JP2012025826A - Metallic pigment composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallic pigment composition overcoming defects of prior art, and to provide a metallic pigment composition which can be used for a coating composition or an ink composition, especially a water-based coating or a water-based ink, is excellent in storage stability of the coating and is further excellent in adhesion property and chemical-resistance when it is made as a coating film and in which reduction of brightness, concealment property and flip-flop feeling is further less when it is made as a coating film.SOLUTION: The metallic pigment composition includes a polymer composition including a condensation polycyclic hydrocarbon skeleton and/or a condensation heterocyclic skeleton, and metal particles.

Description

  The present invention relates to a metal pigment composition suitable for a paint composition or an ink composition, particularly an aqueous paint or an aqueous ink.

Conventionally, metal pigments are used for metallic paints, printing inks, plastics kneading, and the like for the purpose of obtaining a cosmetic effect that emphasizes a metallic feeling. In these applications, there are cases where adhesion of a coating film obtained using a metal pigment and chemical resistance such as acid resistance or alkali resistance are required.
In recent years, in the paint field, there is an increasing need to switch to water-based paints that use less organic solvents as a resource-saving and non-polluting measure. There are few examples of practical water-based paints. This is because metal pigments are easily corroded in water-based paints. When metal powder is present in the water-based paint, corrosion by water occurs in one of acidic, neutral, basic, or a plurality of regions based on the properties of various metals, and hydrogen gas is generated. This is an extremely important safety issue in paint and ink manufacturing processes in paint manufacturers and ink manufacturers, and in painting and printing processes in automobiles, home appliance manufacturers, printing manufacturers, and the like. Hereinafter, the corrosion resistance of metal pigments in water, water-based paints or water-based inks is referred to as “storage stability”.

  Patent Document 1 discloses a method for forming a coating film in which an aluminum pigment is uniformly and highly three-dimensionally cross-linked in order to prevent color tone deterioration and to exhibit adhesion and chemical resistance. Stability was insufficient.

International Publication No. 1996/38506 Pamphlet

  The present invention provides a metal pigment composition that overcomes the disadvantages of the prior art, that is, it can be used for paint compositions or ink compositions, particularly aqueous paints or aqueous inks, and has excellent storage stability of paints. In addition, an object is to provide a metal pigment composition that has excellent adhesion and chemical resistance when formed into a coating film, and has little reduction in brightness, concealment, flip-flop feeling, etc. when formed into a coating film. It is what.

By using a metal pigment composition containing a polymer composition containing a condensed polycyclic hydrocarbon skeleton or a condensed heterocyclic skeleton and metal particles, the present inventors have excellent storage stability and excellent adhesion. It has been found that it is possible to obtain a metal pigment composition having both properties, chemical resistance and color tone, and the present invention has been completed.
That is, the present invention is as follows.
(1) A metal pigment composition containing a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, and metal particles.
(2) The metal pigment composition according to (1), wherein the polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton coats metal particles.
(3) The metal pigment composition according to (1) or (2), wherein the metal particles are aluminum.
(4) The polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton is at least one selected from an acrylic or vinyl resin and a polyester resin, from (1) to (3) The metal pigment composition according to any one of the above.
(5) A polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton comprises (A) a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one polymerizable double bond; At least one selected from a condensed heterocyclic skeleton-containing monomer having one or more polymerizable double bonds, and (B) a polymerizable unsaturated carboxylic acid, a phosphoric acid or phosphonic acid ester having a polymerizable double bond, polymerizable A compound having a double bond and an isocyanate group, a compound having a polymerizable double bond and an epoxy group, a compound having a polymerizable double bond and an amino group, a compound having a polymerizable double bond and a hydrolyzable silyl group, polymerization A copolymer having at least one selected from the group consisting of a compound having a polymerizable double bond and a sulfone group, a compound having a polymerizable double bond and a hydroxyl group, or (A) at least At least one selected from a condensed polycyclic hydrocarbon skeleton-containing monomer having one or more polymerizable double bonds, and a condensed heterocyclic skeleton-containing monomer having at least one polymerizable double bond, and (B) polymerizable Unsaturated carboxylic acid, phosphoric acid or phosphonic acid ester having polymerizable double bond, compound having polymerizable double bond and isocyanate group, compound having polymerizable double bond and epoxy group, polymerizable double bond and amino A compound having a group, a compound having a polymerizable double bond and a hydrolyzable silyl group, a compound having a polymerizable double bond and a sulfone group, and at least one selected from the group of compounds having a polymerizable double bond and a hydroxyl group (C) The metal pigment composition according to (1) to (4), which is a copolymer with another monomer.
(6) A polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton is (A) a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one polymerizable double bond, and at least Coordination of at least one selected from a condensed heterocyclic skeleton-containing monomer having one or more polymerizable double bonds and (B) at least one selected from compounds having two or more polymerizable double bonds in one molecule. Polymer or (A) a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one polymerizable double bond and a condensed heterocyclic skeleton-containing monomer having at least one polymerizable double bond (B) a copolymer of at least one selected from compounds having two or more polymerizable double bonds in one molecule and (C) another monomer, Metal pigment composition according to (4).
(7) The metal pigment composition according to (1) to (6), wherein the condensed polycyclic hydrocarbon skeleton is a fluorene skeleton.
(8) Any of (1) to (7), wherein the polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton is present in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the metal particles. The metal pigment composition described in 1.
(9) Further, at least one selected from an antioxidant, a light stabilizer, and a polymerization inhibitor is present in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the metal particles, (1) to (8) The metal pigment composition according to any one of the above.
(10) The metal pigment composition according to any one of (1) to (9), wherein the surfactant is further present in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the metal particles.
(11) Polymerizing a polymerizable monomer having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton in a solvent, or a polymer containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton. The method for producing a metal pigment composition according to any one of (1) to (10), wherein the coalescence composition is mixed.
(12) A coating composition comprising the metal pigment composition according to any one of (1) to (10).
(13) An ink composition comprising the metal pigment composition according to any one of (1) to (10).

  When the metal pigment composition of the present invention is used in a paint composition or an ink composition, particularly an aqueous paint or an aqueous ink, a coating film excellent in storage stability and adhesion, chemical resistance and color tone is obtained. Obtainable.

Hereinafter, the present invention will be described in detail with a focus on preferred embodiments.
As metal particles used in the present invention, particles of base metals such as aluminum, zinc, iron, magnesium, copper and nickel, and particles of their alloys can be preferably used.
As the shape, the average particle diameter (d50) is preferably 2 to 40 μm, the average thickness (t) is preferably in the range of 0.01 to 10 μm, and the average aspect ratio is preferably in the range of 1 to 2500. . Here, the average aspect ratio is a value obtained by dividing the average particle diameter (d50) of the metal particles by the average thickness (t).
When the metal particles are used as a pigment, scaly ones are preferable.
Particularly suitable are aluminum flakes which are frequently used as metallic pigments. As the aluminum flakes used in the present invention, those having surface properties, particle sizes and shapes required for metallic pigments such as surface gloss, whiteness, and glitter are suitable.
Aluminum flakes are usually marketed in a paste state and may be used as they are, or may be used after removing fatty acids on the surface with an organic solvent or the like in advance. A so-called aluminum vapor-deposited foil having an average particle diameter (d50) of 3 to 30 μm and an average thickness (t) of 5 to 50 nm can also be used.
These metal pigments may optionally contain at least one selected from metal oxo acids and / or salts of metal oxo acids, hydrolysates of silicon-containing compounds and / or condensates thereof, which will be described later.

As the polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, which is an essential component of the present invention, an acrylic (or vinyl) resin and / or a polyester resin are preferably used.
The acrylic (or vinyl) resin contains a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one polymerizable double bond and / or a condensed heterocyclic skeleton having at least one polymerizable double bond. It can be obtained by polymerization of the monomer and, if necessary, other monomers. Hereinafter, first, a condensed polycyclic hydrocarbon skeleton-containing acrylic or vinyl monomer having at least one polymerizable double bond and / or a condensed heterocyclic skeleton-containing acrylic having at least one polymerizable double bond. The monomer or vinyl monomer will be described.

Examples of the condensed polycyclic hydrocarbon skeleton include skeletons such as pentalene, indene, naphthalene, azulene, heptalene, biphenylene, indacene, fluorene, 9,9-bisphenylfluorene, phenanthrene, anthracene, triphenylene, pyrene, and perylene. Examples of the heterocyclic skeleton include skeletons such as indole, quinoline, indolizine, carbazole, acridine, and phenoxazine.
Examples of monomers having a polymerizable double bond in these skeletons include 1-vinylnaphthalene, 2-vinylnaphthalene, acetylvinylnaphthalene, t-butoxyvinylnaphthalene, 2-hydroxy-6-vinylnaphthalene, 2-acetoxy- 6-vinylnaphthalene, 2-acetoxy-6-vinylnaphthalene, 2-tert-butoxycarbonyloxy-6-vinylnaphthalene, 2- (1-ethoxyethoxy) -6-vinylnaphthalene, 2- (1-n-butoxyethoxy) ) -6-vinylnaphthalene, 1,5-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene, 2-vinylanthracene, 9-vinylanthracene, 9,10-divinyl Anthracene, 9-vinyl-9-H-fluorene, -Vinylfluorene, 2,7-divinyl-9-fluorene, N-vinylcarbazole, N-allylcarbazole, N-methacryloylcarbazole, N-acryloylcarbazole, N-vinylindole, 5-vinyl-8-hydroxyindole, 2 -Vinyl quinoline, N-vinyl phthalimide, etc. are mentioned. Divinyl compounds such as divinylnaphthalene, divinylanthracene and divinylfluorene are preferred.

