KR101292720B1 - Dispersion of inorganic particle, energy-ray curable resin composition, and film - Google Patents

Abstract

The subject of this invention is providing the dispersion which is high in hardened | cured material, excellent in dispersion stability, and also provides the manufacturing method of the dispersion which has the said characteristic.
In the dispersion in which the surface-treated inorganic particles (A) are dispersed in a reactive dispersant,
1) The surface-treated inorganic particle (A) is obtained by surface-treating an inorganic particle (b1) with the compound (B) which has a (meth) acryloyl group,
2) Reaction dispersing agent adds and reacts the (meth) acryloyl group and the monomer which has a carboxyl group to the (meth) acryl polymer which has an epoxy group, or the (meth) acryl to the (meth) acryl polymer which has a carboxyl group As a reaction product formed by addition reaction of a monomer having a diary and an epoxy group, a (meth) acryloyl equivalent is 200 to 600 and a hydroxyl value is 90 to 280 mg / KOH. Solve it.

Description

Inorganic particle dispersion, energy ray curable resin composition, and film {DISPERSION OF INORGANIC PARTICLE, ENERGY-RAY CURABLE RESIN COMPOSITION, AND FILM}

This invention relates to the dispersion in which the surface-treated inorganic particle (A) was disperse | distributed to the reactive dispersing agent, and also relates to the manufacturing method, the curable resin composition containing the said dispersion, and the film obtained by hardening | curing the said composition. .

In order to raise the hardness of the cured coating film obtained by hardening | curing an active energy ray curable resin composition, there exists a method of disperse | distributing a silica microparticle to an active energy ray curable resin composition. Silica fine particles include colloidal silica produced by a wet method and fumed silica manufactured by a dry method. The surface of the silica fine particles has a silanol group, and the silica fine particles are hydrophilic. Therefore, affinity with the organic phase which is a main component in compositions, such as an active energy ray hardening-type monomer and an oligomer, is bad. In addition, the silica fine particles have a larger specific gravity than the organic phase. Therefore, it is generally difficult to stably and disperse the silica fine particles in the active energy ray-curable resin composition over a long period of time, and the active energy ray-curable resin composition containing the silica fine particles causes the silica fine particles to aggregate or settle when left for a long time. , Storage stability is poor. In addition, the silica fine particles are usually agglomerated strongly by the intermolecular force, the electrostatic force or the like acting between the primary particles, which also adversely affects the storage stability.

As a method of stably dispersing silica fine particles in an active energy ray-curable resin composition, for example, a method of hydrophobizing a surface of silica fine particles by surface treating the silica fine particles with a reactive silane coupling agent having a hydrophobic group is described ( For example, refer patent document 1). However, even if it is the silica fine particle obtained by the method of patent document 1, dispersion stability in an active energy ray curable resin composition is not enough, and although description of each evaluation of haze, fingerprint wiping property, and oily dye wiping is clear, it is clear. It is not about the hardness of hardened | cured material.

Japanese Patent Laid-Open No. 2006-348196

In this invention, in view of the said background art, it is providing the dispersion which is high in hardened | cured material and excellent in dispersion stability. Moreover, this invention makes it a subject to provide the manufacturing method of the dispersion which has the said characteristic.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining, in the dispersion in which the inorganic particle (A) surface-treated was disperse | distributed to the reactive dispersing agent,

1) The surface-treated inorganic particle (A) is obtained by surface-treating an inorganic particle (b1) with the compound (B) which has a (meth) acryloyl group,

2) Reaction dispersing agent adds and reacts the (meth) acryloyl group and the monomer which has a carboxyl group to the (meth) acryl polymer which has an epoxy group, or the (meth) acryl to the (meth) acryl polymer which has a carboxyl group As a reaction product formed by addition reaction of a monomer having a diary and an epoxy group, a dispersion characterized by a (meth) acryloyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH is extremely useful for solving the above problems. It was found that the present invention was completed.

That is, this invention is a dispersion in which the surface-treated inorganic particle (A) was disperse | distributed to the reactive dispersing agent,

1) The surface-treated inorganic particle (A) is obtained by surface-treating an inorganic particle (b1) with the compound (B) which has a (meth) acryloyl group,

2) Reaction dispersing agent adds and reacts the (meth) acryloyl group and the monomer which has a carboxyl group to the (meth) acryl polymer which has an epoxy group, or the (meth) acryl to the (meth) acryl polymer which has a carboxyl group It is a reaction product formed by addition reaction of the monomer which has a diary and an epoxy group, The (meth) acryloyl equivalent is 200-600, The hydroxyl value is 90-280 mg / KOH, The dispersion characterized by the above-mentioned is provided.

The present invention also provides a slurry containing the surface-treated inorganic particles (A) and a reactive dispersant at a cylindrical stator, a supply port of the slurry provided at one end of the stator, and the other end of the stator. The outlet of the slurry to be prepared, the rotor to stir-mix the media supplied in the stator and the slurry supplied from the supply port, and are connected to the outlet, and rotated integrally with the rotor, or rotated independently from the rotor, In a wet stirred ball mill comprising an impeller-type separator which separates the media and the slurry by the action of centrifugal force and discharges the slurry from the discharge port, the shaft center of the shaft for rotating the separator to the hollow discharge path communicating with the discharge port. The media is supplied to the stator filled with media from the supply port of one stirring ball mill, and the sludge in the stator After carrying out the dispersion of the inorganic particles in the milling and reactive dispersant of the present invention is to provide a method for manufacturing a dispersion, characterized in that for separating the media from the slurry.

Moreover, this invention provides the energy-beam curable resin composition containing the said dispersion, hardened | cured material formed by hardening the said composition, and a film.

According to this invention, the hardened | cured material and film which have high hardness, and the dispersion used for the said hardened | cured material and a film are attained.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram of the raw material slurry grinding | pulverization processing cycle provided with the said wet stirring ball mill used by the manufacturing method of the dispersion of this invention.
Fig. 2 is a longitudinal sectional view of the wet stirred 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 during slurry supply of the wet stirred ball mill used in the method for producing a dispersion of the present invention.
Fig. 4 is a longitudinal sectional view of a supply port at the time of media discharge.
Fig. 5 is a longitudinal sectional view of still another example of the wet stirred ball mill used in the method for producing a dispersion of the present invention.
FIG. 6 is a cross-sectional view of a separator of the wet stirred ball mill shown in FIG. 5. FIG.

That is, the present invention,

1. A dispersion in which the surface treated inorganic particles (A) are dispersed in a reactive dispersant,

1) The surface-treated inorganic particle (A) is obtained by surface-treating an inorganic particle (b1) with the compound (B) which has a (meth) acryloyl group,

2) Reaction dispersing agent adds and reacts the (meth) acryloyl group and the monomer which has a carboxyl group to the (meth) acryl polymer which has an epoxy group, or the (meth) acryl to the (meth) acryl polymer which has a carboxyl group A reaction product formed by addition reaction of a monomer having a diary and an epoxy group, wherein the (meth) acryloyl equivalent is 200 to 600, and a hydroxyl value is 90 to 280 mg / KOH.

2. Dispersion as described in 1. whose (meth) acryloyl equivalent of a reactive dispersing agent is 200-400, and whose hydroxyl value is 140-280 mg / KOH,

3. Dispersion as described in 1. or 2. in which reactive dispersant add-reacts (meth) acrylic acid to the (meth) acryl polymer which has an epoxy group obtained by superposing | polymerizing glycidyl (meth) acrylate,

4. The dispersion according to any one of 1. to 3, wherein the weight average molecular weight of the reactive dispersant is 5,000 to 100,000,

5. Dispersion as described in any one of 1.-4 whose primary particle diameter of inorganic particle (b1) is 10 nm-300 nm,

6. Dispersion as described in any one of 1.-5 whose inorganic particle (b1) is a silica fine particle,

7. The compound (B) which has a (meth) acryloyl group is General formula (1)

However,

(In formula, R <_1> , R <_2> , R <_3> is a C1-C4 alkyl group each independently, n is an integer of 1-6.)

The dispersion as described in any one of 1.-6 which is an organosilane compound represented by

8. Energy-beam curable resin composition containing the dispersion as described in any one of 1.-7.

9. A cylindrical stator, a supply port for slurry provided at one end of the stator, a discharge port of slurry provided at the other end of the stator, a rotor for stirring and mixing the slurry supplied from the supply port with the media filled in the stator, and a discharge port. A wet stirring ball, which is connected to the rotor and rotates integrally with the rotor, or rotates independently from the rotor, separates into media and slurry by the action of centrifugal force, and discharges the slurry from the outlet. As a method for producing a dispersion using a mill,

From the supply port of the stirring ball mill which made the slurry containing the inorganic particle (A) and reactive dispersing agent as described in any one of 1.-7 into the hollow discharge path through which the shaft center of the shaft which drives a separator rotates through the said discharge port, A method for producing a dispersion, wherein the medium is separated from the slurry after supplying to a packed stator and pulverizing the silica fine particles in the slurry and dispersing it in a dispersant in the stator.

10. The method for producing the dispersion according to 9., wherein the media is zirconia fine particles having a particle size of 15 to 100 µm.

An energy ray curable resin composition comprising the dispersion obtained by the production method described in 11. 9.

It has a cured layer obtained by hardening | curing the energy-beam curable resin composition of 12. 8. or 11. on a film-form base material, The film characterized by the above-mentioned.

13. Said film-form base material is 1 or more types of film-form base material chosen from the group which consists of a film-form base material of polyethylene terephthalate resin (PET), the film-form base material of polycarbonate resin, and the film-form base material of acetylated cellulose resin. The film described in

14. The film as described in 12. or 13. whose film thickness of the said hardened layer is 3 to 100% with respect to the film thickness of a film-form base material.

.

The dispersion of the present invention is characterized in that the surface-treated inorganic particles (A) are dispersed in a reactive dispersant.

Although the surface-treated inorganic particle (A) has the characteristics surface-treated with the compound (B) which has a (meth) acryloyl group, the compound (B) which has such a (meth) acryloyl group is an inorganic particle (b1). ) And there is no limitation as long as the compound (B) having a (meth) acryloyl group is introduced into the surface of the inorganic particle (b1).

As a compound (B) which has a (meth) acryloyl group which can be used, since the reactivity with an inorganic particle (b1) is high, the organosilane compound which has a (meth) acryloyl group is mentioned, for example.

More specifically, general formula (1)

[Figure 2]

(In formula, R <_1> , R <_2> , R <_3> is a C1-C4 alkyl group each independently, n is an integer of 1-6.)

Particularly preferred are the compounds represented by.

It is necessary to have a group which forms a chemical bond with the compound (B) which has a (meth) acryloyl group on the surface of an inorganic particle (b1), For example, when using silica fine particles as an inorganic particle (b1), The silanol group functions as a group forming a bond. Reaction conditions for forming a chemical bond may be conventional reaction conditions, or a catalyst may be used to promote the reaction. Although there is no restriction | limiting in the catalyst used, For example, phosphate ester is mentioned.

