JP2011201938A - Inorganic particle dispersion, energy ray-curable resin composition, and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion, whose cured product has high hardness and which is excellent in dispersion stability, and furthermore to provide a method for producing the dispersion with the characteristics.SOLUTION: The dispersion includes a surface-treated inorganic particle (A), and a reactive dispersant in which the inorganic particle (A) is dispersed, wherein (1) the surface-treated inorganic particle (A) is a product obtained by surface-treating an inorganic particle (b1) with a (meth)acryloyl group-containing compound (B), (2) the reactive dispersant is a reaction product obtained by performing addition-reaction of an epoxy group-containing (meth)acrylic polymer with a (meth)acryloyl group and carboxyl group-containing monomer; or a reaction product obtained by performing addition-reaction of a carboxyl group-containing (meth)acrylic polymer with a (meth)acryloyl group and epoxy group-containing monomer; and has a (meth)acryloyl equivalent of 200-600, and a hydroxyl value of 90-280 mg/KOH.

Description

The present invention relates to a dispersion in which surface-treated inorganic particles (A) are dispersed in a reactive dispersant, and further a method for producing the dispersion, a curable resin composition containing the dispersion, and curing the composition It is related with the film obtained.

  In order to increase the hardness of a 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 over 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 silica fine particles in an active energy ray-curable resin composition, for example, silica fine particles are surface-treated with a reactive silane coupling agent having a hydrophobic group to make the surface of silica fine particles hydrophobic. A method for achieving this is described (for example, see Patent Document 1). However, even the silica fine particles obtained by the method described in Patent Document 1 are not sufficient in dispersion stability in the active energy ray-curable resin composition, and each evaluation of haze, fingerprint wiping property and oily dye wiping property However, there is no clear hardness of the cured product.

JP 2006-348196 A

  In the present invention, in view of the above background art, it is an object to provide a dispersion in which the hardness of a cured product is high and the dispersion stability is excellent. Furthermore, this invention makes it a subject to provide the manufacturing method of the dispersion which has the said characteristic.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in the dispersion in which the surface-treated inorganic particles (A) are dispersed in the reactive dispersant,
1) Surface-treated inorganic particles (A) are obtained by surface-treating inorganic particles (b1) with a compound (B) having a (meth) acryloyl group,
2) The reactive dispersant has a reaction product obtained by adding a monomer having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer having an epoxy group, or a carboxyl group (meta) ) A reaction product obtained by addition reaction of a monomer having a (meth) acryloyl group and an epoxy group to an acrylic polymer, wherein the (meth) acryloyl equivalent is 200 to 600, and the hydroxyl value is 90 to 280 mg / KOH. The present inventors have found that a dispersion characterized by the above is extremely useful for solving the above problems, and completed the present invention.

That is, the present invention provides a dispersion in which the surface-treated inorganic particles (A) are dispersed in a reactive dispersant.
1) Surface-treated inorganic particles (A) are obtained by surface-treating inorganic particles (b1) with a compound (B) having a (meth) acryloyl group,
2) The reactive dispersant has a reaction product obtained by adding a monomer having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer having an epoxy group, or a carboxyl group (meta) ) A reaction product obtained by addition reaction of a monomer having a (meth) acryloyl group and an epoxy group to an acrylic polymer, wherein the (meth) acryloyl equivalent is 200 to 600, and the hydroxyl value is 90 to 280 mg / KOH. A dispersion characterized by the above is provided.

  In the present invention, the slurry containing the surface-treated inorganic particles (A) and reactive dispersion is provided at the cylindrical stator, the slurry supply port provided at one end of the stator, and the other end of the stator. A slurry discharge port, a medium filled in the stator, and a rotor for stirring and mixing the slurry supplied from the supply port, and connected to the discharge port and rotated integrally with the rotor, or separated from the rotor In a wet stirring ball mill comprising an impeller-type separator that rotates independently and is separated into media and slurry by the action of centrifugal force and discharges the slurry from the discharge port, the axis of the shaft for driving the separator to rotate is described above. A stir ball mill supply port that is a hollow discharge path that communicates with the discharge port is supplied to the stator filled with media, and the slurry is filled in the stator. After dispersion into comminuted reactive dispersing agent of the inorganic particles in chromatography, there is provided a method for producing a dispersion and separating the media from the slurry.

  The present invention also provides an energy ray curable resin composition containing the dispersion, a cured product obtained by curing the composition, and a film.

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material and film which have high hardness, and the dispersion used for this hardened | cured material and a film can be provided.

It is the schematic of the raw material slurry grinding | pulverization processing cycle provided with the said wet stirring ball mill used with the manufacturing method of the dispersion of this invention. It is a longitudinal cross-sectional view of the said wet stirring 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 the slurry supply of the said wet stirring 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 wet stirring ball mill used in the method for producing a dispersion of the present invention. It is the figure showing the cross-sectional view of the separator of the wet stirring ball mill shown in FIG.

That is, the present invention
1. In the dispersion in which the surface-treated inorganic particles (A) are dispersed in the reactive dispersant,
1) Surface-treated inorganic particles (A) are obtained by surface-treating inorganic particles (b1) with a compound (B) having a (meth) acryloyl group,
2) The reactive dispersant has a reaction product obtained by adding a monomer having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer having an epoxy group, or a carboxyl group (meta) ) A reaction product obtained by addition reaction of a monomer having a (meth) acryloyl group and an epoxy group to an acrylic polymer, wherein the (meth) acryloyl equivalent is 200 to 600, and the hydroxyl value is 90 to 280 mg / KOH. A dispersion characterized in that
2. (Meth) acryloyl equivalent of the reactive dispersant is 200 to 400, and the hydroxyl value is 140 to 280 mg / KOH. A dispersion according to
3. 1. A reactive dispersant is obtained by addition-reacting (meth) acrylic acid to a (meth) acrylic polymer having an epoxy group obtained by polymerizing glycidyl (meth) acrylate. Or 2. A dispersion according to
4). 1. The weight average molecular weight of the reactive dispersant is 5,000 to 100,000. ~ 3. A dispersion according to any one of
5. 1. The primary particle diameter of the inorganic particles (b1) is 10 nm to 300 nm. ~ 4. A dispersion according to any one of
6). 1. Inorganic particles (b1) are silica fine particles ~ 5. A dispersion according to any one of
7). The compound (B) having a (meth) acryloyl group is represented by the general formula (1)

