JP2013040229A - Active energy ray-curable composition, production method of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition including an organic/inorganic composite microparticle and formable of a coating film excellent in solvent resistance, adhesiveness, scratch resistance and chemical resistance.SOLUTION: This active energy ray-curable composition includes a radically polymerizable unsaturated group-containing compound (A), an organic/inorganic composite microparticle (B) and a photopolymerization initiator (C), where the organic/inorganic composite microparticle (B) is obtained by reacting a living polymer (b), inorganic microparticles (b) having a polymerizable unsaturated group, etc., in the presence of a solvent and, if necessary, vaporizing the solvent; and the living polymer (b) is obtained by living-radical polymerization of an unsaturated monomer (b) added with an aminoether compound (b), or a nitroxide compound and a radical polymerization initiator, as the initiator of living radical polymerization.

Description

  The present invention provides an active energy ray-curable composition containing organic-inorganic composite fine particles (B), a method for producing the active energy ray-curable composition, an article coated with the active energy ray-curable composition, and the activity The present invention relates to a laminate including a coating layer formed from an energy ray-curable composition and an article having the laminate on the surface.

  The active energy ray-curable composition is easily cured by irradiating active energy rays such as ultraviolet rays, and can form a cured film (hard coat film) excellent in hardness, scratch resistance, transparency, etc. on the surface of the article. Therefore, it is widely used as a protective film for plastic materials and the like. In addition, for example, a hard coating is applied to a film-like substrate containing a pattern layer (printing layer, metal deposition layer) for imparting decorativeness, designability, etc. to various electrical products, cosmetic containers, automobile interior and exterior parts, etc. In order to do this, an active energy ray-curable composition is being applied.

In addition, in order to form a hard coat film on the surface of an article, it has been studied to add inorganic fine particles to the active energy ray-curable composition.
However, a dispersion of inorganic fine particles, for example, inorganic fine particles having a particle diameter of 200 nm or less dispersed in an organic solvent, is unstable when the primary particles of the inorganic fine particles are mixed with other compounds. May aggregate and settle. In addition, even when the dispersion and the resin solution can be mixed so that the particles do not aggregate, when the organic solvent is volatilized for the purpose of molding or the like, the inorganic fine particles are aggregated, and the obtained molded product or the like In some cases, the characteristics of the film deteriorated.

  In order to prevent such aggregation of inorganic fine particles, a dispersion of organic-inorganic composite fine particles in which inorganic fine particles are coated with a polymer has been studied. Since the dispersion is applied to various organic materials such as a coating film, a film, a thermoplastic resin, and a thermosetting resin, a polymer covering inorganic fine particles is required to have a wide range of designs related to various characteristics. In order to meet these requirements, industrially available unsaturated monomers are used, and composite fine particles of polymer and inorganic fine particles obtained by the polymerization reaction are being studied.

  Patent Document 1 includes an addition reaction of a carboxyl group-containing (meth) acrylic compound (a2) to a polymer obtained by polymerizing a polymerization component (a1) containing a vinyl compound having an epoxy group in the molecule. Active energy ray-curable composition containing reaction product (A), colloidal silica (B), phosphoric acid compound (C), and polyfunctional (meth) acrylic compound (D), and the above active energy ray-curable composition An article having excellent scratch resistance formed from a product is disclosed.

  However, when the active energy ray-curable composition described in Patent Document 1 contains a large amount of the reaction product (A), the adhesiveness is increased due to an increase in internal stress of the resulting coating film. In the active energy ray-curable composition described in Patent Document 1, when the proportion of colloidal silica (B) is increased, the hardness and scratch resistance of the resulting coating film are improved. There was a tendency for the sex to decline.

Patent Document 2 discloses an active energy ray-curable composition containing an acrylic polymer (A), and when the composition is applied to a plastic substrate, high hardness is obtained and cured. In that case, it is described that a cured coating film with less warping (curl) of the film and excellent transparency can be obtained.
However, in the composition described in Patent Document 2, when the ratio of the acrylic polymer (A) is increased, chemical resistance may be lowered.

JP 2009-286972 A JP 2010-83960 A

As described above, the conventional active energy ray-curable composition containing organic-inorganic composite fine particles has the above-described problems.
Therefore, the present invention is an active energy ray-curable composition containing organic-inorganic composite fine particles having excellent stability, and forms a coating film having excellent solvent resistance, adhesion, scratch resistance, and chemical resistance. An object of the present invention is to provide an active energy ray-curable composition that can be used.

As a result of intensive studies to achieve the above object, the present inventors have obtained a radical-polymerizable unsaturated group-containing compound (A), organic-inorganic composite fine particles (B), and a photopolymerization initiator (C). An active energy ray-curable composition containing organic-inorganic composite fine particles (B), wherein a living polymer (b ₁ ) and inorganic fine particles (b ₂ ) having a polymerizable unsaturated group are reacted in the presence of a solvent. Produced by evaporating the solvent, if desired, or reacting the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the unsaturated monomer (b ₃ ) in the presence of the solvent. And the living polymer (b ₁ ) was used as a living radical polymerization initiator as an amino ether compound (b ₁₁ ), or a nitroxide compound and a radical. It has been found that the above problem can be solved by an active energy ray-curable composition obtained by adding a polymerization initiator and conducting living radical polymerization of an unsaturated monomer (b ₁₂ ). It came to be completed.
That is, this invention consists of the following aspects.

[Aspect 1]
An active energy ray-curable composition comprising a radical polymerizable unsaturated group-containing compound (A), organic-inorganic composite fine particles (B), and a photopolymerization initiator (C),
Was the organic-inorganic composite fine particle (B) produced by reacting the living polymer (b ₁ ) with the inorganic fine particle (b ₂ ) having a polymerizable unsaturated group in the presence of a solvent and optionally evaporating the solvent? Or the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the unsaturated monomer (b ₃ ) are reacted in the presence of a solvent and optionally the solvent is evaporated. And the living polymer (b ₁ ) added an amino ether compound (b ₁₁ ), or a nitroxide compound and a radical polymerization initiator as a living radical polymerization initiator, and the living radical polymerization of the unsaturated monomer (b ₁₂ ). Obtained by doing
The active energy ray-curable composition as described above.

（式中、
Ｒ¹は、炭素原子数が１〜３の、直鎖又は分岐鎖のアルキル基であり、そして
Ｒ²は、水素原子、炭素数が１〜８の、直鎖又は分子鎖の、アルキル基、フェニル基、アルカリ金属、又はＮ₄Ｈ⁺である）
で表される化合物である、態様１に記載の活性エネルギー線硬化組成物。 [Aspect 2]
The amino ether compound (b ₁₁ ) has the following formula (1):

(Where
R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a hydrogen atom, a linear or molecular alkyl group having 1 to 8 carbon atoms, A phenyl group, an alkali metal, or N ₄ H ⁺ )
The active energy ray hardening composition of aspect 1 which is a compound represented by these.

[Aspect 3]
The active energy ray-curable composition according to embodiment 1 or 2, wherein the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group are colloidal silica having a polymerizable unsaturated group.
[Aspect 4]
The active energy ray-curable composition according to any one of Embodiments 1 to 3, wherein the organic-inorganic composite fine particles (B) have an unsaturated group.

[Aspect 5]
As a living radical polymerization initiator, an amino ether compound (b ₁₁ ), or a nitroxide compound and a radical polymerization initiator are added, and living radical polymerization of an unsaturated monomer (b ₁₂ ) is carried out to obtain a living polymer (b ₁ ). Obtaining step,
The living polymer (b ₁ ) and inorganic fine particles (b ₂ ) having a polymerizable unsaturated group are reacted in the presence of a solvent, and the solvent is evaporated if desired, or the living polymer (b ₁ ) and the polymerizable unsaturated group are polymerized. A step of forming organic-inorganic composite fine particles (B) by reacting inorganic fine particles (b ₂ ) having a saturated group with unsaturated monomers (b ₃ ) in the presence of a solvent and evaporating the solvent if desired.
A step of mixing the organic-inorganic composite fine particles (B) with the radical polymerizable unsaturated group-containing compound (A) and the photopolymerization initiator (C);
A process for producing an active energy ray-curable composition, comprising:

[Aspect 6]
An article coated with the active energy ray-curable composition according to any one of aspects 1 to 4.
[Aspect 7]
A laminate comprising a film-like substrate layer and a cured or uncured coating layer formed from the active energy ray-curable composition according to any one of aspects 1 to 4.

[Aspect 8]
An article having the laminate according to aspect 7 on its surface,
The laminate includes a cured coating layer formed from the active energy ray-curable composition according to any one of aspects 1 to 4.
The above article.

  The active energy ray-curable composition of the present invention contains organic / inorganic composite fine particles having excellent stability, and can form a coating film having excellent solvent resistance, adhesion, scratch resistance, and chemical resistance.

Hereinafter, the present invention will be described in detail.
[Radically polymerizable unsaturated group-containing compound (A)]
As a radically polymerizable unsaturated group containing compound (A) used for this invention, a monofunctional radically polymerizable unsaturated group containing compound and a polyfunctional radically polymerizable unsaturated group containing compound are mentioned, for example.

  Examples of the monofunctional radical polymerizable unsaturated group-containing compound include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide.

  Examples of the monofunctional radical polymerizable unsaturated group-containing compound include hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; acrylic acid and methacrylic acid Carboxyl group-containing (meth) acrylates such as acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and 5-carboxypentyl (meth) acrylate; Glycidyl group-containing radically polymerizable unsaturated group-containing compounds such as glycidyl (meth) acrylate and allyl glycidyl ether; Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; N, N-dimethyl Nitrogen-containing alkyl (meth) acrylates such as tilaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) ) Acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Polymerizable amides such as dimethylaminopropyl (meth) acrylamide and N, N-dimethylaminoethyl (meth) acrylamide.

  Examples of the polyfunctional radical polymerizable unsaturated group-containing compound include esterified products of polyhydric alcohol and (meth) acrylic acid. Specific examples of the polyfunctional radical polymerizable unsaturated group-containing compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth). ) Acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (Meth) acrylate, pentaerythritol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, bisphenol A Di (meth) acrylate compounds such as tylene oxide modified di (meth) acrylate; glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide Modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanurate, tris (2-acryloyloxyethyl) isocyanurate, tris (2-acryloyloxypropyl) isocyanurate, etc. Tri (meth) acrylate compounds; tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; Examples include lithitol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

  Further, as the polyfunctional radical polymerizable unsaturated group-containing compound, radical polymerizable unsaturated group-containing acrylic resin, radical polymerizable unsaturated group-containing polyurethane resin, radical polymerizable unsaturated group-containing polyester resin, radical polymerizable unsaturated group Examples thereof include a group-containing epoxy resin, a radical polymerizable unsaturated group-containing polyamide resin, and a radical polymerizable unsaturated group-containing silicone resin.

