JP2022109477A - Primer coating composition - Google Patents
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- JP2022109477A JP2022109477A JP2021004805A JP2021004805A JP2022109477A JP 2022109477 A JP2022109477 A JP 2022109477A JP 2021004805 A JP2021004805 A JP 2021004805A JP 2021004805 A JP2021004805 A JP 2021004805A JP 2022109477 A JP2022109477 A JP 2022109477A
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- 239000002987 primer (paints) Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 239000000049 pigment Substances 0.000 claims abstract description 58
- 239000003822 epoxy resin Substances 0.000 claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 45
- 229910052623 talc Inorganic materials 0.000 claims abstract description 39
- 239000010459 dolomite Substances 0.000 claims abstract description 38
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 38
- 239000000454 talc Substances 0.000 claims abstract description 36
- 239000004606 Fillers/Extenders Substances 0.000 claims abstract description 32
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims description 23
- 239000003973 paint Substances 0.000 claims description 6
- 239000013522 chelant Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 18
- 239000004918 carbon fiber reinforced polymer Substances 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 10
- 239000008199 coating composition Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- -1 aliphatic amines Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本開示は、プライマー塗料組成物に関する。 The present disclosure relates to primer coating compositions.
エポキシ樹脂をベースとした塗料組成物において、タルク又はドロマイトなどの体質顔料を使用した塗料組成物が提案されている（例えば、特許文献１，２を参照。）。 Among epoxy resin-based coating compositions, coating compositions using extender pigments such as talc and dolomite have been proposed (see, for example, Patent Documents 1 and 2).
炭素繊維強化プラスチック（ＣＦＲＰ）成形品はその素材特性から繊維による凹凸が成形品の表面に存在するため、ＣＦＲＰ成形品への塗装では、成形品表面の凹凸が塗装後にピンホールと呼ばれる不具合が残り、手作業でパテ埋めをするなど工程数が増加する問題があった。そこで、ＣＦＲＰ成形品の表面に下塗りを施してから、上塗りを施すことが行われる場合がある。下塗りを施す場合、下塗り組成物は、基材との密着性及び上塗り組成物との密着性の双方に優れることが重要である。特許文献１、２の塗料組成物は、鉄鋼などの防食を目的としており、ＣＦＲＰ成形品に対する塗装における上記問題を解決する手段について何ら開示されていない。また、体質顔料の使用について、タルク及びドロマイトを併用する具体的な形態は開示されていない。 Carbon fiber reinforced plastic (CFRP) molded products have unevenness due to fibers on the surface of the molded product due to its material characteristics. , there was a problem that the number of processes increased, such as filling with putty manually. Therefore, in some cases, the surface of a CFRP molded product is first coated with a primer and then topcoated. When applying an undercoat, it is important that the undercoat composition has excellent adhesion to both the substrate and the topcoat composition. The coating compositions of Patent Documents 1 and 2 are intended to prevent corrosion of steel and the like, and do not disclose any means for solving the above problems in coating CFRP molded articles. In addition, regarding the use of extender pigments, no specific form of using talc and dolomite in combination is disclosed.
本開示は、特にＣＦＲＰ基材との密着性及び上塗り組成物との密着性の双方に優れるプライマー塗料組成物を提供することを目的とする。 An object of the present disclosure is to provide a primer coating composition that is particularly excellent in both adhesion to a CFRP substrate and adhesion to a topcoat composition.
本発明に係るプライマー塗料組成物は、主剤と硬化剤とを含有する２液系のプライマー塗料組成物において、前記主剤が、ビスフェノールＡ型エポキシ樹脂を変性させた変性ビスフェノールＡ型エポキシ樹脂とキレート変性エポキシ樹脂とを含有し、前記主剤若しくは前記硬化剤のいずれか一方又は両方は、顔料として少なくとも体質顔料を含有し、該体質顔料は少なくともタルクとドロマイトとであることを特徴とする。 The primer coating composition according to the present invention is a two-component primer coating composition containing a main agent and a curing agent, wherein the main agent is a modified bisphenol A epoxy resin obtained by modifying a bisphenol A epoxy resin and a chelate-modified Either or both of the main agent and the curing agent contain at least an extender pigment as a pigment, and the extender pigment is at least talc and dolomite.
本発明に係るプライマー塗料組成物では、前記変性ビスフェノールＡ型エポキシ樹脂の重量平均分子量が１００００～５００００であることが好ましい。ＣＦＲＰ材との密着性をより高めることができる。 In the primer coating composition according to the present invention, the modified bisphenol A type epoxy resin preferably has a weight average molecular weight of 10,000 to 50,000. Adhesion to the CFRP material can be further enhanced.
本発明に係るプライマー塗料組成物では、前記タルクの含有量に対する前記ドロマイトの含有量の割合は、５０～８００質量％であることが好ましい。上塗り層との密着性をより高めることができる。 In the primer coating composition according to the present invention, the ratio of the dolomite content to the talc content is preferably 50 to 800% by mass. Adhesion to the topcoat layer can be further enhanced.
本発明に係るプライマー塗料組成物では、前記主剤若しくは前記硬化剤のいずれか一方又は両方は、前記顔料として着色顔料を更に含有することが好ましい。意匠性を付与することができる。 In the primer coating composition according to the present invention, it is preferable that one or both of the main agent and the curing agent further contain a coloring pigment as the pigment. Designability can be imparted.
本発明に係るプライマー塗料組成物では、前記顔料の合計含有量に対する前記体質顔料の合計含有量の割合は、１５～１００質量％であることが好ましい。基材との密着性及び上塗り層との密着性の双方をより高めることができる。 In the primer coating composition according to the present invention, the ratio of the total content of the extender pigments to the total content of the pigments is preferably 15 to 100% by mass. Both adhesion to the base material and adhesion to the topcoat layer can be enhanced.
