JP2017171908A - Method for producing varnish for (meth) acrylic ester paint - Google Patents
Method for producing varnish for (meth) acrylic ester paint Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
【課題】分子量および分散度が低く酸価の上昇が抑制された（メタ）アクリル酸エステル系塗料用ワニスの、製造方法、ならびにポリマーの酸価の上昇を抑制することが可能な（メタ）アクリル酸エステル系塗料用ワニスの製造方法を提供すること。【解決手段】（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー混合物；７０〜８０質量部、（Ｂ）水酸基含有（メタ）アクリル酸エステル；２０〜２８質量部、（Ｃ）カルボン酸基含有モノマー；０．１〜１０質量部、および（Ｄ）一般式（Ｉ）で表される有機過酸化物；（Ａ）〜（Ｃ）の混合物１００質量部に対して５〜１５質量部を（Ａ）：（Ｂ）＝１：０．２５〜１：０．４０となるように含む塗料用重合モノマー混合物を、有機溶媒中にて重合する（メタ）アクリル酸エステル系塗料用ワニスの製造方法。【選択図】なし[PROBLEMS] To provide a method for producing a (meth) acrylic acid ester paint varnish having a low molecular weight and a low degree of dispersion to suppress an increase in acid value, and (meth) acryl capable of suppressing an increase in acid value of a polymer. To provide a method for producing a varnish for an acid ester paint. (A) Vinyl monomer mixture containing (meth) acrylic acid ester; 70 to 80 parts by mass, (B) Hydroxyl group-containing (meth) acrylic acid ester; 20 to 28 parts by mass, (C) Carboxylic acid group containing Monomer: 0.1 to 10 parts by mass, and (D) an organic peroxide represented by the general formula (I): 5 to 15 parts by mass with respect to 100 parts by mass of the mixture of (A) to (C) ( A): (B) = 1: 0.25 to 1: 0.40 A polymerization monomer mixture for coating is polymerized in an organic solvent, and a method for producing a (meth) acrylic ester coating varnish . [Selection figure] None
Description
本発明は、塗料用ワニスの製造方法に関する。詳しくは、（メタ）アクリル酸エステルを含むビニルモノマーと水酸基含有（メタ）アクリル酸エステルを特定の比率で含み、かつ特定の構造を有する有機過酸化物を含むモノマー混合物を重合する（メタ）アクリル酸エステル系塗料用ワニスの製造方法に関する。 The present invention relates to a method for producing a paint varnish. Specifically, (meth) acrylic polymerizes a monomer mixture containing a vinyl monomer containing (meth) acrylic acid ester and a hydroxyl group-containing (meth) acrylic acid ester in a specific ratio and containing an organic peroxide having a specific structure. The present invention relates to a method for producing an acid ester paint varnish.
塗料用ワニスは、主に（メタ）アクリル酸エステルを含むビニルモノマー、溶媒、重合開始剤等を用いて製造される。この際、重合開始剤には有機過酸化物やアゾ化合物等が主に使用される。 The paint varnish is produced mainly using a vinyl monomer containing a (meth) acrylic acid ester, a solvent, a polymerization initiator, and the like. At this time, an organic peroxide, an azo compound or the like is mainly used as the polymerization initiator.
重合開始剤は、コスト、重合設備の温度調整能力、目的とする樹脂の品質等に鑑み適宜選択されるが、高温下での重合が必要な場合は、重合温度に適した高い半減期温度を有する重合開始剤が選択される。有機過酸化物はアゾ化合物と比べ高い半減期温度を有する化合物が多く存在し、例えば特公昭４８−２６３８６号公報、特開昭５３−４９０９２号公報、特開昭５６−６５０１１号公報などに記載されるように、高温下での重合では、ジ−ｔ−ブチルペルオキシドが一般的に広く使用される。 The polymerization initiator is appropriately selected in view of the cost, the temperature adjustment capability of the polymerization equipment, the quality of the target resin, etc., but when polymerization at a high temperature is required, a high half-life temperature suitable for the polymerization temperature is used. The polymerization initiator is selected. Many organic peroxides have a half-life temperature higher than that of an azo compound, and are described in, for example, JP-B-48-26386, JP-A-53-49092, JP-A-56-65011, and the like. As can be seen, di-tert-butyl peroxide is generally widely used for polymerization at high temperatures.
近年、ＶＯＣ（揮発性有機化合物）低減の観点から、溶媒成分の少ないハイソリッド塗料が求められている。溶媒成分を減らすには、ワニスの粘度を下げることが一つの方法であり、ワニスの分子量を低くすること、かつ単分散にすることで達成されることが知られている。この際、一般的に重合開始剤の添加量を増やす、重合温度を上げる等の方法がとられる。 In recent years, from the viewpoint of reducing VOC (volatile organic compounds), a high solid paint having a small amount of solvent components has been demanded. In order to reduce the solvent component, it is known that reducing the viscosity of the varnish is one method, and it can be achieved by lowering the molecular weight of the varnish and making it monodisperse. At this time, generally, methods such as increasing the addition amount of the polymerization initiator and raising the polymerization temperature are taken.
