llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllI111Illl USOO5180766A United States Patent [191 [11] Patent Number: 5,180,766 Hayama et al. [45] Date of Patent: Jan. 19, 1993

[54] RESIN COMPOSITION FOR PRIMER USE FOREIGN PATENT DOCUMENTS AND PRIMER COMPOSITION EMPLOYING THE SAME 0308146 3/1989 European Pat. Off, . 2424308 11/1979 France . [75] Inventors: Kazuhide Hayama; Kazuyuki Hata; Katsuhiko Yamada; Keizo Abe; OTHER PUBLICATIONS Takahiro Ozu, all of Mic, Japan Patent Abstracts of Japan, vol. 12, No. 242 (C—510) [73] Assignee: Mitsubishi Petrochemical Co., Ltd., [3089], Jul. 8th, 1988; & JP'A-63 033 406 (Dainippon Tokyo, Japan Ink & Chem. Inc.) Feb. 13, 1988, WPIL, File Supplier, AN=88—101759, Derwent Publi [21] Appl. NO.I 687,517 cations Ltd, London, GB; & JP-A-63 051 477 (Mit [22] Filed: Apr. 19, 1991 subishi Petrochem.) Mar. 4, 1988. Primary Examiner—Jacob Ziegler [30] Foreign Application Priority Data Attorney, Agent, or Firm-Oblon, Spivak, McClelland, May 14, 1990 [JP] Japan ...... 2-123854 Maier & Neustadt [51] Int. Cl.5 ...... C08F 255/02; CO8K 5/06; [57] ABSTRACT CO8K 5/07; C08K 5/10 A resin composition for primer use is described, which [52] US. Cl...... 524/315; 524/356; contains a copolymer of (I) a radical-polymerizable 524/366; 524/474; 524/482; 524/484; 525/276; ole?n resin and (c) a monomer copolymerizable with 525/285; 525/286; 525/293; 525/301; 525/309 said ole?n resin (I) and containing an (meth)acry [58] Field of Search ...... 524/315, 356, 366, 474, late and/or a fluorine-containing unsaturated monomer 524/482, 484; 525/276, 285, 286, 293, 301, 309 as essential ingredients, said radical-polymerizable ole [56] References Cited ?n resin (I) being a product of the reaction of (a) an ole?n resin having at least one per U.S. PATENT DOCUMENTS molecule with (b) a radical-polymerizable monomer 3,832,423 8/1974 Milkovich et al...... , 525/292 having a functional group reactive to the functional 3.842.146 10/1974 Milkovich et al. . group contained in said ole?n resin (a). 3,929,935 12/1975 Kinstle . A primer composition is also described. 4,190,569 2/1980 Kroker ...... 524/484 4,789,568 12/1988 Matoba et al. .. 525/285 4,839,414 6/1989 Bederke et al...... 524/315 8 Claims, No Drawings 5,180,766 1 2 the above resin composition dissolved in an organic RESIN COMPOSITION FOR PRIMER USE AND solvent. PRIMER COMPOSITION EMPLOYING THE SAME DETAILED DESCRIPTION OF THE INVENTION FIELD OF THE INVENTION The ole?n resin (a) which has at least one functional The present invention relates to a resin composition group per molecule and is used as a raw material for which gives a primer useful for enhancing the adhesion producing the radical~polymerizable ole?n resin (I) to between polyole?n resin substrates and ?uorine-con be used for producing the composition of the present tained resins, and also relates to a primer composition invention has a weight-average molecular weight of employing the above resin composition. preferably about from 1,000 to 200,000, more preferably about from 10,000 to 100,000. If the molecular weight of BACKGROUND OF THE INVENTION the ole?n resin (a) is too low, the ?nal primer composi Fluorine-contained resins have excellent hardness, tion shows poor adhesion to substrates, If the molecular abrasion resistance, chemical resistance, solvent resis weight thereof is too high, the radical-polymerizable tance, and weatherability. Because of these properties, ole?n resin (I) to be obtained from such an ole?n resin which are very desirable to covering materials, fluo (a) tends more to suffer gelation when copolymerized rine-contained resins are extensively used as coating with a monomer (c). materials on various substrates. The ole?n resin (a) having at least one functional However, ?uorine-contained resins are defective in 20 group per molecule can be obtained by reacting an that since their adhesion to various substrates is poor, ordinary polyole?n with an unsaturated compound coating ?lms formed by applying ?uorine-contained having a desired functional group. Examples of the resins on surfaces of various substrates are apt to peel precursor polyole?n include homopolymers or copoly off. mers of a-ole?ns, such as polyethylene, polypropylene, As expedients for improving the poor adhesion of 25 poly(butene-1), -propylene copolymers, and ?uorine-contained resins to, for example, metallic sub ethylene-butene copolymers; copolymers of a-ole?ns strates, use ofa composition, as a primer, comprising an and conjugated dienes, such as ethylene-propylene - resin. a vinylidene fluoride resin, a meth diene copolymers and isobutene-isoprene copolymers; acrylate resin, etc. is disclosed in JP-A-l-l49880 (the poly(conjugated diene)s such as polybutadiene and term “JP-A” as used herein means an “Unexamined 30 polyisoprene; copolymers of aromatic vinyl compounds published Japanese patent application”) and, further, and conjugated dienes, such as styrene-butadiene co use of a composition. as a primer, comprising a polyol‘ polymers, styrene-butadiene-styrene block copolymers, resin, a polyisocyanate compound, and a thermoplastic hydrogenated styrene-butadiene-styrene block copoly acrylic resin as essential ingredients is disclosed in JP 35 mers, styrene-isoprene copolymers, styrene-isoprene A~1-l46965. styrene block copolymers, and hydrogenated styrene Techniques of coating a fluorine-contained resin on isoprene-styrene block copolymers; chlorinated poly substrates made of polyole?n resins represented by ole?ns obtained by chlorinating the above polyole?ns; polyethylene and polypropylene, however, are still insuf?cient, and the defect that coating ?lms formed are and the like. Examples of the unsaturated compound that has a functional group and is to be reacted with the prone to peel off still remains unsolved. precursor polyole?n include: unsaturated carboxylic SUMMARY OF THE INVENTION acids and anhydrides thereof such as (meth), An object of the present invention is to provide a fumaric acid, maleic acid and its anhydride, itaconic resin composition suited for use in a primer for enhanc acid and its anhydride, crotonic acid and its anhydride, ing the adhesion between polyole?n resins and fluorine 45 citraconic acid and its anhydride, and the like, in the contained resins. case of incorporating a group or a car Another object of the present invention is to provide boxylic acid anhydride group into the precursor poly a primer composition employing the above resin com ole?n; glycidyl of unsaturated carboxylic acids position. such as glycidyl (meth)acrylate, mono- or diglycidyl Other objects and effects of the present invention will of maleic acid, mono- or diglycidyl ester of ita be apparent from the following description. conic acid, and mono- or diglycidyl ester of allylsuc The present inventors have made intensive studies cinic acid, glycidyl ester of p-styrene-carboxylic acid, and, as a result, it has now been found that the above glycidyl such as ally glycidyl , Z-methylallyl objects are accomplished with the composition speci glycidyl ether, and styrene p-glycidyl ether, p-glyci ?ed below. 55 dylstyrene, epoxyole?ns such as 3,4-epoxy-l-butene and That is, the present invention provides a resin compo 3,4-epoxy‘3-methyl-l-butene, vinylcyclohexene mo sition for primer use which contains a copolymer of (I) nooxide, and the like, in the case of incorporating an a radical-polymerizable ole?n resin and (c) a monomer epoxy group; hydroxyalkyl (meth) such as copolymerizable with the ole?n resin (I) and containing 2-hydroxyethyl (meth)acrylate, Z-hydroxypropyl an alkyl (meth)acrylate and/or a fluorine-containing (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, unsaturated monomer as essential ingredients, the radi N-methylol(meth)acrylamide, addition polymers of cal-polymerizable ole?n resin (I) being a product of the 2-hydroxyethyl acrylate and 6-hexanolide, alkenyl alco reaction of (a) an ole?n resin having at least one func hols such as 2-propen-l-ol, alkynyl such as tional group per molecule with (b) a radical-polymeriz 2-propyn-l-ol, hydroxyvinyl ethers, and the like, in the able monomer having a functional group reactive to the 65 case of incorporating a hydroxyl group; and 2 functional group contained in the ole?n resin (a). isocyanatoethyl (meth)acrylate, methacryloyl isocya The present invention further provides a primer com nate, and the like, in the case of incorporating an isocya position for ?uorine-contained resins which comprises nate group. The reaction of a polyole?n with an unsatu 5,180,766 3 4 rated compound having a functional group may be (meth)acrylate. 