JP2011021152A - Active energy ray-curable coating composition and heat-resistant brightness part - Google Patents
Active energy ray-curable coating composition and heat-resistant brightness part Download PDFInfo
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- JP2011021152A JP2011021152A JP2009169153A JP2009169153A JP2011021152A JP 2011021152 A JP2011021152 A JP 2011021152A JP 2009169153 A JP2009169153 A JP 2009169153A JP 2009169153 A JP2009169153 A JP 2009169153A JP 2011021152 A JP2011021152 A JP 2011021152A
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- meth
- coating composition
- active energy
- energy ray
- coating film
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Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、活性エネルギー線硬化型塗料組成物、および耐熱性光輝部品に関する。 The present invention relates to an active energy ray-curable coating composition and a heat-resistant bright part.
自動車部品などの基材の表面には、蒸着法等により金属薄膜が形成される。このような自動車部品において、特にヘッドランプレンズの反射鏡等には、優れた耐熱性が求められる。
近年、自動車部品に用いられる基材としては、ＢＭＣ（バルクモールディングコンパウンド）、ＰＰＳ（ポリフェニレンサルファイド）、ＡＬＤ（アルミダイキャスト）、ＰＢＴ（ポリブチレンテレフタレート）／ＰＥＴ（ポリエチレンテレフタレート）アロイ樹脂等の耐熱性材料（以下、「耐熱素材」という場合がある。）が用いられることがある。これら耐熱素材は軽量耐衝撃性に優れており、耐熱素材を基材として用いた自動車部品は、例えば反射鏡として好適である。
A metal thin film is formed on the surface of a substrate such as an automobile part by vapor deposition or the like. In such automotive parts, excellent heat resistance is required particularly for a reflector of a headlamp lens.
In recent years, as a base material used for automobile parts, heat resistance such as BMC (bulk molding compound), PPS (polyphenylene sulfide), ALD (aluminum die cast), PBT (polybutylene terephthalate) / PET (polyethylene terephthalate) alloy resin, etc. Materials (hereinafter sometimes referred to as “heat-resistant materials”) may be used. These heat-resistant materials are excellent in lightweight impact resistance, and automobile parts using the heat-resistant materials as base materials are suitable as, for example, reflecting mirrors.
しかし、このような耐熱素材からなる基材上に、アルミニウム等の金属を蒸着すると、得られる部品の表面平滑性が低下し、金属の光輝感が得られにくかった。特に、自動車反射鏡に用いる場合、反射鏡として必要な光学特性を確保することが困難であった。
そのため、金属薄膜を形成する前に、予め基材表面に下塗り塗料を塗布し硬化させて塗膜を形成することで、部品の表面の平滑性を維持し、光学特性を改善している。
However, when a metal such as aluminum is vapor-deposited on a base material made of such a heat-resistant material, the surface smoothness of the resulting component is lowered, and it is difficult to obtain a metallic glitter. In particular, when used in an automobile reflector, it has been difficult to ensure optical characteristics necessary for the reflector.
For this reason, before the metal thin film is formed, the surface of the part is maintained and the optical properties are improved by applying a primer coating on the surface of the base material and curing it in advance to form a coating film.
下塗り塗料としては、例えば特許文献１には、ジペンタエリスリトールの多官能アクリレートと、イソシアヌレート型ポリイソシアネートとを含有して成るＦＲＰ金属蒸着用紫外線硬化型下塗り液状組成物が開示されている。
また、特許文献２には、分子内に少なくとも２個の（メタ）アクリロイル基を有する化合物２０〜８０重量部と、油変性アルキド樹脂８０〜２０重量部と、増感剤２〜１５重量部を含有してなるＦＲＰ用金属蒸着用紫外線硬化型下塗り液状組成物が開示されている。
また、特許文献３には、マレイン酸、フタル酸、フマル酸、テトラヒドロフタル酸等で油変性された、酸価が２０〜８０ｍｇＫＯ／ｇである酸変性アルキド樹脂、分子内に少なくとも２個の（メタ）アクリロイル基を有する化合物、および光重合開始剤を含有してなる紫外線硬化型樹脂組成物が開示されている。
As an undercoat paint, for example, Patent Document 1 discloses an ultraviolet curable undercoat liquid composition for FRP metal deposition containing a polyfunctional acrylate of dipentaerythritol and an isocyanurate type polyisocyanate.
Patent Document 2 discloses that 20 to 80 parts by weight of a compound having at least two (meth) acryloyl groups in the molecule, 80 to 20 parts by weight of an oil-modified alkyd resin, and 2 to 15 parts by weight of a sensitizer. An ultraviolet curable undercoat liquid composition for metal vapor deposition for FRP is disclosed.
Patent Document 3 discloses an acid-modified alkyd resin having an acid value of 20 to 80 mg KO / g, which is oil-modified with maleic acid, phthalic acid, fumaric acid, tetrahydrophthalic acid, etc., and at least two ( An ultraviolet curable resin composition comprising a compound having a (meth) acryloyl group and a photopolymerization initiator is disclosed.
しかしながら、特許文献１に記載の下塗り塗料は２液型であるため、使用する前に主剤と硬化剤とを混合する必要があり、手間がかかりやすかった。また、主剤と硬化剤とを混合してから塗料を使用できるまでの使用可能時間（ポットライフ）が短く制限されやすかった。さらに、特許文献１に記載の下塗り塗料では、これより形成される塗膜と、基材との密着性を必ずしも満足することができなかった。加えて、塗膜の耐熱性が不十分であるため、耐熱性に優れた部品が得られにくかった。
特許文献２、３に記載の下塗り塗料は、１液型であるため２液型に比べてポットライフは制限されにくいものの、貯蔵安定性が低下しやすかった。また、特許文献２、３に記載の下塗り塗料では、基材の材質として一般的に用いられるＦＲＰ（繊維強化複合材料）に比べて、より高い耐熱性を有するＢＭＣやＰＰＳ等の耐熱素材からなる基材に適用する場合には、塗膜と基材との密着性や、塗膜の耐熱性を必ずしも満足することができなかった。
However, since the undercoat paint described in Patent Document 1 is a two-component type, it is necessary to mix the main agent and the curing agent before use, which is troublesome. In addition, the usable time (pot life) from mixing the main agent and the curing agent to the time when the paint can be used is short and easily limited. Further, the undercoat paint described in Patent Document 1 cannot always satisfy the adhesion between the coating film formed therefrom and the substrate. In addition, since the heat resistance of the coating film is insufficient, it is difficult to obtain a part having excellent heat resistance.
Since the undercoat paint described in Patent Documents 2 and 3 is a one-component type, the pot life is less restricted than the two-component type, but the storage stability is likely to be lowered. The undercoat paints described in Patent Documents 2 and 3 are made of a heat-resistant material such as BMC or PPS having higher heat resistance than FRP (fiber reinforced composite material) generally used as the material of the base material. When applied to a substrate, the adhesion between the coating film and the substrate and the heat resistance of the coating film could not always be satisfied.
本発明は上記事情を鑑みてなされたもので、ポットライフが制限されにくい１液型でありながら貯蔵安定性に優れ、かつ基材との密着性、および耐熱性に優れた塗膜を形成できる活性エネルギー線硬化型塗料組成物、および耐熱性光輝部品の提供を目的とする。 The present invention has been made in view of the above circumstances, and can form a coating film that is excellent in storage stability, adhesiveness to a substrate, and heat resistance while being a one-pack type in which pot life is hardly restricted. An object of the present invention is to provide an active energy ray-curable coating composition and a heat-resistant bright part.
本発明者らは鋭意検討した結果、下塗り塗料の成分として、特定のアクリル−スチレン共重合体と、特定の活性エネルギー線硬化性化合物を用い、かつ下塗り塗料のアミン価を規定することで、貯蔵安定性に優れ、基材との密着性、および耐熱性に優れた塗膜を形成できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the inventors of the present invention used a specific acrylic-styrene copolymer and a specific active energy ray-curable compound as components of the undercoating material, and specified the amine value of the undercoating material for storage. The inventors have found that a coating film excellent in stability, adhesion to a substrate, and heat resistance can be formed, and the present invention has been completed.
すなわち、本発明の活性エネルギー線硬化型塗料組成物は、塗膜形成成分と、光重合開始剤と、溶剤とを含む、金属薄膜の下塗り用の活性エネルギー線硬化型塗料組成物において、前記塗膜形成成分は、スチレン単量体、アルキロール（メタ）アクリルアミド単量体、および（メタ）アクリロイル単量体を含む単量体混合物を共重合して得られる、ガラス転移点が−６０〜２０℃である共重合体（Ａ）と、活性エネルギー線硬化性化合物（Ｂ）とを含有し、かつ前記塗膜形成成分は、アミン価が１５〜２００ｍｇＫＯＨ／ｇであることを特徴とする。
また、前記塗膜形成成分１００質量％中、前記共重合体（Ａ）の含有量が２０〜７５質量％、前記活性エネルギー線硬化性化合物（Ｂ）の含有量が２０〜７５質量％であることが好ましい。
さらに、前記塗膜形成成分は、アミノ基を有する化合物（Ｃ）をさらに含有することが好ましい。
また、前記（メタ）アクリロイル単量体が、アミノ基を有する（メタ）アクリロイル単量体を含むことが好ましい。
さらに、前記単量体混合物１００質量％中、スチレン単量体の含有量が５〜５０質量％、アルキロール（メタ）アクリルアミド単量体の含有量が２〜４０質量％であることが好ましい。
また、前記光重合開始剤の含有量が、前記活性エネルギー線硬化性化合物（Ｂ）１００質量部に対して、１〜２０質量部であることが好ましい。
That is, the active energy ray-curable coating composition of the present invention is the active energy ray-curable coating composition for undercoating a metal thin film comprising a coating film-forming component, a photopolymerization initiator, and a solvent. The film forming component has a glass transition point of -60 to 20 obtained by copolymerizing a monomer mixture containing a styrene monomer, an alkylol (meth) acrylamide monomer, and a (meth) acryloyl monomer. It contains a copolymer (A) at a temperature of C and an active energy ray-curable compound (B), and the coating film forming component has an amine value of 15 to 200 mgKOH / g.
Further, in 100% by mass of the coating film forming component, the content of the copolymer (A) is 20 to 75% by mass, and the content of the active energy ray-curable compound (B) is 20 to 75% by mass. It is preferable.
Furthermore, it is preferable that the coating film forming component further contains a compound (C) having an amino group.
Moreover, it is preferable that the said (meth) acryloyl monomer contains the (meth) acryloyl monomer which has an amino group.
Further, in 100% by mass of the monomer mixture, the content of the styrene monomer is preferably 5 to 50% by mass, and the content of the alkylol (meth) acrylamide monomer is preferably 2 to 40% by mass.
Moreover, it is preferable that content of the said photoinitiator is 1-20 mass parts with respect to 100 mass parts of said active energy ray hardening compounds (B).