ジ−ｔ−ブチルペルオキシドの添加量を増やすことで、ポリマー分子量および分散度の低減が可能であるものの、得られるワニスの酸価が予測される値より高くなることが判明した。通常、ポリマー酸価は、アクリル酸やメタクリル酸等のカルボン酸基含有モノマーの量で調整される。しかしながら、本願ではカルボン酸基含有モノマーの量が同じでも、特定のモノマー組成とジ−ｔ−ブチルペルオキシドの組合せでは、ポリマーの酸価が高くなることを見出した。 It was found that by increasing the amount of di-t-butyl peroxide added, the polymer molecular weight and the degree of dispersion can be reduced, but the acid value of the varnish obtained is higher than expected. Usually, a polymer acid value is adjusted with the quantity of carboxylic acid group containing monomers, such as acrylic acid and methacrylic acid. However, in the present application, it has been found that even when the amount of the carboxylic acid group-containing monomer is the same, the combination of a specific monomer composition and di-t-butyl peroxide increases the acid value of the polymer.
得られるポリマーの酸価が、初期設計にて想定した目標酸価より高くなると、ワニスの極性が変化するため、ワニスとワニスが塗布される基材との間の密着性に問題が生じる。また、イソシアネート樹脂、エポキシ樹脂等の他の樹脂成分と混合し、一液とした際に、その保存性（樹脂のポットライフ）に問題が生じる。 When the acid value of the resulting polymer is higher than the target acid value assumed in the initial design, the polarity of the varnish changes, which causes a problem in the adhesion between the varnish and the substrate to which the varnish is applied. Moreover, when it mixes with other resin components, such as an isocyanate resin and an epoxy resin, and makes it 1 liquid, a problem arises in the preservability (resin pot life).
本発明は、分子量および分散度が低く酸価の上昇が抑制された（メタ）アクリル酸エステル系塗料用ワニスの、製造方法を提供するものである。また本発明は、ポリマーの酸価の上昇を抑制することが可能な（メタ）アクリル酸エステル系塗料用ワニスの製造方法を提供するものである。 The present invention provides a method for producing a varnish for a (meth) acrylic acid ester-based paint having a low molecular weight and a low degree of dispersion and in which an increase in acid value is suppressed. Moreover, this invention provides the manufacturing method of the varnish for (meth) acrylic acid ester type coating materials which can suppress the raise of the acid value of a polymer.
すなわち本発明は、
（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー混合物；７０〜８０質量部、
（Ｂ）水酸基含有（メタ）アクリル酸エステル；２０〜２８質量部、
（Ｃ）カルボン酸基含有モノマー；０．１〜１０質量部、および
（Ｄ）一般式（Ｉ）
で表される有機過酸化物；（Ａ）〜（Ｃ）の混合物１００質量部に対して５〜１５質量部を（Ａ）：（Ｂ）＝１：０．２５〜１：０．４０となるように含む塗料用重合モノマー混合物を、有機溶媒中にて重合する（メタ）アクリル酸エステル系塗料用ワニスの製造方法である。
That is, the present invention
(A) vinyl monomer mixture containing (meth) acrylic acid ester; 70-80 parts by mass,
(B) hydroxyl group-containing (meth) acrylic acid ester; 20-28 parts by mass,
(C) Carboxylic acid group-containing monomer; 0.1 to 10 parts by mass, and (D) General formula (I)
5 to 15 parts by mass of (A) :( B) = 1: 0.25 to 1: 0.40 with respect to 100 parts by mass of the mixture of (A) to (C) This is a method for producing a varnish for a (meth) acrylic acid ester-based paint, in which a polymerization monomer mixture for paint that is contained is polymerized in an organic solvent.
本発明の製造方法により、低分子量、低分散度で、かつ初期設計通りの酸価を実現可能な（メタ）アクリル酸エステル系塗料用ワニスを得ることができる。ここで「初期設計通り」とは、原体酸価（実測値）と理論酸価との差（酸価差分）が、ワニスの所望の特性を維持できるほど微小であることをいう。 By the production method of the present invention, it is possible to obtain a varnish for a (meth) acrylic acid ester-based paint having a low molecular weight, a low dispersity, and an acid value as initially designed. Here, “according to the initial design” means that the difference between the raw acid value (measured value) and the theoretical acid value (acid value difference) is so small that the desired characteristics of the varnish can be maintained.
本発明の（メタ）アクリル酸エステル系塗料用ワニスの製造方法は、（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー、（Ｂ）水酸基含有（メタ）アクリル酸エステル、（Ｃ）カルボン酸基含有モノマー、および（Ｄ）有機過酸化物を含むモノマー混合物を、有機溶媒中にて重合する。 The method for producing a varnish for a (meth) acrylic acid ester paint of the present invention includes (A) a vinyl monomer containing (meth) acrylic acid ester, (B) a hydroxyl group-containing (meth) acrylic acid ester, and (C) a carboxylic acid group. The monomer mixture containing the monomer and (D) the organic peroxide is polymerized in an organic solvent.
本発明において、（メタ）アクリル酸エステルは、アクリル酸エステルおよびメタクリル酸エステルの総称である。 In the present invention, (meth) acrylic acid ester is a general term for acrylic acid ester and methacrylic acid ester.