（式中、Ｑは置換基を有していてもよい縮合多環炭化水素骨格および／または縮合複素環骨格を表し、Ｓは一般式（２）または（３）または（４）を表し、Ｄは一般式（５）または（６）を表す。ｎは０から３０の数を表し、ｍは骨格Ｑが有する水酸基の価数以下の数で、１から４の数を表す。）

（式中、Ｒ１、Ｒ２およびＲ３は炭素原子数２から６の直鎖または分岐のアルキレン基である。）

（式中、Ｒ４、Ｒ６は水素原子もしくはメチル基であり、Ｒ５は炭素原子数２から６の直鎖または分岐のアルキレン基である。） Furthermore, a monomer represented by the following general formula (1) having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton and starting from a mono- or polyhydric alcohol is also useful.

Wherein Q represents a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton which may have a substituent, S represents the general formula (2) or (3) or (4), and D Represents general formula (5) or (6), n represents a number from 0 to 30, m represents a number equal to or less than the valence of the hydroxyl group of skeleton Q, and represents a number from 1 to 4.

(Wherein R1, R2 and R3 are linear or branched alkylene groups having 2 to 6 carbon atoms.)

(Wherein R4 and R6 are a hydrogen atom or a methyl group, and R5 is a linear or branched alkylene group having 2 to 6 carbon atoms.)

Specific examples of mono- or polyhydric alcohols having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton Q, which are starting materials of the monomer group represented by the general formula (1), include 1-naphthol, for example. 2-naphthol, 2-methyl-1-naphthol, 2-ethoxy-1-naphthol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 2-methyl-1,4- Naphthalenediol, 1,2-dihydro-1β, 2β-naphthalenediol, anthracene-1-ol, 9,10-anthracenediol, 1,4-dihydro-9,10-anthracenediol, 1,2,10-anthracentriol 2-hydroxy-9H-fluorene, 9H-fluorene-2,6-diol, 9H-fluorene-3,6- Alcohols having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton such as diol; 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) Fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (3-hydroxy-6-methylphenyl) fluorene, 9,9-bis (2-hydroxy-4-methylphenyl) ) 9,9-bis (alkylhydroxyphenyl) fluorene such as fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) fluorene; 9,9-bis (4-hydroxy-3,5-dimethylphenyl) 9,9-bis (dia) such as fluorene, 9,9-bis (4-hydroxy-3,5-di-tert-butylphenyl) fluorene Kill hydroxyphenyl) fluorene; 9,9-bis (cycloalkylhydroxyphenyl) fluorene such as 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene; 9,9-bis (4-hydroxy-3-phenyl) 9,9-bis (arylhydroxyphenyl) fluorenes such as phenyl) fluorene; 9,9-bis ((substituted) hydroxyphenyl) fluorenes such as and the like. Among these, diols are preferable, and 9,9-bis ((substituted) hydroxyphenyl) fluorenes are more preferable. Particularly preferred are 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene. 9,9-bis (3-hydroxy-6-methylphenyl) fluorene, 9,9-bis (2-hydroxy-4-methylphenyl) fluorene, 9,9-bis (4-hydroxy-2-methylphenyl) Fluorene is mentioned.
Specific examples of the S moiety connecting the condensed polycyclic hydrocarbon skeleton and / or the condensed heterocyclic skeleton Q and the polymerizable double bond site D include — (CH ₂ —CH ₂ —O) _n —, — (CH ₂ — Ether bond such as CH (CH ₃ ) —O) _n —, — (CH (CH ₃ ) —CH ₂ —O) _n —, etc .; — (CO—O—CH ₂ —CH ₂ —O) _n —, — _{(CO-O-CH 2 -CH} (CH 3) -O) n -, - (CO-O-CH (CH 3) -CH 2 -O) n -, a carbonate bond of equal ;-( CO- (CH ₂ ) _5- O) _n- , etc. ester bonds; are preferably used. (However, n represents a number of 1 or more.)

（式中、Ｒ７は水素原子、シアノ基、ハロゲン原子またはアルキル基を表し、Ｒ８は水素原子または炭化水素基を表し、Ｒ９は炭素原子数２から３の直鎖または分岐のアルキレン基を表し、Ｒ１０は炭素原子数２から６の直鎖または分岐のアルキレン基を表し、Ｒ１１は水素原子またはメチル基を表す。ｎおよびｍは０または１を表し、ｐおよびｑはそれぞれ独立に０から１０の数を表す。）
最も好ましいものとして、下記式（８）に示す９，９−ビス［４−（（メタ）アクリロイルオキシエトキシ）フェニル］フルオレン、９，９−ビス［４−（（メタ）アクリロイルオキシ−２（または１）メチルエトキシ）フェニル］フルオレン、下記式（９）に示す９，９−ビス［４−（（メタ）アクリロイルオキシエトキシカルボニルオキシ）フェニル］フルオレンが挙げられる。
また、式（８）で表される化合物としては、新中村化学工業株式会社製、商品名「Ａ−ＢＰＥＦ」、大阪ガスケミカル株式会社製、商品名「オグソール」等を用いることができる。

A preferred embodiment as the condensed polycyclic hydrocarbon skeleton-containing monomer is represented by the general formula (7).

(Wherein R7 represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group, R8 represents a hydrogen atom or a hydrocarbon group, R9 represents a linear or branched alkylene group having 2 to 3 carbon atoms, R10 represents a linear or branched alkylene group having 2 to 6 carbon atoms, R11 represents a hydrogen atom or a methyl group, n and m represent 0 or 1, and p and q each independently represent 0 to 10 Represents a number.)
Most preferably, 9,9-bis [4-((meth) acryloyloxyethoxy) phenyl] fluorene represented by the following formula (8), 9,9-bis [4-((meth) acryloyloxy-2 (or 1) methylethoxy) phenyl] fluorene, and 9,9-bis [4-((meth) acryloyloxyethoxycarbonyloxy) phenyl] fluorene represented by the following formula (9).
Moreover, as a compound represented by Formula (8), Shin-Nakamura Chemical Co., Ltd. make, brand name "A-BPEF", Osaka Gas Chemical Co., Ltd. brand name, "Ogsol", etc. can be used.

  The polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton included in the present invention contains coexisting metal particles, optionally further coexisting metal oxoacids and / or salts of metal oxoacids, silicon It preferably interacts with at least one of the hydrolyzate of the containing compound and / or its condensate.

  Therefore, in the case of an acrylic or vinyl resin, examples of the interacting monomers include radical (and / or ion) polymerizable unsaturated carboxylic acid; phosphorus having a radical (and / or ion) polymerizable double bond. Acid or phosphonic acid ester; compound having radical (and / or ion) polymerizable double bond and isocyanate group; compound having radical (and / or ion) polymerizable double bond and epoxy group; radical (and / or ion) ) Compound having polymerizable double bond and amino group; Compound having radical (and / or ion) polymerizable double bond and hydrolyzable silyl group; Radical (and / or ion) polymerizable double bond and sulfone group A compound having a radical; radical (and / or ion) polymerizable double bond and hydroxyl group It is preferred to use at least one selected from the group consisting of a copolymerizable monomer; compounds having.

  Examples of the radical (and / or ionic) polymerizable unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, fumaric acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, Monooctyl maleate, monomethyl fumarate, monoethyl fumarate, monooctyl fumarate, β-carboxyethyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydro Phthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl phthalic acid, myristoleic acid, oleic acid, D Kosajien acid, docosadienoic acid, and the like. Among these, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride and the like are preferably used.

（式中、Ｒ１、Ｒ２およびＲ３は同じでも異なってもよく、水素原子、または炭素原子数１から３０の、任意にエーテル結合、エステル結合、水酸基、カルボニル基、チオール基を含んでもよい１価もしくは２価の炭化水素基であり、任意にＲ１とＲ２は一緒になって５員もしくは６員のシクロアルキル基を形成するか、または任意にＲ１とＲ２は窒素原子と一緒になって、架橋員として付加的に窒素もしくは酸素原子を含むことができる５員もしくは６員環を形成するか、または任意にＲ１、Ｒ２およびＲ３は一緒になって、１個以上の付加的な窒素原子および／または酸素原子を架橋員として含むことができる多員の多重環組成物を形成する。Ｒ１、Ｒ２およびＲ３は同時に水素原子にはならない。ｎは１から２の数を表す。） As a phosphoric acid or phosphonic acid ester having a radical (and / or ionic) polymerizable double bond, a mono- or diester of phosphoric acid or phosphonic acid is used. Specific examples thereof include 2- (meth) acryloyloxy. Ethyl acid phosphate, di-2- (meth) acryloyloxyethyl acid phosphate, tri-2- (meth) acryloyloxyethyl phosphate and any mixtures thereof; 2- (meth) acryloyloxypropyl acid phosphate, di-2- (Meth) acryloyloxypropyl acid phosphate, tri-2- (meth) acryloyloxypropyl phosphate and any mixtures thereof; phenyl-2- (meth) acryloyloxyethyl acid phosphate, butyl-2- ( T) Acrylyloxyethyl acid phosphate, Octyl-2- (meth) acryloyloxyethyl acid phosphate, Bis (2-chloroethyl) vinylphosphonate, 3-Chloro-2-acid phosphooxypropyl (meth) acrylate, Acid phosphooxy-poly Examples thereof include oxyethylene glycol mono (meth) acrylate and acid phosphooxy-polyoxypropylene glycol mono (meth) acrylate. These can be arbitrarily used in the form of a salt with an inorganic base or an organic amine. The organic amine used here is represented by the following general formula (10).

(In the formula, R 1, R 2 and R 3 may be the same or different, and may be a hydrogen atom or a monovalent group having 1 to 30 carbon atoms and optionally containing an ether bond, an ester bond, a hydroxyl group, a carbonyl group, or a thiol group. Or a divalent hydrocarbon group, optionally R1 and R2 taken together to form a 5- or 6-membered cycloalkyl group, or optionally R1 and R2 taken together with a nitrogen atom to form a bridge Forms a 5- or 6-membered ring which may additionally contain nitrogen or oxygen atoms as members, or optionally R1, R2 and R3 together form one or more additional nitrogen atoms and / or Or a multi-membered multi-ring composition that can contain an oxygen atom as a bridging member, R1, R2, and R3 cannot simultaneously be hydrogen atoms, n represents a number from 1 to 2.)

