JPH0826103B2 - Addition-type copolymer for paint and paint composition - Google Patents
Addition-type copolymer for paint and paint compositionInfo
- Publication number
- JPH0826103B2 JPH0826103B2 JP9296786A JP9296786A JPH0826103B2 JP H0826103 B2 JPH0826103 B2 JP H0826103B2 JP 9296786 A JP9296786 A JP 9296786A JP 9296786 A JP9296786 A JP 9296786A JP H0826103 B2 JPH0826103 B2 JP H0826103B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- monomer
- coating
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001577 copolymer Polymers 0.000 title claims description 37
- 239000003973 paint Substances 0.000 title description 12
- 239000000203 mixture Substances 0.000 title description 11
- 238000000576 coating method Methods 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 28
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 239000008199 coating composition Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 description 45
- 239000000463 material Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000005372 silanol group Chemical group 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HVQPNKXSWMVRDZ-UHFFFAOYSA-N 3-isocyanatopropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCN=C=O HVQPNKXSWMVRDZ-UHFFFAOYSA-N 0.000 description 2
- BFFQFGGITJXTFP-UHFFFAOYSA-N 3-methyldioxetane Chemical compound CC1COO1 BFFQFGGITJXTFP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AJMJSPWGPLXRSJ-UHFFFAOYSA-N silyl but-3-enoate Chemical compound [SiH3]OC(=O)CC=C AJMJSPWGPLXRSJ-UHFFFAOYSA-N 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- ORTCGSWQDZPULK-UHFFFAOYSA-N 3-isocyanatopropyl prop-2-enoate Chemical compound C=CC(=O)OCCCN=C=O ORTCGSWQDZPULK-UHFFFAOYSA-N 0.000 description 1
- TUXPQPLAXQYORY-UHFFFAOYSA-N 3-methyldioxane Chemical compound CC1CCCOO1 TUXPQPLAXQYORY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は特に塗料原料として有用な塗料用付加系共重
合体および該塗料用付加系共重合体を使用した塗料組成
物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an addition-type copolymer for a coating, which is particularly useful as a coating material, and a coating composition using the addition-type copolymer for a coating.
従来、加水分解可能なシリル基、例えばアルコキシシ
リル基やトリハロシリル基を有するアクリルエステルや
メタクリルエステルを共重合した共重合体からなる塗料
が提供されている。このような加水分解可能なシリル基
を有する塗料は塗膜形成過程において該シリル基が加水
分解されてシラノール基となり、更に該シラノール基が
縮合してシロキサン結合を形成して硬化するものであ
る。そしてその塗膜は耐薬品性、耐候性、無機材との密
着性に優れる。Conventionally, there has been provided a coating material comprising a copolymer obtained by copolymerizing an acrylic ester or a methacrylic ester having a hydrolyzable silyl group such as an alkoxysilyl group or a trihalosilyl group. Such a coating material having a hydrolyzable silyl group is one in which the silyl group is hydrolyzed into a silanol group in the process of forming a coating film, and the silanol group is condensed to form a siloxane bond to cure. And the coating film is excellent in chemical resistance, weather resistance and adhesion to an inorganic material.
上記従来の加水分解可能なシリル基を有する塗料は上
記利点を有する一方有機材との密着性に劣り、またシリ
コン自体の分子間力が非常に小さいので溶剤に対して膨
潤し易く耐溶剤性にも劣る。更にシリル基の加水分解は
外気の水分を取入れることによって行われるので硬化が
遅く、また外気と接触する表面部分が選択的に硬化され
内部まで硬化が進行するのに時間を要するので塗膜形成
初期の耐溶剤性が更に劣るものになると云う問題点を有
する。The above-mentioned conventional coating having a hydrolyzable silyl group has the above-mentioned advantages, but is poor in adhesion to an organic material, and since the intermolecular force of silicon itself is very small, it easily swells in a solvent and has solvent resistance. Is also inferior. Furthermore, the silyl group is hydrolyzed by taking in moisture from the outside air, so the curing is slow, and it takes time for the surface portion in contact with the outside air to be selectively cured and to proceed to the inside, thus forming a coating film. There is a problem that the initial solvent resistance is further deteriorated.
