JP5701530B2 - Metal pigment composition - Google Patents

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 metal pigment containing a molybdate amine salt and coated with a three-dimensionally cross-linked resin in order to achieve both storage stability in water-based paint or water-based ink and adhesion and chemical resistance. Disclosed. However, the method described in this prior document has insufficient storage stability.

JP 2008-201821 A

  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.

（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。）
（９）イソポリ酸、ヘテロポリ酸、混合配位型ヘテロポリ酸、およびそれらの水和物が、（５）に記載のイソポリ酸、ヘテロポリ酸、混合配位型ヘテロポリ酸、およびそれらの水和物である、（８）に記載の金属顔料組成物。
（１０）縮合多環炭化水素骨格および／または縮合複素環骨格を含む重合体組成物が、アクリル系もしくはビニル系樹脂、及びポリエステル樹脂から選ばれる少なくとも一種である、（１）から（９）のいずれかに記載の金属顔料組成物。
（１１）縮合多環炭化水素骨格および／または縮合複素環骨格を含む重合体組成物が、（Ａ）少なくとも一つ以上の重合性二重結合を有する縮合多環炭化水素骨格含有モノマー、少なくとも一つ以上の重合性二重結合を有する縮合複素環骨格含有モノマーから選ばれる少なくとも一種と、（Ｂ）重合性不飽和カルボン酸、重合性二重結合を有するリン酸またはホスホン酸エステル、重合性二重結合とイソシアネート基を有する化合物、重合性二重結合とエポキシ基を有する化合物、重合性二重結合とアミノ基を有する化合物、重合性二重結合と加水分解性シリル基を有する化合物、重合性二重結合とスルホン基を有する化合物、重合性二重結合と水酸基を有する化合物の群から選ばれる少なくとも一種との共重合体、または（Ａ）少なくとも一つ以上の重合性二重結合を有する縮合多環炭化水素骨格含有モノマー、少なくとも一つ以上の重合性二重結合を有する縮合複素環骨格含有モノマーから選ばれる少なくとも一種と、（Ｂ）重合性不飽和カルボン酸、重合性二重結合を有するリン酸またはホスホン酸エステル、重合性二重結合とイソシアネート基を有する化合物、重合性二重結合とエポキシ基を有する化合物、重合性二重結合とアミノ基を有する化合物、重合性二重結合と加水分解性シリル基を有する化合物、重合性二重結合とスルホン基を有する化合物、重合性二重結合と水酸基を有する化合物の群から選ばれる少なくとも一種と、（Ｃ）他のモノマーとの共重合体である、（１）から（１０）のいずれかに記載の金属顔料組成物。
（１２）縮合多環炭化水素骨格および／または縮合複素環骨格を含む重合体組成物が、（Ａ）少なくとも一つ以上の重合性二重結合を有する縮合多環炭化水素骨格含有モノマー、少なくとも一つ以上の重合性二重結合を有する縮合複素環骨格含有モノマーから選ばれる少なくとも一種と、（Ｂ）一分子中に重合性二重結合を二つ以上有する化合物から選ばれる少なくとも一種との共重合体、または（Ａ）少なくとも一つ以上の重合性二重結合を有する縮合多環炭化水素骨格含有モノマー、少なくとも一つ以上の重合性二重結合を有する縮合複素環骨格含有モノマーから選ばれる少なくとも一種と、（Ｂ）一分子中に重合性二重結合を二つ以上有する化合物から選ばれる少なくとも一種と、（Ｃ）他のモノマーとの共重合体である、（１）から（１０）のいずれかに記載の金属顔料組成物。
（１３）縮合多環炭化水素骨格がフルオレン骨格である、（１）から（１２）のいずれかに記載の金属顔料組成物。
（１４）金属オキソ酸および／または金属オキソ酸の塩から選ばれる少なくとも一種が、金属粒子１００重量部に対し、０．０１から１０重量部存在する、（１）から（１３）のいずれかに記載の金属顔料組成物。
（１５）縮合多環炭化水素骨格および／または縮合複素環骨格を含む重合体組成物が、金属粒子１００重量部に対し、１から５０重量部存在する、（１）から（１４）のいずれかに記載の金属顔料組成物。
（１６）更にシリコン含有化合物の加水分解物および／またはその縮合物が、金属粒子１００重量部に対し、０．０１から５０重量部存在する、（１）から（１５）のいずれかに記載の金属顔料組成物。
（１７）更に酸化防止剤、光安定剤、及び重合禁止剤の中から選ばれる少なくとも一種が、金属粒子１００重量部に対し、０．０１から５重量部存在する、（１）から（１６）のいずれかに記載の金属顔料組成物。
（１８）更に界面活性剤が金属粒子１００重量部に対し、０．０１から３０重量部存在する、（１）から（１７）のいずれかに記載の金属顔料組成物。
（１９）金属粒子を、溶媒中で、金属オキソ酸および／または金属オキソ酸の塩から選ばれる少なくとも一種で混合処理した後、縮合多環炭化水素骨格および／または縮合複素環骨格を有する重合性モノマーを重合、または、縮合多環炭化水素骨格および／または縮合複素環骨格を含む重合体組成物を混合処理する、（１）から（１８）のいずれかに記載の金属顔料組成物の製造方法。
（２０）（１）から（１８）のいずれかに記載の金属顔料組成物を含む、塗料組成物。
（２１）（１）から（１８）のいずれかに記載の金属顔料組成物を含む、インキ組成物。 The present inventors include at least one selected from metal oxoacids and / or salts of metal oxoacids, a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, and metal particles. By using the metal pigment composition, the present inventors have found that a metal pigment composition having excellent storage stability and excellent adhesion, chemical resistance and color tone can be obtained, and the present invention has been completed. It came to do.
That is, the present invention is as follows.
(1) A metal pigment containing at least one selected from metal oxoacids and / or salts of metal oxoacids, a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, and metal particles Composition.
(2) A polymer composition comprising at least one selected from metal oxoacids and / or salts of metal oxoacids and a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton coats metal particles ( The metal pigment composition as described in 1).
(3) The metal pigment composition according to (1) or (2), wherein the metal particles are aluminum.
(4) Isopolyacids, heteropolyacids, mixed coordination type heteropolyacids in which the metal oxo acid is composed of transition metal elements of groups IVA, VA, VIA, and VIIA, and elements of groups IIIB, IVB, and VB And the metal pigment composition according to any one of (1) to (3), which is at least one selected from hydrates thereof.
(5) the isopolyacid is titanic acid, vanadic acid, molybdic acid, or tungstic acid, and the heteropolyacid is silicomolybdic acid, silicotungstic acid, phosphomolybdic acid, or phosphotungstic acid; (4) The metal pigment composition according to (4), wherein the acid is cavernadomolybdic acid, caitangus molybdic acid, phosphovanadomolybdic acid, or phosphotungstomolybdic acid.
(6) Isopolyacids, heteropolyacids, and mixed coordination types, wherein the metal oxoacid salt is composed of transition metal elements of groups IVA, VA, VIA, and VIIA, and elements of groups IIIB, IVB, and VB Any one of (1) to (3), which is a salt of at least one selected from heteropolyacids and hydrates thereof and at least one selected from the group consisting of alkali metals, alkaline earth metals, and ammonium. The metal pigment composition described.
(7) The isopolyacid, heteropolyacid, mixed coordination type heteropolyacid, and hydrate thereof are the isopolyacid, heteropolyacid, mixed coordination type heteropolyacid, and hydrate thereof according to (5). The metal pigment composition according to (6), wherein
(8) Isopolyacids, heteropolyacids, and mixed coordination types, wherein the metal oxoacid salt is composed of transition metal elements of groups IVA, VA, VIA, and VIIA, and elements of groups IIIB, IVB, and VB A salt of at least one selected from heteropolyacids and hydrates thereof and at least one selected from amine compounds represented by the following general formula (1): The metal pigment composition described.

