JP2011026561A - Method for producing silica dispersing element, energy-ray curable resin composition, and film - Google Patents

Abstract

An object of the present invention is to provide a production method for easily and simply producing a dispersion in which silica fine particles are dispersed in an active energy ray-curable resin composition and having excellent storage stability.
A (meth) acryloyl group and a hydroxyl group are included in a molecular structure, a (meth) acryloyl equivalent is in a range of 200 to 600 g / eq, and a hydroxyl value is in a range of 90 to 280 mgKOH / g. A wet ball mill 3 having an impeller-type separator 4 is used as a method for producing a dispersion in which silica fine particles (F) are dispersed in a (meth) acrylic polymer (B), and media and slurry are stirred inside the wet ball mill. While mixing, the silica fine particles (F) in the slurry are pulverized and dispersed in the (meth) acrylic polymer (B), and the slurry and media are separated by the action of centrifugal force in the impeller type separator. A dispersion is obtained.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a dispersion in which silica fine particles are dispersed in an active energy ray-curable resin composition and having excellent storage stability, and energy ray curing containing the dispersion obtained by the production method. The present invention relates to a mold resin composition, a film having a cured layer obtained by curing the composition, a reactive dispersion medium for silica fine particles, and a reactive dispersant for silica fine particles.

  In order to increase the hardness of the cured coating film obtained by curing the active energy ray-curable resin composition, there is a method of dispersing silica fine particles in the active energy ray-curable resin composition. Silica fine particles include colloidal silica produced by a wet method and fumed silica produced by a dry method. There are silanol groups on the surface of the silica fine particles, and the silica fine particles are hydrophilic. Therefore, it is not compatible with the organic phase which is the main component in the composition such as the active energy ray-curable monomer or oligomer. Silica fine particles have a higher specific gravity than the organic phase. Therefore, it is generally difficult to stably disperse the silica fine particles in the active energy ray-curable resin composition for a long period of time, and the active energy ray-curable resin composition containing the silica fine particles is left to stand for a long period of time. It is inferior in storage stability, such as silica fine particles agglomerating or sedimenting. In addition, the silica fine particles are usually strongly agglomerated due to intermolecular force or electrostatic force acting between the primary particles, which also adversely affects storage stability.

  As a method for stably dispersing the silica fine particles in the active energy ray-curable resin composition, for example, the surface of the silica fine particles can be made hydrophobic by subjecting the silica fine particles to a surface treatment with a reactive silane coupling agent having a hydrophobic group. However, the dispersion stability in the active energy ray-curable resin composition is sufficient even with silica fine particles obtained by the method described in Patent Document 1. Rather, when stored for 1 week at room temperature, a precipitate of silica fine particles is generated. In addition, complicated manufacturing processes such as distilling off by-products after surface treatment using a silane coupling agent and solvent concentration and solvent replacement to provide storage stability are also required. It is not excellent at all.

JP 2006-348196 (Page 12)

  The problem to be solved by the present invention is a production method for easily and simply producing a dispersion in which silica fine particles are dispersed in an active energy ray-curable resin composition and having excellent storage stability, and this production method An energy beam curable resin composition containing the dispersion obtained in the above and capable of maintaining a dispersed state stably over a long period of time, and a film having a hardened layer of the energy beam curable resin composition as a hard coat layer Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have a (meth) acryloyl group and a hydroxyl group in the molecular structure, and a (meth) acryloyl equivalent is in the range of 200 to 600 g / eq. A wet ball mill having an impeller-type separator is used as a method for producing a dispersion in which silica fine particles (F) are dispersed in a (meth) acrylic polymer (B) having a hydroxyl value in the range of 90 to 280 mgKOH / g. In the wet ball mill, the media and the slurry are stirred and mixed, and the silica fine particles (F) in the slurry are pulverized and dispersed in the (meth) acrylic polymer (B), and the impeller type separator is centrifuged. By using a method of separating the slurry and media by the action of force to obtain a dispersion, a silica dispersion with excellent storage stability can be easily and simply Heading the like can be produced, which resulted in the completion of the present invention.

That is, the present invention has a (meth) acryloyl group and a hydroxyl group in the molecular structure, a (meth) acryloyl equivalent is in the range of 200 to 600 g / eq, and the hydroxyl value is in the range of 90 to 280 mgKOH / g. A slurry containing the (meth) acrylic polymer (B) and the silica fine particles (F),
1) a cylindrical stator filled with media;
2) a slurry supply port provided at the lower end of the stator;
3) a rotationally driven shaft that is located at the axial center of the stator and that is provided with a hollow liquid discharge passage at an upper portion thereof;
4) a rotor that rotates coaxially with the shaft;
5) The supply of the wet ball mill including an impeller-type separator that is rotationally driven and is arranged coaxially on the shaft and configured to discharge the separated liquid in communication with the hollow liquid discharge path. The rotor is driven to rotate in the stator, the medium and the slurry are agitated and mixed to pulverize the silica fine particles (F) in the slurry, and to the (meth) acrylic polymer (B). Dispersing, separating the slurry and the media by the action of centrifugal force in the rotationally driven separator, and discharging the slurry attracted to the axial center of the separator from the hollow discharge passage in the shaft The present invention relates to a method for producing a dispersion.

  The present invention further relates to an energy beam curable resin composition comprising a dispersion obtained by the above production method.

  The present invention further relates to a film comprising a cured layer obtained by curing the energy beam curable resin composition on a film-like substrate.

  The present invention further has a (meth) acryloyl group and a hydroxyl group in the molecular structure, has a (meth) acryloyl equivalent in the range of 200 to 600 g / eq, and a hydroxyl value in the range of 90 to 280 mgKOH / g. The present invention relates to a reactive dispersion medium for silica fine particles characterized by containing a (meth) acrylic polymer (B).

  The present invention further has a (meth) acryloyl group and a hydroxyl group in the molecular structure, has a (meth) acryloyl equivalent in the range of 200 to 600 g / eq, and a hydroxyl value in the range of 90 to 280 mgKOH / g. The present invention relates to a reactive dispersant for silica fine particles characterized by containing a (meth) acrylic polymer (B).

  According to the present invention, a silica dispersion in which silica fine particles are dispersed in an active energy ray-curable resin composition and excellent in storage stability can be easily and easily produced. Moreover, the energy ray curable resin composition which can maintain a dispersed state stably for a long period of time can be provided. Moreover, this invention can provide the film which has a hardened layer with high hardness. Furthermore, the present invention can provide a reactive dispersant that can be suitably used for dispersing silica fine particles.

It is the schematic of the raw material slurry grinding | pulverization processing cycle provided with the said wet ball mill used with the manufacturing method of the dispersion of this invention. It is a longitudinal cross-sectional view of the said wet ball mill used with the manufacturing method of the dispersion of this invention. It is a longitudinal cross-sectional view of the supply port at the time of slurry supply of the said wet ball mill used with the manufacturing method of the dispersion of this invention. It is a longitudinal cross-sectional view of the supply port at the time of media discharge. It is a longitudinal cross-sectional view of another example of the said wet ball mill used with the manufacturing method of the dispersion of this invention. It is the figure showing the cross-sectional view of the separator of the wet ball mill shown in FIG.

  The (meth) acrylic polymer (B) used in the present invention is a reactive dispersion medium for dispersing the silica fine particles (F) or (meth) other than the (meth) acrylic polymer (B) described later. It is used as a dispersant for dispersing silica fine particles (F) in a compound having an acryloyl group, has a (meth) acryloyl group and a hydroxyl group in the molecular structure, and has a (meth) acryloyl equivalent of 200. It is the range of -600 g / eq, and the hydroxyl value is the range of 90-280 mgKOH / g. Here, (meth) acrylic equivalent means (meth) acryloyl group (meaning acryloyl group and / or methacryloyl group) solid content weight (g / eq) of (meth) acrylic polymer (B) per mole ). By setting the (meth) acryloyl equivalent in the range of 200 to 600 g / eq, high crosslink density can be achieved, and as a result, high hardness can be achieved. Further, the (meth) acrylic polymer (B) of the present invention has a hydroxyl group, and this hydroxyl group is hydrogen-bonded to a silanol group present on the surface of the silica fine particles. By setting the hydroxyl value in the range of 90 to 280 mgKOH / g, the silica surface can be densely covered with the (meth) acrylic polymer (B), and high dispersibility can be expressed. Thereby, the silica particles dispersed in the (meth) acrylic polymer (B) can be stably present in the active energy ray-curable resin composition for a long period of time.

  The (meth) acryloyl equivalent of the (meth) acrylic polymer (B) of the present invention is preferably in the range of 200 to 400 g / eq. The hydroxyl value is preferably in the range of 140 to 280 mgKOH / g. By setting the (meth) acryloyl equivalent and the hydroxyl value within these ranges, the resulting dispersion is excellent in dispersion stability, and the cured coating film of the active energy ray-curable resin composition using the dispersion is improved. It can be set as a coating film with hardness.

  The (meth) acrylic polymer (B) is obtained by, for example, subjecting a (meth) acrylic polymer (a1) having an epoxy group to a monomer (c) having a (meth) acryloyl group and a carboxyl group. A reaction product (b1) obtained by addition reaction of a monomer (d) having a (meth) acryloyl group and an epoxy group to a (meth) acrylic polymer (a2) having a carboxyl group ( b2), and a reaction product (b3) obtained by adding one isocyanate group and a monomer (e) having a (meth) acryloyl group to a (meth) acrylic polymer (a3) having a hydroxyl group. Can be mentioned.

  The (meth) acrylic polymer (a1) having an epoxy group used for the preparation of the reaction product (b1) is, for example, a homopolymerization reaction of a polymerizable monomer having a (meth) acryloyl group and an epoxy group, It can be obtained by copolymerization reaction with other polymerizable monomers.

  Examples of the polymerizable monomer having a (meth) acryloyl group and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n-butyl (meth) acrylate glycidyl, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl , Α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4 -Epoxycyclohexyl, vinylcyclohexene oxide and the like. These may be used alone or in combination of two or more.

  The (meth) acrylic polymer (a1) may be a homopolymer of a polymerizable monomer having a (meth) acryloyl group and an epoxy group, or may be a copolymer with another polymerizable monomer. When a copolymer with other polymerizable unsaturated monomer is used, [polymerizable monomer having (meth) acryloyl group and epoxy group]: [other polymerizable monomer] is 25 to 100. It is preferably used in the range of 75 to 0 parts by mass, more preferably in the range of 40 to 100 parts by mass: 60 to 0 parts by mass.

  The (meth) acrylic polymer (a2) having a carboxyl group used for the preparation of the reaction product (b2) is, for example, a homopolymerization reaction of a polymerizable monomer having a (meth) acryloyl group and a carboxyl group, It can be obtained by copolymerization reaction with other polymerizable monomers.

  Examples of the polymerizable monomer having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethylphthalic acid. Examples include 2-acryloyloxyethyl hexahydrophthalic acid and unsaturated monocarboxylic acids having an ester bond such as modified lactones thereof; maleic acid and the like. These may be used alone or in combination of two or more.