本発明は上記従来の問題点を解決する手段として、イ
ソシアナート基含有単量体A20〜60重量部と、加水分解
可能なシリル基含有単量体B5〜25重量部と、該単量体Ａ
および単量体Ｂと共重合可能な単量体Ｃとからなる塗料
用付加系共重合体および該塗料用付加系共重合体と活性
水素を有する官能基を含有するポリマーとからなる塗料
組成物を提供するものである。As a means for solving the above conventional problems, the present invention comprises 20 to 60 parts by weight of an isocyanate group-containing monomer A, 5 to 25 parts by weight of a hydrolyzable silyl group-containing monomer B, and the monomer A.
And an addition system copolymer for a coating composition comprising a monomer B and a copolymerizable monomer C, and a coating composition comprising the addition system copolymer for a coating composition and a polymer containing a functional group having active hydrogen Is provided.
本発明に用いられるイソシアナート基含有単量体（以
下単量体Ａと云う）とはβ−イソシアナートエチルアク
リレート、β−イソシアナートエチルメタクリレート、
γ−イソシアナートプロピルアクリレート、γ−イソシ
アナートプロピルメタクリレート等のイソシアナート基
含有アクリルエステルもしくはメタクリルエステル、ビ
ニルイソシアナート等重合可能なビニル基とイソシアナ
ート基とを一分子中に含有するものである。The isocyanate group-containing monomer used in the present invention (hereinafter referred to as monomer A) is β-isocyanatoethyl acrylate, β-isocyanatoethyl methacrylate,
Isocyanate group-containing acrylic ester or methacrylic ester such as γ-isocyanatopropyl acrylate and γ-isocyanatopropyl methacrylate, vinyl isocyanate, and the like containing a polymerizable vinyl group and an isocyanate group in one molecule.
本発明に用いる加水分解可能なシリル基含有単量体
（以下単量体Ｂと云う）とはγ−メタクリロキシプロピ
ルトリメトキシシラン、ビニルアセトキシシラン、ビニ
ルトリメトキシシラン等重合可能なビニル基と加水分解
可能なシリル基とを一分子中に含有するもので活性水素
を有する官能基を含まないものである。The hydrolyzable silyl group-containing monomer used in the present invention (hereinafter referred to as monomer B) is a polymerizable vinyl group such as γ-methacryloxypropyltrimethoxysilane, vinylacetoxysilane, vinyltrimethoxysilane and the like. It contains a degradable silyl group in one molecule and does not contain a functional group having active hydrogen.
上記単量体A,Bの他、本発明の塗料用付加系共重合体
においては更に上記単量体A,Bと共重合可能でかつ活性
水素を有する官能基を含まない単量体（以下単量体Ｃと
云う）、例えばメチルアクリレート、エチルアクリレー
ト、ｎ−ブチルアクリレート、iso−ブチルアクリレー
ト、２−エチルヘキシルアクリレート、メチルメタクリ
レート、エチルメタクリレート、ｎ−ブチルメタクリレ
ート、iso−ブチルメタクリレート、２−エチルヘキシ
ルメタクリレート、ラウリルメタクリレート等のアクリ
ルエステルまたはメタクリルエステル、スチレン、アク
リロニトリル、メタクリロニトリル、塩化ビニル、塩化
ビニリデン、弗化ビニル、弗化ビニリデン、メチルビニ
ルエーテル、エチルビニルテーテル、酢酸ビニル等の単
量体が共重合される。In addition to the monomers A and B, the addition system copolymer for the coating material of the present invention further comprises a monomer that is copolymerizable with the monomers A and B and does not contain a functional group having active hydrogen (hereinafter Monomer C), for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate. , Acrylic acid or methacrylic ester such as lauryl methacrylate, styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, methyl vinyl ether, ethyl vinyl ether, vinyl acetate, etc. To be done.
本発明の塗料用付加系共重合体中に単量体Ａは20〜60
重量部、望ましくは30〜50重量部、単量体Ｂは５〜25重
量部、望ましくは10〜20重量部が共重合せられる。The monomer A in the addition-type copolymer for coating material of the present invention is 20-60
Parts by weight, preferably 30 to 50 parts by weight, 5 to 25 parts by weight, preferably 10 to 20 parts by weight of the monomer B are copolymerized.