(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.)
(9) The isopolyacid, heteropolyacid, mixed coordination heteropolyacid, and hydrate thereof are the isopolyacid, heteropolyacid, mixed coordination heteropolyacid, and hydrate thereof according to (5). The metal pigment composition according to (8), wherein
(10) 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 (9) The metal pigment composition according to any one of the above.
(11) 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, at least one At least one selected from condensed heterocyclic skeleton-containing monomers having one or more polymerizable double bonds, (B) a polymerizable unsaturated carboxylic acid, a phosphoric acid or phosphonic acid ester having a polymerizable double bond, Compound having a heavy bond and an isocyanate group, Compound having a polymerizable double bond and an epoxy group, Compound having a polymerizable double bond and an amino group, Compound having a polymerizable double bond and a hydrolyzable silyl group, Polymerizability A copolymer having at least one selected from the group consisting of a compound having a 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; Saturated carboxylic acid, phosphoric acid or phosphonic acid ester having a polymerizable double bond, a compound having a polymerizable double bond and an isocyanate group, a compound having a polymerizable double bond and an epoxy group, a polymerizable double bond and an amino group At least one selected from the group consisting of 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, (C) The metal pigment composition according to any one of (1) to (10), which is a copolymer with another monomer.
(12) 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, at least one Copolymerization of at least one selected from condensed heterocyclic skeleton-containing monomers 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 Or at least one selected from (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 And (B) a copolymer of at least one selected from compounds having two or more polymerizable double bonds in one molecule and (C) another monomer, from (1) Metal pigment composition according to any one of 10).
(13) The metal pigment composition according to any one of (1) to (12), wherein the condensed polycyclic hydrocarbon skeleton is a fluorene skeleton.
(14) In any one of (1) to (13), at least one selected from metal oxoacids and / or salts of metal oxoacids is present in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of metal particles The metal pigment composition described.
(15) Any of (1) to (14), 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.
(16) The hydrolyzate of a silicon-containing compound and / or its condensate is present in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight of the metal particles, according to any one of (1) to (15) Metal pigment composition.
(17) 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 (16) The metal pigment composition according to any one of the above.
(18) The metal pigment composition according to any one of (1) to (17), 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.
(19) Polymerization having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton after mixing the metal particles with at least one selected from metal oxo acids and / or salts of metal oxo acids in a solvent. The method for producing a metal pigment composition according to any one of (1) to (18), wherein a monomer is polymerized or a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton is mixed. .
(20) A coating composition comprising the metal pigment composition according to any one of (1) to (18).
(21) An ink composition comprising the metal pigment composition according to any one of (1) to (18).