The inorganic particle (b1) is not particularly limited, but may be an inorganic particle that can be surface-treated with an organosilane compound such as silica fine particles, zirconia fine particles, alumina fine particles cerium oxide fine particles, titanium fine particles, or barium titanate fine particles, in particular silica. Fine particles are preferred. The preferable primary particle diameter of these microparticles | fine-particles can mention the range of 10-300 nm. If it is 10 nm or less, dispersion of the inorganic particle in a dispersion will become inadequate, and if it is 300 nm or more, since sufficient strength of a cured film cannot be maintained, it is not preferable.

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

In the present invention, the reactive dispersant means that it is a reactive dispersant that polymerizes with an active energy ray. The (meth) acrylic equivalent means the solid content weight (g / eq) of the reactive dispersing agent per mole of (meth) acryloyl group (meaning acryloyl group or methacryloyl group).

The reactive dispersant of the present invention will be briefly described as follows for convenience.

As a reactive dispersing agent, the reactive dispersing agent (A1) formed by addition-reacting the monomer (b1) which has a (meth) acryloyl group and a carboxyl group to the (meth) acryl polymer (a1) which has an epoxy group, or the (meth) acryl polymer which has a carboxyl group Although the reactive dispersing agent (A2) formed by addition-reacting the monomer (b2) which has a (meth) acryloyl group and an epoxy group to (a2) is mentioned, Any of (A1) and (A2) as a reactive dispersing agent of this invention is mentioned. You can do it.

The (meth) acrylic polymer (a1) used for production of the reactive dispersant (A1) is, for example, a copolymerization reaction of a polymerizable monomer having a (meth) acryloyl group and an epoxy group with another polymerizable monomer, if necessary. Obtained by

As a polymerizable monomer which has the said (meth) acryloyl group and an epoxy group, it is (meth) acrylic-acid glycidyl, (alpha) -ethyl (meth) acrylate glycidyl, and (alpha) -n-propyl (meth) acrylate, for example. Dill, α-n-butyl (meth) acrylic acid 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, etc. are mentioned. These may be used independently and may use 2 or more types together.

In adjusting a (meth) acryl polymer (a1), the usage-amount of the polymerizable monomer which has a (meth) acryloyl group and an epoxy group is 25-100 weight part normally, Preferably it is 40-100 weight part. The other polymerizable monomer is an optional component, and the amount of use thereof is usually 0 to 75 parts by weight, preferably 0 to 60 parts by weight.

The (meth) acrylic polymer (a2) used for the production of the reactive dispersant (A2) is, for example, a copolymerization reaction of a polymerizable monomer having a (meth) acryloyl group and a carboxyl group with another polymerizable monomer as necessary. Obtained by

As a polymerizable monomer which has a (meth) acryloyl group and a carboxy group, For example, (meth) acrylic acid; Unsaturated having ester bonds such as β-carboxyethyl (meth) acrylate, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, and their lactone modified substances Monocarboxylic acid; Maleic acid; and the like. These may be used independently and may use 2 or more types together.

In adjusting a (meth) acryl polymer (a2), the usage-amount of the polymerizable monomer which has a (meth) acryloyl group and a carboxy group is 25-100 weight part normally, Preferably it is 40-100 weight part. The other polymerizable monomer is an optional component, and the amount of use thereof is usually 0 to 75 parts by weight, preferably 0 to 60 parts by weight.

As another polymerizable unsaturated monomer to copolymerize as needed at the time of manufacture of a (meth) acryl polymer (a1) and a (meth) acryl polymer (a2), the following polymerizable monomers are mentioned, for example.

(1) Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, (meth) (Meth) acrylic acid ester which has a C1-C22 alkyl group, such as octadecyl acrylate and docosyl (meth) acrylate;

(2) (meth) acrylic acid ester which has alicyclic alkyl groups, such as cyclohexyl (meth) acrylate, isoboroyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl oxyethyl (meth) acrylate ;

(3) Benzoyl oxyethyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, phenethyl ethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy- (meth) acrylate (Meth) acrylic acid esters having aromatic rings such as 3-phenoxypropyl;

(4) hydroxyethyl (meth) acrylate; Hydroxypropyl (meth) acrylate, butyl butyl (meth) acrylate, and glycerol (meth) acrylate; Acrylic esters having hydroxyalkyl groups such as (meth) acrylic acid esters having polyalkylene glycol groups such as lactone-modified (meth) acrylate hydroxyethyl, (meth) acrylate polyethylene glycol, and (meth) acrylate 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 and methyl ethyl itaconate;

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

(7) diene-based compounds such as butadiene, isoprene, biperylene, and 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 and vinylidene cyanide;

(13) acrylamide and alkyd substituted amides thereof;

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

(15) fluorine-containing α-olefins such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene; Or (per) fluorine having 1 to 18 carbon atoms in the (per) fluoroalkyl group, such as trifluoromethyltrifluorovinylether, pentafluoroethyltrifluorovinylether, or heptafluoropropyltrifluorovinylether Low alkyl perfluoro vinyl ethers; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, (Per) fluorine having from 1 to 18 carbon atoms of (per) fluoroalkyl groups such as 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Fluorine-containing ethylenically unsaturated monomers such as roalkyl (meth) acrylates;

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

(17) N, N-di, such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, or N, N-diethylaminopropyl (meth) acrylate Alkyl aminoalkyl (meth) acrylate etc. are mentioned.

The other polymerizable unsaturated monomers used when manufacturing these (meth) acryl polymer (a1) and (meth) acrylic polymer (a2) may be used independently, and may use 2 or more types together.

The said (meth) acryl polymer (a1) and (a2) are obtained when it superposes | polymerizes (copolymerizes) using a well-known method, and the copolymerization form is not specifically limited. In the presence of a catalyst (polymerization initiator), it can be produced by addition polymerization, and may be any of a random copolymer, a block copolymer, a graft copolymer, and the like. Moreover, well-known polymerization methods, such as a block polymerization method, a solution polymerization method, suspension polymerization method, and emulsion polymerization method, can also be used for a copolymerization method.

Here, as a solvent which can be used for solution polymerization etc., a typical thing is mentioned, 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 poron;

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 and tetrahydrofuran;

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

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

Hydrocarbon solvents, such as toluene, xylene, sorbet 100, sorbet 150, ssol 1800, ssol sol 310, isoper E, isoper G, exonnaphtha 5, and exonnaphtha 6, are mentioned. These may be used independently and may use 2 or more types together, but the reaction of the (meth) acryl polymer (a1) which has an epoxy group used as a 2nd-stage reaction, and the monomer (b1) which has a carboxyl group, or (meth) which has a carboxyl group In order to perform reaction of an acryl-type monomer (a2) and the monomer (b2) which has an epoxy group efficiently, it is preferable to carry out at high temperature of 100-150 degreeC, From this viewpoint, the boiling point of a solvent is 100 degreeC or more, Preferably it is 100- It is preferable to use 150 degreeC thing.

Moreover, as the catalyst mentioned above, what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvalero Azo compounds such as nitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, t-butylperoxyethylhexanoate, 1,1'-bis- (t-butylperoxy) cyclohexane, t-amylperoxy- Organic peroxides, such as 2-ethylhexanoate and t-hexyl peroxy-2-ethylhexanoate, hydrogen peroxide etc. are mentioned.

When using a peroxide as a catalyst, you may use a peroxide together with a reducing agent as a redox type initiator.

The reactive dispersant (A1) reacts the (meth) acryl polymer (a1) having an epoxy group with the monomer (b1) having a (meth) acryloyl group and a carboxy group as described above. As a monomer (b1) which has a (meth) acryloyl group and a carboxy group, it is (meth) acrylic acid, for example; Unsaturated having ester bonds such as β-carboxyethyl (meth) acrylate, 2-acryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, and their lactone modified substances Monocarboxylic acid; Maleic acid; and the like.

Moreover, after making anhydrides, such as succinic anhydride and maleic anhydride, react with hydroxyl-containing polyfunctional (meth) acrylate monomers, such as pentaerythritol triacrylate, as a monomer (b1), a carboxyl group-containing polyfunctional (meth) acrylate You may use what made into the monomer. The monomer (b1) which has these (meth) acryloyl group and a carboxy group may be used independently, respectively and may use 2 or more types together.

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, the carboxy group in a monomer (b1) per mole of an epoxy group is usually used. It is preferable to make the number-of-moles into 0.4-1.1 mol.

The reactive dispersant (A2) is obtained by reacting the (meth) acryl polymer (a2) having a carboxy group with the monomer (b2) having a (meth) acryloyl group and an epoxy group as described above. As a monomer (b2) which has a (meth) acryloyl group and an epoxy group, it is (meth) acrylic-acid glycidyl, (alpha) -ethyl (meth) acrylate glycidyl, and (alpha) -n-propyl (meth) acrylate, for example. Dill, α-n-butyl (meth) acrylic acid 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, etc. are mentioned. These may be used independently and may use 2 or more types together.

Reaction of a polymer (a2) 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, the epoxy group in monomer (b1) with respect to 1 mol of carboxyl groups is common. It is preferable to make the number-of-moles into 0.4-1.1 mol.

Reaction of the (meth) acryl polymer (a1) which has the said epoxy group, the monomer (b1) which has a (meth) acryloyl group, and a carboxyl group, the (meth) acryl polymer (a2) which has a carboxyl group, (meth) acryloyl group, and Reaction with the monomer (b2) which has an epoxy group can also be performed, for example with the following method.

Method 1: The method of superposing | polymerizing a (meth) acryl polymer (a1) by the solution polymerization method and adding and reacting the monomer (b1) which has a (meth) acryloyl group and a carboxy group to a reaction system.

Method 2: The method of superposing | polymerizing a (meth) acryl polymer (a2) by the solution polymerization method, adding the monomer (b2) which has a (meth) acryloyl group and an epoxy group, and makes it react.

The reactive dispersant of the present invention is preferably a polymer having a main skeleton of a structure obtained by polymerizing a monomer having one polymerizable unsaturated double bond per molecule, but is preferably a polymerizable unsaturated double bond within a range that does not cause gelation during polymerization. You may use together the monomer which has two or more.

As described above, the reactive dispersant of the present invention is a reactive dispersant (A1) [a polymer obtained by reacting a (meth) acryl polymer (a1) having an epoxy group with a monomer (b1) having a (meth) acryloyl group and a carboxyl group]. Preference is given to an acrylic polymer obtained by reacting an epoxy group-containing acrylic polymer obtained by polymerizing a polymerizable monomer containing glycidyl (meth) acrylate with (meth) acrylic acid.

As epoxy equivalent of the said epoxy group containing acrylic polymer (a1), 140-500 g / eq is preferable and 140-300 g / eq is more preferable. Moreover, as 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 addition, in this invention, an epoxy equivalent is a value defined by JIS-K-7236.

In this invention, the measurement of the weight average molecular weight and the number average molecular weight was calculated | required by the following conditions using the gel permeation chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation

column; Guard column H _XL- H made by Toso Corporation

TSKgel G5000H _{XL made by} + Toso Corporation

TSKgel G4000H _{XL made in} + Toso Corporation

TSKgel G3000H _{XL made by} + Toso Corporation

TSKgel G2000H _{XL made by} + Toso Corporation

Detector; RI (differential refractometer)

Data processing: SC-8010, manufactured by Tosoh Corp.