また、本発明の耐熱性光輝部品は、プラスチック基材と、該プラスチック基材の表面に、前記活性エネルギー線硬化型塗料組成物を塗布して形成された塗膜と、該塗膜上に形成された金属薄膜と、該金属薄膜上に形成された保護膜とを備えたことを特徴とする。
さらに、前記保護膜が、ケイ素有機化合物のプラズマ重合により形成されたことが好ましい。
Further, the heat-resistant bright part of the present invention is formed on a plastic substrate, a coating film formed by applying the active energy ray-curable coating composition on the surface of the plastic substrate, and the coating film. And a protective film formed on the metal thin film.
Furthermore, it is preferable that the protective film is formed by plasma polymerization of a silicon organic compound.
本発明によれば、ポットライフが制限されにくい１液型でありながら貯蔵安定性に優れ、かつ基材との密着性、および耐熱性に優れた塗膜を形成できる活性エネルギー線硬化型塗料組成物、および耐熱性光輝部品が得られる。
また、本発明の耐熱性光輝部品は、耐熱性に優れる。
ADVANTAGE OF THE INVENTION According to this invention, the active energy ray hardening-type coating composition which can form the coating film which was excellent in storage stability, and was excellent in the adhesiveness with a base material, and heat resistance, though it is a one-pack type in which pot life is hard to be restrict | limited. Products and heat-resistant bright parts.
In addition, the heat-resistant bright part of the present invention is excellent in heat resistance.
以下、本発明について詳細に説明する。
［活性エネルギー線硬化型塗料組成物］
本発明の活性エネルギー線硬化型塗料組成物（以下、「塗料組成物」という。）は、プラスチック基材等の基材上に金属薄膜を形成する前に、下塗りとして塗膜を形成するために使用される、活性エネルギー線硬化型の金属薄膜用の塗料組成物である。
本発明の塗料組成物は、塗膜形成成分と、光重合開始剤と、溶剤とを含む。
なお、本発明において、「（メタ）アクリルアミド」とは、メタクリルアミドとアクリルアミドの両方を示し、「（メタ）アクリロイル」とは、メタクリロイルとアクリロイルの両方を示し、「（メタ）アクリレート」とは、メタクリレートとアクリレートの両方を示すものとする。
Hereinafter, the present invention will be described in detail.
[Active energy ray-curable coating composition]
The active energy ray-curable coating composition of the present invention (hereinafter referred to as “coating composition”) is used to form a coating film as an undercoat before forming a metal thin film on a substrate such as a plastic substrate. It is the coating composition for active energy ray hardening-type metal thin films used.
The coating composition of this invention contains a coating-film formation component, a photoinitiator, and a solvent.
In the present invention, “(meth) acrylamide” refers to both methacrylamide and acrylamide, “(meth) acryloyl” refers to both methacryloyl and acryloyl, and “(meth) acrylate” Both methacrylate and acrylate shall be indicated.
＜塗膜形成成分＞
塗膜形成成分は、共重合体（Ａ）と活性エネルギー線硬化性化合物（Ｂ）とを含有する。
（共重合体（Ａ））
共重合体（Ａ）（以下、「（Ａ）成分」という場合がある。）は、スチレン単量体、アルキロール（メタ）アクリルアミド単量体、および（メタ）アクリロイル単量体を含む単量体混合物を共重合して得られる。
<Coating film forming component>
A coating-film formation component contains a copolymer (A) and an active energy ray hardening compound (B).
(Copolymer (A))
Copolymer (A) (hereinafter sometimes referred to as “component (A)”) is a single monomer containing a styrene monomer, an alkylol (meth) acrylamide monomer, and a (meth) acryloyl monomer. It is obtained by copolymerizing the body mixture.
スチレン単量体は、塗料組成物より形成される塗膜の、基材（特に耐熱素材からなる基材）に対する密着性を向上させることを目的として配合される。
スチレン単量体としては、例えばスチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−クロロスチレンなどが挙げられる。これらの中でもスチレンが好ましい。
スチレン単量体の含有量は、単量体混合物１００質量％中、５〜５０質量％が好ましく、１５〜４０質量％がより好ましい。スチレン単量体の含有量が５質量％以上であれば、塗膜の基材に対する密着性がより向上する。一方、スチレン単量体の含有量が５０質量％以下であれば、塗膜の平滑性を良好に維持できる。
A styrene monomer is mix | blended in order to improve the adhesiveness with respect to the base material (especially the base material which consists of heat-resistant materials) of the coating film formed from a coating composition.
Examples of the styrene monomer include styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene. Of these, styrene is preferred.
5-50 mass% is preferable in 100 mass% of monomer mixtures, and, as for content of a styrene monomer, 15-40 mass% is more preferable. If content of a styrene monomer is 5 mass% or more, the adhesiveness with respect to the base material of a coating film will improve more. On the other hand, if the content of the styrene monomer is 50% by mass or less, the smoothness of the coating film can be maintained satisfactorily.
アルキロール（メタ）アクリルアミド単量体は、塗料組成物より形成される塗膜を加熱することで架橋を進行させ、耐熱性を向上させることを目的として配合される。
アルキロール（メタ）アクリルアミド単量体としては、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−イソプロピルアクリルアミド、ジアセトンアクリルアミド、Ｎ−ｎ−ブチルアクリルアミド、Ｎ−ｉ−ブチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノアクリルアミド、ジメチルアミノプロピルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミドなどが挙げられる。
The alkylol (meth) acrylamide monomer is blended for the purpose of promoting crosslinking by heating a coating film formed from the coating composition and improving heat resistance.
As an alkylol (meth) acrylamide monomer, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, Nn-butylacrylamide, Ni-butylacrylamide, N, N-dimethylaminoacrylamide, Examples include dimethylaminopropyl acrylamide, isopropyl acrylamide, and diethyl acrylamide.
また、アルキロール（メタ）アクリルアミド単量体としては、下記一般式（１）、（２）で表される化合物を用いることが好ましい。 Moreover, as an alkylol (meth) acrylamide monomer, it is preferable to use the compound represented by following General formula (1), (2).
式（１）中、Ｒ１は水素またはメチル基であり、Ｒ２〜Ｒ３は水素または炭素数１〜１０の炭化水素基であり、ｎ１〜ｎ２は１〜５の整数である。
式（２）中、Ｒ４は水素またはメチル基であり、Ｒ５は水素または炭素数１〜１０の炭化水素基であり、ｎ３は１〜５の整数である。
炭化水素基は、飽和であってもよく不飽和であってもよく、また鎖式であってもよく環式であってもよい。炭化水素基としては、飽和鎖式炭化水素基が好ましく、具体的にはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などが挙げられる。
In Formula (1), R 1 is hydrogen or a methyl group, R 2 to R 3 are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n 1 to n 2 are integers of 1 to 5.
In formula (2), R 4 is hydrogen or a methyl group, R 5 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n 3 is an integer of 1 to 5.
The hydrocarbon group may be saturated or unsaturated, and may be chain or cyclic. The hydrocarbon group is preferably a saturated chain hydrocarbon group, specifically, a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Can be mentioned.
上記一般式（１）で表される化合物としては、例えばＮ，Ｎ−ジヒドロキシメチルアクリルアミド、Ｎ−ヒドロキシメチル−Ｎ−ブトキシアクリルアミドなどが挙げられる。
一方、上記一般式（２）で表される化合物としては、例えばＮ−（ｉ−ブトキシメチル）アクリルアミド、Ｎ−（ｎ−ブトキシメチル）アクリルアミド、Ｎ−（メトキシメチル）アクリルアミド、Ｎ−（ヒドロキシエチル）アクリルアミドなどが挙げられる。
これらの中でも耐熱性に優れる観点から、Ｎ−（ｎ−ブトキシメチル）アクリルアミド、Ｎ−（ヒドロキシエチル）アクリルアミドが好ましい。
Examples of the compound represented by the general formula (1) include N, N-dihydroxymethylacrylamide, N-hydroxymethyl-N-butoxyacrylamide and the like.
On the other hand, examples of the compound represented by the general formula (2) include N- (i-butoxymethyl) acrylamide, N- (n-butoxymethyl) acrylamide, N- (methoxymethyl) acrylamide, and N- (hydroxyethyl). ) Acrylamide and the like.
Among these, N- (n-butoxymethyl) acrylamide and N- (hydroxyethyl) acrylamide are preferable from the viewpoint of excellent heat resistance.
上述したアルキロール（メタ）アクリルアミド単量体は、１種単独で用いてもよく、２種以上を併用してもよい。アルキロール（メタ）アクリルアミド単量体を含むことにより、塗料組成物より形成される塗膜は、加熱することで反応して熱硬化し、網目状に自己架橋し、塗膜の耐熱性が向上する。
アルキロール（メタ）アクリルアミド単量体の含有量は、単量体混合物１００質量％中、２〜４０質量％が好ましく、５〜２０質量％がより好ましい。アルキロール（メタ）アクリルアミド単量体の含有量が２質量％以上であれば、塗料組成物から形成される塗膜の耐熱性がより向上する。一方、アルキロール（メタ）アクリルアミド単量体の含有量が４０質量％以下であれば、クラックの発生を抑制できると共に、塗料組成物の貯蔵安定性を良好に維持できる。
The alkylol (meth) acrylamide monomer mentioned above may be used individually by 1 type, and may use 2 or more types together. By including an alkylol (meth) acrylamide monomer, the coating film formed from the coating composition reacts by heating and heat cures, and self-crosslinks in a network, improving the heat resistance of the coating film. To do.
2-40 mass% is preferable in 100 mass% of monomer mixtures, and, as for content of an alkylol (meth) acrylamide monomer, 5-20 mass% is more preferable. If content of an alkylol (meth) acrylamide monomer is 2 mass% or more, the heat resistance of the coating film formed from a coating composition will improve more. On the other hand, when the content of the alkylol (meth) acrylamide monomer is 40% by mass or less, the occurrence of cracks can be suppressed and the storage stability of the coating composition can be favorably maintained.
（メタ）アクリロイル単量体は、主に共重合体（Ａ）のガラス転移点を調整するために配合される。
（メタ）アクリロイル単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ −ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２−ジシクロペンテノキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、メトキシエトキシエチル（メタ）アクリレート、エトキシエトキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ステアリル（メタ）アクリレート、アクリロイルモルホリンなどが挙げられる。これら（メタ）アクリロイル単量体は、１種単独で用いてもよく、２種以上を併用してもよい。
The (meth) acryloyl monomer is blended mainly for adjusting the glass transition point of the copolymer (A).
(Meth) acryloyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, Ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, stearyl (Meth) acrylate, acryloylmorpholine, etc. are mentioned. These (meth) acryloyl monomers may be used individually by 1 type, and may use 2 or more types together.