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6).
1. An organosilane compound represented by ~ 6. A dispersion according to any one of
8.1. ~ 7. An energy ray-curable resin composition containing the dispersion according to any one of
9.1. ~ 7. The slurry containing the surface-treated inorganic particles (A) and reactive dispersion according to any one of the above is provided in a cylindrical stator, a slurry supply port provided at one end of the stator, and the other end of the stator. A slurry discharge port, a medium filled in the stator, and a rotor for stirring and mixing the slurry supplied from the supply port, and connected to the discharge port and rotated integrally with the rotor, or separated from the rotor In a wet stirring ball mill comprising an impeller-type separator that rotates independently and is separated into media and slurry by the action of centrifugal force and discharges the slurry from the discharge port, the axis of the shaft for driving the separator to rotate is described above. A stir ball mill supply port that is a hollow discharge path that communicates with the discharge port is supplied to the stator filled with media, and the slurry is filled in the stator. After dispersion into comminuted reactive dispersing agent of the inorganic particles in chromatography, a method of manufacturing a dispersion and separating the media from the slurry,
10. 8. The medium is zirconia fine particles having a particle diameter of 15 to 100 μm. A method for producing the dispersion according to claim 1,
11.9. An energy ray-curable resin composition comprising a dispersion obtained by the production method described in 1.
12.8. Or 11. A film having a cured layer obtained by curing the energy ray-curable resin composition described in 1.
13. 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. There is 12. A film according to
14 The film thickness of the cured layer is 3 to 100% with respect to the film thickness of the film-like substrate. Or 13. It relates to the film described in 1.

The dispersion of the present invention is characterized in that the surface-treated inorganic particles (A) are dispersed in a reactive dispersant.
The surface-treated inorganic particles (A) have a feature that they are surfaced with a compound (B) having a (meth) acryloyl group, and the compound (B) having such a (meth) acryloyl group is an inorganic particle ( There is no limitation as long as the compound (B) having a (meth) acryloyl group is introduced into the surface of the inorganic particles (b1) by treating with b1).

Examples of the compound (B) having a (meth) acryloyl group that can be used include an organosilane compound having a (meth) acryloyl group because of its high reactivity with the inorganic particles (b1).

More specifically, the general formula (1)

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6).
Is particularly preferred.

The surface of the inorganic particle (b1) needs to have a group that forms a chemical bond with the compound (B) having a (meth) acryloyl group. For example, when silica fine particles are used as the inorganic particle (b1) Functions as a group in which a silanol group forms a bond. Reaction conditions for forming a chemical bond may be conventional reaction conditions, and a catalyst may be used to promote the reaction. Although there is no restriction | limiting in the catalyst used, For example, phosphate ester can be mentioned.

The inorganic particle (b1) is not particularly limited as long as it is an inorganic particle that can be surface-treated with an organosilane compound such as silica fine particles, zirconia fine particles, alumina fine particles, acid value cerium fine particles, titanium fine particles, or barium titanate fine particles. Silica fine particles are particularly preferable. The preferred primary particle diameter of these fine particles can be in the range of 10 to 300 nm. If it is 10 nm or less, the dispersion of the inorganic particles in the dispersion becomes insufficient, and if it is 300 nm or more, it is not preferable because sufficient strength of the cured film cannot be maintained.

As for the (meth) acryloyl equivalent which the reactive dispersing agent of this invention has, 200-400 are preferable. The hydroxyl equivalent is preferably 140 to 280.

  In the present invention, the reactive dispersant means a reactive dispersant that undergoes a polymerization reaction with active energy rays. The (meth) acryl equivalent means the solid content weight (g / eq) of the reactive dispersant per mole of (meth) acryloyl group (meaning acryloyl group or methacryloyl group).

The reactive dispersant of the present invention is abbreviated and explained as follows for convenience.
As the reactive dispersant, a reactive dispersant (A1) obtained by addition-reacting a monomer (b1) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having an epoxy group. Or a reactive dispersant (A2) obtained by addition-reacting a monomer (b2) having a (meth) acryloyl group and an epoxy group to a (meth) acrylic polymer (a2) having a carboxyl group, The reactive dispersant of the present invention may be either (A1) or (A2).

  The (meth) acrylic polymer (a1) used for the preparation of the reactive dispersant (A1) is, for example, a polymerizable monomer having a (meth) acryloyl group and an epoxy group, and other polymerizable as required. Obtained by copolymerization reaction with monomers.

  Examples of the polymerizable monomer having a (meth) acryloyl group and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, and glycidyl α-n-propyl (meth) acrylate. , Glycidyl α-n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxy Pentyl, 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 can be mentioned. These may be used alone or in combination of two or more.

  In adjusting the (meth) acrylic polymer (a1), the amount of the polymerizable monomer having a (meth) acryloyl group and an epoxy group is usually 25 to 100 parts by weight, preferably 40 to 100 parts by weight. The other polymerizable monomer is an optional component, and its use amount is usually 0 to 75 parts by weight, preferably 0 to 60 parts by weight.

  The (meth) acrylic polymer (a2) used for the preparation of the reactive dispersant (A2) is, for example, a polymerizable monomer having a (meth) acryloyl group and a carboxyl group and, if necessary, other polymerizable monomers. It is obtained by a copolymerization reaction with a monomer.

  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.