  The (meth) acrylic polymer (a2) may be a homopolymer of a polymerizable monomer having a (meth) acryloyl group and a carboxyl group, or may be a copolymer with another polymerizable monomer. When a copolymer with other polymerizable monomer is used, 25 to 100 parts by mass of [polymerizable monomer having (meth) acryloyl group and carboxyl group]: [other polymerizable monomer] : It is preferable to use in the range used as 75-0 mass part, and it is more preferable to use in the range used as 40-100 mass part: 60-0 mass part.

  The (meth) acrylic polymer (a3) having a hydroxyl group used for the preparation of the reaction product (b3) is, for example, a homopolymerization reaction of a polymerizable monomer having a (meth) acryloyl group and a hydroxyl group, It is obtained by a copolymerization reaction with a polymerizable monomer.

  Examples of the polymerizable monomer having a (meth) acryloyl group and a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 2-hydroxyethyl methacrylate. 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, and the like. These may be used alone or in combination of two or more.

  (The (meth) acrylic polymer (a3) may be a homopolymer of a polymerizable monomer having a (meth) acryloyl group and a hydroxyl group, or may be a copolymer with another polymerizable monomer. When a copolymer with other polymerizable monomer is used, 25 to 100 parts by mass of [polymerizable monomer having (meth) acryloyl group and hydroxyl group]: [other polymerizable monomer]: It is preferably used in the range of 75 to 0 parts by mass, more preferably 40 to 100 parts by mass: in the range of 60 to 0 parts by mass.

  As said other polymerizable monomer copolymerized at the time of preparation of (meth) acrylic-type polymer (a1), (a2), and (a3), the following polymerizable monomers etc. are mentioned, for example.

  (1) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acrylate-t-butyl, (meth) acrylate hexyl , Heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms such as stearyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate;

(2) (meth) having an alicyclic alkyl group such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Acrylic esters;

(3) Benzoyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acrylic acid 2- (Meth) acrylic acid esters having an aromatic ring such as hydroxy-3-phenoxypropyl;

(4) Hydroxyethyl (meth) acrylate; hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerol (meth) acrylate; lactone-modified hydroxyethyl (meth) acrylate, polyethylene (meth) acrylate Acrylic acid esters having a hydroxyalkyl group such as glycol, (meth) acrylic acid ester having a polyalkylene glycol group such as (meth) acrylic acid polypropylene glycol;

(5) Unsaturated dicarboxylic acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, dibutyl itaconate, methyl ethyl fumarate, methyl butyl fumarate, methyl ethyl itaconate;

(6) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene;

(7) Diene compounds such as butadiene, isoprene, piperylene, dimethylbutadiene;

(8) Vinyl halides and vinylidene halides such as vinyl chloride and vinyl bromide;

(9) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone;

(10) Vinyl esters such as vinyl acetate and vinyl butyrate;

(11) Vinyl ethers such as methyl vinyl ether and butyl vinyl ether;

(12) Vinyl cyanides such as acrylonitrile, methacrylonitrile, vinylidene cyanide;

(13) Acrylamide and its alkyd-substituted amides;

(14) N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

(15) Fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; or trifluoromethyltrifluorovinyl ether, penta (Per) fluoroalkyl perfluorovinyl ethers having a (per) fluoroalkyl group of 1 to 18 carbon atoms such as fluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether; 2,2,2-trifluoroethyl (meta ) Acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 2H, Fluorine-containing such as (per) fluoroalkyl (meth) acrylates having 1 to 18 carbon atoms in the (per) fluoroalkyl group such as H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Ethylenically unsaturated monomers;

(16) Silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane;

(17) N, N-dialkylaminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate Is mentioned.

  Other polymerizable unsaturated monomers used in preparing these (meth) acrylic polymers (a1), (a2) and (a3) may be used alone or in combination of two or more. You may do it.

  The (meth) acrylic polymers (a1), (a2) and (a3) can be obtained by polymerization (copolymerization) using a known and commonly used method, and the copolymerization form is not particularly limited. It can be produced by addition polymerization in the presence of a catalyst (polymerization initiator), and any of a random copolymer, a block copolymer, a graft copolymer and the like may be used. As the copolymerization method, a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method can be used.

  Here, as typical solvents that can be used for solution polymerization, for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl- ketone solvents such as n-amyl ketone, methyl-n-hexyl ketone, diethyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, and holon;

Ether solvents such as ethyl ether, isopropyl ether, n-butyl ether, diisoamyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran;

Ethyl formate, propyl formate, n-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl Ester solvents such as ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate;

Alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3-methyl-3-methoxybutanol;

  Examples thereof include hydrocarbon solvents such as toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon Naphtha 5 and Exxon Naphtha 6. These may be used alone or in combination of two or more.

  As a solvent used when polymerizing the (meth) acrylic polymer (a1) or (a2), the (meth) acrylic polymer (a1) and the monomer which are the second-stage reaction following these polymerizations Since the reaction with (c) and the reaction between the (meth) acrylic polymer (a2) and the monomer (d) are preferably performed at a high temperature of 100 to 150 ° C. in terms of reaction efficiency, the boiling point is 100. It is preferable to use a solvent having a temperature of 100 ° C. or higher, preferably 100 to 150 ° C. As a solvent used when polymerizing the (meth) acrylic polymer (a3), the (meth) acrylic polymer (a3), the monomer (e), which is a second-stage reaction following the polymerization, It is preferable to use a solvent having a boiling point of 60 ° C. or higher, preferably 60 ° C. to 150 ° C. in view of reaction efficiency.

  Further, as the above-mentioned catalyst, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvalero) can be used. Nitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and the like; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate 1,1'-bis- (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, organic peroxides such as t-hexylperoxy-2-ethylhexanoate, hydrogen peroxide, etc. Is mentioned.

  When using a peroxide as a catalyst, it is good also as a redox type initiator using a peroxide with a reducing agent.

  The reaction product (b1) is obtained by reacting the (meth) acrylic polymer (a1) having an epoxy group with the monomer (c) having a (meth) acryloyl group and a carboxyl group as described above. . Examples of the monomer (c) having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethylphthalate. Examples include acids, 2-acryloyloxyethyl hexahydrophthalic acid, and unsaturated monocarboxylic acids having an ester bond such as lactone-modified products thereof; maleic acid and the like.

  Further, after reacting an anhydride such as succinic anhydride or maleic anhydride with a hydroxyl group-containing polyfunctional (meth) acrylate monomer such as pentaerythritol triacrylate as the monomer (c), a carboxyl group-containing polyfunctional (meth) An acrylate monomer may be used. These monomers (c) having a (meth) acryloyl group and a carboxyl group may be used alone or in combination of two or more.

  The reaction between the (meth) acrylic polymer (a1) and the monomer (c) is usually performed by mixing both components and heating to about 80 to 120 ° C. The amount of the (meth) acrylic polymer (a1) and the monomer (c) used is such that the (meth) acrylic equivalent of the resulting reaction product (b1) is in the range of 200 to 600 g / eq. Although not particularly limited, usually, the mole number of the carboxyl group in the monomer (c) is in the range of 0.4 to 1.1 mol with respect to 1 mol of the epoxy group in the (meth) acrylic polymer (a1). It is preferable that

  The reaction product (b2) is obtained by reacting the (meth) acrylic polymer (a2) having a carboxyl group with the monomer (d) having a (meth) acryloyl group and an epoxy group as described above. It is done. Examples of the monomer (d) having a (meth) acryloyl group and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n-butyl (meth) acrylate glycidyl, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl , Α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4 -Epoxycyclohexyl, vinylcyclohexene oxide and the like. These may be used alone or in combination of two or more.

  The reaction between the (meth) acrylic polymer (a2) and the monomer (d) is usually performed by mixing both components and heating to about 80 to 120 ° C. The amount of the (meth) acrylic polymer (a2) and monomer (d) used is such that the (meth) acrylic equivalent of the resulting reaction product (b2) is in the range of 200 to 600 g / eq. Although not particularly limited, usually, the number of moles of epoxy groups in monomer (d) is in the range of 0.4 to 1.1 moles relative to 1 mole of carboxyl groups in (meth) acrylic polymer (a2). It is preferable that

  The reaction product (b3) is obtained by reacting the (meth) acrylic polymer (a3) having a hydroxyl group with the monomer (e) having one isocyanate group and (meth) acryloyl group as described above. can get. Examples of the monomer (e) having one isocyanate group and (meth) acryloyl group include a monomer having one isocyanate group and one (meth) acryloyl group, one isocyanate group and two (meth) acrylic groups. ) A monomer having an acryloyl group, a monomer having one isocyanate group and three (meth) acryloyl groups, a monomer having one isocyanate group and four (meth) acryloyl groups, and one isocyanate group And monomers having five (meth) acryloyl groups. As such a monomer, for example, a compound represented by the following general formula 1 can be preferably exemplified.

In general formula (1), R ₁ is a hydrogen atom or a methyl group. R ₂ is an alkylene group having 2 to 4 carbon atoms. n represents an integer of 1 to 5. These include, for example, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and specifically, Karenz AOI, Karenz MOI, Karenz BEI (trade name, Showa Denko ( And other products). Other examples include a reaction adduct of a diisocyanate compound and hydroxy acrylate. Here, as a diisocyanate compound, a well-known thing can be used without being specifically limited, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. are mentioned. The hydroxy acrylate is not particularly limited as long as it is a compound having a hydroxyl group and a (meth) acryl group, and a known one can be used. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Examples thereof include hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like. Among these, those having two or more (meth) acryloyl groups in one molecule, such as Karenz BEI, are preferable in that the crosslinking density can be increased. These may be used alone or in combination of two or more.

  The method for reacting the (meth) acrylic polymer (a3) with the monomer (e) is not particularly limited, and a known method can be employed. Specifically, for example, the monomer (e) is added dropwise to the (meth) acrylic polymer (a3), and the reaction is performed by heating to 50 to 120 ° C, more preferably 60 to 90 ° C. good. The amount of the (meth) acrylic polymer (a3) and monomer (e) used is such that the (meth) acrylic equivalent of the resulting reaction product (b3) is in the range of 200 to 600 g / eq. The number of moles of isocyanate groups in the monomer (e) is usually 0.8 to 1.2 moles with respect to 1 mole of hydroxyl groups in the (meth) acrylic polymer (a3). It is preferable to set it as the range.

  Reaction of (meth) acrylic polymer (a1) having epoxy group with monomer (c) having (meth) acryloyl group and carboxyl group, (meth) acrylic polymer (a2) having carboxyl group And a monomer having a (meth) acryloyl group and an epoxy group (d), and a (meth) acrylic polymer (a3) having a hydroxyl group and a single monomer having one isocyanate group and a (meth) acryloyl group The reaction with the body (e) can also be performed, for example, by the following method.

  Method 1: A method in which a (meth) acrylic polymer (a1) is polymerized by a solution polymerization method, and a monomer (c) having a (meth) acryloyl group and a carboxyl group is added to the reaction system and reacted.

  Method 2: A method in which a (meth) acrylic polymer (a2) is polymerized by a solution polymerization method, and a monomer (d) having a (meth) acryloyl group and an epoxy group is added to the reaction system and reacted.