  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. Can be obtained.

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 contain at least one selected from hydrolyzates of silicon-containing compounds and / or condensates thereof, as will be described later.

  The metal oxo acid used in the present invention is composed of transition metal elements of groups IVA, VA, VIA, and VIIA, and elements of groups IIIB, IVB, and VB. Isopolyacids, heteropolyacids, mixed coordination type heteropolyacids And in the form of their hydrates.

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 hydrates thereof.
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 ]), phosphotungsto molybdic acid (eg, H ₃ [PW _x Mo _12-x O ₄₀ ]),
And their hydrates. (However, 1 ≦ x ≦ 11)

  The metal oxo acid salt includes at least one selected from the aforementioned isopolyacids, heteropolyacids, and mixed coordination type heteropolyacids, and at least one selected from the group consisting of alkali metals, alkaline earth metals, ammonia, and amine compounds. The salt of is preferred.

（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。） 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 (2).

(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.

At least one selected from metal oxo acids and / or metal oxo acid salts 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 metal particles.
At least one selected from metal oxoacids and / or metal oxoacid salts 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, the paste may be kneaded in a paste state with a small amount of solvent. Further, at least one selected from metal oxo acids and / or salts of metal oxo acids may be added to the metal particles as they are, or may be added after being 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 And propylene glycol and glycols of ethylene propylene glycol. Further, it may be added by dissolving with an acid or alkali.

  As the polymer composition containing the condensed polycyclic hydrocarbon skeleton and / or the condensed heterocyclic skeleton of the present invention, acrylic (or vinyl) resins and / or polyester resins 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 in which these skeletons have a polymerizable double bond include 1-vinylnaphthalene, 2-vinylnaphthalene, acetylvinylnaphthalene, t-butoxyvinylnaphthalene, 2-hydroxy-6-vinylnaphthalene, and 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-divinylanthracene 9-vinyl-9-H-fluorene 2-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（４）または（５）または（６）を表し、Ｄは一般式（７）または（８）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 (3) 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 a general formula (4) or (5) or (6), and D Represents general formula (7) or (8), 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 (3), include, for example, 1-naphthol 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（１０）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（１１）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。 A preferred embodiment as the condensed polycyclic hydrocarbon skeleton-containing monomer is represented by the general formula (9).