本発明の塗料用付加系共重合体は上記単量体A,Bおよ
び上記単量体Ｃを混合した混合単量体をトルエン、キシ
レン、酢酸エチル、酢酸ｎ−ブチル、メチルエチルケト
ン、メチルイソブチルケトン、セロソルブアセテート、
ｎ−ブチルセロソルブ、ミネラルターペン、ミネラルス
ピリット等の活性水素を有する官能基を含まない有機溶
剤中でベンゾイルパーオキシド、ラウリルパーオキシ
ド、クメンハイドロパーオキシド、アゾビスイソブチロ
ニトリル等の油溶性開始剤を用いて重合することにより
得られるが、上記有機溶剤は必須のものではなく、共重
合体は塊状重合、懸濁重合等によって製造されてもよ
い。更に上記重合の際には連鎖移動剤としてラウリルメ
ルカプタン、四塩化炭素等が添加されてもよい。The addition-type copolymer for paints of the present invention is a mixed monomer obtained by mixing the above-mentioned monomers A and B and the above-mentioned monomer C with toluene, xylene, ethyl acetate, n-butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, Cellosolve acetate,
Oil-soluble initiators such as benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, and azobisisobutyronitrile are used in organic solvents that do not contain a functional group having active hydrogen, such as n-butyl cellosolve, mineral terpene, and mineral spirit. The organic solvent is not essential, but the copolymer may be produced by bulk polymerization, suspension polymerization or the like. Further, lauryl mercaptan, carbon tetrachloride or the like may be added as a chain transfer agent in the above polymerization.
本発明の塗料用付加系共重合体は一分子中にイソシア
ナート基と加水分解可能なシリル基とを有し、該塗料用
付加系共重合体単独で塗膜形成材料として用いられる
が、所望なればポリエステル、ポリ（オキシプロピレン
エーテル）ポリオール、ポリ（オキシエチレン−プロピ
レンエーテル）ポリオール、アクリルポリオール、水酸
基含有スチレンブタジエンゴム、水酸基含有アクリロニ
トリルブタジエンゴム、ヒマシ油誘導体、トール油誘導
体等のポリヒドロキシ化合物、カルボキシル基含有アク
リル樹脂、カルボキシル基含有スチレンブタジエンゴ
ム、カルボキシル基含有アクリロニトリルブタジエンゴ
ム等のカルボキシル基含有ポリマー、グリシジル基含有
ポリマー、アミノ基含有ポリマー、第３級アミン含有ポ
リマー等の活性水素を顕在的もしくは潜在的に有する官
能基を含有するポリマーと混合され常温でも速やかに硬
化して塗膜を形成する。所望なれば上記混合物には更に
アミン等の触媒が添加されてもよい。The addition system copolymer for paints of the present invention has an isocyanate group and a hydrolyzable silyl group in one molecule, and the addition system copolymer for paints can be used alone as a film-forming material. Polyester, poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol, acrylic polyol, hydroxyl group-containing styrene butadiene rubber, hydroxyl group-containing acrylonitrile butadiene rubber, castor oil derivative, tall oil derivative and other polyhydroxy compounds, Reveals active hydrogen such as carboxyl group-containing acrylic resin, carboxyl group-containing styrene butadiene rubber, carboxyl group-containing acrylonitrile butadiene rubber and other carboxyl group-containing polymers, glycidyl group-containing polymers, amino group-containing polymers and tertiary amine-containing polymers It is mixed with a polymer containing functional groups cured rapidly even at room temperature to form a coating film having a specific or potential. If desired, further catalysts such as amines may be added to the above mixture.
本発明の作用は下記の通りである。 The operation of the present invention is as follows.
