JP2008095012A - Coating composition for decorated molded product, and decorated molded product - Google Patents
Coating composition for decorated molded product, and decorated molded product Download PDFInfo
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本発明は、ポリプロピレン系樹脂成形品の表面に水圧転写印刷層を有する加飾成形品の、水圧転写印刷層の表面に塗布される加飾成形品用塗料組成物、およびポリプロピレン系樹脂成形品の表面に水圧転写印刷層を有する加飾成形品に関する。 The present invention relates to a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product, a decorative molded product coating composition applied to the surface of a hydraulic transfer printing layer, and a polypropylene resin molded product. The present invention relates to a decorative molded product having a hydraulic transfer printing layer on the surface.
自動車の内装部品には、プラスチック成形品の表面に水圧転写印刷を施した加飾成形品が用いられている。該加飾成形品の水圧転写印刷層の表面には、耐久性、耐水性、耐薬品性、耐光性等を付与する目的で、保護用の塗膜が設けられている。プラスチック成形品の材料としては、主に、ＡＢＳ（アクリロニトリル−ブタジエン−スチレン）樹脂、ポリカーボネート、ポリウレタンが用いられている。近年、リサイクル性、コスト等の点から、プラスチック成形品の材料としては、ポリプロピレン系樹脂が用いられるようになってきている。しかし、難付着性であるポリプロピレン系樹脂は、水圧転写印刷層との密着性に乏しいという問題がある。そのため、ポリプロピレン系樹脂成形品と水圧転写印刷層との間にプライマー処理を施す必要がある。または、水圧転写印刷層と保護用の塗膜との間にプライマー処理を施し、プライマーを水圧転写印刷層に浸透させることにより、ポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性を改善する必要がある。しかし、プライマー処理には手間およびコストがかかるため、プライマー処理を施した場合には、低コストというポリプロピレン系樹脂の利点を生かしきれない。 For interior parts of automobiles, decorative molded products obtained by performing hydraulic transfer printing on the surface of plastic molded products are used. The surface of the hydraulic transfer printing layer of the decorative molded product is provided with a protective coating film for the purpose of imparting durability, water resistance, chemical resistance, light resistance and the like. As materials for plastic molded articles, ABS (acrylonitrile-butadiene-styrene) resin, polycarbonate, and polyurethane are mainly used. In recent years, polypropylene resins have come to be used as materials for plastic molded products from the viewpoint of recyclability and cost. However, polypropylene resins that are difficult to adhere have a problem of poor adhesion to the hydraulic transfer printing layer. Therefore, it is necessary to perform a primer treatment between the polypropylene resin molded product and the hydraulic transfer printing layer. Alternatively, by applying a primer treatment between the hydraulic transfer printing layer and the protective coating, and allowing the primer to penetrate into the hydraulic transfer printing layer, the adhesion between the polypropylene resin molded product and the hydraulic transfer printing layer is improved. There is a need to improve. However, since the primer treatment takes time and cost, when the primer treatment is performed, the advantage of the polypropylene resin, which is low cost, cannot be fully utilized.
プライマー処理が不要な加飾成形品用塗料組成物としては、下記組成物が提案されている。
（イ）スチレン２０〜７０質量％およびメタクリル酸イソブチルまたはメタクリル酸ｔｅｒｔ−ブチル２０〜７０質量％を含む単量体成分を溶液重合して得られるポリオール樹脂であって、ポリスチレン換算での質量平均分子量が３０００〜２００００であり、水酸基価が１０〜１００ｍｇＫＯＨ／ｇであり、酸価が０〜３０ｍｇＫＯＨ／ｇであり、ガラス転移温度が５０℃以上であるポリオール樹脂と、（ロ）前記ポリオール樹脂の水酸基と反応可能なイソシアネート化合物とからなる硬化性樹脂組成物（特許文献１）。
The following composition is proposed as a coating composition for decorative molded articles that do not require primer treatment.
(A) A polyol resin obtained by solution polymerization of a monomer component containing 20 to 70% by mass of styrene and 20 to 70% by mass of isobutyl methacrylate or tert-butyl methacrylate, and having a mass average molecular weight in terms of polystyrene Is a polyol resin having a hydroxyl value of 10 to 100 mgKOH / g, an acid value of 0 to 30 mgKOH / g, and a glass transition temperature of 50 ° C. or higher, and (b) a hydroxyl group of the polyol resin. A curable resin composition comprising an isocyanate compound capable of reacting with (Patent Document 1).
該硬化性樹脂組成物からなる塗膜は、比較的硬く、かつ強度が高いため、各種プラスチック成形品と水圧転写印刷層との間の不完全な密着性を補うことができる。しかし、該硬化性樹脂組成物を、ポリプロピレン系樹脂成形品の表面に転写された水圧転写印刷層の表面に塗布した場合、塗布直後におけるポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性（初期密着性）は充分であるものの、塗膜がガソリン、油脂等にさらされると、水圧転写印刷層への塗膜の密着性が著しく低下し、その結果、ポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性も低下してしまう。
よって、本発明の目的は、水圧転写印刷層への密着性、耐ガソリン性、耐油性に優れ、かつプライマー処理を施すことなくポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性を改善できる塗膜を形成できる加飾成形品用塗料組成物、およびプライマー処理を施すことなくポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性に優れ、かつガソリン、油脂等にさらされても該密着性が低下しにくい加飾成形品を提供することにある。 Therefore, the object of the present invention is excellent in adhesion to the hydraulic transfer printing layer, gasoline resistance, oil resistance, and adhesion between the polypropylene resin molded product and the hydraulic transfer printing layer without applying a primer treatment. Coating compositions for decorative molded products that can form coatings that can be improved, and excellent adhesion between polypropylene resin molded products and hydraulic transfer printing layers without primer treatment, and are exposed to gasoline, fats and oils, etc. However, the present invention is to provide a decorative molded product in which the adhesion is not easily lowered.
