35 dyne/cnn. (5) able to form coats with good weatherability and 25 effective, when mixed with other organic resins, in EXAMPLE 3 improving the weatherability, Phenyltrimethoxysilane (48 moles) was reacted with (6) high in mar resistance, 2 moles of y-methacryloxyethyltriethoxysilane in the (7) outstanding in heat resistance, and same manner as in Example 1. The polysiloxane-type (8) excellent in stain resistance. 30 macromonomer thus obtained was found to have a The invention will be described below in greater number-average molecular weight of about 5,000 and to detail with reference to the following Examples. possess, on an average, one vinyl group and 5 to 10 methoxy groups, per molecule. The macromonomer EXAMPLE (500 g) was copolymerized with 500 g of the vinyl mon 35 omer of the type used in Example 1 in the same manner Methyltrimethoxysilane 2,720 g (20 moles) as in Example 1. The resulting copolymer was found to y-Methacryloxypropyl 256 g (1 mole) have a number-average molecular weight of about trimethoxysilane deionized water 1,134 g 60,000. 6% hydrochloric acid 2 g The copolymer was tested by the same method as in Hydroquinone g Example 1 with the result that the coat thus formed was 81% in gel fraction ratio and 35 dyne/cm in surface These components were mixed together and reacted tension. at 80' C. for 5 hours. The polysiloxane-type macromo EXAMPLE 4 nomer thus obtained was found to have a number-aver 45 Methyltrimethoxysilane (29.1 moles) was reacted age molecular weight of about 2,000 and to possess, on with 0.9 mole of y-acryloxyethyltriethoxysilane in the an average, one vinyl group (polymerizable unsaturated same manner as in Example 1. The polysiloxane-type bond) and 4 hydroxyl groups, per molecule. The mac macromonomer thus obtained was found to have a romonomer (300 g) thus prepared was mixed with the number-average molecular weight of about 15,000 and other components listed below. to possess, on an average, one vinyl group and 5 to 10 Styrene: 100 g methoxy groups, per molecule. The macromonomer Methyl methacrylate: 100 g (400 g) was copolymerized with 600 g of the vinyl mon n-Butyl acrylate: 500 g oner of the type used in Example 1 in the same manner Azoisobutyronitrile: 20 g as in Example 1. The resulting copolymer was found to The mixture was added dropwise to 1,000 g of xylene at 55 have a number-average molecular weight of about 120' C. for copolymerization, giving a transparent co 70,000. polymer. The copolymer was found to have a number The copolymer was tested by the same method as in average molecular weight of about 20,000. Example 1 with the result that the coat thus formed was The copolymer was applied to the surface of a steel 92% in gel fraction ratio and 29 dyne/cm in surface plate and the coated plate was baked at 120' C. for 30 tension. minutes. The coat was found to have a gel fraction ratio of 73% (with acetone unextracted) and a surface tension EXAMPLE 5 of 29 dyne/cm. Methyltrimethoxysilane (15 moles) was reacted with EXAMPLE 2 1 mole of y-methacryloxypropylmethyldimethoxysi 65 lane in the same manner as in Example 1. The polysilox ane-type macromonomer thus obtained was found to Phenyltrisiianol 7,800 g (50 moles) have a number-average molecular weight of about 3,000 y-Acryloxypropyltrisilanol 200 g ( mole) and to possess, on an average, one vinyl group and 5 to 5,079,312 10 0 methoxy groups, per molecule. The macromonomer 2. A polysiloxane-containing resin according to claim (500 g) was copolymerized with 500 g of the vinyl mon 1 wherein R1 in the compound (A) is methyl or phenyl. omer of the type used in Example 2 in the same manner 3. A polysiloxane-containing resin according to claim as in Example 2. The resulting copolymer was to have 1 wherein R2, R3 and R4 in the compound (A) are each a number-average molecular weight of about 40,000. methoxy, ethoxy, propoxy, butoxy or hydroxyl. The copolymer was tested by the same method as in 4. A polysiloxane-containing resin according to claim Example 1 with the result that the coat thus formed was 1 wherein R8, R7 and Rs in the compound (B) are each 95% in gel fraction ratio and 29 dyne/cm in surface methoxy, ethoxy, or hydroxyl. tension. 