From the viewpoint of hard coat properties, the polyfunctional radically polymerizable unsaturated group-containing compound is a radically polymerizable unsaturated group-containing acrylic resin, a radically polymerizable unsaturated group-containing polyurethane resin, and / or a radically polymerizable unsaturated group-containing compound. A polyester resin is preferred.
The radical polymerizable unsaturated group-containing acrylic resin is, for example,
1) A method of adding a carboxyl group-containing unsaturated compound to an epoxy group-containing acrylic resin,
2) A method of adding an epoxy group-containing unsaturated compound to a carboxyl group-containing acrylic resin,
3) A method of adding an isocyanate group-containing unsaturated compound to a hydroxyl group-containing acrylic resin,
4) A method of reacting an isocyanate group-containing acrylic resin with a hydroxyl group-containing unsaturated compound,
Etc.

  Functional group-containing acrylic resins such as the above-mentioned epoxy group-containing acrylic resins, carboxyl group-containing acrylic resins, hydroxyl group-containing acrylic resins, carboxyl group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, isocyanate group-containing unsaturated compounds, hydroxyl group-containing The addition reaction with a radically polymerizable unsaturated compound such as an unsaturated compound is usually carried out in an organic solvent at about 40 to about 160 ° C., optionally adding a catalyst. In addition, although the said functional group containing acrylic resin can be melted and addition reaction can also be implemented, it is preferable to implement reaction in an organic solvent from a viewpoint of the simplicity of manufacture.

  Examples of the carboxyl group-containing unsaturated compound (hereinafter, sometimes referred to as “carboxyl group-containing polymerizable unsaturated monomer”) include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and isocrotonic acid, and maleic acid. Examples include α, β-unsaturated dicarboxylic acids such as acids, fumaric acid, itaconic acid, citraconic acid, and chlorinated maleic acid, or half esters thereof.

  The epoxy group-containing unsaturated compound (hereinafter sometimes referred to as “epoxy group-containing polymerizable unsaturated monomer”) is a compound having one epoxy group and one radical polymerizable unsaturated group in one molecule. Representative, for example, epoxy group-containing monomer compounds such as glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, glycidyl vinyl ether, allyl glycidyl ether; (2-oxo-1,3-oxolane) methyl (2-oxo-1,3-oxolane) group-containing vinyl monomer compounds such as (meth) acrylate; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3, Contains alicyclic epoxy groups such as 4-epoxycyclohexylethyl (meth) acrylate Alkenyl monomers and the like.

  The isocyanate group-containing unsaturated compound (hereinafter sometimes referred to as “isocyanate group-containing polymerizable unsaturated monomer”) is typically a compound having one isocyanate group and one radically polymerizable unsaturated group. Yes, for example, isocyanate methyl (meth) acrylate, isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, isocyanate octyl (meth) acrylate, p-methacryloxy-α, α′-dimethylbenzyl isocyanate, m-acryloxy-α , Α′-dimethylbenzyl isocyanate, m- or p-isopropenyl-α, α′-dimethylbenzyl isocyanate, and the like. Examples of the isocyanate group-containing unsaturated compound include those obtained by reacting a part of the isocyanate of a polyisocyanate compound with a hydroxyl group-containing unsaturated compound.

  The hydroxyl group-containing unsaturated compound (hereinafter sometimes referred to as “hydroxyl group-containing polymerizable unsaturated monomer”) is typically a compound having one hydroxyl group and one radically polymerizable unsaturated group. , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono ( And a ring-opening reaction product of a (meth) acrylate, a polypropyne glycol mono (meth) acrylate, a (meth) acrylate compound and an ε-caprolactone compound. Examples of the hydroxyl group-containing unsaturated compound include trimethylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate.

  The functional group-containing acrylic resin can be prepared by various methods, but the carboxyl group-containing polymerizable unsaturated monomer, epoxy group-containing polymerizable unsaturated monomer, isocyanate group-containing polymerizable unsaturated monomer, and hydroxyl group-containing A method in which a polymerizable unsaturated monomer selected from the group consisting of polymerizable unsaturated monomers is copolymerized in an organic solvent together with other polymerizable unsaturated monomers as desired is most convenient and preferred.

  The polymerization initiator and organic solvent used for the polymerization are not particularly limited, and various polymerization initiators and organic solvents can be used. In preparing the epoxy group-containing acrylic resin, the carboxyl group-containing polymerizable unsaturated monomer, the isocyanate group-containing polymerizable unsaturated monomer, and the hydroxyl group-containing polymerizable unsaturated monomer are used in preparing the carboxyl group-containing acrylic resin. , Epoxy group-containing polymerizable unsaturated monomer, isocyanate group-containing polymerizable unsaturated monomer, and hydroxyl group-containing polymerizable unsaturated monomer, in preparing a hydroxyl group-containing acrylic resin, carboxyl group-containing polymerizable unsaturated monomer, epoxy group-containing A polymerizable unsaturated monomer, an isocyanate group-containing polymerizable unsaturated monomer, and in preparing an isocyanate group-containing acrylic resin, a carboxyl group-containing polymerizable unsaturated monomer, an epoxy group-containing polymerizable unsaturated monomer, and a hydroxyl group-containing polymerization Unsaturated monomer But it is treated as the other polymerizable unsaturated monomer.

  Examples of the other polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethyl (Meth) acrylic acid alkyl esters such as octyl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; benzyl ( ) Acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, alkyl carbitol (meth) acrylate such as ethyl carbitol (meth) acrylate; isobornyl (meth) acrylate, di Other (meth) acrylic esters such as cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate; γ- (meth) acryloyloxypropyltrimethoxysilane, γ Hydrolyzable silyl group-containing polymerizable unsaturated monomers such as-(meth) acryloyloxypropyltriethoxysilane and γ- (meth) acryloyloxypropylmethyldimethoxysilane; vinyl fluoride, vinylidide fluoride Fluorine-containing α-olefin compounds such as trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, hexafluoropropylene; trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, Fluorine-containing vinyl polymerizability such as perfluoroalkyl perfluorovinyl ether such as heptafluoropropyl trifluorovinyl ether or (per) fluoroalkyl vinyl ether (wherein the alkyl group has about 1 to about 18 carbon atoms) Unsaturated monomers: various polyvalent carboxyl group-containing polymerizable unsaturated monomers represented by fumaric acid, maleic acid, itaconic acid, etc., and monoalkyl amines having 1 to 18 carbon atoms Mono- or diester compounds with coal; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, p-tert-butylstyrene; (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl ( (Meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-amyl (meth) acrylamide, N- (meth) acrylamide, N-hexyl (meth) acrylamide, N-heptyl (meth) acrylamide, N-2-ethylhexyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide , N, N-die Chill (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meta ) Acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-tert-butoxymethyl (meth) acrylamide, N-amyloxymethyl acrylamide, N-hexyloxy (meth) acrylamide, Amino group-containing amino acids such as N-heptyloxymethyl (meth) acrylamide, N-octyloxymethyl (meth) acrylamide, N-2-ethyl-hexyloxymethyl (meth) acrylamide, diacetone (meth) acrylamide, etc. Polymerizable unsaturated monomers; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and other (meth) acrylate dialkylaminoalkyl compounds; tert-butylaminoethyl (meth) acrylate, tert-butylaminopropyl (Meth) acrylate, aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate, piperidinylethyl (meth) acrylate, (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinyl Nitrogen-containing polymerizable unsaturated monomers such as caprolactam, N-vinyloxazoline, (meth) acrylonitrile; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate Vinyl laurate, branched aliphatic vinyl carboxylate having about 9 carbon atoms, branched aliphatic vinyl carboxylate having about 10 carbon atoms, branched aliphatic vinyl carboxylate having 11 carbon atoms, vinyl stearate, etc. Aliphatic vinyl carboxylates; vinyl ester compounds of carboxylic acids having a cyclic structure such as vinyl cyclohexane carboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, vinyl p-tert-butylbenzoate; ethyl vinyl ether, hydroxyethyl vinyl ether Alkyl vinyl ether compounds such as hydroxy n-butyl vinyl ether, hydroxyisobutyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether; halogenated compounds other than the above fluoroolefin compounds such as vinyl chloride and vinylidene chloride Olefin compounds; α-olefin compounds such as ethylene, propylene, butene-1, and the like.

  Examples of radical polymerization initiators used in the preparation of functional group-containing acrylic resins such as carboxyl group-containing acrylic resins, epoxy group-containing acrylic resins, hydroxyl group-containing acrylic resins, and isocyanate group-containing acrylic resins include 2,2′-azo. Bisisobutyronitrile, 2,2'-azobis-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis-cyclohexanecarbonitrile, dimethyl-2,2 ' -Azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis- (2-amidinopropene) dihydrochloride, 2-tert-butylazo-2-cyanopropane, 2, 2'-azobis (2-methyl-propionamide) dihydrate, 2,2'-azobis [2- (2-imidazoline Azo compounds such as 2-yl) propene] and 2,2′-azobis (2,2,4-trimethylpentane); benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, potassium persulfate, tert-butylperoxy Neodecanoate, tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, 1,1-bis-tert-butylperoxy-3,3 , 5-trimethylcyclohexane, tert-butylperoxy-laurate, tert-butylperoxyisophthalate, tert-butylperoxyacetate, tert-butylperoxybenzoate, dicumyl peroxide, di-tert-butylper Ketone peroxide compounds such as oxides; Peroxyketal compounds; Hydroperoxide compounds; Dialkyl peroxide compounds; Diacyl peroxide compounds; Peroxyester compounds; Peroxydicarbonate compounds; Is mentioned.

  Examples of the organic solvent used for the preparation of the functional group-containing acrylic resin include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, Alkyl alcohol solvents such as isopentanol; methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether Glycol ether solvents such as benzene, toluene, xylene, ethylbenzene and other aromatic carbonization Motokei solvent Exxon Aromatic Naphtha No. Mixed hydrocarbon solvent containing aromatic hydrocarbon such as 2 (manufactured by Exxon USA); aliphatic hydrocarbon solvent such as n-pentane, n-hexane and n-octane; Isopar C, Isopar E, Exol DSP100 / 140, Exol D30 (all manufactured by Exxon USA), mixed solvent containing aliphatic hydrocarbon such as IP Solvent 1016 (Idemitsu Petrochemical Co., Ltd.); cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. Alicyclic hydrocarbon solvents such as: tetrahydrofuran, dioxane, diisopropyl ether, di-n-butyl ether and other ether solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketone solvents; methyl acetate, ethyl acetate, n-propyl acetate , Isopropyl acetate, n acetate Butyl, isobutyl acetate, n- amyl, isoamyl acetate, hexyl acetate, ethyl propionate, and ester solvents such as butyl propionate. The organic solvent may contain a small amount of water.

  Furthermore, in the preparation of the acrylic resin, a chain transfer agent can be added as desired. Examples of the chain transfer agent include dodecyl mercaptan, lauryl mercaptan, thioglycolic acid ester, mercaptoethanol, α-methylstyrene dimer, and the like.