本発明の（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー混合物の（メタ）アクリル酸エステルとして、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソプロピル、アクリル酸ｎ−ブチル、アクリル酸イソブチル、アクリル酸ｓｅｃ−ブチル、アクリル酸ｔｅｒｔ−ブチル、アクリル酸イソペンチル、アクリル酸ｎ−ヘキシル、アクリル酸シクロヘキシル、アクリル酸ｎ−オクチル、アクリル酸２−エチルヘキシル、アクリル酸イソボルニル、アクリル酸ジシクロペンタニル、アクリル酸ドデシル、アクリル酸テトラデシル、アクリル酸ヘキサデシル、アクリル酸オクタデシル、アクリル酸ドコシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ−プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸ｓｅｃ−ブチル、メタクリル酸ｔｅｒｔ−ブチル、メタクリル酸ｎ−ヘキシル、メタクリル酸シクロヘキシル、メタクリル酸ｎ−オクチル、メタクリル酸２−エチルヘキシル、メタクリル酸イソボルニル、メタクリル酸２−メチル−２−アダマンチル、メタクリル酸２−エチル−２−アダマンチル、メタクリル酸ドデシル、メタクリル酸トリデシル、メタクリル酸２−イソプロピル−２−アダマンチル、メタクリル酸オクタデシル、メタクリル酸グリシジル、メタクリル酸２−（ジメチルアミノ）エチル、メタクリル酸２−（ジエチルアミノ）エチル、メタクリル酸テトラヒドロフルフリル、ポリエチレングリコールモノメタクリレート、メタクリル酸トリメチルシリル、メタクリル酸３−（トリメトキシシリル）プロピル、またはメタクリル酸３−（トリエトキシシリル）プロピル等を用いることができる。 Examples of the (meth) acrylic acid ester of the vinyl monomer mixture containing the (A) (meth) acrylic acid ester of the present invention include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate. , Isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, isopentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, diacrylate Cyclopentanyl, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, docosyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isomethacrylate Propyl, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, 2-isopropyl-2-adamantyl methacrylate, octadecyl methacrylate, glycidyl methacrylate, 2-methacrylic acid 2- (Dimethylamino) ethyl, 2- (diethylamino) ethyl methacrylate, tetrahydrofurfuryl methacrylate, polyethylene glycol monomethacrylate, trimethyl methacrylate Lil, can be used methacrylic acid 3- (trimethoxysilyl) propyl or methacrylic acid 3- (triethoxysilyl) propyl, and the like.
上記（メタ）アクリル酸エステルのうち、メタクリル酸メチル、アクリル酸ｎ−ブチル、メタクリル酸ｎ−ブチル、アクリル酸２−エチルヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシル、アクリル酸イソボルニル、メタクリル酸イソボルニル、メタクリル酸ラウリル、またはメタクリル酸グリシジルを用いることが好ましい。（メタ）アクリル酸エステルは、１種、または２種以上を併せて用いることができる。 Among the above (meth) acrylic acid esters, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, It is preferable to use lauryl methacrylate or glycidyl methacrylate. The (meth) acrylic acid ester can be used alone or in combination of two or more.
塗料用ワニスに対する要求物性に応じて、（メタ）アクリル酸エステルと共に、（メタ）アクリル酸エステルと共重合可能なビニルモノマーを併用することもできる。そのようなビニルモノマーとして、例えばスチレン、α−メチルスチレン、酢酸ビニル、塩化ビニル、ブタジエン、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド、アクリロニトリル、メタクリロニトリル、Ｎ−ビニルピロリドン、および無水マレイン酸等が挙げられる。
本発明の（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー混合物の使用量は、７０〜８０質量部である。また、（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー混合物は、（メタ）アクリル酸エステルからなる混合物が好ましい。
A vinyl monomer copolymerizable with (meth) acrylic acid ester can be used in combination with (meth) acrylic acid ester, depending on the required physical properties of the varnish for paint. Examples of such vinyl monomers include styrene, α-methylstyrene, vinyl acetate, vinyl chloride, butadiene, acrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, and anhydrous And maleic acid.
The usage-amount of the vinyl monomer mixture containing (A) (meth) acrylic acid ester of this invention is 70-80 mass parts. Moreover, the vinyl monomer mixture containing (A) (meth) acrylic acid ester is preferably a mixture composed of (meth) acrylic acid ester.
本発明の（Ｂ）水酸基含有（メタ）アクリル酸エステルとして、例えばアクリル酸２−ヒドロキシエチル、アクリル酸３−ヒドロキシプロピル、アクリル酸４−ヒドロキシブチル、アクリル酸３−ヒドロキシブチル、ポリエチレングリコールモノアクリレート、メタクリル酸２−ヒドロキシエチル、メタクリル酸３−ヒドロキシプロピル、メタクリル酸４−ヒドロキシブチル、またはメタクリル酸３−ヒドロキシ−１−アダマンチル等を用いることができる。 Examples of the (B) hydroxyl group-containing (meth) acrylic acid ester of the present invention include, for example, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, or the like can be used.
上記水酸基含有（メタ）アクリル酸エステルのうち、アクリル酸２−ヒドロキシエチル、およびメタクリル酸２−ヒドロキシエチルを用いることが好ましい。これらはそれぞれ単独で使用しても良いし、併用しても良い。
本発明の（Ｂ）水酸基含有（メタ）アクリル酸エステルの使用量は、２０〜２８質量部である。
Of the hydroxyl group-containing (meth) acrylic acid esters, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferably used. These may be used alone or in combination.
The usage-amount of the (B) hydroxyl-containing (meth) acrylic acid ester of this invention is 20-28 mass parts.
本発明の（Ｃ）カルボン酸基含有モノマーとして、例えばアクリル酸、メタクリル酸、マレイン酸、イタコン酸、またはフマル酸等を用いることができる。 As the (C) carboxylic acid group-containing monomer of the present invention, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid or the like can be used.
上記カルボン酸基含有モノマーのうち、アクリル酸、またはメタクリル酸を用いることが好ましい。これらはそれぞれ単独で使用しても良いし、併用しても良い。
本発明の（Ｃ）カルボン酸基含有モノマーの使用量は、０．１〜１０質量部である。
Of the carboxylic acid group-containing monomers, it is preferable to use acrylic acid or methacrylic acid. These may be used alone or in combination.