本発明の塗料用付加系共重合体単独もしくは該塗料用
付加系共重合体と活性水素を有する官能基を含有するポ
リマーとを混合し塗膜にすると、該塗膜は該塗料用付加
系共重合体のイソシアナート基と外界の水分との反応、
あるいは該塗料用付加系共重合体と該ポリマーの官能基
との反応により常温でも速やかに硬化して塗膜中に尿素
結合やウレタン結合を生成することにより塗膜の凝集力
を高める。塗膜形成過程においては該塗料用付加系共重
合体に由来する加水分解可能なシリル基は該シリル基の
特性である界面移行性により塗膜界面（表裏面）に配向
され、環境に存在する水分によって該シリル基は加水分
解されてシラノール基となり、更に該シラノール基相互
が縮合してシロキサン結合を生成する。更に塗膜裏面、
即ち基材との接触面においては基材がシラノール基を含
むガラスのような無機質であった場合には塗膜のシラノ
ール基が基材のシラノール基と水素結合および／または
シロキサン結合を形成する。When the addition system copolymer for paints of the present invention is used alone or the addition system copolymer for paints and a polymer containing a functional group having active hydrogen are mixed to form a coating film, the coating film shows the addition system copolymer for paints. Reaction of the isocyanate groups of the polymer with the moisture of the outside world,
Alternatively, the cohesive force of the coating film is increased by reacting the addition-type copolymer for coating material with the functional group of the polymer to rapidly cure at room temperature to form a urea bond or a urethane bond in the coating film. In the process of forming a coating film, the hydrolyzable silyl group derived from the addition-type copolymer for paint is oriented to the coating film interface (front and back) due to the interfacial migration property which is a characteristic of the silyl group and exists in the environment. The silyl group is hydrolyzed by water to a silanol group, and the silanol groups are condensed with each other to form a siloxane bond. Furthermore, the back of the coating film,
That is, on the contact surface with the substrate, when the substrate is an inorganic substance such as glass containing silanol groups, the silanol groups of the coating film form hydrogen bonds and / or siloxane bonds with the silanol groups of the substrate.
したがって本発明においては塗膜はシロキサン結合が
生成するに先立ってイソシアナート基と活性水素を有す
る官能基との反応によって硬化するから、硬化速度が常
温でも極めて早く初期の塗膜強度や耐溶剤性等の塗膜物
性は良好であり、そして塗膜表面にはシロキサン結合が
存在するから塗膜の紫外線劣化が防止され長期にわたっ
て良好な光沢を維持する。また基材が無機質の場合は塗
膜と基材との間に化学的結合が生ずるから塗膜の接着性
は極めて優れたものとなるし、更に塗膜中に存在するウ
レタン結合によって有機材との密着性も向上する。Therefore, in the present invention, the coating film is cured by the reaction between the isocyanate group and the functional group having active hydrogen prior to the formation of the siloxane bond, so that the curing speed is extremely fast even at room temperature and the initial coating film strength and solvent resistance are high. The coating film has good physical properties, and the presence of siloxane bonds on the surface of the coating film prevents the coating film from being deteriorated by ultraviolet rays and maintains good gloss over a long period of time. When the base material is inorganic, a chemical bond is generated between the coating film and the base material, so that the adhesiveness of the coating film is extremely excellent. Also improves the adhesion.
実施例１ 下記の組成の混合物を攪拌機、温度計、コンデンサー
を付したフラスコ中に仕込み、窒素雰囲気下に90℃で７
時間反応させる。Example 1 A mixture having the following composition was placed in a flask equipped with a stirrer, a thermometer, and a condenser, and the mixture was kept at 90 ° C. under a nitrogen atmosphere for 7 hours.
React for hours.
β−イソシアナートエチルメタクリレート 40重量部 γ−メタクリロキシプロピルトリメトキシシラン10重量
部 メチルメタクリレート 25重量部 ｎ−ブチルメタクリレート 25重量部 トルエン 66.7重量部 アゾビスイソブチロニトリル 2重量部 ラウリルメルカプタン 2重量部 このようにしてイソシアナート量6.5重量％、数平均
重合度5000〜5500の塗料用付加系共重合体（１）を得
る。β-isocyanatoethyl methacrylate 40 parts by weight γ-methacryloxypropyltrimethoxysilane 10 parts by weight Methyl methacrylate 25 parts by weight n-butyl methacrylate 25 parts by weight Toluene 66.7 parts by weight Azobisisobutyronitrile 2 parts by weight Lauryl mercaptan 2 parts by weight Thus, an addition type copolymer (1) for coatings having an isocyanate amount of 6.5% by weight and a number average degree of polymerization of 5000 to 5500 is obtained.