(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 (10), 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 (11).

本発明に含まれる縮合多環炭化水素骨格および／または縮合複素環骨格を含む重合体組成物は、共存する金属粒子と、金属オキソ酸および／または金属オキソ酸の塩から選ばれる少なくとも一種と、場合によっては更に共存するシリコン含有化合物の加水分解物および／またはその縮合物との少なくともいずれかと相互作用を持つことが好ましい。 Moreover, as a compound represented by Formula (10), 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 includes coexisting metal particles and at least one selected from metal oxoacids and / or salts of metal oxoacids, In some cases, it is preferable to further interact with at least one of the hydrolyzate of the silicon-containing compound and / or the condensate thereof.

  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 (12).

(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.

At least one selected from these coexisting metal particles, metal oxoacids and / or salts of metal oxoacids, and, in some cases, at least one of a hydrolyzate of a silicon-containing compound and / or a condensate thereof may mutually interact. Monomers having an action may be used alone or in combination.
The amount used is generally preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of metal particles.

The acrylic (or 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.

  At least one selected from these coexisting metal particles, metal oxoacids and / or salts of metal oxoacids, and, in some cases, at least one of a hydrolyzate of a silicon-containing compound and / or a condensate thereof may mutually interact. In addition to monomers having an action and monomers having a crosslinked structure, other monomers can be optionally 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 contain at least one kind selected from metal oxoacids and / or salts of metal oxoacids and, if appropriate, hydrolyzates of silicon-containing compounds and / or condensates thereof in metal particles. It may be added at the same time as the addition, but after the addition of the hydrolyzate of the silicon-containing compound and / or the condensate thereof in combination with at least one selected from metal oxoacids and / or salts of metal oxoacids as the case may be. If necessary, it is preferable to carry out polymerization by changing the solvent species.

  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, 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.

  Further, the metal pigment composition of the present invention includes a polymer composition containing at least one selected from metal oxoacids and / or salts of metal oxoacids, and a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton. In addition, a hydrolyzate of a silicon-containing compound and / or a condensate thereof may further be contained.

（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。） The silicon-containing compound is selected from compounds represented by the following general formula (13) or (14) or (15) or (16).

(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 for R6 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. 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 (13), and m = 1 or 2 is more preferable.
Examples of the hydrocarbon group for R7 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 R7s, they may all be the same, partially the same, or all different.

  Examples of such a silicon-containing compound of the formula (13) 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 (14) 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 (14), but p = 1 is more preferable.

  Examples of the hydrocarbon group of R9 in the formula (14) 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 (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. 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 (14) 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 (15) 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 (15) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. Of these, tetraethoxysilane is particularly preferable.

Examples of the hydrocarbon group for R12 in the formula (16) 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 formula (16), and r = 1 to 3 is more preferable.
Examples of the silicon-containing compound represented by the formula (16) include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, octyldimethylchlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, and tetrachlorosilane.

  The general formulas (13) and (14) and (15) and (16) 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, phosphoric acid; benzoic acid, acetic acid, chloroacetic acid, salicylic acid, oxalic acid, picric acid, phthalic 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.

In addition, the hydrolysis reaction and / or condensation reaction of the silicon-containing compound may be performed after the addition to at least one selected from metal particles and metal oxoacids and / or salts of metal oxoacids, or before the addition. May be. 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 adding at least one selected from metal oxoacids and / or metal oxoacid salts to metal particles, or at least selected from metal oxoacids and / or metal oxoacid salts in advance. Although it may be added after mixing with one kind, it is preferable to add at least one kind selected from metal oxo acid and / or salt of metal oxo acid after addition.