本発明に係るプライマー塗料組成物では、前記プライマー塗料組成物の固形分濃度は、３５～６０質量％であることが好ましい。厚塗り塗装が可能となり、ＣＦＲＰ成形品の繊維による凹凸をより効率的に埋めて平滑な塗装面を得ることができる。 In the primer coating composition according to the present invention, the solid content concentration of the primer coating composition is preferably 35 to 60% by mass. Thick coating is possible, and unevenness caused by fibers of CFRP molded products can be filled more efficiently to obtain a smooth coated surface.
本発明に係るプライマー塗料組成物では、前記変性ビスフェノールＡ型エポキシ樹脂の含有量に対する前記キレート変性エポキシ樹脂の含有量の割合は、２０～１００質量％であることが好ましい。基材との密着性及び上塗り層との密着性の双方をより高めることができる。 In the primer coating composition according to the present invention, the ratio of the content of the chelate-modified epoxy resin to the content of the modified bisphenol A epoxy resin is preferably 20 to 100% by mass. Both adhesion to the base material and adhesion to the topcoat layer can be enhanced.
本開示によれば、特にＣＦＲＰ基材との密着性及び上塗り組成物との密着性の双方に優れるプライマー塗料組成物を提供することができる。 According to the present disclosure, it is possible to provide a primer coating composition that is particularly excellent in both adhesion to a CFRP substrate and adhesion to a topcoat composition.
以下、本発明の一態様を説明する。以下に説明する実施形態は本発明の実施例であり、本発明は、以下の実施形態に制限されるものではない。本発明の効果を奏する限り、種々の形態変更をしてもよい。 One embodiment of the present invention is described below. The embodiments described below are examples of the present invention, and the present invention is not limited to the following embodiments. Various modifications may be made as long as the effects of the present invention are achieved.
本実施形態に係るプライマー塗料組成物は、主剤と硬化剤とを含有する２液系のプライマー塗料組成物において、主剤が、ビスフェノールＡ型エポキシ樹脂を変性させた変性ビスフェノールＡ型エポキシ樹脂とキレート変性エポキシ樹脂とを含有し、主剤若しくは硬化剤のいずれか一方又は両方は、顔料として少なくとも体質顔料を含有し、体質顔料は少なくともタルクとドロマイトである。 The primer coating composition according to the present embodiment is a two-component primer coating composition containing a main agent and a curing agent, wherein the main agent is a modified bisphenol A epoxy resin obtained by modifying a bisphenol A epoxy resin and a chelate-modified Either or both of the main agent and the curing agent contain at least an extender pigment as a pigment, and the extender pigment is at least talc and dolomite.
プライマー塗料組成物は、基材の表面上に塗布される下塗り塗料組成物である。 A primer coating composition is a base coating composition that is applied onto the surface of a substrate.
本実施形態では、プライマー塗料組成物に、ベースとなる樹脂として変性ビスフェノールＡ型エポキシ樹脂及びキレート変性エポキシ樹脂の２種類のエポキシ樹脂を併用することで、基材との密着性を確保している。 In this embodiment, two types of epoxy resins, a modified bisphenol A type epoxy resin and a chelate-modified epoxy resin, are used together as base resins in the primer coating composition to ensure adhesion to the substrate. .
変性ビスフェノールＡ型エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂を、変性剤を用いて高分子量化するとともに官能基を付与して高機能化した樹脂であることが好ましい。このような樹脂としては、例えば、ＫＡ－１４３９Ａ（荒川化学工業社製）、アミン変性タイプを用いることができる。 The modified bisphenol A type epoxy resin is preferably a resin obtained by increasing the molecular weight of the bisphenol A type epoxy resin using a modifier and imparting a functional group to the resin to make it highly functional. As such a resin, for example, KA-1439A (manufactured by Arakawa Chemical Industries, Ltd.), amine-modified type can be used.
本実施形態に係るプライマー塗料組成物では、変性ビスフェノールＡ型エポキシ樹脂の重量平均分子量が１００００～５００００であることが好ましく、１５０００～３００００であることがより好ましい。変性ビスフェノールＡ型エポキシ樹脂の重量平均分子量が１００００未満では、基材との密着性が不足する場合がある。変性ビスフェノールＡ型エポキシ樹脂の重量平均分子量が５００００を超えると、塗料粘度が高くなりすぎて塗装作業性が低下する場合がある。 In the primer coating composition according to this embodiment, the weight average molecular weight of the modified bisphenol A type epoxy resin is preferably 10,000 to 50,000, more preferably 15,000 to 30,000. If the weight average molecular weight of the modified bisphenol A type epoxy resin is less than 10,000, the adhesion to the substrate may be insufficient. If the weight-average molecular weight of the modified bisphenol A type epoxy resin exceeds 50,000, the viscosity of the coating becomes too high, which may reduce the workability of the coating.
キレート変性エポキシ樹脂は、分子内にキレートで変性された官能基を有するエポキシ樹脂である。このような樹脂としては、例えば、アデカレジンＥＰ－４９－１０Ｎ（ＡＤＥＫＡ社製）を用いることができる。 A chelate-modified epoxy resin is an epoxy resin having a chelate-modified functional group in the molecule. As such a resin, for example, ADEKA RESIN EP-49-10N (manufactured by ADEKA) can be used.
本実施形態に係るプライマー塗料組成物では、変性ビスフェノールＡ型エポキシ樹脂の含有量に対するキレート変性エポキシ樹脂の含有量の割合は、２０～１００質量％であることが好ましく、３０～８０質量％であることがより好ましい。キレート変性エポキシ樹脂の含有量の割合が２０質量％未満では、耐水性が劣る場合がある。キレート変性エポキシ樹脂の含有量の割合が１００質量％を超えると、密着性が劣る場合がある。 In the primer coating composition according to the present embodiment, the ratio of the content of the chelate-modified epoxy resin to the content of the modified bisphenol A epoxy resin is preferably 20 to 100% by mass, more preferably 30 to 80% by mass. is more preferable. If the content of the chelate-modified epoxy resin is less than 20% by mass, the water resistance may be poor. If the content of the chelate-modified epoxy resin exceeds 100% by mass, adhesion may be poor.
