TWI615445B - Metal particle dispersion and cured film - Google Patents

Abstract

The metal fine particle dispersion liquid of the present invention is a metal fine particle dispersion liquid containing metal fine particles, a dispersion medium, and a metal fine particle dispersant; wherein the metal fine particle dispersant contains: (A) two or more (meth) acrylic hydrazones An anhydride modified body of a polyfunctional (meth) acrylic compound having at least one hydroxyl group and at least one hydroxyl group, and (B) a monofunctional (meth) acrylic compound having one (meth) acrylfluorenyl group. The monofunctional (meth) acrylic compound contains at least one of the compounds represented by the following (b1) to (b3).

(b1) a caprolactone adduct of (meth) acrylic acid represented by the following formula (1): CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1) (formula ( In 1), R ¹ represents a hydrogen atom and a methyl group; n represents 1 to 10.)

(b2) The anhydride modification of the caprolactone adduct of the hydroxyalkyl (meth) acrylate represented by the following formula (2): CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2) (In the formula (2), R ¹ represents a hydrogen atom and a methyl group; R ² represents at least one selected from the group consisting of ethylene, propyl and butyl. 1 species; n is 1 ~ 10.)

(b3) Anhydride modified body of (meth) acrylic acid alkylene oxide adduct of formula (3): CH ₂ = C (R ¹ ) COO (C _m H _2m O) _n H (3) (In formula (3), R ¹ represents a hydrogen atom and a methyl group; m represents 2 to 4; n represents 1 to 10.)

Description

Metal fine particle dispersion and hardened film

The present invention relates to a metal fine particle dispersion liquid and a cured film, and more particularly to a metal fine particle dispersion liquid formed by dispersing metal fine particles using a metal fine particle dispersant, and a cured film obtained by hardening the metal fine particle dispersion liquid.

Various coating agents are conventionally known, so that, for example, mechanical properties, chemical resistance, high refractive index, antistatic properties, and ultraviolet rays can be imparted to a cured film obtained by coating and curing the coating agent. Various physical properties such as infrared blocking properties and scratch resistance are further dispersed with various metal fine particles as pigments and the like.

In addition, such a coating agent may cause aggregation of the metal fine particles depending on the type of the metal fine particles, the solvent, or the binder resin to be blended. Therefore, in order to disperse the metal fine particles well, it is proposed to add a dispersant to the coating agent.

Specifically, for example, there is a proposal to react a mixture of dipentaerythritol pentaerythritol pentaerythritol (acrylate) and dipentaerythritol pentaerythritol (acrylic acid ester) (containing 67 mol% of dipentaerythritol pentaerythritol (acrylate)) with pyromellitic dianhydride. And (carboxy) -containing (meth) acrylate is prepared, and the obtained carboxyl-containing (meth) acrylate, SiOx (x: 1 <x <2) ultrafine particle ethanol dispersion and toluene are mixed, A coating resin composition containing ultrafine particles was prepared (see Patent Document 1 (Example 1)).

Further, for example, there has been a proposal: a mixture of ZnO ultrafine particles in toluene dispersion, a mixture of dipentaerythritol pentaerythr Dipentaerythritol pentaerythritol (acrylic acid 67 mol%) and Aronix M-5300 (ω-carboxycaprolactone monoacrylate) were mixed to prepare a high refractive index resin composition (see Patent Document 1 (Example 6) ).

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 08-244178

On the other hand, the cured film of the coating resin composition for coating as described above is required to have adhesiveness with a substrate, and in particular, moisture-resistant and heat-resistant adhesiveness capable of maintaining the adhesiveness even in a humid and hot environment is required.

Furthermore, as the coating resin composition is required to further improve dispersibility, the cured film is also required to have excellent hardness and transparency in accordance with the application.

An object of the present invention is to provide a metal microparticle dispersion liquid that can achieve excellent dispersion stability of metal microparticles, and can improve the moisture and heat resistance, hardness, and transparency of a cured film, and a hardening obtained by hardening the metal microparticle dispersion liquid. membrane.

The present invention [1] is a metal microparticle dispersion liquid, which is a metal microparticle dispersion liquid containing metal microparticles, a dispersion medium, and a metal microparticle dispersant; wherein the metal microparticle dispersant system contains: (A) two or more (Meth) acrylfluorenyl and an anhydride modified body of a polyfunctional (meth) acrylic compound having at least one hydroxyl group, and (B) a monofunctional (meth) group having one (meth) acrylfluorenyl group An acrylic compound; and the monofunctional (meth) acrylic compound contains the following (b1) to (b3) At least one of the compounds.

(b1) a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).

CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1) (In the formula (1), R ¹ represents a hydrogen atom and a methyl group; n represents 1 to 10.)

(b2) An anhydride-modified body of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).

CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2) (In the formula (2), R ¹ represents a hydrogen atom and a methyl group; R ² represents a ethylenic group. (At least one selected from the group consisting of, propyl, and butyl; n represents 1 to 10.)

(b3) An anhydride-modified body of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).

CH ₂ = C (R ¹ ) COO (C _m H _2m O) _n H (3)

(In formula (3), R ¹ represents a hydrogen atom and a methyl group; m represents 2 to 4; n represents 1 to 10.)

The present invention [2] is the metal fine particle dispersion according to the above [1], wherein (B) the monofunctional (meth) acrylic compound described above contains a compound represented by the above formula (1) and n is 1 to 3 Caprolactone adduct of (meth) acrylic acid.

The present invention [3] is the metal fine particle dispersion liquid according to the above [1], wherein (B) the monofunctional (meth) acrylic compound described above contains a compound represented by the above formula (2), and n is 2 to 5 The anhydride modification of the caprolactone adduct of hydroxyalkyl (meth) acrylate.

The present invention [4] is the metal fine particle dispersion according to the above [1], wherein (B) the monofunctional (meth) acrylic compound described above contains the formula (3), and m is 2 to 3 and n is an anhydride modified body of an alkylene oxide adduct of (meth) acrylic acid of 2 to 5.

The present invention [5] is the metal microstructure as described in any one of the above [1] to [4] The particle dispersion further contains a binder, and the binder contains a (meth) acrylic resin.

The present invention [6] is a hardened film, which is a hardened product containing the metal fine particle dispersion liquid described in any one of the above [1] to [5].

The metal fine particle dispersion liquid of the present invention can obtain a cured film having excellent dispersibility of the metal fine particles, and excellent in moisture and heat resistance, hardness, and transparency.

Therefore, the cured film of the present invention is excellent in moisture and heat resistance, hardness, and transparency.

The metal fine particle dispersion liquid system of the present invention contains metal fine particles, a dispersion medium, and a metal fine particle dispersant.

The metal fine particles are not particularly limited, and examples thereof include: alumina, titanium oxide, zinc oxide, zirconia, tin oxide, yttria, bismuth oxide, antimony oxide, and oxide Fine particles of metal oxides such as cerium, indium oxide, silicon oxide (silicon dioxide, silica, etc.); or, for example, doping such metal oxides with gallium, antimony, tin, fluorine, phosphorus, aluminum And other dissimilar elements to obtain fine particles of metal oxide doped with dissimilar elements. The crystal structure of these metal oxides is not particularly limited, and may be, for example, one of cubic, tetragonal, orthorhombic, monoclinic, triclinic, hexagonal, and trigonal. Either.

Examples of the metal fine particles include alumina, zirconia, and silicon dioxide.

In addition, the metal fine particles may be surface-treated by a known method as necessary.

These metal fine particles can be used alone or in combination of two or more.

The shape of the metal fine particles is not particularly limited, and examples thereof include a block shape, a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fibrous shape, an irregular shape, and mixtures thereof.

The particle size of the metal fine particles is measured based on the primary particle size of the metal fine particles themselves, and is, for example, 200 nm or less, preferably 90 nm or less, more preferably 50 nm or less, and usually 1 nm or more, and preferably 3 nm or more.

When the primary particle diameter of the metal fine particles is within the above range, it is easy to obtain the metal fine particles, and the storage stability of the metal fine particle dispersion liquid and the transparency of the cured film (described later) can be improved.

Examples of the dispersion medium include organic solvents, aqueous solvents, and reactive solvents.

The organic solvent is not particularly limited, and examples thereof include petroleum-based hydrocarbon solvents such as hexane and mineral spirits; for example, aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene; for example, acetone, methyl ethyl ketone, and methyl isobutyl ketone. , Diisobutyl ketone, cyclohexanone and other ketone solvents; for example: methyl acetate, ethyl acetate, butyl acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate and other ester solvents; for example: N, N -Aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, dimethylsulfinium, N-methylpyrrolidone, pyridine, and the like.

Examples of the aqueous solvent system include water; for example, alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; for example, glycol ether solvents such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

The reactive solvent system may have, for example, one or more ethylenically unsaturated bonds. Specific examples of the compound include compounds having one ethylenically unsaturated bond in one molecule (except for (B) monofunctional (meth) acrylic acid compounds in the metal fine particle dispersant described later), and one having 2 in one molecule. Compounds having more than one ethylenically unsaturated bond (except for acid anhydride modifiers of the (A) polyfunctional (meth) acrylic compound in the metal fine particle dispersant described later) and the like.

酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-1-甲基-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-4-羥丁酯、乙氧基二乙二醇(甲基)丙烯酸酯、2-乙基己基-卡必醇(甲基)丙烯酸酯、新戊二醇苯甲酸酯(甲基)丙烯酸酯、壬基苯氧基聚乙二醇(甲基)丙烯酸酯、表氯醇(ECH)改質苯氧基(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸鄰苯基苯氧基乙酯、(甲基)丙烯酸間苯氧基苄酯、(甲基)丙烯酸對苯氧基苄酯、對

基酚環氧乙烷改質(甲基)丙烯酸酯、苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、對甲基苯乙烯、乙烯吡咯啶酮、乙烯己內醯胺、丙烯醯基

啉等。 Examples of compounds having one ethylenically unsaturated bond in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and iso (meth) acrylate. Propyl ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, ( Neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) Cyclohexyl acrylate, isooctyl (meth) acrylate, isostearyl (meth) acrylate, isostearyl (meth) acrylate, isoisopropyl (meth) acrylate

Ester, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1 -methyl-2-hydroxyethyl (meth) acrylate, -2 (meth) acrylic acid -Hydroxypropyl ester, 4-hydroxybutyl (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, 2-ethylhexyl-carbitol (meth) acrylate, neopentyl Alcohol benzoate (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, epichlorohydrin (ECH) modified phenoxy (meth) acrylate, (meth) Phenoxyethyl acrylate, o-phenylphenoxyethyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, p-phenoxybenzyl (meth) acrylate,

Phenolic ethylene oxide modified (meth) acrylate, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, vinylpyrrolidone, ethylene caprolactam, propylene醯 基

Porphyrin, etc.