  Further, the metal pigment composition of the present invention includes a polymer composition containing at least one selected from metal oxoacids and / or salts of metal oxoacids, and a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton. In addition, at least one of an antioxidant, a light stabilizer, a polymerization inhibitor, and a surfactant 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 ″ -tetraphthalimidomethyl)- 5'-methylphenyl] benzotri Azole, 2- (2′-hydroxy-3′-t-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-benzotriazol-2-yl) phenol, methyl-3- [ Condensate of 3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate with polyethylene glycol (molecular weight about 300), 2,4-dihydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydride Loxy-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′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 4- (2-acryloyloxyethoxy) -2-hydroxybenzophenone polymer, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone and others Of 4-substituted benzophenone, 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′-ethyl Succinic acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyl succinic acid bisanilide, succinic acid anilide derivatives, indole, phenyl-4-piperidinyl carbonate, [4- (4-hydroxy-3,5-di- t-butylphenyl) propionyl] -N- (4-hydroxy-3,5-di-t-butylphenyl) methyl-2,2,6,6-tetrame Tilpiperidine, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 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, 1,2,3,4-butanecarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol A condensate of 1,2,3,4-butanecarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6) -Tetramethyl-4-pipe Lysyl) -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'-Tetra Condensate with methyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) 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, sodium polyoxyethylene nonyl phenyl ether 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, stearyltrimethylammonium chloride, cetyltrimethylammonium 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 process of adding these antioxidants, light stabilizers and polymerization inhibitors, the metal oxo acid and / or metal oxo acid salt treatment process of metal particles, a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton The order of the polymer composition treatment step is not limited, but it is preferably added after the polymer composition treatment step including at least a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton. In general, it is preferable to add after treating with a polymer composition containing a metal oxo acid and / or metal oxo acid and 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, the metal oxo acid and / or metal oxo acid salt treatment step of the metal particles, and the polymer composition treatment step including the condensed polycyclic hydrocarbon skeleton and / or the condensed heterocyclic skeleton is as follows: However, it is preferably added after the polymer composition treatment step including at least a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton. In general, it is preferable to add after treating with a polymer composition containing a metal oxo acid and / or metal oxo acid and 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 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]
While stirring a slurry in which 698 g of mineral spirit was added to 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), rim vanado A solution prepared by dissolving 0.5 g of a hydrate of molybdic acid (H ₄ PV ₁ Mo ₁₁ O ₄₀ ) in 30 g of isopropanol was gradually added, and the mixture was stirred for 1 hour while maintaining the slurry temperature at 70 ° C. 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 159 g of an aluminum pigment composition having a nonvolatile content of 68.4%.

[Example 2]
The hydrate of phosphovanadomolybdic acid (H ₄ PV ₁ Mo ₁₁ O ₄₀ ) of Example 1 was converted to the hydrate of phosphotungstomolybdate (H ₃ PW ₆ Mo ₆ O ₄₀ ) with 9,9-bis [ 4- (acryloyloxyethoxy) phenyl] fluorene 8.0 g instead of 6.4 g, and except that 1.6 g of benzyl acrylate was added in addition to Example 1, aluminum pigment having a nonvolatile content of 69.1% 158 g of composition was obtained.

[Production Example 1]
While stirring a slurry in which 560 g of ethylene glycol monobutyl ether was added to 162 g of a commercially available aluminum paste (trade name “GX-3100 (average particle size 10.5 μm, nonvolatile content 74%)” manufactured by Asahi Kasei Chemicals Corporation), A solution prepared by dissolving 1.2 g of ammonium metatungstate ((NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ]) hexahydrate in 10 g of purified water was gradually added, and the mixture was stirred for 2 hours while maintaining the slurry temperature at 70 ° C. did. After completion of the reaction, the slurry was cooled and filtered to obtain 160 g of an aluminum pigment composition having a nonvolatile content of 75.3%.

[Production Example 2]
1.2 g of ammonium metatungstate ((NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ]) hexahydrate of Production Example 1 was converted to ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ ) tetrahydrate. Except having replaced with 0.6 g, it carried out similarly to manufacture example 1, and obtained 160 g of aluminum pigment compositions with a non-volatile content of 75.5%.

[Example 3]
A slurry obtained by adding 700 g of mineral spirit to 133 g of the aluminum pigment composition obtained in Production Example 1 was stirred and stirred for 30 minutes while maintaining the slurry temperature at 70 ° C. Next, 0.75 g of acrylic acid was added and stirred for 30 minutes. Thereafter, 5.6 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene, 2.4 g of trimethylolpropane triacrylate (TMPTA), and 3.0 g of ADVN were dissolved in 80 g of solvent naphtha, and 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 then filtered to obtain 160 g of an aluminum pigment composition having a nonvolatile content of 68.2%.