As the above-mentioned radical polymerizable unsaturated group-containing acrylic resin, radical polymerizable unsaturated group-containing acrylic resin obtained by addition reaction of a carboxyl group-containing unsaturated compound to an epoxy group-containing acrylic resin from the viewpoint of curability, carboxyl group A radically polymerizable unsaturated group-containing acrylic resin obtained by addition-reacting an epoxy group-containing unsaturated compound to the containing acrylic resin is preferred.
On the other hand, the radical polymerizable unsaturated group-containing urethane resin is obtained by copolymerizing an isocyanate compound, a hydroxyl group-containing polymerizable unsaturated monomer, and an optional polyol compound.

  Examples of the isocyanate compound include aliphatic, alicyclic, and aromatic compounds having two or more isocyanate groups in one molecule. Specifically, for example, 2,4-tolylene diene, for example, Isocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 1, 4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3, 3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, and combinations thereof, such as nurate group, burette group, uretdione group, allophanate group, etc. The thing containing is mentioned. Examples of the isocyanate compound include aliphatic diisocyanates such as tetramethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate, and 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, Alicyclic diisocyanates such as isophorone diisocyanate are preferred.

  The hydroxyl group-containing polymerizable unsaturated monomer is used to introduce an unsaturated group into the polyurethane resin skeleton. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol-mono (meth) acrylate, polyethylene glycol-mono (meth) acrylate, polypropylene glycol-mono (meth) acrylate, hydroxy Ε-caprolactone polyaddition of ethyl (meth) acrylate, β-methyl-δ-valerolactone polyaddition of hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meta) (Meth) acrylates such as acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate; allyl compounds such as allyl alcohol, glycerol monoallyl ether, glycerol diallyl ether; C2-C4 alkylene oxide, an adduct, etc. are mentioned.

  Examples of the polyol compound include low molecular weight glycols, high molecular weight glycols, glycol compounds having a carboxyl group, polyester polyols, polycarbonate polyols, and combinations thereof.

  Examples of the low molecular weight glycols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, octanediol, tricyclo Examples include decane dimethylol, hydrogenated bisphenol A, cyclohexanedimethanol, and 1,6 hexanediol. Examples of the high molecular weight glycols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of the polyester polyols include those produced by reacting a glycol component with a dicarboxylic acid component, and can be easily produced by a known method such as an esterification reaction or a transesterification reaction. The polyester polyols 2 include polyester diols obtained by ring-opening reaction of cyclic ester compounds such as ε-caprolactone and co-condensed polyesters thereof.

  Examples of the glycol compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, and condensates thereof, polyester polyol and polyether polyol. Is mentioned. Moreover, the glycol compound containing the carboxyl group may contain a hydroxycarboxylic acid such as 12-hydroxystearic acid, paraoxybenzoic acid, and salicylic acid.

In the synthesis of the above-mentioned radical polymerizable unsaturated group-containing urethane resin, in addition to the isocyanate compound, the hydroxyl group-containing polymerizable unsaturated monomer, and the optional polyol compound, in order to block excess isocyanate groups and adjust the concentration of unsaturated groups Further, a monohydric alcohol can be added.
The radically polymerizable unsaturated group-containing urethane resin is obtained, for example, by reacting the isocyanate compound, the hydroxyl group-containing ethylenically unsaturated compound, and the desired polyol compound at a time or in a plurality of stages. It is done.

  In addition, the radical polymerizable unsaturated group-containing urethane resin is prepared by, for example, reacting an isocyanate compound and a polyol compound to form a prepolymer having an isocyanate terminal, and then the isocyanate of the prepolymer and a hydroxyl group-containing ethylenic resin. It can be produced by a method of reacting with a hydroxyl group in an unsaturated compound. The above reaction is usually performed at a temperature of about 40 to about 180 ° C, preferably about 60 to about 130 ° C.

  The reaction for synthesizing the above radical-polymerizable unsaturated group-containing urethane resin is inert to isocyanate groups such as dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone, tetrahydrofuran, texanol isobutyl ether, and the like. It is desirable to carry out in an organic solvent having a high affinity for water.

  Also, amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine, and the like used in ordinary urethanization reactions to promote the reaction for synthesizing the radical polymerizable unsaturated group-containing urethane resin, and dibutyl Tin-based catalysts such as tin dilaurate and dioctyl tin dilaurate can be added, and in order to prevent polymerization of ethylenically unsaturated compounds during the urethanization reaction, hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, etc. A polymerization inhibitor can be added.

  Commercially available products of the radical polymerizable unsaturated group-containing urethane resin include, for example, CN929, CN940, CN959, CN962, CN964, CN965, CN968, CN980, CN981, CN983, CN989, CN991, CN996, CN9001, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN9011, CN9014, CN9178, CN9788, and CN9893 (above, manufactured by Sartomer Japan Co., Ltd.), EBECRYL204, EBECRYL205, EBECRYL210, EBECRYL220, EBECRYL220, EBECRYL220 , E ECRYL284, EBECRYL401, EBECRYL1290, KRM8200, EBECRYL4858, EBECRYL5129, EBECRYL8210, EBECRYL8402, EBECRYL8804, and EBECRYL9270 (above, Daicel Corp. 1) New Frontier R1214, New Frontier R1220, New Frontier R1301, New Frontier R1304, and New Frontier R1150D (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), AH600, AT600, UA306H, and UF8001 (above, manufactured by Kyoeisha Chemical Co., Ltd.) Can be mentioned

  Examples of the radical polymerizable unsaturated group-containing urethane resin include, for example, a hexamethylene disisocyanate trimer having an iminooxadiazinedione group, a hydroxyalkyl (meth) acrylate, and an isocyanate group in the presence of a catalyst. Examples thereof include urethane (meth) acrylates obtained by adding and reacting with hydroxyl groups so as to have approximately the same amount.

  As a commercial item of the hexamethylene disissocyanate trimer which has the said iminooxadiazinedione group, Desmodur XP2410 (made by Bayer MaterialScience) etc. are mentioned, for example. Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. It is done.

  The reaction of the hexamethylene disisocyanate trimer with hydroxyalkyl (meth) acrylate is, for example, about 0 to about 200 ° C, preferably about 20 to about 200 ° C, more preferably about 20 ° C to about 120 ° C. Can be done at temperature. The reaction is usually completed in about 2 to about 10 hours. A catalyst can be added to the above reaction. Examples of the catalyst include tertiary amines such as triethylamine and organometallic compounds such as dibutyltin dilaurate. A solvent can be added to the above reaction. Examples of the solvent include esters such as ethyl acetate, butyl acetate, methyl benzoate, and methyl propionate; ethers such as tetrahydrofuran, dioxane, and dimethoxyethane; propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and 3-methoxybutyl. Examples include glycol ethers such as acetate; aromatic hydrocarbons such as toluene and xylene, and aliphatic hydrocarbons.

  The above-mentioned radical polymerizable unsaturated group-containing polyester resin is a resin obtained by polycondensation of a polyhydric alcohol and a polybasic acid, and reacts under conditions where hydroxyl groups are excessively present with respect to carboxyl groups. A polyester resin containing a carboxyl group can be obtained by reacting under conditions where the carboxyl group is excessively present relative to the hydroxyl group. Moreover, after obtaining a hydroxyl group-containing polyester resin, a carboxyl group-containing polyester resin can be produced by adding an acid anhydride to the hydroxyl group. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and the like.

  Examples of the polyhydric alcohol that is a raw material for the polyester resin include alkane polyols, oxyalkylene polyols, polyoxyalkylene polyols, and alicyclic polyols. Specifically, ethylene glycol, 1,2-propylene glycol, 1, 3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,3-pentanediol, 1,6-hexanediol 1,5-hexanediol, neopentyl glycol, glycerin, 2-methylglycerin, trimethylolpropane, trimethylolethane, pentaerythritol and other alkane polyols; diethylene glycol and other oxyalkylene polyols; triethyleneglycol , Tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polyoxyalkylene polyols such as polypropylene glycol; 1,4-cyclohexane cycloaliphatic polyols dimethanol, etc., and the like.

  Examples of the polybasic acid to be reacted with the polyhydric alcohol include adipic acid, sebacic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, pimelic acid, azelaic acid, and dodecane. Diacid, cyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, hexahydrophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, butanetricarboxylic acid or their anhydrides Etc.

  In the polycondensation of a polyhydric alcohol and a polybasic acid, a strong proton acid, a heavy metal oxide, or the like can be added as a polycondensation catalyst. Examples of the strong protonic acid include sulfuric acid, benzenesulfonic acid, paratoluenesulfonic acid and the like. Examples of the heavy metal oxide include tetrabutyl titanate, dibutyltin oxide, antimony trioxide, and manganese dioxide.

  In addition, as a commercial item of the said radical polymerizable unsaturated group containing polyester resin, for example, CN292, CN293, CN294, CN296, CN299, CN2200, CN2203, CN2250, CN2251, CN2252, CN2253, CN2255, CN2270, CN2271E, CN2273, CN2276, CN2278, CN2279, CN2280, CN2297A, CN2300 (above, manufactured by Sartomer Japan, Inc.), EBECRYL450, EBECRYL505, EBECRYL525, EBECRYL657, EBECRYL800, EBECRYL800, EBECRYL800, EBECRYL800, EBECRYL800 EBECRYL1870, EBECRYL884 and EBECRYL885 (manufactured by Daicel Cytec Co., Ltd.), Aronix M6100, Aronix M6200, Aronix M6250, Aronix M6500, Aronix M7100, Aronix M8030, Aronix M8030, Aronix M8060, Aronix M8060 (Above, manufactured by Toa Gosei Co., Ltd.), New Frontier R2402, and New Frontier R2403 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Aronix M203, Aronix M215, Aronix M220, Aronix M240, Aronix M309, Aronix M310 , Allo Axix M313, Aronix M315, Aronix M325, Aronix M350, Aronix M402, Aronix M408, Aronix M450 (manufactured by Toa Gosei Co., Ltd.), NK ester A-NPG, NK ester APG-200, NK ester APG-400, and NK Ester 701A (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-551, KAYARAD R-712, KAYARAD R-604, KAYARAD THE-330, KAYARAD TPA-320 , KAYARAD TPA-330, KAYARAD T-1420, KAYARAD RP-1040, KAYARAD DPHA, KAYARAD DP Examples include EA-12, KAYARAD DPHA-2C, KAYARAD D-310, and KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.).

  The weight average molecular weight of the radically polymerizable unsaturated group-containing compound (A) is preferably about 300 or more, more preferably about 400 to about 100,000, and still more preferably about 500 to about 30,000. The unsaturated group equivalent of the radically polymerizable unsaturated group-containing compound (A) is preferably in the range of about 100 to about 5,000 and more preferably in the range of about 200 to about 2,000 from the viewpoint of scratch resistance. preferable. The weight-average molecular weight of the radical polymerizable unsaturated group-containing acrylic resin is preferably in the range of about 1,000 to about 100,000, and more preferably about 3,000 to about 30,000.