また、（メタ）アクリロイル単量体としては、ヒドロキシ基を有する（メタ）アクリロイル単量体を併用するのが好ましい。ヒドロキシ基を有する（メタ）アクリロイル単量体としては、例えば２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、（メタ）アクリル酸などが挙げられる。 Further, as the (meth) acryloyl monomer, it is preferable to use a (meth) acryloyl monomer having a hydroxy group in combination. Examples of the (meth) acryloyl monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and (meth). Examples include acrylic acid.
さらに、（メタ）アクリロイル単量体としては、アミノ基を有する（メタ）アクリロイル単量体を併用することが好ましい。アミノ基を有する（メタ）アクリロイル単量体としては、（メタ）アクリル酸２−（ジメチルアミノ）エチル、（メタ）アクリル酸２−（ジメチルアミノ）プロピル、（メタ）アクリル酸２−（ジメチルアミノ）イソプロピル、（メタ）アクリル酸２−（ジメチルアミノ）ブチル、（メタ）アクリル酸２−（ジメチルアミノ）イソブチルなどが挙げられる。
また、アミノ基を有する（メタ）アクリロイル単量体としては、市販品を用いることができ、例えばＳａｒｔｏｍｅｒ社製の「ＣＮ３７２」、「ＣＮ３７３」、「ＣＮ３８４」、「ＣＮ３８６」などが好適である。
Furthermore, it is preferable to use a (meth) acryloyl monomer having an amino group as the (meth) acryloyl monomer. Examples of the (meth) acryloyl monomer having an amino group include 2- (dimethylamino) ethyl (meth) acrylate, 2- (dimethylamino) propyl (meth) acrylate, and 2- (dimethylamino) (meth) acrylate. ) Isopropyl, 2- (dimethylamino) butyl (meth) acrylate, 2- (dimethylamino) isobutyl (meth) acrylate, and the like.
As the (meth) acryloyl monomer having an amino group, a commercially available product can be used. For example, “CN372”, “CN373”, “CN384”, “CN386” manufactured by Sartomer are suitable.
共重合体（Ａ）の構成成分である（メタ）アクリロイル単量体は、単量体混合物１００質量％中、５〜４０質量％の範囲で上述したヒドロキシ基を有する（メタ）アクリロイル単量体が含まれていることが好ましく、より好ましくは５〜２０質量％である。 The (meth) acryloyl monomer which is a constituent component of the copolymer (A) is a (meth) acryloyl monomer having the hydroxy group described above in the range of 5 to 40% by mass in 100% by mass of the monomer mixture. Is preferably contained, more preferably 5 to 20% by mass.
共重合体（Ａ）は、単量体混合物を共重合することで得られる。共重合の方法としては、公知の方法を用いることができ、例えば懸濁重合、溶液重合、乳化重合、塊状重合などが挙げられる。 A copolymer (A) is obtained by copolymerizing a monomer mixture. As a copolymerization method, a known method can be used, and examples thereof include suspension polymerization, solution polymerization, emulsion polymerization, and bulk polymerization.
このようにして得られる共重合体（Ａ）は、ガラス転移点（Ｔｇ）が−６０〜２０℃である。Ｔｇが上記範囲内であれば、塗料組成物より形成される塗膜の平滑性が向上し、塗膜上に金属薄膜を形成した際に良好な光輝感が得られ、特に自動車反射鏡の用途に用いる場合、反射鏡として必要な光学特性を確保できる。また、塗膜と基材との密着性を向上できる。なお、Ｔｇが−６０℃未満であると、塗膜が軟化しやすくなり耐熱性試験における外観が悪化する。一方、Ｔｇが２０℃を越えると、塗膜の密着性が低下する。
なお、共重合体（Ａ）のガラス転移点は、ＪＩＳ Ｋ７１２１に準拠して測定される値である。
The copolymer (A) thus obtained has a glass transition point (Tg) of −60 to 20 ° C. When Tg is within the above range, the smoothness of the coating film formed from the coating composition is improved, and a good glitter is obtained when a metal thin film is formed on the coating film. When used in the above, it is possible to secure the optical characteristics necessary as a reflecting mirror. Moreover, the adhesiveness of a coating film and a base material can be improved. In addition, when Tg is less than −60 ° C., the coating film is easily softened and the appearance in the heat resistance test is deteriorated. On the other hand, when Tg exceeds 20 ° C., the adhesion of the coating film decreases.
In addition, the glass transition point of a copolymer (A) is a value measured based on JISK7121.
共重合体（Ａ）の含有量は、塗膜形成成分１００質量％中、２０〜７５質量％が好ましく、３０〜６１質量％がより好ましい。共重合体（Ａ）の含有量が２０質量％以上であれば、塗料組成物より形成される塗膜の、基材に対する密着性がより向上する。一方、共重合体（Ａ）の含有量が７５質量％以下であれば、塗膜の耐熱性がより向上する。 The content of the copolymer (A) is preferably 20 to 75% by mass and more preferably 30 to 61% by mass in 100% by mass of the coating film forming component. If content of a copolymer (A) is 20 mass% or more, the adhesiveness with respect to a base material of the coating film formed from a coating composition will improve more. On the other hand, if content of a copolymer (A) is 75 mass% or less, the heat resistance of a coating film will improve more.
（活性エネルギー線硬化性化合物（Ｂ））
活性エネルギー線硬化性化合物（Ｂ）（以下、「（Ｂ）成分」という場合がある。）としては、分子内に少なくとも３個の（メタ）アクリロイル基を有する化合物が好ましい。（メタ）アクリロイル基が３個未満であると、塗料組成物より形成される塗膜の耐熱性が低下する傾向にある。従って、分子内に３個未満の（メタ）アクリロイル基を有する化合物を用いる場合は、その含有量が（Ｂ）成分１００質量％中、３０質量％以下となるように用いるのが好ましい。
(Active energy ray-curable compound (B))
As the active energy ray-curable compound (B) (hereinafter sometimes referred to as “component (B)”), a compound having at least three (meth) acryloyl groups in the molecule is preferable. When the number of (meth) acryloyl groups is less than 3, the heat resistance of the coating film formed from the coating composition tends to decrease. Accordingly, when a compound having less than three (meth) acryloyl groups in the molecule is used, it is preferably used so that the content thereof is 30% by mass or less in 100% by mass of the component (B).
分子内に少なくとも３個の（メタ）アクリロイル基を有する化合物としては、例えばトリス（２−ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロポキシ化トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、ジメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、プロポキシ化ペンタエリスリトールテトラ（メタ）アクリレート、エトキシ化ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。これらの中でも、ペンタエリスリトールトリ（メタ）アクリレート、およびジペンタエリスリトールヘキサ（メタ）アクリレートが好ましい。
また、分子内に少なくとも３個の（メタ）アクリロイル基を有する化合物としては、市販品を用いることができ、例えば日本化薬株式会社製の「カヤラッドＤＰＨＡ」；新中村化学工業株式会社製の「ＮＫエステルＡ−ＴＭＭ−Ｔ」、「ＮＫエステルＡ−ＴＭＭ−３Ｌ」；三菱レイヨン株式会社製の「ダイヤビームＵＫ−４１５４」；日本合成化学工業株式会社製の「紫光ＵＶ−７５１０Ｂ」などが好適である。
Examples of the compound having at least three (meth) acryloyl groups in the molecule include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. , Propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.
Moreover, as a compound which has at least 3 (meth) acryloyl group in a molecule | numerator, a commercial item can be used, for example, "Kayarad DPHA" by Nippon Kayaku Co., Ltd .; “NK Ester A-TMM-T”, “NK Ester A-TMM-3L”; “Diabeam UK-4154” manufactured by Mitsubishi Rayon Co., Ltd .; It is.
分子内に２個の（メタ）アクリロイル基を有する化合物としては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、２−（メタ）アクリロイロキシエチルアシッドホスフェート、１，４ブタンジオールジ（メタ）アクリレート、１，６ヘキサンジオールジ（メタ）アクリレート、１，９ノナンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、３−メチル−１，５ペンタンジオールジ（メタ）アクリレート、２−ブチル−２−エチル−１，３プロパンジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールヒドロキシピバレートジ（メタ）アクリレート、１，３ブタンジオールジ（メタ）アクリレート、ジメチロールジシクロペンタンジ（メタ）アクリレート等が挙げられる。これらの中でも、トリプロピレングリコールジ（メタ）アクリレートが好ましい。
また、分子内に２個の（メタ）アクリロイル基を有する化合物としては、市販品を用いることができ、例えば新中村化学工業株式会社製の「ＮＫエステルＡＰＧ−２００」、三菱レイヨン株式会社製の「ダイヤビームＵＫ−４１０１」、「ダイヤビームＵＫ−６０６３」などが好適である。
Examples of the compound having two (meth) acryloyl groups in the molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). Acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 1,4 butanediol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9 nonanediol di (meth) acrylate, glycerin di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanedi (meth) acrylate, dimethyloltricyclodecane (Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) Examples include acrylate, 1,3-butanediol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and the like. Among these, tripropylene glycol di (meth) acrylate is preferable.
Moreover, as a compound which has two (meth) acryloyl groups in a molecule | numerator, a commercial item can be used, for example, "NK ester APG-200" by Shin-Nakamura Chemical Co., Ltd., Mitsubishi Rayon Co., Ltd. “Diabeam UK-4101”, “Diabeam UK-6063” and the like are preferable.
分子内に１個の（メタ）アクリロイル基を有する化合物としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔ−ブチルシクロヘキシル（メタ）アクリレート、ジシクロヘキシルペンタニル（メタ）アクリレート、トリシクロデカンジメタノール（メタ）アクリレート、イソボロニル（メタ）アクリレート等が挙げられる。
なお、上述した（Ｂ）成分は、１種単独で用いてもよく、２種以上を併用してもよい。
Examples of the compound having one (meth) acryloyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth ) Acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclohexylpentanyl (meth) acrylate, tricyclode Examples include candimethanol (meth) acrylate and isobornyl (meth) acrylate.
In addition, the (B) component mentioned above may be used individually by 1 type, and may use 2 or more types together.
（Ｂ）成分の含有量は、塗膜形成成分１００質量％中、２０〜７５質量％が好ましく、３０〜６０質量％がより好ましい。（Ｂ）成分の含有量が２０質量％以上であれば、塗料組成物より形成される塗膜の耐熱性がより向上する。一方、（Ｂ）成分の含有量が７５質量％以下であれば、塗膜の基材に対する密着性がより向上する。 (B) 20-75 mass% is preferable in 100 mass% of coating-film formation components, and, as for content of a component, 30-60 mass% is more preferable. If content of (B) component is 20 mass% or more, the heat resistance of the coating film formed from a coating composition will improve more. On the other hand, if content of (B) component is 75 mass% or less, the adhesiveness with respect to the base material of a coating film will improve more.