  Method 3: A method in which the (meth) acrylic polymer (a3) is polymerized by a solution polymerization method, and the monomer (e) having one isocyanate group and (meth) acryloyl group is added to the reaction system and reacted.

  The (meth) acrylic polymer (B) used in the present invention is preferably a polymer having a main skeleton having a structure obtained by polymerizing a monomer having one polymerizable unsaturated double bond per molecule. However, a monomer having two or more polymerizable unsaturated double bonds may be used in combination as long as gelation during polymerization does not occur.

  As the (meth) acrylic polymer (B) used in the present invention, a monomer (c) having a (meth) acryloyl group and a carboxyl group is added to the (meth) acrylic polymer (a1) having an epoxy group. The reaction product (b1) obtained by the reaction is preferable. Among them, (meth) acrylic is added to a (meth) acrylic polymer having an epoxy group obtained by polymerizing a polymerizable monomer containing glycidyl (meth) acrylate. A reaction product obtained by addition reaction of an acid is more preferable.

  The epoxy equivalent of the (meth) acrylic polymer (a1) having the epoxy group is preferably in the range of 140 to 500 g / eq, and more preferably in the range of 140 to 300 g / eq. Furthermore, as a glass transition temperature of the (meth) acrylic-type polymer (a1) which has an epoxy group, 30 degreeC or more is preferable and it is more preferable that it is the range of 30-100 degreeC.

  In the present invention, the epoxy equivalent is a value defined in JIS-K-7236.

  In the present invention, the weight average molecular weight and the number average molecular weight were measured using a gel permeation chromatograph (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL- H manufactured by Tosoh Corporation
+ Tosoh Corporation TSKgel G5000H _XL
+ Tosoh Corporation TSKgel G4000H _XL
+ Tosoh Corporation TSKgel G3000H _XL
+ Tosoh Corporation TSKgel G2000H _XL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

  The weight average molecular weight of the (meth) acrylic polymer (B) used in the present invention is preferably in the range of 5,000 to 100,000 from the viewpoints of curing shrinkage effect and leveling properties, and 5,000 to 50. More preferably, it is in the range of 1,000.

  The (meth) acrylic polymer (B) used in the present invention has a hydroxyl group. You may make it react in the range which does not impair the effect of this invention with the hydroxyl group which (meth) acrylic-type polymer (B) has, and the isocyanate group of the monomer which has one isocyanate group and (meth) acryloyl group. Thereby, it is possible to adjust a (meth) acryloyl group equivalent and a hydroxyl group equivalent suitably.

  Examples of the monomer having one isocyanate group and (meth) acryloyl group include a monomer having one isocyanate group and one (meth) acryloyl group, and one isocyanate group and two (meth) acryloyl groups. A monomer having a group, a monomer having one isocyanate group and three (meth) acryloyl groups, a monomer having one isocyanate group and four (meth) acryloyl groups, one isocyanate group and five monomers And monomers having a (meth) acryloyl group. As such a monomer, for example, a compound represented by the following general formula 1 can be preferably exemplified.

In general formula (1), R ₁ is a hydrogen atom or a methyl group. R ₂ is an alkylene group having 2 to 4 carbon atoms. n represents an integer of 1 to 5. These include, for example, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and specifically, Karenz AOI, Karenz MOI, Karenz BEI (trade name, Showa Denko ( And other products). Other examples include a reaction adduct of a diisocyanate compound and hydroxy acrylate. Here, as a diisocyanate compound, a well-known thing can be used without being specifically limited, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. are mentioned. The hydroxy acrylate is not particularly limited as long as it is a compound having a hydroxyl group and a (meth) acryl group, and a known one can be used. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Examples thereof include hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like. Among these, those having two or more (meth) acryloyl groups in one molecule, such as Karenz BEI, are preferable in that the crosslinking density can be increased.

  The method of reacting the (meth) acrylic polymer (B) used in the present invention with a monomer having one isocyanate group and (meth) acryloyl group is not particularly limited, and a known method may be adopted. it can. Specifically, for example, a monomer having one isocyanate group and (meth) acryloyl group is added dropwise to the (meth) acrylic polymer (B) of the present invention, and 50 to 120 ° C., more preferably The reaction may be performed by heating to 60 to 90 ° C. In addition, the usage-amount of the monomer which has a (meth) acrylic-type polymer (B) and one isocyanate group and (meth) acryloyl group is the hydroxyl group (mol) of a (meth) acrylic-type polymer (B) normally. : The isocyanate group (mole) of the monomer having one isocyanate group and (meth) acryloyl group is in the range of 1: 0.1 to 1: 0.9, preferably 1: 0.1 to 1: The range is 0.7.

  In the method for producing a dispersion of the present invention, various silica fine particles can be suitably used. Examples of the silica fine particles include dry silica fine particles and wet silica fine particles. The dry silica fine particles are, for example, silica fine particles obtained by burning silicon tetrachloride in an oxygen or hydrogen flame. The wet silica fine particles are, for example, silica fine particles obtained by neutralizing sodium silicate with a mineral acid. According to the production method of the present invention, even when any silica fine particle is used, the obtained dispersion can maintain good dispersion stability over a long period of time. In addition, even when an active energy ray curable resin composition is prepared by adding the dispersion to an active energy ray curable oligomer such as urethane (meth) acrylate or epoxy (meth) acrylate or an active energy ray curable monomer, In the active energy ray-curable resin composition, the silica fine particles are stably dispersed over a long period of time.

  The silica fine particles (F) used in the present invention preferably have an average primary particle size in the range of 10 nm to 300 nm, and more preferably have an average primary particle size in the range of 10 nm to 200 nm.

  In the present invention, a silica fine particle (F) is dispersed in the (meth) acrylic polymer (B) to prepare a dispersion. The content of each component in the obtained dispersion is not particularly limited, but the (meth) acrylic polymer (B) and the silica fine particles (F) are [[meth) acrylic polymer (B)]: [ Silica fine particles (F)] are preferably contained in a range of 10 to 90 parts by mass: 90 to 10 parts by mass, and 30 to 90 parts by mass: contained in a range of 70 to 10 parts by mass. Is more preferable. The total content of the (meth) acrylic polymer (B) and the silica fine particles (F) in the dispersion obtained in the present invention is in the range of 1 to 50% by mass in terms of solid content. Preferably, it is in the range of 1 to 30% by mass.

  The slurry used in the present invention contains the (meth) acrylic polymer (B) and the silica fine particles (F), but in addition to these, (meth) acryloyl groups other than the (meth) acrylic polymer (B). You may contain the compound which has. Examples of the compound having a (meth) acryloyl group other than the (meth) acrylic polymer (B) include an active energy ray-curable monomer (M) and / or an active energy ray-curable oligomer (O). . The content of each component is not particularly limited, but the (meth) acrylic polymer (B) and the active energy ray-curable monomer (M) and / or the active energy ray-curable oligomer (O) are used as [(meth). Acrylic polymer (B)]: [active energy ray-curable monomer (M) and / or active energy ray-curable oligomer (O)] is in the range of 10 to 90 parts by mass: 90 to 10 parts by mass. It is preferable to contain, and it is more preferable to contain so that it may become the range of 30-90 mass parts: 70-10 mass parts.

  Here, in the case of using a compound having a (meth) acryloyl group other than the (meth) acrylic polymer (B), the (meth) acrylic polymer (B) is composed of the silica fine particles (F) with the meth) acrylic polymer. It can be used as a dispersant for dispersing in a compound having a (meth) acryloyl group other than the polymer (B).

  Examples of the active energy ray-curable monomer (M) include, in addition to the polymerizable monomer used as a raw material for the (meth) acrylic polymer (B), ethylene glycol di (meth) acrylate, and propylene glycol. Di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,

Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 -Butylene glycol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (Meth) acrylate, di (meth) acrylate of a compound obtained by adding caprolactone to neopentyl glycol hydroxypivalate, neopentyl glycol adipate di (meth) acrylate,

(Meth) acrylic to compounds having 3 or more hydroxyl groups such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolmethane, and a hydroxyl group-containing compound obtained by adding 1 to 20 moles of alkylene oxide to them. Examples include compounds in which three or more molecules of acid are ester-bonded.

  Examples of the active energy ray-curable oligomer (O) include acrylic (meth) acrylate other than acrylic polymer (B), urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and the like. One or more (meth) acrylate compounds selected from the group can be mentioned.

  As said urethane (meth) acrylate, the polyfunctional urethane (meth) acrylate formed by making an isocyanate compound and a hydroxyl-containing (meth) acrylate compound react is mentioned, for example. Examples of the isocyanate compound used here include aliphatic or alicyclic diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate; toluene diisocyanate, 4,4 ′ -Aromatic diisocyanates such as diphenylmethane diisocyanate; and isocyanurate type isocyanate prepolymers which are trimers of diisocyanate compounds. In addition, when the polyfunctional urethane (meth) acrylate is produced, a part of the hydroxyl group-containing (meth) acrylate compound to be reacted with the isocyanate compound is substituted with a divalent to tetravalent alcohol and / or polyol compound and polymerized. It may be good.

  Examples of the polyester (meth) acrylate include ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, ethoxylated bisphenol A, ethoxylated hydrogenated bisphenol A, propoxylated bisphenol A, and propoxylated hydrogenated. One or more selected from bisphenol A and a polyhydric alcohol having a valence of 2 or more, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, trianhydride Polyfunctionalized by further (meth) acrylate conversion of an ester polyol having a hydroxyl group obtained by esterifying one or more selected from polybasic acids represented by merit acid and pyromellitic anhydride Such as ester (meth) acrylate.

  Examples of the epoxy acrylate include propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, and hydroxypivalin. Divalent epoxy (meth) acrylate compounds obtained by adding (meth) acrylic acid to diepoxy compounds such as triglycidyl ethers of divalent alcohols such as acid neopentyl glycol, bisphenol A, and ethoxylated bisphenol A; 3 such as methylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, glycerin Epoxy tri (meth) acrylate compound having an average of 3 or more radical polymerizable unsaturated double bonds obtained by adding (meth) acrylic acid to an epoxy compound obtained by epoxidizing alcohol; at least one fragrance Polyfunctional aromatic epoxy acrylates such as phenol novolak and cresol novolak obtained by adding (meth) acrylic acid to an epoxy compound obtained by reacting a polyhydric phenol having a ring or an alkylene oxide adduct thereof with glycidyl ether, and these polyfunctional A polyfunctional alicyclic epoxy acrylate which is a hydrogenated type of an aromatic epoxy acrylate; and further urethanated with a secondary hydroxyl group present in the molecule and one isocyanate group of a diisocyanate compound; Hydroxyl group ( Urethane-modified epoxy acrylate obtained by reacting a motor) acrylate.

  Among these, polyester (meth) acrylates and urethane (meth) acrylates each having an average of 3 or more radically polymerizable unsaturated double bonds are particularly preferred because the cured coating film has good wear resistance.

  You may add an organic solvent to the slurry used by this invention as needed. The slurry preferably contains an organic solvent (S).

  Examples of the organic solvent (S) used in the present invention include ketones such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), cyclic ethers such as tetrahydrofuran (THF) and dioxolane, methyl acetate, ethyl acetate, Examples include esters such as butyl acetate, aromatics such as toluene and xylene, alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether, and these can be used alone or in combination. However, among these, methyl ethyl ketone, which is a synthetic solvent for the reactive dispersant, is preferable from the viewpoints of volatility during coating and solvent recovery.