[Organic / inorganic composite fine particles (B)]
[Living polymer (b ₁ )]
The living polymer (b ₁ ) used in the present invention can be polymerized by (1) nitroxide compound-based radical polymerization method, which is a kind of living radical polymerization method.
On the other hand, “conventional radical polymerization” means radical polymerization other than living radical polymerization in the present specification, and is widely performed industrially to produce resins used for molding materials, paints, adhesives, and the like. Polymerization.

Elementary reaction of “conventional radical polymerization” consists of initiation reaction, growth reaction, chain transfer reaction and termination reaction (“Chemistry of Polymer Synthesis” (2nd edition, author: Takayuki Otsu, published by Kagaku Dojin Co., Ltd.)) Page 47). In the growth reaction, an unsaturated monomer is added in a chain to the growth radical (in which the growth terminal of the polymer is in the state of an active carbon radical species), and the polymerization proceeds. A non-state polymer is produced.
In the present specification, the unsaturated monomer for producing the living polymer (b ₁ ) is referred to as an unsaturated monomer (b ₁₂ ) and is distinguished from an unsaturated monomer (b ₃ ) described later.

  The polymer no longer returns to the growing radical and cannot be reinitiated (a polymer that cannot reinitiate such polymerization may be referred to herein as a “dead polymer”). Living radical polymerization is possible by reversibly generating active carbon radical species from a covalently bonded species (dormant species) where the growth terminal of the polymer is stable. A polymer obtained by such living radical polymerization and having a polymerization reaction activity is referred to as “living polymer” in the present specification). Therefore, in living radical polymerization, if all unsaturated monomers are consumed by polymerization and newly added unsaturated monomers are added, the growth ends of the polymer that has already been formed can be produced without generating another polymer. Can be converted from dormant species to active carbon radical species to reinitiate polymerization.

In the present invention, the reaction of the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the unsaturated monomer (b ₃ ) as desired utilizes the characteristics of this living radical polymerization. Is. That is, when the growing terminal of the living polymer (b ₁ ) is changed from a dormant species to a carbon radical species, it is added to the polymerizable unsaturated group on the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, Alternatively, the organic-inorganic composite fine particles (B) can be obtained by copolymerizing with the polymerizable unsaturated groups on the unsaturated fine particles (b ₃ ) and the inorganic fine particles (b ₂ ) having polymerizable unsaturated groups. . Thus, since the organic-inorganic composite fine particles (B) used in the present invention utilize the living radical polymerization reaction mechanism, they are newly chemically bonded to the inorganic fine particles as in “conventional radical polymerization”. It is possible to coat the inorganic fine particles by chemically bonding the living polymer onto the inorganic fine particles with high efficiency.

[(1) Nitroxide compound-based radical polymerization method]
The above nitroxide compound-based radical polymerization method uses a stable radical compound such as a nitroxide compound as a growth radical scavenger, and controls the living end to be reversibly converted into a dormant species and a carbon radical species. It is a method of radical polymerization, and may be expressed as NMP (Nitroxide Living Living Radical Polymerization). The nitroxide compound-based radical polymerization method is a known method described in JP-A-6-199916, JP-T 2005-534712, Macromolecules, 1994, Vol. 27, 7228, and the like. Can be mentioned.
The living radical polymerization method (1) is preferable from the viewpoint of many types of unsaturated monomers (b ₁₂ ) applicable to the polymerization reaction.

  (1) Nitroxide compound-based radical polymerization includes (1a) polymerization in the presence of an amino ether compound and (1b) polymerization in the presence of a nitroxide compound that is a stable radical and a radical polymerization initiator. Etc. The amino ether compound in (1a) is a compound capable of generating a nitroxide compound that is a stable radical and a polymerization initiation radical by heating.

  As an amino ether compound that can be used in the method (1a), for example, trade name “BlocBuilder MA” of Arkema Co., Ltd., benzoyloxy-2-[(2,2,6,6-tetramethyl-1-piperidinyl) oxy] — Examples include 2-phenylethyl (BS-TEMPO) and 2-benzoyloxy-1-phenylethyl-di-tert-butyl-nitroxide (BS-DBN). Living radical polymerization using BlocBuilder MA can be performed by heating a mixture containing the monomer and Bloc Builder MA. The polymerization temperature can be about 60 to about 200 ° C, preferably about 80 to about 160 ° C, more preferably about 90 to about 120 ° C. When the polymerization temperature is less than about 60 ° C., the polymerization rate is slow, so that the polymerization time becomes long and the production efficiency may be lowered. When the said polymerization temperature becomes higher than about 200 degreeC, the polymer which cannot perform a restart reaction by chain transfer reaction etc. may produce | generate.

  Although it does not specifically limit as a nitroxide compound in the method of (1b), For example, TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy), di-tert- butyl-nitroxide (DBN), 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-carboxy TEMPO), 4-oxo-TEMPO, tetramethyl-isoindoline-1-oxyl, tetraethyl-isoindoline-1-oxyl, N-tert-butyl-N- [1-diethylphosphono- (2,2-dimethylpropyl)] nitroxide (hereinafter abbreviated as DEPN), 2,2,5-trimethyl-4-phenyl-3-azahexane-3 -Is nitroxide (hereinafter abbreviated as TIPNO) and the like easy to control the polymerization rate and molecular weight? , It can be preferably used DEPN and TIPNO.

  In the method (1b), the polymerization is preferably carried out in the same temperature range as in (1a), but the polymerization reaction is carried out as described in Macromolecules, 1994, Vol. 27, page 7228. As a preliminary reaction for carrying out the reaction, a mixture containing a nitroxide compound, a radical polymerization initiator and a monomer is stirred at a temperature lower than the above polymerization temperature for several hours to produce an amino ether compound, and then the reaction temperature is raised to make a living It is preferable to perform radical polymerization.

  The radical polymerization initiator in the method (1b) is not particularly limited, and examples thereof include benzoyl peroxide, paramentane hydroperoxide, cumene hydroperoxide, lauroyl peroxide, cyclohexanone peroxide, 3, 3 , 5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, tert-butyl peroxypivalate, 1,1′-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3 , 3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2′-di (tert-butylperoxy) butane, tert-butylhydroxyperoxide, 2, -Dimethylhexane-2,5-dihydroperoxide, di-tert-butyl peroxide, di-n-propyl peroxydicarbonate, tert-hexylperoxy-2-ethylhexanoate, 1,3-bis ( tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, decanoyl peroxide, lauroyl Peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoyl) -Oxy) peroxide polymerization initiators such as hexane and hydrogen peroxide; 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2, 2′-azobis (2-methylpropionate), 2,2′-di (2-hydroxyethyl) azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert -Butylazo) -2-cyanopropane, 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl 2,2'-azobis (2-methylpropionate), azo polymerization initiators such as 2,2′-azobis- (N-butyl-2-methylpropionamide), persulfate initiators such as potassium persulfate and sodium persulfate, Examples thereof include a redox type initiator composed of a peroxide and a reducing agent.

The molar ratio of the nitroxide compound to the radical polymerization initiator in the method (1b) is about 0.1 to about 5.0, preferably about 0.2 to about 2.0, in the former / latter ratio. It is a range. When the molar ratio exceeds about 5.0, the polymerization rate may decrease and the polymerization time may become longer. When the molar ratio is less than about 0.1, a dead polymer in which a nitroxide compound is not added to the growing end may be generated. The organic / inorganic composite fine particles (B) are prepared by reacting a living polymer (b ₁ ), inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and an optional unsaturated monomer (b ₃ ) in the presence of a solvent. Since it can be obtained by evaporating the solvent as desired, when producing the living polymer (b ₁ ), the radical polymerization is initiated with the nitroxide compound so that the production of dead polymers that cannot perform these reactions is minimized. It is preferable to adjust the molar ratio with the agent within the range of the molar ratio.

  In this specification, the “living radical polymerization initiator” is an initiator capable of initiating a radical polymerization reaction of a polymerizable unsaturated monomer, and the radical polymerization reaction is a polymerization of a living radical polymerization reaction. It means an initiator that proceeds by mechanism.

（式中、
Ｒ¹は、炭素原子数が１〜３の、直鎖又は分岐鎖のアルキル基であり、そして
Ｒ²は、水素原子、炭素数が１〜８の、直鎖又は分子鎖の、アルキル基、フェニル基、アルカリ金属、又はＮ₄Ｈ⁺である）
で表される化合物が挙げられる。 The living polymer (b ₁ ) used in the present invention is prepared by adding an amino ether compound (b ₁₁ ) or a nitroxide compound and a radical polymerization initiator as a living radical polymerization initiator, and then living a living radical of an unsaturated monomer (b ₁₂ ). It is obtained by carrying out polymerization.
Examples of the amino ether compound (b ₁₁ ) include benzoyloxy-2-[(2,2,6,6-tetramethyl-1-piperidinyl) oxy] -2-phenylethyl (BS-TEMPO), and 2- Benzoyloxy-1-phenylethyl-di-tert-butyl-nitroxide (BS-DBN), as well as the following formula (1):

(Where
R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a hydrogen atom, a linear or molecular alkyl group having 1 to 8 carbon atoms, A phenyl group, an alkali metal, or N ₄ H ⁺ )
The compound represented by these is mentioned.

An example of the compound represented by the above formula (I) is BlocBuilder MA manufactured by Arkema.
Living radical polymerization using the above BlocBuilder MA can be performed by heating a mixture containing a polymerizable unsaturated monomer and Bloc Builder MA.
The amino ether compound (b ₁₁ ) can also be obtained by stirring a mixture containing a nitroxide compound, a radical polymerization initiator and a polymerizable unsaturated monomer for several hours at a temperature lower than the polymerization temperature.

Examples of the nitroxide compound for obtaining the amino ether compound (b ₁₁ ) include TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxy), di-tert-butyl-nitroxide (DBN), 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl (4-carboxy TEMPO), 4-oxo-TEMPO, tetramethyl-isoindoline-1-oxyl, tetraethyl-isoindoline-1-oxyl, N-tert-butyl-N- [1-diethylphosphono- (2,2-dimethylpropyl)] nitroxide (hereinafter abbreviated as DEPN), 2,2,5-trimethyl-4-phenyl-3-azahexane-3 -Nitroxide (hereinafter abbreviated as TIPNO) and the like, and from the ease of polymerization rate and molecular weight control DEPN and TIPNO are preferred.

The radical polymerization initiator for obtaining the amino ether compound (b ₁₁ ) is not particularly limited, and examples thereof include benzoyl peroxide, paramentane hydroperoxide, cumene hydroperoxide, lauroyl peroxide, cyclohexanone peroxide. 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, tert-butylperoxypivalate, 1,1′-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxide) Oxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, 2,2′-di (tert-butylperoxy) butane, tert-butylhydroxypa Oxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-tert-butyl peroxide, di-n-propyl peroxydicarbonate, tert-hexylperoxy-2-ethylhexanoate, 1 , 3-bis (tert-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, deca Noyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,5-dimethyl-2,5 Peroxide polymerization initiators such as di (benzoylperoxy) hexane and hydrogen peroxide; 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2′-azobis- (2,4-dimethyl) Valeronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-di (2-hydroxyethyl) azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (t-butylazo) -2-cyanopropane, 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl-2,2′- Azobis 2-methylpropionate), 2,2′-azobis- (N-butyl-2-methylpropionamide) and other azo polymerization initiators, persulfate initiators such as potassium persulfate and sodium persulfate, Examples thereof include a redox initiator composed of an oxide and a reducing agent.