（アミノ基を有する化合物（Ｃ））
塗膜形成成分は、アミノ基を有する化合物（Ｃ）（以下、「（Ｃ）成分」という場合がある。）を含有することが好ましい。（Ｃ）成分を含有することで、後述する塗膜形成成分のアミン価の値を容易に調整できる。
（Ｃ）成分としては、アミン価を有するものであれば特に制限されないが、例えば第一級アミン類、第二級アミン類、第三級アミン類、アルコールアミン類、エーテルアミン類、ポリアミン類、ポリアミドアミン類などが挙げられる。
なお、本発明において「アミン価」とは、ＪＩＳ Ｋ７２３７に準拠して測定される値のことである。
(Compound having an amino group (C))
The coating film-forming component preferably contains a compound (C) having an amino group (hereinafter sometimes referred to as “(C) component”). By containing the component (C), it is possible to easily adjust the value of the amine value of the coating film forming component described later.
The component (C) is not particularly limited as long as it has an amine value. For example, primary amines, secondary amines, tertiary amines, alcohol amines, ether amines, polyamines, Polyamide amines and the like can be mentioned.
In the present invention, the “amine value” is a value measured according to JIS K7237.
第一級アミン類としては、例えばアンモニア、メチルアミン、エチルアミン、ｎ−プロピルアミン、イソプロピルアミン、ｎ−ブチルアミン、イソブチルアミン、ｓｅｃ−ブチルアミン、ｔｅｒｔ−ブチルアミン、ペンチルアミン、ｔｅｒｔ−アミルアミン、シクロペンチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ドデシルアミン、セチルアミン、メチレンジアミン、エチレンジアミン、テトラエチレンペンタミンなどが挙げられる。 Examples of primary amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, and hexyl. Examples include amine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine.
第二級アミン類としては、例えばジメチルアミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ジイソプロピルアミン、ジ−ｎ−ブチルアミン、ジイソブチルアミン、ジ−ｓｅｃ−ブチルアミン、ジペンチルアミン、ジシクロペンチルアミン、ジヘキシルアミン、ジシクロヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、ジノニルアミン、ジデシルアミン、ジドデシルアミン、ジセチルアミン、Ｎ，Ｎ−ジメチルメチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチルテトラエチレンペンタミンなどが挙げられる。 Examples of secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, and dicyclohexyl. Examples include amine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, and N, N-dimethyltetraethylenepentamine.
第三級アミン類としては、例えばトリメチルアミン、トリエチルアミン、トリ−ｎ−プロピルアミン、トリイソプロピルアミン、トリ−ｎ−ブチルアミン、トリイソブチルアミン、トリ−ｓｅｃ−ブチルアミン、トリペンチルアミン、トリシクロペンチルアミン、トリヘキシルアミン、トリシクロヘキシルアミン、トリヘプチルアミン、トリオクチルアミン、トリノニルアミン、トリデシルアミン、トリドデシルアミン、トリセチルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルメチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルテトラエチレンペンタミンなどが挙げられる。 Tertiary amines include, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexyl. Amine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N Examples include ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like.
アルコールアミン類としては、例えばＮ−メチルエタノールアミン、エタノールアミン、ジメチルエタノールアミン、トリエタノールアミン、トリエタノールアミン、ジエタノールアミン、Ｎ−メチルジエタノールアミンなどが挙げられる。 Examples of alcohol amines include N-methylethanolamine, ethanolamine, dimethylethanolamine, triethanolamine, triethanolamine, diethanolamine, and N-methyldiethanolamine.
エーテルアミン類としては、例えば１−アミノ−２−メトキシエタン、１−アミノ−２−エトキシエタン、１−アミノ−２−ブトキシエタン、１−アミノ−２−エトキシブタンなどが挙げられる。 Examples of ether amines include 1-amino-2-methoxyethane, 1-amino-2-ethoxyethane, 1-amino-2-butoxyethane, 1-amino-2-ethoxybutane, and the like.
ポリアミン類としては、例えばＤＩＣ株式会社製の「エピクロンＢ−３１５０」、「エピクロンＢ−３２６０」、「エピクロンＢ−０５３」、「エピクロンＢ−０６５」、「エピクロンＥＸＢ−３５３」；株式会社ＡＤＥＫＡ製の「アデカハードナーＥＨ−５４０−５」、「アデカハードナーＥＨ−５５１ＣＨ」などが挙げられる。 As polyamines, for example, “Epicron B-3150”, “Epicron B-3260”, “Epicron B-053”, “Epicron B-065”, “Epicron EXB-353” manufactured by DIC Corporation; "Adeka Hardener EH-540-5", "Adeka Hardener EH-551CH" and the like.
ポリアミドアミン類としては、例えば株式会社ＡＤＥＫＡ製の「アデカハードナーＧＭ−６４０」、「アデカハードナーＧＭ−６４５」、「アデカハードナーＧＭ−６５０」、「アデカハードナーＧＭ−６５６」、「アデカハードナーＧＭ−６６０」、「アデカハードナーＧＭ−６６５」などが挙げられる。 Examples of the polyamide amines are “ADEKA HARDNER GM-640”, “ADEKA HARDNER GM-645”, “ADEKA HARDNER GM-650”, “ADEKA HARDNER GM-656”, “ADEKA HARDNER GM-660” manufactured by ADEKA Corporation. And “Adeka Hardener GM-665”.
上述した（Ｃ）成分は、１種単独で用いてもよく、２種以上を併用してもよい。
なお、（Ｃ）成分として低分子量の化合物を用いると、塗料組成物より形成される塗膜の耐熱性が低下する場合がある。従って、（Ｃ）成分としては高分子量の化合物を用いるのが好ましい。
(C) component mentioned above may be used individually by 1 type, and may use 2 or more types together.
In addition, when a low molecular weight compound is used as the component (C), the heat resistance of the coating film formed from the coating composition may be lowered. Therefore, it is preferable to use a high molecular weight compound as the component (C).
（Ｃ）成分は塗膜形成成分のアミン価を容易に調整できる成分であり、塗膜形成成分のアミン価が所望の値となるように、（Ｃ）成分の含有量は適宜決定される。 (C) component is a component which can adjust the amine value of a coating-film formation component easily, and content of (C) component is suitably determined so that the amine value of a coating-film formation component may become a desired value.
（その他）
塗膜形成成分は、塗料組成物の流動性を改質するために熱可塑性樹脂をさらに含んでもよい。熱可塑性樹脂としては、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ブチル、ポリメタクリル酸２−エチルヘキシルなどのホモポリマーや、これらの共重合体などの（メタ）アクリル樹脂が例示できる。これらの中でも、ポリメタクリル酸メチルが好ましい。
(Other)
The coating film forming component may further contain a thermoplastic resin in order to modify the fluidity of the coating composition. Examples of the thermoplastic resin include homopolymers such as polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, and 2-ethylhexyl polymethacrylate, and (meth) acrylic resins such as copolymers thereof. Among these, polymethyl methacrylate is preferable.
熱可塑性樹脂は、得られる塗料組成物の用途に応じて添加されるものであり、その含有量は塗膜形成成分１００質量％中、０〜１５質量％が好ましく、０〜１０質量％がより好ましい。熱可塑性樹脂を含有しない場合であっても、本発明の効果は十分に発揮されるが、含有量が上記範囲内であれば、形成される塗膜の付着性、耐水性、防錆性などの諸物性を保持しつつ、さらに塗料組成物の流動性を改質することができる。 The thermoplastic resin is added depending on the intended use of the resulting coating composition, and its content is preferably 0 to 15% by mass and more preferably 0 to 10% by mass in 100% by mass of the coating film forming component. preferable. Even if it does not contain a thermoplastic resin, the effect of the present invention is sufficiently exerted, but if the content is within the above range, the adhesion of the formed coating film, water resistance, rust prevention, etc. While maintaining these physical properties, the fluidity of the coating composition can be further modified.
（物性）
塗膜形成成分は、アミン価が１５〜２００ｍｇＫＯＨ／ｇである。
塗膜形成成分のアミン価は、（Ｃ）成分など、アミン価を有する化合物を配合することで調整できる。なお、（Ｃ）成分は比較的揮発性が高いので、塗膜形成成分を製造する際に（Ｃ）成分が揮発して、所望のアミン価に調整しにくくなる場合がある。そこで、単量体混合物中にアミン価を有する化合物、すなわちアミノ基を有する（メタ）アクリロイル単量体を配合し、これを共重合させて（Ａ）成分を得れば、塗膜形成成分を製造する際にアミノ基を有する（メタ）アクリロイル単量体が揮発することがないので、より容易にアミン価を調整できる。
(Physical properties)
The coating film-forming component has an amine value of 15 to 200 mgKOH / g.
The amine value of the coating film forming component can be adjusted by blending a compound having an amine value such as the component (C). In addition, since (C) component has comparatively high volatility, when manufacturing a coating-film formation component, (C) component may volatilize and it may become difficult to adjust to a desired amine value. Therefore, a compound having an amine value in the monomer mixture, that is, a (meth) acryloyl monomer having an amino group is blended and copolymerized to obtain the component (A). Since the (meth) acryloyl monomer having an amino group does not volatilize during production, the amine value can be adjusted more easily.
塗膜形成成分のアミン価は、（Ｃ）成分やアミノ基を有する（メタ）アクリロイル単量体の種類や配合量により、所望の値に調整できる。
また、塗膜形成成分のアミン価とは、硬化前の塗膜形成成分をＪＩＳ Ｋ７２３７に準拠して測定した値のことである。
The amine value of the coating film forming component can be adjusted to a desired value depending on the type and amount of the (C) component and the (meth) acryloyl monomer having an amino group.
Moreover, the amine value of a coating-film formation component is the value which measured the coating-film formation component before hardening based on JISK7237.
ところで、上述したように１液型の下塗り塗料は、２液型に比べてポットライフは制限されにくいものの、貯蔵安定性が低下しやすかった。これは、下塗り塗料に含まれる活性エネルギー線硬化性化合物中にアクリル酸が不純物として存在し、該アクリル酸が下塗り塗料の貯蔵の際に遊離してゲル化を引き起こすことが原因と考えられる。また、アクリル酸の遊離は塗膜の状態でも発生しやすい。遊離アクリル酸が発生すると、特に急激な熱が塗膜に加わった際にクラックが生じやすくなり、塗膜の耐熱性が低下することとなる。 By the way, as described above, the one-component undercoat paint has a pot life that is less restricted than the two-component type, but the storage stability is likely to be lowered. This is presumably because acrylic acid is present as an impurity in the active energy ray-curable compound contained in the undercoat paint, and the acrylic acid is liberated during storage of the undercoat paint to cause gelation. Also, liberation of acrylic acid is likely to occur even in the state of the coating film. When free acrylic acid is generated, cracks are likely to occur particularly when abrupt heat is applied to the coating film, and the heat resistance of the coating film decreases.