  In adjusting the (meth) acrylic polymer (a2), the amount of the polymerizable monomer having a (meth) acryloyl group and a carboxyl group is usually 25 to 100 parts by weight, preferably 40 to 100 parts by weight. The other polymerizable monomer is an optional component, and its use amount is usually 0 to 75 parts by weight, preferably 0 to 60 parts by weight.

  Examples of other polymerizable unsaturated monomers that are copolymerized as necessary when preparing the (meth) acrylic polymer (a1) and (meth) acrylic polymer (a2) include the following polymerizable monomers: Etc.

(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 trifluoromethyl trifluorovinyl 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-dialkylaminoethyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate, etc. Is mentioned.

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

  The (meth) acrylic polymers (a1) and (a2) 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 singly or in combination of two or more, but the (meth) acrylic polymer (a1) having an epoxy group and a monomer having a carboxyl group (2) In order to efficiently perform the reaction of b1) or the reaction of the (meth) acrylic monomer (a2) having a carboxyl group and the monomer (b2) having an epoxy group, the reaction is performed at a high temperature of 100 to 150 ° C. From this viewpoint, it is preferable to use a solvent having a boiling point of 100 ° C. or higher, preferably 100 to 150 ° C.

  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.

  As described above, the reactive dispersant (A1) reacts the (meth) acrylic polymer (a1) having an epoxy group with the monomer (b1) having a (meth) acryloyl group and a carboxyl group. Examples of the monomer (b1) having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalate. Examples include acids, 2-acryloyloxyethylhexahydrophthalic acid, and unsaturated monocarboxylic acids having an ester bond such as modified lactones 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 (b1), a carboxyl group-containing polyfunctional (meth) An acrylate monomer may be used. These monomers (b1) having a (meth) acryloyl group and a carboxyl group may be used alone or in combination of two or more.

  Reaction of a polymer (a1) and a monomer (b1) is normally performed by mixing both components and heating to about 80-120 degreeC. Although the usage-amount of a polymer (a1) and a monomer (b1) will not be specifically limited if the (meth) acryl equivalent of (A1) obtained will be 200-600 g / eq, Usually, epoxy group 1 It is preferable that the number of moles of the carboxyl group in the monomer (b1) is 0.4 to 1.1 moles relative to moles.

  The reactive dispersant (A2) is obtained by reacting the (meth) acrylic polymer (a2) having a carboxyl group with the monomer (b2) having a (meth) acryloyl group and an epoxy group as described above. . Examples of the monomer (b2) 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.

  Reaction of a polymer (a2) and a monomer (b1) is normally performed by mixing both components and heating to about 80-120 degreeC. The amount of the polymer (a1) and the monomer (b1) used is not particularly limited as long as the (meth) acrylic equivalent of the obtained (A1) is 200 to 600 g / eq. It is preferable that the number of moles of the epoxy group in the monomer (b1) is 0.4 to 1.1 moles relative to moles.

  Reaction between the (meth) acrylic polymer (a1) having an epoxy group and a monomer (b1) having a (meth) acryloyl group and a carboxyl group, and a (meth) acrylic polymer (a2) having a carboxyl group The reaction with the monomer (b2) having a (meth) acryloyl group and an epoxy group 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 (b1) 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 (b2) having a (meth) acryloyl group and an epoxy group is added and reacted.

  The reactive dispersant of 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. A monomer having two or more polymerizable unsaturated double bonds may be used in combination as long as the above does not occur.

  As described above, the reactive dispersant of the present invention is the reactive dispersant (A1) [(meth) acrylic polymer (a1) having an epoxy group, and a monomer (b1) having a (meth) acryloyl group and a carboxyl group. Is a polymer obtained by reacting an epoxy group-containing acrylic polymer obtained by polymerizing a polymerizable monomer containing glycidyl (meth) acrylate and (meth) acrylic acid. An acrylic polymer obtained in this manner is preferred.

  The epoxy equivalent of the epoxy group-containing acrylic polymer (a1) is preferably 140 to 500 g / eq, more preferably 140 to 300 g / eq. Furthermore, as a glass transition temperature of an epoxy-group-containing acrylic polymer (a1), 30 degreeC or more is preferable and 30-100 degreeC is more preferable.

  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 reactive dispersant of the present invention is preferably from 5,000 to 100,000, more preferably from 5,000 to 50,000, from the viewpoints of curing shrinkage effect and leveling properties.

  In the reactive dispersant of the present invention, the hydroxyl group of the reactive dispersant, one isocyanate, and a monomer having a (meth) acryloyl group may be reacted within a range that does not impair the effects of the present invention. Thereby, it is possible to adjust a (meth) acryloyl group equivalent and a hydroxyl group equivalent suitably.

  Examples of the monomer having one isocyanate and a (meth) acryloyl group include a monomer having one isocyanate and one (meth) acryloyl group, and a monomer having one isocyanate and two (meth) acryloyl groups. Monomer, Monomer having one isocyanate and three (meth) acryloyl groups, Monomer having one isocyanate and four (meth) acryloyl groups, One isocyanate and five (meth) acryloyl groups And the like. As such a monomer, for example, a compound represented by the following formula [Chemical Formula 3] 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. Specifically, for example, in addition to Karenz AOI, Karenz MOI, Karenz BEI (trade name, manufactured by Showa Denko KK), a reaction adduct of a diisocyanate compound and hydroxyacrylate can be exemplified. 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 one isocyanate and a monomer having a (meth) acryloyl group with the reactive dispersant of the present invention is not particularly limited, and a known method can be adopted. Specifically, for example, one isocyanate and a monomer having a (meth) acryloyl group are added dropwise to the reactive dispersant of the present invention and heated to 50 to 120 ° C., more preferably 60 to 90 ° C. And react. In addition, although the usage-amount of the monomer which has a reactive dispersing agent, one isocyanate, and a (meth) acryloyl group is not specifically limited, Usually, the hydroxyl group (mol) of a reactive dispersing agent: One isocyanate and (meth) acryloyl The isocyanate group (mol) of the monomer having a group is 1: 0.1 to 1: 0.9, preferably 1: 0.1 to 1: 0.7.