本発明の加飾成形品用塗料組成物は、ポリプロピレン系樹脂成形品の表面に水圧転写印刷層を有する加飾成形品の、水圧転写印刷層の表面に塗布される塗料組成物であり、下記アクリルポリオール樹脂と、ポリイソシアネート化合物とを含有することを特徴とする。
（アクリルポリオール樹脂）
メタクリル酸メチルを２５〜８５質量％含む単量体成分を重合して得られる共重合体であり、ポリスチレン換算での質量平均分子量が、２０００〜３００００であり、水酸基価が、１０〜１００ｍｇＫＯＨ／ｇであり、ガラス転移温度が、６０℃以上である、アクリルポリオール樹脂。
The coating composition for a decorative molded product of the present invention is a coating composition applied to the surface of a hydraulic transfer printing layer of a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product. An acrylic polyol resin and a polyisocyanate compound are contained.
(Acrylic polyol resin)
A copolymer obtained by polymerizing a monomer component containing 25 to 85% by mass of methyl methacrylate, having a mass average molecular weight in terms of polystyrene of 2000 to 30000, and a hydroxyl value of 10 to 100 mgKOH / g. An acrylic polyol resin having a glass transition temperature of 60 ° C. or higher.
前記単量体成分は、ヒドロキシアルキル基の炭素数が２〜４である（メタ）アクリル酸ヒドロキシアルキルを３〜２０質量％含むことが好ましい。
前記単量体成分は、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ｎ−ブチルおよびスチレンからなる群から選ばれる１種以上を、合計で１〜１５質量％含んでいてもよい。
本発明の加飾成形品は、ポリプロピレン系樹脂成形品の表面に水圧転写印刷層を有する加飾成形品であり、前記水圧転写印刷層の表面に、本発明の加飾成形品用塗料組成物からなる塗膜を有することを特徴とする。
The monomer component preferably contains 3 to 20% by mass of hydroxyalkyl (meth) acrylate having 2 to 4 carbon atoms in the hydroxyalkyl group.
The monomer component is a total of 1 to 15 masses of at least one selected from the group consisting of isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-butyl (meth) acrylate and styrene. % May be included.
The decorative molded product of the present invention is a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product, and the coating composition for a decorative molded product of the present invention on the surface of the hydraulic transfer printed layer. It has the coating film which consists of.
本発明の加飾成形品用塗料組成物は、水圧転写印刷層への密着性、耐ガソリン性、耐油性に優れ、かつプライマー処理を施すことなくポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性を改善できる塗膜を形成できる。
本発明の加飾成形品は、プライマー処理を施すことなくポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性に優れ、かつガソリン、油脂等にさらされても該密着性が低下しにくい。
The coating composition for a decorative molded product of the present invention is excellent in adhesion to a hydraulic transfer printing layer, gasoline resistance and oil resistance, and without being subjected to primer treatment, a polypropylene resin molded product and a hydraulic transfer printing layer. The coating film which can improve the adhesiveness between can be formed.
The decorative molded product of the present invention has excellent adhesion between the polypropylene resin molded product and the hydraulic transfer printing layer without applying a primer treatment, and the adhesion decreases even when exposed to gasoline, fats and oils, etc. Hateful.
＜加飾成形品用塗料組成物＞
本発明の加飾成形品用塗料組成物は、ポリプロピレン系樹脂成形品の表面に水圧転写印刷層を有する加飾成形品の、水圧転写印刷層の表面に塗布される塗料組成物であり、特定のアクリルポリオール樹脂と、ポリイソシアネート化合物とを含有する組成物である。
<Coating composition for decorative molded product>
The coating composition for a decorative molded product of the present invention is a coating composition applied to the surface of a hydraulic transfer printing layer of a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product. It is a composition containing the acrylic polyol resin and polyisocyanate compound.
（アクリルポリオール樹脂）
アクリルポリオール樹脂は、メタクリル酸メチルを２５〜８５質量％含む単量体成分を重合して得られる共重合体である。
メタクリル酸メチルが単量体成分（１００質量％）中２５質量％以上であれば、耐ガソリン性、耐油性、耐久性に優れる塗膜を形成できる。メタクリル酸メチルが単量体成分（１００質量％）中８５質量％以下であれば、耐水性、耐アルカリ性、耐酸性に優れる塗膜を形成できる。メタクリル酸メチルの量は、単量体成分（１００質量％）中、２５〜７５質量％が好ましく、２５〜６５質量％がより好ましい。
(Acrylic polyol resin)
The acrylic polyol resin is a copolymer obtained by polymerizing a monomer component containing 25 to 85% by mass of methyl methacrylate.
When methyl methacrylate is 25% by mass or more in the monomer component (100% by mass), a coating film having excellent gasoline resistance, oil resistance and durability can be formed. If methyl methacrylate is 85 mass% or less in a monomer component (100 mass%), the coating film which is excellent in water resistance, alkali resistance, and acid resistance can be formed. The amount of methyl methacrylate is preferably 25 to 75% by mass and more preferably 25 to 65% by mass in the monomer component (100% by mass).
単量体成分は、メタクリル酸メチル以外の単量体（以下、他の単量体と記す。）を含んでいてもよい。
他の単量体としては、スチレン、α−メチルスチレン、（メタ）アクリル酸、アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸イソペンタニル、（メタ）アクリル酸フェノキシエチル等が挙げられる。（メタ）アクリル酸は、アクリル酸またはメタクリル酸を意味する。
The monomer component may contain a monomer other than methyl methacrylate (hereinafter referred to as other monomer).
Other monomers include styrene, α-methylstyrene, (meth) acrylic acid, methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth ) Tert-butyl acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, isopentanyl (meth) acrylate And phenoxyethyl (meth) acrylate. (Meth) acrylic acid means acrylic acid or methacrylic acid.