実施例２ 下記の組成の混合物を実施例１と同様に反応させてイ
ソシアナート量6.8重量％、数平均重合度5000〜5500の
塗料用付加系共重合体（２）を得る。Example 2 A mixture having the following composition was reacted in the same manner as in Example 1 to obtain an addition type copolymer (2) for coating composition having an isocyanate amount of 6.8% by weight and a number average degree of polymerization of 5000 to 5500.
γ−イソシアナートプロピルメタクリレート45重量部 ビニルアセトキシシラン 10重量部 エチルメタクリレート 35重量部 エチルアクリレート 10重量部 酢酸ｎ−ブチル 66.7重量部 ベンゾイルパーオキシド 2重量部 ラウリルメルカプタン 2重量部 比較例 下記の組成の混合物を実施例１と同様に反応させて塗
料用付加系共重合体（３）を得る。γ-Isocyanatopropyl methacrylate 45 parts by weight Vinylacetoxysilane 10 parts by weight Ethyl methacrylate 35 parts by weight Ethyl acrylate 10 parts by weight n-Butyl acetate 66.7 parts by weight Benzoyl peroxide 2 parts by weight Lauryl mercaptan 2 parts by weight Comparative Example Mixture of the following compositions Is reacted in the same manner as in Example 1 to obtain an addition type copolymer (3) for paint.
スチレン 20重量部 メチルメタクリレート 40重量部 ｎ−ブチルメタクリレート 15重量部 ｎ−ブチルアクリレート 10重量部 γ−メタクリロキシプロピルトリメトキシシラン15重量
部 アゾビスイソブチロニトリル ２重量部 ラウリルメルカプタン ２重量部 キシレン 66.7重量部 実施例３ 下記の処方を攪拌機、温度計、コンデンサーを付した
フラスコ中に入れ75℃で15時間攪拌して40重量％のアク
リルポリオールを得る。Styrene 20 parts by weight Methyl methacrylate 40 parts by weight n-Butyl methacrylate 15 parts by weight n-Butyl acrylate 10 parts by weight γ-methacryloxypropyltrimethoxysilane 15 parts by weight Azobisisobutyronitrile 2 parts by weight Lauryl mercaptan 2 parts by weight xylene 66.7 Parts by weight Example 3 The following formulation is placed in a flask equipped with a stirrer, a thermometer, and a condenser and stirred at 75 ° C for 15 hours to obtain 40% by weight of acrylic polyol.
メチルメタクリレート 200重量部 ｎ−ブチルアクリレート 160重量部 ２−ヒドロキシエチルアクリレート 40重量部 ベンゾイルパーオキシド 2重量部 トルエン 600重量部 実施例４ 実施例１の塗料用付加系共重合体（１）100重量部と
数平均重合度3000のポリ（オキシプロピレンエーテル）
ポリオール100重量部とを混合して得られた組成物の塗
膜を所定の基板上に４ミルのドクターブレードにより形
成し、110℃、２時間のキュアーを行ない試料１を作成
した。Methyl methacrylate 200 parts by weight n-Butyl acrylate 160 parts by weight 2-Hydroxyethyl acrylate 40 parts by weight Benzoyl peroxide 2 parts by weight Toluene 600 parts by weight Example 4 100 parts by weight of the addition system copolymer (1) for paint of Example 1 And poly (oxypropylene ether) with number average degree of polymerization of 3000
A coating film of the composition obtained by mixing with 100 parts by weight of polyol was formed on a predetermined substrate with a doctor blade of 4 mil, and cured at 110 ° C. for 2 hours to prepare Sample 1.
実施例５ 塗料用付加系共重合体（１）に代えて塗料用付加系共
重合体（２）を用い実施例４と同様にして試料２を作成
した。Example 5 Sample 2 was prepared in the same manner as in Example 4 except that the coating addition system copolymer (1) was replaced with the coating addition system copolymer (2).
実施例６ 塗料用付加系共重合体（１）に代えて塗料用付加系共
重合体（３）を用い実施例４と同様にして試料３を作成
した。Example 6 Sample 3 was prepared in the same manner as in Example 4 except that the coating addition system copolymer (1) was replaced with the coating addition system copolymer (3).