Measurement condition: column temperature 40 ℃

Solvent tetrahydrofuran

Flow rate 1.0 ml / min

Standard; polystyrene

sample; A tetrahydrofuran solution of 0.4% by weight in terms of the solid content of the resin was filtered with a microfilter (100 μl)

As a weight average molecular weight of the reactive dispersing agent of this invention, 5,000-100,000 are preferable from a viewpoint of a cure shrinkage effect and a leveling property, and 5,000-50,000 are more preferable.

You may make the reactive dispersing agent of this invention react the hydroxyl group which a reactive dispersing agent has, and the monomer which has one isocyanate and a (meth) acryloyl group in the range which does not impair the effect of this invention. Thereby, it is possible to adjust a (meth) acryloyl group equivalent and hydroxyl group equivalent suitably.

As a monomer which has the said one isocyanate and a (meth) acryloyl group, For example, the monomer which has one isocyanate and one (meth) acryloyl group, and has one isocyanate and two (meth) acryloyl groups Monomers, monomers having one isocyanate and three (meth) acryloyl groups, monomers having one isocyanate and four (meth) acryloyl groups, monomers having one isocyanate and five (meth) acryloyl groups, etc. Can be mentioned. As such a monomer, the compound represented, for example by following formula [hwa 3] can be illustrated preferably.

[Figure 3]

In General Formula (1), R ₁ is a hydrogen atom or a methyl group. R <_2> is a C2-C4 alkylene group. n represents the integer of 1-5. Specifically, the reaction adduct of a diisocyanate compound and hydroxyacrylate, etc. can be illustrated besides Kalenz AOI, Kalenz MOI, Kalenz BEI (brand name, the product made by Showa Denko Co., Ltd.), for example. have. Here, as a diisocyanate compound, a well-known thing can be used without particular limitation, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. are mentioned. It will not specifically limit, if it is a compound which has a hydroxyl group and a (meth) acryl group as a hydroxyacrylate, A well-known thing can be used, For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropanediacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like. Especially, since the crosslinking density can be improved, it is preferable to have two or more (meth) acryloyl groups in 1 molecule like Kalenz BEI.

The method of making the isocyanate and the monomer which has a (meth) acryloyl group react with the reactive dispersing agent of this invention is not specifically limited, A well-known method can be employ | adopted. Specifically, for example, a monomer having one isocyanate and a (meth) acryloyl group is added dropwise to the reactive dispersant of the present invention, and the reaction is carried out by heating to 50 to 120 ° C, more preferably to 60 to 90 ° C. Just do it. Moreover, 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: of the monomer which has one isocyanate and a (meth) acryloyl group Isocyanate group (mol) = 1: 0.1-1: 0.9, Preferably it is 1: 0.1-1: 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. Dry silica fine particles are silica fine particles obtained by, for example, burning silicon tetrachloride in oxygen or hydrogen flame. The wet silica fine particles are, for example, silica fine particles obtained by neutralizing sodium silicate with a photoacid. The reactive dispersant of the present invention has high dispersibility of silica fine particles. Therefore, the dispersion which disperse | distributed inorganic particle in the reactive dispersing agent of this invention maintains dispersion stability favorable over a long term. Moreover, even if the said dispersion is added to active-energy-ray-curable oligomers, such as a urethane (meth) acrylate and an epoxy (meth) acrylate, or an active-energy-ray-curable monomer, and an active energy ray-curable resin composition is manufactured, the said active energy ray In the curable resin composition, the inorganic particles are stable and dispersed for a long time. As described above, since the dispersibility of the inorganic particles is high, the reactive dispersant of the present invention is preferably used as a reactive dispersant when dispersing the inorganic particles having poor dispersibility stability in the composition. In addition, it is preferable to use the reactive dispersing agent of this invention as a reactive dispersing agent used when disperse | distributing an inorganic particle to the compound which has 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.

The reactive dispersant obtained by dispersing inorganic particles can be produced using the reactive dispersant of the present invention. The content of each component in the reactive dispersion is not particularly limited, but the reactive dispersant and the silica fine particles of the present invention are 10 to 90 parts by weight: 90 to 10 parts by weight with [(reactive dispersant): (inorganic particles)]. It is preferable to contain, and it is more preferable to contain so that it may be 30-90 weight part: 70-10 weight part. Moreover, 1-50 weight% is preferable in conversion of solid content, and, as for the content rate of the sum total of the reactive dispersing agent and silica fine particles in the dispersion of this invention, 1-30 weight% is more preferable.

When manufacturing a reactive dispersion, it can be set as an energy-beam curable resin composition by containing the reactive dispersing agent of this invention, an inorganic particle, and the compound which has (meth) acryloyl groups other than the said reactive dispersing agent. As a compound which has (meth) acryloyl groups other than the said reactive dispersing agent, an active energy ray hardening-type monomer, an active energy ray hardening-type oligomer, etc. are mentioned, for example. The content of each component is not particularly limited, but the reactive dispersant and the active energy ray-curable monomer or active energy ray-curable oligomer of the present invention may be referred to as ((reactive dispersant) :( active energy ray-curable monomer or active energy ray-curable oligomer)]. It is preferable to contain so that it may be 10-90 weight part: 90-10 weight part, and it is more preferable to contain so that it may be 30-90 weight part: 70-10 weight part.

As said active energy ray hardening-type monomer, For example, In addition to the said polymerizable monomer etc. which can be used for manufacture of the reactive dispersing agent of this invention, Ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate; Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,

Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) ) Acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexamethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di ( Di (meth) acrylate of the compound which caprolactone added to meth) acrylate, hydroxy pivalate neopentyl glycol di (meth) acrylate, and hydroxy pivalate neopentyl glycol, neopentyl glycol adipate di (meth) acryl Rate,

Compounds having three or more hydroxyl groups, such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolmethane, and hydroxyl group-containing compounds in which 1-20 mol of alkylene oxide is added thereto ( The compound etc. which meta-acrylic acid ester-bonded 3 or more molecules are mentioned.

As said active energy ray hardening type oligomer, the group which consists of acrylic (meth) acrylate, urethane (meth) acrylate, ester (meth) acrylate, epoxy (meth) acrylate, etc. other than the reactive dispersing agent of this invention, for example. 1 or more types of (meth) acrylate compounds chosen from are mentioned.

As urethane (meth) acrylate, the polyfunctional urethane (meth) acrylate formed by reacting an isocyanate compound with a hydroxyl-containing (meth) acrylate compound is mentioned, for example. As an isocyanate compound used here, aliphatic or alicyclic, such as hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexyl methane diisocyanate, norbornene diisocyanate, for example Diisocyanate compounds; Aromatic diisocyanates such as toluene diisocyanate and 4,4'-diphenylmethane diisocyanate; Isocyanurate type isocyanate prepolymer etc. which are trimers of a diisocyanate compound are mentioned. In addition, when manufacturing the said polyfunctional urethane (meth) acrylate, you may superpose | polymerize and replace a part of hydroxyl-containing (meth) acrylate compound made to react with an isocyanate compound by dihydric-tetravalent alcohol or a polyol compound.

As the ester acrylate, ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, bisphenol A, hydrogenated bisphenol A, ethoxylated bisphenol A, ethoxylated hydrogenated bisphenol A, propoxylated bisphenol A, propoxylated hydrogenated At least one selected from bisphenol A and a dihydric or higher polyhydric alcohol, phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, trimellitic anhydride, anhydride The polyfunctional ester (meth) acrylate etc. which further (meth) acrylated the ester polyol which has a hydroxyl group obtained by esterifying 1 or more types chosen from polybasic acid represented by a pyromellitic acid etc. are mentioned.

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, neo Divalent epoxy (meth) acryl obtained by adding (meth) acrylic acid to diepoxy compounds, such as triglycidyl ether compounds of dihydric alcohols, such as a pentyl glycol, hydroxy pivalate neopentyl glycol, bisphenol A, and ethoxylated bisphenol A, etc. Late compound; An average of three or more radically polymerizable unsaturated double bonds obtained by adding (meth) acrylic acid to an epoxy compound obtained by epoxidizing trihydric alcohols such as trimethylolpropane, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, and glycerin Epoxy tri (meth) acrylate compound which has; Polyfunctional aromatic epoxy acrylates, such as a phenol novolak and a cresol novolak obtained by adding (meth) acrylic acid to the epoxy compound which made glycidyl ether react with the polyhydric phenol which has at least 1 aromatic ring, or its alkylene oxide adduct ; Polyfunctional alicyclic epoxy acrylate which is a hydrogenated type of these polyfunctional aromatic epoxy acrylates; Moreover, urethane modified epoxy acrylate etc. which are obtained by making the secondary hydroxyl group which exists in a molecule | numerator and one isocyanate group of a diisocyanate compound, and then reacting the remaining single-end isocyanate group and hydroxyl group containing (meth) acrylate are mentioned. have.

Among them, ester acrylates and urethane acrylates each having an average of three or more radically polymerizable unsaturated double bonds are particularly preferred because of their good wear resistance of the cured coating film.

Although the manufacturing method of a reactive dispersion is not specifically limited, For example, (meth) acryl formed by addition-reacting the monomer (b1) which has a (meth) acryloyl group and a carboxyl group to the (meth) acryl polymer (a1) which has an epoxy group. A monomer (b2) having a (meth) acryloyl group and an epoxy group is added to a reaction product having a loyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH, or a (meth) acryl polymer (a2) having a carboxyl group. 10-90 parts by weight of a reaction product (hereinafter referred to as a reactive dispersant) having a (meth) acryloyl equivalent obtained by reacting with a hydroxyl value of 90-280 mg / KOH (hereinafter referred to as a reactive dispersant), and a reactive dispersant with The method of diluting with a dispersion medium (organic solvent) so that the total concentration with a silica fine particle may be 1-50 weight%, and disperse | distributes using a mechanical means is mentioned.

As said organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclic ethers, such as tetrahydrofuran (THF) and dioxolane, methyl acetate, ethyl acetate Esters such as butyl acetate, aromatics such as toluene and xylene, alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol and propylene glycol monomethyl ether, and these can be used alone or in combination. Among them, methyl ethyl ketone, which is a synthetic solvent of a reactive dispersant, is preferable in view of volatility and solvent recovery at the time of coating.

As a mechanical means, the disperser which has stirring blades, such as a disper and a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, etc. are mentioned, for example. In order to manufacture a reactive dispersion, when using the obtained dispersion in a coating agent etc., it is based on the bead mill which uses dispersion media, such as glass beads and zirconia beads, in terms of coating property, coating stability, transparency of a hardened film, etc. Dispersion is preferred.