他の単量体としては、ヒドロキシアルキル基の炭素数が２〜４である（メタ）アクリル酸ヒドロキシアルキルが好ましい。該（メタ）アクリル酸ヒドロキシアルキルとしては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル等が挙げられる。 As the other monomer, hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms is preferable. Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Etc.
該（メタ）アクリル酸ヒドロキシアルキルの量は、単量体成分（１００質量％）中、３〜２０質量％が好ましく、５〜１６質量％がより好ましい。該（メタ）アクリル酸ヒドロキシアルキルが３質量％以上であれば、耐薬品性に優れる塗膜を形成できる。該（メタ）アクリル酸ヒドロキシアルキルが２０質量％以下であれば、塗膜の過剰な硬化収縮が抑えられ、水圧転写印刷層への塗膜の密着性が良好となる。 3-20 mass% is preferable in a monomer component (100 mass%), and, as for the quantity of this hydroxyalkyl (meth) acrylate, 5-16 mass% is more preferable. When the hydroxyalkyl (meth) acrylate is 3% by mass or more, a coating film having excellent chemical resistance can be formed. When the hydroxyalkyl (meth) acrylate is 20% by mass or less, excessive curing shrinkage of the coating film is suppressed, and the adhesion of the coating film to the hydraulic transfer printing layer is improved.
単量体成分は、他の単量体として、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ｎ−ブチルおよびスチレンからなる群から選ばれる１種以上を、合計で１〜１５質量％含んでいてもよい。該単量体の合計が１〜１５質量％であれば、外観に優れる塗膜を形成できる。なお、本発明においては、単量体成分がメタクリル酸メチルを２５〜８５質量％含むため、特許文献１に記載の発明に比べ、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ｎ−ブチルおよびスチレンの量を減らしても、充分に外観に優れる塗膜を形成できる。 The monomer component contains, as another monomer, at least one selected from the group consisting of isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-butyl (meth) acrylate, and styrene. You may contain 1-15 mass% in total. When the total amount of the monomers is 1 to 15% by mass, a coating film having excellent appearance can be formed. In addition, in this invention, since a monomer component contains 25-85 mass% of methyl methacrylate, compared with the invention of patent document 1, (butyl) (meth) acrylate, tert-butyl (meth) acrylate, Even if the amount of n-butyl (meth) acrylate and styrene is reduced, a coating film having a sufficiently excellent appearance can be formed.
アクリルポリオール樹脂の質量平均分子量は、２０００〜３００００であり、４０００〜２５０００が好ましく、４０００〜２００００がより好ましい。アクリルポリオール樹脂の質量平均分子量が２０００以上であれば、耐久性に優れる塗膜を形成できる。アクリルポリオール樹脂の質量平均分子量が３００００以下であれば、塗膜が水圧転写印刷層の凹凸の影響を受けにくくなり、平滑な塗膜が形成され、外観に優れる塗膜が形成される。さらに、アクリルポリオール樹脂の質量平均分子量が２００００以下であれば、肉厚で、かつ透明な塗膜が形成されるため、水圧転写印刷層の柄が鮮明となり、しかも水圧転写印刷層に奥行き感、肉持ち感を付与できる。その結果、高品質な外観を有し、意匠性に優れるポリプロピレン系樹脂成形品を得ることができる。
アクリルポリオール樹脂の質量平均分子量は、ゲルパーミエイションクロマトグラフィーによって測定される、スチレン換算の質量平均分子量である。
The mass average molecular weight of the acrylic polyol resin is 2000 to 30000, preferably 4000 to 25000, and more preferably 4000 to 20000. When the acrylic polyol resin has a mass average molecular weight of 2000 or more, a coating film having excellent durability can be formed. When the mass average molecular weight of the acrylic polyol resin is 30000 or less, the coating film is hardly affected by the unevenness of the hydraulic transfer printing layer, a smooth coating film is formed, and a coating film having excellent appearance is formed. Furthermore, if the weight average molecular weight of the acrylic polyol resin is 20000 or less, a thick and transparent coating film is formed, so that the pattern of the hydraulic transfer printing layer becomes clear, and the hydraulic transfer printing layer has a sense of depth, A feeling of flesh can be given. As a result, it is possible to obtain a polypropylene resin molded product having a high quality appearance and excellent design.
The mass average molecular weight of the acrylic polyol resin is a styrene equivalent mass average molecular weight measured by gel permeation chromatography.
アクリルポリオール樹脂の水酸基価は、１０〜１００ｍｇＫＯＨ／ｇであり、２０〜８０ｍｇＫＯＨ／ｇが好ましく、３０〜７０ｍｇＫＯＨ／ｇがより好ましい。アクリルポリオールの水酸基価が１０ｍｇＫＯＨ／ｇ以上であれば、充分な架橋密度でウレタン結合が形成され、耐薬品性等が向上する。アクリルポリオールの水酸基価が１００ｍｇＫＯＨ／ｇ以下であれば、ウレタン結合の架橋密度が高くなりすぎることなく、塗膜の過剰な硬化収縮が抑えられ、水圧転写印刷層への塗膜の密着性が良好となる。
水酸基価は、試料中の水酸基（−ＯＨ）をアセチル化して、アセチル化に要した酢酸を中和するのに要する水酸化カリウムの量を、試料１．０ｇに対するｍｇ数で表したもので、試料中の水酸基の含有量を示す尺度であり、アセチル化には、各種の試薬が用いられるが、通常、ピリジンおよび無水酢酸（３．１：１．０）が用いられ、アセチル化前後の酸濃度の差を滴定することによって測定される。
The hydroxyl value of the acrylic polyol resin is 10 to 100 mgKOH / g, preferably 20 to 80 mgKOH / g, and more preferably 30 to 70 mgKOH / g. When the hydroxyl value of the acrylic polyol is 10 mgKOH / g or more, a urethane bond is formed with a sufficient crosslinking density, and chemical resistance and the like are improved. If the hydroxyl value of the acrylic polyol is 100 mgKOH / g or less, the crosslinking density of the urethane bond does not become too high, excessive curing shrinkage of the coating film is suppressed, and the adhesion of the coating film to the hydraulic transfer printing layer is good. It becomes.