2-hydroxypropyl (meth)acrylate. and conducted in an ordinary manner using a free-radical 2-hydroxybutyl (meth)-acrylate. N-methylol(meth)a initiator. Most preferred of the above-enumerated poly crylamide, addition polymers of Z-hydroxyethyl acry ole?ns are styrene-based elastomers such as styrene late and é-hexanolide, alkenyl alcohols such as 2-pro butadiene-styrene block copolymers or their hydroge pen-l-ol, alkynyl alcohols such as 2-propyn-l-ol. hy nation products and modi?ed polyole?ns obtained by droxyvinyl ethers, and the like. Examples of the epoxy chlorination of polyole?ns. group-containing radical-polymerizable monomer (b) In the reaction of a polyole?n with an unsaturated include glycidyl esters of unsaturated carboxylic acids compound having a functional group, the proportion of such as glycidyl (meth)acrylate, mono- or diglycidyl the unsaturated compound to the polyole?n is deter 0 ester of maleic acid, mono- or diglycidyl ester of ita mined so as to yield an ole?n resin (a) in which the conic acid, and mono- or diglycidyl ester of allylsuc content of units derived from the unsaturated com cinic acid, glycidyl ester of p-styrenecarboxylic acid, pound having the desired functional group is from 0.1 to glycidyl ethers such as ally glycidyl ether, Z-methylallyl 10% by weight, preferably from 0.5 to 5% by weight. glycidyl ether, and styrene p-glycidyl ether, p-glyci If the content of units derived from the functional dylstyrene, epoxyole?ns such as 3,4-epoxy-l-butene and group-containing unsaturated compound in the ole?n 3,4-epoxy-3-methyl-l-butene, vinylcyclohexe monoox resin (a) is less than 0.1% by weight, a radical-polymer ide, and the like. Examples of the group-con izable ole?n resin (I) to be obtained by reacting the taining radical-polymerizable monomer (b) include 2 ole?n resin (a) with a radical-polymerizable monomer isocyanatoethyl (meth)acrylate, methacryloyl isocya (b) having a functional group reactive to the functional nate, and the like. Of these radical-polymerizable mono group contained in the ole?n resin (a) has too low a mers, those having a hydroxyl group are most pre radical-polymerizable group content and, as a result, the ferred. ?nal resin composition to be obtained through the copo In the case where the ole?n resin (a) contains an lymerization reaction of such a radical-polymerizable epoxy group, the functional group contained in the ole?n resin (I) with a monomer (c) is disadvantageous in radical-polymerizable monomer (b) and reactive to the that the content of homopolymer of the monomer (c) in epoxy group may be carboxyl group or hydroxyl group. the resin composition is too high. On the other hand, if Examples of the carboxyl group-containing radical the content of units derived from the functional group polymerizable monomer (b) include unsaturated acids containing unsaturated compound in the ole?n resin (a) such as (meth)acrylic acid, carboxyalkyl vinyl ethers exceeds 10% by weight, gelation tends more to occur in such as carboxyethyl vinyl ether and carboxypropyl the copolymerization thereof with a monomer (c). vinyl ether, and the like. Examples of the hydroxyl The reaction of a polyole?n with a functional group group-containing radical-polymerizable monomer (b) containing unsaturated compound may be conducted by include the monomers enumerated above as examples of a method in which these raw materials are melt the radical-polymerizable monomer (b) having a hy kneaded with an extruder at 50° to 300° C. for 1 to 30 35 droxyl group reactive to a carboxylic acid group or minutes in the presence of a free-radical initiator, a carboxylic acid anhydride group contained in the ole?n method in which these raw materials are dissolved with resin (a). Of these radical-polymerizable monomers, heating in an organic solvent such as toluene, xylene, or those having a carboxyl group are most preferred. chlorobenzene and allowed to react at 50° to 200° C. for In the case where the ole?n resin (a) contains a hy l to 10 hours, or by other methods. droxyl group, the functional group contained in the As the free-radical initiator, an ordinarily used one radical-polymerizable monomer (b) and reactive to the may be employed. Examples thereof include alkyl per hydroxyl group may be isocyanate group, carboxyl oxides such as di-t-butyl peroxide and t~butyl hydroper group, or epoxy group. Examples of the isocyanate oxide, aryl peroxides such as dicumyl peroxide and group-containing radical-polymerizable monomer (b) cumyl , acyl peroxides such as dilauroyl 45 and examples of the epoxy group-containing radical peroxide, aroyl peroxides such as dibenzoyl peroxide, polymerizable monomer (b) include the monomers enu peroxides such as methyl ethyl ketone peroxide, merated above as examples of those reactive to a car azonitriles such as azobisisobutyronitrile, and the like. boxylic acid group or carboxylic acid anhydride group The thus-obtained ole?n resin (a) having at least one in the