硬化剤は、キレート変性エポキシ樹脂と反応・硬化する成分であり、例えば、アミン系硬化剤又はイソシアネート系硬化剤である。アミン系硬化剤は、例えば、脂肪族アミン、ポリエーテルアミン、脂環式アミン又は芳香族アミンである。イソシアネート系硬化剤は、例えば、２，４‐トリレンジイソシアネート、ジフェニルメタン‐４，４’‐ジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、リジンメチルエステルジイソシアネート、メチルシクロヘキシルジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ｎ‐ペンタン‐１，４‐ジイソシアネート、トリレンジイソシアネート又はジフェニルメタンジイソシアネートである。このうち、硬化剤は、硬化速度が速い点で、アミン系硬化剤であることがより好ましい。 The curing agent is a component that reacts and cures with the chelate-modified epoxy resin, and is, for example, an amine-based curing agent or an isocyanate-based curing agent. Amine-based curing agents are, for example, aliphatic amines, polyetheramines, cycloaliphatic amines or aromatic amines. Isocyanate-based curing agents include, for example, 2,4-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, tolylene diisocyanate or diphenylmethane diisocyanate. Among these, the curing agent is more preferably an amine-based curing agent because of its high curing speed.
硬化剤がアミン系硬化剤である場合、主剤と硬化剤との配合割合は、キレート変性エポキシ基のエポキシ基に対して、アミン系硬化剤のアミノ基の活性水素が０．５～２．０モル当量となる量であることが好ましく、０．８～１．２モル当量となる量であることがより好ましい。０．５モル当量未満では、耐水性が不足する場合がある。２．０モル当量を超えると、鉛筆硬度が不足する場合がある。 When the curing agent is an amine-based curing agent, the mixing ratio of the main agent and the curing agent is such that the active hydrogen of the amino group of the amine-based curing agent is 0.5 to 2.0 with respect to the epoxy group of the chelate-modified epoxy group. It is preferably an amount that provides a molar equivalent, and more preferably an amount that provides 0.8 to 1.2 molar equivalents. If the amount is less than 0.5 molar equivalents, water resistance may be insufficient. If it exceeds 2.0 molar equivalents, the pencil hardness may be insufficient.
体質顔料は、主剤のみに含有されることが好ましい。体質顔料とは、白色又は無色の顔料であって、塗膜の強度などを補強する顔料である。本実施形態では、体質顔料は、少なくともタルクとドロマイトとである。本実施形態では、体質顔料としてタルク及びドロマイトの２種類を併用することで、基材への密着性及び上塗り層への密着性の両方を満たすことができる。 The extender pigment is preferably contained only in the main agent. Extender pigments are white or colorless pigments that reinforce the strength of coating films. In this embodiment, the extender pigment is at least talc and dolomite. In this embodiment, by using both talc and dolomite as extender pigments, both adhesion to the base material and adhesion to the topcoat layer can be satisfied.
タルクは、鱗片形状をしており、プライマー塗料組成物の硬化物である塗膜の面内方向に対する膜強度を補強し、硬化時の効果収縮を緩和することができる。このため、基材との密着性を向上する役割をもつ。タルクの粒径は、０．５～３０μｍであることが好ましく、２～１５μｍであることがより好ましい。このような範囲とすることで基材との密着性をより高めることができる。 Talc has a scaly shape, and can reinforce the film strength in the in-plane direction of the coating film, which is the cured product of the primer coating composition, and can alleviate effective shrinkage during curing. Therefore, it has the role of improving the adhesion to the substrate. The particle size of talc is preferably 0.5 to 30 μm, more preferably 2 to 15 μm. Adhesion to the base material can be further enhanced by setting it to such a range.
ドロマイトは、粒形状をしている。タルクのような鱗片形状の顔料は、塗膜表面に配向した場合、上塗り層との密着性が低下するおそれがある。そこで、ドロマイトのような粒形状の顔料と組み合わせて配合することで、上塗り層との密着性を向上することができる。ドロマイトの粒径は、０．１～１０μｍであることが好ましく、１～５μｍであることがより好ましい。このような範囲とすることで、上塗り層との密着性をより高めることができる。 Dolomite has a granular shape. When scaly pigments such as talc are oriented on the coating film surface, there is a possibility that the adhesion to the topcoat layer is lowered. Therefore, by blending with a granular pigment such as dolomite, the adhesion to the topcoat layer can be improved. The particle size of dolomite is preferably 0.1 to 10 μm, more preferably 1 to 5 μm. By setting it as such a range, the adhesiveness with a topcoat can be improved more.
本実施形態に係るプライマー塗料組成物では、タルクの含有量に対するドロマイトの含有量の割合は、５０～８００質量％であることが好ましく、８０～４００質量％であることがより好ましく、１００～３００質量％であることが更に好ましい。ドロマイトの含有量の割合が５０質量％未満では、上塗り層との密着性が不足する場合がある。ドロマイトの含有量の割合が８００質量％を超えると、基材との密着性が低下する場合がある。 In the primer coating composition according to the present embodiment, the ratio of the dolomite content to the talc content is preferably 50 to 800% by mass, more preferably 80 to 400% by mass, and 100 to 300% by mass. % by mass is more preferred. If the content of dolomite is less than 50% by mass, the adhesion to the topcoat layer may be insufficient. If the content of dolomite exceeds 800% by mass, the adhesion to the substrate may deteriorate.
主剤又は硬化剤は、本発明の効果を損なわない限りにおいて、希釈溶媒などの溶媒、又は耐候剤、レベリング剤、消泡剤、増粘剤、つや消し剤、スリップ剤、無機フィラー、光輝材、可塑剤、分散剤、乳化剤、流動調整剤、紫外線吸収剤若しくは光安定剤などの各種助剤を含有してもよい。また、主剤は、本発明の効果を損なわない限りにおいて、タルク及びドロマイト以外のその他の体質顔料を含有していてもよい。その他の体質顔料の含有量は、タルク及びドロマイトの合計含有量に対して、２５０質量％以下であることが好ましく、１２０質量％以下であることがより好ましい。 The main agent or curing agent is a solvent such as a diluent solvent, or a weathering agent, leveling agent, antifoaming agent, thickener, matting agent, slip agent, inorganic filler, glittering agent, plasticizer, as long as it does not impair the effects of the present invention. It may contain various auxiliary agents such as agents, dispersants, emulsifiers, fluidity modifiers, ultraviolet absorbers or light stabilizers. In addition, the main agent may contain extender pigments other than talc and dolomite as long as they do not impair the effects of the present invention. The content of other extender pigments is preferably 250% by mass or less, more preferably 120% by mass or less, relative to the total content of talc and dolomite.
