JP4733360B2 - Surface conditioner for thermosetting film forming composition - Google Patents
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- 239000000203 mixture Substances 0.000 title claims description 58
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 189
- 238000004132 cross linking Methods 0.000 claims description 139
- 125000000524 functional group Chemical group 0.000 claims description 65
- 239000000178 monomer Substances 0.000 claims description 54
- 230000001939 inductive effect Effects 0.000 claims description 49
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 230000003750 conditioning effect Effects 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 5
- 150000008064 anhydrides Chemical group 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 70
- 239000008096 xylene Substances 0.000 description 70
- 239000000243 solution Substances 0.000 description 66
- 238000004519 manufacturing process Methods 0.000 description 61
- 239000003973 paint Substances 0.000 description 29
- 239000007787 solid Substances 0.000 description 26
- 239000000341 volatile oil Substances 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 229920000877 Melamine resin Polymers 0.000 description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 15
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 11
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 11
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 11
- 230000003254 anti-foaming effect Effects 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000007865 diluting Methods 0.000 description 8
- -1 polydimethylsiloxane Polymers 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 125000004112 carboxyamino group Chemical group [H]OC(=O)N([H])[*] 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 230000002087 whitening effect Effects 0.000 description 6
- 239000004640 Melamine resin Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000007974 melamines Chemical class 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 238000009499 grossing Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
Description
本発明は、熱硬化被膜形成組成物に添加されるもので、この組成物を熱硬化させて形成される被膜の表面の物性を改善するための表面調整剤に関するものである。 The present invention relates to a surface conditioner that is added to a thermosetting film-forming composition and improves the physical properties of the surface of a film formed by thermosetting the composition.
プラスチック部材、プレコートメタル、建材、自動車ボディーは、外観の美粧性を高めるとともに、それらの基材を保護するため、基材の表面に、焼き付け型塗料や焼き付け型コーティング剤のような熱硬化被膜形成組成物を塗布してから熱処理して硬化させて、被膜が形成されている。このような組成物は、被膜表面を平滑にさせる平滑剤、焼き付けの際の急激な加熱によるピンホール（ワキ）を防止するワキ防止剤、消泡剤のような表面調整剤が添加されている。 Plastic members, pre-coated metals, building materials, and automobile bodies are made of thermosetting coatings such as baking paints and baking coating agents on the surface of the substrates to enhance the cosmetic appearance and protect those substrates. The composition is applied and then heat-treated and cured to form a film. Such a composition is added with a surface smoothing agent such as a smoothing agent that smoothes the surface of the coating, an anti-waxing agent that prevents pinholes due to rapid heating during baking, and an antifoaming agent. .
表面調整剤として、ポリ（メタ）アクリレート、ポリビニルエーテル、変性ポリブタジエン、オレフィン系共重合物、ポリジメチルシロキサンの変性物が、知られている。これを応用した化合物として、例えば、特許文献１に（メタ）アクリレートと、モノカルボン酸またはモノアミンが結合したイソシアネート変性アクリル類との共重合物が開示され、特許文献２に（メタ）アクリロイル基を有するアルコキシシラン単量体と、（メタ）アクリロイル基を有する単量体との共重合物が開示され、特許文献３にイソシアネート基を有するモノマーと従来から使用されてきたモノマーとの共重合物が開示されている。 Known surface conditioning agents include poly (meth) acrylates, polyvinyl ethers, modified polybutadienes, olefin copolymers, and modified products of polydimethylsiloxane. As a compound to which this is applied, for example, Patent Document 1 discloses a copolymer of (meth) acrylate and an isocyanate-modified acrylic bonded with a monocarboxylic acid or a monoamine, and Patent Document 2 has a (meth) acryloyl group. A copolymer of an alkoxysilane monomer having a monomer and a monomer having a (meth) acryloyl group is disclosed, and Patent Document 3 discloses a copolymer of a monomer having an isocyanate group and a conventionally used monomer. It is disclosed.
一般的にこのような表面調整剤を添加した熱硬化被膜形成組成物は消泡性が向上しており、それを塗布して熱硬化させた被膜は、ワキ防止性、平滑性が向上している。しかし表面調整剤を含有した硬化被膜は、ガソリンまたは揮発油を布に含ませて拭くと表面調整剤が脱落してしまう所為で白化する場合があり、耐揮発油性が悪い。特に透明性を重視するクリアー塗料のような被膜形成組成物で形成される硬化被膜は、白化してしまうと美粧性の点で深刻な問題となる。 In general, a thermosetting film-forming composition to which such a surface conditioner is added has improved antifoaming properties, and a film that has been heat-cured by applying it has improved anti-flammability and smoothness. Yes. However, a cured coating containing a surface conditioner may be whitened because the surface conditioner may fall off when the cloth is wiped with gasoline or volatile oil, and the resistance to volatile oil is poor. In particular, a cured film formed of a film-forming composition such as a clear paint that places importance on transparency becomes a serious problem in terms of cosmetics when whitened.
従来の（メタ）アクリル系共重合物からなる表面調整剤は、その分子量を大きくするほど、表面調整剤が添加された組成物を熱硬化させて形成された被膜の耐揮発油性を向上させる。この被膜は、白化が幾分抑制されるが、表面調整剤を含まない硬化被膜のように殆んど白化しないというレベルには遥かに及ばない。さらにこの表面調整剤がかえって、表面調整剤を含まない被膜形成組成物のような濁りや消泡性の低下を引き起こしてしまう。 The surface adjustment agent which consists of a conventional (meth) acrylic-type copolymer improves the volatile oil resistance of the film formed by thermosetting the composition to which the surface adjustment agent was added, so that the molecular weight was enlarged. This coating is somewhat less whitened, but far below the level of little whitening like a cured coating that does not contain a surface modifier. Furthermore, this surface conditioner will cause turbidity and a decrease in defoaming properties as in a film-forming composition that does not contain a surface conditioner.
本発明は前記の課題を解決するためになされたもので、十分な消泡性、ワキ防止性、平滑性を付与するとともに、優れた耐揮発油性を発現させるために、熱硬化被膜形成組成物に添加される表面調整剤を提供することを目的とする。 The present invention has been made in order to solve the above-mentioned problems, and in order to impart sufficient antifoaming properties, anti-cracking properties, smoothness and to exhibit excellent volatile oil resistance, a thermosetting film-forming composition An object of the present invention is to provide a surface conditioner to be added to the surface.
前記の目的を達成するためになされた、特許請求の範囲の請求項１に記載された本発明の熱硬化被膜形成組成物用の表面調整剤は、保護されていてもよい、カルボキシル基、無水ジカルボン酸基、エポキシ基、イソシアネート基、及びメラミン基の少なくとも何れかである架橋反応活性官能基と、それへ反応するもので、保護されていてもよい、カルボキシル基、アミノ基、水酸基、エポキシ基、及びメラミン基の少なくとも何れかである架橋反応誘起性官能基とを含有し、それらにより分子間の架橋を形成する共重合性物質が、含まれており、該共重合性物質の重量平均分子量が２０００〜２０００００であることを特徴とする。
The surface conditioner for the thermosetting film-forming composition of the present invention described in claim 1 made to achieve the above object is an optionally protected carboxyl group, anhydrous A carboxyl group, an amino group, a hydroxyl group, and an epoxy group that react with and react with a crosslinking reaction active functional group that is at least one of a dicarboxylic acid group, an epoxy group, an isocyanate group, and a melamine group. And a copolymerizable substance containing a crosslinking reaction-inducing functional group that is at least one of melamine groups and thereby forming a crosslink between the molecules, and the weight average molecular weight of the copolymerizable substance is included. Is 2000-200000.
この共重合性物質は、少なくとも１種類の共重合体からなる。この共重合性物質は、例えば加熱されることにより、架橋反応活性官能基と架橋反応誘起性官能基とが架橋反応を起こして分子間で３次元的な網目状に架橋する結果、高分子量化するものである。 This copolymerizable material consists of at least one copolymer. This copolymerizable material has a high molecular weight as a result of, for example, being heated, a crosslinking reaction-active functional group and a crosslinking reaction-inducing functional group undergo a crosslinking reaction to crosslink in a three-dimensional network between molecules. To do.
この表面調整剤は、熱硬化被膜形成組成物例えば塗料に添加して使用される。表面調整剤は、この組成物に十分な消泡性を付与し、この組成物を熱硬化させて形成された被膜に優れた耐油性と、十分なワキ防止性及び平滑性とを発現させる。 This surface conditioner is used by being added to a thermosetting film forming composition such as a paint. The surface conditioner imparts sufficient antifoaming property to the composition, and exhibits excellent oil resistance, sufficient anti-boilability and smoothness in a film formed by thermosetting the composition.
同じく請求項２に記載された表面調整剤は、前記架橋反応活性官能基と、前記架橋反応誘起性官能基とがそれぞれ、
カルボキシル基と、エポキシ基、水酸基、アミノ基、またはイソシアネート基とであり、
無水ジカルボン酸基と、アミノ基、水酸基、またはメラミン基とであり、
エポキシ基と、カルボキシル基、水酸基、またはアミノ基とであり、
イソシアネート基と、カルボキシル基、水酸基、またはアミノ基とであり、
または
メラミン基と、メラミン基、または水酸基とであることを特徴とする。
Similarly, in the surface conditioning agent according to claim 2, the crosslinking reaction active functional group and the crosslinking reaction inducing functional group are respectively
A carboxyl group and an epoxy group, a hydroxyl group, an amino group, or an isocyanate group,
A dicarboxylic anhydride group and an amino group, a hydroxyl group, or a melamine group,
An epoxy group and a carboxyl group, a hydroxyl group, or an amino group,
An isocyanate group, a carboxyl group, a hydroxyl group, or an amino group,
Or
It is characterized by being a melamine group, a melamine group, or a hydroxyl group .