  The reactive dispersant of the present invention can be suitably used as a reactive dispersant for various inorganic particles. Examples of the inorganic 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. The reactive dispersant of the present invention has high dispersibility of silica fine particles. Therefore, a dispersion in which inorganic particles are dispersed in the reactive dispersant of the present invention maintains good dispersion stability over a long period of time. Further, 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 inorganic particles are stably dispersed over a long period of time. As described above, since the reactive dispersant of the present invention has high dispersibility of inorganic particles, it is preferably used as a reactive dispersant when dispersing inorganic particles having poor dispersibility stability in the composition. The reactive dispersant of the present invention is preferably used as a reactive dispersant used when dispersing inorganic particles in a compound having a (meth) acryloyl group.

  The reactive dispersant of the present invention is preferably used as a reactive dispersant for inorganic particles having an average primary particle size of 10 nm to 300 nm, and more preferably used as a reactive dispersant for inorganic particles having an average primary particle size of 10 nm to 200 nm. .

  A reactive dispersion in which inorganic particles are dispersed using the reactive dispersant of the present invention can be prepared. The content of each component in the reactive dispersion is not particularly limited, but the reactive dispersant of the present invention and the silica fine particles are 10 to 90 parts by weight: 90 in [(reactive dispersant) :( inorganic particles)]. The content is preferably 10 to 10 parts by weight, and more preferably 30 to 90 parts by weight: 70 to 10 parts by weight. The total content of the reactive dispersant and the silica fine particles in the dispersion of the present invention is preferably 1 to 50% by weight, more preferably 1 to 30% by weight in terms of solid content.

  When the reactive dispersion is produced, the energy ray-curable resin composition contains the reactive dispersant of the present invention, inorganic particles, and a compound having a (meth) acryloyl group other than the reactive dispersant; can do. Examples of the compound having a (meth) acryloyl group other than the reactive dispersant include an active energy ray-curable monomer and an active energy ray-curable oligomer. The content of each component is not particularly limited, but the reactive dispersant of the present invention and the active energy ray-curable monomer or active energy ray-curable oligomer may be combined with [(reactive dispersant): (active energy ray-curable monomer. Or 10 to 90 parts by weight: 90 to 10 parts by weight, and preferably 30 to 90 parts by weight: 70 to 10 parts by weight. More preferred.

  Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meta), in addition to the polymerizable monomer that can be used in the preparation of the reactive dispersant of the present invention. ) 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 three or more hydroxyl groups such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolmethane, and a hydroxyl group-containing compound in which 1 to 20 mol of alkylene oxide is added thereto. Examples include compounds in which three or more molecules of acid are ester-bonded.

  The active energy ray-curable oligomer is selected from the group consisting of acrylic (meth) acrylate, urethane (meth) acrylate, ester (meth) acrylate, epoxy (meth) acrylate and the like other than the reactive dispersant of the present invention. 1 or more types of (meth) acrylate compounds which are mentioned.

  Examples of the urethane (meth) acrylate include polyfunctional urethane (meth) acrylate obtained by reacting an isocyanate compound with a hydroxyl group-containing (meth) acrylate compound. Examples of the isocyanate compound used herein include aliphatic or cycloaliphatic 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 that reacts with the isocyanate compound is substituted with a divalent to tetravalent alcohol or polyol compound and polymerized. But it ’s okay.

  The ester acrylates 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 bisphenol A. And one or more selected from dihydric or higher polyhydric alcohols, and phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, trimellitic anhydride , A polyfunctional ester obtained by further esterifying an ester polyol having a hydroxyl group obtained by esterifying one or more selected from polybasic acids typified by pyromellitic anhydride ( Data), such as acrylate, and the like.

  Further, as the epoxy acrylate, for example, propylene glycol, butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hydroxy A divalent epoxy (meth) acrylate compound obtained by adding (meth) acrylic acid to a diepoxy compound such as a triglycidyl etherified product of a divalent alcohol such as neopentyl glycol pivalate, bisphenol A, and ethoxylated bisphenol A; Such as trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, glycerin, etc. An epoxy tri (meth) acrylate compound having an average of three or more radically polymerizable unsaturated double bonds obtained by adding (meth) acrylic acid to an epoxy compound obtained by epoxidizing a monohydric alcohol; at least one 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 an aromatic ring or an alkylene oxide adduct thereof with glycidyl ether; Polyfunctional alicyclic epoxy acrylate, which is a hydrogenated type of functional aromatic epoxy acrylate; and further urethanated with a secondary hydroxyl group present in the molecule and one isocyanate group of the diisocyanate compound, and then the remaining isocyanate group at one end And hydroxyl Urethane-modified epoxy acrylate obtained by containing (meth) acrylate is reacted and the like.

  Among these, ester acrylates and urethane acrylates each having an average of 3 or more radically polymerizable unsaturated double bonds are particularly preferable because the cured film has good wear resistance.

  Although the manufacturing method of a reactive dispersion is not specifically limited, For example, the (meth) acrylic polymer (a1) which has an epoxy group is made to add and react the monomer (b1) which has a (meth) acryloyl group and a carboxyl group. A reaction product having a (meth) acryloyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH, or a (meth) acrylic polymer (a2) having a carboxyl group and having a (meth) acryloyl group and an epoxy group. 10 to 90 parts by weight of a reaction product (hereinafter referred to as a reactive dispersant) having an (meth) acryloyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH obtained by addition reaction of the monomer (b2) and inorganic particles 90 to 10 parts by weight are diluted with a dispersion medium (organic solvent) so that the total concentration of the reactive dispersant and the silica fine particles is 1 to 50% by weight. , And a method of dispersing by using a mechanical means.