Examples of compounds having two or more ethylenically unsaturated bonds in one molecule include: compounds having two ethylenically unsaturated bonds in one molecule, compounds having three ethylenically unsaturated bonds in one molecule, and one molecule A compound having four ethylenically unsaturated bonds in the compound, a compound having five ethylenically unsaturated bonds in one molecule, a compound having six ethylenically unsaturated bonds in one molecule, and the like.

Examples of compounds having two ethylenically unsaturated bonds in one molecule include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. Isoalkylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol Polyalkylene glycol di (meth) acrylate such as di (meth) acrylate; 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylic acid Ester, 1,9-nonanediol di (meth) acrylate, dicyclopentadiene di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxy (trimethyl Acetic acid) neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclopentyl di (meth) acrylate; pentaerythritol di (meth) acrylate, 9 , 9-bis [4- (2- (meth) acryloxyethoxy) phenyl] pyrene, bisphenol A ethylene oxide (EO) addition diacrylate, caprolactone modified di ( Dicyclopentenyl methacrylate, ethylene oxide modified bis (methyl phosphate) ) Acrylate, allyl cyclohexyl di (meth) acrylate, isotricyanate di (meth) acrylate or these alkylene oxide modifiers; divinylbenzene, butanediol-1, 4-Divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether, triethylene glycol divinyl ether, phenyl glycidyl ether acrylic acid Ester hexamethylene diisocyanate amine prepolymer (trade name "AH-600" manufactured by Kyoeisha Chemical Co., Ltd.), phenylglycidyl ether acrylate toluene diisocyanate amine prepolymer (Kyoeisha Chemical Co., Ltd. Name "AT-600"), etc.

Examples of compounds having three ethylenically unsaturated bonds in one molecule include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tris (methyl) Base) acrylate, tris (acryloxyethyl) isotricyanate or alkylene oxide modifiers of this type, and tris (meth) acrylates of alkylene oxide modifiers of isotrimeric cyanate Wait.

Examples of compounds having four ethylenically unsaturated bonds in one molecule include di (trimethylol) propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and diglycerol tetra (methyl) ) Acrylate or such alkylene oxide modifiers.

The compound having five ethylenically unsaturated bonds in one molecule is, for example, dipentaerythritol penta (meth) acrylate or an alkylene oxide modifier thereof.

Examples of compounds having 6 ethylenically unsaturated bonds in one molecule include dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate amine prepolymer (produced by Kyoeisha Chemical Co., Ltd.) Trade name "UA-306H"), caprolactone modified dipentaerythritol hexa (meth) acrylate or alkylene oxide modified body and the like.

In addition, the dispersion medium can also be obtained from commercial products. Specific examples of petroleum-based hydrocarbon solvents are AF solvents 4 to 7 (the above are all made by "Nippon Petroleum Corporation"), and aromatic hydrocarbon-based solvents. Examples include ink solvent No. 0, Solvesso 100, 150, and 200 manufactured by Exxon Chemical Co. (the above are all manufactured by "Nippon Petroleum Corporation").

These dispersion media can be used alone or in combination of two or more.

The dispersion medium is preferably an organic solvent, an aqueous solvent, more preferably an organic solvent, and particularly preferably methyl isobutyl ketone from the viewpoints of adhesion to the substrate, hardness, and the like.

In addition, the dispersion medium is preferably a reactive solvent from the viewpoints of improving productivity during film formation, suppressing substrate damage, and responding to high-definition shapes, and more preferably, for example, phenoxyethyl (meth) acrylate O-phenylphenoxyethyl (meth) acrylate, (a M-phenoxybenzyl acrylate, p-phenoxybenzyl (meth) acrylate, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, tetraethylene glycol di (Meth) acrylate, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, trimethylolpropane tri (meth) acrylate epoxy Alkane modifiers, alkylene oxide modifiers of diglycerol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

The metal microparticle dispersant is an additive for improving the dispersibility of metal microparticles in a dispersion medium. The metal microparticle dispersant contains (A) an anhydride modified form of a polyfunctional (meth) acrylic compound, and (B) a monofunctional (meth) acrylic compound. .

The "(meth) acrylic compound" is defined as "acrylic compound" and / or "methacrylic compound".

Furthermore, "(meth) acryl" is also defined as "propenyl" and / or "methacryl"; and "(meth) acryl" is also defined as "acryl" And / or "methacryl"; "(meth) acrylate" is also defined as "acrylate" and / or "methacrylate".

(A) An anhydride modified body of a polyfunctional (meth) acrylic compound, specifically, for example, a polyfunctional (meth) acrylic compound having two or more (meth) acrylfluorenyl groups and at least one hydroxyl group (Hereinafter also referred to as "hydroxy-containing polyfunctional (meth) acrylic compound") an anhydride modified body.

Polyfunctional (meth) acrylic compounds containing hydroxyl groups can be used, for example, for polyhydric alcohols [eg: glycerol (hydroxyl number 3), trimethylolpropane (hydroxyl number 3), tris (2-hydroxyethyl) isotris Polycyanate (hydroxyl number 3), diglycerol (hydroxyl number 4), bis (trimethylol) propane (hydroxyl number 4), pentaerythritol (hydroxyl number 4), dipentaerythritol (hydroxyl number 6), tripentaerythritol ( Known polyfunctional alcohols such as hydroxyl number 8), etc., with respect to the hydroxyl group of the polyol The number of adducts (adducts) of (Meth) acrylic acid after addition is not sufficient.

Examples of the hydroxyl-containing polyfunctional (meth) acrylic compounds include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, bis (trimethylol) propane di (meth) acrylate, bis (trimethylol) propane tri (meth) acrylate , Tri-2-hydroxyethyl isotricyanate di (meth) acrylate, glycerol di (meth) acrylate, diglycerol di (meth) acrylate, diglycerol tri (meth) acrylate , And such alkylene oxide (ethylene oxide, propylene oxide, etc.) adducts (including random adducts, block adducts), and mixtures of these.

These hydroxyl-containing polyfunctional (meth) acrylic compounds can be used alone or in combination of two or more.

The hydroxyl-containing polyfunctional (meth) acrylic compound is preferably dipentaerythritol penta (acrylate).

In addition, a polyfunctional (meth) acrylic compound containing a hydroxyl group may be used in a suitable ratio in combination with a polyfunctional (meth) acrylic compound not containing a hydroxyl group described later.

Examples of the acid anhydride system include dicarboxylic acid monoanhydride, tricarboxylic acid monoanhydride, and tetracarboxylic dianhydride.

Examples of dicarboxylic acid anhydrides include: oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12 ~ C18) succinic anhydride, tetrahydrophthalic anhydride, humic anhydride, hexahydrophthalic anhydride, Tetrabromophthalic anhydride, tetrachlorophthalic anhydride, etc.

Examples of the tricarboxylic acid monoanhydride system include trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and the like.

Examples of tetracarboxylic dianhydride systems include pyromellitic anhydride, diphenylketone tetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2,5-oxotetrahydrofuranyl) -3-methyl-3-ring Hexene-1,2-dicarboxylic anhydride and the like.

These anhydrides can be used alone or in combination of two or more.

The acid anhydride is preferably, for example, a dicarboxylic acid monoanhydride or a tetracarboxylic dianhydride, and more preferably, is a succinic anhydride, a phthalic anhydride, or a pyromellitic anhydride. The acid anhydride is preferably, for example, a dicarboxylic acid monoanhydride, and is more preferably, for example, succinic anhydride or phthalic anhydride from the viewpoint of the hardness of a cured film (to be described later).

When obtaining an anhydride modified body of a hydroxyl-containing polyfunctional (meth) acrylic compound, for example, a hydroxyl-containing polyfunctional (meth) acrylic compound and an acid anhydride are blended, and the reaction is performed by heating in a solvent as necessary.

Blend ratio of a hydroxyl-containing polyfunctional (meth) acrylic compound and an acid anhydride, for example, an equivalent ratio of a carboxylic acid anhydride group of the acid anhydride to a hydroxyl group of the hydroxyl-containing polyfunctional (meth) acrylic compound (carboxylic acid anhydride / hydroxyl group) ) Is, for example, 0.5 or more, preferably 0.67 or more, and for example, 1 or less, and preferably 0.91 or less.

Examples of the solvent system include the organic solvent (the dispersion medium is the organic solvent), the aqueous solvent (the dispersion medium is the aqueous solvent), the reactive solvent (the dispersion medium is the reactive solvent), and the like. These solvents can be used alone or in combination of two or more. The solvent is preferably a solvent that is inert to a hydroxyl-containing polyfunctional (meth) acrylic compound and an acid anhydride, and specifically a solvent that does not have a carboxyl group and a hydroxyl group. Such a solvent is preferably an organic solvent, more preferably a ketone solvent, and particularly preferably a methyl isobutyl ketone.

Moreover, a catalyst may be added to this reaction as needed.

Examples of the catalyst system include metals, organometallic compounds, metal halides, and amine compounds.

Examples of the metal system include alkali metals such as sodium and potassium.

Examples of the organometallic compound include the alkali metal alkoxides. (Alkali metal alkoxides) and their derivatives, such as alkyl aluminum compounds such as triethylaluminum and their derivatives); and, for example: titanium alkoxy compounds such as tetrabutyl titanate; tin 2-ethylhexanoate, Organotin compounds such as tin octoate and dibutyltin laurate.

Examples of the metal halide system include tin halides such as tin chloride (specifically, tin dichloride: SnCl ₂ ).

Examples of the amine compound include: N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, and tetramethyl bromide Ammonium, cetyltrimethylammonium bromide, etc.

These catalysts can be used alone or in combination of two or more.

Preferred catalysts are, for example, amine compounds, more preferred are N, N-dimethylbenzylamine, triethylamine, tributylamine, and particularly preferred are triethylamine.