しかし、本発明の塗料組成物は、アミン価が１５〜２００ｍｇＫＯＨ／ｇの塗膜形成成分を含んでいる。アミン価を調整するための配合成分、すなわち（Ｃ）成分やアミノ基を有する（メタ）アクリロイル単量体は、遊離アクリル酸を捕獲するトラップ機能を有する。従って、（Ｂ）成分からアクリル酸が遊離しても、遊離アクリル酸をトラップしてゲル化の発生を抑制できるので、本発明の塗料組成物は１液型でありながら貯蔵安定性に優れると共に、耐熱性に優れた塗膜を形成できる。
塗膜形成成分のアミン価が１５ｍｇＫＯＨ／ｇ以上であれば、塗料組成物の貯蔵安定性の低下を抑制できると共に、塗料組成物より形成される塗膜の耐熱性を向上できる。一方、アミン価が２００ｍｇＫＯＨ／ｇ以下であれば、塗膜や該塗膜上に形成される金属薄膜の外観に虹や白化が生じるのを抑制でき、光輝性を維持できる。アミン価の下限値は５０ｍｇＫＯＨ／ｇ以上が好ましい。一方、上限値は１００ｍｇＫＯＨ／ｇ以下が好ましい。
However, the coating composition of the present invention contains a film-forming component having an amine value of 15 to 200 mgKOH / g. The compounding component for adjusting the amine value, that is, the component (C) and the (meth) acryloyl monomer having an amino group have a trap function for capturing free acrylic acid. Therefore, even if acrylic acid is liberated from the component (B), it is possible to trap the free acrylic acid and suppress the occurrence of gelation. Therefore, the coating composition of the present invention is excellent in storage stability while being one-pack type. A film having excellent heat resistance can be formed.
When the amine value of the coating film-forming component is 15 mgKOH / g or more, the storage stability of the coating composition can be prevented from being lowered, and the heat resistance of the coating film formed from the coating composition can be improved. On the other hand, if the amine value is 200 mgKOH / g or less, it is possible to suppress the occurrence of rainbows and whitening in the appearance of the coating film and the metal thin film formed on the coating film, and the glitter can be maintained. The lower limit of the amine value is preferably 50 mgKOH / g or more. On the other hand, the upper limit is preferably 100 mgKOH / g or less.
＜光重合開始剤＞
光重合開始剤としては特に限定されないが、例えばチバ・スペシャルティ・ケミカルズ株式会社製の「イルガキュア１８４Ｄ」、「イルガキュア１４９」、「イルガキュア６５１」、「イルガキュア９０７」、「イルガキュア７５４」、「イルガキュア８１９」、「イルガキュア５００」、「イルガキュア１０００」、「イルガキュア１８００」、「イルガキュア７５４」；ＢＡＳＦ社製の「ルシリンＴＰＯ」；日本化薬株式会社製の「カヤキュアＤＥＴＸ−Ｓ」、「カヤキュアＥＰＡ」、「カヤキュアＤＭＢＩ」などが挙げられる。
これら光重合開始剤は、１種単独で用いてもよく、２種以上を併用してもよい。
<Photopolymerization initiator>
Although it does not specifically limit as a photoinitiator, For example, "Irgacure 184D", "Irgacure 149", "Irgacure 651", "Irgacure 907", "Irgacure 754", "Irgacure 819" by Ciba Specialty Chemicals Co., Ltd. “Irgacure 500”, “Irgacure 1000”, “Irgacure 1800”, “Irgacure 754”; “Lucirin TPO” manufactured by BASF; “Kayacure DETX-S”, “Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd., “ Kayacure DMBI ”and the like.
These photopolymerization initiators may be used alone or in combination of two or more.
光重合開始剤の含有量は、（Ｂ）成分１００質量部に対して、１〜２０質量部が好ましく、２〜１２質量部がより好ましい。光重合開始剤の含有量が１質量部以上であれば、塗料組成物より形成される塗膜の、基材に対する密着性、および耐熱性がより向上する。一方、光重合開始剤の含有量が２０質量部以下であれば、塗膜上に形成される金属薄膜の外観に虹や白化が生じるのを抑制でき、光輝性を良好に維持できる。 1-20 mass parts is preferable with respect to 100 mass parts of (B) component, and, as for content of a photoinitiator, 2-12 mass parts is more preferable. If content of a photoinitiator is 1 mass part or more, the adhesiveness with respect to a base material of the coating film formed from a coating composition, and heat resistance will improve more. On the other hand, if content of a photoinitiator is 20 mass parts or less, it can suppress that a rainbow and whitening generate | occur | produce in the external appearance of the metal thin film formed on a coating film, and can maintain the brightness | luminance favorably.
＜溶剤＞
溶剤としては特に限定されないが、塗料組成物の濡れ性を高めるためには表面張力の低い溶剤を用いるのが好ましい。このような溶剤としては、例えばアルコール系溶剤、ケトン系溶剤などが挙げられる。さらにこれらの溶剤に加えて、蒸発速度やコスト等を考慮して、酢酸エチル、酢酸ブチル、トルエン、キシレン等を併用することもできる。
これら溶剤は、１種単独で用いてもよく、２種以上を併用してもよい。
<Solvent>
Although it does not specifically limit as a solvent, In order to improve the wettability of a coating composition, it is preferable to use a solvent with low surface tension. Examples of such solvents include alcohol solvents and ketone solvents. In addition to these solvents, ethyl acetate, butyl acetate, toluene, xylene and the like can be used in combination in consideration of the evaporation rate and cost.
These solvents may be used alone or in combination of two or more.
＜その他の成分＞
本発明の塗料組成物は、必要に応じて各種表面調整剤を含有していてもよい。表面調整剤としては、例えばフッ素系添加剤、セルロース系添加剤などが挙げられる。
フッ素系添加剤は、塗料組成物の表面張力を低下させて塗料組成物の濡れ性を高めることにより、基材に塗布する際のハジキを防止する作用を示す。フッ素系添加剤としては、例えばＤＩＣ株式会社製の「メガファックＦ−４７７」などが挙げられる。
セルロース系添加剤は、塗料組成物を基材に塗布する際に、造膜性を付与する作用を示す。セルロース系添加剤としては、塗料組成物の流動性を低下させることを目的として、数平均分子量が１５０００以上の高分子量のものが好ましく、具体的には、セルロース−アセテート−ブチレート樹脂などが挙げられる。
<Other ingredients>
The coating composition of the present invention may contain various surface conditioners as necessary. Examples of the surface conditioner include a fluorine-based additive and a cellulose-based additive.
The fluorine-based additive exhibits an action of preventing repelling when applied to a substrate by reducing the surface tension of the coating composition and increasing the wettability of the coating composition. Examples of the fluorine-based additive include “Megafac F-477” manufactured by DIC Corporation.
Cellulose-based additives exhibit an effect of imparting film-forming properties when a coating composition is applied to a substrate. The cellulose-based additive preferably has a high molecular weight having a number average molecular weight of 15000 or more for the purpose of lowering the fluidity of the coating composition, and specifically includes cellulose-acetate-butyrate resin. .
フッ素系添加剤は、その含有量が多くなると塗料組成物より形成される塗膜と、該塗膜上に形成される金属薄膜や、保護膜との密着性が低下する傾向にある。一方、セルロース系添加剤は、その含有量が多くなると基材に対する塗膜の付着性が低下する傾向にある。従って、表面調整剤を含有させる場合は、フッ素系添加剤とセルロース系添加剤の含有量の合計が、塗膜形成成分１００質量部に対して０．０１〜３．００質量部が好ましい。
なお、フッ素系添加剤を単独で用いる場合は、塗膜形成成分１００質量部に対して０．０１〜１．００質量部が好ましく、セルロース系添加剤を単独で用いる場合は、塗膜形成成分１００質量部に対して０．５〜５．０質量部が好ましい。
When the content of the fluorine-based additive increases, the adhesion between the coating film formed from the coating composition, the metal thin film formed on the coating film, and the protective film tends to decrease. On the other hand, when the content of the cellulose-based additive increases, the adhesion of the coating film to the substrate tends to decrease. Therefore, when the surface conditioner is contained, the total content of the fluorine-based additive and the cellulose-based additive is preferably 0.01 to 3.00 parts by mass with respect to 100 parts by mass of the coating film forming component.
In addition, when using a fluorine-type additive independently, 0.01-1.00 mass part is preferable with respect to 100 mass parts of coating-film formation components, and when using a cellulose-type additive independently, a coating-film formation component 0.5-5.0 mass parts is preferable with respect to 100 mass parts.
＜塗料組成物の製造＞
塗料組成物は、アミン価が上記範囲内となるように、（Ａ）成分と、（Ｂ）成分と、必要に応じて（Ｃ）成分等を配合して塗膜形成成分を調製し、得られた塗膜形成成分と、光重合開始剤と、溶剤と、必要に応じて表面調整剤等のその他の成分とを混合することにより製造できる。
塗料組成物中の塗膜形成成分の割合は、用いる塗装形態に合わせて自由に設定できる。
<Manufacture of coating composition>
The coating composition is prepared by blending the component (A), the component (B), and the component (C) as necessary so that the amine value falls within the above range. It can manufacture by mixing the obtained coating-film formation component, a photoinitiator, a solvent, and other components, such as a surface modifier as needed.
The ratio of the coating film forming component in the coating composition can be freely set according to the coating form to be used.
こうして製造された塗料組成物は、硬化後の塗膜の膜厚が１０〜３０μｍ程度となるように、スプレー塗装法、刷毛塗り法、ローラ塗装法、カーテンコート法、フローコート法、浸漬塗り法等で基材表面に塗装される。
ついで熱風乾燥炉等で、乾燥温度４０〜１００℃程度、乾燥時間５〜２０分程度の条件にて加熱乾燥され、溶剤が除去されると共に、熱硬化する。
さらにその後に１００〜３０００ｍＪ／ｃｍ２程度（日本電池株式会社製「ＵＶＲ−Ｎ１」による測定値）の紫外線をヒュージョンランプ、高圧水銀灯、メタルハライドランプ等を用いて照射し、光硬化し、塗膜を形成する。活性エネルギー線としては、紫外線の他、電子線、ガンマ線等も使用できる。
The coating composition thus produced has a spray coating method, a brush coating method, a roller coating method, a curtain coating method, a flow coating method, and a dip coating method so that the thickness of the cured coating film is about 10 to 30 μm. Etc. are applied to the substrate surface.
Then, in a hot air drying furnace or the like, it is heat-dried under conditions of a drying temperature of about 40 to 100 ° C. and a drying time of about 5 to 20 minutes, and the solvent is removed and thermosetting is performed.
After that, ultraviolet rays of about 100 to 3000 mJ / cm 2 (measured by “UVR-N1” manufactured by Nippon Battery Co., Ltd.) were irradiated using a fusion lamp, a high-pressure mercury lamp, a metal halide lamp, etc., photocured, and the coating film was applied. Form. As an active energy ray, an electron beam, a gamma ray, etc. other than an ultraviolet-ray can be used.