5. A polysiloxane-containing resin according to claim O 1 wherein n in the compound (B) is 2 to 4. We claim: 6. A polysiloxane-containing resin according to claim 1. A polysiloxane-containing resin dissolved or dis 1 wherein the compound (A) is at least one compound persed in an organic solvent and prepared by a process selected from the group consisting of methyltrimeth which comprises copolymerizing a polysiloxane mac oxysilane, phenyltrimethoxysilane, butyltrimethoxysi romonomer with a vinyl monomer in an organic sol 5 lane, methyltriethoxysilane, methyltributoxysilane, phe vent, characterized in that the polysiloxane macromo nyltrisilanol and methyltrisilanol and the compound (B) nomer is prepared by reacting ahout 70 to about 99.999 is at least one compound selected from the group con mole % of a compound (A) represented by the formula sisting of y-methacryloxypropyltrimethoxysilane, y methacryloxypropyltriethoxysilane, y-acryloxypropyl 20 trimethoxysilane, y-methacryloxybutyltriethoxysilane (I) and y-acryloxypropyltrisilanol. 7. A polysiloxane-containing resin according to claim 1 wherein the compound (A) is at least one compound selected from the group consisting of methyltrimeth 25 oxysilane, phenyltrimethoxysilane and phenyltrisilanol wherein R represents aliphatic hydrocarbon group and the compound (B) is at least one compound selected having 1 to 8 carbon atoms or phenyl group, and R2, R3 from the group consisting of y-methacryloxypropyl and R4 each represent alkoxyl group having 1 to 4 car trimethoxysilane, y-methacryloxypropyltriethoxysilane bon atoms or hydroxyl group with about 30 to about and y-acryloxypropyltrisilanol. 0.002 mole % of a compound (B) represented by the 30 8. A polysiloxane-containing resin according to claim formula 1 wherein about 90 to about 99.9 mole % of the com pound (A) is reacted with about 10 to about 0.1 mole % of the compound (B). R6 (II) / 9. A polysiloxane-containing resin according to claim CH2=C-COO(CH2)Si-R7 35 1 wherein about 95 to about 99 mole % of the com N pound (A) is reacted with about 5 to about 1 mole % of R5 R8 the compound (B). 10. A polysiloxane-containing resin according to wherein R5 represents hydrogen atom or methyl group, claim 1 wherein the polysiloxane macromonomer has Re, R7 and R8 each represent hydroxyl group, alkoxyl polymerizable unsaturated bonds numbering, on an group having 1 to 4 carbon atoms or aliphatic hydrocar average, about 0.9 to about 1.2 per molecule. bon having 1 to 8 carbon atoms with the proviso that 11. A polysiloxane-containing resin according to Re, R7 and Rs cannot be aliphatic hydrocarbon groups claim 1 wherein the polysiloxane macromonomer has a having 1 to 8 carbon atoms at the same time, and n is an number-average molecular weight of about 1,000 and integer of 1 to 6, the polysiloxane macromonomer hav 45 about 20,000. ing at least two free functional groups per molecule 12. A polysiloxane-containing resin according to which are selected from the group consisting of hy claim 1 wherein about 1 to about 95% by weight of the droxyl and alkoxyl groups and are attached to Si, the polysiloxane macromonomer is reacted with about 99 to macromonomer having a number-average molecular about 5% by weight of the vinyl monomer. weight of about 400 to about 10,000 and having poly 50 13. A polysiloxane-containing resin according to merizable unsaturated bonds numbering, on an average, claim 1 wherein about 10 to about 70% by weight of the about 0.6 to about 1.4 per molecule and the resulting polysiloxane macromonomer is reacted with about 90 to polysiloxane-containing resin having a number average about 30% by weight of the vinyl monomer. molecular weight of 3,000 to 500,000. B. : : B 55

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