As said bead mill, For example, the star mill made by Ashiyaza Fine Tech Co., Ltd .; MSC-MILL, SC-MILL, ATTOR MA01SC by Mitsigo-San Co., Ltd .; Asanotek Co., Ltd. NanoGran Mill, PicoGran Mill, PureGran Mill, MegaCapperGran Mill, CerapowerGran Mill, DualGran Mill, AD Mill, Twin AD Mill, Basket Mill, Twin Basket Mill; The apex mill, an ultra apex mill, a super apex mill, etc. made by Kotobuki Kogyo Co., Ltd. are mentioned.

The ultra apex mill is provided with a cylindrical stator, a supply port of a slurry provided at one end of the stator (a mixture of the reactive dispersant and silica fine particles of the present invention, hereinafter identical), a discharge port of the slurry provided at the other end of the stator, and a stator. It is connected to the rotor by stirring and mixing the media supplied and the slurry supplied from the supply port with the outlet, and rotated integrally with the rotor, or rotated independently from the rotor, and the media and slurry by the action of centrifugal force A wet stirred ball mill comprising an impeller-type separator for discharging a slurry from a discharge port, wherein the shaft center of the shaft for rotating the separator is a hollow discharge path communicating with the discharge port. The method for producing a dispersion using the same is a reactive dispersant and The slurry containing the Rica fine particles is supplied to the stator filled with the media from the supply port of the wet stirring ball mill, and the media are separated from the slurry after pulverizing the silica fine particles in the slurry and dispersing the reactive dispersant in the stator. That's how.

EMBODIMENT OF THE INVENTION Hereinafter, with reference to drawings, the manufacturing method of this invention using the above ball mill is demonstrated in detail.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram of the raw material slurry grinding | pulverization processing cycle provided with the said wet stirring ball mill used by the manufacturing method of the dispersion of this invention, FIG. 2 is the said wet stirring ball used by the manufacturing method of the dispersion of this invention. 3 is a longitudinal cross-sectional view of the supply port during slurry supply of the wet stirred ball mill used in the method for producing a dispersion according to the present invention, FIG. 4 is a longitudinal cross-sectional view of the supply port during media discharge, and FIG. The longitudinal cross-sectional view of still another example of the said wet stirring ball mill used by the manufacturing method of the dispersion of this invention, FIG. 6: is a figure which shows 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 which stores a slurry to the raw material pump 2 is supplied to the longitudinal grinding type wet stirring ball mill 3, and the said After being pulverized by stirring with the media in the mill 3, the media is separated by the separator 4, discharged through the shaft center of the shaft 5, and circulated and pulverized along the path back to the tank 1. have.

An organic solvent, various additives, etc. can be added suitably to a slurry as needed. It is preferable to contain an organic solvent in a slurry.

As the usage-amount of the said organic solvent, 150-500 weight part is preferable with respect to a total of 100 weight part of the reactive dispersing agent of this invention, and a silica fine particle, and especially 200-300 weight part is favorable separation of a slurry and a media at the time of a bead mill operation. Moreover, since the process at the time of slurry concentration becomes short, it is preferable.

In order to manufacture a slurry, after adding an organic solvent to the reactive dispersing agent of this invention, obtaining the organic solvent solution of a reactive dispersing agent, it is preferable to add a silica fine particle.

As said various additives, a coupling agent is mentioned, for example. As the coupling agent, for example, a vinyl silane coupling agent, an epoxy silane coupling agent, a styrene silane coupling agent, a methacryloxy silane coupling agent, an acryloxy silane coupling agent, or an amino silane Coupling agents, ureido-based silane coupling agents, chloropropyl-based silane coupling agents, mercapto-based silane coupling agents, sulfide-based silane coupling agents, isocyanate-based silane coupling agents, aluminum-based silane coupling agents, and the like. Can be.

As a vinyl-type silane coupling agent, vinyl trichlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane, 3-glycid, for example. Doxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) pro Hydrochloride of amine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, special aminosilane, 3-ureidopropyltriethoxy Silane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxy Silane, allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris ( 2-methoxyethoxy) silane can be mentioned.

As an epoxy-type silane coupling agent, diethoxy (glycidyl oxypropyl) methylsilane, 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane, and 3-glycidoxy propyl trimethoxysilane are mentioned, for example. , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

As a styrene silane coupling agent, p-styryl trimethoxysilane etc. are mentioned, for example.

As a methacryloxy-type silane coupling agent, 3-methacryloxypropyl methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacrylone, for example. Kryloxypropyltriethoxysilane is illustrated.

As an acryloxy silane coupling agent, 3-acryloxypropyl trimethoxysilane etc. are mentioned, for example.

As an amino-type silane coupling agent, N-2 (amino ethyl) 3-aminopropyl methyl dimethoxy silane, N-2 (amino ethyl) 3- aminopropyl trimethoxysilane, N-2 (amino ethyl, for example) ) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine And N-phenyl-3-aminopropyltrimethoxysilane.

As a urea-type silane coupling agent, 3-ureidopropyl triethoxysilane etc. are mentioned, for example.

As a chloropropyl silane coupling agent, 3-chloropropyl trimethoxysilane is illustrated, for example.

As a mercapto-type silane coupling agent, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. are mentioned, for example.

Examples of the sulfide silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide and the like.

As an isocyanate type silane coupling agent, 3-isocyanate propyl triethoxysilane etc. are mentioned, for example.

As an aluminum coupling agent, acetoalkoxy aluminum diisopropylate etc. are mentioned, for example.

As shown in detail in FIG. 2, the mill 3 has a stator 7 having a longitudinal cylindrical shape and a jacket 6 through which cooling water for mill cooling passes, and an axis of the stator 7. Is located in the upper part of the stator so as to be rotatable, and a mechanical seal is provided in the bearing part, and the shaft 5 in which the upper core is formed as a hollow discharge path 9 and a radially protruding part in the lower end of the shaft ( 핀) the rotor 11 on the pin to disk, the pulley 13 of the motor 12 shown in FIG. 1, the pulley 14 belted, and the shaft upper end A rotary joint 15 mounted at the end, a separator 4 for separating the media fixed to the shaft 5 near the upper part in the stator, and a shaft end of the shaft 5 at the bottom of the stator are provided. Supply port 16 of the raw material slurry, and the stator It consists of the screen 18 which isolate | separates on the grid-shaped screen support 17 provided in the product slurry outlet 19 provided in the eccentric position of a bottom part, and separates a media.

The separator 4 comprises a pair of disks 21 fixed to the shaft 5 at regular intervals, and a blade 22 connecting both disks 21 to constitute an impeller, and together with the shaft 5 The centrifugal force is imparted to the media and the slurry interposed between the disks, and the media are blown outward in the radial direction by the specific gravity difference, 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 supply port 16 of the raw material slurry has an inverted trapezoidal shape that is fitted to the valve seat 24 and the valve seat 24 so that the valve seat 24 can be lifted and lowered. The bottomed cylindrical body 26 which protruded downward from the valve body 25 and the stator bottom part, and formed the inlet opening 27 of a raw material slurry, and protruded downward from the said cylindrical body, and the air inlet port ( A bottomed cylindrical body 28 having a 29, a piston 31 fitted to the cylinder body 28 so as to be lifted and lowered, a rod 32 connecting the piston 31 and the valve body 25, A rod 33 mounted on the piston in the cylindrical body 28, which pushes down the piston 31 to bias the valve body 25 in a downward direction, and a rod protruding from the cylindrical body 28; Consisting of a nut 34 clamped at the end and adjustable in position, by supplying a raw material slurry When the body 25 is pushed up, an annular slit is formed between the valve seat 24 and the raw material slurry is supplied into the mill, but the width of the slit clamps the nut 34, or When the raw material is supplied, even when the nut 34 touches the cylindrical body 28 and is as wide as possible, it is set to a width that the media cannot pass through. The valve body 25 at the time of raw material supply rises in response to the pressure in the mill and the action of the spring 33 by the supply pressure of the raw material slurry fed into the cylindrical body 26, and between the valve seat 24 and the valve seat 24. Although the slit is formed, 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 thus the nut 34 and the cylindrical body ( There is some room between 28).

Crude particles are contained in the raw material slurry supplied into the mill through the slit formed between the valve seat 24 and the valve body 25, and this flows in between the valve seat and the valve body and prevents clogging. Although it is anticipated to generate | occur | produce, when the blockage generate | occur | produces by inheriting, the valve body 25 raises to a limit maximum by raising supply pressure, and the slit width is maximized. For this reason, the introduced particle flows out and the blockage is eliminated. When the blockage is eliminated, the supply pressure drops, and the valve body 25 drops.

In order to eliminate the clogging in the slit, in the illustrated example, compressed air is also introduced from the inlet 29 through the regulator 23 via the regulator 23 from the compressed air source (not shown). The air is supplied into the sieve 28, and compressed air is intermittently supplied by switching the electromagnetic switching valve 30 to ON-OFF repeatedly in a short cycle, whereby the valve body 25 is supplied in a short cycle. The up and down movement that rises to the upper limit position is repeated so as to eliminate the inheritance.

The vibration of the valve body 25 may be performed at all times, or may be performed when a large amount of coarse particles are contained in the raw material slurry, and when the supply pressure of the raw material slurry is increased due to clogging, the vibration of the valve body 25 is performed in conjunction with this. You may do so.

When taking out the stirred media together with the product slurry after extraction, or after taking out the product slurry, the attachment position of the nut 34 is lowered as shown in the figure. Then, the electromagnetic switching valve 30 is turned ON. As a result, the valve body 25 is lifted above the edge of the valve seat 24 by the compressed air introduced from the inlet port 29.

In the said embodiment, although the rotor 11 and the separator 4 are fixed to the same shaft 5, in another embodiment, it is fixed to the other shaft arrange | positioned coaxially and is rotationally driven separately.

In the above-described embodiment in which the rotor and the separator are attached to the same shaft, since the drive may be one, the structure is simplified, and the rotor and the shaft are attached to separate shafts and rotated by separate drive devices. In the latter embodiment, the rotor and the separator can be driven to rotate at optimum rotation speeds, respectively.

The ball mill shown in FIG. 5 makes the shaft 43 an end shaft, subtracts the separator 44 from the lower end of the shaft, and then alternates the spacer 45 and the disk-to-pin rotor 46. 감), and then the stopper 47 is attached to the lower end of the shaft by the screw 48, and the separator 44 and the spacer are formed by the end 43a and the stopper 47 of the shaft 43. A pair of disks 52 in which the blades 44 and the rotors 46 are inserted and connected to each other and fixed, and the separators 44 respectively have blade fitting grooves 51 formed on the inner surface of the separator 44 as shown in FIG. 6. And an annular shape formed between the two disks with the blades 53 fitted in the blade fitting grooves 51 and the two disks 52 at regular intervals to form holes 55 through the discharge path 54. The impeller is comprised by the spacer 56 of this.

Next, the grinding | pulverization method of the slurry using the apparatus shown in FIG. 1 is demonstrated. The media is filled in the stator 7 of the ball mill 3. As the media, for example, various micro beads are used. As a raw material of microbeads, zirconia, glass, titanium oxide, copper, zirconia silicate, etc. are mentioned, for example.