ole?n resin (a). Examples of the carboxyl group functional group per molecule can, in some cases, con~ 50 containing radical-polymerizable monomer (b) include tain a small proportion of an unmodi?ed polyole?n. the monomers enumerated above as examples of that Such an ole?n resin, however, may be used as it is as a reactive to an epoxy group in the ole?n resin (a). Of reactant material for producing a radical-polymerizable these radical-polymerizable monomers, those having an ole?n resin (I). isocyanate group are most preferred. The radical-polymerizable ole?n resin (I) to be used 55 In the case where the ole?n resin (a) contains an for producing the resin composition of the present in isocyanate group, the functional group contained in the vention is obtained by reacting the functional group radical-polymerizable monomer (b) and reactive tb the contained in the ole?n resin (at) with a radical-polymer isocyanate group may be hydroxyl group or carboxyl izable monomer (b) having a functional group reactive group. Examples of the radical-polymerizable monomer to the functional group of the ole?n resin (a). In the case 60 (b) containing a hydroxyl group and of that containing where the ole?n resin (a) contains a carboxylic acid a carboxyl group are as enumerated above. Of these group or a carboxylic acid anhydride group, the func radical-polymerizable monomers, those having a hy tional group contained in the radical-polymerizable droxyl group are most preferred. monomer (b) and reactive to the functional group in the In conducting the reaction of an ole?n resin (a) with ole?n resin (a) may be hydroxyl group, epoxy group, or 65 a radical-polymerizable monomer (b), the preferred isocyanate group. Examples of the hydroxyl group-con amounts of these reactants used are such that the taining radical-polymerizable monomer (b) include hy amount of the functional group inthe radical-polymer droxyalkyl (meth)acrylates such as 2-hydroxyethyl izable monomer (b) is from 0.1 to 10 equivalents to the 5,180,766 5 6 functional group in the ole?n resin (a). If the radical alcohols, such as ethylene glycol di(meth)acrylate and polymerizable monomer amount is less than 0.1 equiva propylene glycol (meth)acrylate; urethane-modi?ed lent in terms of functional group amount, the copoly polyacrylates containing a (meth)acryloyl group in merization of the resulting radical-polymerizable ole?n each molecule; vinyl acetate; vinyl chloride; vinyl resin (1) and a monomer (c) copolymerizable therewith ethers' such as ethyl vinyl ether, butyl vinyl ether, and disadvantageously yields a reaction product in which hexyl vinyl ether; -containing aromatic the content of homopolymer of the monomer (c) is too compounds such as vinyltoluene, styrene. and a-meth high. On the other hand, if the amount thereof is larger ylstyrene; ole?ns such as ethylene, propylene, butene, than 10 equivalents, gelation tends more to occur. and isoprene; and the like. The reaction temperature is generally from 20° to In the monomer (c), the content of the essential in 150° C., preferably from 50° to 120° C. In order to gredient(s) should be 30% by weight or more, prefera accelerate the reaction, a catalyst may be used. Exem bly 50% by weight or more, based on the total amount plary catalysts in the case of an esteri?cationreaction of all the monomer ingredients constituting the mono include acids or basic compounds such as sulfuric acid, mer (c). If the content thereof is less than 30% by p-toluenesulfonic acid, zinc chloride, , triethyl 5 weight, the resin composition to be produced shows , dimethylbenzylamine, and the like. Exemplary insufficient adhesion to ?uorine-contained resins. catalysts in the case of a urethane-forming reaction The resin composition of the present invention can be include dibutyl tin dilaurate and the like. It is preferable obtained by copolymerizing the radical-polymerizable that for the purpose of preventing a radical-polymeriza ole?n resin (1) obtained as described above and the ble monomer (b) from polymerizing to yield its homo speci?c monomer (0) described above. The amount of polymer, the reaction be conducted in an or air the monomer (c) used in the copolymerization with the atmosphere and a polymerization inhibitor, such as ole?n resin (I) is preferably from 10 to 90% by weight hydroquinone, hydroquinone monomethyl ether, phe based on the total amount of the ole?n resin (a) in the nothiazine, or the like, be added to the reaction system radical‘polymerizable ole?n resin (I) and the monomer in