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 alkyl (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 functional group 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), ethylene-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 epoxy-acrylate 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)acrylic acid, 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 carboxylic acid 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 esters of unsaturated carboxylic acids position. such as glycidyl (meth)acrylate, mono- or diglycidyl Other objects and effects of the present invention will ester 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 ethers such as ally glycidyl ether, 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)acrylates 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 alcohols 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.