[Example 4]
The aluminum pigment composition obtained in Production Example 1 of Example 3 was added to the aluminum pigment composition obtained in Production Example 2 with 5.6 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene. And TMPTA (2.4 g) were replaced with n-vinylcarbazole (4.0 g), TMPTA (2.8 g), and di-trimethylolpropane tetraacrylate (DTMPTA) (1.2 g) in the same manner as in Example 3 except that the nonvolatile content was 70.5%. 153 g of an aluminum pigment composition was obtained.

[Production Example 3]
While stirring a slurry in which 560 g of ethylene glycol monobutyl ether was added to 162 g of a commercially available aluminum paste (trade name “GX-3100 (average particle size 10.5 μm, nonvolatile content 74%)” manufactured by Asahi Kasei Chemicals Corporation), A solution of 1.5 g of sodium phosphomolybdate (Na ₃ PMo ₁₂ O ₄₀ ) hydrate dissolved in 10 g of purified water was gradually added, and the mixture was stirred for 2 hours while maintaining the slurry temperature at 70 ° C. Next, 2.4 g of 2-acryloyloxyethyl acid phosphate was added and stirred for 2 hours. After completion of the reaction, the slurry was cooled and the slurry was filtered to obtain 164 g of an aluminum pigment composition having a nonvolatile content of 75.2%.

[Example 5]
A slurry in which 700 g of mineral spirit was added and dispersed in 133 g of the aluminum pigment composition obtained in Production Example 3 was stirred, and stirred for 30 minutes while maintaining the slurry temperature at 70 ° C. Thereafter, 4.0 g of 2-vinylnaphthalene, 2.8 g of TMPTA, 1.2 g of DTMPTA, and 3.0 g of ADVN were dissolved in 80 g of solvent naphtha, and 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 161 g of an aluminum pigment composition having a nonvolatile content of 67.8%.

[Production Example 4]
135 g of commercially available aluminum paste (trade name “GX-3100 (average particle size 10.5 μm, non-volatile content 74%)” manufactured by Asahi Kasei Chemicals Co., Ltd.) was added molybdate ditridecylamine molybdate and aluminum in the aluminum paste. It added so that it might become 1.0 weight part with respect to 100 weight part of metal components, and it stirred at 70 degreeC for 6 hours.

[Example 6]
In Example 3, 133 g of the aluminum pigment composition obtained in Production Example 1, 135 g of the aluminum pigment composition obtained in Production Example 4, 0.75 g of acrylic acid, and 2.0 g of 2-acryloyloxyethyl acid phosphate 5.6 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene and 2.4 g of TMPTA, 6.4 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene and benzyl acrylate Except having replaced with 1.6 g, it carried out like Example 3 and obtained 162 g of aluminum pigment compositions with a non-volatile content of 67.6%.

[Production Example 5]
While stirring a slurry in which 558 g of ethylene glycol monobutyl ether was added to 162 g of a commercially available aluminum paste (trade name “GX-3100 (average particle size 10.5 μm, nonvolatile content 74%)” manufactured by Asahi Kasei Chemicals Corporation), A solution of 1.2 g of silicotungstic acid hydrate dissolved in 30 g of ethylene glycol monobutyl ether was gradually added, and the mixture was stirred for 2 hours while maintaining the slurry temperature at 70 ° C. Then, after further adding 12.0 g of tetraethoxysilane, 3.8 g of 25% ammonia water and 6.2 g of purified water were added and stirred for 2 hours. Then, it heated up at 140 degreeC and stirred for 4 hours. After completion of the reaction, the slurry was cooled and then the slurry was filtered to obtain an aluminum pigment composition having a nonvolatile content of 61%.

[Example 7]
In Example 3, 133 g of the aluminum pigment composition obtained in Production Example 1 was added to 164 g of the aluminum pigment composition obtained in Production Example 5, and 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene 5 0.6 g and 2.4 g of TMPTA were carried out in the same manner as in Example 3 except that 8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene was used, and an aluminum pigment composition having a nonvolatile content of 57.5% 189 g of product was obtained.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that the acrylic acid of Example 1, 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene, and ADVN were added and the polymerization step was omitted. A 75% aluminum pigment composition was obtained.