このように、本発明の塗料組成物は、塗膜形成成分中に熱硬化性の（Ａ）成分と、光硬化性の（Ｂ）成分を含有する。従って、本発明の塗料組成物より形成される塗膜は、熱硬化と光硬化を経て得られるで、熱硬化および光硬化のいずれか一方のみで形成される塗膜に比べて硬く、耐熱性に優れる。また、基材に対する密着性にも優れる。 Thus, the coating composition of this invention contains a thermosetting (A) component and a photocurable (B) component in a coating-film formation component. Therefore, the coating film formed from the coating composition of the present invention is obtained through thermal curing and photocuring, and is harder and heat resistant than a coating film formed by only one of thermal curing and photocuring. Excellent. Moreover, it is excellent also in the adhesiveness with respect to a base material.
また、本発明の塗料組成物は、特定のアミン価を有する塗膜形成成分を含むので、（Ｂ）成分から遊離するアクリル酸を捕獲できる。従って、ポットライフが制限されにくい１液型でありながら、貯蔵安定性に優れると共に、耐熱性に優れた塗膜を形成できる。 Moreover, since the coating composition of this invention contains the coating-film formation component which has a specific amine value, it can capture | acquire the acrylic acid liberated from (B) component. Therefore, it is possible to form a coating film having excellent storage stability and heat resistance while being a one-component type in which the pot life is not easily restricted.
［耐熱性光輝部品］
本発明の耐熱性光輝部品は、プラスチック基材と、該プラスチック基材の表面に本発明の塗料組成物を塗布して形成された塗膜と、該塗膜上に形成された金属薄膜と、該金属薄膜上に形成された保護膜とを備える。
プラスチック基材の材料としては、ＢＭＣ（バルクモールディングコンパウンド）、ＰＰＳ（ポリフェニレンサルファイド）、ＰＢＴ（ポリブチレンテレフタレート）／ＰＥＴ（ポリエチレンテレフタレート）アロイ樹脂等の耐熱素材が使用できる。
[Heat-resistant bright parts]
The heat-resistant bright part of the present invention comprises a plastic substrate, a coating film formed by applying the coating composition of the present invention to the surface of the plastic substrate, a metal thin film formed on the coating film, And a protective film formed on the metal thin film.
As a material for the plastic substrate, a heat-resistant material such as BMC (bulk molding compound), PPS (polyphenylene sulfide), PBT (polybutylene terephthalate) / PET (polyethylene terephthalate) alloy resin can be used.
金属薄膜は、プラスチック基材表面に本発明の塗料組成物を塗布して塗膜を形成した後、蒸着法またはスパッタリング法により形成される。
金属薄膜の材質としては、アルミニウム、鉄、ニッケル、クロム、銅、銀、亜鉛、スズ、インジウム、マグネシウム、これらの酸化物、およびこれらの合金などが挙げられる。
金属薄膜の厚さは、１０〜５００ｎｍが好ましく、５０〜２００ｎｍがより好ましい。金属薄膜の厚さが１０ｎｍ以上であれば、反射率の低下を抑制し、十分な光輝感が得られる。一方、金属薄膜の厚さが５００ｎｍ以下であれば、外観の白化等の発生を抑制できる。
The metal thin film is formed by vapor deposition or sputtering after applying the coating composition of the present invention to the surface of a plastic substrate to form a coating film.
Examples of the material of the metal thin film include aluminum, iron, nickel, chromium, copper, silver, zinc, tin, indium, magnesium, oxides thereof, and alloys thereof.
10-500 nm is preferable and, as for the thickness of a metal thin film, 50-200 nm is more preferable. When the thickness of the metal thin film is 10 nm or more, a decrease in reflectivity is suppressed, and sufficient glitter is obtained. On the other hand, if the thickness of the metal thin film is 500 nm or less, the occurrence of whitening of the appearance can be suppressed.
保護膜は、金属薄膜を被覆して腐食を防止するものであり、金属薄膜用塗料を硬化後の保護膜の膜厚が１〜１０μｍ程度となるように金属薄膜上に塗布し、１００〜１２０℃で５〜１５分程度の条件で加熱乾燥することで形成できる。
金属薄膜用塗料としては、例えば金属薄膜の光輝感を損なうことのないクリヤー塗料が好ましく、例えばアクリル系ラッカー塗料、アクリルメラミン硬化系クリヤー塗料、アルミキレート型アクリル系塗料などが挙げられる。
The protective film covers the metal thin film to prevent corrosion, and the metal thin film coating is applied on the metal thin film so that the thickness of the protective film after curing is about 1 to 10 μm. It can be formed by heating and drying at 5 ° C. for about 5 to 15 minutes.
As the coating for the metal thin film, for example, a clear coating that does not impair the glitter of the metal thin film is preferable, and examples thereof include an acrylic lacquer coating, an acrylic melamine curing clear coating, and an aluminum chelate acrylic coating.
また、保護膜は、ケイ素有機系化合物ガスをプラズマ化することでも形成できる。プラズマ化の方法としては、公知の方法を用いることができる。例えば、本発明の塗料組成物よりなる塗膜および金属薄膜が順次形成されたプラスチック基材をプラズマ重合装置に備え、減圧下、ヘキサメチレンジシロキサンガスと酸素ガスを通気しながら放電させてプラズマを発生させることで、金属薄膜上に保護膜が形成される。放電の際の圧力や電力等は特に制限されないが、保護膜の厚さが１０〜３００μｍになるように、圧力や電力等を調整するのが好ましい。 The protective film can also be formed by converting silicon organic compound gas into plasma. A known method can be used as the method for converting to plasma. For example, the plasma polymerization apparatus is provided with a plastic substrate on which a coating film and a metal thin film formed of the coating composition of the present invention are sequentially formed, and plasma is generated by discharging hexamethylenedisiloxane gas and oxygen gas under reduced pressure. By generating, a protective film is formed on the metal thin film. There are no particular restrictions on the pressure, power, etc. during discharge, but it is preferable to adjust the pressure, power, etc. so that the thickness of the protective film is 10-300 μm.
このようにして得られる本発明の耐熱性光輝部品の用途としては特に限定されないが、例えばプラスチック基材として耐熱素材を用いれば、ヘッドランプ、タールランプ、サイドランプ等の自動車反射鏡などに好適に用いることができる。特に比較的大光量が必要なヘッドランプ用として好適である。 The use of the heat-resistant bright part of the present invention thus obtained is not particularly limited. For example, if a heat-resistant material is used as a plastic base material, it is suitable for automobile reflectors such as headlamps, tar lamps and side lamps. Can be used. It is particularly suitable for a headlamp that requires a relatively large amount of light.
本発明の耐熱性光輝部品は、プラスチック基材上に金属薄膜を形成する前に、本発明の塗料組成物より形成される塗膜を形成するので、部品表面が平滑となり、良好な光学特性を維持できる。また、本発明の耐熱性光輝部品は、優れた耐熱性を有すると共に、プラスチック基材と塗膜との密着性が良好であるため、プラスチック基材として耐熱素材を用いることができ、軽量耐衝撃性にも優れる。 Since the heat-resistant glitter component of the present invention forms a coating film formed from the coating composition of the present invention before forming a metal thin film on a plastic substrate, the surface of the component becomes smooth and has good optical properties. Can be maintained. In addition, the heat-resistant glitter component of the present invention has excellent heat resistance and good adhesion between the plastic substrate and the coating film, so that a heat-resistant material can be used as the plastic substrate, and lightweight impact resistance Excellent in properties.
［共重合体（Ａ）（Ａ−１〜Ａ−１１）の調製］
冷却機、温度計、撹拌機およびモノマー滴下装置を備えた１リットルの四つ口フラスコに、表１に示す組成（１）の各成分を仕込み、撹拌下、内温９０℃になるまで加温した。ついで、表１に示す組成（２）の単量体混合物を９０分間にわたって滴下し、９０℃で８０分保持した。その後、表１に示す組成（３）を加え９２℃に昇温して２００分保持し、不揮発分４５％の共重合体（Ａ）（Ａ−１〜Ａ−１１）を得た。
表１中の重合開始剤は以下の通りである。
・重合開始剤Ａ：２，２’−アゾビス（２，４−ジメチルバレロニトリル）（和光純薬工業株式会社製）。
・重合開始剤Ｂ：パーブチルＯ（日本油脂株式会社製）。
[Preparation of copolymer (A) (A-1 to A-11)]
Each component of composition (1) shown in Table 1 is charged into a 1 liter four-necked flask equipped with a cooler, a thermometer, a stirrer, and a monomer dropping device, and heated under stirring to an internal temperature of 90 ° C. did. Next, a monomer mixture having the composition (2) shown in Table 1 was added dropwise over 90 minutes and held at 90 ° C. for 80 minutes. Thereafter, the composition (3) shown in Table 1 was added, the temperature was raised to 92 ° C. and held for 200 minutes to obtain copolymers (A) (A-1 to A-11) having a nonvolatile content of 45%.
The polymerization initiators in Table 1 are as follows.
Polymerization initiator A: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.).
-Polymerization initiator B: Perbutyl O (made by NOF Corporation).
得られた共重合体（Ａ）のガラス転移点を、ＪＩＳ Ｋ７１２１に準拠して測定した。結果を表１に示す。 The glass transition point of the obtained copolymer (A) was measured according to JIS K7121. The results are shown in Table 1.
［実施例１］
＜塗料組成物の調製＞
表２に示す固形分比率（質量比）で（Ａ）成分、（Ｂ）成分、（Ｃ）成分を混合して塗膜形成成分を調製し、これに光重合開始剤と、表面調整剤と、溶剤とを表２に示す固形分比率（質量比）で混合して、液状の塗料組成物を調製した。
[Example 1]
<Preparation of coating composition>
(A) component, (B) component, and (C) component are mixed by solid content ratio (mass ratio) shown in Table 2, and a coating-film formation component is prepared, A photoinitiator, a surface conditioner, and this are mixed. The solvent was mixed at a solid content ratio (mass ratio) shown in Table 2 to prepare a liquid coating composition.
（アミン価の測定）
硬化前の塗膜形成成分のアミン価を、ＪＩＳ Ｋ７２３７に準拠して測定し、これを塗膜形成成分のアミン価とした。結果を表２に示す。
(Measurement of amine value)
The amine value of the coating film-forming component before curing was measured according to JIS K7237, and this was used as the amine value of the coating film-forming component. The results are shown in Table 2.
（貯蔵安定性の評価）
得られた塗料組成物を４０℃で１カ月間保存し、その貯蔵安定性を目視にて観察し、以下に示す評価基準にて評価した。結果を表２に示す。
○：粘度変化が僅かであり、かつゲルが発生していない。
△：粘度の上昇は見られるが、ゲルは発生しておらず、塗装可能である。
×：粘度の上昇が著しく塗装不可能であるか、またはゲルが発生している。
(Evaluation of storage stability)
The obtained coating composition was stored at 40 ° C. for 1 month, its storage stability was visually observed, and evaluated according to the following evaluation criteria. The results are shown in Table 2.