本実施形態に係るプライマー塗料組成物では、主剤は、顔料として着色顔料を更に含有することが好ましい。着色顔料は、主剤のみに含有されることが好ましい。着色顔料は、白色、黒色、青色、黄色又は赤色などの着色を目的として配合される顔料であればよく、その種類は特に限定されない。プライマー塗料組成物が着色顔料を含有することで、プライマー塗料組成物の硬化膜がカラー層となり、ＣＦＲＰの有する強度などの物性を活かした自動車のボディーなどの多岐にわたる用途に適用できる。 In the primer paint composition according to this embodiment, the main agent preferably further contains a color pigment as a pigment. Color pigments are preferably contained only in the main agent. The coloring pigment is not particularly limited as long as it is a pigment blended for the purpose of coloring such as white, black, blue, yellow, or red. By containing a coloring pigment in the primer coating composition, the cured film of the primer coating composition becomes a color layer, and can be applied to a wide variety of applications such as automobile bodies that take advantage of physical properties such as strength of CFRP.
本実施形態に係るプライマー塗料組成物では、顔料の合計含有量に対する体質顔料の合計含有量の割合は、１５～１００質量％であることが好ましく、２０～８０質量％であることがより好ましく、３０～７０質量％であることが更に好ましい。体質顔料の合計含有量の割合が１５質量％未満では、基材との密着性及び上塗り層との密着性が不足する場合がある。顔料の合計含有量は、例えば、体質顔料の合計含有量と着色顔料の合計含有量との和である。体質顔料の合計含有量は、例えば、タルクの含有量とドロマイトの含有量との和であるか、又はタルクの含有量とドロマイトの含有量とタルク及びドロマイト以外の体質顔料の含有量との和である。 In the primer coating composition according to the present embodiment, the ratio of the total content of the extender pigment to the total content of the pigment is preferably 15 to 100% by mass, more preferably 20 to 80% by mass. More preferably, it is 30 to 70% by mass. If the total content of the extender pigment is less than 15% by mass, the adhesion to the substrate and the adhesion to the topcoat layer may be insufficient. The total content of pigments is, for example, the sum of the total content of extender pigments and the total content of color pigments. The total content of the extender is, for example, the sum of the talc content and the dolomite content, or the sum of the talc content, the dolomite content, and the content of extender pigments other than talc and dolomite. is.
本実施形態に係るプライマー塗料組成物では、プライマー塗料組成物の固形分濃度は、３５～６０質量％であることが好ましく、４０～５８質量％であることがより好ましく、４５～５５質量％であることが更に好ましい。ここで、プライマー塗料組成物の固形分濃度は、塗装時における塗料組成物の固形分濃度である。このように、プライマー塗料組成物をハイソリッド化することで、厚塗り塗装が可能となり、ＣＦＲＰ成形品の繊維による凹凸をより効率的に埋めて平滑な塗装面を得ることができる。固形分が高くなると一般的に高粘度となり、塗料の流動性を確保しにくくなるが、本実施形態では、主樹脂であるエポキシ樹脂の分子量を適度に調整することで、塗料の流動性を確保することができる。 In the primer coating composition according to the present embodiment, the solid content concentration of the primer coating composition is preferably 35 to 60% by mass, more preferably 40 to 58% by mass, and 45 to 55% by mass. It is even more preferable to have Here, the solid content concentration of the primer coating composition is the solid content concentration of the coating composition at the time of coating. In this way, by making the primer coating composition high-solid, thick coating becomes possible, and unevenness caused by the fibers of the CFRP molded product can be filled more efficiently to obtain a smooth coated surface. When the solid content increases, the viscosity generally increases, making it difficult to ensure the fluidity of the paint. can do.
本実施形態に係る塗装品は、炭素繊維強化プラスチック製又は金属製の基材と、基材の表面上に設けられた塗膜と、を備える塗装品において、塗膜は、基材の表面上に設けられたプライマー層とプライマー層の表面上に設けられた上塗り層とを有し、プライマー層は、本実施形態に係るプライマー塗料組成物の硬化物からなることが好ましい。 The coated article according to the present embodiment includes a substrate made of carbon fiber reinforced plastic or metal, and a coating film provided on the surface of the substrate, wherein the coating film is on the surface of the substrate and a topcoat layer provided on the surface of the primer layer, and the primer layer preferably comprises a cured product of the primer coating composition according to the present embodiment.
基材は、ＣＦＲＰ製の部材であることが好ましい。基材の種類は特に限定されないが、例えば、自動車の外装などの自動車部品を構成する部材、又はラケット若しくは釣り竿などのレジャー用品を構成する部材である。また、基材は、金属製の部材であってもよい。 The base material is preferably a member made of CFRP. The type of base material is not particularly limited, but it is, for example, a member that constitutes an automobile part such as an automobile exterior, or a member that constitutes leisure goods such as a racket or a fishing rod. Also, the substrate may be a member made of metal.
プライマー層は、本実施形態に係るプライマー塗料組成物の硬化物からなり、膜状をなす。この硬化物は、主剤のキレート変性エポキシ樹脂と硬化剤とが反応・硬化することによって形成されたエポキシ系樹脂からなる。プライマー層は、着色顔料を含有するカラー層であってもよい。 The primer layer is made of a cured product of the primer coating composition according to the present embodiment and has a film shape. This cured product is composed of an epoxy resin formed by reacting and curing a chelate-modified epoxy resin as a main agent and a curing agent. The primer layer may be a color layer containing color pigments.