  Specifically, for example, linear primary amines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, laurylamine, tridecylamine, stearylamine; isopropylamine, isobutylamine, 2-ethylhexylamine, branched Branched primary amines such as tridecylamine; linear secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, dilaurylamine, ditridecylamine, distearylamine; Branched secondary amines such as diisopropylamine, diisobutylamine, di-2-ethylhexylamine, dibranched tridecylamine; N-methylbutylamine, N-ethylbutylamine, N-ethylhexylamine, N-ethyl Asymmetric secondary amines such as lulaurylamine, N-ethylstearylamine, N-isopropyloctylamine, N-isobutyl-2-ethylhexylamine; trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, trilauryl Linear tertiary amines such as amine, tritridecylamine, tristearylamine; branched tertiary amines such as triisopropylamine, triisobutylamine, tri-2-ethylhexylamine, tri-branched tridecylamine; N, N In addition to tertiary amines having mixed hydrocarbon groups such as dimethyloctylamine, N, N-dimethyllaurylamine, N, N-dimethylstearylamine, N, N-diethyllaurylamine, allylamine, diallylamine , Amines having an alkenyl group such as triallylamine, N, N-dimethylallylamine, alicyclic primary amines such as cyclohexylamine and 2-methylcyclohexylamine; aromatic rings such as aniline, benzylamine and 4-methylbenzylamine Primary amines having substituents; alicyclic secondary amines such as N, N-dicyclohexylamine and N, N-di-2-methylcyclohexylamine; dibenzylamine, N, N-di-4-methylbenzyl Secondary amines with aromatic ring substituents such as amines; asymmetric secondary amines such as N-cyclohexyl-2-ethylhexylamine, N-cyclohexylbenzylamine, N-stearylbenzylamine, N-2-ethylhexylbenzylamine N, N-dimethylbenzylamine, N, N-dimethylsilane Alicyclic tertiary amines such as cyclohexylamine and tricyclohexylamine; tertiary amines having an aromatic ring substituent such as tribenzylamine and tri-4-methylbenzylamine; morpholine, 3-methoxypropylamine, Amines having an ether bond such as 3-ethoxypropylamine, 3-butoxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine; monoethanolamine, diethanolamine, monoisopropanolamine, monopropanolamine, butanol Amine, triethanolamine, N, N-dimethylethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanol Alkanols such as amines, N-butylethanolamine, N-cyclohexyl-N-methylaminoethanol, N-benzyl-N-propylaminoethanol, or N-hydroxyethylpyrrolidine, N-hydroxyethylpiperazine, N-hydroxyethylmorpholine Amines; ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N— Diamines such as dimethyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, N-decyl-1,3-propanediamine, N-isotridecyl-1,3-propanediamine; N, N '-Dimethylpiperazine, Cyclic amines such as methoxyphenylpiperazine, N-methylpiperidine, N-ethylpiperidine, quinuclidine, diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene; Examples include aromatic amines such as pyridine and quinoline, or any mixture thereof.

  Among these, preferable examples include at least one kind selected from primary, secondary, or tertiary amines having a total of 3 to 60 carbon atoms, or alkanolamines, such as butylamine, Primary amines such as hexylamine, cyclohexylamine, octylamine, tridecylamine, stearylamine, etc .; diethylamine, dibutylamine, dihexylamine, dicyclohexylamine, di-2-ethylhexylamine, linear or branched ditridecylamine, distearyl Secondary amines such as amines; tertiary amines such as triethylamine, tributylamine, trioctylamine, linear or branched tritridecylamine, tristearylamine; N, N-dimethylethanolamine, N, N-diethylethanol Triethanolamine, N- methyldiethanolamine, triethanolamine, alkanolamines and the like; and morpholine can be given as specific examples.

  Among these, 2- (meth) acryloyloxyethyl acid phosphate, di-2- (meth) acryloyloxyethyl acid phosphate, tri-2- (meth) acryloyloxyethyl phosphate and any mixture thereof; 2- (meth) acryloyl Oxypropyl acid phosphate, di-2- (meth) acryloyloxypropyl acid phosphate, tri-2- (meth) acryloyloxypropyl phosphate and any mixtures thereof, and organic amine salts thereof, particularly ethanolamine salts, A morpholine salt or the like is preferably used.

  Examples of the compound having a radical (and / or ionic) polymerizable double bond and an isocyanate group include 2-isocyanatoethyl (meth) acrylate, 2-isocyanatoethoxyethyl (meth) acrylate, and 1,1-bis (acryloyl). And oxymethyl) ethyl isocyanate, methacryloyloxyphenyl isocyanate, and the like.

  Examples of the compound having a radical (and / or ion) polymerizable double bond and an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and epoxidized polybutadiene. , Etc.

Examples of the compound having a radical (and / or ionic) polymerizable double bond and an amino group include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth). Acrylate, morpholinoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, 2-aminoethyl vinyl ether, 2-dimethylaminoethyl vinyl ether, N, N-dimethylaminopropyl (meth) acrylamide, aminostyrene, N , N-dimethylaminostyrene, vinylbenzylamine, allylamine and the like.
Of these, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, allylamine and the like are preferably used.

  Examples of the compound having a radical (and / or ionic) polymerizable double bond and a hydrolyzable silyl group include (meth) acryloyloxypropyltrimethoxysilane, (meth) acryloyloxypropyltriethoxysilane, and (meth) acryloyloxy. Examples include propylmethyldimethoxysilane, (meth) acryloyloxypropylmethyldiethoxysilane, (meth) acryloyloxyethoxypropyltrimethoxysilane, (meth) acryloyloxymethyldimethylsilanol, vinyltrimethoxysilane, vinyltriethoxysilane, and the like. . Of these, (meth) acryloyloxypropyltrimethoxysilane, (meth) acryloyloxypropyltriethoxysilane, and the like are preferably used.

  Examples of the compound having a radical (and / or ionic) polymerizable double bond and a sulfone group include p-styrene sulfonic acid, allyl sulfosuccinic acid, 3-sulfopropyl (meth) acrylate, and the like.

Examples of the compound having a radical (and / or ionic) polymerizable double bond and a hydroxyl group include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and (meth) acrylic acid-2. -Hydroxybutyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, (4-hydroxymethylcyclohexyl) (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, caprolactone modified hydro (Meth) acrylic acid esters having active hydrogen such as ciethyl (meth) acrylate, glycerol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, etc .; 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, hydroxycyclohexyl Hydroxyalkyl vinyl ethers such as vinyl ether; unsaturated alcohols such as buten-1-ol-3, 2-methylbuten-3-ol-2, 3-methylbuten-3-ol-1, 3-methylbuten-2-ol-1 Class; N-methylol (meth) acrylamide, and the like.
Among these, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, and the like are preferably used.

Monomers that interact with at least one of these coexisting metal particles, optionally further coexisting metal oxoacids and / or salts of metal oxoacids, hydrolysates of silicon-containing compounds and / or condensates thereof, One kind or a mixture of two or more kinds may be used.
The amount used is generally preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of metal particles.

In addition, the acrylic (vinyl) resin preferably has a crosslinked structure using a monomer having two or more radical (and / or ionic) polymerizable double bonds in one molecule.
Examples of monomers having two radical (and / or ionic) polymerizable double bonds in one molecule include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate of neopentyl glycol propylene oxide adduct Relate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, bisphenol A ethylene oxide adduct di ( (Meth) acrylate, hydrogenated bisphenol A propylene oxide adduct di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, glycerin methacrylate acrylate, divinylbenzene, vinyl adipate, vinyl (meth) acrylate, vinyl crotonate , Vinyl cinnamate, allyl vinyl ether, isopropenyl vinyl ether, and the like.

Examples of the monomer having three or more radical (and / or ionic) polymerizable double bonds in one molecule include trimethylolpropane tri (meth) acrylate, glycerin ethylene oxide adduct tri (meth) acrylate, and trimethylolpropane propylene. Oxide adduct tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol caprolactone adduct Hexa (meth) acrylate, dipentaerythritol tri (meth) acrylate tripropionate, dipentaerythritol hexa (meth) acrylate mono Ropioneto, and the like.
These monomers having a crosslinked structure having two or more radical (and / or ionic) polymerizable double bonds in one molecule may be used singly or in combination.
The amount used is generally 1 to 50 parts by weight, preferably 2 to 30 parts by weight per 100 parts by weight of metal particles.
Monomers that interact with at least one of these coexisting metal particles, optionally further coexisting metal oxoacids and / or salts of metal oxoacids, hydrolysates of silicon-containing compounds and / or condensates thereof, In addition to monomers having a crosslinked structure, other monomers can optionally be copolymerized.

Examples of other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acrylate-hexyl, (meth) Acrylic acid-cyclohexyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid lauryl, (meth) acrylic acid benzyl, (meth) acrylic acid isobornyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid (Meth) acrylic acid esters such as furfuryl; trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, etc. (Meth) acrylic acid esters having fluorine side chains; (meth) acrylamide, N, -Unsaturated amides such as dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl caprate, stearic acid Vinyl esters such as vinyl and vinyl benzoate; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether; tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro Fluorinated olefins such as pentene-1; and styrene, α-methylstyrene, vinyltoluene, (meth) acrylonitrile, fumarate Examples thereof include dibutyl acid and the like, and one or two or more of them may be used in combination.
The amount used is typically about 0 to 30 parts by weight per 100 parts by weight of metal particles.
These (meth) acrylic monomers are polymerized by a known method such as radical polymerization or ionic polymerization, but it is usually easy to use a radical polymerization method using a polymerization initiator.