実施例７ 塗料用付加系共重合体（１）60重量部と実施例３で作
成したアクリルポリオール100重量部とを混合し実施例
４と同様にして試料４を作成した。Example 7 Sample 4 was prepared in the same manner as in Example 4 by mixing 60 parts by weight of the addition system copolymer (1) for coating material and 100 parts by weight of the acrylic polyol prepared in Example 3.
実施例８ 塗料用付加系共重合体（１）に代えて塗料用付加系共
重合体（２）を用い実施例７と同様にして試料５を作成
した。Example 8 Sample 5 was prepared in the same manner as in Example 7 except that the coating addition system copolymer (1) was replaced with the coating addition system copolymer (2).
実施例９ 塗料用付加系共重合体（１）に代えて塗料用付加系共
重合体（３）を用い実施例７と同様にして試料６を作成
した。Example 9 Sample 6 was prepared in the same manner as in Example 7 except that the coating addition system copolymer (1) was replaced with the coating addition system copolymer (3).
実施例10 塗料用付加系共重合体（１）100重量部に対し、ジブ
チルチンジラウレート（硬化触媒）２重量部加えて混合
し、実施例４と同様にして試料７を作成した。Example 10 2 parts by weight of dibutyltin dilaurate (curing catalyst) was added to and mixed with 100 parts by weight of the addition system copolymer (1) for coating material, and Sample 7 was prepared in the same manner as in Example 4.
実施例11 塗料用付加系共重合体（１）に代えて塗料用付加系共
重合体（２）を用い実施例10と同様にして試料８を作成
した。Example 11 Sample 8 was prepared in the same manner as in Example 10 except that the coating addition system copolymer (1) was replaced with the coating addition system copolymer (2).
実施例12 塗料用付加系共重合体（１）に代えて塗料用付加系共
重合体（３）を用い実施例10と同様にして試料９を作成
した。Example 12 Sample 9 was prepared in the same manner as in Example 10 except that the coating addition system copolymer (1) was replaced with the coating addition system copolymer (3).
上記実施例４〜12により作成した試料１〜９の塗膜性
能を第１表に示す。Table 1 shows the coating film performance of Samples 1 to 9 prepared in Examples 4 to 12 above.
密着性1:熱硬化性アクリル樹脂塗料を0.8mm厚の軟鋼板
に４ミル厚で塗布し150℃、30分間焼付けた塗装板を基
材として用い塗膜を1mm間隔で縦横10本のクロスカット
を行ない、セロテープによる剥離試験を行った。 Adhesion 1: A thermosetting acrylic resin paint was applied to a 0.8 mm thick mild steel plate at a thickness of 4 mils and baked at 150 ° C for 30 minutes. Using a coated plate as a base material, the coating film was cross-cut at 1 mm intervals in 10 rows and 10 columns. Then, a peeling test using cellophane tape was performed.
密着性2:基材としてガラス板を用いる。Adhesion 2: A glass plate is used as a base material.
可撓性 :基材として0.5mm厚のブリキ板を用い所定の径
のマンドレル試験を行なう。Flexible: Perform a mandrel test with a specified diameter using a 0.5 mm tin plate as the base material.
耐熱性 :基材としてガラス板を用いウェザオメーターに
より1500時間の耐候性試験を行なう。Heat resistance: A glass plate is used as a base material and a weather resistance test is performed for 1,500 hours using a weatherometer.
耐ガソリン性：基材としてガラス板を用いガソリンに２
時間浸漬した。Gasoline resistance: 2 for gasoline using glass plate as base material
Soak for hours.
耐薬品性：基材としてガラス板を用い0.5N−HCl水溶液
に５時間浸漬した。Chemical resistance: A glass plate was used as a substrate and immersed in a 0.5N-HCl aqueous solution for 5 hours.