架橋反応活性官能基がカルボキシル基であるとき、架橋反応誘起性官能基がエポキシ基、水酸基、アミノ基、またはイソシアネート基であることが好ましい。前記架橋反応活性官能基が無水ジカルボン酸基であるとき、架橋反応誘起性官能基が、アミノ基、水酸基、またはメラミン基であることが好ましい。架橋反応活性官能基がエポキシ基であるとき、架橋反応誘起性官能基がカルボキシル基、水酸基、アミノ基であることが好ましい。架橋反応活性官能基がイソシアネート基であるとき、架橋反応誘起性官能基がカルボキシル基、水酸基、アミノ基であることが好ましい。架橋反応活性官能基がメラミン基であるとき、架橋反応誘起性官能基がメラミン基、水酸基であることが好ましい。これらメラミン基同士がホルムアルデヒドを介して架橋反応してもよい。 When the crosslinking reaction active functional group is a carboxyl group, the crosslinking reaction inducing functional group is preferably an epoxy group, a hydroxyl group, an amino group, or an isocyanate group. When the crosslinking reaction-active functional group is a dicarboxylic anhydride group, the crosslinking reaction-inducing functional group is preferably an amino group, a hydroxyl group, or a melamine group. When the crosslinking reaction active functional group is an epoxy group, the crosslinking reaction inducing functional group is preferably a carboxyl group, a hydroxyl group, or an amino group. When the crosslinking reaction active functional group is an isocyanate group, the crosslinking reaction inducing functional group is preferably a carboxyl group, a hydroxyl group, or an amino group. When the crosslinking reaction active functional group is a melamine group, the crosslinking reaction inducing functional group is preferably a melamine group or a hydroxyl group. These melamine groups may undergo a crosslinking reaction via formaldehyde.
中でも、架橋反応活性官能基がエポキシ基で架橋反応誘起性官能基がカルボキシル基、または架橋反応活性官能基がイソシアネート基で架橋反応誘起性官能基が水酸基であると、なお一層好ましい。 Among them, it is even more preferable that the crosslinking reaction active functional group is an epoxy group and the crosslinking reaction inducing functional group is a carboxyl group, or the crosslinking reaction active functional group is an isocyanate group and the crosslinking reaction inducing functional group is a hydroxyl group.
これらの架橋反応活性官能基や架橋反応誘起性官能基は、熱硬化被膜形成組成物の貯蔵時に安定で架橋反応を起こさないが、組成物の焼き付け温度付近で架橋反応を起こすものである。架橋反応活性官能基や架橋反応誘起性官能基は、貯蔵時の安定性を高めるために、保護されていてもよい。例えば、イソシアネート基は、一般的に知られているブロック剤で保護された等価体具体的にはＯ−（１′−メチルプロピリデン アミノ）カルボキシアミノ基であってもよく、またカルボキシル基は、ビニルエーテルにより保護されてヘミアセタールエステル結合とした等価体であってもよい。 These crosslinking reaction-active functional groups and crosslinking reaction-inducing functional groups are stable during storage of the thermosetting film-forming composition and do not cause a crosslinking reaction, but cause a crosslinking reaction near the baking temperature of the composition. The cross-linking reaction active functional group and the cross-linking reaction inducing functional group may be protected in order to enhance the stability during storage. For example, the isocyanate group may be a generally known blocking agent-protected equivalent, specifically an O- (1'-methylpropylideneamino) carboxyamino group, and the carboxyl group is An equivalent compound protected with vinyl ether to form a hemiacetal ester bond may be used.
同じく請求項３に記載の表面調整剤は、共重合性物質が、前記架橋反応活性官能基を含有する不飽和モノマー及び非架橋性不飽和モノマーを共重合させた架橋反応活性共重合体と、前記架橋反応誘起性官能基を含有する不飽和モノマー及び別な非架橋性不飽和モノマーを共重合させた架橋反応誘起性共重合体との混合物であることを特徴とする。この共重合性物質は、少なくとも２種類の共重合体で構成されている。 Similarly, the surface conditioning agent according to claim 3, wherein the copolymerizable material is a cross-linked reactive active copolymer obtained by copolymerizing the unsaturated monomer containing the cross-linking reactive functional group and the non-crosslinkable unsaturated monomer, It is a mixture of an unsaturated monomer containing the crosslinking reaction-inducing functional group and a crosslinking reaction-inducing copolymer obtained by copolymerizing another non-crosslinking unsaturated monomer. This copolymerizable material is composed of at least two types of copolymers.
架橋反応活性官能基を含有する不飽和モノマーや、架橋反応誘起性官能基を含有する不飽和モノマーは、多種多様であり、架橋反応ができる組合わせであれば特に限定されない。 There are a wide variety of unsaturated monomers containing a crosslinking reaction-active functional group and unsaturated monomers containing a crosslinking reaction-inducing functional group, and there is no particular limitation as long as it is a combination capable of crosslinking reaction.
架橋反応活性官能基を含有する不飽和モノマーとして、例えば、アクリル酸やメタクリル酸である（メタ）アクリル酸、イソシアナトエチル（メタ）アクリレート、グリシジル（メタ）アクリレートのような（メタ）アクリル系モノマー；無水マレイン酸のような酸無水物モノマー；マレイン酸モノエステルのような部分エステルモノマーが挙げられる。 Examples of unsaturated monomers containing a crosslinking reaction active functional group include (meth) acrylic monomers such as acrylic acid and methacrylic acid (meth) acrylic acid, isocyanatoethyl (meth) acrylate, and glycidyl (meth) acrylate. An acid anhydride monomer such as maleic anhydride; a partial ester monomer such as maleic acid monoester.
また、その架橋反応活性官能基に応じ架橋反応し得る架橋反応誘起性官能基を含有する不飽和モノマーとして、例えば、（メタ）アクリル酸、２−ヒドロキシエチル（メタ）アクリレート、Ｎ−（ヒドロキシメチル）（メタ）アクリルアミドのような（メタ）アクリル系モノマー；マレイン酸モノエステルのような部分エステルモノマーが挙げられる。 Further, examples of unsaturated monomers containing a crosslinking reaction-inducing functional group that can undergo a crosslinking reaction according to the crosslinking reaction active functional group include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and N- (hydroxymethyl). ) (Meth) acrylic monomers such as (meth) acrylamide; and partial ester monomers such as maleic acid monoester.
非架橋性不飽和モノマーは、多種多様であり、架橋反応活性官能基も架橋反応誘起性官能基も有しないもので、付加重合性の不飽和基を有するものであれば特に限定されない。非架橋性不飽和モノマーは、具体的には、アルキル（メタ）アクリレート、アラルキル（メタ）アクリレート、ビニル基含有エーテル、スチレン類が挙げられる。架橋反応活性共重合体と架橋反応誘起性共重合体とを構成している夫々の非架橋性不飽和モノマーは、同種であっても異種であってもよく、構成比が同一であっても異なっていてもよい。 The non-crosslinkable unsaturated monomers are various and are not particularly limited as long as they have neither a crosslinking reaction-active functional group nor a crosslinking reaction-inducing functional group and an addition-polymerizable unsaturated group. Specific examples of the non-crosslinkable unsaturated monomer include alkyl (meth) acrylates, aralkyl (meth) acrylates, vinyl group-containing ethers, and styrenes. Each of the non-crosslinkable unsaturated monomers constituting the cross-linking reaction-active copolymer and the cross-linking reaction-inducing copolymer may be the same or different, and the composition ratio may be the same. May be different.
共重合性物質であるこれらの共重合体夫々の重量平均分子量が２０００未満または２０００００を超えると、表面調整剤は消泡性、平滑性及び耐揮発油性の全てをバランスよく優れたものにするのが困難になる。この重量平均分子量が６０００〜６００００であるとより好ましい。 When the weight average molecular weight of each of these copolymers, which are copolymerizable substances, is less than 2000 or more than 200000, the surface modifier makes all of defoaming property, smoothness and volatile oil resistance excellent in a balanced manner. Becomes difficult. The weight average molecular weight is more preferably 6000 to 60000.
架橋反応活性共重合体と架橋反応誘起性共重合体とは、夫々の重量平均分子量が近いほど、互いに相溶性が良くなり、架橋性が高くなるので、好ましい。 The cross-linking reaction-active copolymer and the cross-linking reaction-inducing copolymer are preferable because the closer the respective weight average molecular weights, the better the compatibility with each other and the higher the cross-linking property.
同じく請求項４に記載された表面調整剤は、前記架橋反応活性共重合体が、前記架橋反応活性官能基を含有する不飽和モノマーを０．１〜５０重量部、前記非架橋性不飽和モノマーを９９．９〜５０重量部とするもので５〜９５重量％であり、前記架橋反応誘起性共重合体は、前記架橋反応誘起性官能基を含有する不飽和モノマーを０．１〜５０重量部、前記別な非架橋性不飽和モノマーを９９．９〜５０重量部とするもので９５〜５重量％であることを特徴とする。 Similarly, in the surface conditioning agent according to claim 4, the crosslinking reaction active copolymer includes 0.1 to 50 parts by weight of the unsaturated monomer containing the crosslinking reaction active functional group, and the non-crosslinkable unsaturated monomer. 99.9 to 50 parts by weight, and the crosslinking reaction-inducing copolymer contains 0.1 to 50% by weight of the unsaturated monomer containing the crosslinking reaction-inducing functional group. Part of the non-crosslinkable unsaturated monomer is 99.9 to 50 parts by weight, and is 95 to 5% by weight.
表面調整剤は、架橋反応活性官能基を含有する不飽和モノマー、及び架橋反応誘起性官能基を含有する不飽和モノマーが０．１重量部より少ないと、耐揮発油性を悪化させてしまい、一方、５０重量部より多いと消泡性または平滑性を悪化させてしまう。夫々の不飽和モノマーが、１〜１０重量部であるとより好ましい。 When the amount of unsaturated monomer containing a crosslinking reaction-active functional group and unsaturated monomer containing a crosslinking reaction-inducing functional group is less than 0.1 parts by weight, the surface conditioner deteriorates volatile oil resistance. When the amount is more than 50 parts by weight, the defoaming property or smoothness is deteriorated. It is more preferable that each unsaturated monomer is 1 to 10 parts by weight.
表面調整剤は、架橋反応活性共重合体と架橋反応誘起性共重合体との何れかが５重量％未満であると、優れた耐揮発油性を発揮させることができない。これらの共重合体の重量比が等しくなるほど好ましい。 If the surface conditioning agent is less than 5% by weight of either the crosslinking reaction-active copolymer or the crosslinking reaction-inducing copolymer, it cannot exhibit excellent volatile oil resistance. It is preferable that the weight ratios of these copolymers are equal.
表面調整剤は、架橋反応活性共重合体と架橋反応誘起性共重合体とを予め混合させたものであってもよく、熱硬化被膜形成組成物に添加する直前に混合させたものであってもよい。熱硬化被膜形成組成物へ架橋反応活性共重合体と架橋反応誘起性共重合体とを別々に添加されたものであってもよい。 The surface conditioning agent may be a mixture of a crosslinking reaction-active copolymer and a crosslinking reaction-inducible copolymer in advance, or a mixture prepared immediately before being added to the thermosetting film-forming composition. Also good. The thermosetting film-forming composition may be prepared by separately adding a crosslinking reaction-active copolymer and a crosslinking reaction-inducing copolymer.