The molar ratio of the nitroxide compound to the radical polymerization initiator in the reaction for obtaining the amino ether compound (b ₁₁ ) is preferably in the range of about 0.1 to about 5.0, and about 0.2 to More preferably, it is in the range of about 2.0. When the molar ratio exceeds about 5.0, the polymerization rate may decrease and the polymerization time may become longer. When the molar ratio is less than about 0.1, a dead polymer in which a nitroxide compound is not added to the growing end may be generated.

The unsaturated monomer (b ₁₂ ) that can be used to obtain the living polymer (b ₁ ) is not particularly limited as long as it is capable of living radical polymerization. Things can be mentioned.

  (I) alkyl or cycloalkyl (meth) acrylate: for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl ( (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) ) Acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate.

(Ii) Unsaturated monomer having an isobornyl group: for example, isobornyl (meth) acrylate.
(Iii) Unsaturated monomer having an adamantyl group: for example, adamantyl (meth) acrylate and the like.
(Iv) Unsaturated monomer having a tricyclodecenyl group: for example, tricyclodecenyl (meth) acrylate.

(V) Aromatic ring-containing unsaturated monomer: For example, benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene and the like.
(Vi) Unsaturated monomer having an alkoxysilyl group: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) Acryloyloxypropyltriethoxysilane and the like.

(Vii) Unsaturated monomer having a fluorinated alkyl group: for example, perfluoroalkyl (meth) acrylate such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate; fluoroolefin and the like.
(Viii) An unsaturated monomer having a photopolymerizable functional group such as a maleimide group.
(Ix) Vinyl compound: For example, N-vinyl-2-pyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate and the like.

(X) Phosphoric acid group-containing unsaturated monomer: for example, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxypropyl acid phosphate, 2-methacryloyloxypropyl acid phosphate, and the like.
(Xi) Hydroxyl group-containing unsaturated monomer: For example, (meta) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. ) Monoesterified product of acrylic acid and C2-8 dihydric alcohol; ε-caprolactone modified product of monoesterified product of (meth) acrylic acid and C2-8 dihydric alcohol; N-hydroxy Methyl (meth) acrylamide; allyl alcohol; (meth) acrylate having a polyoxyethylene chain having a hydroxyl group at the molecular end.

(Xii) Carboxyl group-containing unsaturated monomer: For example, (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like.
(Xiii) Nitrogen-containing unsaturated monomer: For example, (meth) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylamino Propyl (meth) acrylamide, methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 2- (methacryloyloxy) ethyltrimethylammonium chloride, adducts of glycidyl (meth) acrylate and amines.

(Xiv) Unsaturated monomer having at least two polymerizable unsaturated groups in one molecule: for example, allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc.
(Xv) Epoxy group-containing unsaturated monomer: for example, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate 3,4-epoxycyclohexylpropyl (meth) acrylate, allyl glycidyl ether, 4- (glycidyloxy) butyl (meth) acrylate, and the like.

(Xvi) (meth) acrylate having a polyoxyethylene chain whose molecular end is an alkoxy group.
(Xvii) unsaturated monomers having a sulfonic acid group: for example, 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; sodium salts of these sulfonic acids And ammonium salts.

  (Xviii) Unsaturated monomer having a UV-absorbing functional group: for example, 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxy Propoxy) benzophenone, 2,2′-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2′-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and the like.

  (Xix) photostable unsaturated monomer: for example, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6- Tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6 -Tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6- Tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-te La-methylpiperidine and the like.

(Xx) Unsaturated monomer having a carbonyl group: for example, acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinyl alkyl ketone having about 4 to about 7 carbon atoms (for example, vinyl Methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like.
(Xxi) An unsaturated monomer having an acid anhydride group: for example, maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
Unsaturated monomer (b ₁₂₎ may be used alone or in combination of two or more kinds.

The living polymerization reaction for obtaining the living polymer (b ₁ ) by heating the mixture containing the amino ether compound (b ₁₁ ) and the unsaturated monomer (b ₁₂ ) is preferably about 60 to about 200 ° C., more preferably about It is carried out at 80 to about 160 ° C, and more preferably at about 90 to about 120 ° C. When the polymerization temperature is less than about 60 ° C., the polymerization rate is slow, so the polymerization time becomes long, and the production efficiency may decrease. When the polymerization temperature is higher than about 200 ° C., a polymer that cannot be restarted may be generated due to a chain transfer reaction or the like.

  In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylic acid” means acrylic acid or methacrylic acid. In addition, “(meth) acryloyl” means acryloyl or methacryloyl, and (meth) acrylamide ”means“ acrylamide or methacrylamide ”.

  The living radical polymerization described above may be performed without a solvent or may be performed in a solvent. Examples of the solvent include aromatic compounds such as benzene, toluene, xylene, and ethylbenzene, hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclohexane, cycloheptane, and mineral spirits, ethyl acetate, n-butyl acetate, Ester solvents such as isobutyl acetate, methyl cellosolve acetate, butyl carbitol acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, ethyl 3-ethoxypropionate, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone , Methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol, ethylene Alcohol solvents such as glycol monomethyl ether and ethylene glycol monoethyl ether, ether solvents such as n-butyl ether, dioxane, and ethylene glycol dimethyl ether, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, water, etc., or combinations thereof be able to.

The number average molecular weight of the living polymer (b ₁ ) obtained by living radical polymerization is preferably in the range of about 500 to about 500,000, more preferably about 1,000 to about 30,000. This is because the organic-inorganic composite fine particles (B) in the dispersion state have a low handling viscosity.

  In this specification, the number average molecular weight and the weight average molecular weight are the retention time (retention capacity) measured using a gel permeation chromatograph (GPC) and the retention time of a standard polystyrene with a known molecular weight measured under the same conditions. (Retention capacity) is a value obtained by converting to the molecular weight of polystyrene. Specifically, “HLC8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G-4000HXL”, “TSKgel G-3000HXL”, “TSKgel G-2500HXL” are used as columns. ”And“ TSKgel G-2000HXL ”(trade names, all manufactured by Tosoh Corporation), a differential refractometer is used as a detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: It can be measured under the condition of 1 mL / min.

In the living radical polymerization for obtaining the living polymer (b ₁ ), the polymerization rate of the unsaturated monomer (b ₁₂ ) may be about 100% by mass or less than about 100% by mass. Even when the polymerization rate is less than about 100% by mass, the reaction between the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the desired unsaturated monomer (b ₃ ) Of the unsaturated monomer (b ₁₂ ) in the living radical polymerization for obtaining the living polymer (b ₁ ), an unreacted monomer (hereinafter sometimes referred to as “unreacted unsaturated monomer (b ₁₂ )”). Can be done in the presence.

The polymerization rate of the unsaturated monomer (b ₁₂ ) in the living radical polymerization for obtaining the living polymer (b ₁ ) is about 30% by mass or more, preferably about 50% by mass or more, more preferably about 80% by mass or more. be able to. When the polymerization rate is less than about 30% by mass, in the reaction of a living polymer (b ₁ ) described later, inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and an unsaturated monomer (b ₃ ) as desired. The reaction time becomes long and the production efficiency may be reduced. In addition, the unreacted unsaturated monomer (b ₁₂ ), the solvent used in the polymerization, etc. are removed under reduced pressure, or the living polymer (b ₁ ) is precipitated using a solvent that does not dissolve the living polymer (b ₁ ). After isolating (b ₁ ), it may be used for the reaction with inorganic fine particles (b ₂ ) having a polymerizable unsaturated group.

In the production of the living polymer (b ₁ ), the living radical polymerization reaction is preferably performed while the liquid layer and the gas phase of the reaction system in the reaction vessel are replaced with an inert gas and stirred. Examples of the inert gas include nitrogen gas and argon gas. The reaction temperature, reaction time, and the like can be appropriately selected depending on the molecular weight of the amino ether compound (b ₁₁ ), the type of unsaturated monomer (b ₁₂ ), and the like. The pressure during the polymerization is usually normal pressure, but may be increased or decreased.

[Inorganic fine particles having a polymerizable unsaturated group (b ₂ )]
The inorganic fine particles (b ₂ ) having a polymerizable unsaturated group can be obtained by reacting inorganic fine particles with a monomer having a hydrolyzable silyl group. As the inorganic fine particles, any inorganic fine particles can be used as long as they form a covalent bond by reaction with a monomer having a hydrolyzable silyl group described later and can be surface-modified with a polymerizable unsaturated group. Examples of such inorganic fine particles include silica fine particles, zinc oxide fine particles, titanium oxide fine particles, zirconium oxide fine particles, aluminum oxide fine particles, tin oxide fine particles, and composite oxide fine particles containing these as main components. Among these, silica fine particles, particularly colloidal silica which is silica fine particles having a hydroxyl group and / or an alkoxy group on the particle surface and dispersed in a dispersion medium is preferable.

Examples of the dispersion medium include water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; polyhydric alcohol solvents such as ethylene glycol; ethylene glycol monoethyl ether, ethylene glycol Examples thereof include polyhydric alcohol derivatives such as monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol. As the dispersion medium, a lower alcohol solvent having 3 or less carbon atoms is preferable. This is because it is easy to remove in the solvent removal step in the production of the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group.

  Examples of the colloidal silica include methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, PGM-ST, ST-UP, ST-OUP, ST-20, ST-40. ST-C, ST-N, ST-O, ST-50, ST-OL (all manufactured by Nissan Chemical Industries, Ltd.), Adelite AT-20A, Adelite AT-2045 (manufactured by Adeka Co., Ltd., trade name) Can be mentioned.

The average primary particle size of the colloidal silica is preferably about 1 to about 200 nm, more preferably about 5 to about 80 nm. When the average primary particle diameter is less than about 1 nm, when the organic / inorganic composite fine particles (B) are used in a mixture with other organic materials, the effect of improving the mechanical properties and the like of the materials may be reduced. When the average primary particle diameter is about 200 nm or more, the transparency of the material may be impaired.
In this specification, the “average primary particle diameter” means a median diameter (d50) of a volume-based particle size distribution measured by a dynamic light scattering method. For example, a nanotrack particle size distribution measuring apparatus manufactured by Nikkiso Co., Ltd. is used. Can be measured.

  Examples of the monomer having a hydrolyzable silyl group include 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 2 -(Meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 2- (meth) acryloyloxyethylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, Examples include allyltriethoxysilane, a monomer having a hydrolyzable silyl group obtained by a reaction between various silane coupling agents and an unsaturated compound, or a hydrolyzate thereof.

