JP2013129778A - Method for producing metal oxide particle dispersion, energy ray-curable resin composition, and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a dispersion high in hardness of its cured material and excellent in dispersion stability.SOLUTION: In the method for producing the dispersion, the dispersion is produced by dispersing the metal oxide particle (B) treated with a surface-treating agent (A) in a reactive dispersant, wherein: the reactive dispersant is an active energy ray-curable resin composition having a hydrogen-bonding functional group; and the production method includes a process of kneading the surface-treating agent (A) and the metal oxide particle (B) by the planetary movement of a plurality of blades.

Description

  The present invention relates to a method for producing a dispersion in which metal oxide particles (B) surface-treated with a surface treatment agent (A) are dispersed in a reactive dispersant.

  The present invention also relates to an energy ray-curable resin composition containing a dispersion obtained by the production method, and a film obtained by curing the composition.

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

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

  Patent Document 2 uses a specific acrylic acrylate as a reactive dispersant for dispersing silica particles, whereby silica particles are stably dispersed in an active energy ray-curable resin composition for a long period of time. It describes what you can do.

  Furthermore, in order to develop a high pencil hardness, the silica particles are surface-modified using a silane coupling agent having a (meth) acryloyl group, and a specific reactive dispersant is used to interact with each other at the silica particle interface. Attempts have been made to enhance the action (Patent Document 3). However, since the method using a normal flask or bead mill can be dispersed only with a low-viscosity slurry, the surface cannot be modified unless the solid content concentration of the system is lowered and a large amount of silane coupling agent is used. A low solid content concentration has a problem such as a decrease in productivity, and a large amount of silane coupling agent causes a decrease in the storage stability of the coating liquid and the coating film hardness.

  On the other hand, as an example of kneading using a planetary mixer preferably used in the present invention, for example, Patent Document 4 describes an example used for kneading pigments.

JP 2006-348196 A JP 2011-26561 A JP 2011-201938 A Japanese Patent No. 4340951

  In the present invention, in view of the above background art, it is an object of the present invention to provide a method for producing a dispersion that can provide a dispersion having high hardness and excellent dispersion stability.

As a result of intensive investigations to solve the above problems, the present inventors have made a method for producing a dispersion in which metal oxide particles (B) treated with a surface treatment agent (A) are dispersed in a reactive dispersant. In
1) The reactive dispersant is an active energy ray-curable resin composition having a hydrogen bonding functional group,
2) A step of kneading the surface treatment agent (A) and the metal oxide particles (B) by causing a plurality of blades to perform planetary motion,
A method for producing the dispersion,
However, the present invention has been completed by finding that it is extremely useful for solving the above problems.

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

  According to the present invention, it is possible to provide a cured product and film having high hardness, and a dispersion used for the cured product and film.

That is, the present invention
In the method for producing a dispersion in which the metal oxide particles (B) treated with the surface treatment agent (A) are dispersed in the reactive dispersant,
1) The reactive dispersant is an active energy ray-curable resin composition having a hydrogen bonding functional group,
2) A step of kneading the surface treatment agent (A) and the metal oxide particles (B) by causing a plurality of blades to perform planetary motion,
The present invention relates to a method for producing the dispersion.

The dispersion of the present invention is characterized in that the metal oxide particles (B) treated with the surface treatment agent (A) are dispersed in a reactive dispersant.

  The metal oxide particle (B) treated with the surface treatment agent (A) is a surface treatment agent capable of treating the surface of metal oxide particles such as a coupling agent having a (meth) acryloyl group. With processed features.

  The surface treating agent (A) that can be used is not particularly limited as long as the surface treatment of the metal oxide particles (B) can be performed. For example, an organosilane compound having a (meth) acryloyl group is preferable. Can do.

  More specifically, the general formula (1)

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

  It is necessary to have a group that forms a chemical bond with the surface treatment agent (A) on the surface of the metal oxide particles (B). Reaction conditions for forming a chemical bond may be conventional reaction conditions, and a catalyst may be used to promote the reaction. Although there is no restriction | limiting in the catalyst used, For example, phosphate ester can be mentioned.

When a coupling agent having a (meth) acryloyl group is used as the surface treatment agent (A), the (meth) acryloyl equivalent is preferably 200 to 600. The hydroxyl equivalent is preferably 90 to 280 mg / KOH.