The blending ratio of the catalyst is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more, and, for example, 5 parts by mass with respect to 100 parts by mass of the total amount of the hydroxyl-containing polyfunctional (meth) acrylic compound and the acid anhydride. The content is preferably 0.5 parts by mass or less.

Moreover, this reaction can also add a polymerization inhibitor as needed.

、二苯基苯二胺、二萘基苯二胺、對胺基二苯胺、N-烷基-N'-苯二胺等芳香族胺類；例如：4-羥-2,2,6,6-四甲基哌啶、4-乙醯氧基-1-氧基-2,2,6,6-四甲基哌啶、4-苯甲醯氧基-1-氧基-2,2,6,6-四甲基哌啶、4-烷氧基-1-氧基-2,2,6,6-四甲基哌啶、雙(1-氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯的2,2,6,6-四甲基哌啶之N- 氧基衍生物、N-亞硝化二苯胺、二乙基二硫胺基甲酸的銅鹽、對苯醌等。 Examples of polymerization inhibitors include: p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, catechol, third butyl catechol, 2,6-di-third butyl-hydroxytoluene, 4- Phenol compounds such as tert-butyl-1,2-dihydroxybenzene, 2,2'-methylene-bis (4-methyl-6-tert-butylcatechol); for example: phenothiazine

, Diphenylphenylenediamine, dinaphthylphenylenediamine, p-aminodiphenylamine, N-alkyl-N'-phenylenediamine and other aromatic amines; for example: 4-hydroxy-2,2,6, 6-tetramethylpiperidine, 4-ethoxyl-1-oxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-1-oxy-2,2 , 6,6-tetramethylpiperidine, 4-alkoxy-1-oxy-2,2,6,6-tetramethylpiperidine, bis (1-oxy-2,2,6,6 -Tetramethylpiperidin-4-yl) sebacate N-oxy derivative of 2,2,6,6-tetramethylpiperidine, N-nitrosated diphenylamine, diethyldithiamine Copper salt of carboxylic acid, p-benzoquinone, etc.

These polymerization inhibitors can be used alone or in combination of two or more.

The polymerization inhibitor is preferably, for example, p-methoxyphenol.

The blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more, and for example, 1.0 part by mass with respect to 100 parts by mass of the total amount of the hydroxyl-containing polyfunctional (meth) acrylic compound and the anhydride. The content is preferably 0.1 part by mass or less.

The reaction conditions are under an oxygen gas environment or an inert gas-oxygen mixed gas environment, and the heating temperature is, for example, 60 ° C or higher, preferably 80 ° C or higher, and, for example, 140 ° C or lower, preferably 110 ° C or lower. The heating time is, for example, 4 hours or more, preferably 8 hours or more, and, for example, 20 hours or less, and preferably 12 hours or less.

Thereby, the polyfunctional (meth) acrylic compound containing a hydroxyl group can be modified with an acid anhydride, and the (A) polyanhydride (meth) acrylic acid compound can be obtained as an anhydride-modified body.

(A) The polyanhydride (meth) acrylic acid anhydride modified body can be more systematic. For example: dipentaerythritol pentaerythritol (acrylate) phthalic acid modified product, pentaerythritol triacrylate phthalic acid modified product, dipentaerythritol five (Acrylate) succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, and the like.

(A) The acid value of the anhydride-modified body of the polyfunctional (meth) acrylic compound is, for example, 20 mgKOH / g or more, preferably 73 mgKOH / g or more, preferably 80 mgKOH / g or more, and, for example, 500 mgKOH / g or less, preferably 300 mgKOH / g or less.

In addition, the hydroxyl value of the (A) anhydride-modified body of the polyfunctional (meth) acrylic compound is, for example, more than 0 mgKOH / g, preferably 1 mgKOH / g or more, and for example, 350 mgKOH / g or less, preferably 230 mgKOH / g the following.

The blending ratio of (A) the anhydride modification of the polyfunctional (meth) acrylic compound with respect to 100 parts by mass of the metal fine particles is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 7 parts by mass It is at least 200 parts by mass, preferably at most 100 parts by mass, more preferably at most 70 parts by mass, and particularly preferably at most 50 parts by mass.

(B) The monofunctional (meth) acrylic compound is specifically a compound having one (meth) acrylfluorenyl group, and contains at least one of the compounds represented by the following (b1) to (b3).

(b1) a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).

CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1)

(In formula (1), R ¹ represents a hydrogen atom and a methyl group; n represents 1 to 10.)

(b2) An anhydride-modified body of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).

CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2)

(In formula (2), R ¹ represents a hydrogen atom and a methyl group; R ² represents at least one selected from the group consisting of ethylene, propyl and butyl; n represents 1 to 10. )

(b3) An anhydride-modified body of an alkylene oxide adduct of (meth) acrylic acid represented by the following formula (3).

CH ₂ = C (R ¹ ) COO (C _m H _2m O) _n H (3)

(In formula (3), R ¹ represents a hydrogen atom and a methyl group; m represents 2 to 4; n represents 1 to 10.)

Hereinafter, the compounds represented by the above (b1) to (b3) will be described in detail.

The compound represented by (b1) is a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).

CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1)

(In formula (1), R ¹ represents a hydrogen atom and a methyl group; n represents 1 to 10.)

In the formula (1), R ¹ represents a hydrogen atom and / or a methyl group, and is preferably a hydrogen atom.

Furthermore, in the above formula (1), the average addition mole number of n-caprolactone to 1 mol (meth) acrylic acid is usually 1 or more, preferably 2 or more, and 10 or less, preferably Department 5 or less, more preferably Department 3 or less.

Such a (meth) acrylic acid caprolactone addition product is obtained by subjecting ε -caprolactone to an (meth) acrylic acid addition reaction (ring-opening addition).

(Meth) acrylic acrylic acid and / or methacrylic acid, preferably acrylic acid.

ε-caprolactone is not particularly limited, and a commercially available product can be used as it is.

The method of reacting (meth) acrylic acid with ε-caprolactone (ring-opening addition) is not particularly limited, and a known method (for example, Japanese Patent Laid-Open No. 62-135521, Japanese Patent Laid-Open No. 60-67446) can be adopted. Etc.).

More specifically, for example, (meth) acrylic acid and ε -caprolactone are blended, and if necessary, heating and stirring are performed in the presence of a catalyst and a solvent.

The blending ratio of (meth) acrylic acid and ε-caprolactone is the molecular weight of the target compound (the compound represented by the above formula (1)), that is, the average addition of ε-caprolactone to (meth) acrylic acid Ear number n), and then set appropriately.

For example, for 1 mol of (meth) acrylic acid, ε -caprolactone is, for example, 1 mol or more, preferably 2 mol or more, and for example, 10 mol or less, preferably 5 mol or less, and more preferably 3 Moore below.

In addition, for example, ε-caprolactone is, for example, 50 parts by mass or more, preferably 150 parts by mass or more, and, for example, 10,000 parts by mass or less, and preferably 2000 parts by mass or less with respect to 100 parts by mass of (meth) acrylic acid.

The reaction conditions are under an inert gas or an inert gas-oxygen mixed gas environment, and the reaction temperature is, for example, 80 ° C. or higher, preferably 120 ° C. or higher, and for example, 240 ° C. or lower, preferably 200 ° C. or lower. The reaction time is, for example, 4 hours or more, preferably 6 hours or more, and, for example, 20 hours or less, and preferably 12 hours or less.

Examples of the catalyst system include Lewis acid such as aluminum chloride and tin (IV) chloride; and acids such as sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, sulfonic acid-type ion exchange resin, and other acids Catalyst, etc.

These catalysts can be used alone or in combination of two or more.

From the viewpoint of solubility in the reaction solution, the catalyst is preferably, for example, sulfuric acid, p-toluenesulfonic acid, and benzenesulfonic acid.

The blending ratio of the catalyst with respect to 100 parts by mass of (meth) acrylic acid is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, and, for example, 50 parts by mass or less, and preferably 20 parts by mass or less.

Examples of the solvent system include aromatic hydrocarbons such as benzene, toluene, and xylene.

The blending ratio of the solvent is not particularly limited, and can be appropriately set according to the purpose and application.

The ε-caprolactone adduct of (meth) acrylic acid can also be produced without a solvent.

In the reaction, the above-mentioned polymerization inhibitor may be added as necessary.

The polymerization inhibitor is preferably, for example, p-methoxyphenol.

The blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more, and, for example, 1.0 part by mass or less, with respect to 100 parts by mass of the total amount of (meth) acrylic acid and ε -caprolactone. 0.1 parts by mass or less.

Further, a caprolactone addition system of (meth) acrylic acid can also be obtained by an esterification reaction (condensation polymerization) of (meth) acrylic acid with omega -hydroxyhexanoic acid ring-opened by caprolactone.

The caprolactone adduct of (meth) acrylic acid can also be obtained from a commercially available product. Examples of such a commercially available product include Aronix M-5300 (ω-carboxycaprolactone monoacrylate, manufactured by Toa Kosei), and the like.

(b1) The acid value of the caprolactone adduct of (meth) acrylic acid represented by the above formula (1) is, for example, 45 mgKOH / g or more, preferably 135 mgKOH / g or more, and for example, 310 mgKOH / g or less.

The compound represented by (b2) is an anhydride-modified body of a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the following formula (2).

CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2)

(In formula (2), R ¹ represents a hydrogen atom and a methyl group; R ² represents at least one selected from the group consisting of ethylene, propyl and butyl; n represents 1 to 10. )

In the formula (2), R ¹ represents a hydrogen atom and / or a methyl group, and is preferably a hydrogen atom.

In the above formula (2), R ² represents at least one selected from the group consisting of ethylene, propyl and butyl, and is preferably ethyl.

Furthermore, in the above formula (2), the average addition mole number of n-type caprolactone to 1 mol (hydroxy) methacrylate is 1 or more, preferably 2 or more, and 10 or less, It is preferably 5 or less.

In order to obtain the compound shown in (b2), for example, (meth) propylene The hydroxyalkyl acid ester is reacted with ε-caprolactone (ring-opening addition) to obtain a caprolactone adduct of a hydroxyalkyl (meth) acrylate represented by the above formula (2). Then, the caprolactone adduct of the hydroxyalkyl (meth) acrylate represented by the above formula (2) is reacted with an acid anhydride.

The hydroxyalkyl (meth) acrylate is, for example, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 4 carbon atoms, and specific examples include 2-hydroxyethyl (meth) acrylate , 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

These hydroxyalkyl (meth) acrylates can be used alone or in combination of two or more.