The hydroxyl value represents the amount of potassium hydroxide required to neutralize acetic acid required for acetylation by acetylating the hydroxyl group (—OH) in the sample, expressed in mg per 1.0 g of the sample, This is a scale indicating the hydroxyl group content in a sample. Various reagents are used for acetylation, but pyridine and acetic anhydride (3.1: 1.0) are usually used, and acid before and after acetylation. It is measured by titrating the difference in concentration.
アクリルポリオール樹脂のガラス転移温度は、６０℃以上であり、７０℃以上が好ましく、８０℃以上がより好ましい。アクリルポリオール樹脂のガラス転移温度が６０℃以上であれば、充分な硬さおよび強度を有する塗膜が形成される。充分な硬さおよび強度を有する塗膜が、水圧転写印刷層と強固に密着することにより、ポリプロピレン系樹脂成形品と水圧転写印刷層との間の不完全な密着性を補うことができる。その結果、ポリプロピレン系樹脂成形品と水圧転写印刷との間の密着性が向上する。アクリルポリオール樹脂のガラス転移温度の上限は、９８℃である。 The glass transition temperature of the acrylic polyol resin is 60 ° C. or higher, preferably 70 ° C. or higher, and more preferably 80 ° C. or higher. When the glass transition temperature of the acrylic polyol resin is 60 ° C. or higher, a coating film having sufficient hardness and strength is formed. When the coating film having sufficient hardness and strength adheres firmly to the hydraulic transfer printing layer, incomplete adhesion between the polypropylene-based resin molded product and the hydraulic transfer printing layer can be compensated. As a result, the adhesion between the polypropylene resin molded product and the hydraulic transfer printing is improved. The upper limit of the glass transition temperature of the acrylic polyol resin is 98 ° C.
アクリルポリオール樹脂のガラス転移温度（Ｔｇ）は、単量体ａ，ｂ，ｃ・・・からなる共重合体の場合は、以下の式（ＦＯＸの式）で求められる。
１／Ｔｇ＝ｍａ／Ｔｇａ＋ｍｂ／Ｔｇｂ＋ｍｃ／Ｔｇｃ＋・・・
ｍａ：単量体ａの質量分率、Ｔｇａ：単量体ａから得られる単独重合体のＴｇ［Ｋ］、
ｍｂ：単量体ｂの質量分率、Ｔｇｂ：単量体ｂから得られる単独重合体のＴｇ［Ｋ］、
ｍｃ：単量体ｃの質量分率、Ｔｇｃ：単量体ｃから得られる単独重合体のＴｇ［Ｋ］。
The glass transition temperature (Tg) of the acrylic polyol resin is determined by the following formula (FOX formula) in the case of a copolymer composed of monomers a, b, c.
1 / Tg = m a / Tg a + m b / Tg b + m c / Tg c +...
m a : mass fraction of monomer a, Tg a : Tg [K] of a homopolymer obtained from monomer a,
m b : mass fraction of monomer b, Tg b : Tg [K] of a homopolymer obtained from monomer b,
m c : mass fraction of monomer c, Tg c : Tg [K] of a homopolymer obtained from monomer c.
アクリルポリオール樹脂は、公知の重合法によって製造でき、生産効率の点から、溶液重合法が好ましい。
溶液重合法としては、単量体成分を有機溶媒に溶解し、撹拌しながら、重合開始剤の存在下に窒素雰囲気下で６０〜１８０℃の温度で加熱する方法が挙げられる。重合時間は、通常、１〜１０時間である。
The acrylic polyol resin can be produced by a known polymerization method, and a solution polymerization method is preferable from the viewpoint of production efficiency.
Examples of the solution polymerization method include a method in which a monomer component is dissolved in an organic solvent and heated at a temperature of 60 to 180 ° C. in a nitrogen atmosphere in the presence of a polymerization initiator while stirring. The polymerization time is usually 1 to 10 hours.
有機溶媒としては、ケトン系溶媒、エステル系溶媒、炭化水素系溶媒等が挙げられる。
重合開始剤としては、過酸化ベンゾイル、ｔｅｒｔ−ブチルパーオキシ−２−エチルヘキサノエート等の過酸化物；アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル等のアゾ化合物等が挙げられる。
Examples of the organic solvent include ketone solvents, ester solvents, hydrocarbon solvents, and the like.
Examples of the polymerization initiator include peroxides such as benzoyl peroxide and tert-butylperoxy-2-ethylhexanoate; azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile.
（ポリイソシアネート化合物）
ポリイソシアネート化合物は、アクリルポリオール樹脂を硬化させるために用いられる。ポリイソシアネート化合物としては、トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族ポリイソシアネート化合物；トリメチルヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート化合物；イソホロンジイソシアネート、ノルボルナンジイソシアネート等の脂環式ポリイソシアネート化合物；これらの変性体等が挙げられ、塗膜の耐候性、耐薬品性、および外観の点から、脂肪族ポリイソシアネート化合物または脂環式ポリイソシアネート化合物が好ましい。
(Polyisocyanate compound)
The polyisocyanate compound is used for curing the acrylic polyol resin. Examples of the polyisocyanate compound include aromatic polyisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate and diphenylmethane diisocyanate; aliphatic polyisocyanate compounds such as trimethylhexamethylene diisocyanate; alicyclic polyisocyanate compounds such as isophorone diisocyanate and norbornane diisocyanate; These modified bodies can be mentioned, and from the viewpoint of weather resistance, chemical resistance and appearance of the coating film, an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound is preferable.