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

  Examples of the mechanical means include a disperser, a disperser having a stirring blade such as a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, and a bead mill. In order to produce a reactive dispersion, when the obtained dispersion is used as a coating agent, it is possible to disperse glass beads, zirconia beads, etc. from the viewpoints of coatability, paint stability and transparency of the cured film. Dispersion with a bead mill using media is preferred.

  Examples of the bead mill include: Star mill manufactured by Ashizawa Finetech Co., Ltd .; MSC-MILL, SC-MILL, Attritor MA01SC manufactured by Mitsui Mining Co., Ltd .; Nano Glen Mill, Pico Glen Mill, Pure Glen Mill manufactured by Asada Tekko Co. , Mega Capper Glen Mill, Sera Power Glen Mill, Dual Glen Mill, AD Mill, Twin AD Mill, Basket Mill, Twin Basket Mill: Aspec Mill, Ultra Aspec Mill, Super Aspec Mill, etc. Is mentioned.

  The Ultra Aspec Mill is provided at a cylindrical stator, a supply port of slurry (a mixture of the reactive dispersant and silica fine particles of the present invention, the same applies hereinafter) provided at one end of the stator, and the other end of the stator. A slurry discharge port, a medium filled in the stator, and a rotor for stirring and mixing the slurry supplied from the supply port, and connected to the discharge port and rotated integrally with the rotor, or separated from the rotor In a wet stirring ball mill comprising an impeller-type separator that rotates independently and is separated into media and slurry by the action of centrifugal force and discharges the slurry from the discharge port, the axis of the shaft for driving the separator to rotate is described above. A wet stirring ball mill characterized by having a hollow discharge passage communicating with a discharge port, and a method for producing a dispersion using the same A slurry containing a reactive dispersant and fine silica particles is supplied from a supply port of the wet stirring ball mill to a stator filled with media, and the fine silica particles in the slurry are pulverized and dispersed in the reactive dispersant in the stator. And then separating the media from the slurry.

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

  FIG. 1 is a schematic diagram of a raw slurry pulverization treatment cycle provided with the wet stirring ball mill used in the method for producing a dispersion of the present invention, and FIG. 2 is a longitudinal section of the wet stirring ball mill used in the method for producing a dispersion of the present invention. FIG. 3 is a longitudinal sectional view of a supply port at the time of slurry supply of the wet stirring ball mill used in the method for producing a dispersion according to the present invention, and FIG. 4 is a longitudinal sectional view of a supply port at the time of media discharge. These are the longitudinal cross-sectional views of another example of the said wet stirring ball mill used with the manufacturing method of the dispersion of this invention, FIG. 6 is the figure showing the cross-sectional view of the separator of the wet stirring ball mill shown in FIG.

  In FIG. 1, the slurry extracted from the raw material tank 1 storing the slurry by the raw material pump 2 is supplied to a vertical grinding type wet stirring ball mill 3 and pulverized by being stirred together with media in the mill 3. After that, the media is separated by the separator 4 and discharged through the axis of the shaft 5, followed by a path returning to the tank 1, and circulated and crushed.

  An organic solvent, various additives, etc. can be suitably added to a slurry as needed. The slurry preferably contains an organic solvent.

  The amount of the organic solvent used is preferably 150 to 500 parts by weight with respect to a total of 100 parts by weight of the reactive dispersant of the present invention and the silica fine particles, and 200 to 300 parts by weight of the slurry and the media during the bead mill operation. It is preferable because the separation is good and the process for concentrating the slurry can be completed in a short time.

  In order to prepare the slurry, it is preferable to add silica fine particles after adding an organic solvent to the reactive dispersant of the present invention to obtain an organic solvent solution of the reactive dispersant.

  Examples of the various additives 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.

  As shown in detail in FIG. 2, the mill 3 includes a stator 7 having a longitudinally cylindrical shape and a jacket 6 through which cooling water for cooling the mill is passed, and a shaft 7. The shaft 5 is rotatably supported at the upper portion of the stator, has a mechanical seal at the bearing portion, and has a hollow shaft 9 having a hollow shaft at the upper portion, and is radially provided at the lower end portion of the shaft. A pin or disk-shaped rotor 11, a pulley 13 of a motor 12 shown in FIG. 1, which is fastened to a belt, a belt 14 and a rotary joint 15 attached to an open end of an upper end of the shaft, A separator 4 for separating media fixed to the shaft 5 near the top, and a raw material slurry supply port 16 provided at the bottom of the stator to face the shaft end of the shaft 5. , Is attached onto a grid-like screen support 17 to be installed in the product slurry outlet 19 provided at an eccentric position of the stator bottom, has the screen 18 for separating the media.

  The separator 4 is composed of a pair of discs 21 fixed to the shaft 5 at a predetermined interval and a blade 22 connecting the discs 21 to form an impeller. The separator 4 rotates with the shaft 5 and enters between the discs. A centrifugal force is applied to the medium and the slurry, and the medium is blown outward in the radial direction due to the difference in specific gravity, while the slurry is discharged through the discharge path 9 of the shaft center of the shaft 5.

  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 projecting downward and forming a raw material slurry inlet 27, a bottomed cylindrical body 28 projecting downward from the cylindrical body and provided with an air inlet 29, and ascending and descending to the cylindrical body 28 A piston 31 that can be fitted, a rod 32 that connects the piston 31 and the valve body 25, and a spring that is mounted on the piston in the cylindrical body 28 and pushes down the piston 31 to constantly bias the valve body 25 downward. 33 and a nut 34 that is screwed into the rod end protruding from the cylindrical body 28 and is attached so as to be adjustable in position. When the valve body 25 is pushed up by the supply of the raw slurry, the valve seat 25 is annularly formed. Slit From this, the raw material slurry is supplied into the mill, and the width of the slit can be adjusted by screwing or loosening the nut 34. When the raw material is supplied, the nut 34 hits the cylindrical body 28. The width is set so that the media cannot pass through even when it reaches the maximum. The valve body 25 at the time of supplying the raw material rises against the pressure in the mill 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. 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, and therefore, between the nut 34 and the cylindrical body 28. Has some room.