The hydroxyalkyl (meth) acrylate is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 carbon atoms, and more preferably 2-hydroxyethyl (meth) acrylate.

ε-caprolactone is not particularly limited, and a commercially available product can be used as it is.

The method for reacting (hydroxy ring-opening addition) of hydroxyalkyl (meth) acrylate with ε-caprolactone is not particularly limited, and a known method (for example, as described in Japanese Patent Laid-Open No. 10-7774) can be used. Methods).

Specifically, for example, hydroxyalkyl (meth) acrylate and ε -caprolactone are blended, and if necessary, heating and stirring are performed in the presence of the catalyst and the solvent.

The blending ratio of hydroxyalkyl (meth) acrylate and ε-caprolactone is the molecular weight of the target compound (the compound represented by the above formula (2)), that is, ε-caprolactone to (meth) acrylic acid The average addition mole number n of the hydroxyalkyl ester is appropriately set.

For example, with respect to 1 mol of hydroxyalkyl (meth) acrylate, ε -caprolactone is, for example, 1 mol or more, preferably 2 mol or more, and, for example, 10 mol or less, preferably 5 mol or less.

In addition, for example, ε-caprolactone is 90 parts by mass or more, preferably 190 parts by mass or more, based on 100 parts by mass of hydroxyalkyl (meth) acrylate, and, for example, 1,000 parts by mass or less, preferably 500 parts by mass or less.

Furthermore, the reaction conditions are under an oxygen or mixed gas atmosphere of inert gas and oxygen, and the reaction temperature is, for example, 60 ° C or higher, preferably 90 ° C or higher, and for example, 140 ° C or lower, preferably 120 ° C or lower. The reaction time is, for example, 4 hours or more, preferably 8 hours or more, and, for example, 20 hours or less, and preferably 12 hours or less.

In the reaction, the above-mentioned polymerization inhibitor may be added as necessary.

The polymerization inhibitor is preferably, for example, p-methoxyphenol.

The blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more, and for example, 1.0 part by mass with respect to 100 parts by mass of the total amount of the hydroxyalkyl (meth) acrylate and ε -caprolactone. The content is preferably 0.1 part by mass or less.

The caprolactone adduct of hydroxyalkyl (meth) acrylate can also be obtained from a commercially available product. Examples of such commercially available products are: PLACCEL FA-1, PLACCEL FA-2, PLACCEL FA-2D, PLACCEL FA-3, PLACCEL FA-4, PLACCEL FA-5, PLACCEL FA-10L, PLACCEL FM-1, PLACCEL FM-2, PLACCEL FM-2D, PLACCEL FM-3, PLACCEL FM-4, PLACCEL FM-5 (all of which are manufactured by Daicel Chemical Co., Ltd.) (PLACCEL is a registered trademark) and so on.

The caprolactone addition system of these hydroxyalkyl (meth) acrylates can be used alone or in combination of two or more.

Furthermore, by reacting the caprolactone adduct of the hydroxyalkyl (meth) acrylate with an acid anhydride, the anhydride modification of the caprolactone adduct of the hydroxyalkyl (meth) acrylate can be obtained. Plastid (i.e. the compound represented by (b2)).

The acid anhydride system may be, for example, the aforementioned acid anhydride [(A) an acid anhydride used in the production of an acid anhydride modified body of a polyfunctional (meth) acrylic acid compound], and is preferably a dicarboxylic acid monoanhydride, From the viewpoint of the hardness of the cured film (to be described later), succinic anhydride and phthalic anhydride are more preferred, and succinic anhydride is particularly preferred.

In addition, the reaction of the caprolactone adduct of hydroxyalkyl (meth) acrylate and an acid anhydride is, for example, blending a caprolactone adduct of hydroxyalkyl (meth) acrylate and an acid anhydride, if necessary Heating is performed in the presence of a solvent, a catalyst, and the like.

Examples of the solvent system include the organic solvent (the dispersion medium is the organic solvent), the aqueous solvent (the dispersion medium is the aqueous solvent), the reactive solvent (the dispersion medium is the reactive solvent), and the like. These solvents can be used alone or in combination of two or more. The solvent is preferably a solvent which is inert to the caprolactone adduct of hydroxyalkyl (meth) acrylate and the acid anhydride, and specifically, a solvent which does not have a carboxyl group and a hydroxyl group, for example. Such a solvent is preferably an organic solvent, more preferably a ketone solvent, and particularly preferably a methyl isobutyl ketone.

The catalyst may be, for example, the above-mentioned catalyst [(A) A catalyst used in the production of an anhydride reformer of a polyfunctional (meth) acrylic compound]. These catalysts can be used alone or in combination of two or more. Preferred catalysts are, for example, amine compounds, more preferred are N, N-dimethylbenzylamine, triethylamine, tributylamine, and particularly preferred are triethylamine.

The blending ratio of the caprolactone adduct of hydroxyalkyl (meth) acrylate to the acid anhydride is, for example, the carboxylic acid anhydride group in the acid anhydride, relative to the caprolactone adduct of hydroxyalkyl (meth) acrylate The hydroxyl equivalent ratio (carboxylic anhydride group / hydroxyl) in the formula is, for example, 0.5 or more, preferably 0.67 or more, and for example, 1 or less, and preferably 0.91 or less.

In addition, the reaction conditions are under an oxygen gas or an inert gas-oxygen mixed gas environment, and the heating temperature is, for example, 60 ° C or higher, preferably 80 ° C or higher, and for example, 140 ° C or lower, preferably 110 ° C or lower. The heating time is, for example, 4 hours or more, preferably 8 hours or more, and, for example, 20 hours or less, and preferably 12 hours or less.

Thereby, a caprolactone adduct of a hydroxyalkyl (meth) acrylate can be obtained Acid anhydride modified body (ie, the compound shown in (b2)).

(b2) the acid value of the acid anhydride modifier of the caprolactone adduct of the hydroxyalkyl (meth) acrylate represented by the above formula (2) is, for example, 40 mgKOH / g or more, preferably 60 mgKOH / g or more, and For example, it is 280 mgKOH / g or less, and preferably 150 mgKOH / g or less.

The compound represented by (b3) is an anhydride modified form of an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3).

CH ₂ = C (R ¹ ) COO (C _m H _2m O) _n H (3)

(In formula (3), R ¹ represents a hydrogen atom and a methyl group; m represents 2 to 4; n represents 1 to 10.)

In the formula (3), R ¹ represents a hydrogen atom and / or a methyl group, and is preferably a hydrogen atom.

In the above formula (3), m is 2 or more and 4 or less, and preferably 3 or less.

That is, the (meth) acrylic acid alkylene oxide addition system represented by the above formula (3) has an oxyalkylene group (C _m H _2m O) having 2 to 4 carbon atoms.

Examples of oxyalkylene groups having 2 to 4 carbon atoms are: oxyethylene (-CH ₂ CH ₂ O-), oxytrimethylene (-CH ₂ CH ₂ CH ₂ O-), and oxytetramethylene (-CH ₂ CH ₂ CH ₂ CH ₂ O-) and other linear oxyalkylenes; for example: oxypropyl (-CH ₂ CH (CH ₃ ) O-), oxybutyl (-CH ₂ CH (CH ₂ CH ₃ ) O-, -CH (CH ₃ ) CH (CH ₃ ) O-) and other branched oxyalkylene groups, etc., preferably linear oxyalkylene groups, more preferably oxyethylene groups .

Furthermore, in the above formula (3), the average addition mole number of n-type alkylene oxide to 1 mol (meth) acrylic acid is 1 or more, preferably 2 or more, and 10 or less, preferably 5 the following.

In order to obtain the compound shown in (b3), for example, (meth) propylene The acid reacts with the alkylene oxide (ring-opening addition) to obtain an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3). Then, the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is further reacted with an acid anhydride.

(Meth) acrylic acrylic acid and / or methacrylic acid, preferably acrylic acid.

The alkylene oxide can be, for example, an alkylene oxide having 2 to 4 carbon atoms, and specific examples can include ethylene oxide, propylene oxide, trimethylene oxide (oxetane), and epoxy. A cyclic ether compound having 2 to 4 carbon atoms such as butane.

These alkylene oxides can be used alone or in combination of two or more.

In addition, when two or more kinds of alkylene oxides are used in combination, the addition form is not particularly limited, and examples thereof include random addition and block addition.

Preferred examples of the alkylene oxide include ethylene oxide and propylene oxide, and more preferred is ethylene oxide.

The method of adding (meth) acrylic acid to alkylene oxide is not particularly limited, and a known method can be adopted.

More specifically, for example, (meth) acrylic acid and an alkylene oxide are blended, and if necessary, heating and stirring are performed in the presence of the catalyst and the solvent.

The blending ratio of (meth) acrylic acid and alkylene oxide is based on the molecular weight of the target compound (the compound represented by the above formula (3)), that is, the average addition mole number n of alkylene oxide to (meth) acrylic acid, Then set appropriately.

For example, for 1 mol (meth) acrylic acid, the alkylene oxide is, for example, 1 mol or more, preferably 2 mol or more, and, for example, 10 mol or less, and preferably 5 mol or less.

In addition, for example, with respect to 100 parts by mass of (meth) acrylic acid, the alkylene oxide is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, and, for example, 5000 parts by mass The content is preferably 1500 parts by mass or less.

Furthermore, the reaction conditions are under a gas environment of an inert gas-oxygen mixed gas, and the reaction temperature is, for example, 40 ° C or higher, preferably 100 ° C or higher, and for example, 240 ° C or lower, preferably 200 ° C or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and, for example, 20 hours or less, and preferably 12 hours or less.

Thereby, an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) can be obtained.

The alkylene oxide adduct of (meth) acrylic acid can be further exemplified by polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) Acrylate, polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol- Butylene glycol) mono (meth) acrylate, poly (propylene glycol-butanediol) mono (meth) acrylate, and other polyhydroxyalkylene glycol mono (meth) acrylates with terminal hydroxyl groups; for example: ( Mono) ethylene glycol mono (meth) acrylate, (mono) propylene glycol mono (meth) acrylate, (mono) propylene glycol mono (meth) acrylate, (mono) butanediol mono (meth) acrylic acid Esters, (mono) butanediol mono (meth) acrylate, and other monoalkylene glycol mono (meth) acrylates having terminal hydroxyl groups, and the like.