Examples of radical polymerization initiators include, for example, peroxides such as benzoyl peroxide, lauroyl peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate; and 2,2′-azobis-isobutyronitrile. Azo compounds such as 2,2′-azobis-2,4-dimethylvaleronitrile, and the like.
The amount used is not particularly limited, but is usually about 0.1 to 20 parts by weight per 100 parts by weight of the monomer having a radical polymerizable double bond.
Polymerization is carried out by adding a monomer and a polymerization initiator simultaneously or separately in a lump, or simultaneously or separately, or simultaneously or separately continuously in a slurry state in which a solvent is added to metal particles and dispersed. . Among these, a method in which a monomer and a polymerization initiator are separately or separately added is preferably used.
These monomers and polymerization initiators may be added at the same time as the metal oxo acid and / or metal oxo acid salt, the hydrolyzate of the silicon-containing compound and / or the condensate thereof are added to the metal particles. However, after the addition of the metal oxo acid and / or the metal oxo acid salt and the hydrolyzate of the silicon-containing compound and / or its condensate, the polymerization may be carried out by changing the solvent species if necessary. Is preferred.

The solvent during the addition or polymerization reaction may be a hydrophobic solvent or a hydrophilic solvent. Hydrophobic solvents include mineral spirits, solvent naphtha, LAWS (Low Aromatic White Spirit), HAWS (High Aromatic White Spirit), hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; methyl ethyl ketone and methyl Ketones such as isobutyl ketone and cyclohexanone; and the like. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol, isopropanol, and octanol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene And ether alcohols such as glycol monomethyl ether and dipropylene glycol monomethyl ether and esters thereof. Propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, and ethylene propylene glycol glycols can also be used. These can be used alone or in combination.
Less polar solvents such as mineral spirits, solvent naphtha, LAWS, HAWS, toluene, xylene, butyl acetate, methyl isobutyl ketone, cyclohexanone, octanol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol More preferable examples include ether alcohols such as monobutyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and esters thereof;

In the polymerization reaction in a slurry state, the concentration of metal particles in the slurry is preferably 5 to 20% by weight. The polymerization temperature and time are appropriately determined according to the progress of the reaction. The temperature is usually about 0 ° C. to 150 ° C., and the polymerization time is about 0.5 to 48 hours.
As polyester resins having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, at least one selected from the above-mentioned mono- or polyhydric alcohols having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, For example, condensation with a single or mixture selected from the group of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid Examples thereof include polyester resins obtained by the reaction.

In this case, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6- Hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentane Diol, 2-butyl-2-ethyl-1,3-propanediol, 2, Diols such as diethyl-1,3-propanediol; triols such as glycerin and trimethylolpropane; polyhydric alcohols selected from the group of tetraols such as diglycerin, dimethylolpropane and pentaerythritol You may use individually or in combination.
The amount used is generally 1 to 50 parts by weight, preferably 1 to 30 parts by weight per 100 parts by weight of metal particles.
The polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton used in the present invention is obtained by adding a condensed polycyclic hydrocarbon skeleton-containing monomer and / or a condensed heterocyclic skeleton-containing monomer to metal particles. It may be obtained by starting polycondensation at the same time or thereafter, or may be added in the form of an oligomer or polymer in advance, but it is preferable to obtain it by performing polycondensation.

In addition to the polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, the metal pigment composition of the present invention includes a metal oxo acid and / or a metal oxo acid salt, and a silicon-containing composition. A hydrolyzate of the compound and / or a condensate thereof may be contained.
Metal oxo acids are composed of transition metal elements of groups IVA, VA, VIA, and VIIA, and elements of groups IIIB, IVB, and VB, isopolyacids; heteropolyacids; mixed coordination heteropolyacids; and their It is preferably used in the form of a hydrate.
The isopolyacid is represented by H _p [M _q O _r ], and M is selected from transition metal elements of groups IVA, VA, VIA, and VIIA. Among these, M is preferably Ti, Zr, V, Nb, Ta, Mo, or W. (However, p, q, and r represent the number of atoms.)
Particularly preferred examples are titanic acid, vanadic acid, molybdic acid, tungstic acid and their hydrates.

The heteropolyacid is represented by H _p [X _s M _q O _r ], X is selected from elements of Group IIIB, IVB, and VB, and M is a transition metal element of Groups IVA, VA, VIA, and VIIA Chosen from. Among these, X is preferably B, Si, or P, and M is preferably Ti, Zr, V, Nb, Ta, Mo, or W. (However, p, q, r, and s represent the number of atoms.)
Preferred examples among these combinations, silicomolybdic acid _{(e.g., H 4 [SiMo 12 O 40} ]), silicotungstic acid _{(e.g., H 4 [SiW 12 O 40} ]), phosphomolybdic acid (e.g., _{H 3} [PMo ₁₂ O ₄₀ ]), phosphotungstic acid (eg, H ₃ [PW ₁₂ O ₄₀ ]), and hydrates thereof.

The mixed coordination type heteropolyacid is represented by H _p [X _s M _q N _t O _r ], X is selected from elements of IIIB, IVB, and VB groups, and M and N are groups of IVA, VA, VIA Selected from transition metal elements of group VIIA. Among these, X is preferably B, Si, and P, and M and N are preferably Ti, Zr, V, Nb, Ta, Mo, and W. (P, q, r, s, and t represent the number of atoms.)
Among these combinations, preferred examples include a cayvanadomolybdic acid (eg, H _{4 + x} [SiV _x Mo _12-x O ₄₀ ]) and a cayton gust molybdic acid (eg, H ₄ [SiW _x Mo _12-x O ₄₀ ]). ), Phosphovanadomolybdic acid (eg, H _{3 + x} [PV _x Mo _12-x O ₄₀ ]), lintongue molybdic acid (eg, H ₃ [PW _x Mo _12-x O ₄₀ ]), and hydrates thereof It is. (However, 1 ≦ x ≦ 11)

（式中、Ｒ１、Ｒ２およびＲ３は同じでも異なってもよく、水素原子、または炭素原子数１から３０の、任意にエーテル結合、エステル結合、水酸基、カルボニル基、チオール基を含んでもよい１価もしくは２価の炭化水素基であり、任意にＲ１とＲ２は一緒になって５員もしくは６員のシクロアルキル基を形成するか、または任意にＲ１とＲ２は窒素原子と一緒になって、架橋員として付加的に窒素もしくは酸素原子を含むことができる５員もしくは６員環を形成するか、または任意にＲ１、Ｒ２およびＲ３は一緒になって、１個以上の付加的な窒素原子および／または酸素原子を架橋員として含むことができる多員の多重環組成物を形成する。Ｒ１、Ｒ２およびＲ３は同時に水素原子にはならない。ｎは１から２の数を表す。） The metal oxo acid salt includes at least one selected from the group consisting of the above-mentioned isopolyacids; heteropolyacids; mixed coordination heteropolyacids; and alkali metals; alkaline earth metals; ammonia; amine compounds; One salt is preferred.
Examples of the alkali metal constituting the salt include lithium, sodium, potassium, rubidium, cesium and the like. Examples of alkaline earth metals include magnesium, calcium, strontium, barium and the like. In addition, metals such as manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, and lead may be used. Moreover, at least 1 type chosen from inorganic components, such as ammonia, and the amine compound etc. which are organic components, is mentioned. The amine component constituting the organic amine salt is represented by the following general formula (11).

(In the formula, R 1, R 2 and R 3 may be the same or different, and may be a hydrogen atom or a monovalent group having 1 to 30 carbon atoms and optionally containing an ether bond, an ester bond, a hydroxyl group, a carbonyl group, or a thiol group. Or a divalent hydrocarbon group, optionally R1 and R2 taken together to form a 5- or 6-membered cycloalkyl group, or optionally R1 and R2 taken together with a nitrogen atom to form a bridge Forms a 5- or 6-membered ring which may additionally contain nitrogen or oxygen atoms as members, or optionally R1, R2 and R3 together form one or more additional nitrogen atoms and / or Or a multi-membered multi-ring composition that can contain an oxygen atom as a bridging member, R1, R2, and R3 cannot simultaneously be hydrogen atoms, n represents a number from 1 to 2.)

  Specifically, for example, linear primary amines such as ethylamine, propylamine, butylamine, hexylamine, octylamine, laurylamine, tridecylamine, stearylamine; isopropylamine, isobutylamine, 2-ethylhexylamine, branched Branched primary amines such as tridecylamine; linear secondary amines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, dilaurylamine, ditridecylamine, distearylamine; Branched secondary amines such as diisopropylamine, diisobutylamine, di-2-ethylhexylamine, dibranched tridecylamine; N-methylbutylamine, N-ethylbutylamine, N-ethylhexylamine, N-ethyl Asymmetric secondary amines such as lulaurylamine, N-ethylstearylamine, N-isopropyloctylamine, N-isobutyl-2-ethylhexylamine; trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, trilauryl Linear tertiary amines such as amine, tritridecylamine, tristearylamine; branched tertiary amines such as triisopropylamine, triisobutylamine, tri-2-ethylhexylamine, tri-branched tridecylamine; N, N In addition to tertiary amines having mixed hydrocarbon groups such as dimethyloctylamine, N, N-dimethyllaurylamine, N, N-dimethylstearylamine, N, N-diethyllaurylamine, allylamine, diallylamine , Amines having an alkenyl group such as triallylamine, N, N-dimethylallylamine, alicyclic primary amines such as cyclohexylamine and 2-methylcyclohexylamine; aromatic rings such as aniline, benzylamine and 4-methylbenzylamine Primary amines having substituents; alicyclic secondary amines such as N, N-dicyclohexylamine and N, N-di-2-methylcyclohexylamine; dibenzylamine, N, N-di-4-methylbenzyl Secondary amines with aromatic ring substituents such as amines; asymmetric secondary amines such as N-cyclohexyl-2-ethylhexylamine, N-cyclohexylbenzylamine, N-stearylbenzylamine, N-2-ethylhexylbenzylamine N, N-dimethylbenzylamine, N, N-dimethylsilane Alicyclic tertiary amines such as cyclohexylamine and tricyclohexylamine; tertiary amines having an aromatic ring substituent such as tribenzylamine and tri-4-methylbenzylamine; morpholine, 3-methoxypropylamine, Amines having an ether bond such as 3-ethoxypropylamine, 3-butoxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine; monoethanolamine, diethanolamine, monoisopropanolamine, monopropanolamine, butanol Amine, triethanolamine, N, N-dimethylethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanol Alkanols such as amines, N-butylethanolamine, N-cyclohexyl-N-methylaminoethanol, N-benzyl-N-propylaminoethanol, or N-hydroxyethylpyrrolidine, N-hydroxyethylpiperazine, N-hydroxyethylmorpholine Amines; ethylenediamine, N-methylethylenediamine, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, N, N— Diamines such as dimethyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, N-decyl-1,3-propanediamine, N-isotridecyl-1,3-propanediamine; N, N '-Dimethylpiperazine, Cyclic amines such as methoxyphenylpiperazine, N-methylpiperidine, N-ethylpiperidine, quinuclidine, diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene; Examples include aromatic amines such as pyridine and quinoline, or any mixture thereof.