a proper amount. The reaction is preferably per (c). If the monomer (c) amount is less than 10% by formed in a suitable organic solvent such as, for exam weight, the resulting resin composition shows insuf? ple, toluene, xylene, methyl ethyl ketone, methyl isobu cient adhesion to fluorine-contained resins. If the tyl ketone. butyl acetate, Cellosolve acetate, or the like. amount thereof exceeds 90% by weight, adhesion to The monomer (c) to be copolymerized with the various substrates becomes insuf?cient. The copolymer above-described radical-polymerizable ole?n resin (I) ization reaction of ingredient (I) with ingredient (c) may to produce the resin composition of the present inven be conducted with heating at 50 to 200° C. for l to 20 tion is a monomer containing an alkyl (meth)acrylate hours in an organic solvent, as reaction medium, such as and/or a fluorine-containing unsaturated monomer as toluene, xylene, methyl ethyl ketone, methyl isobutyl essential ingredients. ketone, butyl acetate, Cellosolve acetate, ethanol, buta Examples of the alkyl (meth)acrylate as an essential nol, propanol, or the like, using a peroxide, such as ingredient include methyl (meth)acrylate, ethyl (meth benzoyl peroxide, di-t-butyl peroxide, cumene hydro )acrylate. butyl (meth)acrylate, 2-ethylhexyl (meth)a peroxide, etc., an azobis-type compound such as azobis crylate, and the like, with methyl acrylate and methyl isobutyronitrile, or the like as a polymerization catalyst methacrylate being most preferred. Examples of the in an amount of from 0.1 to 10% by weight, preferably fluorine-containing unsaturated monomer include fluo 40 from 1 to 5% by weight, based on the amount of ingre roalkyl (meth)acrylates such as tri?uoroethyl (meth)a dient (c). It is preferable that in this copolymerization, crylate, tetra?uoropropyl (meth)acrylate, hexa the reaction medium be used in such an amount that the ?uorobutyl (meth)acrylate, octatluoropentyl (meth)a total amount of ingredients (I) and (c) present in the crylate, heptadecafluorononyl (meth)acrylate, and hep reaction system is from 5 to 50% by weight based on the tadecafluorodecyl (meth)acrylate; fluorine-containing 45 total amount of the reaction mixture. It is also prefera ole?ns such as tetrafluoroethylene, tri?uoroethylene, ble to carry out the reaction in an atmosphere or stream vinylidene fluoride, vinyl ?uoride, monochlorotrifluo of an inert gas such as nitrogen gas. For the purpose of roethylene, 1-chloro-2,2-di?uoroethylene, 1,1-dichloro reducing the amount of residual monomers, an azobis 2,2-di?uoroethylene, vinylidene chlorofluoride, hexa type compound and a peroxide may be used in combina tluoropropene, 3,3,3,2-tetra?uoropropene, tri?uorome tion as a polymerization initiator. thylethylene, Z-?uoropropene, 2-chloro-l,l,3,3,3-penta The copolymer obtained by the copolymerization ?uoropropene, l,l,2-trichloro-3-trifluoropropene, per described above consists mainly of a backbone polymer ?uoro- l-butene, perfluoro l -p per?uorobutylethylene, which is the ole?n resin (a) and graft segments which perfluoro-l-heptene, perfluoro-l-nonene, 8-H-per are polymers made up of units derived from the mono ?uoro-l-octene, per?uorohexylethylene, per?uorooc 55 mer (c) containing an alkyl (meth)acrylate and/or a tylethylene, per?uorodecylethylene, and per ?uorine-containing unsaturated monomer. The back fluorododecylethylene; and the like. Of these, fluoroal bone polymer and the graft segments are bonded with kyl (meth)acrylates are most preferred. each other through the medium of an organic bond Other copolymerizable monomers, for example, in containing a hetero-atom and formed by the reaction of clude a, B-unsaturated carboxylic acids such as (meth 60 the functional group of the ole?n resin (a) with the )acrylic acid and monoalkyl esters of maleic acid; hy functional group of the radical-polymerizable monomer droxyalkyl (meth)acrylates such as Z-hydroxyethyl (b) in which the functional group is reactive to the (meth)acrylate, Z-hydroxypropyl (meth)acrylate, and functional group of the ole?n resin (a). 