同じく請求項５に記載の表面調整剤は、Ｆｅｄｏｒｓ法（Ｒ．Ｆ．Ｆｅｄｏｒｓ：Ｐｏｌｙｍ．Ｅｎｇ．Ｓｃｉ．，１４［２］１４７（１９７４））に準拠した、前記架橋反応活性共重合体と、前記架橋誘起性共重合体との計算溶解性パラメータ（ＳＰ）差が、０．５以下であることを特徴とする。 Similarly, the surface conditioning agent according to claim 5 is based on the Fedors method (R.F.Fedors: Polym.Eng.Sci., 14 [2] 147 (1974)), The calculated solubility parameter (SP) difference from the crosslinkable copolymer is 0.5 or less.
Ｆｅｄｏｒｓ法による溶解性パラメータδは下記式（１）で表される。 The solubility parameter δ by the Fedors method is expressed by the following formula (1).
前記式（１）より、架橋反応活性共重合体と架橋反応誘起性共重合体との組成を元に、共重合体の化学構造からδを算出し、それを共重合体の計算溶解性パラメータ（ＳＰ）とした。 From the above formula (1), δ is calculated from the chemical structure of the copolymer based on the composition of the cross-linking reaction-active copolymer and the cross-linking reaction-inducing copolymer, and the calculated solubility parameter of the copolymer is calculated. (SP).
このＳＰ差が、０．５を超えると両共重合体間で、相溶性が悪くなるため、架橋性が悪くなり、表面調整剤は充分な消泡性、平滑性及び耐揮発油性を発現させることができなくなってしまう。 If this SP difference exceeds 0.5, the compatibility between both copolymers will be poor, so the crosslinkability will be poor, and the surface conditioner will exhibit sufficient antifoaming properties, smoothness and volatile oil resistance. It becomes impossible to do.
同じく請求項６に記載の表面調整剤は、共重合性物質が、前記架橋反応活性官能基を含有する不飽和モノマーと、前記架橋反応誘起性官能基を含有する不飽和モノマーと、非架橋性不飽和モノマーとを共重合させた、架橋反応活性と架橋誘起性とを有する共重合体からなることを特徴とする。 Similarly, in the surface conditioning agent according to claim 6, the copolymerizable material includes an unsaturated monomer containing the crosslinking reaction-active functional group, an unsaturated monomer containing the crosslinking reaction-inducing functional group, and a non-crosslinking property. It is characterized by comprising a copolymer having a crosslinking reaction activity and a crosslinking induction property, copolymerized with an unsaturated monomer.
架橋反応活性官能基と架橋反応誘起性官能基とも前記例示のとおりであり、表面調整剤の貯蔵時の安定性を高めるため予め保護されていてもよい。また、３つの不飽和モノマーとも前記例示のとおりである。 Both the crosslinking reaction-active functional group and the crosslinking reaction-inducing functional group are as described above, and may be protected in advance in order to increase the stability of the surface conditioner during storage. The three unsaturated monomers are as illustrated above.
共重合性物質であるこの架橋反応活性と架橋誘起性とを有する共重合体の重量平均分子量が２０００未満または２０００００を超えると、表面調整剤は消泡性、平滑性及び耐揮発油性の全てをバランスよく優れたものにするのが困難になる。この重量平均分子量が６０００〜６００００であるとより好ましい。 When the weight average molecular weight of the copolymer having the crosslinking reaction activity and the crosslinking inducing property, which is a copolymerizable material, is less than 2,000 or more than 200,000, the surface modifier has all of antifoaming property, smoothness and volatile oil resistance. It becomes difficult to make a good balance. The weight average molecular weight is more preferably 6000 to 60000.
同じく請求項７に記載の表面調整剤は、前記共重合体が、前記架橋反応活性官能基を含有する不飽和モノマーを０．１〜３０重量部、前記架橋誘起性官能基を含有する不飽和モノマーを０．１〜３０重量部、前記非架橋性不飽和モノマーを９９．８〜４０重量部とすることを特徴とする。 Similarly, in the surface conditioning agent according to claim 7, the copolymer is an unsaturated monomer containing 0.1 to 30 parts by weight of the unsaturated monomer containing the crosslinking reaction active functional group and the crosslinking inducing functional group. The monomer is 0.1 to 30 parts by weight, and the non-crosslinkable unsaturated monomer is 99.8 to 40 parts by weight.
表面調整剤は、架橋反応活性官能基を含有する不飽和モノマーと架橋誘起性官能基を含有する不飽和モノマーとが、０．１重量部未満であると、耐揮発油性を悪化させてしまい、一方、３０重量部より多いと消泡性または平滑性を悪化させてしまう。何れの不飽和モノマーも１〜１０重量部であるとより好ましい。 The surface conditioner deteriorates the resistance to volatile oil when the unsaturated monomer containing a crosslinking reaction active functional group and the unsaturated monomer containing a crosslinking inducing functional group are less than 0.1 parts by weight, On the other hand, if it exceeds 30 parts by weight, the defoaming property or smoothness will be deteriorated. Any unsaturated monomer is more preferably 1 to 10 parts by weight.
本発明の表面調整剤が配合される熱硬化被膜形成組成物は、前記の表面調整剤と、一般的な塗料に用いられているアクリルメラミン硬化塗料、ポリエステルメラミン硬化塗料、酸エポキシ硬化塗料のような熱硬化性基材樹脂を含んでいるものであればいずれのものでもよい。 The thermosetting film forming composition in which the surface conditioner of the present invention is blended includes the above-mentioned surface conditioner and acrylic melamine cured paint, polyester melamine cured paint, acid epoxy cured paint used in general paints. Any material may be used as long as it contains a suitable thermosetting base resin.
この組成物に配合される表面調整剤は、従来の表面調整剤と同様に少量でよく、具体的には、組成物の塗料樹脂の不揮発成分に対し、表面調整剤の不揮発成分として０．１〜１重量％であることが好ましい。この表面調整剤がこの範囲で配合された組成物は、優れた消泡性を発現する。 The surface conditioner blended in this composition may be a small amount as in the case of the conventional surface conditioner. Specifically, the surface conditioner is 0.1% as the non-volatile component of the surface conditioner relative to the non-volatile component of the coating resin of the composition. It is preferably ˜1% by weight. A composition containing this surface conditioner in this range exhibits excellent antifoaming properties.
この組成物を例えば塗布し焼き付けのような熱処理により硬化させた被膜表面は、ワキ防止性に優れ平滑である。さらにこの被膜表面は、従来の表面調整剤を配合した組成物を熱硬化させた場合のような耐揮発油性の低下がなく、耐揮発油性が優れている。 The surface of the coating obtained by applying this composition and curing it by a heat treatment such as baking is excellent in anti-flaking properties and is smooth. Furthermore, this coating surface is excellent in volatile oil resistance without causing a decrease in volatile oil resistance as in the case of thermally curing a composition containing a conventional surface conditioner.
この表面調整剤が、この熱処理により架橋反応を起こし、平滑性及び耐揮発油性の効果を発現する。従って、被膜形成樹脂組成物を単に熱処理して硬化させて被膜を形成する場合だけでなく、被膜形成樹脂組成物を紫外線照射して硬化させて被膜を形成した後、熱処理して表面調整剤の共重合体を架橋させる場合でも、所望の効果を発現する。 This surface conditioner causes a crosslinking reaction by this heat treatment, and exhibits the effects of smoothness and resistance to volatile oil. Therefore, not only when the film-forming resin composition is simply heat-treated and cured to form a film, but also after the film-forming resin composition is cured by UV irradiation to form a film, the film is heat-treated to form a surface-adjusting agent. Even when the copolymer is crosslinked, a desired effect is exhibited.
熱処理は、比較的低温の加熱であってもよく、８０〜３００℃のような比較的高温の焼き付けであってもよい。 The heat treatment may be heating at a relatively low temperature, or baking at a relatively high temperature such as 80 to 300 ° C.
従来の表面調整剤が配合された硬化被膜では、表面調整剤の分子量がさほど大きくないため、有機溶剤を用いて拭き取ることにより表面調整剤が溶出して脱落し、表面の平滑性が失われ入射光の乱反射により白化すると考えられる。それに対し、本発明の被膜が、熱硬化被膜形成組成物中に少量配合された表面調整剤によって、耐揮発油性を低下させない詳細は明らかではないが、以下のような理由によるものと推察される。 In the cured film containing the conventional surface conditioner, the molecular weight of the surface conditioner is not so large, so the surface conditioner elutes and falls off by wiping with an organic solvent, and the surface smoothness is lost and incident. It is thought that whitening occurs due to irregular reflection of light. On the other hand, the details of the coating composition of the present invention not reducing the resistance to volatile oil by the surface conditioner blended in a small amount in the thermosetting film-forming composition is not clear, but is presumed to be due to the following reasons. .
本発明の表面調整剤は、消泡性やワキ防止性や平滑性を発現する際に、適度な基材樹脂への不相溶性を持っている。この表面調整剤は、それを配合した塗料樹脂溶液のような組成物を焼き付け熱硬化させて硬化被膜を形成させる際に、被膜表面近傍に高密度に、微粒子として均一に分散して存在し、３次元的な網目状に架橋反応を起こし分子量が増大する。さらに表面調整剤の共重合性物質が有する官能基の種類によっては、被膜形成組成物中の別な構成成分分子が有する官能基とも架橋反応が起っている場合もある。そのため、架橋した表面調整剤は、有機溶剤に溶解し難くなり、有機溶剤による表面の拭き取りによる表面調整剤の脱落が防止できるようになった結果、表面調整剤を含まない硬化被膜のような本来の耐揮発油性を、低下させることなく維持できるようになり、白化を起こさないようになったものと推察される。 The surface conditioner of the present invention has an appropriate incompatibility with a base resin when it exhibits antifoaming properties, anti-flaking properties, and smoothness. This surface conditioner is present in the vicinity of the coating surface at high density and uniformly dispersed as fine particles when a cured coating film is formed by baking and thermosetting a composition such as a coating resin solution containing the surface conditioning agent, The molecular weight is increased by causing a crosslinking reaction in a three-dimensional network. Furthermore, depending on the type of functional group possessed by the copolymerizable material of the surface modifier, there may be a crosslinking reaction with functional groups possessed by other component molecules in the film-forming composition. For this reason, the cross-linked surface conditioner becomes difficult to dissolve in an organic solvent, and the surface conditioner can be prevented from falling off by wiping the surface with an organic solvent. It is presumed that the volatile oil resistance of No. 1 can be maintained without deteriorating and no whitening occurs.