The method for reacting the silica fine particles with the monomer having a hydrolyzable silyl group is not particularly limited. For example, [i] a method in which silica fine particles and a monomer having a hydrolyzable silyl group are mixed in the presence of an organic solvent containing water and hydrolytic condensation is performed, and [ii] water is added in the presence of an organic solvent containing water. The method of condensing the hydrolyzate obtained after hydrolyzing the monomer which has a decomposable silyl group, and silica fine particles is mentioned.
Here, the water used in these production methods may be water contained in the raw material, for example, water that is a dispersion medium of colloidal silica.

A method for producing inorganic fine particles (b ₂ ) having a polymerizable unsaturated group will be described more specifically. The inorganic fine particles (b ₂ ) having a polymerizable unsaturated group include, for example, a colloidal silica dispersion medium in the presence of colloidal silica, a monomer having a hydrolyzable silyl group, and optionally a lower alcohol, and a lower alcohol. (Including a lower alcohol produced by hydrolyzing a monomer having a hydrolyzable silyl group) is azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium has the above high boiling point. It can manufacture by making it dehydrate-condensation reaction under a heating, after substituting for the solvent of, or after substitution.

  In this production method, if necessary, a hydrolysis catalyst is added to a mixture of colloidal silica, which is fine silica particles, a monomer having a hydrolyzable silyl group, and a desired lower alcohol, and the mixture is stirred at room temperature or under heating. According to the method, a monomer having a hydrolyzable silyl group is hydrolyzed. Subsequently, the dispersion medium of colloidal silica and the lower alcohol are azeotropically distilled together with a solvent having a boiling point higher than that of the lower alcohol under normal pressure or reduced pressure, and the dispersion medium is replaced with the above-mentioned high boiling point solvent. At a temperature of 150 ° C., preferably about 80 to about 130 ° C., the non-volatile component concentration is usually kept in the range of about 5 to about 50 mass%, and the reaction is conducted for about 0.5 to about 10 hours with stirring. After the reaction, it is preferable to azeotropically distill water and lower alcohol generated by condensation reaction or hydrolysis together with a solvent having a boiling point higher than that of the lower alcohol.

  Examples of the solvent used in the above reaction include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cyclohexane; halogenated hydrocarbons such as trichloroethylene and tetrachloroethylene; 1,4-dioxane, dibutyl ether, and the like. Ethers; ketones such as methyl isobutyl ketone; esters such as n-butyl acetate, isobutyl acetate, ethyl acetate and ethyl propionate; polyhydric alcohol derivatives such as ethylene glycol monobutyl ether;

  The non-volatile content concentration during the reaction is preferably in the range of about 5 to about 50% by mass. When the non-volatile content concentration is less than about 5% by mass, that is, the solvent exceeds about 95% by mass, the reaction time between the silica fine particles and the monomer having a hydrolyzable silyl group becomes long, and the production efficiency may decrease. On the other hand, when the non-volatile content concentration exceeds about 50% by mass, the product may be gelled.

By these production methods, the silicon atom on the surface of the silica fine particle and the silicon atom of the monomer having a hydrolyzable silyl group are bonded via an oxygen atom, whereby the silica fine particle and the monomer having a hydrolyzable silyl group are chemically synthesized. Inorganic fine particles (b ₂ ) having a polymerizable unsaturated group bonded to are obtained.

The blending ratio of the monomer having a hydrolyzable silyl group in obtaining the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group is preferably about 0.2 parts by mass to about 95 parts per 100 parts by mass of the silica fine particles. Parts by weight, more preferably from about 0.5 parts by weight to about 90 parts by weight, and even more preferably from about 1.0 parts by weight to about 80 parts by weight. When the proportion of the monomer having a hydrolyzable silyl group is less than about 0.2 parts by mass, the organic / inorganic composite fine particles (B) to be produced may be poor in stability in the dispersion medium. When the proportion of the monomer having a hydrolyzable silyl group is more than about 95 parts by mass, the monomer having a hydrolyzable silyl group remains unreacted in the reaction with the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group. May remain.

[Unsaturated monomer (b ₃ )]
The organic / inorganic composite fine particles (B) also react the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the unsaturated monomer (b ₃ ) in the presence of a solvent. It can also be obtained by evaporating the solvent if desired.

The unsaturated monomer (b ₃ ) can be one listed in the section of the unsaturated monomer (b ₁₂ ) for producing the living polymer (b ₁ ), or a combination thereof. Further, the polymerization rate of the unsaturated monomer (b ₁₂ ) in the production of the living polymer (b ₁ ) is less than about 100%, and the unreacted unsaturated monomer (b ₁₂ ) is converted from the living polymer (b ₁ ). When brought in, the unreacted unsaturated monomer (b ₁₂ ) is included in the unsaturated monomer (b ₃ ). The amount of the unsaturated monomer (b ₃ ) used can be about 230 parts by mass or less, preferably about 100 parts by mass or less with respect to 100 parts by mass of the living polymer (b ₁ ). When unsaturated monomer (b ₃₎ is more than about 230 parts by weight, there is a case where the reaction time decreases longer be manufactured efficiently.

The organic / inorganic composite fine particles (B) are prepared by reacting a living polymer (b ₁ ), inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and an unsaturated monomer (b ₃ ) as desired in the presence of a solvent. And optionally by evaporation of the solvent.
When the solvent is not evaporated, the organic / inorganic composite fine particles (B) are obtained as a dispersion, and when the solvent is evaporated, the organic / inorganic composite fine particles (B) are obtained as a powder.

In the above reaction, a catalyst, a radical polymerization initiator and the like are appropriately added to the living polymer (b ₁ ) obtained by the nitroxide compound-based radical polymerization method, for example, the living polymer (b ₁ ) and polymerizable unsaturated The organic-inorganic composite fine particles (B) can be obtained as a dispersion by heating a mixture of the inorganic fine particles (b ₂ ) having a group and the desired unsaturated monomer (b ₃ ).

The total mass of the living polymer (b ₁ ) and the optionally unsaturated monomer (b ₃ ) and the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group is about 5: about 95 to about 95: about 5, preferably about 20: about 80 to about 80: about 20. When the mass ratio is less than about 5:95, the storage stability of the resulting organic-inorganic composite fine particles (B) may be inferior. When the mass ratio is greater than about 95: about 5, when the organic / inorganic composite fine particles (B) are used by mixing with other organic materials, the effect of improving the mechanical properties of the organic materials may be reduced. .

The reaction of the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the optionally unsaturated monomer (b ₃ ) can be carried out in a solvent. The total mass concentration of the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the optionally unsaturated monomer (b ₃ ) is about 10% by mass to about 90% by mass, preferably Can be from about 20% to about 70% by weight. When the total mass concentration is less than about 10 mass%, the reaction time may be long and the production efficiency may be reduced. When the total mass concentration is higher than about 90% by mass, the viscosity of the reaction system becomes high and stirring may be difficult. As the solvent, the solvent used in the production of the living polymer (b ₁ ), the solvent used as a dispersion medium for the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the like can be used.

Reaction between the growing terminal of the living polymer (b ₁ ) and the polymerizable unsaturated group of the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, or the growing terminal of the living polymer (b ₁ ) and the polymerizable unsaturated group The reaction between the polymerizable unsaturated group of the inorganic fine particles (b ₂ ) having a group and the polymerizable unsaturated group of the unsaturated monomer (b ₃ ) is inactive in the gas phase in the reaction vessel as in the case of the living radical polymerization. It is preferable to carry out stirring while substituting with gas. The reaction temperature and reaction time can be appropriately selected depending on the method of living radical polymerization in the production of the living polymer (b ₁ ), the type of unsaturated monomer (b ₃ ), etc. The reaction temperature is about 0 to about 250 ° C. The reaction time is preferably in the range of 1 to 72 hours. The reaction is usually performed under normal pressure, but can be performed under pressure or reduced pressure.

The polymerization rate of the unsaturated monomer (b ₃ ) in the above reaction can be about 90% by mass or more, preferably about 95% by mass or more. When the polymerization rate of the unsaturated monomer (b ₃ ) is less than about 90% by mass, in the active energy ray-curable composition of the present invention, unreacted unsaturated monomer (b ₃ ) in the organic-inorganic composite fine particles (B). Odor due to the odor may be a problem. The unreacted monomer may be consumed by extending the reaction time, or when the amount of unreacted monomer is small, a radical polymerization initiator may be added and consumed by the polymerization reaction. Moreover, in the obtained organic-inorganic composite fine particles (B), the solvent may be replaced with another solvent such as water, if desired.

The organic-inorganic composite fine particles (B) are produced by reacting the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the desired unsaturated monomer (b ₃ ). . In the above reaction, the growth terminal of the living polymer (b ₁ ) attacks the polymerizable unsaturated group on the inorganic fine particle or the polymerizable unsaturated group of the unsaturated monomer (b ₃ ) in an active carbon radical state, It proceeds by the reaction mechanism of living radical polymerization.

  In the above reaction mechanism, the viscosity is increased by bonding the particles or the reaction of gelling the system does not occur, so that it is possible to produce organic-inorganic composite fine particles (B) as a dispersion having a low viscosity. Because there is almost no formation of unreacted polymer that is not bonded to inorganic fine particles, even when mixed with other organic materials, the properties and functions resulting from the inorganic fine particles can be efficiently exhibited without damaging the properties. Can do.

The organic / inorganic composite fine particles (B) may have an unsaturated group. By introducing an unsaturated group into the organic / inorganic composite fine particles (B), the active energy ray-curable composition of the present invention can form a coating layer having excellent adhesion, scratch resistance and the like.
In order to introduce an unsaturated group into the organic-inorganic composite fine particle (B), for example, an organic-inorganic composite fine particle (B) having no unsaturated group is converted into a functional group (eg, hydroxyl group) possessed by the organic-inorganic composite fine particle (B). Group) and a compound having a functional group capable of reacting with the unsaturated group, for example, 2-methacryloyloxyethyl isocyanate.

[Photoinitiator (C)]
The photopolymerization initiator (C) can be used without particular limitation as long as it is an initiator that absorbs active energy rays and generates radicals.
Examples of the photopolymerization initiator (C) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone, 2, Thioxanthones such as 4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Michler's ketones; acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy Ci-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Acetophenones such as -butan-1-one, α-isohydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxycyclohexyl-phenyl-ketone; 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphine oxides such as oxide and bis (acyl) phosphine oxide; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogens such as phenacyl chloride, trihalomethylphenylsulfone, and tris (trihalomethyl) -s-triazine Compounds, peroxides such as di-tert-butyl peroxide, and combinations thereof.