Among these, preferable examples include at least one selected from primary, secondary, or tertiary amines of linear or branched alkyl having 4 to 20 carbon atoms, or alkanolamines, such as butylamine, hexyl, and the like. Amine, cyclohexylamine, octylamine, tridecylamine, stearylamine, dihexylamine, di-2-ethylhexylamine, linear or branched ditridecylamine, distearylamine, tributylamine, trioctylamine, linear or branched tritridecyl Specific examples include amine, tristearylamine, N, N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, morpholine and the like.
The metal oxo acid and / or metal oxo acid salt is added in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the metal particles.

  The metal oxo acid and / or metal oxo acid salt may be added when the raw metal powder is pulverized or spread by a ball mill, or may be mixed in a slurry state in which a solvent is added to metal particles, or a solvent. You may knead | mix in the paste state which reduced the quantity of. In addition, the metal oxo acid and / or the metal oxo acid salt may be added to the metal particles as they are, or may be diluted with a solvent. In order to obtain a uniform mixed state, it is preferable to dilute with a solvent in advance. Solvents used for dilution are, for example, water, alcohols such as methanol, ethanol, propanol, butanol, isopropanol, octanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Ether alcohols such as ethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and esters thereof, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, polyoxyethylene glycol, polyoxy Examples include propylene glycol and ethylene propylene glycol glycols. Further, it may be added by dissolving with an acid or alkali.

（式中、Ｒ６は水素原子、または炭素原子数１から３０の、任意にハロゲン基を含んでもよい炭化水素基であり、Ｒ７は水素原子、または炭素原子数１から８の炭化水素基である。Ｒ６とＲ７は同一でも異なってもよく、Ｒ６とＲ７が２つ以上ある場合は、２つ以上あるＲ６は、すべて同一でも、一部同一でも、すべて異なっていてもよいし、２つ以上あるＲ７は、すべて同一でも、一部同一でも、すべて異なっていてもよい。１≦ｍ≦３である。）

（式中、Ｒ８は他の官能基と化学結合し得る反応基を含む基であり、Ｒ９は水素原子、または炭素原子数１から３０の、任意にハロゲン基を含んでもよい炭化水素基であり、Ｒ１０は水素原子、または炭素原子数１から８の炭化水素基である。Ｒ８とＲ９とＲ１０が２つ以上ある場合は、２つ以上あるＲ８は、すべて同一でも、一部同一でも、すべて異なっていてもよいし、２つ以上あるＲ９は、すべて同一でも、一部同一でも、すべて異なっていてもよいし、２つ以上あるＲ１０は、すべて同一でも、一部同一でも、すべて異なっていてもよい。１≦ｐ≦３であり、０≦ｑ≦２であり、１≦ｐ＋ｑ≦３である。）

（式中、Ｒ１１は水素原子、または炭素原子数１から８の炭化水素基であり、４つのＲ１１は、すべて同一でも、一部同一でも、すべて異なっていてもよい。）

（式中、Ｒ１２は水素原子、または炭素原子数１から３０の、任意にハロゲン基を含んでもよい炭化水素基であり、Ｒ１２が２つ以上ある場合は、すべて同一でも、一部同一でも、すべて異なっていてもよい。０≦ｒ≦３である。）
式（１２）のＲ６における炭化水素基としては、メチル、エチル、プロピル、ブチル、ヘキシル、オクチル、デシル、ドデシル、オレイル、ステアリル、シクロヘキシル、フェニル、ベンジル、ナフチル等が挙げられ、これらは分岐していても直鎖状であっても、フッ素、塩素、臭素等のハロゲン基を含んでいてもよい。これらの中でも、とくに炭素数が１から１８の炭化水素基が好ましい。また、Ｒ６が２つ以上ある場合には、すべて同一でも、一部同一でも、すべて異なっていてもよい。分子中のＲ６の数は、式（１２）において、ｍ＝１から３であるが、ｍ＝１または２がより好ましい。 The silicon-containing compound is selected from compounds represented by the following general formula (12) or (13) or (14) or (15).

(In the formula, R6 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms and optionally containing a halogen group, and R7 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R6 and R7 may be the same or different, and when there are two or more R6 and R7, two or more R6s may be all the same, partially the same or all different, or two or more R7 may be all the same, partly the same or all different, and 1 ≦ m ≦ 3.)

(In the formula, R8 is a group containing a reactive group capable of chemically bonding to other functional groups, and R9 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms and optionally containing a halogen group. , R10 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and when there are two or more R8, R9 and R10, two or more R8s are all the same, partly the same or all They may be different, or two or more R9s may be all the same, partly the same or all different, and two or more R9s may be the same, partly the same or all different. 1 ≦ p ≦ 3, 0 ≦ q ≦ 2, and 1 ≦ p + q ≦ 3.

(In the formula, R11 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and all four R11s may be the same, partially the same, or all different.)

(In the formula, R12 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, which may optionally contain a halogen group, and when there are two or more R12, they are all the same or partially the same, All may be different, 0 ≦ r ≦ 3.)
Examples of the hydrocarbon group in R6 of the formula (12) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl, phenyl, benzyl, naphthyl, etc., which are branched. Even if it is linear, it may contain halogen groups such as fluorine, chlorine and bromine. Among these, a hydrocarbon group having 1 to 18 carbon atoms is particularly preferable. Further, when there are two or more R6, they may all be the same, partially the same, or all different. The number of R6 in the molecule is m = 1 to 3 in Formula (12), and m = 1 or 2 is more preferable.

  Examples of the hydrocarbon group for R7 in the formula (12) include methyl, ethyl, propyl, butyl, hexyl, octyl and the like, and these may be branched or linear. Of these hydrocarbon groups, methyl, ethyl, propyl and butyl are particularly preferable. Moreover, when there are two or more R7s, they may all be the same, partially the same, or all different.

  Examples of the silicon-containing compound of formula (12) include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, trimethylmethoxysilane, and trimethylethoxysilane. N-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dibutyldibutoxysilane , Isobutyltrimethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, dihexyldimethoxysilane, dihexyldi Toxisilane, Octyltrimethoxysilane, Octyltriethoxysilane, Dioctyldimethoxysilane, Dioctyldiethoxysilane, Dioctylethoxybutoxysilane, Decyltrimethoxysilane, Decyltriethoxysilane, Didecyldimethoxysilane, Didecyldiethoxysilane, Octadecyltrimethoxy Silane, octadecyltriethoxysilane, dioctadecyldimethoxysilane, dioctadecyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxy Silane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriate Shishiran, 3-chloropropyl trimethoxy silane, 3-chloropropyl triethoxy silane, 3-chloropropyl tributoxysilane silane, and the like.

Examples of the reactive group that can chemically bond with other functional groups in R8 of the formula (13) include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a mercapto group, a polysulfide group, and an isocyanate group. Etc.
Moreover, when there are two or more R8s, they may all be the same, partially the same, or all different. The number of R8 in the molecule is p = 1 to 3 in the formula (13), but p = 1 is more preferable.
Examples of the hydrocarbon group of R9 in the formula (13) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl, phenyl, benzyl, naphthyl, etc., which are branched. Even if it is linear, it may contain halogen groups such as fluorine, chlorine and bromine. Among these, a hydrocarbon group having 1 to 18 carbon atoms is particularly preferable. When there are two or more R9s, they may all be the same, partly the same, or all different.
Examples of the hydrocarbon group for R10 in the formula (13) include methyl, ethyl, propyl, butyl, hexyl, octyl and the like, and these may be branched or linear. Of these hydrocarbon groups, methyl, ethyl, propyl and butyl are particularly preferable. Moreover, when there are two or more R10s, they may all be the same, partially the same, or all different.

  Such silicon-containing compounds of formula (13) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris (2-methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacrylic Roxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-methyl-3-aminopropyl-trimethoxysilane N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl-tri Ethoxysilane, bis Triethoxysilylpropyl) tetrasulfide, 3-isocyanate propyl triethoxysilane, and the like.

Examples of the hydrocarbon group for R11 in the formula (14) include methyl, ethyl, propyl, butyl, hexyl, octyl and the like, and these may be branched or linear. Of these hydrocarbon groups, methyl, ethyl, propyl and butyl are particularly preferable. The four R11s may be all the same, partly the same, or all different.
Examples of such a silicon-containing compound of formula (14) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. Of these, tetraethoxysilane is particularly preferable.

Examples of the hydrocarbon group for R12 in the formula (15) include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, oleyl, stearyl, cyclohexyl, phenyl, benzyl, naphthyl, etc., which are branched. Even if it is linear, it may contain halogen groups such as fluorine, chlorine and bromine. Among these, a hydrocarbon group having 1 to 12 carbon atoms is particularly preferable. Moreover, when there are two or more R12s, they may all be the same, partially the same, or all different. The number of R12 in the molecule is r = 0 to 3 in the formula (15), and r = 1 to 3 is more preferable.
Examples of the silicon-containing compound represented by the formula (15) include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyldimethylchlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, and tetrachlorosilane.