2-hydroxybutyl (meth)acrylate; polymerizable mono Besides the graft copolymer, the reaction product mers having an oxirane group such as glycidyl (meth)a 65 resulting from the copolymerization reaction of ingredi crylate; unsaturated such as (meth)acrylamide; ents (I) and (c) also contains a small proportion of a (meth)acrylonitrile; epoxy acrylates; (meth)acrylates of chain polymer of the monomer (c). This reaction prod alkylene oxide adducts; (meth)acrylates of polyhydric uct, however, can be used as it is as a resin composition 5,180,766 7 8 for use in a primer. If required and necessary, the reac The present invention will be explained below with tion product may be used after the chain polymer is reference to the following examples, which should not separated by extraction. be construed to be limiting the scope of the invention. The thus-obtained resin composition containing a copolymer of ole?n resin (I) and monomer (c) of this EXAMPLE 1 inventionfor primer use (ingredient (A)) is normally Polv(methvl methacrvlate)-crafted hydrogenated used after being dissolved in an organic solvent, ingredi styrene-butadiene-styrene block copolymer modi?ed ent (B), that dissolves the resin mixture. with maleic anhydride Examples of ingredient (B), the organic solvent dis Into a glass ?ask equipped with a stirrer, re?ux con solving ingredient (A), include such as acetone, denser, dropping funnel, and thermometer were intro methyl ethyl ketone, and methyl isobutyl ketone, ethers duced 100 g of a hydrogenated styrene-butadiene-sty such as dioxane and tetrahydrofuran, esters such as rene block copolymer (Kraton G-l652, manufactured ethyl acetate, butyl acetate, and Cellosolve' acetate, by Shell Chemical Co.) and 1,000 g of xylene. The air aromatic hydrocarbons such as toluene, xylene, and inside the ?ask was replaced with nitrogen and the chlorobenzene, TETRALIN (T.M.) is tetrahydronaph temperature was raised to 125° C. Thereto were then thalene, mineral spirits, and mixtures thereof. The used added dropwise over a period of 6 hours a solution amount of ingredient (A) is generally from 0.5 to 50% prepared by dissolving 4.0 g of maleic anhydride and by weight, preferably from 2 to 30% by weight, and 0.6 g of dicumyl peroxide in 80 g of xylene. After com that of the organic solvent, ingredient (B), is generally pletion of the reaction, the reaction system was cooled from 99.5 to 50% by weight, preferably from 98 to 70% 20 by weight, based on the total amount of ingredients (A) to around room temperature and acetone was then added thereto to reprecipitate the hydrogenated sty and (B). rene-butadiene-styrene block copolymer modified with The primer composition of the present invention may be prepared by isolating ingredient (A) from the reac maleic anhydride. The precipitate was then ?ltered off tion mixture and mixing it with ingredient (B). Nor 25 and dried, thereby obtaining a modi?ed resin (a) in a mally, however, the solution resulting from the poly white powder form. This modi?ed resin was analyzed merization reaction for yielding ingredient (A) may be by infrared spectroscopy and neutralization titration and, as a result, the maleic anhydride content was found used as it is, as described hereinabove. to be 1.5% by weight. Subsequently, 20 g of the thus Additives such as anti-oxidants, light stabilizers, UV absorbers, slipping agents, ?ame retardants, surface obtained, maleic anhydride-modi?ed hydrogenated modi?ers, viscosity modi?ers, and suspension agents styrene-butadiene-styrene block copolymer and 150 g may be incorporated into the primer composition of this of toluene were placed in a glass ?ask equipped with a invention if required and necessary. stirrer, re?ux condenser, dropping funnel, and ther mometer, and the contents were heated to 70° C. in an The primer composition of the present invention can 35 be applied to substrates made of various polyole?n air stream to dissolve the copolymer. Thereto was resins. Examples of the polyole?n resins include poly added a solution prepared by dissolving 0.36 g of 2 ethylene, polypropylene, ethylene-propylene copoly hydroxyethyl acrylate (b), l g of dimethylbenzylamine, mers, ethylene-propylene-diene copolymers, styrene and 0.06 g of hydroquinone monomethyl ether in 30 g of butadiene copolymers and hydrogenation products toluene. Reaction was then allowed to proceed at that thereof, polystyrene, and the like. The resin substrates temperature for 5 hours. The resulting reaction product are not particularly limited in shape, but it is preferable (I) was analyzed by infrared spectroscopy and, as a that the surfaces of the substrates have undergone such result, it was found that 55% of the grafted maleic anhy a treatment as corona discharge treatment, chromic dride was in the form of half ester with Z-hydroxyethyl acrylate. Subsequently, the temperature of the reaction acid treatment, flame treatment, or organic solvent 45 treatment. system was raised to 80° C. in a nitrogen