These (meth) acrylic acid alkylene oxide adducts can be used alone or in combination of two or more.

The alkylene oxide adduct of (meth) acrylic acid is preferably a polyalkylene glycol mono (meth) acrylate having a terminal hydroxyl group, more preferably a polyethylene glycol mono (meth) acrylate.

The alkylene oxide adduct of (meth) acrylic acid can also be obtained from a commercially available product. Examples of such commercially available products are: BLEMMER PE series, BLEMMER AE Series, BLEMMER PP series, BLEMMER AP series, BLEMMER PEP series, BLEMMER AEP series, BLEMMER PET series, BLEMMER AET series, BLEMMER PPT series, BLEMMER APT series (the above are all made by "Japan Oil"). These systems can be used alone or in combination of two or more.

Furthermore, by reacting the above-mentioned (meth) acrylic acid alkylene oxide adduct with an acid anhydride, an acid anhydride modified body of (meth) acrylic acid alkylene oxide adduct can be obtained (that is, (b3) Show compound).

The acid anhydride system may be, for example, the above-mentioned acid anhydride [an acid anhydride used in the production of an acid anhydride modified body of the ((A) polyfunctional (meth) acrylic acid compound]), preferably a dicarboxylic acid monoanhydride, from a cured product (to be described later) From the viewpoint of hardness, more preferred is succinic anhydride and phthalic anhydride, and particularly preferred is succinic anhydride.

In addition, the reaction of the alkylene oxide adduct of (meth) acrylic acid with an acid anhydride is, for example, the addition of an alkylene oxide adduct of (meth) acrylic acid and an acid anhydride, and the reaction is performed in the presence of a solvent, a catalyst, etc., if necessary heating.

Examples of the solvent system include the organic solvent (the dispersion medium is the organic solvent), the aqueous solvent (the dispersion medium is the aqueous solvent), and the like. These solvents can be used alone or in combination of two or more. The solvent is preferably a solvent that is inert to (meth) acrylic acid alkylene oxide adducts and acid anhydrides, and specifically, a solvent that does not have a carboxyl group and a hydroxyl group, for example. Such a solvent is preferably an organic solvent, more preferably a ketone solvent, and particularly preferably a methyl isobutyl ketone.

The catalyst may be, for example, the above-mentioned catalyst [(A) A catalyst used in the production of an anhydride reformer of a polyfunctional (meth) acrylic compound]. These catalysts can be used alone or in combination of two or more. Preferred catalysts are, for example, amine compounds, more preferred are N, N-dimethylbenzylamine, triethylamine, tributylamine, and particularly preferred are triethylamine.

The blending ratio of the caprolactone adduct of (meth) acrylic acid alkylene adduct to the acid anhydride is, for example, the carboxylic acid anhydride group in the acid anhydride, relative to the (meth) acrylic acid alkylene oxide adduct The equivalent ratio of the hydroxyl group (carboxylic anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, and, for example, 1 or less, and preferably 0.91 or less.

The reaction conditions are under an oxygen gas environment or an inert gas-oxygen mixed gas environment, and the heating temperature is, for example, 60 ° C or higher, preferably 80 ° C or higher, and, for example, 140 ° C or lower, preferably 110 ° C or lower. The heating time is, for example, 4 hours or more, preferably 8 hours or more, and, for example, 20 hours or less, and preferably 12 hours or less.

Thereby, an anhydride-modified body of an alkylene oxide adduct of (meth) acrylic acid (that is, a compound represented by (b3)) can be obtained.

(b3) The acid value of the anhydride modified body of the (meth) acrylic acid alkylene oxide adduct of the above formula (3) is, for example, 55 mgKOH / g or more, preferably 95 mgKOH / g or more, and for example, 400 mgKOH / g or less, preferably 300 mgKOH / g or less.

These (B) monofunctional (meth) acrylic compounds may be used alone or in combination of two or more.

(B) The monofunctional (meth) acrylic compound is preferably a compound represented by (b1), and more preferably (B) the monofunctional group from the viewpoint of improving the dispersion stability of the metal fine particle dispersion. The (meth) acrylic compound contains a caprolactone adduct of (meth) acrylic acid having n of 1 to 3 represented by the above formula (1).

Moreover, (B) a monofunctional (meth) acrylic compound is preferably a compound represented by (b2) from the viewpoint of improving the hardness of a cured film (to be described later), and more preferably (B) the above-mentioned monomer The functional group (meth) acrylic compound is, for example, an acid anhydride modified body containing a caprolactone adduct of a hydroxyalkyl (meth) acrylate of n to 2 to 5 represented by the above formula (2).

Furthermore, (B) a monofunctional (meth) acrylic compound is preferably a compound represented by (b3), more preferably (B), from the viewpoint of improving the transparency of a cured film (to be described later). The monofunctional (meth) acrylic acid compound contains an anhydride modified body of an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) and m is 2 to 3 and n is 2 to 5.

In the metal fine particle dispersant, the content ratio of (A) the anhydride modified body of the polyfunctional (meth) acrylic compound and (B) the monofunctional (meth) acrylic compound is 100 parts by mass based on the total amount of these (A) The anhydride modification system of the polyfunctional (meth) acrylic compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and for example, 95 parts by mass or less, preferably 90 parts by mass the following. The (B) monofunctional (meth) acrylic compound is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and for example, 95 parts by mass or less, preferably 90 parts by mass or less, and more preferably 85 parts by mass or less.

Furthermore, the metal fine particles, the dispersion medium, and the metal fine particle dispersant are collectively or sequentially blended, and a metal fine particle dispersion liquid can be obtained by mixing.

The mixing ratio of each component of the metal fine particle dispersion liquid is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and, for example, 200 parts by mass or less, preferably 100 parts by mass or less with respect to 100 parts by mass of the metal fine particles. And more preferably 70 parts by mass or less. The metal fine particles are, for example, 0.5 parts by mass or more, preferably 2.5 parts by mass or more, and 50 parts by mass or less, preferably 40 parts by mass or less, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the metal fine particle dispersion liquid.

In addition, the blending ratio of the dispersion medium is appropriately set according to the purpose and use. For example, it is set to, for example, 50 parts by mass or more, preferably 150 parts by mass or more, and 2000 parts by mass or less with respect to 100 parts by mass of the metal fine particles. Jia1000 Mass parts or less.

The metal fine particle dispersion may further contain a binder.

Examples of the binder system include synthetic resins such as (meth) acrylic resin, polyvinyl butyral resin, polyvinyl alcohol resin, vinyl acetate resin, and amine ester resin. These adhesives can be used alone or in combination of two or more.

From the viewpoint of improving adhesiveness (normal temperature), the binder is preferably a (meth) acrylic resin.

The (meth) acrylic resin can be obtained, for example, by polymerization of a monomer component containing an alkyl (meth) acrylate.

酯等碳數1~30之直鏈狀、分支狀或環狀烷基的(甲基)丙烯酸酯等。 Examples of the alkyl (meth) acrylate system include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) ) N-butyl acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, neopentyl (meth) acrylate Ester, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, (meth) acrylic acid- 2-ethylhexyl, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, thirteen (meth) acrylate Alkyl ester, tetradecyl (meth) acrylate, 1-methyltridecyl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate (Stearyl (meth) acrylate), Isostearyl (meth) acrylate, Alkyl (meth) acrylate, Dialkyl (meth) acrylate, [(Meth) acrylic acid廿 Dialkyl (Behenyl) ester, 廿 (meth) acrylate Ester, (meth) acrylic acid alkyl ester thirty, (meth) acrylate, (meth) acrylate

(Meth) acrylic acid esters, such as linear, branched or cyclic alkyl groups having 1 to 30 carbon atoms, such as esters.

In addition, the monomer component may contain a copolymer with an alkyl (meth) acrylate. Polymerized other monomers.

Specific examples of the other monomer include an aromatic ring-containing monomer, a hydroxyl-containing monomer, and an anionic group-containing monomer.

Monocyclic systems containing aromatic rings include, for example: phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate (Meth) acrylates containing aromatic rings such as o-phenylphenoxyethyl (meth) acrylate and phenoxybenzyl (meth) acrylate; for example, styrene such as styrene and α-methylstyrene Department of monomers and so on.

When the monomer component contains an aromatic ring-containing monomer, the content ratio is, for example, 10% by mass or more, preferably 20% by mass or more, and, for example, 95% by mass or less, preferably 80% by mass, relative to the total amount of the monomer component. the following.

In addition, when the monomer component contains an aromatic ring-containing monomer, the (meth) acrylic resin is a (meth) acrylic resin containing an aromatic ring.

Examples of the hydroxyl-containing monosystem include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and -1- (meth) acrylate Hydroxy-containing (meth) acrylates such as methyl-2-hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, preferably (meth) 2-hydroxyethyl acrylate.

When the monomer component contains a hydroxyl-containing monomer, the content ratio of the hydroxyl-containing monomer relative to the total amount of the monomer component is, for example, 0.1% by mass or more, preferably 1% by mass or more, and 50% by mass or less, for example. Better than 30% by mass.

In addition, when the monomer component contains a hydroxyl-containing monomer, a (meth) acrylic resin can obtain a hydroxyl-containing (meth) acrylic resin.

In the anionic group-containing monomer, the anionic group may be, for example, a carboxyl group, a phosphate group, or a sulfonic acid group. Specific examples of the anionic group-containing monomer include: Carboxy-containing monomers such as alpha, beta-unsaturated carboxylic acids such as enoic acid, itaconic acid, maleic acid, and fumaric acid, or salts thereof; for example: acidic oxypolyoxypropylene glycol mono (methyl) Phosphate group-containing monomers such as (meth) acrylates containing phosphate groups, such as acrylate, acidic oxyethyl (meth) acrylate, and mono ((meth) acrylate-2-hydroxyethyl) phosphate; for example; : 2-acrylamido-2-methylpropanesulfonic acid and other monomers containing sulfonic acid groups.

When the monomer component contains an anionic group-containing monomer, the content ratio of the anionic group-containing monomer with respect to the total amount of the monomer component is, for example, 0.1% by mass or more, preferably 1% by mass or more, and, for example, 30% by mass % Or less, preferably 5 mass% or less.

In addition, when the monomer component contains an anionic group-containing monomer, the (meth) acrylic resin can obtain a (meth) acrylic resin containing an anionic group.