The usage-amount of the (C) carboxylic acid group containing monomer of this invention is 0.1-10 mass parts.
本発明の製造方法においては、従来公知の有機溶媒を用いることができる。有機溶媒の具体例として、例えばトルエン、エチルベンゼン、キシレン、芳香族石油ナフサ、テトラリン、ソルベッソ１００（エクソンモービル社登録商標）、ソルベッソ１５０（エクソンモービル社登録商標）、およびソルベッソ２００（エクソンモービル社登録商標）等の芳香族炭化水素類；メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、メチルイソアミルケトン、メチルｎ−ブチルケトン、エチルアミルケトン、シクロヘキサノン、ジアセトンアルコール、ジイソブチルケトン、ジエチルケトン、ジブチルケトン、メチルイソプロピルケトン、およびジイソブチルケトン等のケトン類；酢酸エチル、酢酸ｎ−プロピル、酢酸イソプロピル、酢酸ｎ−ブチル、酢酸イソブチル、酢酸アミル、酢酸エチレングリコールモノエチルエーテル、酢酸プロピレングリコールモノエチルエーテル、酢酸メトキシブチル、プロピオン酸プロピル、プロピオン酸ブチル、およびプロピオン酸エトキシエチル等のエステル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、およびジエチレングリコールジエチルエーテル等のエーテル類；およびイソプロピルアルコール、ｎ−ブタノール、イソブタノール、シクロヘキサノール、ベンジルアルコール、２−エチルヘキサノール、および３，３，５−トリメチル−１−ヘキサノール等のアルコール類；が挙げられる。有機溶媒は２種以上を混合して使用することもできる。有機溶媒の使用量は、用いられる全ビニルモノマー１００質量部に対して通常２０〜２００質量部とすることができる。 In the production method of the present invention, a conventionally known organic solvent can be used. Specific examples of the organic solvent include, for example, toluene, ethylbenzene, xylene, aromatic petroleum naphtha, tetralin, Solvesso 100 (registered trademark of ExxonMobil), Solvesso 150 (registered trademark of ExxonMobil), and Solvesso 200 (registered trademark of ExxonMobil). Aromatic hydrocarbons such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl n-butyl ketone, ethyl amyl ketone, cyclohexanone, diacetone alcohol, diisobutyl ketone, diethyl ketone, dibutyl ketone, methyl isopropyl ketone And ketones such as diisobutyl ketone; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol Esters such as monoethyl ether, propylene glycol acetate monoethyl ether, methoxybutyl acetate, propyl propionate, butyl propionate, and ethoxyethyl propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Ethers such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; and isopropyl alcohol, n-butanol, isobutanol, cyclohexanol, benzyl alcohol, 2-ethylhexanol And 3,3,5 alcohols such as trimethyl-1-hexanol; and the like. Two or more organic solvents can be mixed and used. The usage-amount of an organic solvent can be normally 20-200 mass parts with respect to 100 mass parts of all the vinyl monomers used.
上記有機溶媒のうち、キシレン、ソルベッソ１００（エクソンモービル社登録商標）、およびソルベッソ１５０（エクソンモービル社登録商標）等の芳香族化合物；メチルイソブチルケトン、メチルアミルケトン、およびシクロヘキサノン等のケトン類；酢酸ｎ−ブチル、酢酸アミル、および３−エトキシプロピオン酸エチル等のエステル類；または１−ペンタノール、１−ヘキサノール、イソアミルアルコール、シクロヘキサノール、および２−エチルヘキサノール等のアルコール類；を用いることが好ましい。 Among the organic solvents, aromatic compounds such as xylene, Solvesso 100 (registered trademark of ExxonMobil), and Solvesso 150 (registered trademark of ExxonMobil); ketones such as methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone; acetic acid It is preferable to use esters such as n-butyl, amyl acetate, and ethyl 3-ethoxypropionate; or alcohols such as 1-pentanol, 1-hexanol, isoamyl alcohol, cyclohexanol, and 2-ethylhexanol; .
本発明の（Ｄ）一般式（Ｉ）で表される有機過酸化物として、ジ−ｔ−ヘキシルペルオキシド（式（Ｉ）のＲ＝メチル基）、およびジ−ｔ−アミルペルオキシド（式（Ｉ）のＲ＝水素原子）が挙げられる。 As the organic peroxide represented by (D) general formula (I) of the present invention, di-t-hexyl peroxide (R = methyl group in formula (I)) and di-t-amyl peroxide (formula (I R = hydrogen atom).
ジ−ｔ−ヘキシルペルオキシド、およびジ−ｔ−アミルペルオキシドは、それぞれ単独で使用しても良いし、併用しても良い。また、重合反応の後期に残存モノマー低減のために、さらに追加することも可能である。 Di-t-hexyl peroxide and di-t-amyl peroxide may be used alone or in combination. Further, it is possible to add further to reduce the residual monomer at the latter stage of the polymerization reaction.