プライマー層の形成では、主剤と硬化剤とを所定の割合で混合し、必要に応じて希釈溶媒で適度な固形分濃度に調整した本実施形態に係るプライマー塗料組成物を、基材の表面上に塗布・乾燥して硬化膜を形成する。塗布方法は、公知の塗布方法を採用でき、例えば、ロールコート法、スプレー法、ディップ法又ははけ塗り法である。希釈溶媒は、特に限定されず、例えば、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒、酢酸エチル、酢酸ノルマルブチルなどのエステル系溶媒、トルエン、キシレンなどの炭化水素系溶媒、ノルマルブタノール、イソブタノールなどのアルコール類である。 In the formation of the primer layer, the main agent and the curing agent are mixed in a predetermined ratio, and the primer coating composition according to the present embodiment, which is adjusted to an appropriate solid content concentration with a diluent solvent as necessary, is applied on the surface of the substrate. and dried to form a cured film. A known coating method can be used as the coating method, and examples thereof include a roll coating method, a spray method, a dipping method, and a brush coating method. The diluent solvent is not particularly limited, and examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and normal butyl acetate, hydrocarbon solvents such as toluene and xylene, normal butanol and isobutanol. of alcohol.
プライマー層の厚さは、特に限定されないが、２５～６０μｍであることが好ましく、３０～５０μｍであることがより好ましい。このような範囲とすることで、基材の表面の繊維による凹凸を埋めて、平滑な表面を得ることができる。プライマー層を所望の厚さとするために、複数回の塗装を行ってもよい。 Although the thickness of the primer layer is not particularly limited, it is preferably 25 to 60 μm, more preferably 30 to 50 μm. With such a range, unevenness caused by the fibers on the surface of the base material can be filled, and a smooth surface can be obtained. Multiple coats may be applied to achieve the desired thickness of the primer layer.
本実施形態に係る塗装品では、塗膜は、プライマー層の表面上に設けられた上塗り層を更に有することが好ましい。 In the coated article according to the present embodiment, the coating preferably further has a topcoat layer provided on the surface of the primer layer.
上塗り層の材質は特に限定されず、例えば、エポキシ系樹脂、アクリル系樹脂、アクリルウレタン系樹脂又はアクリルシリコン系樹脂である。上塗り層は、クリア層であるか、又はカラー層であってもよい。また、上塗り層がカラー層であることで、ＣＦＲＰの有する強度などの物性を活かした自動車のボディーなどの多岐にわたる用途に適用できる。 The material of the overcoat layer is not particularly limited, and examples thereof include epoxy-based resin, acrylic-based resin, acrylic-urethane-based resin, and acrylic-silicon-based resin. The overcoat layer may be a clear layer or a color layer. In addition, since the topcoat layer is a color layer, it can be applied to a wide variety of applications, such as automobile bodies, taking advantage of the strength and other physical properties of CFRP.
上塗り層の形成は、適度な固形分濃度に調整した上塗り層形成用塗料組成物を、プライマー層の形成と同様の方法で形成することができる。上塗り層の厚さは、特に限定されず、例えば、１０～４０μｍであることが好ましく、１５～３０μｍであることがより好ましい。 The topcoat layer can be formed by using a coating composition for forming a topcoat layer adjusted to an appropriate solid content concentration in the same manner as in the formation of the primer layer. The thickness of the overcoat layer is not particularly limited, and is preferably 10 to 40 μm, more preferably 15 to 30 μm.
以下、実施例に基づき本発明をさらに詳細に説明するが、本発明は、かかる実施例に何ら限定されるものではない。 EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
（実施例１）
主剤として、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１４３９Ａ、荒川化学工業社製；重量平均分子量３５０００、固形分濃度４０質量％）を２５質量部と、キレート変性エポキシ樹脂（アデカレジンＥＰ－４９－１０Ｎ、ＡＤＥＫＡ社製；固形分濃度１００質量％）を８質量部と、体質顔料として、タルク（ミクロエースＰ－２、日本タルク社製；粒径７μｍ）を６質量部とドロマイト（マイクロドール＃１、ＯＭＹＡ社製；粒径１～５μｍ）を６質量部と、着色顔料として酸化チタン（タイオキサイドＴＲ－９２、ＨＵＮＴＳＭＡＮ社製）を２０質量部と、分散剤（ＢＹＫ－１１１、ＢＹＫ社製）を０．５質量部と、沈降防止剤としてアマイド（Ａ－Ｓ－Ａ ＴＳ８１３、伊藤製油社製）を３質量部と、酢酸ブチルを１０．５質量部と、ｎ－ブタノールを１０．５質量部と、プロピレングリコールモノメチルエーテルアセテートを１０．４５質量部と、レベリング剤（シリコン系表面調整剤ＢＹＫ－３０２、ＢＹＫ社製）を０．０５質量部とを配合した。得られた主剤１００質量部に対して、硬化剤としてアミン系硬化剤（１，３－ＢＡＣ、三菱ガス化学社製）を５質量部と、シンナー（オリジンシンナーＭＧ－３、オリジン社製）を３０質量部とを配合して、プライマー塗料組成物を得た。このプライマー塗料組成物の固形分濃度は、４１．３質量％であった。
(Example 1)
As the main agent, 25 parts by mass of a modified bisphenol A type epoxy resin (Arakid KA-1439A, manufactured by Arakawa Chemical Industries; weight average molecular weight 35000, solid content concentration 40% by mass), and a chelate modified epoxy resin (ADEKA RESIN EP-49-10N , manufactured by ADEKA; solid content concentration 100% by mass) and 8 parts by mass of talc (Micro Ace P-2, manufactured by Nippon Talc Co., Ltd.; particle size 7 μm) as an extender pigment and dolomite (Microdol #1 , manufactured by OMYA; particle size 1 to 5 μm), 20 parts by mass of titanium oxide (Tioxide TR-92, manufactured by HUNTSMAN) as a coloring pigment, and a dispersant (BYK-111, manufactured by BYK). 0.5 parts by mass, 3 parts by mass of amide (ASA TS813, manufactured by Ito Oil Co., Ltd.) as an anti-settling agent, 10.5 parts by mass of butyl acetate, and 10.5 parts by mass of n-butanol 10.45 parts by mass of propylene glycol monomethyl ether acetate and 0.05 parts by mass of a leveling agent (silicon-based surface conditioner BYK-302, manufactured by BYK). 5 parts by mass of an amine curing agent (1,3-BAC, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and a thinner (Origin Thinner MG-3, manufactured by Origin Co., Ltd.) are added to 100 parts by mass of the obtained main agent. 30 parts by mass were mixed to obtain a primer coating composition. The solid content concentration of this primer coating composition was 41.3% by mass.