In addition, the other single systems may include, for example, (meth) acrylic acid methyl isocyanate, (meth) acrylic acid 2-isocyanatoethyl, and (meth) acrylic acid 3-isocyanate Propyl ester, 1-methyl-2-isocyanate (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 4-isocyanate (meth) acrylate Isobutyl ester, etc., isocyanate group-containing (meth) acrylic monomers, etc. Isocyanate group-containing monomers; for example, glycidyl (meth) acrylate, allyl glycidyl ether, etc. Body; for example, vinyl acetate monomers such as vinyl acetate, vinyl propionate, and the like.

These other single systems can be used alone or in combination of two or more.

Examples of the other monomers include aromatic ring-containing monomers and hydroxyl-containing monomers, and more preferably both aromatic ring-containing monomers and hydroxyl-containing monomers.

When the monomer component contains an aromatic ring-containing monomer [that is, the (meth) acrylic resin-based (meth) acrylic resin containing an aromatic ring]), the moisture and heat resistance of the cured film (described later) can be improved.

Furthermore, if the monomer component contains a hydroxyl-containing monomer [that is, (meth) propylene Acid resin is a (meth) acrylic resin containing a hydroxyl group], and the (meth) acrylfluorenyl group can be easily introduced into the side chain of the (meth) acrylic resin by the method described later, and a cured film can be obtained (see later) ) Improved moisture and heat resistance.

In addition, from the viewpoint of improving the moisture and heat resistance of the cured film (to be described later), the content ratio of the anionic monomer relative to the total amount of the monomer component is preferably 5% by mass or less, and more preferably the monomer component is not included. Anionic group-containing monomer.

When the monomer component contains the other monomers [monomers other than the alkyl (meth) acrylate], the content ratio of the alkyl (meth) acrylate relative to the total amount of the monomer component is, for example, 10% by mass or more, preferably 20% by mass or more, and, for example, 90% by mass or less, and preferably 80% by mass or less.

In addition, the method for producing the (meth) acrylic resin is not particularly limited. For example, in a known solvent, the monomer components are mixed in the above-mentioned proportions, and a known radical polymerization initiator (for example, an azo compound) is used. , Peroxo-based compounds, etc.) and polymerize by heating.

The polymerization conditions differ depending on the formula of the monomer component or the type of the radical polymerization initiator, and the polymerization temperature is, for example, 30 ° C or higher, preferably 60 ° C or higher, and for example, 150 ° C or lower, preferably 120 ° C or lower. The polymerization time is, for example, 2 hours or more, preferably 4 hours or more, and, for example, 20 hours or less, and preferably 8 hours or less.

Thereby, a (meth) acrylic resin can be obtained.

The weight average molecular weight (GPC measurement: polystyrene conversion) of the (meth) acrylic resin is, for example, 2,000 or more, preferably 3,000 or more, and for example, 100,000 or less, preferably 50,000 or less, and more preferably 15,000 or less.

The (meth) acrylic resin is preferably, for example, (Meth) acrylic acid-based (meth) acrylic resin. A (meth) acrylic resin having a (meth) acrylfluorene group in a side chain can be obtained, for example, according to the following method.

That is, the (meth) acrylic resin obtained by the above method may have a hydroxyl group. More specifically, when the monomer component of the (meth) acrylic resin raw material is a hydroxyl-containing monomer, the (meth) acrylic resin obtained by the above polymerization has a hydroxyl group.

In this case, for example, by reacting a (meth) acrylic resin having a hydroxyl group with a (meth) acrylic monomer containing an isocyanate group, a (meth) acrylic resin can be introduced into the side chain of the (meth) acrylic resin. ) Acrylofluorenyl.

Examples of the (meth) acrylic monomer containing an isocyanate group are: (meth) acrylic acid methyl isocyanate, (meth) acrylic acid 2-isocyanate ethyl ester, (meth) acrylic acid- 3-isocyanatopropyl, 1-methyl-2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, (meth) acrylic acid- 4-isocyanatobutyl and the like.

These isocyanate group-containing (meth) acrylic acid monosystems can be used alone or in combination of two or more.

The isocyanate group-containing (meth) acrylic monomer is preferably, for example, 2-isocyanatoethyl (meth) acrylate.

When the (meth) acrylic resin having a hydroxyl group is reacted with the (meth) acrylic acid monomer containing an isocyanate group, there is no particular limitation, for example, a (meth) acrylic resin having a hydroxyl group and an isocyanate group are blended. The (meth) acrylic monomer is heated in the presence of a known catalyst and a solvent, if necessary.

The blending ratio of the (meth) acrylic resin having a hydroxyl group and the (meth) acrylic monomer containing an isocyanate group is 1 mole relative to the hydroxyl group of the (meth) acrylic resin having a hydroxyl group, and Group) the isocyanate group of the acrylic monomer is, for example, 0.1 mol or more, preferably 0.8 mol or more, and for example, 2.0 mol or less, and preferably 1.2 mol or less.

The reaction conditions are, for example, in an air environment, and the reaction temperature is, for example, 40 ° C or higher, preferably 60 ° C or higher, and, for example, 200 ° C or lower, preferably 150 ° C or lower. The reaction time is, for example, 1 hour or more, preferably 2 hours or more, and for example, 20 hours or less, and preferably 12 hours or less.

In the reaction, the above-mentioned polymerization inhibitor may be added as necessary.

The polymerization inhibitor is preferably, for example, p-methoxyphenol.

The blending ratio of the polymerization inhibitor is 100 parts by mass relative to the total amount of the (meth) acrylic resin having a hydroxyl group and the (meth) acrylic monomer containing an isocyanate group, such as 0.0001 part by mass or more, and preferably 0.01 part by mass The above is, for example, 1.0 part by mass or less, and preferably 0.1 part by mass or less.

Thereby, the hydroxy group of the (meth) acrylic resin having a hydroxyl group and the isocyanate group of the (meth) acrylic monomer containing an isocyanate group undergo an amine ester reaction.

As a result, an isocyanate group-containing (meth) acrylic monomer was bonded to the side chain of the (meth) acrylic resin, and a (meth) acrylfluorenyl group was introduced at the end of the side chain.

The method of introducing a (meth) acrylfluorenyl group into the side chain of the (meth) acrylic resin is not limited to the above method, and a known method can be adopted.

For example, when the monomer component contains an isocyanate group-containing monomer, the (meth) acrylic resin has an isocyanate group. Therefore, by subjecting a (meth) acrylic resin having an isocyanate group to an amine ester reaction with a hydroxyl group-containing (meth) acrylate, it is also possible to introduce a (meth) acrylfluorenyl group into the side chain of the (meth) acrylic resin .

Furthermore, for example, when the monomer component contains an anionic group-containing monomer (for example, a carboxyl group-containing monomer), the (meth) acrylic resin has an anionic group (for example, (Such as carboxyl, etc.). Therefore, by esterifying a (meth) acrylic resin having an anionic group with a (meth) acrylic acid ester containing an epoxy group, a (meth) acrylic resin can also be introduced into the side chain of the (meth) acrylic resin. ) Acrylofluorenyl.

In addition, for example, when the monomer component contains a glycidyl monomer, the (meth) acrylic resin has a glycidyl group. Therefore, by performing an esterification reaction between a (meth) acrylic resin having an epoxy group and an (meth) acrylate containing an anionic group (for example, a carboxyl-containing (meth) acrylate, etc.), A (meth) acrylfluorenyl group is introduced into the side chain of the (meth) acrylic resin.

When the (meth) acrylic resin-based side chain for blending as a binder has a (meth) acrylic acid fluorenyl group, the moisture and heat resistance of a cured film (described later) can be improved.

In the (meth) acrylic resin having a (meth) acrylfluorenyl group in a side chain, the (meth) acrylfluorenyl equivalent is, for example, 400 or more, preferably 800 or more, and for example, 30,000 or less, preferably 10,000 or less.

The (meth) acryl equivalent is defined as the polymer mass (double bond equivalent) per 1 mol of the double bond.

When the metal fine particle dispersion contains a binder, the content ratio is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 50 parts by mass or less, preferably 30 parts by mass, with respect to 100 parts by mass of the metal fine particle dispersion. the following.

Moreover, the metal microparticle dispersion liquid may contain a polymerization initiator as needed.

啉基丙烷-1-酮、2-苄基-2-二甲胺基 -1-(4-

啉基苯基)-丁酮-1、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、2,4,6-三甲基苯甲醯基-二苯基-氧化膦、4-甲基二苯基酮、二苯基酮、2-羥-1-{4-[4-(2-羥-2-甲基丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮等光聚合起始劑等。 Examples of the polymerization initiator are: 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 1-cyclohexylphenyl ketone, 2- Hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 -Ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-

Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-

Phenylphenyl) -butanone-1, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl -Phosphine oxide, 4-methyldiphenyl ketone, diphenyl ketone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanyl) -benzyl] phenyl} Photopolymerization initiators such as 2-methyl-propane-1-one.

These polymerization initiators can be used alone or in combination of two or more.

The blending ratio of the polymerization initiator is 100 parts by mass, for example, 1 part by mass or more, preferably 3 parts by mass or more, and 10 parts by mass or less, preferably 7 parts by mass or less, with respect to the total amount of the metal fine particle dispersant.

In addition, the time of blending the binder and the polymerization initiator is not particularly limited. For example, when the metal fine particles, the solvent and the metal fine particle dispersant are mixed, they can be blended at the same time. In addition to the microparticle dispersant, a binder and a polymerization initiator are separately or sequentially incorporated.

In addition, the preparation of the metal fine particle dispersion liquid is not particularly limited. When mixing the metal fine particles, the solvent, and the metal fine particle dispersant (and a binder and a polymerization initiator mixed as necessary), for example, paint dispersion can be used. Well-known dispersers such as vibrators, roll crushers, ball mills, mills, sand mills, bead mills, and ultrasonic dispersers.

When the metal fine particle dispersion is used as a coating agent (to be described later), a ball mill, a bead mill, or a bead mill is more preferred from the viewpoint of improving the transparency of the cured film (to be described later).

When a bead mill is used as the dispersing machine, known dispersing media such as zirconia ball beads and glass beads can be used.

The bead diameter of the dispersion medium is not particularly limited, and is, for example, 10 μm or more, and for example, 500 μm or less, and preferably 100 μm or less. The filling rate of the dispersion medium is appropriately set according to the purpose and application.