As the particle diameter of the media, the separation of the dispersion media in the separator 44 is good, the dispersion of the silica fine particles in the rotor 11 is also good, the time taken for dispersion is hard to be long, and the impact on the silica particles. 15-100 micrometers is preferable and 15-50 micrometers is more preferable because this is not too strong and a super-dispersion phenomenon by the destruction of a silica fine particle hardly arises.

The above superdispersion phenomenon refers to a phenomenon in which new active surfaces are generated by destruction of silica fine particles, causing reaggregation. When overdispersed, the dispersion becomes a jelly phase.

As a filling rate in the stator of a media, it is 80 to 90% of the stator inner volume, for example. By setting the filling rate to 80 to 90% of the stator inner volume, the power required to obtain a product slurry of unit weight is the smallest. That is, grinding can be performed most efficiently.

After filling the media in the stator 7 of the ball mill 3, the valves 58, 59, and 60 are closed, and the motor 12 is first driven with the valves 61 and 62 open, and then the raw material. The pump 2 is driven. The rotor 11 and the separator 4 are driven to rotate by the driving of the former motor 12, while the raw material slurry in the raw material tank 1 is supplied at a constant amount by the driving of the latter raw material pump 2 ( It is sent to the inlet opening 27 of 16, and is supplied in the mill through the slit formed between the edge of the valve seat 24 and the valve body 25 by this.

When the motor 12 is driven to rotate the rotor 11 and the separator 4, the larger the rotation speed and the larger the peripheral speed, the greater the centrifugal force, and the greater the impact when the media collides with the silica fine particles. As the media, the circumferential speed when using a media having a particle diameter of 15 µm is preferably 15 m / sec or more. As for the media, the circumferential speed when using a media having a particle diameter of 30 µm is preferably 8 m / sec or more.

The slurry and the media in the mill are stirred and mixed by the rotation of the rotor 11, and the slurry is pulverized, and the media and the slurry in the separator are separated by the specific gravity difference by the rotation of the separator 4, and the specific gravity is heavy. As the media is blown outward in the radial direction, a slurry having a light specific gravity is discharged through the discharge passage 9 formed at 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 supplied to the mill by the raw material pump 2 again, and grinding | pulverization advances. In the stage where the grinding has progressed to a certain degree, the particle size of the slurry is properly measured, and once the desired particle size is reached, the raw material pump is once stopped, the motor 12 is then stopped to stop the operation of the mill 3, and the grinding is finished. . Thereafter, the valves 58 and 59 are closed, the valves 61 and 62 are closed, the raw material pump and the motor 12 are restarted, and the valve 60 is opened. Then, the product slurry in the raw material tank 1 is drawn out by the raw material pump 2 and sent to the product tank 63, while the product slurry in the mill is stirred by the rotation of the rotor 7 while the valve 60 And compressed air or N ₂ gas supplied into the mill through the discharge passage 9 or from the top of the mill, and 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 recovered to the product tank 63.

As the time taken to disperse the silica fine particles, since the dispersion becomes good and the productivity becomes good, when the cycle (circulating flow rate) in which the slurry is supplied to the mill by the raw material pump 2 is 1.5 L / hour, 5-60 minutes are preferable and 10-40 minutes are more preferable.

Moreover, 5-15 L / hour is preferable and, as for the said circulation flow volume, 8-10 L / hour is more preferable.

Moreover, in order to rotate the rotor 7, at the time of product collection, in order to prevent clogging on the screen 18, mixing is performed so that the media do not settle in the mill and are unevenly distributed in the lower layer of the mill. Compressed air or N ₂ gas is introduced from the outlet 19 as appropriate, and the screen 18 is backwashed.

Moreover, in the manufacturing method of this invention, the star density made by Ashizawa Fine-Tech Co., Ltd. can be used preferably. The star mill has a normal container having a slurry inlet at one end, a stirring shaft of a rotating material disposed to extend in the longitudinal direction in the container, and a drive connected to the stirring shaft outside of the container. An apparatus is provided, The stirring shaft has a stirring member, a grinding medium enters into a space between the stirring shaft and the inner surface of the container, and the stirring shaft is rotated by the driving device while introducing a slurry from the slurry inlet. By driving, silica fine particles in the slurry are pulverized, and the stirring shaft has a hollow portion having a media inlet near the other end of the vessel, and the hollow shaft is formed between the stirring shaft and the inner surface of the vessel. A slit communicating with the space of the container is formed, and the slit communicating with the operation of the slurry reaches the vicinity of the other end of the container. A medium is a media stirring type grinding device in which a media enters the hollow portion of the stirring shaft from the slurry inlet and returns from the slit to the space between the stirring shaft and the container inner surface, wherein the media of the stirring shaft And a slurry outlet is disposed in the hollow portion, a screen is provided to surround the slurry outlet in the hollow portion, and the screen is driven to rotate.

In the media stirring type grinding device, the screen for separating the media from the slurry is driven to rotate, so that rotational motion is induced to the slurry and the media near the screen, and the centrifugal force due to the rotational motion is more media than the slurry. As it rises, the media creates a negative force away from the screen. Because of this, the media is circulating without accessing the screen. Therefore, it becomes possible to remove a media efficiently from a slurry.

The dispersion obtained by the manufacturing method of this invention can be made into an active energy ray curable resin composition by mixing with another compound. As these compounds, the above-mentioned active energy ray-curable monomers, active energy ray-curable oligomers, ultraviolet absorbers, antioxidants, silicone additives, fluorine additives, rheology control agents, defoamers, mold release agents, silane coupling agents, antistatic agents, antifogging agents and coloring agents Etc. can be mentioned.

As said ultraviolet absorber, for example, 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- Triazine derivatives such as dimethylphenyl) -1,3,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5 '-Methylphenyl) benzotriazole, 2-xanthene carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, etc. are mentioned.

As said antioxidant, a hindered phenol type antioxidant, a hindered amine type antioxidant, an organic sulfur type antioxidant, a phosphate ester type antioxidant, etc. are mentioned, for example.

Examples of the silicone additives include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethyl. And polyorganosiloxanes having alkyl or phenyl groups such as polysiloxane copolymers.

As the usage-amount of the various additives as mentioned above, since the effect is fully exhibited and it does not inhibit UV hardening, it is 0.01-0.05 each with respect to 100 weight part of active energy ray curable resin compositions for mold polymerization. It is preferable that it is the range of 10 weight part.

As a photoinitiator which can be added to the dispersion of this invention, for example, benzophenone, 3,3'- dimethyl- 4-methoxy benzophenone, 4,4'-bisdimethylamino benzophenone, 4,4'- Benzophenones such as bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthones and thioxanthones such as xanthone, thioxanthone, 2-methyl thioxanthone, 2-chloro thioxanthone and 2,4-diethyl thioxanthone; Acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether;

? -Diketones such as benzyl and diacetyl; Sulfides such as tetramethylthiuram disulfide and p-tolyldisulfide; Benzoic acids such as 4-dimethylaminobenzoic acid and 4-dimethylaminobenzoic acid ethyl;

2-methyl-2-methyl-2-methyl-2-methylpropane, 3,3'-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone Benzyl dimethyl ketal, benzyl-beta-methoxy ethyl acetal, methyl o-benzoyl benzoate, bis (4-dimethylaminophenyl) ketone, p- dimethylaminoacetophenone,?,? -Dichloro- Pentyl-4-dimethylaminobenzo , 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S -Triazine, 2,4-bis-trichloromethyl-6- (4-ethoxy) phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4- Methoxy) phenyl-S-triazineanthraquinone, 2-t-butyl anthraquinone, 2-amyl anthraquinone, (beta) -chloro anthraquinone, etc. are mentioned.

The said photoinitiator can also be used individually or in combination of 2 or more types. The amount of use thereof is not particularly limited, but in order to maintain good sensitivity and prevent precipitation of crystals, deterioration of coating film properties, etc., it is preferable to use 0.05 to 20 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin composition. Especially, 0.1-10 weight part is especially preferable.

As said photoinitiator, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2- Hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone Active energy ray-curable resin for coating, in which one or two or more types of mixed systems selected from the group of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one are highly curable It is especially preferable because a composition is obtained.

As a commercial item of the said photoinitiator, Irgacure-184, East 149, East 261, East 369, East 500, East 651, East 754, East 784, East 819, East 907, East 1116, East 1664, East 1700, East 1800, East 1850, East 2959, East 4043, Darocur (Darocur) -1173 (made by Chiba Specialty Chemicals), Lucirin TPO (made by BASFF), Kayacure (KAYACURE)- DETX, East MBP, East DMBI, East EPA, East OA (manufactured by Nippon Kayaku Co., Ltd.), Bicure (VICURE) -10, East 55 (manufactured by STAUFFER Co. LTD.), Trigonal (TRIGONAL) P1 (AKZO Co. LTD), Sandori (SANDORY) 1000 (SANDOZ Co. LTD), DEAP (APJOHN Co. LTD), Quantacure (QUANTACURE) -PDO, Dong ITX, East EPD (made by WARDBLEKINSOP Co. LTD), etc. Can be mentioned.

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

Moreover, an active energy ray curable resin composition can use another resin together for the purpose of the adhesive improvement to a film base material, etc.

As said other resin, For example, Acrylic resin, such as a methyl methacrylate resin and a methyl methacrylate type copolymer; Polystyrene, methyl methacrylate-styrene copolymer; Polyester resin; Polyurethane resin; Polybutadiene resins such as polybutadiene and butadiene-acrylonitrile copolymers; Epoxy resins such as bisphenol type epoxy resin, phenoxy resin and novolak type epoxy resin, and the like.

In the active energy ray-curable resin composition using the dispersion obtained by the production method of the present invention, hardness is obtained even when coating a plastic substrate of a thin film, such as a film substrate, in particular, and at the time of curing, the film is curtailed with low shrinkage. (Curl) has a characteristic of low. Therefore, it can use suitably for coating of a film base material.

As the application amount at the time of coating on the film substrate, for example, on a variety of film base, the weight after drying 0.1~30g / m ^2, preferably it is preferred to apply so that 1~20g / m ^2. 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, since the hardness as a hard coat is easy to achieve, it is preferable. Especially, the film whose cured layer is 3-100% with respect to the film thickness of a film-form base material is more preferable, The film thickness of a cured layer is 5-100% with respect to the film thickness of a film-form base material. This is still more preferable, and the film thickness of the cured layer is particularly preferably 5 to 50% relative to the film thickness of the film-like substrate.

As a film base material which apply | coats an active energy ray curable resin composition, it can use with various well-known base materials. Specifically, a plastic film-like base material etc. are mentioned, for example. As a plastic film form base material, For example, polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, cyclic olefin And film substrates such as polyimide resin.

The coating method of the active energy ray-curable resin composition is not particularly limited, and a known method can be adopted, and examples thereof include bar coater coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, and plaque. Flexographic printing, screen printing, and the like.

As an active energy ray to irradiate, an ultraviolet-ray or an electron beam is mentioned, for example. 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 the light source, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary. It is preferable to harden | cure at the conveyance speed 5-50 m / min with respect to the lamp 1 lamp which has a light quantity of / cm. On the other hand, when hardening with an electron beam, it is preferable to harden | cure at the conveyance speed of 5-50 m / min with the electron beam acceleration apparatus which has an acceleration voltage of 10-300 kV normally.