  As the usage-amount of the said organic solvent, the range of 150-500 mass parts is preferable with respect to a total of 100 mass parts of a (meth) acrylic-type polymer (B) and a silica fine particle (F), Especially 200-300 mass parts is preferable. The range is preferable because the separation of the slurry and the medium is good during the bead mill operation, and the time required for the slurry concentration is short.

  When preparing the slurry, it is preferable to add silica fine particles (F) after adding an organic solvent to the (meth) acrylic polymer (B) to obtain an organic solvent solution.

  You may add various additives to the slurry used by this invention as needed.

  Examples of various additives used in the present invention include a coupling agent. As the coupling agent, for example, vinyl silane coupling agent, epoxy silane coupling agent, styrene silane coupling agent, methacryloxy silane coupling agent, acryloxy silane coupling agent, amino Silane coupling agent, ureido silane coupling agent, chloropropyl silane coupling agent, mercapto silane coupling agent, sulfide silane coupling agent, isocyanate silane coupling agent, aluminum A silane coupling agent etc. are mentioned.

  Examples of vinyl-based silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacrylic Loxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxy Hydrochloride of silyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane , Special aminosilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate Propyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane Can be mentioned.

  Examples of the epoxy-based silane coupling agent include diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxy. Examples thereof include propylmethyldiethoxysilane and 3-bridoxypropyltriethoxysilane.

  Examples of the styrene-based silane coupling agent include p-styryltrimethoxysilane.

  Examples of methacryloxy-based silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Is done.

  Examples of the acryloxy-based silane coupling agent include 3-acryloxypropyltrimethoxysilane.

  Examples of amino silane coupling agents include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and N-2 (aminoethyl) 3. -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-amino And propyltrimethoxysilane.

  Examples of ureido silane coupling agents include 3-ureidopropyltriethoxysilane.

  Examples of the chloropropyl silane coupling agent include 3-chloropropyltrimethoxysilane.

  Examples of mercapto-based silane coupling agents include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethinesilane, and the like.

  Examples of the sulfide-based silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide.

  Examples of the isocyanate-based silane coupling agent include 3-isocyanatopropyltriethoxysilane.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

In the method for producing a dispersion according to the present invention, the slurry described above is used.
1) a cylindrical stator filled with media;
2) a slurry supply port provided at the lower end of the stator;
3) a rotationally driven shaft that is located at the axial center of the stator and that is provided with a hollow liquid discharge passage at an upper portion thereof;
4) a rotor that rotates coaxially with the shaft;
5) The supply of the wet ball mill including an impeller-type separator that is rotationally driven and is arranged coaxially on the shaft and configured to discharge the separated liquid in communication with the hollow liquid discharge path. In the stator, the rotor is driven to rotate in the stator, and the media and slurry are stirred and mixed to pulverize the silica fine particles in the slurry and disperse them in the dispersing agent. The slurry and the medium are separated by the action of centrifugal force, and the slurry attracted to the axial center portion of the separator is discharged from a hollow discharge passage in the shaft.

  Hereinafter, the manufacturing method of the present invention using the wet ball mill as described above will be described in detail with reference to the drawings.

  In FIG. 1, the slurry extracted by the raw material pump 2 from the raw material tank 1 for storing the slurry is supplied to the wet ball mill 3 from the supply port 16. Specific examples of the wet ball mill include a cylindrical stator 7 in FIG. The stator 7 is filled with a medium, and the slurry and the medium are stirred and mixed by a rotor 11 that is driven to rotate, whereby the silica fine particles (F) are pulverized and dispersed in the (meth) acrylic polymer (B). In addition, the medium and the slurry are separated by the action of centrifugal force by the impeller-type separator 4 that is driven to rotate. At this time, the medium with a high specific gravity is blown outward in the radial direction, while the slurry with a low specific gravity is attracted to the axial center of the separator 4 and passes through the hollow liquid discharge passage 9 provided at the upper part of the shaft 5. Then, the silica fine particles are circulated and pulverized by being returned to the tank 1 via the valve 64. The particle size of the slurry is appropriately measured during the cyclic pulverization, and the process ends when the desired value is reached.

  In the production method of the present invention, the circulation flow rate at which the slurry is supplied to the wet ball mill 3 by the raw material pump 2 is usually in the range of 30 to 100 L / hour and 50 to 80 L / hour per liter of the internal volume of the wet ball mill 3. The range of is preferable. By setting the circulation flow rate within this range, the residence time of the slurry in the wet ball mill 3 becomes a suitable condition and the dispersion efficiency is increased. At this time, the time required for dispersion is usually preferably in the range of 5 to 60 minutes, more preferably in the range of 10 to 40 minutes.

  For example, various micro beads are used as the medium filled in the stator 7. Examples of the microbead material include zirconia, glass, titanium oxide, copper, and zirconia silicate.

  As for the particle size of the media, the separation of the media from the slurry in the separator 4 is good, the silica fine particles are pulverized well in the rotor 11, the time required for dispersion is not long, and the silica fine particles are reduced. The average particle size is preferably in the range of 15 to 300 μm, more preferably in the range of 15 to 50 μm in terms of the median diameter.

  The overdispersion phenomenon refers to a phenomenon in which a new active surface is generated by the destruction of silica fine particles and reaggregation occurs. When overdispersed, the dispersion becomes jelly-like.

  It is preferable that the filling rate of the medium in the stator is usually in the range of 80 to 90% by volume of the stator internal volume. By setting the filling rate within the range of 80 to 90% by volume of the stator internal volume, the power required to obtain a unit weight of product slurry is minimized. That is, grinding can be performed most efficiently.

  The procedure for supplying the slurry to the stator 7 is as follows. After the medium is filled in the stator 7 of the wet ball mill 3, the motor 12 is first driven with the valves 58, 59 and 60 closed and the valves 61, 62 and 64 opened, and then the raw material pump 2 is driven. The rotor 11 and the separator 4 are driven to rotate by driving the former motor 12, while the raw material slurry in the raw material tank 1 is sent to the introduction port 27 of the supply port 16 by a certain amount by driving the latter raw material pump 2. Is fed into the wet ball mill through a slit formed between the edge of the valve seat 24 and the valve body 25.

  When the motor 12 is driven and the rotor 11 and the separator 4 are rotated, the larger the rotational speed and the higher the peripheral speed, the greater the centrifugal force, and the greater the impact when the medium collides with the silica particles. The peripheral speed when using a medium having a particle diameter of 15 μm as the medium is preferably 15 m / sec or more. The peripheral speed when using a medium having a particle diameter of 30 μm as the medium is preferably 8 m / sec or more.

  The wet ball mill 3 shown in FIG. 1 has a takeout port 19 for discharging the slurry after the dispersion is completed, but in the present invention, the ball mill 3 does not have the takeout port 19. Also good.

  Dispersion is performed as described above, and the procedure when the particle size of the slurry reaches a desired value and the dispersion is finished is as follows.

  First, in the form in which the wet ball mill 3 does not have the take-out port 19, the raw material pump 2 is once stopped, and then the motor 12 is stopped to stop the operation of the wet ball mill 3, and the pulverization is finished. Thereafter, the valve 61 is closed, and then the valve 59 is opened. Next, by restarting the raw material pump 2, the product slurry in the raw material tank 1 is transferred from the discharge port 66 into the product tank 67. On the other hand, in order to extract the product slurry remaining in the stator 7, the raw material pump 2 is stopped and the valve 59 is closed. Next, the line that returns to the raw material tank 1 via the valve 64 is connected to the product tank 67. In the same manner as the procedure of filling the empty raw material tank 1 with the solvent as the raw material and supplying the slurry to the stator 7, the motor 12 is re-driven and the raw material pump is re-driven, so that the stator 7 And a method of collecting the product slurry remaining in the product tank in a product tank.

  In the form in which the wet ball mill 3 has the take-out port 19, the procedure for finishing the dispersion is as follows.

The raw material pump 2 is stopped once, then the motor 12 is stopped, the operation of the wet ball mill 3 is stopped, and the pulverization is finished. Thereafter, the valves 58 and 59 are opened, the valves 61, 62 and 64 are closed, and after the material pump 2 and the motor 12 are restarted, the valve 60 is opened. Thereby, the product slurry in the raw material tank 1 is extracted by the raw material pump 2 and sent from the discharge port 66 into the product tank 67. On the other hand, the product slurry in the wet ball mill 3 passes through the screen 18 with compressed air or N ₂ gas supplied into the wet ball mill 3 through the valve 60 and the hollow liquid discharge passage 9 while being stirred by the rotation of the rotor 7. The product is pushed out and sent from the outlet 65 to the product tank 67 through the outlet 19. The product slurry in the raw material tank 1 and the wet ball mill 3 is collected in the product tank 67 as described above.

When the wet ball mill 3 having the take-out port 19 is used, the rotor 7 is rotated at the time of product recovery because the media settles and is mixed so that it is not unevenly distributed in the lower layer portion in the wet ball mill 3. This is to prevent clogging. Further, in order to eliminate clogging, the screen 18 can be back-washed by appropriately introducing compressed air or N ₂ gas through the outlet 19 by opening the valve 63.

  The apparatus used in the production method of the present invention will be described in more detail with reference to FIGS.

  As shown in detail in FIG. 2, the wet ball mill 3 has a longitudinally cylindrical shape, a stator 7 having a jacket 6 through which cooling water is passed, a slurry supply port 16 provided at the lower end of the stator, A shaft 5 that is rotationally driven and is provided with a hollow liquid discharge passage 9 that communicates with the raw material tank 1 at the top of the stator 7, and a shaft projecting radially from the lower end of the shaft. A pin or disk-shaped rotor 11 that is driven to rotate coaxially, a pulley 14 that is fastened to the top of the shaft and is belted with the pulley 13 of the motor 12 shown in FIG. 1, and a rotary joint that is mounted on the open end of the shaft. 15 and a separator 4 for separating media fixed to the shaft 5 near the upper part in the stator. Further, when the take-out port 19 is provided at the bottom of the stator, the take-out port 19 is disposed at an eccentric position of the bottom of the stator, and specifically, a lattice-like screen support 17 and an attachment on the screen support 17. And a screen 18 for separating media.

  The separator 4 is composed of a pair of disks 21 fixed to the shaft 5 at a predetermined interval and a blade 22 that connects both disks 21 to form an impeller. Centrifugal force is applied to the medium and the slurry that has entered, and the medium is caused to fly radially outward due to the difference in specific gravity, while the slurry is discharged through the hollow liquid discharge passage 9 provided in the shaft center of the shaft 5. I have to.