stream, and a For applying the primer composition of this inven solution prepared by dissolving 20 g of methyl methac tion on a surface of a resin substrate, an ordinary coat rylate (c) and 0.2 g of azobisisobutyronitrile in 80 g of ing technique may be used such as, for example, brush toluene was added thereto dropwise over a period of 4 ing, spray coating, dip coating, cast coating, or the like. 50 hours. Thereafter, 0.2 g of azobisisobutyronitrile was The spread rate for the primer composition varies de further added to the reaction mixture and reaction was pending on the kind of the resin substrate to be coated, conducted for 6 hours, and then 0.2 g of azobisisobutyr the proportion of each component in the primer compo onitrile was added again and reaction was conducted sition, and other factors, but in general, the primer com for another 5 hours. Thus, a primer composition having position is applied at a dry thickness of from 1 to 100 55 an ingredient (A) concentration of 13.3% by weight pm. After coating, the primer composition applied may was obtained. be dried at a temperature between room temperature A polypropylene resin substrate (FY 6C, manufac and 150° C. to remove the organic solvent and other tured by Mitsubishi Petrochemical Co., Ltd., Japan) volatile components contained in the composition ap having dimensions of 3 mm by 70 mm by 150 mm was plied. Thereafter, a ?uorine-contained resin coating degreased with 1,1,1-trichloroethane solution. On the may be formed thereon by extrusion lamination, co degreased surface, the above-obtained primer composi extrusion lamination, ?uidization dip coating, electro tion was coated with a bar coater and dried in an oven static coating, rotational molding, or the like. drier set at 80° C for 2 minutes to obtain a primer-coated The primer composition according to the present substrate containing a coating having a dry thickness of invention enhances the adhesion of ?uorine-contained 65 5 um. Subsequently, a top coat layer (?lm thickness, 20 resins applied on surfaces of polyole?n resins and, um) was formed from a poly(vinylidene ?uoride) resin hence, brings about a suf?cient effect when used as a on the primer-coated substrate surface by a heat lamina primer. tion method (150° C., 20 kg/cmz). 5,180,766 10 The adhesion ofthe coating was evaluated by a cross EXAMPLES 14 TO 22 AND COMPARATIVE cut tape test in which the coating layer of the above EXAMPLES 3 AND 4 obtained laminate was crosshatched at a depth reaching the substrate to make 100 l-mm squares and a cello Polv(methvl methacrvlate)-grafted chlorinated phane tape was used to examine the adhesion of the 5 polypropylene modi?ed with maleic anhydride crosshatched portion of the coating. As a result, 84 Into a glass ?ask equipped with a stirrer. reflux con squares remained unpeeled. denser, dropping funnel, and thermometer were intro duced 20 g of a chlorinated, maleic anhydride-modi?ed EXAMPLES 2 TO 9 AND COMPARATIVE polypropylene (a) (Superchlon 822, manufactured by EXAMPLES 1 AND 2 Sanyo-Kokusaku Pulp Co., Ltd, Japan) and 150 g of Primer compositions were obtained in the same man xylene. In an air stream, the contents in the ?ask were ner as in Example 1 except that 20 g each of the mono heated to 70° C. to dissolve the polymer. Thereto was mers shown in Table l were used as ingredient (c) in added a solution prepared by mixing 0.59 g of Z-hydrox place of methyl methacrylate used in Example 1. yethyl acrylate (b), l g of dimethylbenzylamine, 0.06 of Using the thus-obtained primer compositions, an ad hydroquinone monomethyl ether, and 30 g of xylene. Reaction was then allowed to proceed at that tempera hesion test was conducted in the same manner as in ture for 5 hours. Subsequently, using 20 g each of the Example 1. The results obtained are shown in Table 1. monomers (0) shown in Table 3, graft reaction was Criteria for Evaluation 20 conducted in the same manner as in Example 1, thereby obtaining reaction products having an ingredient (A) TABLE 1 concentration of 13.3% by weight, Ingredient (c) (wt (7:) Evaluation Using the thus-obtained reaction products as primer Example 2 Methyl methacrylate (90) @ compositions, an adhesion test was conducted in the Heptadecafluorononyl (l0) 25 same manner as in Example 1. The results obtained are methacrylate shown in Table 3. Example 3 Methyl methacrylate (90) Tri?uoroethyl methacrylate (I0) TABLE 3 Example 4 Methyl methacrylate (50) Q] Ingredient (c) (wt ‘72) Evaluation I-leptadecafluorononyl (50) methacrylate Example 