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

Next, the reactive dispersant of the present invention will be described.
The reactive dispersant is not particularly limited as long as it is an active energy ray-curable resin composition having a hydrogen bonding functional group. Here, the hydrogen bonding functional group is not particularly limited as long as it is a functional group involved in hydrogen bonding, specifically, a hydroxyl group, an amino group, a carboxy group, a thiol group, a urethane group, an ester group, Examples include groups selected from amide groups, imide groups, and ether groups.

  As a more specific example of the reaction dispersant, mention may be made of an addition reaction of (meth) acrylic acid to a (meth) acrylic polymer having an epoxy group obtained by polymerizing glycidyl (meth) acrylate. it can.

  More specifically, a reactive dispersant (A1) obtained by addition reaction of a monomer (b1) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having an epoxy group, or a carboxyl Although the reactive dispersing agent (A2) formed by carrying out addition reaction of the monomer (b2) which has a (meth) acryloyl group and an epoxy group to the (meth) acrylic polymer (a2) which has group is mentioned, As the reactive dispersant, either (A1) or (A2) may be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(13) Acrylamide and its alkyd-substituted amides;

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

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

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

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

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

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

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

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

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

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

  Examples thereof include hydrocarbon solvents such as toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E, Isopar G, Exxon Naphtha 5 and Exxon Naphtha 6. These may be used singly or in combination of two or more, but the (meth) acrylic polymer (a1) having an epoxy group and a monomer having a carboxyl group (2) In order to efficiently perform the reaction of b1) or the reaction of the (meth) acrylic monomer (a2) having a carboxyl group and the monomer (b2) having an epoxy group, the reaction is performed at a high temperature of 100 to 150 ° C. From this viewpoint, it is preferable to use a solvent having a boiling point of 100 ° C. or higher, preferably 100 to 150 ° C.

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

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

  As described above, the reactive dispersant (A1) reacts the (meth) acrylic polymer (a1) having an epoxy group with the monomer (b1) having a (meth) acryloyl group and a carboxyl group. Examples of the monomer (b1) having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid; β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, and 2-acryloyloxyethyl phthalate. Examples include acids, 2-acryloyloxyethylhexahydrophthalic acid, and unsaturated monocarboxylic acids having an ester bond such as modified lactones thereof; maleic acid and the like.

  Further, after reacting an anhydride such as succinic anhydride or maleic anhydride with a hydroxyl group-containing polyfunctional (meth) acrylate monomer such as pentaerythritol triacrylate as the monomer (b1), a carboxyl group-containing polyfunctional (meth) An acrylate monomer may be used. These monomers (b1) having a (meth) acryloyl group and a carboxyl group may be used alone or in combination of two or more.

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

  The reactive dispersant (A2) is obtained by reacting the (meth) acrylic polymer (a2) having a carboxyl group with the monomer (b2) having a (meth) acryloyl group and an epoxy group as described above. . Examples of the monomer (b2) having a (meth) acryloyl group and an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n-butyl (meth) acrylate glycidyl, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxypentyl , Α-ethyl (meth) acrylic acid-6,7-epoxypentyl, β-methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone-modified (meth) acrylic acid-3,4 -Epoxycyclohexyl, vinylcyclohexene oxide and the like. These may be used alone or in combination of two or more.

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

  Reaction between the (meth) acrylic polymer (a1) having an epoxy group and a monomer (b1) having a (meth) acryloyl group and a carboxyl group, and a (meth) acrylic polymer (a2) having a carboxyl group The reaction with the monomer (b2) having a (meth) acryloyl group and an epoxy group can also be performed, for example, by the following method.

Method 1: A method in which a (meth) acrylic polymer (a1) is polymerized by a solution polymerization method, and a monomer (b1) having a (meth) acryloyl group and a carboxyl group is added to the reaction system and reacted.

Method 2: A method in which a (meth) acrylic polymer (a2) is polymerized by a solution polymerization method, and a monomer (b2) having a (meth) acryloyl group and an epoxy group is added and reacted.

  The reactive dispersant of the present invention is preferably a polymer having a main skeleton having a structure obtained by polymerizing a monomer having one polymerizable unsaturated double bond per molecule. A monomer having two or more polymerizable unsaturated double bonds may be used in combination as long as the above does not occur.

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

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

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

  In the present invention, the measurement of the mass average molecular weight and the number average molecular weight was performed under the following conditions using a gel permeation chromatograph (GPC).