脂肪族ポリイソシアネート化合物の市販品としては、旭化成工業社製のデュラネート２４Ａ−１００、デュラネートＴＰＡ−１００、デュラネートＴＫＡ−１００、デュラネートＥ４０２−９０Ｔ；住化バイエルウレタン社製のスミジュールＮ−３３００、スミジュールＮ−３２００、スミジュールＮ−７５；日本ポリウレタン工業社製のコロネートＨＸ、コロネートＥＨ；三井武田化学社製のタケネートＤ−１６５Ｎ等が挙げられる。
脂環式ポリイソシアネート化合物の市販品としては、住化バイエルウレタン社製のデスモジュール４４７０ＢＡ；デグサジャパン社製のＶＥＳＴＡＮＡＴ Ｔ１８９０Ｅ等が挙げられる。
As commercial products of aliphatic polyisocyanate compounds, Duranate 24A-100, Duranate TPA-100, Duranate TKA-100, Duranate E402-90T manufactured by Asahi Kasei Kogyo Co., Ltd., Sumidur N-3300 manufactured by Sumika Bayer Urethane Co., Ltd. Joule N-3200, Sumidur N-75; Coronate HX, Coronate EH manufactured by Nippon Polyurethane Industry Co., Ltd .; Takenate D-165N manufactured by Mitsui Takeda Chemical Co., Ltd.
Examples of commercially available alicyclic polyisocyanate compounds include Desmodule 4470BA manufactured by Sumika Bayer Urethane Co., Ltd., and VESTANAT T1890E manufactured by Degussa Japan.
ポリイソシアネート化合物のＮＣＯ基とアクリルポリオール樹脂の水酸基との当量比（ＮＣＯ／ＯＨ）は、０．５〜２．０が好ましく、０．８〜１．５がより好ましい。ＮＣＯ／ＯＨが０．５以上であれば、耐薬品性、耐久性等が良好となる。ＮＣＯ／ＯＨが１．５以下であれば、塗膜の過剰な硬化収縮が抑えられ、水圧転写印刷層への塗膜の密着性が良好となる。 The equivalent ratio (NCO / OH) between the NCO group of the polyisocyanate compound and the hydroxyl group of the acrylic polyol resin is preferably 0.5 to 2.0, and more preferably 0.8 to 1.5. When NCO / OH is 0.5 or more, chemical resistance, durability and the like are good. When NCO / OH is 1.5 or less, excessive curing shrinkage of the coating film is suppressed, and the adhesion of the coating film to the hydraulic transfer printing layer is improved.
本発明の加飾成形品用塗料組成物は、本発明の効果を損なわない範囲で、必要に応じて、ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、アクリル樹脂、繊維素系樹脂等の他の樹脂を含んでいてもよい。
本発明の加飾成形品用塗料組成物は、必要に応じて、塗面調整剤、流動性調整剤、紫外線吸収剤、光安定剤、硬化触媒、体質顔料、着色顔料、金属顔料、マイカ粉顔料、染料等の公知の添加剤を含んでいてもよい。
The coating composition for a decorative molded article of the present invention may contain other resins such as a polyester resin, an alkyd resin, an epoxy resin, an acrylic resin, and a fiber-based resin as necessary, as long as the effects of the present invention are not impaired. May be included.
The coating composition for a decorative molded product of the present invention includes a coating surface adjusting agent, a fluidity adjusting agent, an ultraviolet absorber, a light stabilizer, a curing catalyst, an extender pigment, a coloring pigment, a metal pigment, and mica powder as necessary. It may contain known additives such as pigments and dyes.
本発明の加飾成形品用塗料組成物は、通常、有機溶媒で希釈して用いられる。有機溶媒としては、トルエン、キシレン等の炭化水素系溶媒；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ジオキサン、エチレングリコールジエチルエーテル等のエーテル系溶媒等が挙げられる。有機溶媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。 The coating composition for decorative molded articles of the present invention is usually used after diluted with an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as dioxane and ethylene glycol diethyl ether. Can be mentioned. An organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
本発明の加飾成形品用塗料組成物の固形分濃度は、塗布性の点から、塗料組成物（１００質量％）中、３０〜５０質量％が好ましい。固形分とは、有機溶媒等、塗膜を形成する際に蒸発する成分を塗料組成物から除いたものである。 The solid content concentration of the coating composition for a decorative molded article of the present invention is preferably 30 to 50% by mass in the coating composition (100% by mass) from the viewpoint of applicability. The solid content is obtained by removing, from the coating composition, components that evaporate when forming a coating film, such as an organic solvent.
＜加飾成形品＞
図１は、本発明の加飾成形品の一例を示す断面図である。加飾成形品１０は、ポリプロピレン系樹脂成形品１２の表面に水圧転写印刷層１４を有し、水圧転写印刷層１４の表面に、本発明の加飾成形品用塗料組成物からなる塗膜１６を有するものである。
<Decorated molded products>
FIG. 1 is a cross-sectional view showing an example of a decorative molded product of the present invention. The decorative molded
ポリプロピレン系樹脂成形品１２は、射出成形法等の公知の成形法により、ポリプロピレン系樹脂を所望の形状に成形したものである。
ポリプロピレン系樹脂としては、ポリプロピレンの単独重合体、プロピレンと他のオレフィン（エチレン等。）とのブロック共重合体、プロピレンと他のオレフィン（エチレン等。）とのランダム共重合体等が挙げられる。
The polypropylene resin molded
Examples of polypropylene resins include polypropylene homopolymers, block copolymers of propylene and other olefins (such as ethylene), and random copolymers of propylene and other olefins (such as ethylene).