本発明の表面調整剤は、熱硬化被膜形成組成物に少量添加されただけで、十分な消泡性を発現する。またこの組成物を熱硬化させると、優れた耐揮発油性と、十分なワキ防止性、平滑性とを発現した被膜を形成する。 The surface conditioner of the present invention exhibits sufficient antifoaming properties only by adding a small amount to the thermosetting film-forming composition. Moreover, when this composition is heat-cured, a film that exhibits excellent resistance to volatile oil, sufficient anti-flaking properties, and smoothness is formed.
以下、本発明の表面調整剤を調製し、それを熱硬化被膜形成組成物に添加して、熱硬化させて被膜を形成させた実施例について、詳細に説明する。 Hereinafter, examples in which the surface conditioner of the present invention was prepared, added to the thermosetting film forming composition, and thermally cured to form a film will be described in detail.
本発明を適用する実施例１〜５、及び本発明を適用外の比較例１〜１０では、主に消泡剤として作用する表面調整剤を含む熱硬化被膜形成組成物であるアクリルメラミン硬化クリアー塗料を調製し硬化させて、被膜を形成させた例を示す。 In Examples 1 to 5 to which the present invention is applied and Comparative Examples 1 to 10 to which the present invention is not applied, an acrylic melamine cured clear which is a thermosetting film forming composition containing a surface conditioner mainly acting as an antifoaming agent An example in which a coating is formed by preparing and curing a paint is shown.
先ず、実施例１〜５及び比較例１〜１０で使用される表面調整剤の共重合性物質を構成する、架橋反応活性共重合体、架橋反応誘起性共重合体、または架橋反応活性と架橋誘起性とを有する共重合体を以下のようにして製造した。 First, a cross-linking reaction-active copolymer, a cross-linking reaction-inducing copolymer, or a cross-linking reaction activity and cross-linking constituting the copolymer of the surface conditioner used in Examples 1 to 5 and Comparative Examples 1 to 10 A copolymer having inductivity was produced as follows.
なお、共重合体の重量平均分子量は全て、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析装置（昭和電工株式会社製 Ｓｈｏｄｅｘ ＧＰＣ ｓｙｓｔｅｍ）を用いて測定した値である。またＳＰは全て、前記の方法によって算出したものである。 In addition, all the weight average molecular weights of a copolymer are the values measured using the gel permeation chromatography (GPC) analyzer (Shodex GPC system by Showa Denko KK). All SPs are calculated by the above method.
（共重合体(Ａ−１)の製造例）
撹拌装置、還流冷却管、滴下ロート、温度計及び窒素ガス吹き込み口を備えた１０００ｍｌの反応容器に、キシレン１００重量部を仕込み、窒素ガスを導入しながら１００℃に昇温した。そこへ、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ａ−１)を、滴下ロートにより、２時間で等速滴下した。滴下終了後、１００℃の温度を維持しつつ５時間反応させた。反応終了後、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ａ−１)のキシレン液を製造した。この共重合体の重量平均分子量は２００００であった。この共重合体のＳＰは９．６２となる。
(Production example of copolymer (A-1))
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, 100 parts by weight of xylene was charged, and the temperature was raised to 100 ° C. while introducing nitrogen gas. There, 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 15 parts by weight of 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 100 parts by weight of xylene, t-butylperoxy-2 -Ethylhexanoate A drop solution (a-1) mixed with 5 parts by weight was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the reaction was carried out for 5 hours while maintaining the temperature of 100 ° C. After the completion of the reaction, the solid content was adjusted to 30% by diluting with xylene to produce a xylene solution of the crosslinking reaction active copolymer (A-1). The weight average molecular weight of this copolymer was 20000. The SP of this copolymer is 9.62.
（共重合体(Ａ−２)の製造例）
共重合体(Ａ−１)の製造例の滴下溶液(ａ−１)に代えて、ラウリルメタクリレート １８５重量部、スチレン １００重量部、グリシジルメタクリレート １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ａ−２)を用いたこと以外は、共重合体(Ａ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ａ−２)のキシレン液を製造した。この共重合体の重量平均分子量は、２１０００であった。なお、この共重合体のＳＰは９．５８となる。
(Production example of copolymer (A-2))
Instead of the dropping solution (a-1) in the production example of the copolymer (A-1), 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 15 parts by weight of glycidyl methacrylate, 100 parts by weight of xylene, t-butylperoxy 2-Ethylhexanoate Diluted with xylene in the same manner as in the production example of the copolymer (A-1) except that the dropping solution (a-2) mixed with 5 parts by weight was used. The solid content was adjusted to 30% to produce a xylene solution of a crosslinking reaction active copolymer (A-2). The copolymer had a weight average molecular weight of 21,000. The SP of this copolymer is 9.58.
（共重合体(Ａ−３)の製造例）
共重合体(Ａ−１)の製造例の滴下溶液(ａ−１)に代えて、ラウリルメタクリレート １８５重量部、スチレン １００重量部、２−ヒドロキシエチルメタクリレート １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液（ａ−３）を用いたこと以外は、共重合体(Ａ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応誘起性共重合体(Ａ−３)のキシレン液を製造した。この共重合体の重量平均分子量は、２１０００であった。なお、この共重合体のＳＰは９．７０となる。
(Production example of copolymer (A-3))
Instead of the dropping solution (a-1) in the production example of the copolymer (A-1), 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 15 parts by weight of 2-hydroxyethyl methacrylate, 100 parts by weight of xylene, t- Butyl peroxy-2-ethylhexanoate In the same manner as in the production example of copolymer (A-1), except that a dropping solution (a-3) mixed with 5 parts by weight was used, xylene was used. Dilution was performed to adjust the solid content to 30%, and a xylene solution of a crosslinking reaction-inducing copolymer (A-3) was produced. The copolymer had a weight average molecular weight of 21,000. The SP of this copolymer is 9.70.
（共重合体(Ａ−４)の製造例）
前記共重合体(Ａ−１)の製造例の滴下溶液(ａ−１)に代えて、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸 １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ａ−４)を用いたこと以外は、共重合体(Ａ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応誘起性共重合体(Ａ−４)のキシレン液を製造した。この共重合体の重量平均分子量は、２００００であった。なお、この共重合体のＳＰは９．６４となる。
(Production example of copolymer (A-4))
Instead of the dropping solution (a-1) in the production example of the copolymer (A-1), 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 15 parts by weight of methacrylic acid, 100 parts by weight of xylene, t-butyl par Dilute with xylene in the same manner as in the production example of copolymer (A-1), except that the dropping solution (a-4) mixed with 5 parts by weight of oxy-2-ethylhexanoate was used. Thus, the solid content was adjusted to 30% to produce a xylene solution of a crosslinking reaction-inducing copolymer (A-4). The weight average molecular weight of this copolymer was 20000. Note that the SP of this copolymer is 9.64.
（共重合体(Ａ−５)の製造例）
前記共重合体(Ａ−１)の製造例の滴下溶液(ａ−１)に代えて、ラウリルメタクリレート ２８５重量部、グリシジルメタクリレート １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ａ−５)を用いたこと以外は、共重合体(Ａ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ａ−５)のキシレン液を製造した。この共重合体の重量平均分子量は、１８０００であった。なお、この共重合体のＳＰは９．１０となる。
(Production example of copolymer (A-5))
In place of the dropping solution (a-1) in the production example of the copolymer (A-1), 285 parts by weight of lauryl methacrylate, 15 parts by weight of glycidyl methacrylate, 100 parts by weight of xylene, t-butylperoxy-2-ethyl Except for using the dropping solution (a-5) mixed with 5 parts by weight of hexanoate, it was diluted with xylene in the same manner as in the production example of the copolymer (A-1) to obtain a solid content of 30. %, A xylene solution of a crosslinking reaction active copolymer (A-5) was produced. The weight average molecular weight of this copolymer was 18000. Note that the SP of this copolymer is 9.10.
（共重合体(Ａ−６)の製造例）
前記共重合体(Ａ−１)の製造例の滴下溶液(ａ−１)に代えて、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル ７．５重量部、２−ヒドロキシエチルメタクリレート ７．５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ａ−６)を用いたこと以外は、共重合体(Ａ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有する共重合体(Ａ−６)のキシレン液を製造した。この共重合体の重量平均分子量は、２２０００であった。なお、この共重合体のＳＰは９．６６となる。
(Production example of copolymer (A-6))
In place of the dropping solution (a-1) in the production example of the copolymer (A-1), 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 2- (O- [1′-methylpropylidene amino acid) ] A drop solution (a) in which 7.5 parts by weight of carboxyamino) ethyl, 7.5 parts by weight of 2-hydroxyethyl methacrylate, 100 parts by weight of xylene and 5 parts by weight of t-butylperoxy-2-ethylhexanoate are mixed. Except that -6) was used, the solid content was adjusted to 30% by diluting with xylene in the same manner as in the production example of the copolymer (A-1). A xylene solution of the copolymer (A-6) was prepared. The copolymer had a weight average molecular weight of 22,000. The copolymer has an SP of 9.66.
（共重合体(Ａ−７)の製造例）
前記共重合体(Ａ−１)の製造例の滴下溶液(ａ−１)に代えて、ラウリルメタクリレート １９５重量部、スチレン １０５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ａ−７)を用いたこと以外は、共重合体(Ａ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有しない共重合体(Ａ−７)のキシレン液を製造した。この共重合体の重量平均分子量は、２００００であった。なお、この共重合体のＳＰは９．５１となる。
(Production example of copolymer (A-7))
Instead of the dropping solution (a-1) in the production example of the copolymer (A-1), 195 parts by weight of lauryl methacrylate, 105 parts by weight of styrene, 100 parts by weight of xylene, t-butylperoxy-2-ethylhexa 30% solid content was obtained by diluting with xylene in the same manner as in the production example of copolymer (A-1) except that the dropping solution (a-7) mixed with 5 parts by weight of Noate was used. To prepare a xylene solution of a copolymer (A-7) having no cross-linking reaction activity and no cross-linking activity. The weight average molecular weight of this copolymer was 20000. The SP of this copolymer is 9.51.