  Examples of commercially available photopolymerization initiators (C) include IRGACURE-184, IRGACURE-261, IRGACURE-500, IRGACURE-651, IRGACURE-907, and IRGACURE-CGI-1700 (manufactured by Ciba Specialty Chemicals). , Trade name), Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, and Darocur-4064 (trade name, manufactured by Merck Japan Ltd.), KAYACURE-MBP, Kayacure-DETX-S , Kayacure-DMBI, Kayacure-EPA, and Kayacure-OA (trade name) manufactured by Nippon Kayaku Co., Ltd., VICURE-10, and Vicure 55 [STAUFFER Co., L D.), product name], TRIGONAL P1 [manufactured by AKZO Co., LTD., Product name], Sandray 1000 (SANDORZ Co., Ltd.), product Name], Deep (DEAP) [manufactured by APJOHN Co., LTD., Trade name], and CantaCure-PDO, CantaCure-ITX, and CantaCure-EPD [WARDBLEKINSOP Co. , LTD.), Product name] and the like.

  The content of the radically polymerizable unsaturated group-containing compound (A) is preferably about 1 to about 98 mass with respect to 100 mass parts of the solid content of the active energy ray-curable composition of the present invention, from the viewpoint of transparency. Parts, and more preferably from about 10 to about 85 parts by weight. Further, the content of the organic-inorganic composite fine particles (B) is preferably about 1 to about 70 parts by mass with respect to 100 parts by mass of the solid content of the active energy ray-curable composition of the present invention, from the viewpoint of scratch resistance. And more preferably from about 10 to about 60 parts by weight. In addition, the content of the photopolymerization initiator (C) is preferably about 1 to about 100 parts by weight with respect to 100 parts by mass of the solid content of the active energy ray-curable composition of the present invention, from the viewpoint of reactivity with active energy rays. 8 parts by weight, and more preferably about 2 to about 6 parts by weight.

[Active energy ray-curable composition]
The active energy ray-curable composition of the present invention may optionally contain additives such as UV absorbers, antioxidants, silicone additives, fluorine additives, rheology control agents, defoaming agents, release agents. Further, a silane coupling agent, an antistatic agent, an antifogging agent, a colorant and the like can be added.

  Examples of the ultraviolet absorber include 2- [4-{(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- [4-{(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, Triazine derivatives such as 3,5-triazine, 2- (2′-xanthenecarboxy-5′-methylphenyl) benzotriazole, 2- (2′-o-nitrobenzyloxy-5′-methylphenyl) benzotriazole, 2 -Xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like.

Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants.
Examples of the silicone additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified. Examples thereof include polyorganosiloxanes having an alkyl group, a phenyl group, and the like, such as a dimethylpolysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.

  The amount of the additive is not particularly limited as long as the effect is sufficiently exhibited and the ultraviolet curing is not inhibited. For example, the amount of the additive is about 0.01 with respect to 100 parts by mass of the active energy ray-curable composition. It is preferably in the range of about 10 parts by mass.

[Coating film forming method]
The active energy ray-curable composition of the present invention can form a coating film on an article by directly coating the article. It does not specifically limit as a raw material of the articles | goods which coat the active energy ray curable composition of this invention. Specific examples include metals, ceramics, glass, plastics, and wood. Further, for example, a primer layer, an electrodeposition coating layer, an intermediate coating layer, a top coating layer, etc. are formed in advance on the article by applying a primer coating, a cationic electrodeposition coating, an intermediate coating, a top coating, or the like. It may be.

  In addition, the method of coating the active energy ray-curable composition of the present invention on an article is not particularly limited. For example, roller coating, roll coater coating, spin coater coating, curtain roll coater coating, slit coater coating, Examples include spray coating, electrostatic coating, dip coating, silk printing, and spin coating.

  The active energy ray-curable composition of the present invention is applied to an article as a laminate including a film-like substrate layer and a coating film layer, which is laminated on a film-like substrate by coating, for example, to form a coating film layer. sell. The coating layer in the laminate may be cured or uncured.

Examples of the film-like substrate include polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyethylene terephthalate, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, and the like. From the viewpoint of properties, polyethylene terephthalate is preferable.
The thickness of the film-like substrate is preferably about 10 to about 250 μm, more preferably about 40 to about 200 μm, and even more preferably about 50 to about 190 μm. The film-like substrate may be subjected to a surface treatment.

  The laminate can be used as a hard coat film, and can be applied by bonding to an article. The coating layer may be cured before being applied to the article, or may be cured after being applied to the article. In addition, the laminate includes a picture layer between the film-like base material and the coating film layer, or contains a picture layer on the surface of the film-like base material opposite to the coating film layer, or a film. An adhesive layer can be included on the surface of the shaped substrate opposite to the coating layer.

  The active energy ray-curable composition of the present invention is applied on a film-like substrate, for example, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, It can be laminated by a screen printing method or the like.

  The above laminates are car exterior parts such as wheel caps, bumper moldings, foil garnishes, grill radiators, back panels, door mirror covers, door handles, automobile interior parts such as meter clusters, center clusters, center consoles, and air conditioner housings. It is suitably used for applications other than automobile parts such as mobile phones, notebook computers, and cosmetic containers.

  The active energy ray-curable composition of the present invention is applied to an article by the above-described method and the like, the formed uncured coating film is dried, and then the uncured coating film is irradiated with active energy rays. Thus, an article coated with the active energy ray-curable composition can be obtained. In addition, the active energy ray-curable composition of the present invention is laminated on a film-like substrate, the formed uncured coating film is dried, and then the uncured coating film is irradiated with active energy rays as desired. Thus, a laminate can be formed. When the laminate includes an uncured coating layer, the laminate can be applied to the article and then irradiated with active energy rays to cure the uncured coating layer in the laminate.

  The active energy ray-curable composition of the present invention has a film thickness after drying of preferably about 1 to about 50 μm, more preferably about 2 to about 30 μm, and even more preferably about 3 to about 20 μm. It is preferably applied to an article or a film-like substrate.

Examples of active energy rays to be irradiated include electron beams, ultraviolet rays, visible light, and infrared rays. When curing with ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp can be used as the light source, and the amount of light and the arrangement of the light source are adjusted as necessary. In general, it is preferable to irradiate an active energy amount of about 50 to about 5000 mJ / cm ² from one lamp having a light amount of about 80 to about 250 mW / cm ² . On the other hand, in the case of curing with an electron beam, it is preferably cured with an active energy amount of about 0.1 to about 10 Mrad from an electron beam accelerator having an acceleration voltage of about 10 to about 300 kV.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. Hereinafter, both “parts” and “%” are based on mass.

[Production of radically polymerizable unsaturated group-containing compound (A)]
[Production Example 1]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping device, 80 parts of xylene were charged, nitrogen gas was blown, and the mixture was kept at 100 ° C. with stirring. In this, 10 parts of styrene, 40 parts of methyl methacrylate were added. A mixture of 50 parts of glycidyl methacrylate and 5 parts of 2,2′-azobisisobutyronitrile was added dropwise at a uniform rate over 3 hours, and further aged at the same temperature for 2 hours. Thereafter, a mixture of 10 parts of xylene and 0.5 part of 2,2′-azobisisobutyronitrile was added dropwise to the reaction vessel over 1 hour, and after completion of the addition, the mixture was aged for 1 hour. Resin No. A solution of 1 was obtained. Acrylic resin no. The weight average molecular weight of 1 was 12,000.

[Production Example 2]
In the reaction vessel, the acrylic resin No. obtained in Production Example 1 was used. 1 solution 1055 parts (solid content 580 parts), acrylic acid 170 parts, hydroquinone monomethyl ether 0.4 parts, butyl acetate 277 parts, and triphenylphosphine 0.2 parts were charged, and the reaction vessel 80 was blown while blowing air. The temperature was raised to 0 ° C. and kept at that temperature for 5 hours. After confirming that all of the carboxyl groups and epoxy groups had reacted substantially, the mixture was cooled to a radical polymerizable unsaturated group-containing compound (A A solution of -1) was obtained. The weight average molecular weight of the radically polymerizable unsaturated group-containing compound (A-1) was 14,000.

[Production of organic-inorganic composite fine particles (B)]
[Production of Living Polymer (b ₁ )]
[Production Example 3]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 7.5 parts of BlocBuilder MA (trade name, manufactured by Arkema Co., Ltd.), 50 parts of styrene, 50 parts of butyl acrylate, and 3 -Charged 20 parts of ethyl ethoxypropionate. Thereafter, nitrogen was heated to 120 ° C. while vented to the flask, and stirred at the same temperature for 8 hours to obtain a solution of living polymer (b ₁ -1). The number average molecular weight (Mn) of the living polymer (b ₁ -1) was 5,200, the molecular weight distribution (Mw / Mn) was 1.3, and the polymerization rate (%) (Note 1) was 99%.

(Note 1) The polymerization rate was calculated by the following formula 1.
Polymerization rate (%)
= 100 × (actually measured nonvolatile content (%) / calculated nonvolatile content (%)) (Formula 1)
The “measured non-volatile content (%)” in Equation 1 is obtained by weighing 2.0 g to 2.2 g of the polymerization solution and measuring the mass of the drying residual after heating at 130 ° C. for 3 hours with a hot air drier before drying. It is expressed as a percentage with respect to the mass of the polymerization solution.

“Calculated non-volatile content (%)” in Equation 1 was calculated by Equation 2 below.
Calculated non-volatile content (%)
= 100 × (mass of unsaturated monomer used + mass of living polymerization initiator used × actually measured nonvolatile content of living polymerization initiator (%) ÷ 100) / (mass of all raw materials used) (Formula 2)
The “living polymerization initiator” in Formula 2 is a component such as an initiator, a chain transfer agent, and a terminator essential for performing living polymerization other than the monomer and the solvent. For example, when BlocBuilder MA manufactured by Arkema was used as an initiator for living polymerization, the actually measured non-volatile content (%) was 20%, so that value was used as the actually measured non-volatile content.

[Production Examples 4 to 9]
A living polymer (b ₁ -2) to (b ₁ -7) solution was obtained in the same manner as in Production Example 3 except that the formulation and conditions were changed as shown in Table 1.

[Production of inorganic fine particles (b ₂ ) having a polymerizable unsaturated group]
[Production Example 10]
In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, colloidal silica (dispersion medium: isopropanol, silica concentration: 30% by mass, average primary particle size: 12 nm, trade name: IPA-ST, manufactured by Nissan Chemical Industries, Ltd.) ) After mixing 333 parts (silica fine particles 100 parts), 3-acryloyloxypropyltrimethoxysilane 5 parts, p-methoxyphenol 0.2 parts and isopropanol 233 parts, the temperature was increased with stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system.

Then, after performing a dehydration condensation reaction at 95 ° C. for 2 hours with stirring, the temperature was lowered to 60 ° C., 0.03 part of tetrabutylammonium fluoride was added, and the mixture was further reacted for 1 hour with stirring. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. Solvent was replaced by performing azeotropic distillation by adding propylene glycol monomethyl ether several times, and inorganic fine particles (b ₂ -1) having a polymerizable unsaturated group (measured nonvolatile content 40%) Obtained as a dispersion.

[Production Examples 11 to 14]
In the same manner as in Production Example 10 except that the formulation was changed as described in Table 2, inorganic fine particles (b ₂ -2) to (b ₂ -5) having polymerizable unsaturated groups were obtained as dispersions. It was.