  The above general formulas (12), (13), (14) and (15) of the present invention may be used alone or in combination of two or more.

  A hydrolyzate of a silicon-containing compound and / or a condensation reaction product thereof can be obtained by stirring and mixing a silicon-containing compound, an amount of water necessary for carrying out the hydrolysis reaction, and a hydrolysis catalyst. In that case, a hydrophilic solvent can also be used as needed. The time for the hydrolysis reaction is adjusted according to the type of silicon-containing compound, the temperature during hydrolysis, the type of hydrolysis catalyst, and the concentration thereof.

  Examples of the catalyst for the hydrolysis reaction of the silicon-containing compound and / or its condensation reaction include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; Organic acids such as malonic acid; phosphonic acids such as vinylphosphonic acid, 2-carboxyethanephosphonic acid, 2-aminoethanephosphonic acid, and octanephosphonic acid. These hydrolysis catalysts may be used alone or in combination of two or more. Also, for example, inorganic alkalis such as ammonia, sodium hydroxide, potassium hydroxide; inorganic alkali salts such as ammonium carbonate, ammonium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine , Amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, ethylenediamine, pyridine, aniline, choline, tetramethylammonium hydroxide, guanidine; ammonium formate, ammonium acetate, monomethylamine formate Organic acid salts such as dimethylamine acetate, pyridine lactate, guanidinoacetic acid, and aniline acetate can also be used. These hydrolysis catalysts may be used alone or in combination of two or more.

As a raw material for the hydrolysis reaction of the silicon-containing compound and / or the condensation reaction thereof, a partially condensed oligomer may be used.
The condensation reaction of the hydrolyzate of the silicon-containing compound may be performed simultaneously with the hydrolysis reaction of the silicon-containing compound, or may be performed by dividing the process and changing the catalyst if necessary. In that case, you may heat as needed.
Further, the hydrolysis reaction and / or condensation reaction of the silicon-containing compound may be performed after adding to the metal particles and the metal oxo acid and / or the salt of the metal oxo acid, or may be performed before the addition. It may not be completely hydrolyzed.

  The hydrolysis reaction and / or condensation reaction of the silicon-containing compound is preferably performed using a solvent. Solvents used for dilution are, for example, water, alcohols such as methanol, ethanol, propanol, butanol, isopropanol, octanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol mono Ether alcohols such as ethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and esters thereof, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, polyoxyethylene glycol, polyoxy Examples include propylene glycol and ethylene propylene glycol glycols. When alcohols or ether alcohols are used as the solvent, an exchange reaction between the alkoxy group of the silicon-containing compound and the solvent may occur, but it may be used as it is in the hydrolysis reaction.

The hydrolyzate of the silicon-containing compound and / or the condensate thereof is added in an amount of 0.01 to 50 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of the metal particles.
The hydrolyzate of the silicon-containing compound and / or the condensate thereof may be added when the raw metal powder is pulverized or spread with a ball mill, or may be mixed in a slurry state in which a solvent is added to the metal particles. Alternatively, the paste may be kneaded in a paste state with a reduced amount of solvent.
Further, the planned addition amount may be added all at once in the initial stage, or may be added continuously over a predetermined time. These may be added before the metal oxo acid and / or metal oxo acid salt is added to the metal particles, or may be added after previously mixing with the metal oxo acid and / or metal oxo acid salt. However, it is preferable to add the metal oxo acid and / or salt of the metal oxo acid after the addition.
In addition to the polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, the metal pigment composition of the present invention further includes an antioxidant, a light stabilizer, a polymerization inhibitor, a surface activity. At least one agent can be added.

  Examples of the antioxidant include phenolic compounds, phosphorus compounds, and sulfur compounds. Suitable compounds include 2,6-di-t-butylphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol (BHT), 2,6-di- -T-butyl-4-ethyl-phenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butyl-4-s-butylphenol, butylhydroxyanisole (BHA), tocopherol, 2, 6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl-β- (4′-hydroxy 3′5′-di-t-butylphenyl) propionate, 2-t-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, propyl gallate, octyl gallate, Uryl gallate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di) -T-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethyldiphenylmethane 2,2′-dimethylene-bis- (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-t-butylphenol), 2,2′-butylidene -Bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethyleneglycol -N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, bis [2-tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis [2- {3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-t-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-thiobis (4-methyl-6-t-butylphenol), bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, 4,4'-di and tri-thiobis (2,6-di-t-butylphenol), 2,2-thiodiethylenebis- [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-t-butylanilino) -1 , 3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide, N, N′-bis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyl] hydrazine, calcium (3,5-di-tert-butyl-4-hydroxybenzylmonoethyl phosphonate), alkylated bisphenol, 1,1,3-tris (2 Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris ( 3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t- Butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris [2 [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] isocyanate Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, butyric acid, 3,3-bis (3-tert-butyl) -4-hydroxyphenyl) ethylene ester, triphenyl phosphite, diphenylnonylphenyl phosphite, tris- (2,4-di-t-butylphenyl) phosphite, trisnonylphenyl phosphite, tris- (mono and di mixed) Nonylphenyl) phosphite, diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenylisodecyl phosphite, diphenylmono (tridecyl) phosphite, 2, 2′-ethylidenebis (4,6-di-t-butylphenol) fluorophosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphine Ite, tris (tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite, 4,4'-isopropyl Ridendiphenol alkyl (C12-C15) phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) di-tridecyl phosphite, distearyl-pentaerythritol diphosphite, bis (nonylphenyl) ) Pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl phosphite), Phenyl-bisphenol A pentae Thritol diphosphite, tetraphenyldipropylene glycol diphosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetraphenyltetra (tridecyl) ) Pentaerythritol tetraphosphite, zinc dialkyldithiophosphate (ZnDTP), 3,4,5,6-dibenzo-1,2-oxaphosphan-2-oxide, 3,5-di-t-butyl-4- Hydroxybenzyl phosphite-diethyl ester, hydrogenated bisphenol A phosphite polymer, dilauryl-3,3′-thiodipropionic acid ester (DLTTDP), ditridecyl-3,3′-thiodipropionic acid ester, dimyristyl-3,3 '-Thiodipropionic acid ester (DMTDP), Stearyl-3,3′-thiodipropionate (DSTDP), laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetra (β-lauryl-thiopropionate) ester, stearylthiopropionamide, Bis [2-methyl-4- (3-n-alkyl (C12-C14) thiopropionyloxy) -5-t-butylphenyl] sulfide, dioctadecyl disulfide, 2-mercaptonbenzimidazole, 2-mercapto-6- Examples include methylbenzimidazole, 1,1′-thiobis (2-naphthol), ascorbic acid and the like.

  Some light stabilizers are used as the above-mentioned antioxidants, but benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylates, oxalic acid derivatives, hindered amine compounds (HALS), hindered phenols. Typified by series compounds. Suitable compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 3 ″, 4 ″, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-4′-t-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′) , 5′-bis (α, α-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetraphthalimid) Domethyl) -5′-methylphenyl] benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′) , 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2 -Yl) phenol, methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate and a condensation product of polyethylene glycol (molecular weight about 300), 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydride Xyl-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4 ′ Polymers of -dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 4- (2-acryloyloxyethoxy) -2-hydroxybenzophenone, 2,2 ' -Dihydroxy-4,4'-dimethoxybenzopheno And other 4-substituted benzophenones, phenyl salicylate, 2,5-di-t-butyl-4-hydroxybenzoic acid-n-hexadecyl ester, 4-t-butylphenyl salicylate, 4- t-octylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, ethyl (β, β-diphenyl) cyanoacrylate, 2- Ethylhexyl (β, β-diphenyl) cyanoacrylate, 2-ethoxy-2′-ethylsuccinic acid bisanilide, 2-ethoxy-5-tert-butyl-2′-ethylsuccinic acid bisanilide, oxalic acid anilide derivatives, indole, phenyl-4- Piperidinyl carbonate, [4- (4-hydroxy-3,5-di-t-butylphenyl) propionyl] -N- (4-H Roxy-3,5-di-t-butylphenyl) methyl-2,2,6,6-tetramethylpiperidine, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetra Methylpiperazineone), bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- [N-methyl-2,2,6,6-tetramethyl-piperidinyl sebacate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1,2,3 Condensation product of 4-butanecarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanecarboxylic acid and 1,2,2,6,6 -Pentamethyl-4-piperidinol and tride Condensates with alcohols, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly [[6- (1,1,3,3-tetramethylbutylamino) -1,3,5-triazine-2, 4-diyl] [(2,2,6,6-tetramethylpiperidine) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]], poly [6-morpholino-s-triazine- 2,4-diyl-2,2,6,6-tetramethylpiperidylimino-hexamethylene] [2,2,6,6-tetramethylpiperidylimino]], 1,2,3,4-butanetetracarboxylic Acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5 ] Undecane) condensate with diethanol, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ', 1'-tetramethyl-4,4'-(methylene-di-p- Phenylene) disemicarbazide and the like.

  Examples of the polymerization inhibitor include phenols, quinones, nitro compounds, nitroso compounds, amines, and sulfides. Suitable compounds include hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, catechol, p-tert-butylcatechol, p-methoxyphenol, p-tert-butylcatechol, 2,6-di-tert-butyl- phenols such as m-cresol, pyrogallol, β-naphthol, 4-methoxy-1-naphthol; quinones such as benzoquinone, 2,5-diphenyl-p-benzoquinone, p-toluquinone, p-xyloquinone; nitromethane, nitroethane, Nitrobutane, nitrobenzene, nitrobenzenesulfonic acid compound, m-dinitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-tert-butylnitrone, 5,5-dimethyl-1-pyrroline-1-oxide, and other nitro Compounds or nitroso compounds; amines such as chloranyl-amine, diphenylamine, diphenylpicrylhydrazine, phenol-α-naphthylamine, pyridine, phenothiazine; sulfides such as dithiobenzoyl sulfide and dibenzyltetrasulfide.