（共重合体(Ａ−８)の製造例）
撹拌装置、還流冷却管、滴下ロート、温度計及び窒素ガス吹き込み口を備えた１０００ｍｌの反応容器に、キシレン３００重量部を仕込み、窒素ガスを導入しながら１２０℃に昇温した。そこへ、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト １５重量部が混合された滴下溶液(ａ−８)を滴下ロートにより、２時間で等速滴下した。滴下終了後、さらに１２０℃の温度を維持しつつ１時間反応させた。反応終了後、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ａ−８)を得た。この共重合体の重量平均分子量は、１８００であった。なお、この共重合体のＳＰは９．６２となる。
(Production example of copolymer (A-8))
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, 300 parts by weight of xylene was charged, and the temperature was raised to 120 ° C. while introducing nitrogen gas. There, 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 15 parts by weight of 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, 100 parts by weight of xylene, t-butylperoxy-2 -Ethylhexanoate A drop solution (a-8) mixed with 15 parts by weight was dropped at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the reaction was further continued for 1 hour while maintaining a temperature of 120 ° C. After completion of the reaction, the reaction mixture was diluted with xylene to adjust the solid content to 30% to obtain a crosslinking reaction active copolymer (A-8). The copolymer had a weight average molecular weight of 1800. The copolymer has an SP of 9.62.
（共重合体(Ａ−９)の製造例）
撹拌装置、還流冷却管、滴下ロート、温度計、及び窒素ガス吹き込み口を備えた１０００ｍｌの反応容器に、キシレン１００重量部を仕込み、窒素ガスを導入しながら８０℃に昇温した。そこへ、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル １５重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト５重量部が混合された滴下溶液（ａ−９）を滴下ロートにより、２時間で等速滴下した。滴下終了後、さらに８０℃の温度を維持しつつ６時間反応させた。反応終了後、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ａ−９)を得た。この共重合体の重量平均分子量は、２１５０００であった。なお、この共重合体のＳＰは９．６２となる。
(Production example of copolymer (A-9))
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas blowing port, 100 parts by weight of xylene was charged and heated to 80 ° C. while introducing nitrogen gas. There, 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 15 parts by weight of 2- (O- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, t-butylperoxy-2-ethylhexanoate The dropping solution (a-9) mixed with 5 parts by weight was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the reaction was further continued for 6 hours while maintaining the temperature of 80 ° C. After completion of the reaction, the reaction mixture was diluted with xylene to adjust the solid content to 30% to obtain a crosslinking reaction active copolymer (A-9). The copolymer had a weight average molecular weight of 215,000. The copolymer has an SP of 9.62.
（共重合体(Ａ−１０)の製造例）
前記共重合体(Ａ−８)の製造例の滴下溶液(ａ−８)に代えて、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル ７．５重量部、２−ヒドロキシエチルメタクリレート ７．５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト １５重量部が混合された滴下溶液(ａ−１０)を用いたこと以外は、共重合体(Ａ−８)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有する共重合体(Ａ−１０)のキシレン液を製造した。この共重合体の重量平均分子量は、１８００であった。なお、この共重合体のＳＰは９．６６となる。
(Production example of copolymer (A-10))
In place of the dropping solution (a-8) in the production example of the copolymer (A-8), 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 2- (O- [1′-methylpropylidene amino methacrylate) ] A drop solution (a) in which 7.5 parts by weight of carboxyamino) ethyl, 7.5 parts by weight of 2-hydroxyethyl methacrylate, 100 parts by weight of xylene and 15 parts by weight of t-butylperoxy-2-ethylhexanoate are mixed. Except for using -10), the solid content was adjusted to 30% by diluting with xylene in the same manner as in the production example of the copolymer (A-8), and the crosslinking reaction activity and crosslinking inductivity were adjusted. A xylene solution of the copolymer (A-10) was prepared. The copolymer had a weight average molecular weight of 1800. The copolymer has an SP of 9.66.
（共重合体(Ａ−１１)の製造例）
前記共重合体(Ａ−９)の製造例の滴下溶液(ａ−９)に代えて、ラウリルメタクリレート １８５重量部、スチレン １００重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル ７．５重量部、２−ヒドロキシエチルメタクリレート ７．５重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト５重量部が混合された滴下溶液(ａ−１１)を用いたこと以外は、共重合体(Ａ−９)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有する共重合体(Ａ−１１)のキシレン液を製造した。この共重合体の重量平均分子量は、２１００００であった。なお、この共重合体のＳＰは９．６６となる。
(Production example of copolymer (A-11))
In place of the dropping solution (a-9) in the production example of the copolymer (A-9), 185 parts by weight of lauryl methacrylate, 100 parts by weight of styrene, 2- (O- [1′-methylpropylideneamino) methacrylate ] A drop solution (a-11) in which 7.5 parts by weight of carboxyamino) ethyl, 7.5 parts by weight of 2-hydroxyethyl methacrylate, and 5 parts by weight of t-butylperoxy-2-ethylhexanoate were mixed was used. Except for the above, it was diluted with xylene to adjust the solid content to 30% by the same method as in the production example of the copolymer (A-9). A xylene solution of A-11) was produced. The copolymer had a weight average molecular weight of 210000. The copolymer has an SP of 9.66.
実施例１〜５及び比較例１〜１０は、共重合体(Ａ−１)〜(Ａ−１１)を用い、試験塗料として熱硬化被膜形成組成物であるアクリルメラミン硬化クリアー塗料を調製し、硬化させたものである。 Examples 1 to 5 and Comparative Examples 1 to 10 use copolymers (A-1) to (A-11) to prepare an acrylic melamine cured clear paint that is a thermosetting film forming composition as a test paint, It has been cured.
（実施例１〜５及び比較例１〜１０）
まず、焼き付け用アクリル樹脂であるアクリディックＡ−３４５（商品名；大日本インキ株式会社製）１００．０ｇ、ブチル化メラミン樹脂であるスーパーベッカミンＬ−１１７−６０（商品名；大日本インキ株式会社製）１１．５ｇ、メチル化メラミン樹脂であるスーパーベッカミンＬ−１０５−６０（商品名；大日本インキ株式会社製）１１．５ｇの混合物を、高速ディスパーにて、２０００ｒ.ｐ.ｍ.で３０分間混合した。
(Examples 1-5 and Comparative Examples 1-10)
First, ACRIDIC A-345 (trade name; manufactured by Dainippon Ink Co., Ltd.), which is an acrylic resin for baking, and Super Becamine L-117-60 (trade name; Dainippon Ink Co., Ltd.), a butylated melamine resin. 11.5 g of a product (manufactured by Dainippon Ink Co., Ltd.), 11.5 g of a methylated melamine resin, and 11.5 g of a methylated melamine resin, 2000 rpm in a high-speed disper. For 30 minutes.
それの１００ｇずつに、前記製造例で得た共重合体(Ａ−１)〜(Ａ−１１)のキシレン液の夫々を表面調整剤として、表１に示す配合で、固形分換算で０．５％となるように加えた。これらを各々高速ディスパーにて、２０００ｒｐｍで２分間攪拌混合した。各々に、希釈溶剤としてトルエン／ブタノール（重量比＝８／２）を４０ｇ加え均一に混合して、実施例１〜５及び比較例１〜１０のアクリルメラミン硬化クリアー塗料を調製した。 Each 100 g of the xylene liquids of the copolymers (A-1) to (A-11) obtained in the above production examples were used as surface conditioners, with the formulation shown in Table 1, and in terms of solid content. It was added to be 5%. These were each stirred and mixed with a high-speed disper at 2000 rpm for 2 minutes. To each, 40 g of toluene / butanol (weight ratio = 8/2) as a diluent solvent was added and mixed uniformly to prepare acrylic melamine cured clear paints of Examples 1 to 5 and Comparative Examples 1 to 10.
アクリルメラミン硬化クリアー塗料を２０００ｒｐｍで２分間混合し、直ちに一部を２５ｍｌの比重カップに流し込み、それを満たす塗料の重量を測定した。混合せずに半日静置させたアクリルメラミン硬化クリアー塗料を、空の比重カップに流し込み、それを満たす塗料の重量を測定した。静置後の重量を１００％としたとき、静置前の重量の比を百分率で示すことにより、消泡性を評価した。消泡性が悪いと気泡を巻き込み、比重の比が小さくなる。評価基準は、９７％以上を○、９７％未満９５％以上を△、９５％未満を×とした。その結果を表１に示す。 The acrylic melamine cured clear paint was mixed at 2000 rpm for 2 minutes, and a portion was immediately poured into a 25 ml specific gravity cup, and the weight of the paint that filled it was measured. The acrylic melamine-cured clear paint that was allowed to stand for half a day without mixing was poured into an empty specific gravity cup, and the weight of the paint that satisfied it was measured. When the weight after standing was set to 100%, the defoaming property was evaluated by showing the ratio of the weight before standing as a percentage. If the defoaming property is poor, bubbles are involved and the specific gravity ratio becomes small. The evaluation criteria were 97% or more for ◯, less than 97% for 95% or more for Δ, and less than 95% for x. The results are shown in Table 1.
アクリルメラミン硬化クリアー塗料の２５℃での粘度は、ＪＩＳ Ｋ−５４００−４．５．４に準じ、フォードカップＮｏ．４法により測定した。この測定方法は、一定のカップに、一定量の試料を満たし、一定の口径を持つ穴から流下させ、その流下時間を測定することによって、試料の流動性を評価するものである。このアクリルメラミン硬化クリアー塗料の溶液の流下時間は約１８秒であった。 The viscosity of the acrylic melamine cured clear paint at 25 ° C. is according to JIS K-5400-4.5.4, according to Ford Cup No. Measurement was performed by the four methods. This measuring method is to evaluate the fluidity of a sample by filling a certain cup with a certain amount of sample, flowing down from a hole having a certain diameter, and measuring the flowing time. The flow time of the acrylic melamine cured clear paint solution was about 18 seconds.
これを、口径１．０ｍｍで吐出圧３．５ｋｇ／ｃｍ２のエアスプレーにより、温度２５℃、湿度５０％の条件下、２０ｃｍ×３０ｃｍ×０．３ｍｍのアルミ板膜へ、厚さが段階的に変わるよう吹付け塗装した。塗装後、直ちに１５０℃熱風循環式焼付炉内にて２０分間焼き付けると、アルミ板表面に、硬化した塗装膜が形成された。 The thickness is stepped into an aluminum plate film of 20 cm x 30 cm x 0.3 mm under conditions of temperature 25 ° C and humidity 50% by air spraying with a diameter of 1.0 mm and discharge pressure of 3.5 kg / cm 2 Spray painted to change to. Immediately after coating, baking was performed in a 150 ° C. hot-air circulating baking oven for 20 minutes to form a cured coating film on the aluminum plate surface.