本発明において、有機過酸化物の使用量は、（メタ）アクリル酸エステルと共重合可能なビニルモノマーの混合物１００質量部に対して、５〜１５質量部、好ましくは７〜１３質量部である。５質量部未満では未反応ビニルモノマーが多く残存することや、分子量が高くなるため好ましくない。また、１５質量部を越えると、ポリマー酸価の上昇、未反応有機過酸化物の残存、有機過酸化物由来の分解生成物が多く生じるため好ましくない。
また本発明の塗料用重合モノマー混合物における、（Ａ）（メタ）アクリル酸エステルを含むビニルモノマー混合物と（Ｂ）水酸基含有（メタ）アクリル酸エステルの比率は、（Ａ）：（Ｂ）＝１：０．２５〜１：０．４０である。
In this invention, the usage-amount of an organic peroxide is 5-15 mass parts with respect to 100 mass parts of the mixture of the vinyl monomer copolymerizable with (meth) acrylic acid ester, Preferably it is 7-13 mass parts. . Less than 5 parts by mass is not preferable because a large amount of unreacted vinyl monomer remains and the molecular weight increases. On the other hand, when the amount exceeds 15 parts by mass, the polymer acid value increases, the unreacted organic peroxide remains, and many decomposition products derived from the organic peroxide are generated.
The ratio of the (A) vinyl monomer mixture containing (meth) acrylic acid ester to the (B) hydroxyl group-containing (meth) acrylic acid ester in the polymerization monomer mixture for coating of the present invention is (A) :( B) = 1. : 0.25 to 1: 0.40.
また、本発明の有機溶媒中での重合（溶液重合）における各成分の添加方法として、例えば次の方法が挙げられる。
（１）（メタ）アクリル酸エステル、ビニルモノマー、有機過酸化物および有機溶媒の混合物を空の重合槽に、連続的または間欠的に添加して行う方法。
（２）予め有機溶媒を添加した重合槽に、（メタ）アクリル酸エステル、ビニルモノマーおよび有機過酸化物の混合物を連続的または間欠的に添加して行う方法。
（３）予め有機溶媒と有機過酸化物を添加した重合槽に、（メタ）アクリル酸エステルおよびビニルモノマーの混合物を連続的または間欠的に添加して行う方法。
（４）（メタ）アクリル酸エステル、ビニルモノマー、有機過酸化物および有機溶媒を、それぞれ独立に重合槽に添加して行う方法。
上記添加方法に加えて、これらを若干変更する場合、例えば予め使用される有機溶媒の中に（メタ）アクリル酸エステルおよび／またはビニルモノマーの一部が、また逆に（メタ）アクリル酸エステルおよび／またはビニルモノマーの中に有機溶媒の一部がそれぞれ含まれる場合も含むものとする。
Moreover, as the addition method of each component in superposition | polymerization (solution polymerization) in the organic solvent of this invention, the following method is mentioned, for example.
(1) A method in which a mixture of (meth) acrylic acid ester, vinyl monomer, organic peroxide and organic solvent is added continuously or intermittently to an empty polymerization tank.
(2) A method in which a mixture of (meth) acrylic acid ester, vinyl monomer and organic peroxide is added continuously or intermittently to a polymerization tank to which an organic solvent has been added in advance.
(3) A method in which a mixture of (meth) acrylic acid ester and vinyl monomer is continuously or intermittently added to a polymerization tank to which an organic solvent and an organic peroxide have been added in advance.
(4) A method in which (meth) acrylic acid ester, vinyl monomer, organic peroxide, and organic solvent are independently added to the polymerization tank.
In addition to the above addition method, when these are slightly changed, for example, a part of the (meth) acrylic acid ester and / or vinyl monomer in the organic solvent used in advance, and conversely (meth) acrylic acid ester and The case where a part of the organic solvent is included in the vinyl monomer is also included.
重合温度は、通常１００〜２００℃が好ましく、さらに好ましくは１２０〜１８０℃である。重合温度が１００℃未満では重合速度が遅くなり、未反応モノマーが多く残存することや、得られる重合物の分子量が大きくなることから好ましくない。また、２００℃を越えると重合速度が速すぎ、オリゴマーの副生や、安全上の観点から好ましくない。 The polymerization temperature is usually preferably 100 to 200 ° C, more preferably 120 to 180 ° C. When the polymerization temperature is less than 100 ° C., the polymerization rate is slow, and a large amount of unreacted monomer remains, and the molecular weight of the polymer obtained is not preferable. Moreover, when it exceeds 200 degreeC, superposition | polymerization speed | velocity | rate is too fast and it is unpreferable from a viewpoint of by-production of an oligomer and safety | security.
重合時間（滴下時間および反応時間）は、通常２〜１０時間が好ましく、さらに好ましくは３〜７時間である。重合時間が２時間未満では、未反応モノマーや有機過酸化物が多く残存するため好ましくない。また、１０時間を越えると生産性低下の観点から好ましくない。 The polymerization time (dropping time and reaction time) is usually preferably 2 to 10 hours, more preferably 3 to 7 hours. A polymerization time of less than 2 hours is not preferable because a large amount of unreacted monomer and organic peroxide remain. Moreover, when it exceeds 10 hours, it is unpreferable from a viewpoint of productivity fall.
本明細書において、以下の略称を用いることがある。
ＭＭＡ：メタクリル酸メチル
ＢＭＡ：メタクリル酸ｎ−ブチル
ＢＡ：アクリル酸ｎ−ブチル
Ｓｔ：スチレン
ＨＥＭＡ：メタクリル酸２−ヒドロキシエチル
ＨＥＡ：アクリル酸２−ヒドロキシエチル
ＭＡＡ：メタクリル酸
ＡＡ：アクリル酸
ＨｘＤ：ジ−ｔ−ヘキシルペルオキシド（日油社製：パーヘキシル（登録商標）Ｄ）
ＡｍＤ：ジ−ｔ−アミルペルオキシド
ＢｕＤ：ジ−ｔ−ブチルペルオキシド（日油社製：パーブチル（登録商標）Ｄ）
In this specification, the following abbreviations may be used.