  The raw material 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 is raised to the full limit by increasing the 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 in the slit, in the illustrated example, compressed air is further supplied from a compressed air source (not shown) through the regulator 23, through the electromagnetic switching valve 30 and into the cylindrical body 28 through the introduction port 29. Compressed air is intermittently supplied by repeatedly switching the electromagnetic switching valve 30 to ON-OFF in a short cycle, whereby the valve body 25 repeatedly bites up and down to the upper limit position in a short cycle. It is designed to eliminate the trouble.

  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 the compressed air 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-described 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 the separate drive devices are used. In the latter embodiment, which is driven to rotate, the rotor and the separator can be driven to rotate at optimum rotational speeds.

  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.

  Next, a method for grinding the slurry using the apparatus shown in FIG. 1 will be described. The medium is filled in the stator 7 of the ball mill 3. As the medium, for example, various micro beads are used. Examples of the material for the microbeads include zirconia, glass, titanium oxide, copper, and zirconia silicate.

  Regarding the particle size of the media, the separation of the dispersed media in the separator 44 is good, the silica fine particles are well dispersed in the rotor 11, the time required for the dispersion is less likely to be long, the impact on the silica particles Is not too strong, and an overdispersion phenomenon due to the destruction of the silica fine particles hardly occurs.

  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.

  The filling rate of the medium in the stator is, for example, 80 to 90% of the stator internal volume. By making the filling rate 80 to 90% of the internal volume of the stator, the power required to obtain a unit weight of product slurry is minimized. That is, grinding can be performed most efficiently.

  After the medium is filled in the stator 7 of the ball mill 3, the motor 12 is first driven with the valves 58, 59 and 60 closed and the valves 61 and 62 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 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 slurry and media in the mill are agitated and mixed by the rotation of the rotor 11 and the slurry is pulverized. The rotation of the separator 4 separates the media and the slurry that have entered the separator due to the difference in specific gravity. While being blown outward in the radial direction, the slurry having a low specific gravity is discharged through the discharge passage 9 formed in the shaft center of the shaft 5 and returned to the raw material tank 1.

The slurry returned to the raw material tank 1 repeats the cycle of being supplied again to the mill by the raw material pump 2, and pulverization proceeds. When the pulverization has progressed to some extent, the particle size of the slurry is appropriately measured. When the desired particle size is reached, the raw material pump is stopped, then the motor 12 is stopped, the operation of the mill 3 is stopped, and the pulverization is terminated. Thereafter, the valves 58 and 59 are opened, the valves 61 and 62 are closed, and the raw material pump and the motor 12 are restarted, and then the valve 60 is heard. Then, the product slurry in the raw material tank 1 is extracted by the raw material pump 2 and sent into the product tank 63, while the product slurry in the mill is agitated by the rotation of the rotor 7 and passes through the valve 60 and the discharge passage 9. Alternatively, the compressed air or N ₂ gas supplied into the mill from the upper part of the mill is extruded through the screen 18 and sent to the product tank 63. As described above, the product slurry in the raw material tank 1 and the mill 3 is collected in the product tank 63.

  As the time for dispersing the silica fine particles, since the dispersion becomes good and the productivity becomes good, the cycle (circulation flow rate) in which the slurry is supplied to the mill by the raw material pump 2 is 1.5 L / hour. In this case, 5 to 60 minutes is usually preferable, and 10 to 40 minutes is more preferable.

  The circulating flow rate is preferably 5 to 15 L / hour, more preferably 8 to 10 L / hour.

The rotor 7 is rotated when collecting the product in order to prevent clogging at the screen 18 by mixing so that the media settles in the mill and is not unevenly distributed in the lower layer of the mill. Therefore, the compressed air or N ₂ gas is appropriately taken out from the outlet 19 and the screen 18 is backwashed.

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 that have reached 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 made into an active energy ray-curable resin composition by mixing with other compounds. These compounds include the aforementioned active energy ray curable monomers, active energy ray curable oligomers, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoaming agents, and release agents. , Silane coupling agents, antistatic agents, antifogging agents, coloring agents, 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.

  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 casting polymerization is 100 parts by weight. , Each preferably in the range of 0.01 to 10 parts by weight.

  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- -Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, Benzyldimethylketal, 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-eth C) Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazine anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloro Anthraquinone etc. are 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% by weight with respect to 100 parts by weight 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 parts, particularly 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 two or more mixed systems selected from the group of phenyl) -butan-1-one are: Particularly preferred for the resistance is high coating the active energy ray curable resin composition.

  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 (manufactured by Ciba Specialty Chemicals), Lucirin TPO (manufactured by BASF), KAYACURE-DETX, MBP, DMBI, EPA, OA [Nippon Kayaku Co., Ltd.], VICURE-10, 55 (manufactured by STAUFER 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.

The coating amount at the time of applying to the film substrate, for example, on a variety of film substrate, the weight after drying of 0.1 to 30 g / ^{m 2,} the coating preferably such that from 1 to 20 g / ^{m 2} It is preferable to do this. 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 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 5-100 with respect to the film thickness of a film-form base material. % Film is more preferable, and a film having a cured layer thickness 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 employed, 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 conveyance speed of 5 to 50 m / min with respect to one lamp having a light quantity 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 of usually 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 not only used as a protective film for protecting the 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 consists of spray coating a coating agent comprising an active energy ray-curable resin composition, or applying the active energy 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 with active energy rays to produce a crosslinked coating film, or after adhering the transfer material to the surface of the molded product, irradiating with active energy rays to produce a crosslinked coating film, and then the 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. As the transfer material, for example, the active energy ray-curable resin composition is blended alone or with a polyfunctional isocyanate, mixed, coated on a base sheet, and heated to be semi-cured (B -It can be manufactured by making a stage).