As shown in detail in FIG. 3, the raw material slurry supply port 16 includes a valve seat 24 formed at the bottom of the stator, an inverted trapezoidal valve body 25 fitted to the valve seat 24 so as to be movable up and down, and a stator bottom. A bottomed cylindrical body 26 that protrudes further downward and forms an inlet 27 for raw material slurry, and a bottomed cylindrical body 28 that protrudes downward from the cylindrical body and includes an inlet 29 for compressed air or N ₂ gas; The piston 31 fitted to the cylindrical body 28 so as to be movable up and down, the rod 32 connecting the piston 31 and the valve body 25, and the piston in the cylindrical body 28 are mounted on the piston 31. When the valve body 25 is pushed up by the supply of the raw material slurry, the valve seat 24 is formed. Between An annular slit is formed, from which raw material slurry is supplied into the mill. The width of the slit can be adjusted by screwing or loosening the nut 34. When the raw material is supplied, the nut 34 is cylindrical. The width is set such that the media cannot pass through even when it reaches 28 and reaches the maximum extent. The valve body 25 at the time of supplying the raw material rises against the pressure in the wet ball mill 3 and the action of the spring 33 due to the supply pressure of the raw material slurry fed into the cylindrical body 26, and forms a slit between the valve seat 24 and the valve seat 24. However, the supply pressure of the raw material slurry is such that the width of the slit formed by the supply of the raw material slurry is slightly smaller than the maximum slit width regulated by the nut 34. There is some room between.

  The raw slurry supplied into the mill through a slit formed between the valve seat 24 and the valve body 25 contains coarse particles, which are caught between the valve seat and the valve body to clog. Although it is expected to occur, when clogging occurs due to biting, the valve body 25 rises to the full limit due to the increase in supply pressure, and the slit width is maximized. For this reason, the clogged coarse particles flow out and clogging is eliminated. When the clogging is eliminated, the supply pressure is lowered and the valve body 25 is lowered.

In order to eliminate clogging at the slit, in the illustrated example, compressed air or N ₂ gas passes from the compressed air or N ₂ gas source (not shown) through the regulator 23, passes through the electromagnetic switching valve 30, and is cylindrical from the inlet 29. Compressed air or N ₂ gas is intermittently supplied by repeatedly switching the electromagnetic switching valve 30 to ON-OFF in a short cycle, so that the valve body 25 has a short cycle. Thus, it is possible to eliminate the biting by repeatedly moving up and down to the upper limit position.

  The vibration of the valve body 25 may be performed constantly, or may be performed when a large amount of coarse particles are contained in the raw slurry, and when the supply pressure of the raw slurry increases due to clogging, It may be performed in conjunction.

When the agitated media is taken out together with the product slurry or after the product slurry is taken out after the pulverization is finished, the mounting position of the nut 34 is lowered as shown in the figure. Then, the electromagnetic switching valve 30 is switched ON. As a result, the valve body 25 is lifted onto the edge of the valve seat 24 by compressed air or N ₂ gas introduced from the introduction port 29.

  In the above embodiment, the rotor 11 and the separator 4 are fixed to the same shaft 5, but in another embodiment, the rotor 11 and the separator 4 are fixed to separate shafts arranged on the same axis and are driven to rotate separately. In the above embodiment in which the rotor and the separator are attached to the same shaft, the structure is simple because only one drive device is required. On the other hand, the rotor and the shaft are attached to separate shafts and are driven to rotate by separate drive devices. In the embodiment, the rotor and the separator can be driven to rotate at optimum rotation speeds. FIG. 5 is a longitudinal sectional view of the wet stirring ball mill in this embodiment, and FIG. 6 is a cross sectional view of the separator of the wet stirring ball mill shown in FIG.

  The ball mill shown in FIG. 5 has a shaft 43 as a stepped shaft, a separator 44 is inserted from the lower end of the shaft, and then a spacer 45 and a disk or pin-shaped rotor 46 are alternately inserted, and then a stopper 47 is provided at the lower end of the shaft. The separator 44 is fastened by a screw 48, and the separator 44, the spacer 45 and the rotor 46 are sandwiched and connected by a step 43a of the shaft 43 and a stopper 47. The separator 44 is a surface facing the inside as shown in FIG. A pair of discs 52 each having a blade fitting groove 51 formed therein, a blade 53 interposed between the two discs and fitted in the blade fitting groove 51, and the two discs 52 are maintained at a constant interval, and the discharge path An impeller is constituted by an annular spacer 56 in which a hole 55 communicating with 54 is formed.

  In the method for producing a dispersion of the present invention, a wet ball mill is used. The wet ball mill includes, for example, Ashizawa Finetech Co., Ltd. Star Mill; Mitsui Mining Co., Ltd. MSC-MILL, SC-MILL, Attritor MA01SC; Asada Iron Works Co., Ltd. Nano Glen Mill, Pico Glen Mill, Pure Glen Mill, Mega Capper Glen Mill, Sera Power Glen Mill, Dual Glen Mill, AD Mill, Twin AD Mill, Basket Mill, Twin Basket Mill: Products such as Aspec Mill, Ultra Aspec Mill, Super Aspec Mill manufactured by Kotobuki Industry Co., Ltd. Is mentioned. Of these, an ultra spec mill is preferable.

  In the production method of the present invention, a star mill manufactured by Ashizawa Finetech Co., Ltd. can also be preferably used. The star mill includes a cylindrical container having a slurry inlet on one end side, a rotatable stirring shaft disposed in the container so as to extend in a longitudinal direction, and a drive connected to the stirring shaft outside the container. The stirring shaft has a stirring member, a pulverization medium is placed in a space between the stirring shaft and the inner surface of the container, and is introduced by the drive device while introducing the slurry from the slurry inlet. By rotating the stirring shaft, silica fine particles in the slurry are pulverized, and the stirring shaft has a hollow portion having a media inlet formed in the vicinity of the other end of the container. A slit is formed in the shaft to communicate the hollow portion with the space between the stirring shaft and the inner surface of the container, and the media that has reached the vicinity of the other end of the container as the slurry moves. Is a medium agitation type pulverizer that enters the hollow portion of the agitation shaft from the slurry inlet and returns to the space between the agitation shaft and the inner surface of the vessel through the slit. A medium stirring type, wherein a slurry outlet is disposed in the hollow portion of the stirring shaft, a screen is provided so as to surround the slurry outlet in the hollow portion, and the screen is driven to rotate. It is a grinding device.

  In the medium agitation type pulverizer, a screen for separating the media from the slurry is driven to rotate, so that a rotational motion is induced in the slurry and the media reaching the vicinity of the screen, and the centrifugal force due to this rotational motion is greater than that in the slurry. Is higher, so the media has a biasing force away from the screen. For this reason, the media circulates without approaching the screen. Therefore, it is possible to efficiently remove the media from the slurry.

  The dispersion obtained by the production method of the present invention can be adjusted to a concentration suitable for the coating method by appropriately adding a solvent or volatilizing it. Examples of the solvent to be added include the organic solvent (S) described above.

  The dispersion obtained by the production method of the present invention itself can be used as an active energy ray-curable resin composition, or may be used by mixing with other compounds as necessary. These compounds include the aforementioned active energy ray-curable monomer (M), active energy ray-curable oligomer (O), ultraviolet absorber, antioxidant, silicon-based additive, organic beads, fluorine-based additive, rheology control. Agents, defoaming agents, mold release agents, silane coupling agents, antistatic agents, antifogging agents, colorants and the like.

  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 silicon-based 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 or a phenyl group, such as a dimethylpolysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.

  Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. These organic beads have an average particle size of 1 to 10 microns, and any one of them may be used alone or two or more of them may be used in combination.

  The amount of the various additives as described above is sufficient to exert its effect and does not hinder ultraviolet curing, so that the active energy ray-curable resin composition for cast polymerization is 100 parts by mass. , Each preferably in the range of 0.01 to 40 parts by mass.

  Examples of the photopolymerization initiator that can be added to the dispersion of the present invention include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, and 4,4′-bisdiethylamino. Benzophenones such as benzophenone, 4,4'-dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; thioxanthones; acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;

Α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Tylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethyl Ketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4- Dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine, 2 , 4-Bis-trichloromethyl-6- (4-ethoxy Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, etc. Is mentioned.

  The photopolymerization initiators can be used alone or in combination of two or more. The amount used is not particularly limited, but is 0.05 to 20 masses per 100 parts by mass of the active energy ray-curable resin composition in order to maintain good sensitivity and prevent crystal precipitation, coating property deterioration, and the like. It is preferable to use in the range of 0.1 part by weight, and particularly preferable to use in the range of 0.1 to 10 parts by weight.

  Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino One or more mixed systems selected from the group of phenyl) -butan-1-one High curable coating for the active energy ray curable resin composition is particularly preferred because the resulting.

  Examples of commercially available photopolymerization initiators include Irgacure-184, 149, 261, 369, 500, 651, 754, 784, 819, 907, 1116, 1664, 1700, 1800, 1850, 2959, 4043, Darocur-1173 (Ciba Specialty Chemicals), Lucyrin TPO (BASFF), KAYACURE-DETX, MBP, DMBI, EPA, OA [Nippon Kayaku Co., Ltd.], VICURE-10, 55 (manufactured by STAUFFER Co. LTD), TRIGONALP1 (manufactured by AKZO Co. LTD), SANDORY 1000 (manufactured by SANDOZ Co. LTD), DEAP (manufactured by APJOHN Co. LTD) ), QUANTACURE-PDO, the same ITX, EPD (manufactured by WARD BLEKINSOP Co. LTD), and the like.

  Furthermore, in the active energy ray-curable resin composition, various photosensitizers can be used in combination with the photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.

  Furthermore, the active energy ray-curable resin composition can be used in combination with other resins for the purpose of improving adhesion to a film substrate.

  Examples of the other resins include acrylic resins such as methyl methacrylate resin and methyl methacrylate copolymer; polystyrene, methyl methacrylate-styrene copolymer; polyester resin; polyurethane resin; polybutadiene and butadiene-acrylonitrile copolymer. Polybutadiene resins such as bisphenol type epoxy resins, epoxy resins such as phenoxy resins and novolac type epoxy resins, and the like.

  The active energy ray-curable resin composition using the dispersion obtained by the production method of the present invention is particularly hard when applied to a thin film plastic substrate such as a film substrate, and Even when cured, it has low shrinkage and less warpage (curl) of the film. Therefore, it can be suitably used for coating a film substrate.

Examples coating amount at the time of applying the film substrate, for example, on a variety of film substrate, the range weight of 0.1 to 30 g / ^{m 2} after drying, preferably in the range of from 1 to 20 g / ^{m 2} It is preferable to apply so that it becomes. Moreover, since the film thickness of a hardened layer is 3% or more with respect to the film thickness of a film-form base material, it is preferable from being easy to achieve the hardness as a hard coat. Especially, the film whose film thickness of a hardened layer is the range of 3-100% with respect to the film thickness of a film-form base material is more preferable, and the film thickness of a hardened layer is 5 with respect to the film thickness of a film-form base material. A film in the range of ˜100% is more preferable, and a film in which the thickness of the cured layer is in the range of 5 to 50% with respect to the film thickness of the film-like substrate is particularly preferable.

  As a film-like substrate on which the active energy ray-curable resin composition is applied, various known substrates can be used. Specifically, a plastic film base material etc. are mentioned, for example. Examples of the plastic film group include polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin, and the like. Examples include base materials.

  The application method of the active energy ray-curable resin composition is not particularly limited, and a known method can be adopted, for example, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating. Examples of the method include offset printing, offset printing, flexographic printing, and screen printing.