この塗装膜につき電磁式膜厚計（ケット科学研究所製；ケット電磁膜厚計ＬＥ−２００）を用いてワキが発生する最小の膜厚、すなわちワキ限界膜厚を計測した。 その結果を表１に示す。 For this coating film, an electromagnetic film thickness meter (manufactured by Kett Science Laboratory; Kett Electromagnetic Film Thickness Meter LE-200) was used to measure the minimum film thickness at which a crack occurred, that is, the crack limit film thickness. The results are shown in Table 1.
さらに、このアルミ板の表面を、ｎ−へキサンを染込ませたガーゼを用いて軽く拭いた。拭いた部分の白化性を目視にて観察し、耐揮発油性を評価した。評価基準は、全く白化しないものを○、やや白化するものを△、著しく白化するものを×とした。その結果を表１に示す。 Furthermore, the surface of this aluminum plate was lightly wiped using gauze infused with n-hexane. The whitening property of the wiped part was visually observed to evaluate the volatile oil resistance. The evaluation criteria were ◯ for those that were not whitened at all, Δ for those that were slightly whitened, and × that were markedly whitened. The results are shown in Table 1.
表１から明らかなように、実施例の表面調整剤を含む熱硬化被膜形成組成物は消泡性に優れ、それを硬化させた被膜はワキ防止性、耐揮発油性に優れている。なお、反応活性共重合体と架橋反応誘起性共重合体は、その重量％比が９５：５〜５：９５の範囲内で、ＳＰ差が０．５以内であると、耐揮発性が一層良い。一方、比較例のように、架橋反応活性官能基と架橋反応誘起性官能基との両方を含有しなかったり、重量平均分子量２０００〜２０００００から外れたりする共重合体を表面調整剤として含む熱硬化被膜形成組成物は消泡性が劣り、それを硬化させた被膜はワキ防止性、耐揮発油性が劣っている。 As is clear from Table 1, the thermosetting film-forming composition containing the surface conditioner of the example is excellent in antifoaming properties, and the film obtained by curing the composition is excellent in anti-flammability and volatile oil resistance. Note that the reaction-active copolymer and the cross-linking reaction-inducible copolymer have a higher volatility when the weight percentage ratio is within the range of 95: 5 to 5:95 and the SP difference is within 0.5. good. On the other hand, as in the comparative example, a thermosetting containing a copolymer that does not contain both a crosslinking reaction active functional group and a crosslinking reaction inducing functional group or deviates from a weight average molecular weight of 2000 to 200000 as a surface conditioner. The film-forming composition is inferior in antifoaming property, and the film obtained by curing the film-forming composition is inferior in anti-flammability and volatile oil resistance.
次に、本発明を適用する実施例６〜１０、及び本発明を適用外の比較例１１〜２０では、主に平滑剤として作用する表面調整剤を含む熱硬化被膜形成組成物であるポリエステルメラミンクリアー塗料を調製し硬化させ、被膜を形成させた例を示す。 Next, in Examples 6 to 10 to which the present invention is applied and Comparative Examples 11 to 20 to which the present invention is not applied, polyester melamine which is a thermosetting film forming composition containing a surface conditioner mainly acting as a smoothing agent An example in which a clear paint was prepared and cured to form a film is shown.
先ず、実施例６〜１０及び比較例１１〜２０で使用される表面調整剤の共重合性物質を構成する、架橋反応活性共重合体、架橋反応誘起性共重合体、または架橋反応活性と架橋誘起性とを有する共重合体を以下のようにして製造した。 First, a cross-linking reaction-active copolymer, a cross-linking reaction-inducing copolymer, or a cross-linking reaction activity and cross-linking, which constitute the copolymer of the surface conditioner used in Examples 6 to 10 and Comparative Examples 11 to 20 A copolymer having inductivity was produced as follows.
（共重合体(Ｂ−１)の製造例）
撹拌装置、還流冷却管、滴下ロート、温度計及び窒素ガス吹き込み口を備えた１０００ｍｌの反応容器に、キシレン１００重量部を仕込み、窒素ガスを導入しながら１１０℃に昇温した。そこへ、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−１)を、滴下ロートにより、２時間で等速滴下した。滴下終了後、１１０℃の温度を維持しつつ４時間反応させた。反応終了後、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ｂ−１)のキシレン液を製造した。この共重合体の重量平均分子量は１５０００であった。なお、この共重合体のＳＰは９．８８となる。
(Production example of copolymer (B-1))
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 100 parts by weight of xylene was charged, and the temperature was raised to 110 ° C. while introducing nitrogen gas. Thereto, 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, 100 parts by weight of xylene, t-butyl par The dropping solution (b-1) mixed with 5 parts by weight of oxy-2-ethylhexanoate was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropping, the reaction was carried out for 4 hours while maintaining a temperature of 110 ° C. After completion of the reaction, the reaction solution was diluted with xylene to adjust the solid content to 30%, and a xylene solution of a crosslinking reaction active copolymer (B-1) was produced. The weight average molecular weight of this copolymer was 15000. The SP of this copolymer is 9.88.
（共重合体(Ｂ−２)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、グリシジルメタクリレート１５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−２)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ｂ−２)のキシレン液を製造した。この共重合体の重量平均分子量は、１５０００であった。なお、この共重合体のＳＰは９．８４となる。
(Production example of copolymer (B-2))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of glycidyl methacrylate, 100 parts by weight of xylene, t- Butyl peroxy-2-ethylhexanoate In the same manner as in the production example of the copolymer (B-1) except that a dropping solution (b-2) mixed with 5 parts by weight was used, xylene was used. The solid content was adjusted to 30% by dilution, and a xylene solution of a crosslinking reaction active copolymer (B-2) was produced. The copolymer had a weight average molecular weight of 15000. The SP of this copolymer is 9.84.
（共重合体(Ｂ−３)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、２−ヒドロキシエチルメタクリレート１５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−３)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応誘起性共重合体(Ｂ−３)のキシレン液を製造した。この共重合体の重量平均分子量は、１５０００であった。なお、この共重合体のＳＰは９．９６となる。
(Production example of copolymer (B-3))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2-hydroxyethyl methacrylate, 100 parts by weight of xylene , T-butylperoxy-2-ethylhexanoate According to the same method as in the production example of copolymer (B-1), except that a dropping solution (b-3) mixed with 5 parts by weight was used. The solid content was adjusted to 30% by diluting with xylene to produce a xylene solution of a crosslinking reaction inducing copolymer (B-3). The copolymer had a weight average molecular weight of 15000. Note that the SP of this copolymer is 9.96.
（共重合体(Ｂ−４)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸１５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−４)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応誘起性共重合体(Ｂ−４)のキシレン液を製造した。この共重合体の重量平均分子量は、１５０００であった。なお、この共重合体のＳＰは９．９０となる。
(Production example of copolymer (B-4))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of methacrylic acid, 100 parts by weight of xylene, t- Butyl peroxy-2-ethylhexanoate In the same manner as in the production example of the copolymer (B-1) except that a dropping solution (b-4) mixed with 5 parts by weight was used, xylene was used. Dilution was performed to adjust the solid content to 30%, and a xylene solution of a crosslinking reaction-inducing copolymer (B-4) was produced. The copolymer had a weight average molecular weight of 15000. The copolymer has an SP of 9.90.
（共重合体(Ｂ−５)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、２−エチルヘキシルアクリレート ２８５重量部、グリシジルメタクリレート １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−５)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応誘起性共重合体(Ｂ−５)のキシレン液を製造した。この共重合体の重量平均分子量は、１３０００であった。なお、この共重合体のＳＰは９．３０となる。
(Production example of copolymer (B-5))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 285 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of glycidyl methacrylate, 100 parts by weight of xylene, t-butylperoxy-2- The solid content was diluted with xylene in the same manner as in the production example of the copolymer (B-1) except that the dropping solution (b-5) mixed with 5 parts by weight of ethylhexanoate was used. The xylene solution of the crosslink reaction inducing copolymer (B-5) was prepared by adjusting to 30%. The weight average molecular weight of this copolymer was 13000. In addition, SP of this copolymer is 9.30.
（共重合体(Ｂ−６)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチルグリシジルメタクリレート ７．５重量部、２−ヒドロキシエチルメタクリレート ７．５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−６)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有する共重合体(Ｂ−６)のキシレン液を製造した。この共重合体の重量平均分子量は、１５０００であった。なお、この共重合体のＳＰは９．９２となる。
(Production example of copolymer (B-6))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 2- (O- [1'-methylpropiyl methacrylate) Liden amino] carboxyamino) ethyl glycidyl methacrylate 7.5 parts by weight, 2-hydroxyethyl methacrylate 7.5 parts by weight, xylene 100 parts by weight, t-butylperoxy-2-ethylhexanoate 5 parts by weight were mixed. Except for using the dropping solution (b-6), the solid content was adjusted to 30% by diluting with xylene by the same method as in the production example of the copolymer (B-1), and the crosslinking reaction activity and crosslinking A xylene solution of a copolymer (B-6) having inductivity was produced. The copolymer had a weight average molecular weight of 15000. The SP of this copolymer is 9.92.
（共重合体(Ｂ−７)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、エチルアクリレート １７９重量部、２−エチルヘキシルアクリレート １２１重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−７)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有しない共重合体(Ｂ−７)のキシレン液を製造した。この共重合体の重量平均分子量は、１５０００であった。なお、この共重合体のＳＰは９．７８となる。
(Production example of copolymer (B-7))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 179 parts by weight of ethyl acrylate, 121 parts by weight of 2-ethylhexyl acrylate, 100 parts by weight of xylene, t-butylperoxy-2- The solid content was diluted with xylene in the same manner as in the production example of the copolymer (B-1) except that a dropping solution (b-7) mixed with 5 parts by weight of ethylhexanoate was used. Adjusted to 30%, a xylene solution of a copolymer (B-7) having no crosslinking reaction activity and no crosslinking induction was produced. The copolymer had a weight average molecular weight of 15000. Note that the SP of this copolymer is 9.78.