水圧転写印刷層１４は、ポリプロピレン系樹脂成形品１２の表面に、公知の転写フィルムを用いて、公知の水圧転写印刷を施すことによって成形された層である。
水圧転写印刷層１４の柄としては、木目柄、金属柄、格子柄等が挙げられる。
The hydraulic
Examples of the pattern of the hydraulic
塗膜１６は、水圧転写印刷層１４の表面に、本発明の加飾成形品用塗料組成物を塗布、乾燥させることにより形成される。
塗布方法としては、スプレーコート法、ロールコート法、ハケ塗り等の公知の塗布方法が挙げられる。
乾燥条件は、本発明の加飾成形品用塗料組成物が硬化できる条件であればよく、通常は、７０〜８０℃、３０〜４０分である。
塗膜１６の膜厚は、２０〜５０μｍが好ましい。
The
Examples of the coating method include known coating methods such as spray coating, roll coating, and brush coating.
The drying conditions should just be the conditions which can harden the coating composition for decorative molded articles of this invention, and are 70-80 degreeC and 30-40 minutes normally.
As for the film thickness of the
以上説明した本発明の加飾成形品用塗料組成物によれば、水圧転写印刷層への密着性に優れ、かつ充分な硬さおよび強度を有する塗膜を形成できる。充分な硬さおよび強度を有する塗膜が、水圧転写印刷層と強固に密着することにより、ポリプロピレン系樹脂成形品と水圧転写印刷層との間の不完全な密着性を補うことができる。その結果、プライマー処理を施すことなくポリプロピレン系樹脂成形品と水圧転写印刷との間の密着性が向上する。
また、本発明の加飾成形品用塗料組成物によれば、耐ガソリン性、耐油性に優れる塗膜を形成できる。よって、塗膜がガソリン、油脂等にさらされても、水圧転写印刷層への塗膜の密着性が低下しにくく、その結果、ポリプロピレン系樹脂成形品と水圧転写印刷層との間の密着性も低下しにくい。
According to the coating composition for a decorative molded product of the present invention described above, a coating film having excellent adhesion to a hydraulic transfer printing layer and having sufficient hardness and strength can be formed. When the coating film having sufficient hardness and strength adheres firmly to the hydraulic transfer printing layer, incomplete adhesion between the polypropylene-based resin molded product and the hydraulic transfer printing layer can be compensated. As a result, the adhesion between the polypropylene resin molded product and the hydraulic transfer printing is improved without applying a primer treatment.
Moreover, according to the coating composition for a decorative molded product of the present invention, a coating film excellent in gasoline resistance and oil resistance can be formed. Therefore, even if the coating film is exposed to gasoline, fats and oils, the adhesion of the coating film to the hydraulic transfer printing layer is difficult to decrease, and as a result, the adhesion between the polypropylene resin molded product and the hydraulic transfer printing layer. It is hard to decline.
以下、実施例を示して本発明を詳しく説明する。
〔実施例１〜９、比較例１〜１０〕
攪拌機、冷却器、温度計および単量体滴下装置を備えた１リットルの４つ口フラスコに、重合溶媒（酢酸ブチル）を５００ｇ仕込み、攪拌しながら内部温度が１００℃になるまで加熱し、表１〜４に示す種類および量の単量体成分および重合開始剤（アゾビスイソブチロニトリル）の混合溶液を２時間にわたって滴下し、滴下終了後、１００℃で１時間保ち、アクリルポリオール樹脂の溶液を得た。
アクリルポリオール樹脂の溶液を、表１〜４に示す量の希釈溶媒（酢酸エチル）で希釈した後、表１〜４に示す量のポリイソシアネート化合物（住化バイエルウレタン社製、スミジュールＮ３３００）を加え、塗料組成物を得た。
Hereinafter, the present invention will be described in detail with reference to examples.
[Examples 1-9, Comparative Examples 1-10]
A 1-liter four-necked flask equipped with a stirrer, a cooler, a thermometer and a monomer dropping device was charged with 500 g of a polymerization solvent (butyl acetate) and heated while stirring until the internal temperature reached 100 ° C. A mixed solution of monomer components and polymerization initiator (azobisisobutyronitrile) of the types and amounts shown in 1-4 is dropped over 2 hours, and after completion of the dropping, kept at 100 ° C. for 1 hour, A solution was obtained.
After diluting the acrylic polyol resin solution with the diluent solvent (ethyl acetate) in the amounts shown in Tables 1 to 4, polyisocyanate compounds (Sumidule N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) in the amounts shown in Tables 1 to 4 were added. In addition, a coating composition was obtained.
ポリプロピレン（新神戸電機社製、表面未処理ポリプロピレンＰＰ−Ｎ−ＡＮ）を成形して、１００ｍｍ×１００ｍｍ×５ｍｍのポリプロピレン系樹脂成形品を得た。ポリプロピレン系樹脂成形品の表面に、転写フィルム（大日本印刷社製、水圧転写用印刷シート）を用いて水圧転写印刷を施し、加飾成形品を得た。該加飾成形品の水圧転写印刷層の表面に、塗料組成物を、乾燥後の膜厚が２０〜４０μｍとなるようにスプレーコート法により塗布し、８０℃で３０分間乾燥し、塗膜を形成し、塗膜を有する加飾成形品を得た。 Polypropylene (manufactured by Shin-Kobe Electric Machinery Co., Ltd., surface untreated polypropylene PP-N-AN) was molded to obtain a polypropylene resin molded product of 100 mm × 100 mm × 5 mm. The surface of the polypropylene resin molded product was subjected to hydraulic transfer printing using a transfer film (Dai Nippon Printing Co., Ltd., hydraulic transfer printing sheet) to obtain a decorative molded product. The coating composition is applied to the surface of the hydraulic transfer printing layer of the decorative molded product by a spray coating method so that the film thickness after drying is 20 to 40 μm, dried at 80 ° C. for 30 minutes, A decorative molded product having a coating film was formed.
該加飾成形品について、下記評価を行った。結果を表１〜４に示す。
（１）外観：
光沢計を用いて、塗膜の６０°の光沢を測定し、下記基準で評価した。
○：６０゜の光沢が９０以上である。
△：６０゜の光沢が８０以上９０未満である。
×：６０゜の光沢が８０未満である。
The decorative molded product was evaluated as follows. The results are shown in Tables 1-4.