When a bead mill or a ball mill is used as the disperser, the average particle diameter may be adjusted to fall within the above range by pulverizing the metal fine particles using the dispersing medium. In this case, metal fine particles having an average particle diameter larger than the above range can be charged into the disperser.

In addition, for example, pigments, desiccants, rust inhibitors, plasticizers, coating film surface conditioners, antioxidants, ultraviolet absorbers, and dispersants other than the above-mentioned metal fine particle dispersants can be added to the metal fine particle dispersion (for example, : Various additives such as sorbitan fatty acid ester, polyethylene glycol fatty acid ester and other nonionic surfactants). The blending ratio of the additives is appropriately set depending on the purpose and application.

When the dispersion medium contains an organic solvent and / or an aqueous solvent, the non-volatile content of the metal fine particle dispersion is, for example, 0.5% by mass or more, preferably 3% by mass or more, and, for example, 70% by mass or less, and preferably 50% by mass or less. And more preferably below 40% by mass.

When the dispersion medium contains a reactive solvent, an organic solvent and / or an aqueous solvent can be distilled off from the metal fine particle dispersion by a known method, and the reactive medium can be contained only as the dispersion medium.

Furthermore, in this case, when the reactive solvent is a non-volatile component, the non-volatile content of the metal fine particle dispersion liquid may be 100% by mass.

Furthermore, in the metal microparticle dispersion liquid, the particle size of the metal microparticles is determined because the metal microparticles have primary particles or secondary particles, so the average particle diameter (average particle diameter) of these particles is measured, for example, 200 nm or less, preferably 50 nm. Hereinafter, it is usually 1 nm or more, and preferably 3 nm or more.

Furthermore, because such a metal fine particle dispersion system contains the above-mentioned metal fine particles, Since it is a particle dispersant, it has excellent dispersion stability of the metal fine particles, and can obtain a cured film having excellent wet heat resistance, hardness, and transparency.

In order to obtain a cured film, for example, a metal fine particle dispersion is used as a coating agent, and the substrate is coated on a substrate by a known method. After being dried, the substrate is irradiated with active energy rays to be cured.

烯系樹脂等塑膠；例如金屬、木材、紙、玻璃、板岩等。 The substrate is not particularly limited, and examples thereof include polycarbonate, polymethyl methacrylate, polystyrene, polyester (polyethylene terephthalate, etc.), polyolefin, epoxy resin, and melamine resin. , Cellulose triacetate resin, ABS resin, AS resin,

Plastics such as olefin resin; for example, metal, wood, paper, glass, slate, etc.

The coating method is not particularly limited, and for example, a roll coater, a bar coater, a doctor blade, a winding rod, an air knife, etc. can be adopted, and the coating is performed by a machine used for general coating; and screen printing, Well-known coating methods such as lithography, rubber plate rotary printing, brush coating, spray coating, gravure coating, and reverse gravure coating.

In terms of drying conditions, the drying temperature is, for example, 40 ° C or more, preferably 60 ° C or more, and for example, 180 ° C or less, preferably 140 ° C or less, and the drying time is, for example, 1 minute or more, preferably 2 minutes or more, and for example, 60 minutes. It is preferably 30 minutes or less.

The film thickness after drying is, for example, 50 nm or more, preferably 500 nm or more, and, for example, 10 μm or less, and preferably 7 μm or less.

Examples of the active energy ray system include ultraviolet rays and electron beams.

When curing by ultraviolet rays, an ultraviolet irradiation device provided with, for example, a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used as the light source system. The amount of ultraviolet irradiation, the amount of light from the ultraviolet irradiation device, and the arrangement of light sources are appropriately adjusted as necessary. Specifically, in the case of using a high-pressure mercury lamp, for example, the base material coated with the metal fine particle dispersion liquid is transported at a transport speed of 5 to 50 m / min with respect to a lamp having a luminosity of about 80 to 1000 mW / cm ² . The irradiation amount of ultraviolet rays is, for example, 100 to 10,000 mJ / cm ² . When the electron beam is used for hardening, the base material coated with the metal fine particle dispersion liquid is transported by an electron beam acceleration device having an acceleration voltage of 10 to 300 kV at a transport speed of 5 to 50 m / min.

Upon irradiation with such an active energy ray, the (meth) acrylfluorenyl group in the metal fine particle dispersant is crosslinked to form a three-dimensional structure. When the metal fine particle dispersion contains a reactive solvent, the reactive solvent functions as a crosslinking agent. That is, upon irradiation with active energy rays, the ethylenically unsaturated bond of the reactive solvent is crosslinked.

Thereby, a cured film which is a cured product of the metal fine particle dispersion liquid can be obtained.

Moreover, since the obtained hardened film was obtained using the said metal microparticle dispersion liquid, it was excellent in moisture-heat-resistant adhesiveness, hardness, and transparency.

Therefore, the hardened film is suitable for various optical products such as light emitting diodes (LEDs), lenses, and optical devices; precision ceramics, functional films such as conductive films, and optical films.

[Example]

Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by the following examples. In addition, "parts" and "%" refer to "quality standards" unless otherwise stated. In addition, specific numerical values such as the blending ratio (content ratio), physical property values, and parameters used in the following descriptions can be replaced by the corresponding blending ratio (content ratio) and physical property values described in the above-mentioned "Embodiment". , Parameters, etc. The upper limit value (the value defined by "below" and "under full") or the lower limit value ("above", "Exceeded".

<Metal fine particle dispersant> (A) Anhydride-modified body of polyfunctional (meth) acrylic compound [Synthesis example 1]

In a 1 L flask equipped with a stirrer, a thermometer, a reflux cooling tube, and a mixed gas introduction tube, 327.2 parts of methyl isobutyl ketone (solvent), a mixture of dipentaerythritol pentaerythritol (acrylate) and dipentaerythritol hexa (acrylate) were charged. (Aronix M403 manufactured by Toa Synthesis Co., 50-50% of dipentaerythritol penta (acrylate)) 300 parts, 0.33 parts of triethylamine (catalyst) and 0.16 parts of p-methoxyphenol (polymerization inhibitor), heat and stir To 80 ° C.

Next, 27.2 parts of succinic anhydride was added, and a nitrogen-oxygen mixed gas (oxygen concentration of 7%) was introduced, and it was maintained at 80 ° C. for 8 hours. Then, after cooling, a solution of an anhydride reformer of (A) polyfunctional (meth) acrylic acid compound having a solid content of 50% and an acid value of 23 mgKOH / g was obtained.

[Synthesis Examples 2 to 3]

A solution (solid content: 50%) of the anhydride-modified body of (A) polyfunctional (meth) acrylic compound was obtained in the same manner as in Synthesis Example 1 except that the blending formula shown in Table 1 was changed.

The details of the abbreviations in the table are as follows.

Aronix M403: a mixture of dipentaerythritol pentaerythritol pentaerythritol (acrylate) and dipentaerythritol pentaerythritol hexaacrylate (manufactured by Toa Kosei Co., Ltd., 50-50% of dipentaerythritol pentaerythritol (acrylate)) Anhydride Modifier of Caprolactone Adduct [Synthesis Example 4]

A 500 mL flask equipped with a stirrer, a thermometer, a reflux cooling tube, and a mixed gas introduction tube was charged with 143.5 parts of methyl isobutyl ketone (solvent) and caprolactone adduct of hydroxyethyl acrylate (PLACCEL FA by Daicel) -1 caprolactone average addition mole number: 1 mole) 100 parts, triethylamine (catalyst) 0.14 parts and p-methoxyphenol (polymerization inhibitor) 0.07 parts, heat and stir to 80 ° C.

Next, 43.5 parts of succinic anhydride was added, and a hydrogen-oxygen mixed gas (oxygen concentration 7%) was introduced, and it was maintained at 80 ° C. for 8 hours. Then, after cooling, an anhydride modifier solution of a caprolactone adduct of (b2) ethyl hydroxy (meth) acrylate having a solid content of 50% and an acid value of 85 mgKOH / g was obtained.

[Synthesis Examples 5 to 6]

Except changing to the blending formula shown in Table 2, the same procedure as in Synthesis Example 4 was performed to obtain an acid anhydride modified body solution (solid content of (b2) ethyl hydroxy (meth) acrylate caprolactone adduct) 50%).

The details of the abbreviations in the table are as follows.

PLACCEL FA-1: Trade name, made by Daicel, caprolactone adduct of hydroxyethyl acrylate, average addition mole number of caprolactone: 1 mole

PLACCEL FA-2D: Trade name, manufactured by Daicel, caprolactone adduct of hydroxyethyl acrylate, average addition mole number of caprolactone: 2 moles

PLACCEL FA-10L: trade name, made by Daicel, caprolactone adduct of hydroxyethyl acrylate, average addition mole number of caprolactone: 10 moles

(b3) Anhydride modified body of alkylene oxide adduct of (meth) acrylic acid [Synthesis example 7]

A 500 mL flask equipped with a stirrer, a thermometer, a reflux cooling tube, and a mixed gas introduction tube was charged with 186.2 parts of methyl isobutyl ketone (solvent), 100 parts of hydroxyethyl 2-acrylate (manufactured by Osaka Organic Chemical Industry), 0.19 parts of triethylamine (catalyst) and 0.09 parts of p-methoxyphenol (polymerization inhibitor) were heated and stirred to 80 ° C.

Next, 86.2 parts of succinic anhydride was added, and a nitrogen-oxygen mixed gas (oxygen concentration 7%) was introduced, and it was maintained at 80 ° C. for 8 hours. Then, after cooling, an anhydride reformer solution of an ethylene oxide adduct of (b3) (meth) acrylic acid having a solid content of 50% and an acid value of 64 mgKOH / g was obtained.

[Synthesis examples 8 to 9]

Except changing to the blending formula shown in Table 3, the same procedure as in Synthesis Example 7 was performed to obtain an anhydride modified solution of (b3) (meth) acrylic acid propylene oxide adduct (solid content 50%) .

The details of the abbreviations in the table are as follows.

BLEMMER AE-200: Trade name, made by Japan Oil and Fat, acrylic acid ethylene oxide adduct, average alkylene oxide mole number: 4.5 moles

BLEMMER AP-400: trade name, made by Japan Oil and Fat, acrylic acid propylene oxide adduct, average addition mole number of alkylene oxide: 6 mol

<Adhesive> [Synthesis example 10]

A flask equipped with a stirrer, a condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 100 parts of methyl isobutyl ketone, and the temperature was raised to 100 ° C in a nitrogen gas environment.