  The polyfunctional isocyanate used in combination with the active energy ray-curable resin composition is not particularly limited, and various known ones 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 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, preferably It is preferable that it is 1 / 0.05-1 / 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 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, and 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, silicon resin release agents, fluororesin release agents, cellulose derivative release agents, 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 the material of the printing layer, a binder such as polyvinyl resin, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, etc. 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, a screen printing method, or the like 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 may 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 resin layer and an adhesive layer formed into a B-stage 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, the energy layer is cured by irradiation with active energy rays to crosslink and cure the resin layer (transfer method), or the transfer material is sandwiched in the mold 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 crosslink and 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 light quantity 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 portion 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 coating the curable resin composition on the base sheet, if the adhesive force between the base sheet and the curable resin composition is not sufficient,
1. A primer is applied to the surface of the base sheet on which the curable resin composition is to be applied, and then the curable resin composition is applied thereto.
2. 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 that case, the cured resin layer and the adhesive layer can be sequentially formed on the base sheet, and the pattern 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.

  As a method for bonding the molded product and the protective layer forming sheet in the post-adhesion method, for example, an adhesive is applied to the base sheet of the protective layer forming sheet or the surface of the molded product and the base sheet and the molded product of the protective layer forming sheet are used. Method of adhering to the surface, after attaching a double-sided adhesive tape to the base sheet or molded product surface of the protective layer forming sheet, then peeling off the release protective sheet of the double-sided adhesive tape to expose the adhesive surface, the protective layer forming sheet A method for adhering the base sheet and the surface of the molded product, after applying an adhesive to the base sheet of the protective layer forming sheet to form an adhesive surface, a protective layer forming sheet in which the adhesive surface is protected with a release protective sheet is prepared in advance In addition, there may be mentioned a method in which the release 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.

(Production Example 1)
In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, 250 g of glycidyl methacrylate (hereinafter referred to as GMA), 1000 g of methyl isobutyl ketone (hereinafter referred to as MIBK) and t-butylperoxyethyl hexanoate ( Then, 10 g of PO) was charged, and then the system temperature was raised to about 90 ° C. over about 1 hour under a nitrogen stream, and the temperature was kept for 1 hour. 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 referred to 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 the reactive dispersant (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.

(Production Example 2)
Using the same reaction apparatus as in Production Example 1, 125 g of GMA, 125 g of methyl methacrylate (hereinafter referred to as MMA), 1000 g of MIBK, and 10 g of PO were charged, and the system temperature was kept for about 1 hour under a nitrogen stream. The temperature was raised to about 90 ° C. and kept for 1 hour. Next, from a dropping funnel charged beforehand 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 for about 2 hours under a nitrogen stream, 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 and cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reactive dispersant (A-2). The reactive 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.

(Production Example 3)
Using the same reactor as in Production Example 1, after charging 75 g of GMA, 175 g of MMA, 1000 g of MIBK, and 8 g of PO, until the system temperature reaches 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 inlet tube was replaced with an air inlet tube, 152 AA, 2.3 g of methoquinone and 5.6 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 and cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reactive dispersant (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 1
In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and an air inlet, silica fine particles (Aerosil 50, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 30 nm) 50 g, MIBK 500 g and methacryloxypropyltrimethoxysilane (KBM503, Shin-Etsu Chemical) 4 g), 0.88 g of a 5% aqueous solution of phosphoric acid ester (Phoslex A-3, manufactured by SC Organic Chemical) was added, and the temperature rose to 100 ° C. under an air stream. The slurry was incubated for 6 hours to obtain a surface-treated inorganic particle slurry.
25 g of the reactive dispersant (A-1) obtained in Production Example 1 and 50 g of dipentaerythritol hexaacrylate were added to the resulting slurry of the surface-treated inorganic particles (50 g in solid content) Got.

  Dispersion of the silica fine particles in this blend was performed using Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd. The ultra apex mill UAM015 used in FIG. 1 has a mill 3 in which the inner diameter of the stator 7 is 50 mmφ, the inner volume is 0.17 liter, the diameter of the separator 4 is 40 mmφ, and the distance between the disks 21 of the separator 4 is 5 mm. In producing the dispersion, the mill 3 was filled with zirconia beads having a diameter of 30 μm as a medium at 50% of the volume of the mill 3.

  The compound was supplied from the supply port 16 from the raw material tank 1 of FIG. The mill 3 was operated at a constant rotor rotational speed (peripheral speed at the rotor tip was 8 m / sec), and the mixture was pulverized at a flow rate of 1.5 liters 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. The obtained dispersion was taken out from the take-out port of Ultra Apex Mill UAM015, and MIBK was removed using an evaporator to obtain a dispersion having a nonvolatile content concentration of 50%.

  2 parts of Irgacure # 184 (photoinitiator) was added to 100 parts of this 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 produced on the following conditions and the pencil hardness was measured, it was 4H.

(Example 2)
A dispersion was obtained in the same manner as in Example 1, except that silica fine particles modified with methacrylic groups (RM50, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 30 nm) were used instead of the surface-modified silica fine particles of Example 1. Got. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Similarly, the pencil hardness was measured and found to be 4H.

(Example 3)
A dispersion was obtained in the same manner as in Example 1 except that silica fine particles modified with methacrylic groups (R711, manufactured by Nippon Aerosil Co., Ltd., average primary particle size of 12 nm) were used instead of the surface-modified silica fine particles of Example 1. Got. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Similarly, the pencil hardness was measured and found to be 4H.

Example 4
A dispersion was obtained in the same manner as in Example 1 except that silica fine particles (R7200, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 12 nm) were used instead of the surface-modified silica fine particles of Example 1. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Similarly, the pencil hardness was measured and found to be 4H.