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

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

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

  Examples of the monomer having one isocyanate and a (meth) acryloyl group include a monomer having one isocyanate and one (meth) acryloyl group, and a monomer having one isocyanate and two (meth) acryloyl groups. Monomer, Monomer having one isocyanate and three (meth) acryloyl groups, Monomer having one isocyanate and four (meth) acryloyl groups, One isocyanate and five (meth) acryloyl groups And the like. As such a monomer, for example, a compound represented by the following formula [Chemical Formula 3] can be preferably exemplified.

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

  The method of reacting one isocyanate and a monomer having a (meth) acryloyl group with the reactive dispersant of the present invention is not particularly limited, and a known method can be adopted. Specifically, for example, one isocyanate and a monomer having a (meth) acryloyl group are added dropwise to the reactive dispersant of the present invention and heated to 50 to 120 ° C., more preferably 60 to 90 ° C. And react. In addition, although the usage-amount of the monomer which has a reactive dispersing agent, one isocyanate, and a (meth) acryloyl group is not specifically limited, Usually, the hydroxyl group (mol) of a reactive dispersing agent: One isocyanate and (meth) acryloyl The isocyanate group (mol) of the monomer having a group is 1: 0.1 to 1: 0.9, preferably 1: 0.1 to 1: 0.7.

  The reactive dispersant of the present invention can be suitably used as a reactive dispersant for metal oxide particles such as various silica particles. The metal oxide particles that can be used in the present invention are selected from silica particles, zirconium oxide particles, aluminum oxide particles, titanium oxide particles, cerium oxide particles, indium oxide particles, antimony oxide particles, tin oxide particles, and zinc oxide particles. In particular, silica particles are preferable.

  For example, examples of the silica particles include dry silica particles and wet silica particles. The dry silica particles are, for example, silica particles obtained by burning silicon tetrachloride in an oxygen or hydrogen flame. The wet silica particles are silica particles obtained by neutralizing sodium silicate with a mineral acid, for example. The reactive dispersant of the present invention has high dispersibility of silica particles. Therefore, a dispersion in which silica particles are dispersed in the reactive dispersant of the present invention maintains good dispersion stability over a long period of time. Further, even when an active energy ray-curable resin composition is prepared by adding the dispersion to an active energy ray-curable oligomer such as urethane (meth) acrylate or epoxy (meth) acrylate or an active energy ray-curable monomer, In the active energy ray-curable resin composition, the silica particles are stably dispersed over a long period of time. Thus, since the reactive dispersant of the present invention has high dispersibility of silica particles, it is preferably used as a reactive dispersant when dispersing silica particles having poor dispersibility stability in the composition. The reactive dispersant of the present invention is preferably used as a reactive dispersant used when silica particles are dispersed in a compound having a (meth) acryloyl group.

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

A reactive dispersion in which metal oxide particles are dispersed can be prepared 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 of the present invention and the metal oxide particles are 10 to 90 in terms of [(reactive dispersant) :( metal oxide particles)]. It is preferable to contain it so that it may become 90 mass parts: 90-10 mass parts, and it is more preferable to contain so that it may become 30-90 mass parts: 70-10 mass parts. Moreover, 1-60 mass% is preferable in conversion of solid content, and, as for the total content rate of the reactive dispersing agent and metal oxide particle in the dispersion of this invention, 30-50 mass% is more preferable.
In producing the reactive dispersion, the energy ray-curable resin composition is obtained by containing the reactive dispersant of the present invention, metal oxide particles, and a compound having a (meth) acryloyl group other than the reactive dispersant. It can be a thing. Examples of the compound having a (meth) acryloyl group other than the reactive dispersant include an active energy ray-curable monomer and an active energy ray-curable oligomer. The content of each component is not particularly limited, but the reactive dispersant of the present invention and the active energy ray-curable monomer or active energy ray-curable oligomer may be combined with [(reactive dispersant): (active energy ray-curable monomer. Or 10 to 90 parts by mass: 90 to 10 parts by mass, and preferably 30 to 90 parts by mass: 70 to 10 parts by mass. More preferred.

  Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meta), in addition to the polymerizable monomer that can be used in the preparation of the reactive dispersant of the present invention. ) Acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,

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

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

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

  Examples of the urethane (meth) acrylate include polyfunctional urethane (meth) acrylate obtained by reacting an isocyanate compound with a hydroxyl group-containing (meth) acrylate compound. Examples of the isocyanate compound used herein include aliphatic or cycloaliphatic diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate; toluene diisocyanate, 4,4 ′ -Aromatic diisocyanates such as diphenylmethane diisocyanate; and isocyanurate type isocyanate prepolymers which are trimers of diisocyanate compounds. In addition, when the polyfunctional urethane (meth) acrylate is produced, a part of the hydroxyl group-containing (meth) acrylate compound that reacts with the isocyanate compound is substituted with a divalent to tetravalent alcohol or polyol compound and polymerized. But it ’s okay.

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

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

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

  Although the manufacturing method of a reactive dispersion is not specifically limited, For example, the (meth) acrylic polymer (a1) which has an epoxy group is made to add and react the monomer (b1) which has a (meth) acryloyl group and a carboxyl group. (Meth) acryloyl equivalent is 200 to 600, hydroxyl value is 90 to 280 mg / KOH reaction product, or (meth) acrylic polymer (a2) having a carboxyl group has a (meth) acryloyl group and an epoxy group 10 to 90 parts by mass of a reaction product (hereinafter referred to as a reactive dispersant) having a (meth) acryloyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH obtained by addition reaction of the monomer (b2) and a metal 90 to 10 parts by mass of the oxide particles are dispersed in a dispersion medium (organic solvent) so that the total concentration of the reactive dispersant and the metal oxide particles is 1 to 60% by mass. In diluted, and a method of dispersing by using a mechanical means.

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

  Furthermore, as another reactive dispersant of the present invention, for example, a polysiloxane segment (a3) having a structural unit represented by the general formula (2) or the general formula (3) and a silanol group or a hydrolyzable silyl group. ) And a vinyl polymer segment (a4) may be used as an essential component a composite resin in which the vinyl polymer segment (a4) is bonded by a bond represented by the general formula (4).

（一般式（２）及び（３）中、Ｒ_４、Ｒ_５及びＲ_６は、それぞれ独立して、−Ｒ_７−ＣＨ＝ＣＨ_２、−Ｒ_７−Ｃ（ＣＨ_３）＝ＣＨ_２、−Ｒ_７−Ｏ−ＣＯ−Ｃ（ＣＨ_３）＝ＣＨ_２、及び−Ｒ_７−Ｏ−ＣＯ−ＣＨ＝ＣＨ_２からなる群から選ばれる１つの重合性二重結合を有する基（但しＲ_７は単結合又は炭素原子数１〜６のアルキレン基を表す）、炭素原子数が１〜６のアルキル基、炭素原子が３〜８のシクロアルキル基、アリール基、または炭素原子が７〜１２のアラルキル基を表す。）

(In General Formulas (2) and (3), R ₄ , R ₅ and R ₆ are each independently -R ₇ -CH = CH ₂ , -R ₇ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ₇ —O—CO—C (CH ₃ ) ═CH ₂ and —R ₇ —O—CO—CH═CH ₂ (provided that R ₇ is A single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or an aralkyl having 7 to 12 carbon atoms. Represents a group.)

（一般式（４）中、炭素原子は前記ビニル系重合体セグメント（ａ４）の一部分を構成し、酸素原子のみに結合したケイ素原子は、前記ポリシロキサンセグメント（ａ３）の一部分を構成するものとする。）

(In the general formula (4), carbon atoms constitute a part of the vinyl polymer segment (a4), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a3)). To do.)

Next, the manufacturing method of the dispersion of this invention is demonstrated.
In the present invention, in the step of kneading the compound (A) having a (meth) acryloyl group and the metal oxide particles (B), an apparatus capable of performing kneading by a planetary motion of a plurality of blades is used. To disperse.

The device used in the present invention can be used without limitation as long as it has a function of performing kneading by the planetary movement of the plurality of blades. This equipment has a structure that stirs and kneads the kneaded material in the stirring tank using two or more stirring blades that revolve while rotating with each other. The stirring blade reaches the stirring tank. There is little dead space. In addition, since the blade shape is thick and high load can be applied, and the clearance between the blade and the inner wall surface of the stirring tank is narrow, the material to be kneaded between the blade and the inner wall surface of the stirring tank by stirring is very A large shear force is generated. Therefore, dispersion can be carried out even when the viscosity of the system is high.
On the other hand, it can be used like a normal stirrer that rotates a stirring blade in a stirring tank. In addition, by controlling the temperature of the stirring tank, heat can be applied to the material to be kneaded in the tank to promote chemical change. it can.
In this way, from the high load area to the low load area, the width of the material to be kneaded that can be processed is wide, and it can be used like a flask, so it is suitable for the surface modification step of metal oxide particles in the present invention. it can. As such a device, for example, a publicly known planetary mixer can be cited.