評価方法 密着性 ○：全く剥離せず □:10％剥離 △:20％剥離 ×:30％以上剥離 可撓性 ○：径1mmで亀裂を生じない □：径1mmで亀裂を生ずるが径2mmでは亀裂
を生じない △：径2mmで亀裂を生ずるが径3mmでは亀裂
を生じない ×：径3mm以上で亀裂を生ずる 耐候性 ○：黄変しない □：殆んど黄変しない △：若干の黄変 ×：顕著な黄変 耐ガソリン性○：変化なし □：若干膨潤 △：膨潤 ×：膨潤一部溶解 耐薬品性 ○：変化なし □：若干のふくれ △：ふくれ ×：剥離 第１表をみると本発明の試料1,2,4,5,7,8は有機材と
の密着性および耐ガソリン性に優れていることがわかる
が、比較試料3,6,9は有機材との密着性および耐ガソリ
ン性に劣る。Evaluation method Adhesion ○: No peeling □: 10% peeling △: 20% peeling ×: 30% or more peeling Flexibility ○: Crack does not occur at diameter 1 mm □: Crack occurs at diameter 1 mm but diameter 2 mm No cracks were generated. △: Cracks were generated at a diameter of 2 mm, but not at a diameter of 3 mm. ×: Cracks were generated at a diameter of 3 mm or more. Weather resistance ○: No yellowing □: Almost no yellowing △: Some yellowing ×: Remarkable yellowing Gasoline resistance ○: No change □: Swelling slightly: Δ: Swelling ×: Swelling partially dissolved Chemical resistance ○: No change □: Slight swelling △: Swelling ×: Peeling Table 1 It can be seen that Samples 1, 2, 4, 5, 7, and 8 of the present invention have excellent adhesion to organic materials and excellent gasoline resistance, while Comparative Samples 3, 6, and 9 have excellent adhesion to organic materials and Poor gasoline resistance.
Claims (2)
部と、加水分解可能なシリル基含有単量体B5〜25重量部
と、該単量体Ａおよび単量体Ｂと共重合可能な単量体Ｃ
とからなることを特徴とする塗料用付加系共重合体1. Copolymerizable with 20 to 60 parts by weight of an isocyanate group-containing monomer A, 5 to 25 parts by weight of a hydrolyzable silyl group-containing monomer B, and the monomer A and the monomer B. Monomer C
And an addition-type copolymer for coatings
部と、加水分解可能なシリル基含有単量体B5〜25重量部
と、該単量体Ａおよび単量体Ｂと共重合可能な単量体Ｃ
とからなる塗料用付加系共重合体と活性水素を有する官
能基を含有するポリマーとからなる塗料組成物2. Copolymerizable with 20 to 60 parts by weight of an isocyanate group-containing monomer A, 5 to 25 parts by weight of a hydrolyzable silyl group-containing monomer B, and the monomer A and the monomer B. Monomer C
A coating composition comprising an addition-type copolymer for coating composition and a polymer containing a functional group having active hydrogen
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9296786A JPH0826103B2 (en) | 1986-04-22 | 1986-04-22 | Addition-type copolymer for paint and paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9296786A JPH0826103B2 (en) | 1986-04-22 | 1986-04-22 | Addition-type copolymer for paint and paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62250017A JPS62250017A (en) | 1987-10-30 |
| JPH0826103B2 true JPH0826103B2 (en) | 1996-03-13 |
Family
ID=14069191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9296786A Expired - Fee Related JPH0826103B2 (en) | 1986-04-22 | 1986-04-22 | Addition-type copolymer for paint and paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0826103B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06823B2 (en) * | 1986-07-23 | 1994-01-05 | 昭和高分子株式会社 | Room temperature curable copolymer and method for producing the same |
| JP2819412B2 (en) * | 1987-10-09 | 1998-10-30 | 大日本インキ化学工業株式会社 | Resin composition for coating |
| JPH026549A (en) * | 1988-06-24 | 1990-01-10 | Nippon Penuoruto Kk | Coating composition |
| JP2837575B2 (en) * | 1992-03-16 | 1998-12-16 | 昭和高分子株式会社 | Resin for baking paint |
| JP6062661B2 (en) * | 2012-05-16 | 2017-01-18 | 株式会社カネカ | Active energy ray-curable coating resin composition |
-
1986
- 1986-04-22 JP JP9296786A patent/JPH0826103B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62250017A (en) | 1987-10-30 |
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