MMA: Methyl methacrylate BMA: n-butyl methacrylate BA: n-butyl acrylate St: styrene HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate MAA: methacrylate AA: acrylic acid HxD: di- t-Hexyl peroxide (manufactured by NOF Corporation: Perhexyl (registered trademark) D)
AmD: di-t-amyl peroxide BuD: di-t-butyl peroxide (manufactured by NOF Corporation: Perbutyl (registered trademark) D)
以下、本発明を実施例に基づき説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例中に記載される「部」は、全て質量基準である。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples. In addition, all “parts” described in Examples and Comparative Examples are based on mass.
＜（メタ）アクリルエステル系塗料用ワニスの製造＞ <Manufacture of varnish for (meth) acrylic ester paint>
（実施例１）
攪拌機、温度計、還流冷却器、窒素ガス導入管および滴下漏斗を備えた５００ｍｌの四つ口フラスコに、ソルベッソ１００（エクソンモービル社登録商標）３５部を入れ、窒素ガスを導入しながら１５０℃に昇温したのち、滴下漏斗からＭＭＡ／ＢＭＡ／ＨＥＭＡ／ＭＡＡ（４０部／３８部／２０部／２部）の混合モノマー、ジ−ｔ−ヘキシルペルオキシド（日油社製：パーヘキシル（登録商標）Ｄ）１０部からなる混合物を１５０℃で３時間かけて均一速度で滴下した。滴下終了後さらに、重合反応を１５０℃で２時間継続した後、冷却して塗料用ワニスを得た。
Example 1
In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 35 parts of Solvesso 100 (registered trademark of ExxonMobil Co., Ltd.) was placed, and the temperature was raised to 150 ° C. while introducing nitrogen gas After raising the temperature, a mixed monomer of MMA / BMA / HEMA / MAA (40 parts / 38 parts / 20 parts / 2 parts), di-t-hexyl peroxide (manufactured by NOF Corporation: Perhexyl (registered trademark) D) from the dropping funnel ) A mixture of 10 parts was added dropwise at a uniform rate at 150 ° C. over 3 hours. After completion of dropping, the polymerization reaction was continued at 150 ° C. for 2 hours, and then cooled to obtain a paint varnish.
（実施例２）
モノマーをＭＭＡ／ＢＡ／ＨＥＭＡ／ＭＡＡ（４０部／３３部／２５部／２部）に変更した以外は、実施例１と同様にして重合を行い、塗料用ワニスを得た。
(Example 2)
Polymerization was performed in the same manner as in Example 1 except that the monomer was changed to MMA / BA / HEMA / MAA (40 parts / 33 parts / 25 parts / 2 parts) to obtain a paint varnish.
（実施例３）
モノマーをＭＭＡ／ＢＭＡ／ＨＥＭＡ／ＭＡＡ（４０部／３３部／２５部／２部）とし、有機過酸化物をジ−ｔ−アミルペルオキシド１０部に変更した以外は、実施例１と同様にして重合を行い、塗料用ワニスを得た。
(Example 3)
Example 1 except that the monomer was MMA / BMA / HEMA / MAA (40 parts / 33 parts / 25 parts / 2 parts) and the organic peroxide was changed to 10 parts of di-t-amyl peroxide. Polymerization was performed to obtain a paint varnish.
（実施例４）
モノマーをＭＭＡ／ＢＭＡ／ＨＥＭＡ／ＭＡＡ（４０部／３０部／２８部／２部）に変更した以外は、実施例１と同様にして重合を行い、塗料用ワニスを得た。
Example 4
Polymerization was carried out in the same manner as in Example 1 except that the monomer was changed to MMA / BMA / HEMA / MAA (40 parts / 30 parts / 28 parts / 2 parts) to obtain a paint varnish.
（実施例５）
モノマーをＭＭＡ／ＢＭＡ／ＨＥＡ／ＭＡＡ／ＡＡ（４０部／３３部／２５部／１部／１部）に変更した以外は、実施例１と同様にして重合を行い、塗料用ワニスを得た。
(Example 5)
Polymerization was performed in the same manner as in Example 1 except that the monomer was changed to MMA / BMA / HEA / MAA / AA (40 parts / 33 parts / 25 parts / 1 part / 1 part) to obtain a paint varnish. .
（比較例１）
攪拌機、温度計、還流冷却器、窒素ガス導入管および滴下漏斗を備えた５００ｍｌの四つ口フラスコに、ソルベッソ１００（エクソンモービル社登録商標）３５部を入れ、窒素ガスを導入しながら１５０℃に昇温したのち、滴下漏斗からＭＭＡ／ＢＭＡ／ＨＥＭＡ／ＭＡＡ（４０部／３３部／２５部／２部）の混合モノマー、ジ−ｔ−ブチルペルオキシド（日油社製：パーブチル（登録商標）Ｄ）１０部からなる混合物を１５０℃で３時間かけて均一速度で滴下した。滴下終了後さらに、重合反応を１５０℃で２時間継続した後、冷却して塗料用ワニスを得た。
(Comparative Example 1)
In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 35 parts of Solvesso 100 (registered trademark of ExxonMobil Co., Ltd.) was placed, and the temperature was raised to 150 ° C. while introducing nitrogen gas After raising the temperature, a mixed monomer of MMA / BMA / HEMA / MAA (40 parts / 33 parts / 25 parts / 2 parts), di-t-butyl peroxide (manufactured by NOF Corporation: Perbutyl (registered trademark) D) from the dropping funnel ) A mixture of 10 parts was added dropwise at a uniform rate at 150 ° C. over 3 hours. After completion of dropping, the polymerization reaction was continued at 150 ° C. for 2 hours, and then cooled to obtain a paint varnish.