（共重合体(Ｂ−８)の製造例）
撹拌装置、還流冷却管、滴下ロート、温度計及び窒素ガス吹き込み口を備えた１０００ｍｌの反応容器に、キシレン３００重量部を仕込み、窒素ガスを導入しながら１２０℃に昇温した。そこへ、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト １５重量部が混合された滴下溶液(ｂ−８)を滴下ロートにより、２時間で等速滴下した。滴下終了後、さらに１２０℃の温度を維持しつつ１時間反応させた。反応終了後、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ｂ−８)を得た。この共重合体の重量平均分子量は、１８００であった。なお、この共重合体のＳＰは９．８８となる。
(Production example of copolymer (B-8))
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, 300 parts by weight of xylene was charged, and the temperature was raised to 120 ° C. while introducing nitrogen gas. Thereto, 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, 100 parts by weight of xylene, t-butyl par The dropping solution (b-8) mixed with 15 parts by weight of oxy-2-ethylhexanoate was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the reaction was further continued for 1 hour while maintaining a temperature of 120 ° C. After completion of the reaction, the reaction mixture was diluted with xylene to adjust the solid content to 30% to obtain a crosslinking reaction active copolymer (B-8). The copolymer had a weight average molecular weight of 1800. The SP of this copolymer is 9.88.
（共重合体(Ｂ−９)の製造例）
撹拌装置、還流冷却管、滴下ロート、温度計及び窒素ガス吹き込み口を備えた１０００ｍｌの反応容器に、キシレン１００重量部を仕込み、窒素ガスを導入しながら８０℃に昇温した。そこへ、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル １５重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト５重量部が混合された滴下溶液（ｂ−９）を滴下ロートにより、２時間で等速滴下した。滴下終了後、さらに８０℃の温度を維持しつつ９時間反応させた。反応終了後、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ｂ−９)を得た。この共重合体の重量平均分子量は、２２５０００であった。なお、この共重合体のＳＰは９．８８となる。
(Production example of copolymer (B-9))
In a 1000 ml reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, 100 parts by weight of xylene was charged, and the temperature was raised to 80 ° C. while introducing nitrogen gas. Thereto, 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2- (O- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate, t-butylperoxy-2-ethyl A dropping solution (b-9) mixed with 5 parts by weight of hexanoate was added dropwise at a constant rate over 2 hours using a dropping funnel. After completion of the dropwise addition, the reaction was further continued for 9 hours while maintaining a temperature of 80 ° C. After completion of the reaction, the reaction mixture was diluted with xylene to adjust the solid content to 30% to obtain a crosslinking reaction active copolymer (B-9). The copolymer had a weight average molecular weight of 225,000. The SP of this copolymer is 9.88.
（共重合体(Ｂ−１０)の製造例）
前記共重合体(Ｂ−８)の製造例の滴下溶液(ｂ−８)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル７．５重量部、２−ヒドロキシエチルメタクリレート ７．５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト １５重量部が混合された滴下溶液(ｂ−１０)を用いたこと以外は、共重合体(Ｂ−８)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有する共重合体(Ｂ−１０)のキシレン液を製造した。この共重合体の重量平均分子量は、１９００であった。なお、この共重合体のＳＰは９．９２となる。
(Production example of copolymer (B-10))
Instead of the dropping solution (b-8) in the production example of the copolymer (B-8), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 2- (O- [1′-methyl methacrylate) Propyridene amino] carboxyamino) ethyl 7.5 parts by weight, 2-hydroxyethyl methacrylate 7.5 parts by weight, xylene 100 parts by weight, t-butylperoxy-2-ethylhexanoate 15 parts by weight were mixed Except that the solution (b-10) was used, the solid content was adjusted to 30% by diluting with xylene by the same method as in the production example of the copolymer (B-8), and the crosslinking reaction activity and crosslinking induction A xylene solution of a copolymer (B-10) having properties was produced. The weight average molecular weight of this copolymer was 1900. The SP of this copolymer is 9.92.
（共重合体(Ｂ−１１)の製造例）
前記共重合体(Ｂ−９)の製造例の滴下溶液(ｂ−９)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−（Ｏ−［１′−メチルプロピリデン アミノ］カルボキシアミノ）エチル７．５重量部、２−ヒドロキシエチルメタクリレート ７．５重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト５重量部が混合された滴下溶液(ｂ−１１)を用いたこと以外は、共重合体(Ｂ−９)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性と架橋誘起性とを有する共重合体(Ｂ−１１)のキシレン液を製造した。この共重合体の重量平均分子量は、２０５０００であった。なお、この共重合体のＳＰは９．９２となる。
(Production example of copolymer (B-11))
Instead of the dropping solution (b-9) in the production example of the copolymer (B-9), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 2- (O- [1′-methyl methacrylate) Propylideneamino] carboxyamino) ethyl 7.5 parts by weight, 2-hydroxyethyl methacrylate 7.5 parts by weight, t-butylperoxy-2-ethylhexanoate 5 parts by weight mixed solution (b-11) In the same manner as in the production example of the copolymer (B-9), the solid content was adjusted to 30% by the same method as in the production example of the copolymer (B-9). A xylene solution of the polymer (B-11) was produced. The weight average molecular weight of this copolymer was 205000. The SP of this copolymer is 9.92.
実施例６〜１０及び比較例１１〜２０は、共重合体(Ｂ−１)〜(Ｂ−１１)を用い、試験塗料として熱硬化被膜形成組成物であるポリエステルメラミンクリアー塗料を調製し、硬化させたものである。 Examples 6 to 10 and Comparative Examples 11 to 20 use copolymers (B-1) to (B-11), prepare polyester melamine clear paints that are thermosetting film forming compositions as test paints, and cure. It has been made.
（実施例６〜１０及び比較例１１〜２０）
まず、高分子量オイルフリーポリエステル樹脂であるスーパーベッコライトＭ−６８０５−４０（商品名；大日本インキ株式会社製）４５．９重量部と、メチル化メラミン樹脂であるスーパーベッカミンＬ−１０５−６０の３．８重量部、ブチル化メラミン樹脂であるスーパーベッカミンＬ−１１７−６０の３．８重量部、及びシンナー（ソルベッソ１００/シクロヘキサノン/ｎ−ブタノール/ブチルセロソルブ＝６０/３０/５/５重量比）の２１．４重量部をラボディスパーで２０００ｒ.ｐ.ｍ.で３０分間撹拌し混合した。
(Examples 6 to 10 and Comparative Examples 11 to 20)
First, 45.9 parts by weight of Super Beckolite M-6805-40 (trade name; manufactured by Dainippon Ink Co., Ltd.), which is a high molecular weight oil-free polyester resin, and Super Becamine L-105-60, which is a methylated melamine resin. 3.8 parts by weight of Super Becamine L-117-60, which is a butylated melamine resin, and thinner (Solvesso 100 / cyclohexanone / n-butanol / butyl cellosolve = 60/30/5/5 weight) 21.4 parts by weight) was stirred and mixed with a lab disper at 2000 rpm for 30 minutes.
これに、前記製造例で得た共重合体(Ｂ−１)〜(Ｂ−１１)のキシレン液の夫々を表面調整剤として、表１に示す配合で、固形分換算で０．５％となるように加えた。これらを各々高速ディスパーにて、２０００ｒｐｍで２分間攪拌混合して、ポリエステルメラミンクリアー塗料を得た。 To this, each of the xylene solutions of the copolymers (B-1) to (B-11) obtained in the above production examples was used as a surface conditioner, and the formulation shown in Table 1 was 0.5% in terms of solid content. It was added to become. These were each stirred and mixed at 2000 rpm for 2 minutes with a high-speed disper to obtain a polyester melamine clear paint.
ポリエステルメラミンクリアー塗料の２５℃での粘度は、ＪＩＳ Ｋ−５４００−４．５．４に準じ、フォードカップＮｏ．４法により測定した。この測定方法は、一定溶液のカップに、一定量の試料を満たし、一定の口径を持つ穴から流下させ、その流下時間を測定することによって、試料の流動性を評価するものである。このポリエステルメラミンクリアー塗料の溶液の流下時間は約１００秒であった。 The viscosity of the polyester melamine clear paint at 25 ° C. is according to JIS K-5400-4.5.4, Ford Cup No. Measurement was performed by the four methods. In this measurement method, a fluid of a sample is evaluated by filling a certain amount of sample into a cup of a certain solution, flowing down from a hole having a certain diameter, and measuring the flowing time. The flow time of the polyester melamine clear coating solution was about 100 seconds.
ポリエステルメラミンクリアー塗料を調製後直ちに、＃２８バーコーターにより、２０ｃｍ×３０ｃｍ×０．３ｍｍのアルミ板上に塗布し、２１０℃で９０秒間焼き付けて硬化させ、被膜を形成させた。 Immediately after preparation of the polyester melamine clear coating, it was applied onto a 20 cm × 30 cm × 0.3 mm aluminum plate with a # 28 bar coater and baked at 210 ° C. for 90 seconds to be cured to form a film.
得られた被膜について、表面の平滑性を目視で評価した。評価基準は、バーコーター跡が無く平滑性が良好なものを○、バーコーター跡が僅かにあるものを△、バーコーター跡が認められ平滑性が悪いものを×とした。その結果を表２に示す。 About the obtained film, the smoothness of the surface was visually evaluated. Evaluation criteria were as follows: ◯ when there was no bar coater trace and good smoothness, Δ when there was a slight bar coater trace, and x when bar coater trace was observed and poor smoothness. The results are shown in Table 2.
さらに、このアルミ板の表面を、ｎ−へキサンを染込ませたガーゼを用いて軽く拭いた。拭いた部分の白化性を目視にて観察し、耐揮発油性を評価した。評価基準は、全く白化しないものを○、やや白化するものを△、著しく白化するものを×とした。その結果を表２に示す。 Furthermore, the surface of this aluminum plate was lightly wiped using gauze infused with n-hexane. The whitening property of the wiped part was visually observed to evaluate the volatile oil resistance. The evaluation criteria were ◯ for those that were not whitened at all, Δ for those that were slightly whitened, and × that were markedly whitened. The results are shown in Table 2.