More specifically, after homogenizing an organic solvent, a silane coupling agent having a (meth) acryloyl group, and water and a catalyst necessary for hydrolysis polycondensation, silica particles are added to a planetary mixer until a slurry is obtained. Knead at. Then, while heating the kettle with a temperature control device, the slurry is continuously stirred in a planetary mixer until the hydrolysis and polycondensation of the silane coupling is sufficiently promoted. An acryloyl group can be imparted. The set temperature of the temperature controller is preferably 60 ° C. or higher and lower than the boiling point of the organic solvent used, and more preferably 70 to 100 ° C.
As the organic solvent to be used, any organic solvent in which the silane coupling agent and the reactive dispersant are compatible can be used without any particular limitation.

  In order to perform silane coupling treatment of silica particles in an organic solvent, it is usually necessary to suppress the viscosity of the system to a certain level and to stir the flask or disperse the beads. However, since silica particles are hydrophilic and are not well suited to organic solvents, in order to keep the viscosity of the system low, the amount of silane coupling agent must be increased or the solid content concentration must be lowered. Increasing the amount of coupling agent leads to an increase in cost, and a large amount of unbound coupling agent remains in the system, which adversely affects the temporal stability of the dispersion and the coating film hardness. Further, when the solid content concentration is lowered, productivity is lowered and a concentration step may be required.

  However, the above problem can be solved by using a planetary mixer.

  That is, since the planetary mixer can disperse even in a system having a high viscosity, the silane coupling agent is small and the solid content concentration can be increased. When silica dispersion is performed in an organic solvent in the presence of silane coupling, the silane coupling agent gradually binds to silanols on the silica surface, and the silica surface changes from hydrophilic to hydrophobic, making it hydrophobic. Silica improves compatibility with organic solvents. Thereby, the viscosity of the slurry gradually decreases. If the kettle of the planetary mixer is heated in this state, the coupling agent can be bonded to the silica surface as in the reaction in the flask.

  In addition, in the production method of the present invention, it is essential to have a step of kneading by a plurality of blades moving in a planetary motion. Furthermore, a known dispersion bead is used in combination with a known and conventional bead mill. You can also

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

  Examples of the silane coupling agent include 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, Amino silane coupling agents, ureido silane coupling agents, chloropropyl silane coupling agents, mercapto silane coupling agents, sulfide silane coupling agents, isocyanate silane coupling agents, aluminum Silane coupling agents and the like.

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

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

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

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

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

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

  Examples of ureido silane coupling agents include 3-ureidopropyltriethoxysilane.

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

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

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

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

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The dispersion obtained by the production method of the present invention can be made into an active energy ray-curable resin composition by mixing with other compounds. These compounds include the aforementioned active energy ray curable monomers, active energy ray curable oligomers, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoaming agents, and release agents. , Silane coupling agents, antistatic agents, antifogging agents, coloring agents, and the like.

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

  Examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants.

  Examples of the silicon-based additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified. Examples thereof include polyorganosiloxanes having an alkyl group or a phenyl group, such as a dimethylpolysiloxane copolymer and an amino-modified dimethylpolysiloxane copolymer.

  The amount of the various additives as described above is sufficient to exert its effect and does not hinder ultraviolet curing, so that the active energy ray-curable resin composition for casting polymerization is 100 parts by mass. These are each preferably in the range of 0.01 to 10 parts by mass.