（実施例２）
主剤において、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１４３９Ａ、荒川化学工業社製；重量平均分子量３５０００、固形分濃度４０質量％）を、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１５５０、荒川化学工業社製；重量平均分子量１４０００、固形分濃度４０質量％）に変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 2)
In the main agent, modified bisphenol A type epoxy resin (Arakid KA-1439A, manufactured by Arakawa Chemical Industries; weight average molecular weight 35000, solid content concentration 40% by mass), modified bisphenol A type epoxy resin (Arakied KA-1550, Arakawa Chemical Industries) A primer coating composition was obtained in the same manner as in Example 1, except that the primer was changed to 14000 (weight average molecular weight, 40 mass% solid content).
（実施例３）
主剤において、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１４３９Ａ、荒川化学工業社製；重量平均分子量３５０００、固形分濃度４０質量％）を、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１４５６Ｌ、荒川化学工業社製；重量平均分子量５００００、固形分濃度４０質量％）に変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 3)
In the main agent, modified bisphenol A type epoxy resin (Arakid KA-1439A, manufactured by Arakawa Chemical Industries; weight average molecular weight 35000, solid content concentration 40% by mass), modified bisphenol A type epoxy resin (Arakied KA-1456L, Arakawa Chemical Industries) A primer coating composition was obtained in the same manner as in Example 1, except that the primer was changed to 50,000 (weight average molecular weight, 40 mass% solid content).
（実施例４）
酸化チタンの配合割合を１７質量部とし、体質顔料の配合割合を、タルク（ミクロエースＰ－２、日本タルク社製；粒径７μｍ）を１０質量部とドロマイト（マイクロドール＃１、ＯＭＹＡ社製；粒径１～５μｍ）を５質量部とに変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 4)
The blending ratio of titanium oxide is 17 parts by mass, and the blending ratio of the extender pigment is 10 parts by mass of talc (Micro Ace P-2, manufactured by Nippon Talc Co., Ltd.; particle size 7 μm) and dolomite (Microdol #1, manufactured by OMYA). A primer coating composition was obtained in the same manner as in Example 1, except that the particle diameter of 1 to 5 μm) was changed to 5 parts by mass.
（実施例５）
酸化チタンの配合割合を９質量部とし、体質顔料の配合割合を、タルク（ミクロエースＰ－２、日本タルク社製；粒径７μｍ）を３質量部とドロマイト（マイクロドール＃１、ＯＭＹＡ社製；粒径１～５μｍ）を２０質量部とに変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 5)
The blending ratio of titanium oxide is 9 parts by mass, and the blending ratio of the extender pigment is 3 parts by mass of talc (Micro Ace P-2, manufactured by Nippon Talc; particle size 7 μm) and dolomite (Microdol #1, manufactured by OMYA). A primer coating composition was obtained in the same manner as in Example 1, except that the particle diameter of 1 to 5 μm) was changed to 20 parts by mass.
（実施例６）
酸化チタンの配合割合を２６質量部とし、体質顔料の配合割合を、タルク（ミクロエースＰ－２、日本タルク社製；粒径７μｍ）を３質量部とドロマイト（マイクロドール＃１、ＯＭＹＡ社製；粒径１～５μｍ）を３質量部とに変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 6)
The blending ratio of titanium oxide is 26 parts by mass, and the blending ratio of the extender pigment is 3 parts by mass of talc (Micro Ace P-2, manufactured by Nippon Talc; particle size 7 μm) and dolomite (Microdol #1, manufactured by OMYA). A primer coating composition was obtained in the same manner as in Example 1, except that the particle diameter of 1 to 5 μm) was changed to 3 parts by mass.
（実施例７）
着色顔料（酸化チタン）の含有量を０質量部とし、体質顔料の配合割合をタルク（ミクロエースＰ－２、日本タルク社製；粒径７μｍ）を１５質量部とドロマイト（マイクロドール＃１、ＯＭＹＡ社製；粒径１～５μｍ）を１５質量部とに変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 7)
The content of the coloring pigment (titanium oxide) is 0 parts by mass, and the blending ratio of the extender pigment is 15 parts by mass of talc (Micro Ace P-2, manufactured by Nippon Talc Co., Ltd.; particle size 7 μm) and dolomite (Microdol #1, A primer coating composition was obtained in the same manner as in Example 1, except that OMYA;
（実施例８）
シンナーの配合量を５０質量部に変更し、固形分濃度を３６質量％とした以外は、実施例１と同様にして塗装品を得た。
(Example 8)
A coated article was obtained in the same manner as in Example 1, except that the amount of the thinner was changed to 50 parts by mass and the solid content concentration was changed to 36% by mass.
（実施例９）
シンナーの配合量を２０質量部に変更し、固形分濃度を４４．６質量％とした以外は、実施例１と同様にして塗装品を得た。
(Example 9)
A coated product was obtained in the same manner as in Example 1, except that the amount of the thinner was changed to 20 parts by mass and the solid content concentration was changed to 44.6 mass %.
（実施例１０）
エポキシ樹脂の配合割合を、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１４３９Ａ、荒川化学工業社製；重量平均分子量３００００、固形分濃度４０質量％）を３６質量部と、キレート変性エポキシ樹脂（アデカレジンＥＰ－４９－１０Ｎ、ＡＤＥＫＡ社製；固形分濃度１００質量％）を４質量部とに変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 10)
The blending ratio of the epoxy resin is 36 parts by mass of modified bisphenol A type epoxy resin (Arakid KA-1439A, manufactured by Arakawa Chemical Industries; weight average molecular weight 30000, solid content concentration 40% by mass) and chelate modified epoxy resin (ADEKA RESIN EP -49-10N, manufactured by ADEKA; solid content concentration 100% by mass) was changed to 4 parts by mass to obtain a primer coating composition in the same manner as in Example 1.