表２から明らかなように、実施例の表面調整剤を含む熱硬化被膜形成組成物は平滑性に優れ、それを硬化させた被膜は耐揮発油性に優れている。なお、反応活性共重合体と架橋反応誘起性共重合体は、その重量％比が９５：５〜５：９５の範囲内で、ＳＰ差が０．５以内であると、耐揮発性が一層良い。一方、比較例のように、架橋反応活性官能基と架橋反応誘起性官能基との両方を含有しなかったり、重量平均分子量２０００〜２０００００から外れたりする共重合体を表面調整剤として含む熱硬化被膜形成組成物は平滑性が劣り、それを硬化させた被膜は耐揮発油性が劣っている。 As is clear from Table 2, the thermosetting film-forming composition containing the surface conditioner of the example is excellent in smoothness, and the film obtained by curing the composition is excellent in volatile oil resistance. Note that the reaction-active copolymer and the cross-linking reaction-inducible copolymer have a higher volatility when the weight percentage ratio is within the range of 95: 5 to 5:95 and the SP difference is within 0.5. good. On the other hand, as in the comparative example, a thermosetting containing a copolymer that does not contain both a crosslinking reaction active functional group and a crosslinking reaction inducing functional group or deviates from a weight average molecular weight of 2000 to 200000 as a surface conditioner. The film-forming composition has poor smoothness, and the film obtained by curing the film-forming composition has poor resistance to volatile oil.
次に、本発明を適用する実施例１１、及び本発明を適用外の比較例２１〜２３では、主に平滑剤として作用する表面調整剤を含む熱硬化被膜形成組成物である２液型アクリルウレタンクリアー塗料を調製し硬化させて、被膜を形成させた例を示す。 Next, in Example 11 to which the present invention is applied and Comparative Examples 21 to 23 to which the present invention is not applied, a two-component acrylic that is a thermosetting film forming composition containing a surface conditioner mainly acting as a smoothing agent An example in which a urethane clear paint is prepared and cured to form a coating film is shown.
先ず、実施例１１及び比較例２３で使用される表面調整剤の共重合性物質を構成する、架橋反応活性共重合体を以下のようにして製造した。 First, a cross-linking reaction active copolymer constituting the copolymer of the surface conditioner used in Example 11 and Comparative Example 23 was produced as follows.
（共重合体(Ｂ−１２)の製造例）
共重合体(Ｂ−１)の製造例の滴下溶液(ｂ−１)に代えて、エチルアクリレート １７０重量部、２−エチルヘキシルアクリレート １１５重量部、メタクリル酸２−イソイアナトエチル １５重量部、キシレン １００重量部、ｔ−ブチルパーオキシ−２−エチルヘキサノエイト ５重量部が混合された滴下溶液(ｂ−１２)を用いたこと以外は、共重合体(Ｂ−１)の製造例と同様の方法により、キシレンで希釈して固形分を３０％に調整し、架橋反応活性共重合体(Ｂ−１２)のキシレン液を製造した。この共重合体の重量平均分子量は、１５０００であった。なお、この共重合体のＳＰは９．８１となる。
(Production example of copolymer (B-12))
Instead of the dropping solution (b-1) in the production example of the copolymer (B-1), 170 parts by weight of ethyl acrylate, 115 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of 2-isoianatoethyl methacrylate, xylene The same as the production example of the copolymer (B-1) except that a dropping solution (b-12) in which 100 parts by weight and 5 parts by weight of t-butylperoxy-2-ethylhexanoate were mixed was used. By this method, the solid content was adjusted to 30% by diluting with xylene to produce a xylene solution of a crosslinking reaction active copolymer (B-12). The copolymer had a weight average molecular weight of 15000. Note that the SP of this copolymer is 9.81.
実施例１１及び比較例２１〜２３は、共重合体(Ｂ−３)及び(Ｂ−１２)を用い、試験塗料として熱硬化被膜形成組成物である２液型アクリルウレタンクリアー塗料を調製し、硬化させたものである。 Example 11 and Comparative Examples 21 to 23 use the copolymers (B-3) and (B-12) to prepare a two-component acrylic urethane clear paint that is a thermosetting film forming composition as a test paint, It has been cured.
（実施例１１及び比較例２１〜２３）
アクリルポリオールであるアクリディックА−８０１（商品名；大日本インキ株式会社製）４００重量部と、シンナー（キシレン/酢酸ブチル＝５０/５０重量比）５００重量部と、上記の合計９００重量部に対し、前記の製造例で得た共重合体(Ｂ−３)及び(Ｂ−１２)のキシレン液を固形分換算で、表３に記載の所定量添加し、ラボディスパーで２０００ｒｐｍで２分間撹拌した。
(Example 11 and Comparative Examples 21 to 23)
Acrylic polyol ACRIDIC А-801 (trade name; manufactured by Dainippon Ink Co., Ltd.) 400 parts by weight, thinner (xylene / butyl acetate = 50/50 weight ratio) 500 parts by weight, and the above total 900 parts by weight On the other hand, the xylene solutions of the copolymers (B-3) and (B-12) obtained in the above production examples were added in predetermined amounts as shown in Table 3 in terms of solid content, and stirred at 2000 rpm with a lab disper for 2 minutes. did.
その後、デスモジュールＮ−７５（商品名；バイエル製）１００重量部を加え、２０００ｒ.ｐ.ｍ.で１分間撹拌し２液型アクリルウレタンクリアー塗料を得た。 Thereafter, 100 parts by weight of Desmodur N-75 (trade name; manufactured by Bayer) was added and stirred at 2000 rpm for 1 minute to obtain a two-component acrylic urethane clear paint.
２液型アクリルウレタンクリアー塗料の２５℃での粘度は、ＪＩＳ Ｋ−５４００−４．５．４に準じ、フォードカップＮｏ．４法により測定した。この測定方法は、一定のカップに、一定量の試料を満たし、一定の口径を持つ穴から流下させ、その流下時間を測定することによって、試料の流動性を評価するものである。この２液型アクリルウレタンクリアー塗料の溶液の流下時間は約１４秒であった。 The viscosity of the two-component acrylic urethane clear paint at 25 ° C. is according to JIS K-5400-4.5.4, Ford Cup No. Measurement was performed by the four methods. This measuring method is to evaluate the fluidity of a sample by filling a certain cup with a certain amount of sample, flowing down from a hole having a certain diameter, and measuring the flowing time. The flowing time of the solution of this two-component acrylic urethane clear paint was about 14 seconds.
２液型アクリルウレタンクリアー塗料を、口径１．０ｍｍで吐出圧３．５ｋｇ／ｃｍ２のエアスプレーにより、温度２５℃、湿度５０％の条件下、２０ｃｍ×３０ｃｍ×０．３ｍｍのアルミ板に硬化後の膜厚が２５〜３０μｍとなるように塗装後、直ちに８０℃熱風循環式焼付炉内にて２０分間焼き付けると、アルミ板表面に、硬化した塗装膜が形成された。 Curing the two-part acrylic urethane clear paint, by an air spray discharge pressure 3.5 kg / cm 2 in diameter 1.0 mm, temperature of 25 ° C., 50% humidity conditions, an aluminum plate of 20 cm × 30 cm × 0.3 mm Immediately after coating so that the subsequent film thickness was 25 to 30 μm, baking was performed in an 80 ° C. hot-air circulating baking oven for 20 minutes, a cured coating film was formed on the aluminum plate surface.
得られた被膜について、表面の平滑性を目視で評価した。評価基準は、平滑性が良好なものを○、平滑性がやや劣るものを△、平滑性が悪いものを×とした。その結果を表３に示す。 About the obtained film, the smoothness of the surface was visually evaluated. The evaluation criteria were ◯ for smoothness, △ for slightly inferior smoothness, and x for poor smoothness. The results are shown in Table 3.
さらに、このアルミ板の表面を、ｎ−へキサンを染込ませたガーゼを用いて軽く拭いた。拭いた部分の白化性を目視にて観察し、耐揮発油性を評価した。評価基準は、全く白化しないものを○、やや白化するものを△、著しく白化するものを×とした。その結果を表３に示す。 Furthermore, the surface of this aluminum plate was lightly wiped using gauze infused with n-hexane. The whitening property of the wiped part was visually observed to evaluate the volatile oil resistance. The evaluation criteria were ◯ for those that were not whitened at all, Δ for those that were slightly whitened, and × that were markedly whitened. The results are shown in Table 3.
表３から明らかなように、実施例の表面調整剤を含む熱硬化被膜形成組成物は平滑性に優れ、それを硬化させた被膜は耐揮発油性に優れている。一方、比較例のように、架橋反応活性官能基と架橋反応誘起性官能基との両方を含有しない共重合体を表面調整剤として含む熱硬化被膜形成組成物を硬化させた被膜は、耐揮発油性が劣っている。 As is clear from Table 3, the thermosetting film-forming composition containing the surface conditioner of the example is excellent in smoothness, and the film obtained by curing the composition is excellent in volatile oil resistance. On the other hand, as in the comparative example, a film obtained by curing a thermosetting film-forming composition containing a copolymer that does not contain both a crosslinking reaction-active functional group and a crosslinking reaction-inducing functional group as a surface conditioner is resistant to volatilization. Oiliness is inferior.
本発明の熱硬化被膜形成組成物用の表面調整剤は、家電製品のハウジングのようなプラスチック部材、金属やコンクリートのような建材、自動車等のボディー、塗装後に切断加工するプレコートメタル等の表面を被覆する被膜を、熱硬化によって形成する組成物に、添加して使用される。 The surface conditioner for the thermosetting film-forming composition of the present invention can be applied to the surface of a plastic member such as a housing of home appliances, a building material such as metal or concrete, a body such as an automobile, and a pre-coated metal that is cut after coating. The coating film to be coated is used by being added to a composition formed by heat curing.
Claims (7)
カルボキシル基と、エポキシ基、水酸基、アミノ基、またはイソシアネート基とであり、
無水ジカルボン酸基と、アミノ基、水酸基、またはメラミン基とであり、
エポキシ基と、カルボキシル基、水酸基、またはアミノ基とであり、
イソシアネート基と、カルボキシル基、水酸基、またはアミノ基とであり、
または
メラミン基と、メラミン基、または水酸基とであることを特徴とする請求項１に記載の表面調整剤。 Each of the crosslinking reaction-active functional group and the crosslinking reaction-inducing functional group is
A carboxyl group and an epoxy group, a hydroxyl group, an amino group, or an isocyanate group,
A dicarboxylic anhydride group and an amino group, a hydroxyl group, or a melamine group,
An epoxy group and a carboxyl group, a hydroxyl group, or an amino group,
An isocyanate group, a carboxyl group, a hydroxyl group, or an amino group,
Or
The surface conditioning agent according to claim 1, which is a melamine group, a melamine group, or a hydroxyl group .
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