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

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

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

3,3′-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl -1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- -Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, Benzyldimethylketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylaminoacetophenone, α, α-dichloro-4-phenoxyacetophenone, pentyl- 4-dimethylaminobenzoate, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,4-bis-trichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl-S-triazine 2,4-bis-trichloromethyl-6- (4-eth C) Phenyl-S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-ethoxy) phenyl-S-triazine anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloro Anthraquinone etc. are mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The polyfunctional isocyanate used in combination with the active energy ray-curable resin composition is not particularly limited, and various known ones can be used. For example, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexane diisocyanate, the above trimer, a prepolymer obtained by reacting a polyhydric alcohol with the above diisocyanate, or the like is used. be able to. That is, the B-stage is formed by reacting the hydroxyl group contained in the polymer with the isocyanate group of the polyfunctional isocyanate.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As a method for bonding the molded product and the protective layer forming sheet in the post-adhesion method, for example, an adhesive is applied to the base sheet of the protective layer forming sheet or the surface of the molded product, and the base sheet of the protective layer forming sheet and the molded product Method of adhering to the surface, after attaching a double-sided adhesive tape to the base sheet or molded product surface of the protective layer forming sheet, then peeling off the release protective sheet of the double-sided adhesive tape to expose the adhesive surface, the protective layer forming sheet A method for adhering the base sheet and the surface of the molded product, after applying an adhesive to the base sheet of the protective layer forming sheet to form an adhesive surface, a protective layer forming sheet in which the adhesive surface is protected with a release protective sheet is prepared in advance In addition, there may be mentioned a method in which the release protective sheet of the protective layer forming sheet is peeled off, and the adhesion surface of the base sheet and the surface of the molded product are adhered. In the simultaneous molding method, the protective layer forming sheet and the molded product are integrated by integrating the protective layer forming sheet and the molded product by melting the base sheet by heat during in-mold molding without using an adhesive. Can be glued. Here, examples of the adhesive used in the post-adhesion method include urethane adhesives, epoxy adhesives, ester adhesives, acrylic adhesives, and hot melt adhesives.

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

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

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

(Production Example 1) Production of active energy ray-curable resin (A-1) In a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, 250 g of glycidyl methacrylate (hereinafter referred to as GMA), methyl isobutyl ketone After charging 1000 g (hereinafter referred to as MIBK) and 10 g of t-butyl peroxyethyl hexanoate (hereinafter referred to as PO), the system temperature was increased to about 90 ° C. over about 1 hour under a nitrogen stream. The temperature was raised and kept warm for 1 hour. Next, the mixture was dropped into the system for about 2 hours under a nitrogen stream from a dropping funnel charged beforehand with a mixture consisting of 750 g of GMA and 30 g of PO, and kept at the same temperature for 3 hours. Then, it heated up at 120 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., the nitrogen inlet tube was replaced with an air inlet tube, 507 g of acrylic acid, 2.3 g of methoquinone and 9.3 g of triphenylphosphine were charged and mixed, and then heated to 110 ° C. under air bubbling. . After incubating at the same temperature for 8 hours, 1.6 g of methoquinone was charged, cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of the reactive dispersant (A-1).

(Example 1) to (Example 3)
It knead | mixed using the planetary mixer using the reagent of the compounding quantity of Tables 1-3 of Table 1 until it became a slurry state. Then, the surface-treated silica particle dispersion was obtained by stirring in a planetary mixer, heating a kettle with a temperature control apparatus. MIBK was used as the organic solvent.

(Comparative Example 1) to (Comparative Example 6)
It knead | mixed using the mixer of a table | surface until it became a slurry state using the reagent of the compounding quantity of the comparative examples 1-6 of Table 1 similarly to the said Example until it became a slurry state.

<Storage stability of dispersion>
The active energy ray-curable resin (A-1) (solid content 25 parts) and pentaerythritol hexaacrylate prepared in Production Example 1 were added to the silica particle dispersion (solid content 50 parts) surface-treated by the above method. 25 parts of solid content) and adjusting the non-volatile component to 40 wt% using MIBK, and then dispersing in a bead mill until the average particle size of the silica particles is about 120 to 150 nm. The dispersion was stored in an oven at 40 ° C. for 3 months, and the change with time in the B-type viscosity was measured.

<Measuring method of pencil hardness>
4 parts of a photopolymerization initiator (Irgacure 184: manufactured by Ciba Japan Co., Ltd.) is added to 100 parts of the solid content of the nanosilica dispersion produced by the above method, and a coating film is formed with a thickness of 10 μm on a 40 μm TAC film. Then, it dried at 70 degreeC for 5 minute (s), and obtained the hardened | cured material layer by 200 mJ / cm < ² > UV irradiation using the high pressure mercury lamp under nitrogen. The surface of the film having the cured layer was evaluated by a pencil scratch test with a load of 500 g in accordance with JIS K 5400.