(Note 2) IPA-ST: Colloidal silica manufactured by Nissan Chemical Industries, Ltd., average primary particle size 10-20 nm, dispersion medium, isopropanol, silica fine particle concentration, 30% by mass (described on the website of Nissan Chemical Industries) (Excerpt from explanation)
(Note 3) IPA-ST-ZL: Colloidal silica manufactured by Nissan Chemical Industries, Ltd., average primary particle size 70-100 nm, dispersion medium, isopropanol, silica fine particle concentration, 30% by mass (described on the website of Nissan Chemical Industries) (Excerpt from explanation)

[Production of organic-inorganic composite fine particles (B)]
[Production Example 15]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 128 parts of the solution of the living polymer (b ₁ -1) obtained in Production Example 3 was obtained in Production Example 10. 244 parts of inorganic fine particles (b ₂ -1) having a polymerizable unsaturated group as a dispersion were charged. Thereafter, the mixture was heated to 120 ° C. while bubbling nitrogen through the flask, and kept at the same temperature for 10 hours while stirring. Thereafter, ethyl 3-ethoxypropionate was added and the solvent was replaced by azeotropic distillation under reduced pressure to obtain organic-inorganic composite fine particles (B-1) (measured nonvolatile content of 45%) as a dispersion. It was. The Gardner viscosity of the organic-inorganic composite fine particles (B-1) as a dispersion was A3.

[Production Examples 16 to 29]
Organic-inorganic composite fine particles (B-2) to (B-14) were obtained as dispersions in the same manner as in Production Example 15 except that the formulation was changed as shown in Table 3. Their Gardner viscosities are shown in Table 3.

[Comparative Production Example 1]
In a four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen gas inlet, 244 parts of inorganic fine particles (b ₂ -1) having a polymerizable unsaturated group obtained in Production Example 10, and styrene 50. 0 parts, 50.0 parts butyl acrylate, 20.0 parts ethyl 3-ethoxypropionate, and 2.0 parts benzoyl peroxide were charged. Then, while agitating nitrogen through the flask, it was heated to 120 ° C., and the body temperature was maintained for 10 hours while stirring. The polymerization rate was 99%. Thereafter, ethyl 3-ethoxypropionate was added, and the solvent was replaced by azeotropic distillation under reduced pressure. Organic-inorganic composite particles (B′-1) as a dispersion (measured nonvolatile content: 45%) Got. In addition, Table 4 shows the Gardner viscosity of the organic-inorganic composite particles (B′-1) as a dispersion.

[Comparative Production Example 2]
Except that the amount of benzoyl peroxide was changed from 2 parts to 1 part, in the same manner as in Comparative Production Example 1, organic-inorganic composite fine particles (B′-2) (measured nonvolatile content: 45%) were obtained as dispersions. . The polymerization rate determined from the nonvolatile content of the organic-inorganic composite fine particles (B′-2) was 99%. However, since the organic-inorganic composite fine particles (B′-2) are in a gel form, the viscosity could not be measured.

[Comparative Production Examples 3 and 4]
Except for changing the formulation as shown in Table 4, in the same manner as in Comparative Production Example 1, organic-inorganic composite fine particles (B′-3) (measured nonvolatile content of 45%) and organic-inorganic composite fine particles (B ′ -4) (A measured non-volatile content of 45%) was obtained as a dispersion. The polymerization rates of the organic-inorganic composite fine particles (B′-3) and the organic-inorganic composite fine particles (B′-4) were both 99%. Table 4 shows the Gardner viscosity of the organic-inorganic composite fine particles (B′-3) and the organic-inorganic composite fine particles (B′-4).

[Production of active energy ray-curable composition]
[Example 1]
145.5 parts (solid content 80 parts) of the radical polymerizable unsaturated group-containing compound (A-1) obtained in Production Example 2 and organic-inorganic composite fine particles (as a dispersion) obtained in Production Example 15 ( B-1) 36.4 parts (solid content 20 parts) and Darocur 1173 (trade name, manufactured by Merck Japan, photopolymerization initiator) 3.0 parts (solid content 3.0 parts) were uniformly mixed, Further, the solid content was adjusted with butyl acetate, and the active energy ray-curable composition No. 50 having a solid content of 50% was obtained. 1 was obtained.

[Examples 2 to 18]
The active energy ray-curable composition No. 50 having a solid content of 50% was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 5. 2-No. 18 was obtained.

(Note 4) EBECRYL1290: Daicel-Cytec Co., Ltd., trade name, radical polymerizable unsaturated group-containing urethane resin (Note 5) Aronix M309: Toa Gosei Co., Ltd., trade name, radical polymerizable unsaturated group-containing resin ( Note 6) KAYARAD DPHA: Nippon Kayaku Co., Ltd., trade name, radical polymerizable unsaturated group-containing polyester resin (Note 7) Darocur 1173: Merck Japan, trade name, photopolymerization initiator

[Comparative Examples 1-6]
The active energy ray-curable composition No. 50 having a solid content of 50% was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 6. 20-No. 25 was obtained.

[Example 19]
The active energy ray-curable composition No. obtained in Example 1 was applied on a film-like substrate made of a 125 μm-thick biaxially stretched PET film that had been subjected to an easy adhesion treatment. 1 was coated so that the dry film thickness was 5 μm, preheated at a drying temperature of 80 ° C. for 1 minute, and then irradiated with active energy rays using a high-pressure mercury lamp so that the irradiation amount was 500 mJ / cm ^2. , A coating layer was formed, and a laminate No. 1 was obtained. Laminate No. For one coating layer, the solvent resistance, adhesion, scratch resistance and chemical resistance were evaluated according to the following test methods. The results are shown in Table 15.

[Examples 20 to 37]
A laminate No. 1 was prepared in the same manner as in Example 19 except that the active energy ray-curable composition shown in Table 7 was used. 2-No. 18 was obtained. Laminate No. 2-No. Table 7 shows the results of 18 solvent resistance, adhesion, scratch resistance and chemical resistance.

[Comparative Examples 7-12]
Except for using the active energy ray-curable composition shown in Table 8, in the same manner as in Example 19, the laminate no. 19-No. 24 was obtained. The results of solvent resistance, adhesion, scratch resistance and chemical resistance are shown in Table 8.

[Solvent resistance (Note 8)]
Gauze soaked in acetone on the laminate coating surface is reciprocated between about 5 cm length with a load of about 1 kg / cm ² , and the number of times the coating surface is marked is counted. Evaluate solvent resistance according to standards.
◎: Traces are not made even after reciprocating 200 times. ○: Traces are made by reciprocating 100 to 200 times. Δ: Traces are made by reciprocating 50 to 99 times. Get on

[Adhesion (Note 9)]
In accordance with JIS K 5600-5-6 (1990), 100 pieces of 2 mm × 2 mm goby meshes were made on the laminate coating surface, and an adhesive tape was attached thereto, followed by abrupt peeling. Evaluate the number of goby eye coatings remaining on the surface.
A: The remaining number is 100 and there is no edge chipping in the gobang. ○: The remaining number is 100, but there is a chipping edge in the gobang. Δ: The remaining number is 90 to 99. ×: The remaining number is 89 or less

[Abrasion resistance (Note 10)]
A Taber abrasion test (abrasion wheel CF-10P, load 500 g, 100 rotations) is performed on the laminate coating film surface in accordance with ASTM D1044. Subsequently, the glossiness of the coating surface before and after the test is measured according to the specular glossiness (60 °) of JIS K5600-4-7 (1999). The gloss retention (%), which is the gloss after the test relative to the gloss before the test, is evaluated according to the following criteria.
A: Gloss retention is 90% or more. B: Gloss retention is 80% or more and less than 90%. Δ: Gloss retention is 60% or more and less than 80%. X: Gloss retention is less than 60%. It is.

[Chemical resistance (Note 11)]
0.5 mL of 1% sulfuric acid aqueous solution is dropped on the coating surface of the laminate and left in an atmosphere at a temperature of 20 ° C. and a relative humidity of 65% for 24 hours, and then the coating surface is wiped with gauze and the appearance is visually evaluated. .
◎: No abnormality on the surface of the coating film is observed. ○: A trace is observed on the surface of the coating film, but disappears when washed with water. △: Some discoloration or whitening is observed on the coating film surface. Is remarkable.

Claims (8)

An active energy ray-curable composition comprising a radical polymerizable unsaturated group-containing compound (A), organic-inorganic composite fine particles (B), and a photopolymerization initiator (C),
Was the organic-inorganic composite fine particle (B) produced by reacting the living polymer (b ₁ ) with the inorganic fine particle (b ₂ ) having a polymerizable unsaturated group in the presence of a solvent and optionally evaporating the solvent? Or the living polymer (b ₁ ), the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group, and the unsaturated monomer (b ₃ ) are reacted in the presence of a solvent and optionally the solvent is evaporated. And the living polymer (b ₁ ) added an amino ether compound (b ₁₁ ), or a nitroxide compound and a radical polymerization initiator as a living radical polymerization initiator, and the living radical polymerization of the unsaturated monomer (b ₁₂ ). Obtained by doing
The active energy ray-curable composition characterized by the above. The amino ether compound (b ₁₁ ) has the following formula (1):

(Where
R ¹ is a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a hydrogen atom, a linear or molecular alkyl group having 1 to 8 carbon atoms, A phenyl group, an alkali metal, or N ₄ H ⁺ )
The active energy ray hardening composition of Claim 1 which is a compound represented by these. The active energy ray-curable composition according to claim 1 or 2, wherein the inorganic fine particles (b ₂ ) having a polymerizable unsaturated group are colloidal silica having a polymerizable unsaturated group.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the organic-inorganic composite fine particles (B) have an unsaturated group. As a living radical polymerization initiator, an amino ether compound (b ₁₁ ), or a nitroxide compound and a radical polymerization initiator are added, and living radical polymerization of an unsaturated monomer (b ₁₂ ) is carried out to obtain a living polymer (b ₁ ). Obtaining step,
The living polymer (b ₁ ) and inorganic fine particles (b ₂ ) having a polymerizable unsaturated group are reacted in the presence of a solvent, and the solvent is evaporated if desired, or the living polymer (b ₁ ) and the polymerizable unsaturated group are polymerized. A step of forming organic-inorganic composite fine particles (B) by reacting inorganic fine particles (b ₂ ) having a saturated group with unsaturated monomers (b ₃ ) in the presence of a solvent and evaporating the solvent if desired.
A step of mixing the organic-inorganic composite fine particles (B) with the radical polymerizable unsaturated group-containing compound (A) and the photopolymerization initiator (C);
A process for producing an active energy ray-curable composition, comprising:   An article coated with the active energy ray-curable composition according to any one of claims 1 to 4.   A laminate comprising a film-like substrate layer and a cured or uncured coating layer formed from the active energy ray-curable composition according to any one of claims 1 to 4. An article having the laminate according to claim 7 on its surface,
The laminate includes a cured coating layer formed from the active energy ray-curable composition according to any one of claims 1 to 4.
Said article.