（実施例１１）
エポキシ樹脂の配合割合を、変性ビスフェノールＡ型エポキシ樹脂（アラキードＫＡ－１４３９Ａ、荒川化学工業社製；重量平均分子量３００００、固形分濃度４０質量％）を２５質量部と、キレート変性エポキシ樹脂（アデカレジンＥＰ－４９－１０Ｎ、ＡＤＥＫＡ社製；固形分濃度１００質量％）を１０質量部とに変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Example 11)
The blending ratio of the epoxy resin is 25 parts by mass of modified bisphenol A type epoxy resin (Arakid KA-1439A, manufactured by Arakawa Chemical Industries; weight average molecular weight 30000, solid content concentration 40% by mass) and chelate modified epoxy resin (ADEKA RESIN EP -49-10N, manufactured by ADEKA; solid content concentration 100% by mass) was changed to 10 parts by mass to obtain a primer coating composition in the same manner as in Example 1.
（比較例１）
実施例１において、キレート変性エポキシ樹脂（アデカレジンＥＰ－４９－１０Ｎ、ＡＤＥＫＡ社製；固形分濃度１００質量％）の配合量を２０質量部、硬化剤の配合量を１２．５質量部とし、変性ビスフェノールＡ型エポキシ樹脂を配合しなかったこと以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Comparative example 1)
In Example 1, the amount of the chelate-modified epoxy resin (ADEKA RESIN EP-49-10N, manufactured by ADEKA; solid content concentration 100% by mass) was 20 parts by mass, and the amount of the curing agent was 12.5 parts by mass. A primer coating composition was obtained in the same manner as in Example 1, except that the bisphenol A type epoxy resin was not blended.
（比較例２）
実施例１において、タルクをドロマイトに代えることでドロマイトの配合量を１２質量部、タルクの配合量を０質量部に変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Comparative example 2)
A primer coating composition was obtained in the same manner as in Example 1 except that the amount of dolomite was changed to 12 parts by mass and the amount of talc was changed to 0 parts by mass by replacing talc with dolomite.
（比較例３）
実施例１において、ドロマイトをタルクに代えることでタルクの配合量を１２質量部、ドロマイトの配合量を０質量部に変更した以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Comparative Example 3)
A primer coating composition was obtained in the same manner as in Example 1, except that dolomite was replaced with talc so that the amount of talc was changed to 12 parts by mass and the amount of dolomite was changed to 0 parts by mass.
（比較例４）
実施例１において、タルク及びドロマイトを配合しなかった以外は、実施例１と同様にしてプライマー塗料組成物を得た。
(Comparative Example 4)
A primer coating composition was obtained in the same manner as in Example 1, except that talc and dolomite were not blended.
実施例及び比較例のプライマー塗料組成物を、ＣＦＲＰ製基材（チャレンヂ社製、縦１０ｍｍ、横１０ｍｍ、厚さ１ｍｍ）の表面上にスプレー塗装し、８０℃で３０分間乾燥させて、厚さ３０μｍのプライマー層を形成した。次に、プライマー層の表面上に、上塗り層用塗料組成物をスプレー塗装し、８０℃で３０分間乾燥させて、厚さ２５μｍの上塗り層を形成し、各実施例及び各比較例の塗装品を得た。 The primer coating compositions of Examples and Comparative Examples were spray-coated on the surface of a CFRP substrate (manufactured by Challenge Co., 10 mm long, 10 mm wide, 1 mm thick) and dried at 80° C. for 30 minutes to obtain a thickness of A primer layer of 30 μm was formed. Next, the topcoat layer coating composition is spray-coated on the surface of the primer layer and dried at 80° C. for 30 minutes to form a topcoat layer having a thickness of 25 μm. got
得られた各実施例及び各比較例の塗装品について次の評価を行った。プライマー塗料組成物の組成を表１に示す。表１において「キレート変性エポキシ樹脂の含有率」は、変性ビスフェノールＡ型エポキシ樹脂の含有量に対するキレート変性エポキシ樹脂の含有量の割合であり、「ドロマイトの含有率」はタルクの含有量に対するドロマイトの含有量の割合であり、「体質顔料の合計含有率」は、顔料の合計含有量に対する体質顔料の合計量の割合である。評価結果を表２に示す。 The following evaluations were performed on the obtained coated products of each example and each comparative example. Table 1 shows the composition of the primer coating composition. In Table 1, "content of chelate-modified epoxy resin" is the ratio of the content of chelate-modified epoxy resin to the content of modified bisphenol A epoxy resin, and "content of dolomite" is the content of dolomite to the content of talc. It is a content ratio, and the "total content of extender pigments" is the ratio of the total amount of extender pigments to the total content of pigments. Table 2 shows the evaluation results.
（密着性）
ＪＩＳ Ｋ５６００－５－６：１９９９「クロスカット法」に準じて、２ｍｍ×２ｍｍの碁盤目状の切込みを１００個入れ、粘着テープによる剥離試験を行った。評価基準についても同規格に準じて評価を行った。
○：剥離なし（実用レベル）。
×：１升以上の剥離（実用不適）。
(Adhesion)
According to JIS K5600-5-6:1999 "cross-cut method", 100 grid-like incisions of 2 mm x 2 mm were made, and a peeling test was performed using an adhesive tape. Evaluation criteria were also evaluated according to the same standard.
◯: No peeling (practical level).
x: Peeling of 1 square or more (unsuitable for practical use).