  Examples of the active energy rays to be irradiated include ultraviolet rays and electron beams. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp is used as a light source, and the amount of light and the arrangement of the light source are adjusted as necessary. It is preferable to cure at a conveying speed of 5 to 50 m / min with respect to one lamp having a light quantity in a range of ˜160 W / cm. On the other hand, in the case of curing with an electron beam, it is preferably cured with an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.

  As described above, the active energy ray-curable resin composition has low shrinkage during curing and high hardness. Therefore, by using the composition, a film in which a cured layer of the composition is provided on a film substrate can be provided. Such a film can be suitably used for, for example, various protective films represented by a hard coat film for optical articles such as a polarizing plate protective film and a touch panel, an antireflection film, a diffusion film, and a back coating of a prism sheet.

  In addition, the active energy ray-curable resin composition is used not only as a protective film for protecting a planar article such as the polarizing plate and the touch panel, but also as a plastic article other than the planar article such as a mobile phone. It is also suitably used for protecting the surface of molded products such as home appliances and automobile bumpers.

  Examples of a method for forming a protective layer for protecting the surface of a molded product using the active energy ray-curable resin composition include a coating method, a transfer method, a sheet bonding method, and the like.

  The coating method involves spray-coating a coating agent comprising an active energy ray-curable resin composition, or applying the active energy after applying the coating as a top coat to a molded product using a printing device such as a curtain coater, roll coater or gravure coater. This is a method of irradiating a line to crosslink the top coat.

  In the transfer method, a transfer material in which an active energy ray-curable resin composition is coated on a releasable substrate sheet is adhered to the surface of the molded product, and then the substrate sheet is peeled off to top coat the surface of the molded product. And then irradiating active energy rays to create a crosslinked coating film, or after adhering the transfer material to the surface of the molded article, irradiating active energy rays to create a crosslinked coating film, and then substrate In this method, the top coat is transferred to the surface of the molded product by peeling the sheet.

  The sheet bonding method is a method for forming a protective layer on the surface of a molded product by bonding a protective sheet having a protective layer and, if necessary, a decorative layer on a base sheet to a plastic molded product. Among these, the active energy ray-curable resin composition for coating of the present invention can be preferably used for a transfer method or a sheet bonding method. Below, the formation method of the protective layer by a transfer method and a sheet | seat adhesion method is explained in full detail.

  In order to form a protective layer by the transfer method using the active energy ray-curable resin composition, first, a transfer material is prepared. For the transfer material, for example, the active energy ray-curable resin composition is blended alone or with a polyfunctional isocyanate, mixed and then applied onto a base sheet, and then heated to semi-cure the curable resin composition (B -It can be manufactured by making a stage).

  There is no special limitation as polyfunctional isocyanate used together with an active energy ray hardening-type resin composition, Various well-known can be used. For example, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexane diisocyanate, the above trimer, a prepolymer obtained by reacting a polyhydric alcohol with the above diisocyanate, or the like is used. be able to. That is, the B-stage is formed by reacting the hydroxyl group contained in the polymer with the isocyanate group of the polyfunctional isocyanate.

The use ratio of the active energy ray-curable resin composition and the polyfunctional isocyanate is usually such that the ratio of the hydroxyl group of the active energy ray-curable resin composition to the isocyanate group of the polyfunctional isocyanate is 1 / 0.01 to 1/1. The range is preferably 1 / 0.05 to 1 / 0.8.

  As a base material sheet, what has mold release property is preferable. Examples of such a base sheet include a plastic sheet, a metal foil, a cellulose sheet, and a composite of these sheets.

  Examples of the plastic sheet include the plastic film described above.

  Examples of the metal foil include aluminum foil and copper foil. Examples of the cellulose sheet include glassine paper, coated paper, and cellophane.

  The base sheet is preferably a plastic sheet, and more preferably a polyester sheet.

  In order to produce a transfer material, first, an active energy ray-curable resin composition is coated on a base material sheet. This resin composition becomes an outermost layer on the surface of the molded product in a method for forming a protective layer, which will be described later, and a layer for protecting the molded product and the pattern layer on the molded product from chemicals and friction. Examples of the method for applying the curable resin composition for transfer material include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a comma coating method and other coating methods, a gravure printing method, a screen printing method, and the like. The printing method etc. are mentioned. When coating, since the wear resistance and chemical resistance are good, it is preferable to coat so that the thickness of the protective layer is 0.5 to 30 μm. In particular, the thickness of the protective layer is 1 It is more preferable to paint so that it will be-6 micrometers.

  When the protective layer is excellent in peelability from the base sheet, the transfer material curable resin composition may be applied so that the protective layer is directly provided on the base sheet. In order to improve the properties, the release layer may be formed on the entire surface before the protective layer is provided on the base sheet. The release layer is separated from the protective layer together with the base sheet when the base sheet is peeled off from the molded product in order to transfer the protective layer on the transfer material to the surface of the molded product in the method for forming the protective layer of the molded product described later. Type. Examples of the release agent for forming the release layer include melamine resin release agents, silicone resin release agents, fluororesin release agents, cellulose derivative release agents, and urea resin release agents. Polyolefin resin release agents, paraffin release agents, composite release agents thereof, and the like can be used. Examples of the method for forming the release layer include a coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method and a comma coating method, a printing method such as a gravure printing method and a screen printing method.

  The curable resin composition for transfer material is coated on the substrate sheet and then dried. Drying can be performed by heating, for example. When the active energy ray-curable resin composition for coating contains an organic solvent by this heating, the organic solvent is removed. The heating is usually 55 to 160 ° C, preferably 100 to 140 ° C. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.

  The B-staged resin layer on the transfer material of the present invention is easily irradiated with active energy rays because it is easy to print another layer on the resin layer or wind up the transfer material. It is desirable to be tack-free in the previous stage.

  The transfer material may form a pattern layer. The pattern layer is usually formed as a printing layer on the B-staged resin layer. As a material for the printing layer, a binder such as a polyvinyl resin, a polyamide resin, a polyester resin, a polyacrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, or an alkyd resin is used as a binder. And a color ink containing an appropriate color pigment or dye as a colorant may be used. As a method for forming the pattern layer, for example, a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, a comma coating method, or a lip coating method can also be employed. The pattern layer may be provided entirely or partially depending on the pattern to be expressed. The pattern layer may be a metal vapor deposition layer or a combination of a printed layer and a metal vapor deposition layer.

  In addition, when the protective layer and the picture layer have sufficient adhesion to the molded product, the adhesive layer may not be provided, but an adhesive layer may be formed as necessary. An adhesive layer adheres the transfer material which has said each layer to the molded article surface. The adhesive layer is formed on a portion to be adhered on the protective layer or the picture layer. That is, the adhesive layer is formed over the entire surface when the part to be bonded is over the entire surface. Further, if the part to be bonded is partially, an adhesive layer is partially formed. As the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the material of the molded product is appropriately used. For example, when the material of the molded product is a polyacrylic resin, a polyacrylic resin may be used. In addition, when the material of the molded product is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, polystyrene blend resin, polyacrylic resin, polystyrene resin, polyamide having affinity with these resins A series resin or the like may be used. Furthermore, when the material of the molded product is a polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used. Examples of the method for forming the adhesive layer include coating methods such as gravure coating, roll coating, and comma coating, printing methods such as gravure printing, and screen printing.

  The configuration of the transfer material is not limited to the above-described embodiment. For example, when using a transfer material for the purpose of surface protection only, taking advantage of the ground pattern and transparency of the molded product, a base sheet A B-staged resin layer and an adhesive layer can be sequentially formed on the substrate, and the pattern layer can be omitted from the transfer material.

  When the transfer material has a pattern layer or an adhesive layer on the B-staged resin layer, an anchor layer may be provided between these layers. The anchor layer is a resin layer for improving the adhesion between these layers and protecting the molded product and the pattern layer from chemicals. For example, heat is applied to two-component curable urethane resin, melamine resin, epoxy resin, etc. Thermoplastic resins such as curable resins and vinyl chloride copolymer resins can be used. As a method for forming the anchor layer, there are a coating method such as a gravure coating method, a roll coating method and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.

  In order to form a protective layer of a molded product using the transfer material, for example, after bonding the B-staged resin layer of the transfer material and the molded product, the resin layer is formed by irradiating active energy rays. It can be cured. Specifically, for example, the B-staged resin layer of the transfer material is adhered to the surface of the molded product, and then the B-staged resin layer of the transfer material is removed by peeling the base sheet of the transfer material. After transferring onto the surface of the molded product, energy rays are cured by irradiation with active energy rays and the resin layer is crosslinked and cured (transfer method), or the transfer material is sandwiched in the molding die, and the resin is placed in the cavity. At the same time as injection filling to obtain a resin molded product, a transfer material is adhered to the surface, the substrate sheet is peeled off and transferred onto the molded product, and then the energy beam is cured by irradiation with active energy rays to cure the resin layer. And the like (molding simultaneous transfer method).

  In addition, the cross-linking curing and transfer process of the resin layer is performed by adhering the transfer material to the surface of the molded product as shown in the above method, and then transferring the transfer material onto the surface of the molded product by peeling the substrate sheet. Although the order of the energy ray irradiation is preferable, after the transfer material is adhered to the surface of the molded product, the active energy ray is irradiated from the substrate sheet side to cure the protective layer, and then the substrate sheet is peeled off and transferred. The order of steps may be used.

  The molded product is not limited in material, and examples thereof include a resin molded product, a woodwork product, and a composite product thereof. These may be transparent, translucent, or opaque. The molded product may be colored or not colored. Examples of the resin include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, and AS resin. Also, general engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, acrylic resins, polycarbonate modified polyphenylene ether resins, polyethylene terephthalate resins, polybutylene terephthalate resins, ultrahigh molecular weight polyethylene resins, and polysulfone resins. Super engineering resins such as polyphenylene sulfide resins, polyphenylene oxide resins, polyacrylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, and polyallyl heat-resistant resins can also be used. Furthermore, composite resins to which reinforcing materials such as glass fibers and inorganic fillers are added can also be used.

Examples of the active energy ray used in the method for forming the protective layer of the molded article of the present invention include electron beam, ultraviolet ray, and gamma ray. Irradiation conditions are determined according to the composition of the curable resin composition for transfer material used to obtain the protective layer, but it is preferable to irradiate so that the integrated light quantity is usually 50 to 5000 mj / cm ^2. It is more preferable to irradiate so that the amount of light is 500 to 2000 mj / cm ² .

Below, the formation method of the protective layer of the molded article by the said transfer method is demonstrated concretely. First, the transfer material is placed on the molded product with the adhesive layer side down. Next, a heat resistant rubber-like elastic body, for example, a heat transfer rubber set to conditions of a temperature of 80 to 260 ° C. and a pressure of 50 to 200 kg / m ² using a transfer machine such as a roll transfer machine or an up-down transfer machine equipped with silicon rubber. Heat or / and pressure is applied from the substrate sheet side of the transfer material through the elastic body. By doing so, the adhesive layer adheres to the surface of the molded product. Next, when the base sheet is peeled off after cooling, peeling occurs at the interface between the base sheet and the resin layer. Further, when a release layer is provided on the base sheet, if the base sheet is peeled off, peeling occurs at the boundary surface between the release layer and the resin layer. Finally, by irradiating active energy rays, the resin layer transferred to the molded product is completely cross-linked and cured to form a protective layer. In addition, you may perform the process of irradiating an active energy ray before the process of peeling a base sheet.