(Example 5)
In the same manner as in Example 1, except that 8 g of methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical) was used instead of 4 g of methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical) of Example 1, A dispersion was obtained. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Similarly, the pencil hardness was measured and found to be 5H.

<Measuring method of pencil hardness>
1. Method for producing 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 K5400.

(Example 6)
Dispersion was carried out in the same manner as in Example 1 except that 25 g of the reactive dispersant (A-2) obtained in Production Example 2 was used instead of 25 g of the reactive dispersant (A-1) in Example 1. Got the body. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Similarly, the pencil hardness was measured and found to be 5H.

(Example 7)
Dispersion was carried out in the same manner as in Example 1 except that 25 g of the reactive dispersant (A-3) obtained in Production Example 3 was used instead of 25 g of the reactive dispersant (A-1) in Example 1. Got the body. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. Similarly, the pencil hardness was measured and found to be 5H.

(Comparative Example 1)
25 g of the reactive dispersant (A-1) obtained in Production Example 1 in solid content, 25 g of dipentaerythritol hexaacrylate (DPHA), silica fine particles (Aerosil 50 manufactured by Nippon Aerosil Co., Ltd.), average primary particle size of about 12 nm ) 50g and MIBK 200g were blended to obtain a blend. The active energy ray-curable resin composition had good storage stability without precipitation even when stored at room temperature (25 ° C.) for 2 months. A cured coating film was prepared in the same manner as in Example 1, and the pencil hardness was measured, and the pencil hardness was measured.

(Comparative Example 2)
50 g of silica fine particles modified with methacrylic groups (RM50, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 30 nm), 50 g of bisphenol A epoxy acrylate (manufactured by DIC Corporation, Unidic V-5500), and 200 parts of MIBK A reactive dispersion for comparison having a nonvolatile content concentration of 50% was obtained in the same manner as in Example 1 except that 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, when the cured coating film was produced similarly to Example 1 and pencil hardness was measured, it was 2H.

(Comparative Example 3)
Nonvolatile content in the same manner as in Example 1 except that 50 parts of silica fine particles modified with methacrylic groups (R711, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 12 nm), 50 parts of DPHA, and 200 parts of MIBK were used. A reactive dispersion for comparison having a concentration of 50% was obtained.

  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. A cured coating film was produced in the same manner as in Example 4, and the pencil hardness was measured.

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 ... Air inlet 30 ... Electromagnetic switching valve 31 ... Piste 32 ... Rod 33 ... Spring 34 ... Nut 43 ... Shaft 43a ... Shaft 43 step 44 ... Separator 45 ... Spacer 45 ... Rotor 47 ... Stopper 48 ... Screw 51 ... Blade fitting groove 52 ... Disk 53 ... Blade 54 ... ······························· 55 .... Valve 63 ... Product tank

Claims (14)

In the dispersion in which the surface-treated inorganic particles (A) are dispersed in the reactive dispersant,
1) Surface-treated inorganic particles (A) were obtained by surface-treating inorganic particles (C) with a compound (B) having a (meth) acryloyl group, and 2) a reactive dispersant. Is a reaction product obtained by addition reaction of a monomer (b1) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having an epoxy group, or having a carboxyl group (meta ) A reaction product obtained by addition-reacting a monomer (b2) having a (meth) acryloyl group and an epoxy group to the acrylic polymer (a2), the (meth) acryloyl equivalent being 200 to 600, and the hydroxyl value Dispersion characterized in that is 90 to 280 mg / KOH. The dispersion according to claim 1, wherein the reactive dispersant has a (meth) acryloyl equivalent of 200 to 400 and a hydroxyl value of 140 to 280 mg / KOH. The reactive dispersant is obtained by subjecting a (meth) acrylic polymer having an epoxy group obtained by polymerizing glycidyl (meth) acrylate to addition reaction of (meth) acrylic acid. Dispersion. The dispersion according to any one of claims 1 to 3, wherein the reactive dispersant has a weight average molecular weight of 5,000 to 100,000. The dispersion according to any one of claims 1 to 4, wherein the primary particle diameter of the inorganic particles (C) is 10 nm to 300 nm. The dispersion according to any one of claims 1 to 5, wherein the inorganic particles (C) are silica fine particles. The compound (B) having a (meth) acryloyl group is represented by the general formula (1)

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6).
The dispersion according to any one of claims 1 to 6, which is an organosilane compound represented by the formula: The energy beam curable resin composition containing the dispersion in any one of Claims 1-7. A slurry containing the inorganic particles (A) according to any one of claims 1 to 7 and a reactive dispersant, a cylindrical stator, a slurry supply port provided at one end of the stator, and the other end of the stator A slurry discharge port, a medium filled in the stator, and a rotor for stirring and mixing the slurry supplied from the supply port; and a rotor connected to the discharge port and rotating integrally with the rotor; or Is a shaft that rotates and drives the separator in a wet-stirring ball mill that consists of an impeller-type separator that rotates independently and is separated into media and slurry by the action of centrifugal force and discharges the slurry from the discharge port. Is supplied to the stator filled with media from the supply port of the stirring ball mill, which is a hollow discharge passage communicating with the discharge port, and the slurry is filled in the stator. After dispersion into milled with a dispersant of the silica fine particles in chromatography method for producing a dispersion and separating the media from the slurry. The method for producing a dispersion according to claim 9, wherein the medium is zirconia fine particles having a particle diameter of 15 to 100 μm. An energy beam curable resin composition comprising a dispersion obtained by the production method according to claim 9. A film having a cured layer obtained by curing the energy ray-curable resin composition according to claim 8 or 11 on a film-like substrate. The film-like substrate is one or more film-like substrates selected from the group consisting of a film-like substrate of polyethylene terephthalate resin, a film-like substrate of polycarbonate resin, and a film-like substrate of acetylated cellulose resin. 12. The film according to 12. The film according to claim 12 or 13, wherein the thickness of the cured layer is 3 to 100% with respect to the thickness of the film-like substrate.

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