As mentioned above, the said active energy ray curable resin composition is small in shrinkage | contraction property at the time of hardening, and its hardness is also high. Therefore, the film which provided the hardening layer of the said composition on the film base material can be provided by using the said composition. Such a film can be suitably used, for example, in various protective films typified by hard coat films for optical articles such as polarizing plate protective films, touch panels, antireflection films, diffusion films, prism sheets, and the like.

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

The coating method, the transfer method, the sheet adhesion method, etc. are mentioned as a method of forming the protective layer which protects the surface of a molded article using an active energy ray curable resin composition.

The coating method is spray coating a coating agent composed of an active energy ray-curable resin composition, or coating a molded article as a top coat using a printing apparatus such as a curtain coater, a roll coater, a gravure coater, and then irradiating the active energy ray to the top coat. It is a method of crosslinking.

 In the transfer method, after a transfer material coated with an active energy ray curable resin composition is coated on a molded article surface on a base sheet having a releasability, the top coat is transferred to the molded article surface by peeling off the base sheet, and then irradiated with active energy rays. After producing a crosslinked coating film or adhering the said transfer material to the molded article surface, it is a method of transferring a topcoat to the molded article surface by irradiating an active energy ray to produce a crosslinked coating film, and then peeling a base sheet.

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

In order to form a protective layer by the transcription | transfer method using an active energy ray curable resin composition, a transfer material is produced first. The transfer material may be prepared by, for example, blending an active energy ray curable resin composition alone or with a polyfunctional isocyanate, mixing the mixture, applying the mixture onto a base sheet, and heating the curable resin composition to semi-curing (B-stage). Can be.

As a polyfunctional isocyanate used together with an active energy ray curable resin composition, there is no limitation of a differentiation, A well-known various thing can be used. For example, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexane diisocyanate, the trimer, a polyhydric alcohol and the diisocyanate are reacted. The prepolymer etc. which were made into these can be used. That is, B-stage is made by making the hydroxyl group contained in a polymer react with the isocyanate group of polyfunctional isocyanate.

The use ratio of the active energy ray-curable resin composition and the polyfunctional isocyanate is a ratio of the hydroxyl group of the active energy ray-curable resin composition and the isocyanate group of the polyfunctional isocyanate is 1 / 0.01 to 1/1, preferably 1 / 0.05 to 1 / It is preferable that it is 0.8.

As a base material sheet, what has mold release property is preferable. As such a base sheet, a plastic sheet, a metal foil, a cellulose sheet, a composite of these sheets, etc. are mentioned, for example.

As said plastic sheet, said plastic film etc. are mentioned, for example.

As said metal foil, aluminum foil, copper foil, etc. are mentioned, for example. Moreover, as said cellulose sheet, glassine paper, a coated paper, a cellophane etc. are mentioned, for example.

As a base material sheet, a plastic sheet is preferable and a polyester sheet is more preferable especially.

In order to manufacture a transfer material, first, an active energy ray curable resin composition is apply | coated on a base material sheet. This resin composition becomes the outermost layer of the surface of a molded article in the formation method of the protective layer mentioned later, and becomes a layer for protecting the design layer on a molded article or a molded article from chemicals and friction. As a method of coating the curable resin composition for transfer materials, for example, a coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a comma coating method, a gravure printing method, a screen printing method or the like Etc. can be mentioned. When painting, since abrasion resistance and chemical-resistance become favorable, it is preferable to coat so that the thickness of a protective layer may be 0.5-30 micrometers, and it is more preferable to coat so that the thickness of a protective layer may be 1-6 micrometers especially.

When the said protective layer is excellent in peelability from a base sheet, what is necessary is just to coat the curable resin composition for transfer materials so that a protective layer may be provided directly on a base sheet, In order to improve the peelability from the base sheet of a protective layer, Before providing a protective layer on it, you may form a release layer whole surface. In the formation method of the protective layer of the molded article mentioned later, a mold release layer releases from a protective layer with a base sheet, when peeling a base sheet from a molded article in order to transfer the protective layer on a transfer material to the molded article surface. As a mold release agent for forming a mold release layer, a melamine resin mold release agent, a silicone resin mold release agent, a fluororesin mold release agent, a cellulose derivative mold release agent, a urea resin mold release agent, a polyolefin resin mold release agent, a paraffin type mold release agent, these complex mold release agents, etc. can be used, for example. Can be. As a formation method of a release layer, the coating methods, such as the gravure coating method, the roll coating method, the spray coating method, the lip coating method, the comma coating method, the gravure printing method, the screen printing method, etc. are mentioned.

After coating curable resin composition for transfer materials on a base material sheet, it dries. 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. Heating is 55-160 degreeC normally, Preferably it is 100-140 degreeC. The heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes.

Since the B-staged resin layer on the transfer material of the present invention can be easily printed with another layer on the resin layer or wound up the transfer material, in the step before irradiating the active energy ray It is desirable to be in a tack-free state.

The transfer material may form a pattern layer. A design layer is normally formed as a printing layer on the B-staged resin layer. Examples of the material of the printing layer include resins such as polyvinyl resin, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin and alkyd resin. What is necessary is just to use as a binder the coloring ink which contains the pigment or dye of a suitable color as a coloring agent. As a formation method of a design layer, normal printing methods, such as the offset printing method, the gravure printing method, the screen printing method, etc. may be used, for example. In particular, in order to perform multicolor printing and gradation expression, the offset printing method and the gravure printing method are suitable. 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 design layer may be provided entirely or partially, depending on the design to be expressed. The pattern layer may be formed of a metal deposition layer or may be formed of a combination of a printing layer and a metal deposition layer.

In addition, when a protective layer or a design layer has sufficient adhesiveness with respect to a molded article, it is not necessary to provide an adhesive layer, but you may form an adhesive layer as needed. An adhesive layer bonds the transfer material which has said each layer to the molded object surface. An adhesive layer is formed in the part to adhere on a protective layer or a design layer. That is, if the portion to be bonded is the entire surface, the adhesive layer is formed entirely. In addition, if the portion to be bonded is partially, the adhesive layer is partially formed. As the adhesive layer, a thermosensitive or pressure-sensitive resin suitable for the raw material of the molded article is appropriately used. For example, when the material of a molded article is polyacrylic-type resin, polyacrylic-type resin may be used. In addition, when the material of a molded article is polyphenylene oxide polystyrene resin, polycarbonate resin, styrene copolymer system resin, and polystyrene blend resin, polyacrylic resin, polystyrene resin, poly which has affinity with these resins An amide resin etc. may be used. Moreover, when the material of a molded article is polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used. As a formation method of an adhesive layer, the coating methods, such as the gravure coating method, the roll coating method, the comma coating method, the gravure printing method, the screen printing method, etc. are mentioned.

In addition, the structure of a transfer material is not limited to said aspect, For example, when using the transfer material for the purpose of surface protection treatment only by utilizing the pattern and transparency of a molded article, B-stage on a base sheet The patterned resin layer and the adhesive layer may be sequentially formed as described above to omit the design layer from the transfer material.

In addition, when a transfer material has a design layer or an adhesive layer on the B-staged resin layer, you may provide an anchor layer between these layers. The anchor layer is a resin layer for enhancing the adhesion between these layers or protecting the molded article and the pattern layer from chemicals. Examples of the anchor layer include thermosetting resins such as two-component curable urethane resins, melamine resins, epoxy resins, and chlorides. Thermoplastic resins, such as vinyl copolymer resin, can be used. As a method of forming an anchor layer, there exist coating methods, such as the gravure coating method, the roll coating method, the comma coating method, printing methods, such as the gravure printing method and the screen printing method.

In order to form the protective layer of the molded article using the transfer material, for example, after bonding the B-staged resin layer of the transfer material and the molded article, the active layer may be irradiated to cure the resin layer. Specifically, for example, the B-staged resin layer of the transfer material is adhered to the molded article surface, and then the B-staged resin layer of the transfer material is transferred onto the molded article surface by peeling off the base sheet of the transfer material. The method (transfer method) which performs energy ray hardening by active energy ray irradiation, crosslinking hardening of a resin layer, or inserts the said transfer material in a molding die, injection-fills resin in a cavity, and obtains a resin molded article, and After the transfer material is adhered to the surface, the base sheet is peeled off and transferred onto the molded article, and then energy ray curing is performed by active energy ray irradiation (crosslinking curing of the resin layer).

In the crosslinking curing and transfer step of the resin layer, as shown in the above method, the transfer material is adhered to the molded article surface, and then the base sheet is transferred to the molded article surface by peeling off the gas sheet, followed by active energy ray irradiation. Although the process of is preferable, after attaching a transfer material to the surface of a molded article, the process of the order of irradiating an active energy ray from the base sheet side to harden | cure a protective layer, and then peeling off and transferring a base sheet may be sufficient.

Although the material is not limited as said molded article, For example, a resin molded article, a woodworking product, these composite products, etc. are mentioned. These may be either transparent, translucent or opaque. In addition, the molded article may or may not be colored. As resin, general-purpose resin, such as polystyrene resin, polyolefin resin, ABS resin, AS resin, is mentioned. Moreover, polyphenylene oxide polystyrene resin, polycarbonate resin, polyacetal resin, acrylic resin, polycarbonate modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, ultra high molecular weight polyethylene resin, etc. General purpose engineering resin, polysulfone resin, polyphenylene sulfide resin, polyphenylene oxide resin, polyacrylate resin, polyetherimide resin, polyimide resin, liquid crystal polyester resin, polyallyl heat-resistant resin Super engineering resins can also be used. Moreover, the composite resin which added reinforcing materials, such as glass fiber and an inorganic filler, can also be used.

As an active energy ray used by the formation method of the protective layer of the molded article of this invention, an electron beam, an ultraviolet-ray, a gamma ray, etc. are mentioned, for example. Although irradiation conditions are determined according to the composition of the curable resin composition for transfer materials used in order to obtain a protective layer, it is preferable to irradiate so that accumulated light amount may be 50-5000mJ / cm < ² > normally, and the accumulated light amount may be 500-2000mJ / cm <^2> . It is more preferable to irradiate as much as possible.

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 disposed on the molded article with the adhesive layer side facing down. Next, using a heat-resistant rubber-like elastic body, for example, a transfer machine such as a roll transfer machine equipped with a silicone rubber, an up-down transfer machine, and the like, and a heat-resistant high temperature set under the conditions of a temperature of 80 to 260 ° C and a pressure of 50 to 200 kg / m ² . Heat or / and pressure are applied from the gas sheet side of the transfer material via the free-form elastic body. In this way, the adhesive layer adheres to the molded article surface. Subsequently, when the base sheet is peeled off after cooling, peeling occurs at the interface between the base sheet and the resin layer. In addition, when a release layer is provided on a base sheet, peeling will generate | occur | produce in the interface surface of a release layer and a resin layer, if a base sheet is peeled off. Finally, by irradiating an active energy ray, the resin layer transferred to the molded article is completely crosslinked and cured to form a protective layer. Moreover, you may perform the process of irradiating an active energy ray before the process of peeling a base sheet.