  Next, a method for forming a protective layer of a molded product by a simultaneous molding transfer method using injection molding will be specifically described. First, a transfer material is fed into a molding die composed of a movable die and a fixed die with the adhesive layer inside, that is, so that the base sheet is in contact with the fixed die. At this time, a single sheet of transfer material may be fed one by one, or a necessary part of a long transfer material may be intermittently fed. In the case of using a long transfer material, it is preferable to use a feeding device having a positioning mechanism so that the registration of the pattern layer of the transfer material and the molding die coincide. In addition, when the transfer material is intermittently fed, if the transfer material is fixed by the movable mold and the fixed mold after the position of the transfer material is detected by the sensor, the transfer material can always be fixed at the same position. This is convenient because the positional deviation of the pattern layer does not occur. After closing the molding die, molten resin is injected and filled into the die from the gate provided on the movable die, and at the same time as forming the molded product, the transfer material is adhered to the surface. After the resin molded product is cooled, the molding die is opened and the resin molded product is taken out. Finally, after peeling off the base sheet, the resin layer is completely crosslinked and cured by irradiating with active energy rays to form a protective layer. Further, the substrate sheet may be peeled off after irradiation with active energy rays.

  The curable resin composition for transfer materials of the present invention is not only a composition for producing transfer materials, but also coating methods such as the above gravure coating method, roll coating method, comma coating method, gravure printing method and screen. It can also be applied to a molded product such as a film, sheet, or molded product by a printing method such as a printing method or spray coating.

  Next, the sheet bonding method will be described. As the sheet bonding method, for example, a base layer sheet of a protective layer forming sheet prepared in advance and a molded product are bonded, and then heat-cured by heating to form a B-stage to cure the resin layer. Method (post-adhesion method), the protective layer forming sheet is sandwiched in a molding die, and resin is injected and filled into the cavity to obtain a resin molded product. At the same time, the surface and the protective layer forming sheet are bonded. Then, a method of thermally curing by heating and crosslinking and curing the resin layer (simultaneous molding adhesion method) and the like can be mentioned.

  The protective layer forming sheet can be produced by, for example, a method of producing the transfer material. At this time, when the adhesive force between the base sheet and the curable resin composition is not sufficient when the curable resin composition is applied onto the base sheet, 1. A primer is applied to the surface of the base sheet on which the curable resin composition is to be applied, and the curable resin composition is applied thereto. The adhesiveness between the base sheet and the curable resin composition can be improved by a method of activating the surface of the base sheet by corona discharge or the like. 1 above. As a primer to be used in, for example, a thermosetting resin such as a two-component curable urethane resin, a melamine resin, and an epoxy resin, a thermoplastic resin such as an aqueous latex made of a vinyl chloride copolymer resin, and an acrylic resin is used. Can do. Examples of the method for applying the adhesive include coating methods such as a gravure coating method, a roll coating method, and a comma coating method, and printing methods such as a gravure printing method and a screen printing method.

  In the method for producing the transfer material, after the active energy ray-curable resin composition is applied to the base sheet, the active energy ray is irradiated. By irradiation with this active energy ray, the (meth) acryloyl group in the curable resin composition is bonded by a radical polymerization reaction to form a three-dimensional cross-link and the curable resin composition is cured.

  When an active energy ray-curable resin composition containing an organic solvent is used as the active energy ray-curable resin composition, the organic solvent may be removed after application to the substrate sheet. In order to remove the organic solvent, for example, it may be after irradiation with active energy rays or before irradiation with active energy rays. As a method for removing the organic solvent, it may be left as it is to evaporate or may be dried using a dryer or the like, but the temperature at the time of removing the organic solvent is usually 70 to 130 ° C. for 10 seconds. About 10 minutes is preferable.

  The configuration of the protective layer forming sheet is not limited to the above-described embodiment. For example, the protective layer forming sheet is used only for surface protection treatment by taking advantage of the ground pattern and transparency of the molded product. In this case, the cured resin layer and the adhesive layer are sequentially formed on the base sheet, and the picture layer can be omitted from the protective layer forming sheet.

  In addition, when the protective layer forming sheet has a resin layer on the pattern layer, an anchor layer may be provided between these layers. The anchor layer is a resin layer for enhancing the adhesion between these layers. For example, a thermosetting resin such as a two-component curable urethane resin, a melamine resin, or an epoxy resin, a vinyl chloride copolymer resin, or the like. A thermoplastic resin can be used. As a method for forming the anchor layer, there are a coating method such as a gravure coating method, a roll coating method and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.

  As the molded product used in the sheet bonding method, for example, the molded product exemplified in the transfer method can be used.

  Examples of the method for adhering the molded article and the protective layer forming sheet in the post-adhesion method include, for example, applying a base material sheet of the protective layer forming sheet and / or the surface of the molded article to apply the adhesive to the surface of the protective layer forming sheet. Method of adhering to the surface of the molded product, after applying the double-sided adhesive tape to the base sheet of the protective layer forming sheet or / the surface of the molded product, peeling the release protective sheet of the double-sided adhesive tape to expose the adhesive surface to protect Method of adhering the base sheet of the layer forming sheet and the surface of the molded product, and applying the adhesive to the base sheet of the protective layer forming sheet to form an adhesive surface, and then protecting the adhesive surface with a release protective sheet Is prepared in advance, and the peeling protective sheet of the protective layer forming sheet is peeled off, and the adhesion surface of the base sheet and the surface of the molded product are adhered. In the simultaneous molding method, the protective layer forming sheet and the molded product are integrated by integrating the protective layer forming sheet and the molded product by melting the base sheet by heat during in-mold molding without using an adhesive. Can be glued. Here, examples of the adhesive used in the post-adhesion method include urethane adhesives, epoxy adhesives, ester adhesives, acrylic adhesives, and hot melt adhesives.

Below, the formation method of the protective layer of the molded article by the said back adhesion method is demonstrated concretely. First, a protective layer forming sheet is placed on the molded product with the adhesive layer side down. Next, a heat resistant rubber-like elastic body, for example, a heat transfer rubber set to conditions of a temperature of 80 to 260 ° C. and a pressure of 50 to 200 kg / m ² using a transfer machine such as a roll transfer machine or an up-down transfer machine equipped with silicon rubber. Heat or / and pressure is applied from the protective layer side of the protective layer forming sheet through the elastic body. By doing so, the adhesive layer adheres to the surface of the molded product. Finally, by heating, the resin layer formed on the molded product is completely cross-linked and cured to form a protective layer.

  Next, a method for forming a protective layer of a molded article by a simultaneous molding adhesion method using injection molding will be specifically described. First, a protective layer forming sheet is fed into a molding die composed of a movable mold and a fixed mold with the adhesive layer inside, that is, the base sheet is in contact with the fixed mold. At this time, a single sheet of transfer material may be fed one by one, or a necessary portion of a long transfer material may be intermittently fed. In the case of using a long protective layer forming sheet, it is preferable to use a feeding device having a positioning mechanism so that the registration of the pattern layer of the protective layer forming sheet and the molding die coincide. In addition, when the protective layer forming sheet is intermittently fed, it is always the same if the protective layer forming sheet is fixed between the movable type and the fixed type after the position of the protective layer forming sheet is detected by the sensor. It is convenient because the protective layer forming sheet can be fixed at the position, and the pattern layer is not displaced. After closing the molding die, the molten resin is injected and filled into the die from the gate provided on the movable die, and at the same time as forming the molded product, the protective layer forming sheet is adhered to the surface. After the resin molded product is cooled, the molding die is opened and the resin molded product is taken out. Finally, the resin layer is completely crosslinked and cured by heating in a hot air oven or the like to form a protective layer.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Unless otherwise indicated, all parts and percentages in the examples are based on mass.

Example 1
In a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introducing pipe, 250 g of glycidyl methacrylate (hereinafter abbreviated as “GMA”), 1000 g of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) and t- After charging 10 g of butyl peroxyethyl hexanoate (hereinafter abbreviated as “PO”), the system was heated to a temperature of about 90 ° C. over about 1 hour under a nitrogen stream and heated for 1 hour. Keep warm. Next, the mixture was dropped into the system for about 2 hours under a nitrogen stream from a dropping funnel charged beforehand with a mixture consisting of 750 g of GMA and 30 g of PO, and kept at the same temperature for 3 hours. Then, it heated up at 120 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 507 g of acrylic acid (hereinafter abbreviated as “AA”), 2.3 g of methoquinone and 9.3 g of triphenylphosphine were charged and mixed, and then under air bubbling The temperature was raised to 110 ° C. After incubating at the same temperature for 8 hours, 1.6 g of methoquinone was charged, cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of a reactive dispersant for silica fine particles (A-1). The reactive dispersant (A-1) had an acrylic equivalent of about 214 g / eq, a hydroxyl value of about 262 mg KOH / g, and a weight average molecular weight of about 30,000.

Example 2
Using the same reaction apparatus as in Example 1, 125 g of GMA, 125 g of methyl methacrylate (hereinafter abbreviated as “MMA”), 1000 g of MIBK, and 10 g of PO were charged, and then it took about 1 hour under a nitrogen stream. The temperature was raised until the system temperature reached about 90 ° C., and the temperature was kept for 1 hour. Next, from a dropping funnel previously charged with a mixed solution consisting of 375 g of GMA, 375 g of MMA, and 30 g of PO, the mixed solution was dropped into the system under a nitrogen stream for about 2 hours, and the same temperature was maintained for 3 hours. Kept warm. Then, it heated up at 120 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 254 g of AA, 2.3 g of methoquinone and 9.3 g of triphenylphosphine were charged and mixed, and then heated to 110 ° C. under air bubbling. After incubating at the same temperature for 8 hours, 1.6 g of methoquinone was charged, cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of a reactive dispersant for silica fine particles (A-2). The reactive dispersant (A-2) had an acrylic equivalent of about 356 g / eq, a hydroxyl value of about 158 mgKOH / g, and a weight average molecular weight of about 40,000.

Example 3
Using the same reactor as in Example 1, 75 g of GMA, 175 g of MMA, 1000 g of MIBK and 8 g of PO were charged, and then the system temperature was about 90 ° C. over about 1 hour under a nitrogen stream. The temperature was raised and kept warm for 1 hour. Next, the mixture was dripped into the system for about 2 hours under a nitrogen stream from a dropping funnel previously charged with a mixture consisting of 300 g of GMA, 700 g of MMA, and 23 g of PO, and kept at the same temperature for 3 hours. Kept warm. Then, it heated up at 120 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., the nitrogen introduction tube was replaced with an air introduction tube, and AA (152 g), methoquinone (2.3 g) and triphenylphosphine (5.6 g) were charged and mixed, and then heated to 110 ° C. under air bubbling. After incubating at the same temperature for 8 hours, 1.6 g of methoquinone was charged and cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of a reactive dispersant for fine silica particles (A-3). The reactive dispersant (A-3) had an acrylic equivalent of about 545 g / eq, a hydroxyl value of about 103 mg KOH / g, and a weight average molecular weight of about 70,000.