○: Viscosity change is slight and no gel is generated.
Δ: Increase in viscosity is observed, but no gel is generated and coating is possible.
X: The increase in viscosity is remarkably impossible to paint, or gel is generated.
＜耐熱性光輝部品の製造＞
プラスチック基材として、ＢＭＣ（バルクモールディングコンパウンド）素材、およびＰＰＳ（ポリフェニレンサルファイド）素材の自動車反射鏡用の耐熱素材成形品を用いた。
各プラスチック基材をイソプロピルアルコールで洗浄し、乾燥後、先に調製した塗料組成物を硬化後の膜厚が１０〜１５μｍになるように、プラスチック基材の表面にスプレーガンでエアースプレー塗装した。その後、８０℃×１０分の条件でプレヒートして溶剤を除去した。ついで、８０Ｗ／ｃｍのオゾンタイプ拡散型の高圧水銀灯を使用して、１０００ｍＪ／ｃｍ２の照射量の紫外線を照射することで硬化させて、プラスチック基材上に塗膜を形成した。
<Manufacture of heat-resistant bright parts>
As the plastic substrate, a heat-resistant material molded product for an automobile reflector made of BMC (bulk molding compound) material and PPS (polyphenylene sulfide) material was used.
Each plastic substrate was washed with isopropyl alcohol and dried, and then the surface of the plastic substrate was air-sprayed with a spray gun so that the film thickness after curing of the previously prepared coating composition was 10 to 15 μm. Thereafter, the solvent was removed by preheating at 80 ° C. for 10 minutes. Subsequently, using an ozone type diffusion type high pressure mercury lamp of 80 W / cm, it was cured by irradiating with an irradiation amount of 1000 mJ / cm 2 to form a coating film on the plastic substrate.
ついで、蒸着装置（（株）アルバック製「ＥＸ−２００」）にセットし、真空度が１．３×１０−２Ｐａになるまで減圧した後、アルミニウムを７００℃に加熱することで、塗膜上にアルミニウムを真空蒸着させ、金属薄膜（アルミニウム蒸着膜）を形成した。該アルミニウム蒸着膜の厚さは１５０ｎｍであった。 Then, after setting in a vapor deposition apparatus ("EX-200" manufactured by ULVAC, Inc.) and reducing the pressure to 1.3 × 10 −2 Pa, the aluminum was heated to 700 ° C. Aluminum was vacuum deposited thereon to form a metal thin film (aluminum vapor deposition film). The thickness of the aluminum vapor deposition film was 150 nm.
別途、ユピカコート３００２Ａ（日本ユピカ株式会社製）を２０質量部と、トルエンを３５質量部と、ソルベッソ＃１００を４０質量部と、ｎ−ブタノールを５質量部とを混合してクリヤー塗料を調製した。
得られたクリヤー塗料を、乾燥膜厚が３μｍになるように、金属薄膜の表面にスプレーガンでエアースプレー塗装した。その後、１２０℃×１０分の条件で焼き付けて、金属薄膜上に保護膜を形成し、試験片（自動車反射鏡用の耐熱性光輝部品）を製造した。なお、プラスチック基材として、ＢＭＣ素材を用いて得られた自動車反射鏡用の耐熱性光輝部品を「試験片１」、ＰＰＳ素材を用いて得られた自動車反射鏡用の耐熱性光輝部品を「試験片２」とする。
このようにして得られた試験片について、以下に示すように、平滑性の評価、初期評価、耐熱性の評価、耐湿性の評価を実施した。結果を表５に示す。
Separately, 20 parts by mass of Iupika Coat 3002A (manufactured by Nippon Iupika Co., Ltd.), 35 parts by mass of toluene, 40 parts by mass of Solvesso # 100, and 5 parts by mass of n-butanol were mixed to prepare a clear paint. .
The obtained clear paint was air spray-coated with a spray gun on the surface of the metal thin film so that the dry film thickness was 3 μm. Then, it baked on conditions (120 degreeC x 10 minutes), formed the protective film on the metal thin film, and manufactured the test piece (heat-resistant luminescent component for motor vehicle reflectors). In addition, as a plastic substrate, a heat-resistant glittering part for an automobile reflector obtained using a BMC material is “test piece 1”, and a heat-resistant glittering part for an automobile reflector obtained using a PPS material is “ Test piece 2 ”.
The test pieces thus obtained were evaluated for smoothness, initial evaluation, heat resistance, and moisture resistance as shown below. The results are shown in Table 5.
＜平滑性の評価＞
試験片１の製造過程において、塗膜上に金属薄膜を形成した後の蒸着面を目視にて観察し、以下の評価基準にて評価した。
○：ユズ肌が見られない。
△：わずかにユズ肌が見られるが、使用可能な範囲である。
×：明らかにユズ肌が見られる。
<Evaluation of smoothness>
In the manufacturing process of the test piece 1, the vapor deposition surface after forming a metal thin film on a coating film was observed visually, and the following evaluation criteria evaluated.
○: Yuzu skin is not seen.
(Triangle | delta): Although the skin is slightly seen, it is the range which can be used.
X: Yuzu skin is clearly seen.
＜初期評価＞
（外観光沢の評価）
試験片１の外観について、虹や白化等の欠陥の有無を目視にて観察し、以下の評価基準にて評価した。
○：光沢に優れ、虹や白化等の欠陥がない。
△：僅かに虹や白化等の欠陥がある。
×：虹や白化等の欠陥がある。
<Initial evaluation>
(Appearance gloss evaluation)
About the external appearance of the test piece 1, the presence or absence of defects, such as a rainbow and whitening, was observed visually, and the following evaluation criteria evaluated.
○: Excellent gloss and no defects such as rainbow and whitening.
Δ: There are slight defects such as rainbow and whitening.
X: There are defects such as rainbow and whitening.
（外観状態の評価）
試験片１の外観について、クラックやフクレ等の欠陥の有無を目視にて観察し、以下の評価基準にて評価した。
○：クラックやフクレ等の欠陥がない。
△：僅かにクラックやフクレ等の欠陥がある。
×：クラックやフクレ等の欠陥がある。
(Evaluation of appearance)
About the external appearance of the test piece 1, the presence or absence of defects, such as a crack and a blister, was observed visually, and the following evaluation criteria evaluated.
○: There are no defects such as cracks and blisters.
Δ: There are slight defects such as cracks and blisters.
X: There are defects such as cracks and blisters.
（密着性の評価）
試験片１の保護膜上に、２ｍｍ幅で１０×１０の碁盤目状にカッターナイフで切れ目を入れ、その上からセロハン粘着テープを貼着した後、急速に剥がす操作を行い、剥離せずに残存した碁盤目の数を数え、以下の評価基準にて評価した。
○：碁盤目の残存数が１００個。
△：碁盤目の残存数が９１〜９９個。
×：碁盤目の残存数が９０個以下。
(Evaluation of adhesion)
On the protective film of the test piece 1, cut with a cutter knife in a 2 mm width and 10 × 10 grid pattern, and after applying cellophane adhesive tape on top of it, perform the operation of peeling off quickly, without peeling The number of remaining grids was counted and evaluated according to the following evaluation criteria.
○: The number of remaining grids is 100.
(Triangle | delta): 91-99 remaining number of grids.
X: The number of remaining grids is 90 or less.
＜耐熱性の評価１＞
試験片１を１８０℃の熱風循環式乾燥炉の中で９６時間放置した後、取り出し、室温まで放冷し、耐熱試験を実施した。耐熱試験後の試験片１の外観光沢、外観状態、および密着性について、初期評価と同様にして評価した。
<Evaluation of heat resistance 1>
The test piece 1 was left for 96 hours in a hot air circulation drying oven at 180 ° C., then taken out, allowed to cool to room temperature, and subjected to a heat resistance test. The appearance gloss, appearance state, and adhesion of the test piece 1 after the heat test were evaluated in the same manner as the initial evaluation.
＜耐熱性の評価２＞
試験片２を２３０℃の熱風循環式乾燥炉の中で９６時間放置した後、取り出し、室温まで放冷し、耐熱試験を実施した。耐熱試験後の試験片２の外観光沢、外観状態、および密着性について、初期評価と同様にして評価した。
<Evaluation of heat resistance 2>
The test piece 2 was left in a hot air circulation drying oven at 230 ° C. for 96 hours, then taken out, allowed to cool to room temperature, and subjected to a heat resistance test. The appearance gloss, appearance state, and adhesion of the test piece 2 after the heat test were evaluated in the same manner as the initial evaluation.
＜耐湿性の評価＞
試験片１を温度５０℃、湿度９５ＲＨ％の恒温恒湿器の中で２４０時間放置した後、取り出し、軽く布でぬぐい、耐湿試験を実施した。耐湿試験後の試験片１の外観光沢、外観状態、および密着性について、初期評価と同様にして評価した。
<Evaluation of moisture resistance>
The test piece 1 was left in a constant temperature and humidity chamber at a temperature of 50 ° C. and a humidity of 95 RH% for 240 hours, then taken out, lightly wiped with a cloth, and a moisture resistance test was performed. The appearance gloss, appearance state, and adhesion of the test piece 1 after the moisture resistance test were evaluated in the same manner as the initial evaluation.
［実施例２〜１１］
表２、３に示す固形分比率（質量比）で（Ａ）成分、（Ｂ）成分、（Ｃ）成分を混合して塗膜形成成分を調製し、これに光重合開始剤と、表面調整剤と、溶剤とを表２、３に示す固形分比率（質量比）で混合した以外は、実施例１と同様にして、液状の塗料組成物を調製し、各測定および評価を実施した。結果を表２、３に示す。
また、各実施例で得られた塗料組成物を用いた以外は、実施例１と同様にして試験片１、２を製造し、各評価を実施した。結果を表５、６に示す。
[Examples 2 to 11]
(A) component, (B) component, and (C) component are mixed by the solid content ratio (mass ratio) shown in Table 2, 3, and a coating-film formation component is prepared, and a photoinitiator and surface adjustment are prepared for this. A liquid coating composition was prepared in the same manner as in Example 1 except that the agent and the solvent were mixed at a solid content ratio (mass ratio) shown in Tables 2 and 3, and each measurement and evaluation were performed. The results are shown in Tables 2 and 3.
Moreover, the test pieces 1 and 2 were manufactured similarly to Example 1 except having used the coating composition obtained by each Example, and each evaluation was implemented. The results are shown in Tables 5 and 6.