  Examples of the surfactant used in the present invention include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyalkylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, Polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyalkylene alkyl amino ethers such as polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monosteare Sorbitan fatty acid esters such as rate and sorbitan monooleate; polyoxyethylene sorbitan monora Polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate; polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate Polyalkylene glycol fatty acid esters such as acrylate, polyethylene glycol dilaurate, polyethylene glycol distearate; nonionic surfactants typified by glycerin fatty acid esters such as lauric acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, etc. Sodium oxyethylene lauryl ether sulfate, polyoxyethylene octylsulfate Sulfate esters such as sodium nyl ether sulfate, polyoxyethylene nonyl phenyl ether sodium sulfate, triethanolamine lauryl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate; sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, dialkylsulfosuccinic acid Sulfonates such as sodium; anionic surfactants typified by phosphate esters such as potassium alkyl phosphate, and quaternary ammonium such as lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride Examples include cationic surfactants typified by salts, and one or more selected from these Can be used. Among these, particularly preferred examples include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether or a mixture thereof.

  The antioxidant, light stabilizer and polymerization inhibitor used in the present invention may be added when the raw metal powder is pulverized or spread by a ball mill, or mixed in a slurry state in which a solvent is added to metal particles. Alternatively, it may be kneaded in a paste state with a small amount of solvent. The order of adding the antioxidant, light stabilizer, and polymerization inhibitor and the polymer composition treatment step including the condensed polycyclic hydrocarbon skeleton and / or the condensed heterocyclic skeleton of the metal particles is not limited. Specifically, it is preferable to add after treating with a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton. In addition, the metal pigment composition may be added to a water-based paint or water-based ink in which a resin as a coating film-forming component is dissolved or dispersed in a water-based medium. In order to obtain a uniform mixed state, it is preferable to dilute with a solvent in advance. Solvents used for dilution are water, alcohols such as methanol and isopropanol; ether alcohols such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether; and esters thereof; hexane, octane, isooctane, benzene, toluene, xylene, tetralin And hydrocarbon solvents such as decalin; industrial gasoline such as mineral spirit and solvent naphtha; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexane; mineral oil and the like.

  The surfactant used in the present invention may be added when the raw metal powder is pulverized or spread by a ball mill, may be mixed in a slurry state in which a solvent is added to metal particles, or the amount of the solvent You may knead | mix in the paste state which decreased less. The order of the surfactant addition step and the polymer composition treatment step including the condensed polycyclic hydrocarbon skeleton and / or the condensed heterocyclic skeleton of the metal particles is not limited, but generally the condensed polycyclic hydrocarbon skeleton is not limited. It is more preferable to add after processing with a polymer composition containing a condensed heterocyclic skeleton. In addition, the metal pigment composition may be added to a water-based paint or water-based ink in which a resin as a coating film-forming component is dissolved or dispersed in a water-based medium. In order to obtain a uniform mixed state, it is preferable to dilute with a solvent in advance. Solvents used for dilution are water, alcohols such as methanol and isopropanol; ether alcohols such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether; and esters thereof; hexane, octane, isooctane, benzene, toluene, xylene, tetralin And hydrocarbon solvents such as decalin; industrial gasoline such as mineral spirit and solvent naphtha; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexane; mineral oil and the like.

  The antioxidant, light stabilizer, and polymerization inhibitor are added in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight, with respect to 100 parts by weight of the metal component in the metal particles. These are preferably added after being dissolved or dispersed in a solvent in advance.

The surfactant is added in an amount of 0.01 to 30 parts by weight, preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the metal component in the metal particles. These are preferably added after being dissolved or dispersed in a solvent in advance.
This mixture is stirred and mixed at a temperature of 10 to 200 ° C., preferably 20 to 160 ° C. for 10 minutes to 72 hours, preferably 20 minutes to 48 hours. If the solvent is high, remove it to bring the final metal pigment content to the desired 40-90%. The resulting metal pigment composition may be aged at 40 ° C. to 120 ° C., preferably 50 ° C. to 110 ° C. for 6 hours to 3 months, preferably 1 day to 30 days.
The metal pigment composition obtained by the present invention can be used for organic solvent-based paints, inks, and the like, but is an aqueous solution in which resins as coating film forming components are dissolved or dispersed in a medium mainly composed of water. A metallic aqueous paint or metallic water-based ink can be obtained by adding to the paint or water-based ink. It can also be kneaded with a resin or the like and used as a water-resistant binder or filler. An antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant may be added when the metal pigment composition is blended with an aqueous paint or aqueous ink, or a resin.

When the metal pigment composition obtained by the present invention is used in paints and inks, it may be added as it is to (water-based) paint or (water-based) ink, but it is preferable to add it after previously dispersing in a solvent. Examples of the solvent to be used include water, texanol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and the like. Examples of these resins include acrylic resins, polyester resins, polyether resins, epoxy resins, fluororesins, and rosin resins.
As acrylic resins, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acrylate-2-ethylhexyl, ( (Meth) acrylic acid esters such as methacrylic lauryl; (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-2-hydroxybutyl, (meth) ) (Meth) acrylic acid esters having active hydrogen such as acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid Unsaturated amides such as acrylamide, N-methylol acrylamide and diacetone acrylamide And polymerizing a single or a mixture selected from glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, p-styrene sulfonic acid, allyl sulfosuccinic acid and the like. Examples thereof include acrylic resins obtained.

  The polymerization method is generally emulsion polymerization, but can also be produced by suspension polymerization, dispersion polymerization, or solution polymerization. In emulsion polymerization, it can also be polymerized stepwise.

  The polyester resins were selected from the group of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. Alone or in combination with, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1, 6-hexanediol, 1,2-hexanediol, 2 5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, Diols such as 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-diethyl-1,3-propanediol, such as glycerin and trimethylolpropane Triols such as polyester resins obtained by a condensation reaction with a polyhydric alcohol alone or in a mixture selected from the group of tetraols such as diglycerin, dimethylolpropane and pentaerythritol, and for example, the hydroxyl groups of low molecular weight polyols Polycaprola obtained by ring-opening polymerization of ε-caprolactone Examples include kutons.

Polyether resins include, for example, polyhydric hydroxy compounds, alone or in mixture, using a strong basic catalyst such as hydroxides such as lithium, sodium and potassium, alcoholates and alkylamines, ethylene oxide, propylene oxide, Polyether polyols obtained by adding alkylene oxides such as butylene oxide, cyclohexene oxide, styrene oxide alone or in mixture, and polyether polyols obtained by reacting alkylene oxide with polyfunctional compounds such as ethylenediamines, tetrahydrofuran Polyether polyols obtained by ring-opening polymerization of cyclic ethers, etc., and so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium Etc. are included.
These resins are preferably emulsified, dispersed or dissolved in water. Therefore, the carboxyl group, the sulfone group, etc. contained in the resins can be neutralized.

Examples of neutralizing agents for neutralizing carboxyl groups and sulfone groups include ammonia and water-soluble amino compounds such as monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, and isopropylamine. , Diisopropylamine, triethanolamine, butylamine, dibutylamine, 2-ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine and the like can be used. Preferably, tertiary amines such as triethylamine and dimethylethanolamine are used.
Preferred resins are acrylic resins and polyester resins.
If necessary, a resin such as a melamine curing agent, an isocyanate curing agent, or a urethane dispersion can be used in combination. Furthermore, in combination with inorganic pigments, organic pigments, extender pigments, silane coupling agents, titanium coupling agents, dispersants, anti-settling agents, leveling agents, thickeners and antifoaming agents that are generally added to paints. Also good. In order to improve the dispersibility in the paint, a surfactant may be further added, and in order to improve the storage stability of the paint, an antioxidant, a light stabilizer, and a polymerization inhibitor are further added. May be.

Examples of the present invention are shown below.
[Example 1]
700 g of mineral spirit is added to and dispersed in 135 g of a commercially available aluminum paste (trade name “GX-3100 (average particle size 10.5 μm, non-volatile content 74%)” manufactured by Asahi Kasei Chemicals Corporation), and the slurry temperature is kept at 70 ° C. The mixture was stirred for 30 minutes. Next, 0.75 g of acrylic acid was added and stirred for 30 minutes. Thereafter, 8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene and 3.0 g of 2,2′-azobis-2,4-dimethylvaleronitrile (ADVN) were dissolved in 80 g of solvent naphtha. The solution was added over 3 hours. Thereafter, stirring was continued for another 2 hours. After completion of the reaction, the slurry was cooled and the slurry was filtered to obtain 152 g of an aluminum pigment composition having a nonvolatile content of 72.4%.
[Example 2]
The same procedure as in Example 1 was conducted except that 8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene of Example 1 was replaced with 6.4 g, and 1.6 g of benzyl acrylate was added thereto. Thus, 151 g of an aluminum pigment composition having a nonvolatile content of 72.6% was obtained.
[Example 3]
The same procedure as in Example 1 was carried out except that 0.75 g of acrylic acid in Example 1 was replaced with 2.0 g of 2-acryloyloxyethyl acid phosphate to obtain 159 g of an aluminum pigment composition having a nonvolatile content of 68.9%.
[Example 4]
Example 9 except that 8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene of Example 1 was replaced with 5.6 g, and 2.4 g of trimethylolpropane triacrylate (TMPTA) was added thereto. In the same manner as in Example 1, 158 g of an aluminum pigment composition having a nonvolatile content of 69.7% was obtained.
[Example 5]
8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene of Example 1, 4.0 g of n-vinylcarbazole, 2.8 g of TMPTA, and 1.2 g of di-trimethylolpropane tetraacrylate (DTMPTA) Except having replaced with, it carried out like Example 1 and obtained 155g of aluminum pigment compositions with a non-volatile content of 70.0%.
[Example 6]
The same procedure as in Example 5 was carried out except that 0.75 g of acrylic acid in Example 5 was replaced with 2.0 g of 2-acryloyloxyethyl acid phosphate and n-vinylcarbazole was replaced with 2-vinylnaphthalene. 153 g of a 2% aluminum pigment composition was obtained.
[Example 7]
An aluminum pigment having a non-volatile content of 71.5% was prepared in the same manner as in Example 5 except that 0.75 g of acrylic acid in Example 5 was replaced with 0.90 g of methacrylic acid and n-vinylcarbazole was replaced with 9-vinanthracene. 152 g of composition was obtained.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that 8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene of Example 1 was replaced with 5.6 g of TMPTA and 2.4 g of DTMPTA, and a nonvolatile content of 67.1. % 166 g of an aluminum pigment composition was obtained.
[Comparative Example 2]
The same procedure as in Example 1 was conducted except that 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene of Example 1 was replaced with divinylbenzene, and 153 g of an aluminum pigment composition having a nonvolatile content of 69.0% was obtained. Obtained.