14 Methyl meihacrylate (100) Example 5 Methyl methacrylate (50) O Example 15 MethylHeptadeca?uorononyl methacrylate (90)(10) Tri?uoroethyl methacrylate (50) methacrylate Example 6 Heptadecafluorononyl (100) O Example l6 Methyl methacrylate (90) c methacrylate Tri?uoroethyl (l0) Example 7 Tri?uoroethyl methacrylate (100) 0 35 methacrylate Example 8 Methyllflydroxyethyl methacrylate acrylate (10)(90) Example l7 Heptadeca?uorononylMethyl methacrylate (50) Example 9 HydroxyethylMethyl methacrylate methacrylate (70)(30) methacrylate Example 18 TritluoroethylMethyl methacrylate (50) Comparative Hydroxyethyl acrylate (100) X Example 1 methacrylate Comparative Hydroxyethyl methacrylate (100) X Example 19 Heptadecafluorononyl (I00) 0 Example 2 methacrylate Example 20 Tri?uoroethyl (100) O Residual squares methacrylate Example 21 Methyl methacrylate (90) @ 70-50 . . . 0 Hydroxyethyl acrylate (10) 49-0 . . t X 45 Example 22 Methyl methacrylate (70) O Hydroxyethyl methacrylate (30) Comparative Hydroxyethyl acrylate (100) X EXAMPLES 10 TO 13 Example 3 Primer compositions were obtained in the same man Comparative l-lydroxyethyl methacrylate (100) X Example 4 ner as in Example 1 except that the amount of methyl 50 methacrylate (abbreviated as MMA) used in the primer composition preparation was changed as shown in While the invention has been described in detail and with reference to speci?c embodiments thereof, it will Table 2. Using the thus-obtained primer compositions, an ad be apparent to one skilled in the art that various changes 55 and modi?cations can be made therein without depart hesion test was conducted in the same manner as in ing from the spirit and scope thereof. Example 1. The results obtained are shown in Table 2. What is claimed is: I 1. A resin composition for primer use which contains TABLE 2 a copolymer of (I) a radical-polymerizable ole?n resin MMA content Ingredient (A) and (c) a monomer copolymerizable with said ole?n MMA in ingre- concentration resin (I) and containing an alkyl (meth)acrylate, a ?uo amount client (A) in the primer Eval rine-containing unsaturated monomer or mixture (g) (wt f7r) (wt %) uation thereof, said radical-polymerizable ole?n resin (1) being Example 10 2.2 l0 7.9 0 a product of the reaction of (a) an ole?n resin having at Example I] 8.6 30 9.9 @ 65 least one functional group per molecule with (b) a radi Example 12 46.7 70 20.4 @ cal-polymerizable monomer having a functional group Example 13 180 90 435 O reactive to the functional group contained in said ole?n resin (a). 5,180,766 11 12 2. A resin composition as claimed in claim 1. wherein containing an alkyl (meth)acrylate. a fluorine-con said ole?n resin (a) has a weight-average molecular taining unsaturated monomer or mixture thereof. weight of from 1.000 to 200.000. said radical-polymerizable ole?n resin (I) being a 3. A resin composition as claimed in claim 1. wherein product of the reaction of (a) an ole?n resin having the functional group contained in said ole?n resin (a) is at least one functional group per molecule with (b) selected from the group consisting of a carboxylic acid a radical-polymerizable monomer having a func group, a carboxylic acid anhydride group. epoxy group. tional group reactive to the functional group con hydroxyl group, and isocyanate group. tained in said ole?n resin (a), and - 4. A resin composition as claimed in claim 1. wherein (B) an organic solvent, the functional group contained in said radical-polymer said ingredient (A) being dissolved in said ingredient izable monomer (b) is selected from the group consist (B). ing of carboxylic acid group. carboxylic acid anhydride 7. A primer composition as claimed in claim 6. group, hydroxyl group, epoxy group. and isocyanate wherein the content of said ingredient (A) is from 0.5 to group. - 50% by weight based on the total amount of said ingre 5. A resin composition as claimed in claim 1, wherein dients (A) and (B). said alkyl (meth)acrylate is selected from the group 8. A primer composition as claimed in claim 6, consisting of methyl acrylate and methyl methacrylate. wherein said organic solvent (B) is selected from the 6. A primer composition comprising group consisting of ketones, ethers, esters, aromatic (A) a resin composition containing a copolymer of(1) hydrocarbons‘ tetrahydronapthalene mineral spirits and a radical-polymerizable ole?n resin and (c) a mono 20 mixtures thereof. mer copolymerizable with said ole?n resin (I) and * 1= * ‘I *

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