Next, the formation method of the protective layer of the molded article by the molding simultaneous transfer method using injection molding is demonstrated concretely. First, the transfer material is fed into the mold for forming the movable mold and the fixed mold to the inside, that is, the base sheet is in contact with the fixed mold. At this time, the sheet | seat transfer material of sheet | leaf may be fed one by one, and the necessary part of a long transfer material may be intermittently fed. In the case of using an elongate transfer material, a transfer device having a positioning mechanism may be used so that the register between the pattern layer of the transfer material and the molding die is coincident. In addition, when the transfer material is intermittently fed in, if the transfer material is fixed to the movable type and the fixed type after detecting the position of the transfer material by the sensor, the transfer material can be fixed at the same position at all times, and the positional shift of the design layer It is convenient because it does not occur. After closing the mold for molding, molten resin is injected into the mold from a gate provided as a movable mold to form a molded article, and at the same time, the transfer material is adhered to the surface. After cooling the molded resin product, the molding die is opened to take out the molded resin product. Finally, after removing the base sheet, the resin layer is completely crosslinked and cured by irradiating an active energy ray to form a protective layer. In addition, after irradiating an active energy ray, you may peel off a base sheet.

Moreover, the curable resin composition for transfer materials of this invention is not only a composition for manufacture of transfer materials, but also coating methods, such as the above-mentioned gravure coating method, roll coating method, comma coating method, printing method, such as gravure printing method and screen printing method, It is also possible to coat molded articles such as films, sheets, molded articles and the like by spray coating.

Next, the sheet bonding method is demonstrated. As the sheet bonding method, for example, a method of performing crosslinking and curing of a resin layer formed by adhering a gas sheet of a protective layer-forming sheet prepared in advance and a molded article, followed by heat curing by heating and B-staging (post-adhesion) Method) or the sheet for forming the protective layer into a molding die, and injection-filling the resin in the cavity to obtain a resin molded article, and bonding the surface and the sheet for forming the protective layer, followed by thermosetting by heating. The method (shape simultaneous bonding method) etc. which perform crosslinking hardening of a resin layer are mentioned.

The said protective layer formation sheet can be manufactured by the method of manufacturing the said transfer material, etc., for example. At this time, when coating the curable resin composition on the base sheet, when the adhesive force between the base sheet and the curable resin composition is not sufficient,

1. Apply a primer to the surface on which the curable resin composition of the base sheet is coated, and apply the curable resin composition thereon,

2. The adhesiveness of a base sheet and curable resin composition can also be improved by the method of activating the surface of a base sheet by corona discharge etc.

As the primer used in the above 1., for example, a thermosetting resin such as a two-liquid curable urethane resin, a melamine resin, an epoxy resin, a thermoplastic resin such as an aqueous latex made of a vinyl chloride copolymer resin, and an acrylic resin can be used. have. As a method of apply | coating an adhesive agent, the printing methods, such as the coating method, such as the gravure coating method, the roll coating method, the comma coating method, the gravure printing method, the screen printing method, are mentioned, for example.

In the method of manufacturing the said transfer material, after coating an active energy ray curable resin composition to a base sheet, an active energy ray is irradiated. By this active energy ray irradiation, the (meth) acryloyl group in curable resin composition couple | bonds by a radical polymerization reaction, three-dimensional crosslinking is formed and curable resin composition hardens.

When using the active energy ray curable resin composition containing the organic solvent as an active energy ray curable resin composition, you may remove an organic solvent after application | coating to a base sheet. In order to remove an organic solvent, it may be after irradiating an active energy ray, for example, or before irradiating an active energy ray. As a method of removing, it may be left to volatize as it is, and may be dried using a dryer etc., but the temperature at the time of removing an organic solvent is 70-130 degreeC normally, and about 10 second-10 minutes are preferable.

In addition, the structure of the sheet for protective layer formation is not limited to the said aspect, For example, when using the sheet for protective layer formation aiming at surface protection treatment only by utilizing the pattern and transparency of a molded article, , The cured resin layer and the adhesive layer are sequentially formed on the base sheet, and the pattern layer can be omitted from the sheet for protective layer formation.

In addition, when the sheet for protective layer formation has a resin layer on a design layer, you may provide an anchor layer between these layers. The anchor layer is a resin layer for enhancing the adhesion between these layers, and for example, thermoplastic resins such as thermosetting resins such as two-component curable urethane resins, melamine resins and epoxy resins, and vinyl chloride copolymer resins can be used. have. As a method of forming an anchor layer, there exist coating methods, such as the gravure coating method, the roll coating method, the comma coating method, printing methods, such as the gravure printing method and the screen printing method.

As a molded article used by a sheet | seat adhesion method, the molded article illustrated by the said transfer method can be used, for example.

As a method of bonding the molded article and the protective layer forming sheet in the post-adhesion method, for example, an adhesive is applied to the base sheet or the molded article surface of the protective layer forming sheet, and the base sheet and the molded article surface of the protective layer forming sheet. After attaching the double-sided adhesive tape to the substrate sheet or molded article surface of the protective layer-forming sheet, the release protective sheet of the double-sided adhesive tape is peeled off to expose the adhesive surface, the surface of the base sheet and the molded article of the protective layer-forming sheet After the adhesive is applied to the base sheet of the protective layer forming sheet to form an adhesive surface, the protective layer forming sheet which protects the adhesive surface with the peeling protective sheet is produced in advance, and the protective layer forming sheet is peeled off. The method of peeling a protective sheet and adhering the adhesive surface of a base sheet and the surface of a molded article, etc. are mentioned. In the simultaneous molding method, the protective layer-forming sheet and the molded article can be adhered by integrating the protective sheet-forming sheet with the molded article by melting the base sheet by heat during in-mold molding without using an adhesive. Here, as an adhesive agent used by the said post-bonding method, a urethane type adhesive agent, an epoxy type adhesive agent, ester type adhesive agent, an acrylic type adhesive agent, a hot melt type adhesive agent, etc. are mentioned, for example.

Below, the formation method of the protective layer of the molded article by the said post-adhesion method is demonstrated concretely. First, the protective layer forming sheet | seat is arrange | positioned below a contact bonding layer side on a molded article. Next, using a heat-resistant rubber-like elastic body, for example, a transfer machine such as a roll transfer machine equipped with a silicone rubber, an up-down transfer machine, and the like, and a heat-resistant high temperature set under the conditions of a temperature of 80 to 260 ° C and a pressure of 50 to 200 kg / m ² . Heat or / and pressure are applied from the protective layer side of the sheet for protective layer formation via the free-form elastic body. In this way, the adhesive layer adheres to the molded article surface. Finally, by heating, the resin layer formed on the molded article is completely crosslinked and cured to form a protective layer.

Next, the formation method of the protective layer of the molded article by the simultaneous molding method of injection molding using injection molding is demonstrated concretely. First, the adhesive layer is placed in the mold for forming the movable mold and the fixed mold, that is, the sheet for protective layer formation is fed so that the base sheet is in contact with the fixed mold. At this time, one sheet of transfer material may be fed one by one, or a necessary portion of the long transfer material may be fed intermittently. When using the long protective layer formation sheet, what is necessary is just to make the register of the design layer of a protective layer formation sheet | seat and the metal mold | die for shaping | molding match using the transfer apparatus which has a positioning mechanism. When intermittently feeding the protective layer forming sheet, the protective layer forming sheet is fixed to the movable type and the fixed type after detecting the position of the protective layer forming sheet with a sensor. Since a sheet can be fixed and a position shift of a design layer does not occur, it is convenient. After closing the mold for molding, molten resin is injected into the mold from the gate provided in the movable mold to form a molded article, and at the same time, the protective layer forming sheet is adhered to the surface. After cooling the molded resin product, the molding die is opened to take out the molded resin product. Finally, by heating with a hot air oven or the like, the resin layer is completely crosslinked and cured to form a protective layer.

[Example]

An Example and a comparative example are given to the following, and this invention is demonstrated more concretely. The parts and percentages in the examples are all based on mass unless otherwise specified.

(Production Example 1)

In a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube, 250 g of glycidyl methacrylate (hereinafter referred to as GMA), 1000 g of methyl isobutyl ketone (hereinafter referred to as MIBK) and t-butyl After charging 10 g of peroxyethylhexanoate (hereinafter referred to as PO), the temperature was raised to a temperature of about 90 ° C. over about 1 hour under a nitrogen stream, and the temperature was maintained for 1 hour. Subsequently, with the dropping funnel which charged the mixture liquid which consists of 750 g of GMA and 30 g of P-O previously, the mixed liquid was dripped in the system for about 2 hours under nitrogen stream, and it was kept at the same temperature for 3 hours. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, charged with 507 g of acrylic acid (hereinafter referred to as AA), 2.3 g of metoquinone and 9.3 g of triphenylphosphine, and then under air bubbling, 110 It heated up to ° C. After keeping at the same temperature for 8 hours, 1.6 g of metoquinone was charged and cooled, and MIBK was added so that the nonvolatile content became 50% to obtain a solution of the reactive dispersant (A-1). The reactive dispersant (A-1) had an acrylic equivalent weight of about 214 g / eq, a hydroxyl value of about 262 mgKOH / g, and a weight average molecular weight of about 30,000.

(Production Example 2)

Using the same reaction apparatus as in Preparation 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 then the temperature in the system over about 1 hour under a nitrogen stream. It heated up until it became about 90 degreeC, and heat-retained for 1 hour. Subsequently, with the dropping funnel which charged the mixture liquid which consists of 375g of GMA, 375g of MMA, and 30g of P-O previously, the mixed liquid was dripped in the system for about 2 hours under nitrogen stream, and it was kept at room temperature for 3 hours. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 degreeC, the nitrogen inlet tube was replaced with the air inlet tube, 254 g of AA, 2.3 g of metoquinones, and 9.3 g of triphenylphosphines were charged and mixed, and it heated up to 110 degreeC under air bubbling. After keeping at the same temperature for 8 hours, 1.6 g of metoquinone was charged and cooled, MIBK was added so that the nonvolatile content became 50%, and the solution of the reactive dispersing agent (A-2) was obtained. The reactive dispersant (A-2) had an acrylic equivalent weight 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 reaction apparatus as in Preparation Example 1, charging 75 g of GMA, 175 g of MMA, 1000 g of MIBK and 8 g of PO, and raising the temperature in the system to about 90 ° C. over about 1 hour under nitrogen stream. Insulated, 1 hour. Subsequently, a dropping funnel in which a mixed liquid consisting of 300 g of GMA, 700 g of MMA and 23 g of P-O was charged in advance, the mixed liquid was added dropwise into the system under nitrogen stream for about 2 hours, and kept at the same temperature for 3 hours. Then, it heated up at 120 degreeC and kept warm for 2 hours. After cooling to 60 degreeC, the nitrogen inlet tube was replaced with the air inlet tube, 152 g of AA, 2.3 g of metoquinones, and 5.6 g of triphenylphosphines were charged and mixed, and it heated up to 110 degreeC under air bubbling. After keeping at the same temperature for 8 hours, 1.6 g of metoquinone was charged and cooled, MIBK was added so that the nonvolatile content became 50%, and the solution of the reactive dispersing agent (A-3) was obtained. The reactive dispersant (A-3) had an acrylic equivalent weight of about 545 g / eq, a hydroxyl value of about 103 mgKOH / g, and a weight average molecular weight of about 70,000.