（比較例２）
モノマーをＭＭＡ／ＢＭＡ／ＨＥＭＡ／ＭＡＡ（４０部／８部／５０部／２部）に、有機過酸化物をジ−ｔ−ヘキシルペルオキシド（日油社製：パーヘキシル（登録商標）Ｄ）に、そして有機溶媒をプロピオン酸エトキシエチルに変更した以外は、比較例１と同様にして重合を行い、塗料用ワニスを得た。
(Comparative Example 2)
The monomer is MMA / BMA / HEMA / MAA (40 parts / 8 parts / 50 parts / 2 parts), the organic peroxide is di-t-hexyl peroxide (manufactured by NOF Corporation: Perhexyl (registered trademark) D), Polymerization was conducted in the same manner as in Comparative Example 1 except that the organic solvent was changed to ethoxyethyl propionate to obtain a paint varnish.
（比較例３）
モノマーをＭＭＡ／ＢＭＡ／Ｓｔ／ＨＥＭＡ／ＭＡＡ（３０部／１８部／４０部／１０部／２部）に、有機過酸化物をジ−ｔ−ヘキシルペルオキシド（日油社製：パーヘキシル（登録商標）Ｄ）に変更した以外は、比較例１と同様にして重合を行い、塗料用ワニスを得た。
(Comparative Example 3)
The monomer is MMA / BMA / St / HEMA / MAA (30 parts / 18 parts / 40 parts / 10 parts / 2 parts), and the organic peroxide is di-t-hexyl peroxide (manufactured by NOF Corporation: Perhexyl (registered trademark)) ) Polymerization was carried out in the same manner as in Comparative Example 1 except that it was changed to D) to obtain a paint varnish.
＜評価方法＞
各実施例および比較例で得られた塗料用ワニスを、下記試験法によって評価した。得られた評価結果を表１に示す。
<Evaluation method>
The coating varnishes obtained in each Example and Comparative Example were evaluated by the following test methods. The obtained evaluation results are shown in Table 1.
（重量平均分子量および多分散度）
スクリュー管瓶中にポリマー０．０５〜０．０８ｇを計り取り、テトラヒドロフラン約２５ｍｌを加えて完全に溶解させ、０．２０μｍのメンブランフィルターで濾過した後、ゲル浸透クロマトグラフィ（ＧＰＣ）にて測定した。
＜分析条件＞
ＧＰＣ装置：ＴＯＳＯＨ ＨＬＣ−８３２０ＧＰＣ（東ソー社製）
カラム：ＴＯＳＯＨ ＴＳＫｇｅｌ Ｓｕｐｅｒ Ｍｕｌｔｉｐｏｒｅ Ｈｚ−Ｍ、１５ｃｍ、４．６ｍＩＤ（東ソー社製）、２本
カラム温度：４０℃
展開溶媒：テトラヒドロフラン（ＴＨＦ）、０．３５ｍｌ／ｍｉｎ
評価基準：○…分子量（Ｍｗ）が３０００未満の場合
×…分子量（Ｍｗ）が３０００以上
(Weight average molecular weight and polydispersity)
In a screw tube bottle, 0.05 to 0.08 g of the polymer was weighed, and about 25 ml of tetrahydrofuran was added and completely dissolved. After filtration through a 0.20 μm membrane filter, measurement was performed by gel permeation chromatography (GPC).
<Analysis conditions>
GPC device: TOSOH HLC-8320GPC (manufactured by Tosoh Corporation)
Column: TOSOH TSKgel Super Multipore Hz-M, 15 cm, 4.6 mID (manufactured by Tosoh Corporation), column temperature: 40 ° C.
Developing solvent: Tetrahydrofuran (THF), 0.35 ml / min
Evaluation criteria: ○: When the molecular weight (Mw) is less than 3000
X: Molecular weight (Mw) is 3000 or more
（ポリマー原体酸価の測定）
試料５ｇを、ＴＨＦ／エタノール混合溶媒（５０：５０）１００ｍｌに溶解し、１／２０Ｎの水酸化カリウム／エタノール溶液で滴定して得られた結果、およびポリマー固形分の測定結果から、ポリマーの原体酸価を算出した。
評価基準：○…理論酸価と原体酸価の差分が２．０以下の場合
×…理論酸価と原体酸価の差分が２．０より大きい場合
本明細書において、理論酸価は、以下式によって算出されたものである。理論酸価（ＫＯＨｍｇ/ｇ）＝（モノマーおよび有機過酸化物の混合溶液１ｇ中に含まれるカルボン酸基含有モノマーのモル数）×５６．１×１０００
(Measurement of polymer raw acid value)
From the results obtained by dissolving 5 g of a sample in 100 ml of a THF / ethanol mixed solvent (50:50) and titrating with a 1/20 N potassium hydroxide / ethanol solution and the measurement results of polymer solids, The body acid value was calculated.