Example 4
25 g of reactive dispersant (A-1) in solid content, 25 g of dipentaerythritol hexaacrylate (DPHA), 50 g of silica fine particles (“Aerosil 200” manufactured by Nippon Aerosil Co., Ltd., average primary particle size of about 12 nm) and 200 g of MIBK Blended to obtain a blend.

  Dispersion of the silica fine particles in this blend was performed using an ultra apex mill “UAM015” manufactured by Kotobuki Industries Co., Ltd. The ultra apex mill “UAM015” used here is a wet ball mill having an inner diameter of the stator of 50 mmφ, an internal volume of 0.17 liter, a separator diameter of 40 mmφ, and a distance between the separator disks of 5 mm (in FIG. The type without the mouth 19). In producing the dispersion, a wet ball mill was filled with 50% by volume of zirconia beads having a diameter of 30 μm as a medium with respect to the volume of the wet ball mill.

  The said compound in a raw material tank was supplied into the wet ball mill from the supply port using the pump. The wet ball mill was operated at a constant rotor rotational speed (peripheral speed at the rotor tip was 8 m / sec), and the compound was pulverized and circulated at a flow rate of 200 ml per minute. Circulation was performed for 30 minutes to obtain a dispersion in which silica fine particles were dispersed in a mixture of the reactive dispersant (A-1), DPHA and MIBK. MIBK was removed from the obtained dispersion using an evaporator to obtain a reactive dispersion having a nonvolatile content concentration of 50%.

  2 parts of photoinitiator “Irgacure # 184” was added to 100 parts of this reactive dispersion to obtain an active energy ray-curable resin composition. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Moreover, when the cured coating film was created on the following conditions and pencil hardness was measured, it was 5H.

Measuring method of pencil hardness Method for making cured coating film An active energy ray-curable resin composition was applied onto a triacetyl cellulose (TAC) film (film thickness 40 um) with a bar coater (film thickness 10 μm), dried at 70 ° C. for 1 minute, and nitrogen A test piece having a cured coating film was obtained by passing and curing at a dose of 250 mJ / cm ² using a high-pressure mercury lamp.

2. Evaluation Method of Cured Coating Film The cured coating film of the above test piece was evaluated by a pencil scratch test with a load of 500 g in accordance with JIS K 5400.

Examples 5-10
A reactive dispersion was produced in the same manner as in Example 4 except that the formulation shown in Table 1 was used. An active energy ray-curable resin composition was obtained in the same manner as in Example 4 using the obtained reactive dispersion. The storage stability and pencil hardness of the cured coating film were measured in the same manner as in Example 4, and the results are shown in Table 1.

Footnotes in Table 1 Aerosil 200: Silica fine particles manufactured by Nippon Aerosil Co., Ltd. Primary particle size 17 nm.

  Aerosil 50: Silica fine particles manufactured by Nippon Aerosil Co., Ltd. Primary particle size 30 nm.

  EMIX-100: Silica fine particles manufactured by Tatsumori Co., Ltd. Primary particle size 100 nm.

  EMIX-300: Silica fine particles manufactured by Tatsumori Co., Ltd. Primary particle size 300 nm.

  Dispersion stability ○: No settling for 2 months.

Comparative Example 1
50 g of silica fine particles (Nippon Aerosil Co., Ltd., Aerosil 50, average primary particle size of about 30 nm), 50 g of bisphenol A epoxy acrylate (DIC Corporation, Unidic V-5500), and 200 parts of MIBK A comparative reactive dispersion having a non-volatile concentration of 50% was obtained in the same manner as in Example 4 except that it was used.

  2 parts of Irgacure # 184 was added to 100 parts of this reactive dispersion for comparison to obtain an active energy ray-curable resin composition for comparison. The active energy ray-curable resin composition for comparison control generated a precipitate when stored at room temperature (25 ° C.) for 1 hour. Moreover, it was 2H when the cured coating film was created similarly to Example 4 and pencil hardness was measured.

Comparative Example 2
50 parts of silica fine particles (Aerosil 50, average primary particle diameter of about 30 nm), 50 parts of DPHA, 200 parts of MIBK, and 600 parts of zirconia beads (bead diameter of 0.3 mm) are placed in a glass bottle. After mixing and taking out for 2 hours, MIBK was removed using an evaporator to obtain a reactive dispersion for comparison having a nonvolatile content concentration of 50%.

    2 parts of Irgacure # 184 was added to 100 parts of this reactive dispersion for comparison to obtain an active energy ray-curable resin composition for comparison. The active energy ray-curable resin composition for comparison control generated a precipitate when stored at room temperature (25 ° C.) for 1 week. Moreover, when the cured coating film was created and pencil hardness was measured like Example 4, it was 3H.

Comparative Example 3
To a solution consisting of 221 g of mercaptopropyltrimethoxysilane and 1 g of dibutyltin dilaurate in dry air, 222 g of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour while stirring and then stirred at 60 ° C. for 3 hours. 549 g of Aronix M-305 [manufactured by Toagosei Co., Ltd., pentaerythritol triacrylate / pentaerythritol tetraacrylate = 60/40 (wt%)] was added dropwise at 30 ° C. over 1 hour, and then heated at 60 ° C. for 10 hours. The organic compound was obtained by stirring. Under a nitrogen stream, organic compound 3.0 g, methyl ethyl ketone silica sol (Nissan Chemical Industry Co., Ltd., trade name: MEK-ST, number average particle diameter 22 nm, silica concentration 30%) 89.9 g, ion-exchanged water 0.1 g After stirring the mixed solution at 60 ° C. for 4 hours, 1.4 g of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour. Got the body.

  100 parts of this reactive dispersion for comparison, 40 parts of DPHA, and 2 parts of Irgacure # 184 (photoinitiator) were added to obtain an active energy ray-curable resin composition for comparison. The active energy ray-curable resin composition for comparison control generated a precipitate when stored at room temperature (25 ° C.) for 1 week. Moreover, when the cured coating film was created and pencil hardness was measured like Example 1, it was 2H.

1 ... Raw material tank 2 ... Raw material pump 3 ... Grinding type wet stirring ball mill 4 ... Separator 5 ... Shaft 6 ... ··· Jacket 7 ······ Stator 9 ··· Discharge path 11 ··· Rotor 12 ··· Motor 13 ··· Pulley 14 · · · Pulley 15 ... Rotary joint 16 ... Supply port 17 ... Screen support 18 ... Screen 19 ... Eject port 21 ... Disc 22 ... ..Blade 23 ... Regulator 24 ... Valve seat 25 ... Valve body 26 ... Cylinder 27 ... Inlet 28 ... Cylinder 29... Compressed air or N ₂ gas inlet 30... Electromagnetic switching valve 31. ... Piston 32 ... Rod 33 ... Spring 34 ... Nut 43 ... Shaft 43a ... Stage 43 of shaft 43 ... Separator 45 ... Spacer 46 ... Rotor 47 ... Stopper 48 ... Screw 51 ... Blade fitting groove 52 ... Disk 53 ... Blade 54 ... Discharge path 55 ... Hole 56 ... Ring spacer 58 ... Valve 59 ... Valve 60 ... Compressed air or N ₂ Gas valve 61 ... Valve 62 ... Compressed air or N ₂ gas valve 63 ... Compressed air or N ₂ gas valve 64 ... Valve 65 ... Discharge port 66 ... ... Discharge port 67 ... Product tank

Claims (13)

A (meth) acryl having a (meth) acryloyl group and a hydroxyl group in the molecular structure, a (meth) acryloyl equivalent in the range of 200 to 600 g / eq, and a hydroxyl value in the range of 90 to 280 mgKOH / g. A slurry containing the polymer (B) and the silica fine particles (F),
1) a cylindrical stator filled with media;
2) a slurry supply port provided at the lower end of the stator;
3) a rotationally driven shaft that is located at the axial center of the stator and that is provided with a hollow liquid discharge passage at an upper portion thereof;
4) a rotor that rotates coaxially with the shaft;
5) The supply of the wet ball mill including an impeller-type separator that is rotationally driven and is arranged coaxially on the shaft and configured to discharge the separated liquid in communication with the hollow liquid discharge path. The rotor is driven to rotate in the stator, the medium and the slurry are agitated and mixed to pulverize the silica fine particles (F) in the slurry, and to the (meth) acrylic polymer (B). Dispersing, separating the slurry and the media by the action of centrifugal force in the rotationally driven separator, and discharging the slurry attracted to the axial center of the separator from the hollow discharge passage in the shaft A method for producing a dispersion. 2. The dispersion according to claim 1, wherein the (meth) acrylic polymer (B) has a (meth) acryloyl equivalent in the range of 200 to 400 g / eq and a hydroxyl value in the range of 140 to 280 mgKOH / g. Method. The method for producing a dispersion according to claim 1, wherein the weight average molecular weight of the (meth) acrylic polymer (B) is in the range of 5,000 to 100,000. The method for producing a dispersion according to claim 1, wherein a primary particle diameter of the silica fine particles (F) is in the range of 10 nm to 300 nm. The (meth) acrylic polymer (B) is obtained by addition reaction of a monomer (c) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having an epoxy group. A reaction product (b2) or a reaction product (b2) obtained by subjecting a (meth) acrylic polymer (a2) having a carboxyl group to an addition reaction of a monomer (d) having a (meth) acryloyl group and an epoxy group The method for producing a dispersion according to claim 1, wherein The (meth) acrylic polymer (B) has an epoxy group obtained by polymerizing a polymerizable monomer having glycidyl (meth) acrylate as an essential monomer component. The method for producing a dispersion according to claim 1, which is a reaction product obtained by subjecting (meth) acrylic acid to an addition reaction. 2. The method for producing a dispersion according to claim 1, wherein the media are zirconia fine particles having a median particle diameter in the range of 15 to 300 μm. An energy beam curable resin composition comprising the dispersion obtained by the production method according to claim 1. A film having a cured layer obtained by curing the energy ray-curable resin composition according to claim 8 on a film-like substrate. The film-like substrate is one or more film-like substrates selected from the group consisting of a polyethylene terephthalate resin (PET) film-like substrate, a polycarbonate resin film-like substrate and an acetylated cellulose resin film-like substrate. The film according to claim 9. The film according to claim 9, wherein the thickness of the cured layer is in the range of 3 to 100% with respect to the film thickness of the film-like substrate.   A (meth) acryl having a (meth) acryloyl group and a hydroxyl group in the molecular structure, a (meth) acryloyl equivalent in the range of 200 to 600 g / eq, and a hydroxyl value in the range of 90 to 280 mgKOH / g. A reactive dispersion medium for silica fine particles, comprising a polymer (B).   A (meth) acryl having a (meth) acryloyl group and a hydroxyl group in the molecular structure, a (meth) acryloyl equivalent in the range of 200 to 600 g / eq, and a hydroxyl value in the range of 90 to 280 mgKOH / g. A reactive dispersant for silica fine particles, comprising a polymer (B).

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