(1) Appearance:
Using a gloss meter, the 60 ° gloss of the coating film was measured and evaluated according to the following criteria.
○: 60 ° gloss is 90 or more.
(Triangle | delta): The gloss of 60 degrees is 80 or more and less than 90.
X: Gloss at 60 ° is less than 80.
（２）密着性：
ＪＩＳ Ｋ５４００「８．５．１碁盤目法」にしたがって塗膜の密着試験（隙間１ｍｍ、升目数１００）を行い、下記基準で評価した。
○：塗膜の剥離の痕跡が認められない。
△：塗膜の剥離が１升以上１０升未満。
×：塗膜の剥離が１０升以上１００升以下。
(2) Adhesion:
According to JIS K5400 “8.5.1 grid pattern method”, a coating adhesion test (gap 1 mm, grid number 100) was performed and evaluated according to the following criteria.
○: No trace of peeling of the coating film is observed.
(Triangle | delta): The peeling of a coating film is 1 to less than 10 inches.
X: The peeling of the coating film is 10 to 100 mm.
（２−１）初期密着性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した後、塗膜の密着試験を行い、上記基準で評価した。
(2-1) Initial adhesion:
After the decorative molded product after forming the coating film was allowed to stand at room temperature for 72 hours, the adhesion test of the coating film was performed and evaluated according to the above criteria.
（２−２）耐熱密着性：
塗膜を形成した後の加飾成形品を室温で７２時間放置し、さらに８０℃で３００時間加熱した後、塗膜の密着試験を行い、上記基準で評価した。
(2-2) Heat resistant adhesion:
The decorative molded product after the coating film was formed was allowed to stand at room temperature for 72 hours and further heated at 80 ° C. for 300 hours, and then the adhesion test of the coating film was performed and evaluated according to the above criteria.
（２−３）耐湿密着性：
塗膜を形成した後の加飾成形品を室温で７２時間放置し、さらに温度５０℃、湿度９５％ＲＨの雰囲気下で５００時間放置した後、塗膜の密着試験を行い、上記基準で評価した。
(2-3) Moisture resistant adhesion:
The decorative molded product after forming the coating film is allowed to stand at room temperature for 72 hours, and further allowed to stand for 500 hours in an atmosphere at a temperature of 50 ° C. and a humidity of 95% RH. did.
（２−４）耐冷熱サイクル性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した。
８０℃で１０時間の耐熱試験および−３０℃で１０時間の冷熱試験からなるサイクルを、合計１０サイクル行った後、塗膜の密着試験を行い、上記基準で評価した。
(2-4) Cold and heat cycle resistance:
The decorative molded product after forming the coating film was left at room temperature for 72 hours.
A cycle consisting of a heat resistance test at 80 ° C. for 10 hours and a cooling test at -30 ° C. for 10 hours was conducted for a total of 10 cycles, and then a coating adhesion test was conducted and evaluated according to the above criteria.
（３）耐薬品性：
薬品を滴下し、所定時間放置し、純水で洗浄した後の塗膜を目視して下記基準で評価した。
○：塗膜に異常および変色が認められない。
×：塗膜に異常または変色が認められる。
(3) Chemical resistance:
The coating film after dropping the chemical, leaving it for a predetermined time and washing with pure water was visually evaluated according to the following criteria.
○: No abnormality or discoloration is observed in the coating film.
X: Abnormality or discoloration is recognized in the coating film.
（３−１）耐アルカリ性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した後、塗膜上に１質量％水酸化ナトリウム水溶液を２．０ｇ滴下し、２４時間放置した。塗膜を純水で洗浄し、塗膜を目視して上記基準で評価した。
(3-1) Alkali resistance:
After the decorative molded product after forming the coating film was allowed to stand at room temperature for 72 hours, 2.0 g of a 1% by mass aqueous sodium hydroxide solution was dropped on the coating film and allowed to stand for 24 hours. The coating film was washed with pure water, and the coating film was visually observed and evaluated according to the above criteria.
（３−２）耐酸性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した後、塗膜上に１質量％硫酸水溶液を２．０ｇ滴下し、２４時間放置した。塗膜を純水で洗浄し、塗膜を目視して上記基準で評価した。
(3-2) Acid resistance:
After the decorative molded product after forming the coating film was allowed to stand at room temperature for 72 hours, 2.0 g of a 1% by mass sulfuric acid aqueous solution was dropped on the coating film and allowed to stand for 24 hours. The coating film was washed with pure water, and the coating film was visually observed and evaluated according to the above criteria.
（３−３）耐揮発油性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した。塗膜上にポリプロピレン製の円錐状の筒を取り付け、筒内にヘキサンを滴下し、筒の蓋を閉じ、５時間放置した。筒をはずし、塗膜上のヘキサンを拭き取り、塗膜を目視して上記基準で評価した。
(3-3) Volatile oil resistance:
The decorative molded product after forming the coating film was left at room temperature for 72 hours. A polypropylene conical cylinder was attached on the coating film, hexane was dropped into the cylinder, the cylinder lid was closed, and the mixture was left for 5 hours. The cylinder was removed, hexane on the coating film was wiped off, and the coating film was visually observed and evaluated according to the above criteria.
（４）耐ガソリン性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した。加飾成形品を室温のレギュラーガソリン中に４０分間浸漬した後、塗膜上のレギュラーガソリンを布で拭き取り、塗膜を目視して（３）と同じ基準で評価した。
また、塗膜の密着試験を行い、（２）と同じ基準で評価した。
(4) Gasoline resistance:
The decorative molded product after forming the coating film was left at room temperature for 72 hours. After the decorative molded product was immersed in regular gasoline at room temperature for 40 minutes, the regular gasoline on the coating film was wiped off with a cloth, and the coating film was visually observed and evaluated according to the same criteria as (3).