On the other hand, 10 parts of methyl methacrylate, 10 parts of n-butyl acrylate, 10 parts of hydroxyethyl methacrylate, 70 parts of benzyl methacrylate, and azobis-2- 5 parts of methyl butyronitrile were mixed to prepare a monomer mixed solution.

Then, in the flask charged with methyl isobutyl ketone, the monomer mixed solution was dropped over 3 hours, and then a aging reaction was performed for 3 hours.

Thus, a (meth) acrylic resin having a hydroxyl group was obtained.

Then, the reaction temperature was set to 80 ° C., and the environmental conditions were switched from a nitrogen environment to an air environment. Five parts of acrylic acid 2-isocyanatoethyl (Karenz AOI, manufactured by Showa Denko) and methyl isobutyl ketone 5 were added. And 0.1 parts of p-methoxyphenol as a polymerization inhibitor, and further reacted for 4 hours.

Thus, a solution of a (meth) acrylic resin having a solid content of 50% and a (meth) acrylfluorene group in a side chain was obtained. The (meth) acrylfluorenyl equivalent of the (meth) acrylic resin is about 3000.

[Synthesis Example 11]

A solution (solid content: 50%) of a (meth) acrylic resin having a (meth) acrylfluorene group in the side chain was obtained in the same manner as in Synthesis Example 10 except that the blending formula shown in Table 4 was changed.

<Metal fine particle dispersion and cured film> [Example 1]

The (A) anhydride-modified body solution (solid content: 50%) of the (A) polyfunctional (meth) acrylic acid compound obtained in Synthesis Example 1 was 16.8 parts, and the caprolactone addition of (b1) (meth) acrylic acid Aronix M-5300 (manufactured by Toa Synthetic Chemical Industry, 100% solids content) becomes 1.4 parts of zirconia as metal fine particles (UEP-100 zirconia manufactured by Daiichi Element Co., Ltd., average primary particle size 15nm) 28 parts, 53.8 parts of methyl isobutyl ketone as a dispersion medium, and 0.49 parts of IRGACURE184 (1-hydroxycyclohexyl phenyl ketone produced by BASF) as a polymerization initiator. The components were mixed to obtain a metal. Microparticle dispersion.

Then, the obtained metal was coated on a polyethylene terephthalate (PET) film (UH-13 manufactured by Toray Co., Ltd. with a thickness of 125 μm) using a bar coater so that the film thickness became 1 μm after drying. The fine particle dispersion was dried at 80 ° C for 2 minutes.

Next, a high-pressure mercury lamp with an ultraviolet irradiation device (device name: CSOT-40 manufactured by Japan Battery Corporation) was used to irradiate 300 mJ / cm ² and 240 mW / cm ² ultraviolet rays to harden the coating film to obtain a laminate of a substrate and a cured film.

[Examples 2 to 15 and Comparative Examples 1 to 5]

Except for changing to the blending formula shown in Tables 5 to 8, the same procedure as in Example 1 was performed to obtain a laminate of a metal fine particle dispersion, a substrate, and a cured film.

<Evaluation>

The metal fine particle dispersion liquids and hardened films obtained in Examples, Comparative Examples, and the like were evaluated by the following methods. The results are summarized in Tables 5-8.

(1) Dispersibility of metal fine particle dispersion

The metal fine particle dispersion was left to stand at 23 ° C, and the dispersibility of the metal fine particles was visually confirmed. The evaluation criteria are as follows.

A: No precipitate after 3 months.

B: A little precipitate appeared after 3 months.

C: A precipitate appeared after 1 week.

D: A precipitate appeared after 1 day.

(2) Hardness

An iron thin velvet # 0000 was used for the surface of the cured film, and it was subjected to reciprocating abrasion 10 times under the load described below so as to have a width of 40 mm or more. Then, a black tape was stuck on the back surface of the substrate (PET film), and the presence of scratches was confirmed under a three-wavelength fluorescent lamp. The evaluation criteria are as follows.

A ++: No scratch was found under a load of 200 g / cm ² .

A +: No scratch was found under a load of 100 g / cm ² , but a scratch was found under a load of 200 g / cm ² .

A: 1 to 5 scratches were found at a load of 100 g / cm ² .

B: 6 to 10 scratches were found at a load of 100 g / cm ² .

C: According to a load of 100 g / cm ^2, 11 or more scratches were found.

(3) Transparency (HAZE)

After the laminated body of the base material and the cured film was left under normal conditions (23 ° C, 50% relative humidity) for 40 hours, the haze was measured with a haze meter (manufactured by Nippon Denshoku Industries, turbidimeter NDH5000). The haze is measured in accordance with JIS K 7136 "Haze Method for Transparent Materials" (2000 edition).

In addition, at the time of measurement, light was irradiated from one surface on the side of the cured film and measured.

In addition, for the measurement sample, ten samples each having a square hardened film of 50 mm on one side were prepared, and each of them was measured once, and the total measurement was performed 10 times. Then, the average value of each measurement was made into a haze value. Then, transparency was evaluated from the obtained haze value. The evaluation criteria are as follows.

A +: The haze value is less than 1.0%.

A: The haze value is 1.0% or more and less than 1.8%.

B: The haze value is 1.8% or more and less than 2.3%.

C: The haze value is 2.3% or more.

(4) Moisture and heat resistance

The laminated body of the substrate and the cured film is stored in a constant temperature and humidity machine controlled to a humidity of 85% and a temperature of 85 ° C. for 500 hours, and then in a constant temperature and humidity chamber with a humidity of 50% and a temperature of 23 ° C. The laminate was stored for 12 hours, and the laminated body was subjected to a moist heat test.

Then, the laminated body cured film after the moist heat test was cut into a notch with a width of 1 mm in accordance with the cross cutting method described in JIS K 5600-5-6 Part 5-Section 6: Adhesion (1999). Tightness. The evaluation criteria are as follows.

A +: The cutting edge is completely smooth, and no peeling occurs in any of the grid squares.

A: There is a small peeling at the intersection of the cuts (the peeling rate is less than 5%).

B: Peeling occurs (peeling rate is 5% or more and less than 15%).

C: Significant spalling (peeling rate of 15% or more).

The details of the abbreviations in the table are as follows.

Aronix M403: trade name Aronix M403, manufactured by Toa Kosei Co., a mixture of dipentaerythritol pentaerythritol (acrylate) and dipentaerythritol pentaerythritol (acrylate) (dipentaerythritol pentaerythritol pentaerythritol (acrylate) content 50-50%); DA7301: trade name DISPARON DA-7301, 75% by mass solution of amidoamine salt of high molecular weight polyester acid manufactured by Kusumoto Chemical Co., Ltd. (solvent: alkylcyclohexane / propylene glycol monomethyl ether acetate); Aronix M5300: trade name Aronix M -5300, manufactured by East Asia Synthetic, ω-carboxycaprolactone monoacrylate; zirconium dioxide: UEP-100 zirconium oxide manufactured by First Rare Elements Co., Ltd., with an average primary particle diameter of 15nm; Alumina: TM-300 manufactured by Daming Chemical Industry Co., Ltd. with a particle size of 10 nm; Silicon dioxide: AEROSILR 812 manufactured by Evonik with an average primary particle size of 7 nm; MIBK: Methyl isobutyl ketone; IRGACURE 184: Trade name, manufactured by BASF, polymerization Initiator, 1-hydroxycyclohexylphenyl ketone; In addition, although the above-mentioned invention provides an exemplary embodiment of the present invention, it is only limited to the illustration, and is not limited to explanation. For example, those skilled in the art can consider the variations of the present invention within the scope of patent application described below.

(Industrial availability)

The metal fine particle dispersion liquid and the hardened film of the present invention are suitable for functional films such as optical parts, precision ceramics, conductive films, optical films, and the like.

Claims (6)

A metal fine particle dispersion liquid comprising: metal fine particles, a dispersion medium, and a metal fine particle dispersant; wherein the metal fine particles are metal oxide fine particles, and the metal fine particle dispersant contains: (A) a An anhydride modified body of a polyfunctional (meth) acrylic compound having at least one (meth) acrylfluorenyl group and at least one hydroxyl group; and (B) a monofunctional group having one (meth) acrylfluorene group (Meth) acrylic compound; the monofunctional (meth) acrylic compound contains at least one of the compounds represented by the following (b1) to (b3): (b1) ( Caprolactone adduct of (meth) acrylic acid: CH ₂ = C (R ¹ ) CO [O (CH ₂ ) ₅ CO] _n OH (1) (In the formula (1), R ¹ represents a hydrogen atom, N; 1 to 10); (b2) Anhydride reformer of the caprolactone adduct of hydroxyalkyl (meth) acrylate represented by the following formula (2): CH ₂ = C (R ¹ ) COOR ² O [CO (CH ₂ ) ₅ O] _n H (2) (In the formula (2), R ¹ represents a hydrogen atom and a methyl group; R ² represents ethylene, propyl, and butyl. Select at least one of the groups formed by the base; n means 1 ~ 10); (b3) Anhydride modified body of (meth) acrylic acid alkylene oxide adduct of formula (3): CH ₂ = C (R ¹ ) COO (C _m H _2m O) _n H (3) (In formula (3), R ¹ represents a hydrogen atom and a methyl group; m represents 2 to 4; and n represents 1 to 10). The fine metal particle dispersion liquid according to claim 1, wherein (B) the monofunctional (meth) acrylic compound is a caprolactone of (meth) acrylic acid represented by formula (1) and n is 1 to 3 Adduct. The fine metal particle dispersion liquid according to claim 1, wherein (B) the monofunctional (meth) acrylic compound is: (meth) acrylic acid hydroxyalkyl represented by the above formula (2) and n is 2 to 5 Anhydride modification of ester caprolactone adduct. The dispersion liquid of metal fine particles according to claim 1, wherein (B) the monofunctional (meth) acrylic compound described above contains: (m) 2 to 3, and n 2 to 5 ( An anhydride modified body of an alkylene oxide adduct of (meth) acrylic acid. For example, the metal fine particle dispersion of claim 1 further contains a binder, and the binder contains a (meth) acrylic resin. A hardened film containing a hardened metal fine particle dispersion liquid according to claim 1.