[Examples 8 to 14] [Comparative Examples 3 and 4]
For the aluminum pigment compositions obtained in Examples 1 to 7 and the aluminum pigment compositions obtained in Comparative Examples 1 and 2, an aqueous metallic paint and a metallic paint were prepared with the following compositions.
[Adjustment of water-based metallic paint]
Aluminum pigment composition: 12.0 g as non-volatile content
Diethylene glycol monobutyl ether: 18.0g
Polyoxyethylene lauryl ether (nonionic surfactant)
(Matsumoto Yushi Seiyaku Co., Ltd., trade name “Actinol L5”): 6.0 g
Purified water: 12.0g
Acrylic emulsion (acid value 13 mgKOH / g, hydroxyl value 40 mgKOH / g,
Tg 20 ° C., solid content 42%, number average molecular weight 100,000, pH 8.4): 240 g
After mixing the above, the pH is 7.7 to 7.8 with ammonia water, and the viscosity is 650 to 750 mPa · s with carboxylic acid thickener and purified water (B-type viscometer, No. 3 rotor, 60 rotations). Adjusted.
[Adjustment of metallic paint]
Aluminum pigment composition: 5 g as non-volatile content
Thinner (Musashi Paint Co., Ltd., trade name “Plaace Thinner No. 2726”): 50 g
Acrylic resin (Musashi Paint Co., Ltd., trade name “Plaace No. 7160”): 33 g
The following evaluation was performed using the produced water-based metallic paint.
[Evaluation 1 (Storage stability evaluation)]
200 g of the aqueous metallic paint was collected in a flask, and the hydrogen gas cumulative generation amount was observed in a constant temperature water bath at 40 ° C. for 12 hours. It was evaluated as follows according to the amount of gas generated and used as an index of storage stability in the paint.
A: Less than 1.0 ml B: 1.0 or more and less than 5.0 ml X: 5.0 ml or more [Evaluation 2 (color tone evaluation of coating film)]
A coating film was prepared using a water-based metallic paint, and the brightness, flip-flop feeling, and hiding property were evaluated.
The brightness was evaluated using a laser-type metallic feeling measuring apparatus Alcorp LMR-200 manufactured by Kansai Paint Co., Ltd. The optical conditions include a laser light source with an incident angle of 45 degrees and a light receiver with light receiving angles of 0 degrees and -35 degrees. As a measured value, IV value was calculated | required by the light reception angle -35 degree which can obtain the maximum light intensity except the light of the specular reflection area | region reflected on the coating-film surface among the reflected light of a laser. The IV value is a parameter proportional to the intensity of specularly reflected light from the coating film and represents the magnitude of light luminance. The determination method is as follows.
[Examples 8 to 14] [Comparative Example 4]
A: 10 or more higher than Comparative Example 3 ○: Difference from Comparative Example 3 is less than 10 ×: 10 or more lower than Comparative Example 3 Flip-flop feeling is a color change colorimeter manufactured by Suga Test Instruments Co., Ltd. Was used to evaluate. The F / F value was determined from the logarithmic slope of the reflected light intensity (L value) at an observation angle (light receiving angle) of 30 degrees and 80 degrees with respect to a light source having an incident angle of 45 degrees. The F / F value is a parameter proportional to the degree of orientation of the metal pigment, and represents the magnitude of the flip-flop feeling of the pigment. The determination method is as follows.
[Examples 8 to 14] [Comparative Example 4]
◎: 0.05 or higher than Comparative Example 3 ○: Difference from Comparative Example 3 is less than 0.05 ×: 0.05 or lower than Comparative Example 3 The concealability was visually observed. The determination method is as follows.
[Examples 8 to 14] [Comparative Example 4]
○: Equivalent or higher than Comparative Example 3 ×: Inferior to Comparative Example 3 [Examples 8 to 14] [Comparative Examples 3 and 4]
Next, the produced metallic paint was applied to an ABS resin plate with an air spray device so that the dry film thickness was 10 μm, and dried in an oven at 60 ° C. for 30 minutes to obtain a coating plate for evaluation.
The following evaluation was performed using the above-mentioned evaluation coating plate.
[Evaluation 3 (Adhesion)]
Cellotape (registered trademark: manufactured by Nichiban Co., Ltd., CT-24) was brought into close contact with the coating film of the above-described evaluation coating plate, pulled at an angle of 45 degrees, and the degree of peeling of the aluminum pigment particles was visually observed. The determination method is as follows.
○: No peeling
Δ: Slightly peeled ×: Peeled [Evaluation 4 (chemical resistance)]
The lower half of the coating plate for evaluation was immersed in a beaker containing a 0.1N-NaOH aqueous solution and left at 55 ° C. for 4 hours. The coated plate after the test was washed with water and dried, and then the immersion part and the non-immersion part were color-measured according to the condition d (8-d method) of JIS-Z-8722 (1982), and JIS-Z-8730 (1980) The color difference ΔE is obtained according to 6.3.2. The determination was made as follows according to the value of the color difference ΔE. (The smaller the value, the better.)
○: Less than 1.0 ×: 1.0 or more Table 1 shows the results of Evaluations 1 to 4.

  The present invention can be used in paint compositions or ink compositions, particularly water-based paints or water-based inks, and is excellent in the storage stability of paints. Thus, it is possible to provide a metal pigment composition with less decrease in the above.

Claims (13)

  A metal pigment composition comprising a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, and metal particles.   The metal pigment composition according to claim 1, wherein the polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton coats metal particles.   The metal pigment composition according to claim 1 or 2, wherein the metal particles are aluminum.   The polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton is at least one selected from an acrylic or vinyl resin and a polyester resin. Metal pigment composition. A polymer composition comprising a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton,
(A) at least one selected from a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one polymerizable double bond and a condensed heterocyclic skeleton-containing monomer having at least one polymerizable double bond; B) Polymerizable unsaturated carboxylic acid, phosphoric acid or phosphonic acid ester having a polymerizable double bond, compound having a polymerizable double bond and an isocyanate group, compound having a polymerizable double bond and an epoxy group, polymerizable two Selected from the group consisting of a compound having a heavy bond and an amino group, a compound having a polymerizable double bond and a hydrolyzable silyl group, a compound having a polymerizable double bond and a sulfone group, and a compound having a polymerizable double bond and a hydroxyl group At least one copolymer, or (A) a monomer containing a condensed polycyclic hydrocarbon skeleton having at least one polymerizable double bond, at least one At least one selected from the above condensed heterocyclic skeleton-containing monomers having a polymerizable double bond, and (B) a polymerizable unsaturated carboxylic acid, a phosphoric acid or phosphonic acid ester having a polymerizable double bond, a polymerizable double bond Compounds having a bond and an isocyanate group, compounds having a polymerizable double bond and an epoxy group, compounds having a polymerizable double bond and an amino group, compounds having a polymerizable double bond and a hydrolyzable silyl group, polymerizable two 5. The copolymer according to claim 1, which is a copolymer of at least one selected from the group consisting of a compound having a heavy bond and a sulfone group, a compound having a polymerizable double bond and a hydroxyl group, and (C) another monomer. Metal pigment composition. A polymer composition comprising a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton,
(A) at least one selected from a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one polymerizable double bond and a condensed heterocyclic skeleton-containing monomer having at least one polymerizable double bond; B) a copolymer with at least one compound selected from compounds having two or more polymerizable double bonds in one molecule, or (A) a condensed polycyclic hydrocarbon skeleton having at least one polymerizable double bond And at least one selected from a monomer containing a condensed heterocyclic skeleton having at least one polymerizable double bond, and (B) at least selected from a compound having two or more polymerizable double bonds in one molecule. The metal pigment composition according to claim 1, which is a copolymer of one type and (C) another monomer.   The metal pigment composition according to claim 1, wherein the condensed polycyclic hydrocarbon skeleton is a fluorene skeleton.   The metal pigment according to any one of claims 1 to 7, wherein the polymer composition containing the condensed polycyclic hydrocarbon skeleton and / or the condensed heterocyclic skeleton is present in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the metal particles. Composition.   Furthermore, at least 1 type chosen from antioxidant, a light stabilizer, and a polymerization inhibitor exists in 0.01 to 5 weight part with respect to 100 weight part of metal particles, In any one of Claim 1-8. Metal pigment composition.   The metal pigment composition according to any one of claims 1 to 9, wherein the surfactant is further present in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the metal particles.   Polymer composition containing metal particle, polymerized monomer having condensed polycyclic hydrocarbon skeleton and / or condensed heterocyclic skeleton, or condensed polycyclic hydrocarbon skeleton and / or condensed heterocyclic skeleton in solvent The manufacturing method of the metal pigment composition in any one of Claim 1 to 10 which carries out a mixing process.   The coating composition containing the metal pigment composition in any one of Claim 1 to 10.   An ink composition comprising the metal pigment composition according to claim 1.