In addition, the following symbol in a table | surface shows the following, respectively.
Silica particle # 50: Aerosil 50 (manufactured by Nippon Aerosil Co., Ltd.)
Silica particle # 200: Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.)
KBM503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production Example 2) Active energy ray curable resin (A-2)
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet is charged with 415 parts of methyltrimethoxysilane (MTMS) and 756 parts of 3-methacryloyloxypropyltrimethoxysilane (MPTS). The temperature was raised to 60 ° C. with stirring under aeration of gas. Subsequently, a mixture consisting of 0.1 part of “A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 121 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product.
By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75. Obtained 1000 parts of polysiloxane (c1) of 0.0%.
The "active ingredient" is a value obtained by dividing the theoretical yield (parts by weight) when all the methoxy groups of the silane monomer used undergo hydrolysis condensation reaction by the actual yield (parts by weight) after hydrolysis condensation reaction, That is, it is calculated by the formula [theoretical yield when all methoxy groups of the silane monomer undergo hydrolysis condensation reaction (parts by weight) / actual yield after hydrolysis condensation reaction (parts by weight)].

A reaction vessel used in the above reaction was charged with 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 107.7 parts of n-butyl acetate. The temperature was raised to 80 ° C. while stirring. Next, 15 parts of methyl methacrylate (MMA), 45 parts of n-butyl methacrylate (BMA), 39 parts of 2-ethylhexyl methacrylate (EHMA), 1.5 parts of acrylic acid (AA), 4.5 parts of MPTS, 2-hydroxyethyl While stirring a mixture containing 45 parts of methacrylate (HEMA), 15 parts of n-butyl acetate and 15 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) at the same temperature under aeration of nitrogen gas And dropped into the reaction vessel in 4 hours. After further stirring at the same temperature for 2 hours, a mixture of 0.05 part of “A-3” and 12.8 parts of deionized water was dropped into the reaction vessel over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By stirring, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Next, by stirring at the same temperature for 10 hours, a reaction product having a residual amount of TBPEH of 0.1% or less was obtained. The residual amount of TBPEH was measured by an iodometric titration method.

  Next, 162.5 parts of the polysiloxane (c1) obtained above is added to the reaction product and stirred for 5 minutes, and then 27.5 parts of deionized water is added and stirred at 80 ° C. for 4 hours. The reaction product and polysiloxane were subjected to a hydrolytic condensation reaction. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) , 27.3 parts of n-butyl acetate, an active energy ray-curable resin (A-2) comprising a polysiloxane segment and a vinyl polymer segment, and the content of the polysiloxane segment (c1) is 50% by weight 600 parts of a solution (solid content 50.0%) were obtained.

Example 4
It knead | mixed using the reagent of the compounding quantity of Example 4 of Table 2 until it became a slurry state using the planetary mixer. Then, the surface-treated silica particle dispersion was obtained by stirring in a planetary mixer, heating a kettle with a temperature control apparatus.

(Comparative Example 7)
In the same manner as in Example 4, the reagents having the blending amounts described in Comparative Example 7 in Table 2 were used for kneading using the mixer described in the table until a slurry state was obtained.

<Storage stability of dispersion>
The composite resin (A-2) (solid content 50 parts) prepared in the above production example is added to the silica particle dispersion surface-treated by the above method (solid content 50 parts), and MIBK is adjusted so that the nonvolatile component becomes 20 wt%. Then, the mixture was dispersed with a bead mill until the average particle size of the silica particles was about 150 nm. By concentrating this with an evaporator, a nanosilica dispersion having a non-volatile component of 50 wt% was obtained. This was stored in an oven at 40 ° C. for 3 months, and the change with time in the B-type viscosity was measured.

<Measuring method of pencil hardness>
As a reactive compound, 24.3 parts of pentaerythritol triacrylate (PETA) and 15 parts of polyisocyanate (Bernock DN-902S: manufactured by DIC Corporation) are added to 121.4 parts of the solid content of the nanosilica dispersion prepared by the above method. 3.35 parts of a polymerization initiator (Irgacure 184: manufactured by Ciba Japan Co., Ltd.) was added. After forming the above-mentioned coating film with a thickness of 10 μm on a 40 μm PET film, it is dried at 80 ° C. for 4 minutes, irradiated with 1000 mJ / cm ² UV using a high-pressure mercury lamp, and further left for 3 days at 40 ° C. Got. The surface of the film having the cured layer was evaluated by a pencil scratch test with a load of 500 g in accordance with JIS K5400.