［実施例１２］
表３に示す固形分比率（質量比）で（Ａ）成分、（Ｂ）成分、（Ｃ）成分を混合して塗膜形成成分を調製し、これに光重合開始剤と、表面調整剤と、溶剤とを表３に示す固形分比率（質量比）で混合した以外は、実施例１と同様にして、液状の塗料組成物を調製し、各測定および評価を実施した。結果を表３に示す。
また、得られた塗料組成物を用いた以外は、実施例１と同様にして塗膜上に金属薄膜を形成した。ついで、透明塗膜と金属酸化物層が順次形成されたプラスチック基材をプラズマ重合装置（ＵＬＶＡＣ社製、「ＣＰＶ−４５０」）にセットし、減圧下、ヘキサメチレンジシロキサンガスを２０ｓｃｃｍと、酸素ガスを１００ｓｃｃｍの割合で通気しながら、圧力を２．３×１０−１Ｐａに調節・保持し、１３５６ＭＨｚ、８００Ｗ／ｃｍ２の低周波電力を与えながら放電させてプラズマを発生させた。この状態で、８０℃で１０分間保持し、膜厚が０．０６μｍの保護膜を金属薄膜上に形成し、試験片１、２を製造した。
得られた試験片１、２について、実施例１と同様にして各評価を実施した。結果を表６に示す。
[Example 12]
(A) component, (B) component, and (C) component are mixed by solid content ratio (mass ratio) shown in Table 3, and a coating-film formation component is prepared, A photoinitiator, a surface conditioner, and this are mixed. A liquid coating composition was prepared in the same manner as in Example 1 except that the solvent was mixed at a solid content ratio (mass ratio) shown in Table 3, and each measurement and evaluation were performed. The results are shown in Table 3.
Further, a metal thin film was formed on the coating film in the same manner as in Example 1 except that the obtained coating composition was used. Next, a plastic base material on which a transparent coating film and a metal oxide layer are sequentially formed is set in a plasma polymerization apparatus (“CPV-450” manufactured by ULVAC), and under reduced pressure, hexamethylenedisiloxane gas is 20 sccm, oxygen While venting the gas at a rate of 100 sccm, the pressure was adjusted and maintained at 2.3 × 10 −1 Pa, and plasma was generated by discharging while applying low frequency power of 1356 MHz and 800 W / cm 2 . In this state, the specimen was held at 80 ° C. for 10 minutes, and a protective film having a thickness of 0.06 μm was formed on the metal thin film to produce test pieces 1 and 2.
Each test piece 1 and 2 thus obtained was evaluated in the same manner as in Example 1. The results are shown in Table 6.
［比較例１〜６］
表４に示す固形分比率（質量比）で（Ａ）成分、（Ｂ）成分、（Ｃ）成分を混合して塗膜形成成分を調製し、これに光重合開始剤と、表面調整剤と、溶剤とを表４に示す固形分比率（質量比）で混合した以外は、実施例１と同様にして、液状の塗料組成物を調製し、各測定および評価を実施した。結果を表４に示す。
また、各比較例で得られた塗料組成物を用いた以外は、実施例１と同様にして試験片１、２を製造し、各評価を実施した。結果を表７に示す。
[Comparative Examples 1-6]
(A) component, (B) component, and (C) component are mixed by the solid content ratio (mass ratio) shown in Table 4, and a coating-film formation component is prepared, A photoinitiator, a surface conditioner, and this are mixed. A liquid coating composition was prepared in the same manner as in Example 1 except that the solvent and the solvent were mixed at a solid content ratio (mass ratio) shown in Table 4, and each measurement and evaluation were performed. The results are shown in Table 4.
Moreover, the test pieces 1 and 2 were manufactured similarly to Example 1 except having used the coating composition obtained by each comparative example, and each evaluation was implemented. The results are shown in Table 7.
［比較例７］
表４に示す固形分比率（質量比）で（Ａ）成分、（Ｂ）成分、（Ｃ）成分を混合して塗膜形成成分を調製し、これに光重合開始剤と、表面調整剤と、溶剤とを表４に示す固形分比率（質量比）で混合した以外は、実施例１と同様にして、液状の塗料組成物を調製し、各測定および評価を実施した。結果を表４に示す。
また、得られた塗料組成物を用いた以外は、実施例１２と同様にして試験片１、２を製造し、各評価を実施した。結果を表７に示す。
[Comparative Example 7]
(A) component, (B) component, and (C) component are mixed by the solid content ratio (mass ratio) shown in Table 4, and a coating-film formation component is prepared, A photoinitiator, a surface conditioner, and this are mixed. A liquid coating composition was prepared in the same manner as in Example 1 except that the solvent and the solvent were mixed at a solid content ratio (mass ratio) shown in Table 4, and each measurement and evaluation were performed. The results are shown in Table 4.
Moreover, the test pieces 1 and 2 were manufactured similarly to Example 12 except having used the obtained coating composition, and each evaluation was implemented. The results are shown in Table 7.
なお、表２〜４中の各成分は、以下の通りである。
・カヤラッドＤＰＨＡ：ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（日本化薬株式会社製）。
・ＮＫエステルＡ−ＴＭＭ−Ｔ：ペンタエリスリトールテトラアクリレート（新中村化学工業製）。
・ＮＫエステルＡ−ＴＭＭ−３Ｌ：ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物（新中村化学工業製）。
・ＮＫエステルＡＰＧ−２００：トリプロピレングリコールジアクリレート（新中村化学工業製）。
・アデカハードナーＧＭ−６６５：ポリアミドアミン（株式会社ＡＤＥＫＡ製、アミン価７３０ｍｇＫＯＨ／ｇ）。
・エピクロンＥＸＢ−３５３：ポリアミン（ＤＩＣ株式会社製、アミン価１０００〜１１５０ｍｇＫＯＨ／ｇ）。
・イルガキュア６５１：光重合開始剤（チバ・スペシャルティ・ケミカルズ株式会社製）。
・メガファックＦ−４７７：表面改質剤（ＤＩＣ株式会社製）。
In addition, each component in Tables 2-4 is as follows.
Kayrad DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.).
NK ester A-TMM-T: pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
NK ester A-TMM-3L: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.).
NK ester APG-200: tripropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Adeka Hardener GM-665: Polyamidoamine (manufactured by ADEKA Corporation, amine value 730 mgKOH / g).
Epicron EXB-353: polyamine (manufactured by DIC Corporation, amine value 1000 to 1150 mg KOH / g).
-Irgacure 651: Photopolymerization initiator (manufactured by Ciba Specialty Chemicals).
-Megafuck F-477: Surface modifier (made by DIC Corporation).
表５、６から明らかなように、各実施例で得られた塗料組成物は、貯蔵安定性に優れていた。また、該塗料組成物より形成された塗膜は、耐熱素材からなるプラスチック基材との密着性に優れると共に、耐熱性および耐湿性が良好であった。
一方、表７から明らかなように、ガラス転移点が−６７．９℃である共重合体（Ａ）を含む塗料組成物を用いた比較例１の場合、塗膜や金属薄膜の外観に虹や白化等の劣化が生じやすかった。また、塗膜の耐熱性や耐湿性が低かった。
ガラス転移点が３３．７℃である共重合体（Ａ）を含む塗料組成物を用いた比較例２、７の場合、塗膜とプラスチック基材との密着性が低かった。
アミン価が２１９．４ｍｇＫＯＨ／ｇである塗膜形成成分を含む塗料組成物を用いた比較例３の場合、塗膜や金属薄膜の外観に虹や白化等の劣化が生じやすかった。また、塗膜の耐熱性や耐湿性が低かった。
アミン価が１１．１ｍｇＫＯＨ／ｇである塗膜形成成分を含む塗料組成物を用いた比較例４の場合、塗膜の耐熱性が低く、クラックやフクレ等の劣化が生じやすかった。また、塗料組成物の貯蔵安定性が低かった。
スチレン単量体を用いずに共重合して得た共重合体（Ａ）を含む塗料組成物を用いた比較例５の場合、塗膜とプラスチック基材との密着性が低かった。
アルキロール（メタ）アクリルアミド単量体を用いずに共重合して得た共重合体（Ａ）を含む塗料組成物を用いた比較例６の場合、塗膜の耐熱性が低く、塗膜や金属薄膜の外観に虹や白化等の劣化が生じやすかった。
As is clear from Tables 5 and 6, the coating compositions obtained in each Example were excellent in storage stability. In addition, the coating film formed from the coating composition was excellent in adhesion to a plastic substrate made of a heat-resistant material, and good in heat resistance and moisture resistance.
On the other hand, as is clear from Table 7, in the case of Comparative Example 1 using the coating composition containing the copolymer (A) having a glass transition point of −67.9 ° C., the appearance of the coating film and the metal thin film was not reduced. Deterioration such as whitening or whitening was likely to occur. Moreover, the heat resistance and moisture resistance of the coating film were low.
In Comparative Examples 2 and 7 using the coating composition containing the copolymer (A) having a glass transition point of 33.7 ° C., the adhesion between the coating film and the plastic substrate was low.
In the case of Comparative Example 3 using a coating composition containing a coating film forming component having an amine value of 219.4 mg KOH / g, the appearance of the coating film or the metal thin film was likely to deteriorate such as rainbow or whitening. Moreover, the heat resistance and moisture resistance of the coating film were low.
In the case of Comparative Example 4 using a coating composition containing a coating film forming component having an amine value of 11.1 mg KOH / g, the heat resistance of the coating film was low, and deterioration such as cracks and swelling was likely to occur. Moreover, the storage stability of the coating composition was low.
In Comparative Example 5 using a coating composition containing a copolymer (A) obtained by copolymerization without using a styrene monomer, the adhesion between the coating film and the plastic substrate was low.
In the case of Comparative Example 6 using the coating composition containing the copolymer (A) obtained by copolymerization without using an alkylol (meth) acrylamide monomer, the heat resistance of the coating film is low, Deterioration such as rainbow and whitening was likely to occur on the appearance of the metal thin film.
Claims (8)
前記塗膜形成成分は、スチレン単量体、アルキロール（メタ）アクリルアミド単量体、および（メタ）アクリロイル単量体を含む単量体混合物を共重合して得られる、ガラス転移点が−６０〜２０℃である共重合体（Ａ）と、活性エネルギー線硬化性化合物（Ｂ）とを含有し、
かつ前記塗膜形成成分は、アミン価が１５〜２００ｍｇＫＯＨ／ｇであることを特徴とする活性エネルギー線硬化型塗料組成物。 In an active energy ray-curable coating composition for undercoating a metal thin film, comprising a coating film forming component, a photopolymerization initiator, and a solvent,
The coating film-forming component is obtained by copolymerizing a monomer mixture containing a styrene monomer, an alkylol (meth) acrylamide monomer, and a (meth) acryloyl monomer, and has a glass transition point of −60. Containing a copolymer (A) which is -20 ° C and an active energy ray-curable compound (B),
The coating film-forming component has an amine value of 15 to 200 mgKOH / g, and is an active energy ray-curable coating composition.
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