[Comparative Example 2]
An aluminum pigment composition having a non-volatile content of 72.4% was carried out in the same manner as in Example 1 except that the step of adding the hydrate of phosphovanadomolybdic acid (H ₄ PV ₁ Mo ₁₁ O ₄₀ ) of Example 1 was omitted. 152 g of product was obtained.

[Comparative Example 3]
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 non-volatile content of 70.0 % Aluminum pigment composition 161 g was obtained.

[Comparative Example 4]
The liquid obtained by dissolving the hydrate of phosphovanadomolybdic acid (H ₄ PV ₁ Mo ₁₁ O ₄₀ ) of Example 1 in 30 g of isopropanol is replaced with a liquid obtained by dissolving 0.5 g of dioctylamine molybdate in 30 g of solvent naphtha, An aluminum pigment having a nonvolatile content of 70.6% was obtained in the same manner as in Example 1 except that 8.0 g of 9,9-bis [4- (acryloyloxyethoxy) phenyl] fluorene was replaced with 5.6 g of TMPTA and 2.4 g of DTMPTA. 156 g of composition was obtained.

[Examples 8 to 14] [Comparative Examples 5 to 8]
For the aluminum pigment compositions obtained in Examples 1 to 7 and the aluminum pigment compositions obtained in Comparative Examples 1 to 4, water-based metallic paints and metallic paints were produced 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 up to 24 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 Δ: 1.0 or more and less than 5.0 ml ×: 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 Examples 5 to 7]
◎: 10 or more higher than Comparative Example 8 ○: Difference from Comparative Example 8 is less than 10 ×: 10 or more lower than Comparative Example 8 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 Examples 5 to 7]
◎: 0.05 or more higher than Comparative Example 8 ○: Difference from Comparative Example 8 is less than 0.05 ×: 0.05 or more lower than Comparative Example 8 Concealability was visually observed. The determination method is as follows.
[Examples 8 to 14] [Comparative Examples 5 to 7]
○: Same or higher than Comparative Example 8 ×: Inferior to Comparative Example 8 [Examples 8 to 14] [Comparative Examples 5 to 8]
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 (20)

A polymer composition comprising at least one selected from metal oxoacids and / or salts of metal oxoacids, a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton, and metal particles ; A metal pigment composition, wherein the product is at least one selected from an acrylic or vinyl resin and a polyester resin . At least the one selected from a salt of the metal oxo acid and / or metal oxo acid, wherein the polymer composition is a metal pigment composition according to claim 1 covering the metal particles. The metal pigment composition according to claim 1 or 2, wherein the metal particles are aluminum. The metal oxo acid is composed of a transition metal element of Group IVA, VA, VIA, or VIIA, or an element of Group IIIB, IVB, or Group VB, an isopolyacid, a heteropolyacid, a mixed coordination heteropolyacid, and The metal pigment composition according to any one of claims 1 to 3, which is at least one selected from hydrates thereof. The isopolyacids is a titanate, vanadate, molybdate, or tungstate, the heteropolyacid, silicomolybdic acid, a silicotungstic acid, phosphomolybdic acid, or phosphotungstic acid, the mixture coordinated heteropoly The metal pigment composition according to claim 4, wherein the acid is cavanadomolybdic acid, caitangus molybdic acid, phosphovanadomolybdic acid, or lintongost molybdic acid. Isopolyacid, heteropolyacid, mixed coordination type heteropolyacid, wherein the metal oxo acid salt is composed of a transition metal element of group IVA, VA, VIA, or VIIA, or an element of group IIIB, IVB, or VB And a metal pigment according to any one of claims 1 to 3, which is a salt of at least one selected from hydrates thereof and at least one selected from the group consisting of alkali metals, alkaline earth metals, and ammonium. Composition. The isopolyacids is a titanate, vanadate, molybdate, or tungstate, the heteropolyacid, silicomolybdic acid, a silicotungstic acid, phosphomolybdic acid, or phosphotungstic acid, the mixture coordinated heteropoly The metal pigment composition according to claim 6, wherein the acid is caivanadomolybdic acid, caitongustomolybdic acid, phosphovanadomolybdic acid, or lintongostmolybdic acid . Isopolyacid, heteropolyacid, mixed coordination type heteropolyacid, wherein the metal oxo acid salt is composed of a transition metal element of group IVA, VA, VIA, or VIIA, or an element of group IIIB, IVB, or VB And a metal pigment according to any one of claims 1 to 3, which is a salt of at least one selected from hydrates thereof and at least one selected from amine compounds represented by the following general formula (1). Composition.