Evaluation criteria: When the difference between the theoretical acid value and the raw acid value is 2.0 or less
X: When the difference between the theoretical acid value and the raw acid value is larger than 2.0 In this specification, the theoretical acid value is calculated by the following equation. Theoretical acid value (KOHmg / g) = (number of moles of carboxylic acid group-containing monomer contained in 1 g of a mixed solution of monomer and organic peroxide) × 56.1 × 1000
Claims (1)
（Ｂ）水酸基含有（メタ）アクリル酸エステル；２０〜２８質量部、
（Ｃ）カルボン酸基含有モノマー；０．１〜１０質量部、および
（Ｄ）一般式（Ｉ）
で表される有機過酸化物；（Ａ）〜（Ｃ）の混合物１００質量部に対して５〜１５質量部を（Ａ）：（Ｂ）＝１：０．２５〜１：０．４０となるように含む塗料用重合モノマー混合物を、
有機溶媒中にて重合する（メタ）アクリル酸エステル系塗料用ワニスの製造方法。
(A) vinyl monomer mixture containing (meth) acrylic acid ester; 70-80 parts by mass,
(B) hydroxyl group-containing (meth) acrylic acid ester; 20-28 parts by mass,
(C) Carboxylic acid group-containing monomer; 0.1 to 10 parts by mass, and (D) General formula (I)
5 to 15 parts by mass of (A) :( B) = 1: 0.25 to 1: 0.40 with respect to 100 parts by mass of the mixture of (A) to (C) A polymerized monomer mixture for coatings comprising,
A method for producing a varnish for a (meth) acrylic ester-based paint that is polymerized in an organic solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2016055415 | 2016-03-18 | ||
| JP2016055415 | 2016-03-18 |
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| JP2017171908A true JP2017171908A (en) | 2017-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2017050724A Pending JP2017171908A (en) | 2016-03-18 | 2017-03-16 | Method for producing varnish for (meth) acrylic ester paint |
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| Country | Link |
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| JP (1) | JP2017171908A (en) |
| TW (1) | TWI751145B (en) |
| WO (1) | WO2017159817A1 (en) |
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| JPS5525401A (en) * | 1978-08-10 | 1980-02-23 | Kansai Paint Co Ltd | High solid coating composition |
| JPS57209963A (en) * | 1981-06-22 | 1982-12-23 | Toyo Ink Mfg Co Ltd | Aqueous clear varnish composition and method for using same as topcoating agent |
| JPS62195060A (en) * | 1985-12-11 | 1987-08-27 | エクソン ケミカル パテンツ インコ−ポレ−テツド | Improved high solid content acryl base coating |
| JPS63168415A (en) * | 1987-01-02 | 1988-07-12 | ペンウオルト・コ−ポレ−シヨン | Solution polymerization of acrylic acid derivative monomer using t-alkylhydroxyperoxide |
| JPS63171676A (en) * | 1986-12-29 | 1988-07-15 | Kansai Paint Co Ltd | Metallic finishing method |
| JPH11293179A (en) * | 1998-04-15 | 1999-10-26 | Nof Corp | Varnish for paint, method for producing the same, and paint composition |
| JP2001354897A (en) * | 2000-06-12 | 2001-12-25 | Kansai Paint Co Ltd | Thermoset coating composition, method for forming coated film by using the composition, and coated article obtained therefrom |
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| DE4324801A1 (en) * | 1993-07-23 | 1995-01-26 | Hoechst Ag | Process for the preparation of copolymers containing OH groups and their use in high-solids coating compositions |
| BG109974A (en) * | 2007-10-15 | 2009-05-29 | "Оргахим" Ад | Acrylate copolymer, method of obtaining and use thereof |
| JP2009275170A (en) * | 2008-05-16 | 2009-11-26 | Mitsubishi Rayon Co Ltd | Method for producing vinyl polymer, coating containing the vinyl polymer, and method for forming coated film using the coating |
| DE102009046922A1 (en) * | 2009-11-20 | 2011-05-26 | Evonik Röhm Gmbh | Bulk polymerization of (meth) acrylate copolymers, which are soluble in the aqueous-alkaline |
| US10597554B2 (en) * | 2014-04-17 | 2020-03-24 | Ppg Industries Ohio, Inc. | Primer coating composition |
-
2017
- 2017-03-16 TW TW106109051A patent/TWI751145B/en active
- 2017-03-16 JP JP2017050724A patent/JP2017171908A/en active Pending
- 2017-03-16 WO PCT/JP2017/010772 patent/WO2017159817A1/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5525401A (en) * | 1978-08-10 | 1980-02-23 | Kansai Paint Co Ltd | High solid coating composition |
| JPS57209963A (en) * | 1981-06-22 | 1982-12-23 | Toyo Ink Mfg Co Ltd | Aqueous clear varnish composition and method for using same as topcoating agent |
| JPS62195060A (en) * | 1985-12-11 | 1987-08-27 | エクソン ケミカル パテンツ インコ−ポレ−テツド | Improved high solid content acryl base coating |
| JPS63171676A (en) * | 1986-12-29 | 1988-07-15 | Kansai Paint Co Ltd | Metallic finishing method |
| JPS63168415A (en) * | 1987-01-02 | 1988-07-12 | ペンウオルト・コ−ポレ−シヨン | Solution polymerization of acrylic acid derivative monomer using t-alkylhydroxyperoxide |
| JPH11293179A (en) * | 1998-04-15 | 1999-10-26 | Nof Corp | Varnish for paint, method for producing the same, and paint composition |
| JP2001354897A (en) * | 2000-06-12 | 2001-12-25 | Kansai Paint Co Ltd | Thermoset coating composition, method for forming coated film by using the composition, and coated article obtained therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201802126A (en) | 2018-01-16 |
| WO2017159817A1 (en) | 2017-09-21 |
| TWI751145B (en) | 2022-01-01 |
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