（上塗り性）
塗膜を形成した部材に対し、２液型アクリルウレタン系塗料（製品名：オリジプレートＺ）を塗装し、８０℃３０分で乾燥させた後、塗膜の付着性を評価した。評価基準は次のとおりである。
○：剥離なし（実用レベル）。
△：剥離はしないが外観異常あり（実用不適）。
×：剥離する（実用不適）
(Overcoating property)
A two-liquid acrylic urethane paint (product name: Origiplate Z) was applied to the member on which the coating film was formed, and after drying at 80°C for 30 minutes, the adhesion of the coating film was evaluated. Evaluation criteria are as follows.
◯: No peeling (practical level).
Δ: No peeling, but abnormal appearance (unsuitable for practical use).
×: peeled off (unsuitable for practical use)
（耐湿性）
塗膜を形成した部材を５０℃９５％ＲＨの耐湿試験機に２４０時間放置した後、試験機から取り出して、塗膜の付着性を評価した。評価基準は次のとおりである。
○：剥離なし（実用レベル）。
△：剥離はしないが外観異常あり（実用不適）。
×：剥離する（実用不適）
(moisture resistance)
The member on which the coating film was formed was left in a moisture resistance tester at 50° C. and 95% RH for 240 hours, and then removed from the tester to evaluate the adhesion of the coating film. Evaluation criteria are as follows.
◯: No peeling (practical level).
Δ: No peeling, but abnormal appearance (unsuitable for practical use).
×: peeled off (unsuitable for practical use)
（耐水性）
塗膜を形成した部材を４０℃の温水に３６０時間浸漬させた後、温水から取り出して、表面の温水をふき取り、塗膜の付着性を評価した。評価基準は次のとおりである。
○：剥離なし（実用レベル）。
△：剥離はしないが外観異常あり（実用不適）。
×：剥離する（実用不適）。
(water resistant)
After the member with the coating film formed thereon was immersed in warm water of 40° C. for 360 hours, it was taken out from the warm water, and the hot water on the surface was wiped off to evaluate the adhesion of the coating film. Evaluation criteria are as follows.
◯: No peeling (practical level).
Δ: No peeling, but abnormal appearance (unsuitable for practical use).
x: Peeled off (unsuitable for practical use).
（耐熱性）
塗膜を形成した部材を８０℃の恒温槽に７２時間放置した後、試験機から取り出して、外観について評価した。評価基準は次のとおりである。
○：外観異常なし（実用レベル）。
×：外観異常あり（実用不適）。
(Heat-resistant)
After the member on which the coating film was formed was left in a constant temperature bath at 80° C. for 72 hours, it was taken out from the tester and evaluated for appearance. Evaluation criteria are as follows.
◯: No abnormality in appearance (practical level).
x: Appearance abnormal (unsuitable for practical use).
本発明に係るプライマー塗料組成物は、主剤と硬化剤とを含有する２液系のプライマー塗料組成物において、前記主剤が、ビスフェノールＡ型エポキシ樹脂を変性させた変性ビスフェノールＡ型エポキシ樹脂とキレート変性エポキシ樹脂とを含有し、前記主剤若しくは前記硬化剤のいずれか一方又は両方は、顔料として少なくとも体質顔料を含有し、該体質顔料は少なくともタルクとドロマイトとであり、前記タルクは、形状が鱗片形状であり、かつ、粒径が０．５～３０μｍであり、前記ドロマイトは、形状が粒形状であり、かつ、粒径が０．１～１０μｍであり、前記タルクの含有量に対する前記ドロマイトの含有量の割合は、５０～８００質量％であることを特徴とする。タルクの含有量に対するドロマイトの含有量の割合を５０～８００質量％とすることで、上塗り層との密着性をより高めることができる。 The primer coating composition according to the present invention is a two-component primer coating composition containing a main agent and a curing agent, wherein the main agent is a modified bisphenol A epoxy resin obtained by modifying a bisphenol A epoxy resin and a chelate-modified Either one or both of the main agent and the curing agent contain at least an extender pigment as a pigment, the extender pigment being at least talc and dolomite, and the talc having a scale-like shape. The dolomite has a shape and a particle size of 0.5 to 30 μm, the dolomite has a particle shape and a particle size of 0.1 to 10 μm, and the dolomite content with respect to the talc content The content ratio is characterized by being 50 to 800% by mass . By setting the ratio of the content of dolomite to the content of talc to 50 to 800% by mass, the adhesion to the topcoat layer can be further enhanced.
本発明に係るプライマー塗料組成物では、前記変性ビスフェノールＡ型エポキシ樹脂の含有量に対する前記キレート変性エポキシ樹脂の含有量の割合は、２０～１００質量％であることが好ましい。基材との密着性及び上塗り層との密着性の双方をより高めることができる。本発明に係るプライマー塗料組成物は、基材として炭素繊維強化プラスチック製の部材の表面上に塗布される下塗り塗料組成物であって、前記基材の表面の繊維による凹凸を埋めて平滑な表面を得るための塗料であることが好ましい。 In the primer coating composition according to the present invention, the ratio of the content of the chelate-modified epoxy resin to the content of the modified bisphenol A epoxy resin is preferably 20 to 100% by mass. Both adhesion to the base material and adhesion to the topcoat layer can be enhanced. The primer coating composition according to the present invention is an undercoat coating composition that is applied on the surface of a member made of carbon fiber reinforced plastic as a substrate, and fills the irregularities due to the fibers on the surface of the substrate to make the surface smooth. It is preferable that it is a paint for obtaining.
Claims (7)
前記主剤が、ビスフェノールＡ型エポキシ樹脂を変性させた変性ビスフェノールＡ型エポキシ樹脂とキレート変性エポキシ樹脂とを含有し、
前記主剤若しくは前記硬化剤のいずれか一方又は両方は、顔料として少なくとも体質顔料を含有し、該体質顔料は少なくともタルクとドロマイトとであることを特徴とするプライマー塗料組成物。 In a two-component primer paint composition containing a main agent and a curing agent,
The main agent contains a modified bisphenol A type epoxy resin obtained by modifying a bisphenol A type epoxy resin and a chelate modified epoxy resin,
A primer coating composition, wherein either or both of the main agent and the curing agent contain at least an extender pigment as a pigment, and the extender pigment is at least talc and dolomite.
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