(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.) The isopolyacids is a titanate, vanadate, molybdate, or tungstate, the heteropolyacid, silicomolybdic acid, a silicotungstic acid, phosphomolybdic acid, or phosphotungstic acid, the mixture coordinated heteropoly The metal pigment composition according to claim 8, wherein the acid is cavanadomolybdic acid, caitangus molybdic acid, phosphovanadomolybdic acid, or phosphotungstomolybdic acid . The polymer composition comprises (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. At least one selected from (B) a polymerizable unsaturated carboxylic acid, a phosphoric acid or phosphonic acid ester having a polymerizable double bond, a compound having a polymerizable double bond and an isocyanate group, a polymerizable double bond and an epoxy group Compound having a polymerizable double bond and an amino group, compound having a polymerizable double bond and a hydrolyzable silyl group, a compound having a polymerizable double bond and a sulfone group, a polymerizable double bond and a hydroxyl group A copolymer with at least one compound selected from the group of compounds having the following: (A) a condensed polycyclic hydrocarbon skeleton-containing module having at least one polymerizable double bond Mer, at least one selected from condensed heterocyclic skeleton-containing monomers having at least one polymerizable double bond, and (B) a polymerizable unsaturated carboxylic acid, a phosphoric acid or phosphonic acid ester having a polymerizable double bond , A compound having a polymerizable 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, and having a polymerizable double bond and a hydrolyzable silyl group 2. A copolymer of at least one selected from the group consisting of a compound, a compound having a polymerizable double bond and a sulfone group, and a compound having a polymerizable double bond and a hydroxyl group, and (C) another monomer. To 9. The metal pigment composition according to any one of 9 to 9 . The polymer composition comprises (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. A copolymer of at least one selected from (B) at least one selected from a compound having two or more polymerizable double bonds in one molecule, or (A) at least one polymerizable double bond. At least one selected from a condensed polycyclic hydrocarbon skeleton-containing monomer having at least one condensed heterocyclic skeleton-containing monomer having at least one polymerizable double bond, and (B) two polymerizable double bonds in one molecule. The metal pigment composition according to any one of claims 1 to 9 , which is a copolymer of at least one selected from the compounds having the above and (C) another monomer. The metal pigment composition according to any one of claims 1 to 11 , wherein the condensed polycyclic hydrocarbon skeleton is a fluorene skeleton. The metal according to any one of claims 1 to 12 , wherein at least one selected from the metal oxo acid and / or metal oxo acid salt is present in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the metal particles. Pigment composition. The polymer composition is, relative to the metal particles 100 parts by weight, there from 1 50 parts by weight, the metal pigment composition according to any one of claims 1 13. The metal pigment composition according to any one of claims 1 to 14 , wherein the hydrolyzate of the silicon-containing compound and / or the condensate thereof is present in an amount of 0.01 to 50 parts by weight with respect to 100 parts by weight of the metal particles. . Furthermore, at least 1 sort (s) 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 said metal particles, In any one of Claim 1 to 15 The metal pigment composition described. Further with respect to the surfactant of the metal particles 100 parts by weight, there are 30 parts by weight 0.01, metallic pigment composition according to any one of claims 1 16. After the metal particles are mixed in a solvent with at least one selected from metal oxoacids and / or salts of metal oxoacids, polymerizable monomers having a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton are polymerized. The method for producing a metal pigment composition according to any one of claims 1 to 17 , wherein a polymer composition containing a condensed polycyclic hydrocarbon skeleton and / or a condensed heterocyclic skeleton is mixed. The coating composition containing the metal pigment composition in any one of Claim 1 to 17 . To any one of claims 1 17 comprising a metal pigment composition according, the ink composition.