(Example 1)

In a reactor equipped with a stirring device, a cooling tube, a dropping funnel and an air introduction tube, 50 g of silica fine particles (aerosol 50, Nippon aerosol, an average primary particle diameter of 30 nm), 500 g of MIBK, and methacryloxypropyltrimethoxysilane ( After adding 0.88 g of 5% aqueous solution of KBM503, the product made by Shin-Etsu Chemical, and 5% aqueous solution of the phosphate ester (Fors Rex A-3, product made by SC Yuki Chemical), it rose to 100 degreeC under air stream. It heated for 6 hours and obtained the slurry of the surface-treated inorganic particle.

25 g of the reactive dispersant (A-1) obtained in Production Example 1 and 50 g of dipentaerythritol hexaacrylate were added to a slurry of the surface-treated inorganic particles (50 g in solid content) to obtain a compound.

Dispersion of the silica fine particles in this blend was carried out using Ultra-Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. In the used ultra-apex mill UAM015, the inner diameter of the stator 7 is 50 mmφ, the internal volume is 0.17 liters, the diameter of the separator 4 is 40 mmφ, and the space | interval between the disks 21 of the separator 4 is 5 mm. The mill 3 was filled with zirconia beads having a diameter of 30 μm as a medium in the mill 3 in a volume of 50% with respect to the volume of the mill 3.

The compound was supplied from the supply port 16 from the raw material tank 1 of FIG. Then, the mill 3 was operated so that the rotational speed of the rotor was constant (the circumferential speed at the rotor tip is 8 m / sec), and the pulverization of the blend was performed at a flow rate of 1.5 liters per minute. Cyclic milling was performed for 30 minutes to obtain a dispersion in which silica fine particles were dispersed in a mixture of a reactive dispersant (A-1), DPHA, and MIBK. The obtained dispersion was taken out from the outlet of the ultra-apex mill UAM015, MIBK was removed using the evaporator, and the dispersion of 50% of non volatile matter concentration was obtained.

2 parts of Irgacure # 184 (photoinitiator) were added to 100 parts of this dispersion, and the active energy ray curable resin composition was obtained. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. Moreover, it was 4H when the cured coating film was produced on condition of the following, and pencil hardness was measured.

(Example 2)

Instead of the surface-modified silica fine particles of Example 1, a dispersion was obtained in the same manner as in Example 1 except that silica fine particles (RM50, Nippon Aerosol, average primary particle diameter of 30 nm) modified with methacryl groups were used. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. It was 4H when pencil hardness was measured similarly.

(Example 3)

Instead of the surface-modified silica fine particles of Example 1, a dispersion was obtained in the same manner as in Example 1 except that silica fine particles (R711, Nippon Aerosol, an average primary particle diameter of 12 nm) modified with methacryl groups were used. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. It was 4H when pencil hardness was measured similarly.

(Example 4)

A dispersion was obtained in the same manner as in Example 1 except that silica fine particles (R7200, Nippon Aerosol, an average primary particle diameter of 12 nm) were used instead of the surface-modified silica fine particles of Example 1. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. It was 4H when pencil hardness was measured similarly.

(Example 5)

As in Example 1, except that 8 g of methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 4 g of methacryloxypropyltrimethoxysilane (KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) of Example 1. And the dispersion was obtained. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. In the same manner, the pencil hardness was measured and found to be 5H.

<Method of measuring pencil hardness>

1. Production method of cured coating film

The active energy ray-curable resin composition was applied on a triacetyl cellulose (TAC) film (film thickness 40um) with a bar coater (film thickness of 10 μm), dried at 70 ° C. for 1 minute, and 250 mJ / using a high pressure mercury lamp under nitrogen. The test piece which has a cured coating film was obtained by making it pass and harden | cure by the irradiation amount of cm <^2> .

2. Evaluation method of cured coating film

The hardened film of the said test piece was evaluated by the pencil scratch test of 500 g of loads according to JISK5400.

Example 6

A dispersion was obtained 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) of Example 1. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. In the same manner, the pencil hardness was measured and found to be 5H.

(Example 7)

A dispersion was obtained 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) of Example 1. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. In the same manner, 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 as a solid content, 25 g of dipentaerythritol hexaacrylate (DPHA), silica fine particles (Aerosil 50 from Nippon Aerosol Co., Ltd., average primary particle size: about 12 nm) 50 g and 200 g of MIBK were combined to obtain a blend. Even if the active energy ray-curable resin composition was stored at room temperature (25 ° C) for two months, no sediment was generated and the storage stability was good. It was 2H, when the dispersion of this compound was produced like Example 1, the cured coating film was produced, and the pencil hardness was measured.

(Comparative Example 2)

50 g of silica fine particles (RM50, Nippon Aerosol, average primary particle diameter of 30 nm) modified with methacryl group, 50 g of bisphenol A epoxy acrylate (manufactured by DIC Corporation, Unidick V-5500), and 200 parts of MIBK A comparative control reactive dispersion having a nonvolatile content of 50% was obtained in the same manner as in Example 1.

2 parts of Irgacure # 184 was added to 100 parts of this comparative dispersion reactive dispersion, and the active energy ray curable resin composition for comparison control was obtained. The precipitate produced the active energy ray curable resin composition for comparative control at the time of storing for 1 hour at room temperature (25 degreeC). Moreover, it was 2H when the cured coating film was produced like Example 1, and the pencil hardness was measured.

(Comparative Example 3)

Comparison of 50% non-volatile content in the same manner as in Example 1 except that 50 parts of silica fine particles (R711, Nippon Aerosol, average primary particle size 12 nm) modified with methacryl group, 50 parts of DPHA and 200 parts of MIBK were used. A control reactive dispersion was obtained.

2 parts of Irgacure # 184 was added to 100 parts of this comparative dispersion reactive dispersion, and the active energy ray curable resin composition for comparison control was obtained. The precipitate produced the active energy ray curable resin composition for comparative control at the time of storing for 1 week at room temperature (25 degreeC). Moreover, it was 3H when the cured coating film was produced like Example 4 and the pencil hardness was measured.

One… Raw material tank
2… Raw material pump
3 ... Grinding Wet Stirring Ball Mill
4… Separator
5 ... shaft
6 ... jacket
7 ... The stator
9 ... Discharge passage
11 ... Rotor
12... motor
13 ... Pulley
14 ... Pulley
15... Rotary joint
16 ... Supply port
17 ... Screen support
18 ... screen
19 ... Outlet
21 ... disk
22... blade
23 ... regulator
24 ... Valve seat
25... Valve body
26 ... Cylinder
27 ... Introduction port
28 ... Cylinder
29 ... Inlet of Air
30 ... Electronic switching valve
31 ... piston
32 ... road
33 ... spring
34 ... nut
43 ... shaft
43a ... End of shaft 43
44 ... Separator
45 ... Spacer
45 ... Rotor
47 ... stopper
48 ... screw
51 ... Blade fitting groove
52 ... disk
53 ... blade
54 ... Discharge passage
55 ... hole
56 ... Fantasy spacer
58... valve
59 ... valve
60 ... valve
61... valve
62 ... valve
63 ... Product tank

Claims (14)

In the dispersion in which the surface-treated inorganic particles (A) are dispersed in a reactive dispersant,
1) The surface-treated inorganic particle (A) is obtained by surface-treating an inorganic particle (C) with the compound (B) which has a (meth) acryloyl group, and
2) The reaction product in which the reactive dispersing agent add-reacts the (meth) acryloyl group and the monomer (b1) which has a carboxyl group to the (meth) acrylic polymer (a1) which has an epoxy group, or the (meth) acryl polymer which has a carboxyl group As a reaction product formed by addition-reacting the monomer (b2) which has a (meth) acryloyl group and an epoxy group to (a2), (meth) acryloyl equivalent is 200-600 and a hydroxyl value is 90-280 mg / KOH. Dispersion characterized. The method of claim 1,
The dispersion whose (meth) acryloyl equivalent of a reactive dispersing agent is 200-400, and whose hydroxyl value is 140-280 mg / KOH. The method according to claim 1 or 2,
The dispersion in which a reactive dispersing agent add-reacts (meth) acrylic acid to the (meth) acryl polymer which has an epoxy group obtained by superposing | polymerizing glycidyl (meth) acrylate. The method according to claim 1 or 2,
The dispersion whose weight average molecular weight of a reactive dispersing agent is 5,000-100,000. The method according to claim 1 or 2,
The dispersion whose primary particle diameter of an inorganic particle (C) is 10 nm-300 nm. The method according to claim 1 or 2,
The dispersion in which the inorganic particles (C) are silica fine particles. The method according to claim 1 or 2,
Compound (B) which has a (meth) acryloyl group is General formula (1)

(In formula, R <_1> , R <_2> , R <_3> is a C1-C4 alkyl group each independently, n is an integer of 1-6.)
A dispersion which is an organosilane compound represented by. An energy ray curable resin composition containing the dispersion of Claim 1 or 2. Stirring and mixing the cylindrical stator, the supply port of the slurry provided at one end of the stator, the discharge port of the slurry provided at the other end of the stator, the media filled in the stator and the slurry supplied from the supply port An impeller-type separator connected to the rotor and the outlet, and integrally rotated with the rotor, or rotating independently of the rotor, separating the media and slurry by the action of centrifugal force, and discharging the slurry from the outlet. As a manufacturing method of the dispersion using the wet stirring ball mill which consists of
The media from the supply port of the stirring ball mill which made the slurry containing the inorganic particle (A) and reactive dispersing agent of Claim 1 or 2 into the hollow discharge path which communicates with the said discharge port the shaft center of the shaft which drives a separator rotationally. A method for producing a dispersion, characterized in that the medium is separated from the slurry after supplying to a packed stator and pulverizing the silica fine particles in the slurry and dispersing the dispersion into a dispersant. 10. The method of claim 9,
A method for producing a dispersion, wherein the media is zirconia fine particles having a particle size of 15 to 100 µm. The dispersion obtained by the manufacturing method of Claim 9 is contained, The energy ray curable resin composition characterized by the above-mentioned. It has a cured layer obtained by hardening | curing the energy-beam curable resin composition of Claim 8 on a film-form base material, The film characterized by the above-mentioned. The method of claim 12,
The said film-form base material is 1 or more types of film-form base materials chosen from the group which consists of a film-form base material of polyethylene terephthalate resin, the film-form base material of polycarbonate resin, and the film-like base material of acetylated cellulose resin. The method of claim 12,
The film thickness of the said hardened layer is 3 to 100% with respect to the film thickness of a film-form base material.

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