Moreover, the adhesion test of the coating film was conducted and evaluated based on the same standard as (2).
（５）耐油性：
塗膜を形成した後の加飾成形品を室温で７２時間放置した。塗膜上に動物性油を２．０ｇ滴下し、６０℃で２４０時間放置した後、塗膜を中性洗剤で洗浄し、塗膜を目視して（３）と同じ基準で評価した。
また、塗膜の密着試験を行い、（２）と同じ基準で評価した。
(5) Oil resistance:
The decorative molded product after forming the coating film was left at room temperature for 72 hours. After dropping 2.0 g of animal oil onto the coating film and allowing it to stand at 60 ° C. for 240 hours, the coating film was washed with a neutral detergent, and the coating film was visually observed and evaluated according to the same criteria as (3).
Moreover, the adhesion test of the coating film was conducted and evaluated based on the same standard as (2).
表中の略号は下記の通りである。
Ｓｔ：スチレン、
ＭＭＡ：メタクリル酸メチル、
ｔ−ＢＭＡ：メタクリル酸ｔｅｒｔ−ブチル、
ｉ−ＢＭＡ：メタクリル酸イソブチル、
ｎ−ＢＭＡ：メタクリル酸ｎ−ブチル、
ＢＡ：アクリル酸ｎ−ブチル、
ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル。
Abbreviations in the table are as follows.
St: Styrene,
MMA: methyl methacrylate,
t-BMA: tert-butyl methacrylate
i-BMA: isobutyl methacrylate
n-BMA: n-butyl methacrylate,
BA: n-butyl acrylate
HEMA: 2-hydroxyethyl methacrylate.
本発明の加飾成形品用塗料組成物は、ポリプロピレン系樹脂成形品の表面に水圧転写印刷層を有する加飾成形品の、水圧転写印刷層を保護するための塗膜を形成する塗料として有用である。 The coating composition for a decorative molded product of the present invention is useful as a coating material for forming a coating film for protecting a hydraulic transfer printing layer of a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product. It is.
１０ 加飾成形品
１２ ポリプロピレン系樹脂成形品
１４ 水圧転写印刷層
１６ 塗膜
10 Decorative Molded
Claims (4)
下記アクリルポリオール樹脂と、ポリイソシアネート化合物とを含有する、加飾成形品用塗料組成物。
（アクリルポリオール樹脂）
メタクリル酸メチルを２５〜８５質量％含む単量体成分を重合して得られる共重合体であり、
ポリスチレン換算での質量平均分子量が、２０００〜３００００であり、
水酸基価が、１０〜１００ｍｇＫＯＨ／ｇであり、
ガラス転移温度が、６０℃以上である、アクリルポリオール樹脂。 It is a coating composition applied to the surface of a hydraulic transfer printing layer of a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product,
The coating composition for decorative molded articles containing the following acrylic polyol resin and a polyisocyanate compound.
(Acrylic polyol resin)
It is a copolymer obtained by polymerizing a monomer component containing 25 to 85% by mass of methyl methacrylate,
The weight average molecular weight in terms of polystyrene is 2000 to 30000,
The hydroxyl value is 10-100 mg KOH / g,
An acrylic polyol resin having a glass transition temperature of 60 ° C. or higher.
前記水圧転写印刷層の表面に、請求項１〜３のいずれかに記載の加飾成形品用塗料組成物からなる塗膜を有する、加飾成形品。 It is a decorative molded product having a hydraulic transfer printing layer on the surface of a polypropylene resin molded product,
The decorative molded product which has a coating film which consists of the coating composition for decorative molded products in any one of Claims 1-3 on the surface of the said hydraulic transfer printing layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006280309A JP2008095012A (en) | 2006-10-13 | 2006-10-13 | Coating composition for decorated molded product, and decorated molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006280309A JP2008095012A (en) | 2006-10-13 | 2006-10-13 | Coating composition for decorated molded product, and decorated molded product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2008095012A true JP2008095012A (en) | 2008-04-24 |
Family
ID=39378203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006280309A Withdrawn JP2008095012A (en) | 2006-10-13 | 2006-10-13 | Coating composition for decorated molded product, and decorated molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2008095012A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013082216A (en) * | 2011-09-26 | 2013-05-09 | Dainippon Printing Co Ltd | Decorative sheet, method of manufacturing the same, and decorative molded article |
| JP2013082217A (en) * | 2011-09-26 | 2013-05-09 | Dainippon Printing Co Ltd | Decorative sheet, method of manufacturing the same, and decorative molded article |
| JP2017136852A (en) * | 2017-03-06 | 2017-08-10 | 大日本印刷株式会社 | Water pressure transfer film |
| JP2021187967A (en) * | 2020-06-01 | 2021-12-13 | 株式会社オリジン | Coating composition for laser etching, manufacturing method of its main agent, molding and its manufacturing method |
-
2006
- 2006-10-13 JP JP2006280309A patent/JP2008095012A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013082216A (en) * | 2011-09-26 | 2013-05-09 | Dainippon Printing Co Ltd | Decorative sheet, method of manufacturing the same, and decorative molded article |
| JP2013082217A (en) * | 2011-09-26 | 2013-05-09 | Dainippon Printing Co Ltd | Decorative sheet, method of manufacturing the same, and decorative molded article |
| JP2017136852A (en) * | 2017-03-06 | 2017-08-10 | 大日本印刷株式会社 | Water pressure transfer film |
| JP2021187967A (en) * | 2020-06-01 | 2021-12-13 | 株式会社オリジン | Coating composition for laser etching, manufacturing method of its main agent, molding and its manufacturing method |
| JP7160861B2 (en) | 2020-06-01 | 2022-10-25 | 株式会社オリジン | COATING COMPOSITION FOR LASER ETCHING, METHOD FOR MANUFACTURING MAIN INGREDIENT THEREOF, MOLDED BODY AND METHOD FOR FORMING THE SAME |
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