  The method for producing a dispersion according to the present invention can be used for producing a dispersion capable of providing an industrially useful high hardness film.

Claims (18)

In the method for producing a dispersion in which the metal oxide particles (B) treated with the surface treatment agent (A) are dispersed in the reactive dispersant,
1) The reactive dispersant is an active energy ray-curable resin composition having a hydrogen bonding functional group,
2) A step of kneading the surface treatment agent (A) and the metal oxide particles (B) by causing a plurality of blades to perform planetary motion,
A method for producing the dispersion. The method for producing a dispersion according to claim 1, wherein the surface treatment agent (A) can be bonded to the metal oxide particles (B) by a coupling reaction with the metal oxide particles (B). The method for producing a dispersion according to claim 1 or 2, wherein the surface treatment agent (A) is a coupling agent having a (meth) acryloyl group. A coupling agent having a (meth) acryloyl group is represented by the general formula (1)

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6).
The method for producing a dispersion according to claim 3, which is an organosilane compound represented by the formula: The metal oxide particles (B) are any one selected from silica particles, zirconium oxide particles, aluminum oxide particles, titanium oxide particles, cerium oxide particles, indium oxide particles, antimony oxide particles, tin oxide particles, and zinc oxide particles. The manufacturing method of the dispersion in any one of Claims 1-4. The method for producing a dispersion according to any one of claims 1 to 5, wherein the primary particle diameter of the metal oxide particles (B) is 10 to 300 nm. The hydrogen-bonding functional group is any one selected from a hydroxyl group, an amino group, a carboxy group, a thiol group, a urethane group, an ester group, an amide group, an imide group, and an ether group. A method for producing a dispersion. An active energy ray-curable resin composition having a hydrogen bondable functional group,
The dispersion according to any one of claims 1 to 7, wherein (meth) acrylic acid is addition-reacted to a (meth) acrylic polymer having an epoxy group obtained by polymerizing glycidyl (meth) acrylate. Production method. An active energy ray-curable resin composition having a hydrogen bondable functional group,
Reaction product obtained by addition reaction of a monomer (b1) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having an epoxy group, or a (meth) acryl having a carboxyl group The method for producing a dispersion according to any one of claims 1 to 8, which is a reaction product obtained by subjecting a polymer (a2) to an addition reaction of a monomer (b2) having a (meth) acryloyl group and an epoxy group. . The method for producing a dispersion according to claim 8 or 9, wherein the reaction product has a (meth) acryloyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH. An active energy ray-curable resin composition having a hydrogen bondable functional group,
A polysiloxane segment (a3) having a structural unit represented by the general formula (2) or the general formula (3), a silanol group or a hydrolyzable silyl group, and a vinyl polymer segment (a4) The method for producing a dispersion according to any one of claims 1 to 10, wherein the composite resin bound by a bond represented by formula (4) is an essential component.

(In General Formulas (2) and (3), R ₄ , R ₅ and R ₆ are each independently -R ₇ -CH = CH ₂ , -R ₇ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ₇ —O—CO—C (CH ₃ ) ═CH ₂ and —R ₇ —O—CO—CH═CH ₂ (provided that R ₇ is A single bond or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or an aralkyl having 7 to 12 carbon atoms. Represents a group.)

(In the general formula (4), carbon atoms constitute a part of the vinyl polymer segment (a4), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a3)). To do.) The method for producing a dispersion according to claim 11, wherein at least one of R ₄ , R ₅ and R _{6 in} the general formulas (1) and (2) is a group having the polymerizable double bond. The method for producing a dispersion according to claim 11 or 12, wherein the vinyl polymer segment (a4) has an alcoholic hydroxyl group. The method for producing a dispersion according to any one of claims 11 to 13, wherein the content of the polysiloxane segment (a3) is 10 to 90% by weight based on the total solid content of the active energy ray-curable resin composition. The energy-beam curable resin composition containing the dispersion obtained by the manufacturing method of the dispersion in any one of Claims 1-14. A film comprising a cured layer obtained by curing the energy ray-curable resin composition according to claim 15 on a film-like substrate. The film-like substrate is one or more film-like substrates selected from the group consisting of a film-like substrate of polyethylene terephthalate resin, a film-like substrate of polycarbonate resin, and a film-like substrate of acetylated cellulose resin. 16. The film according to 16. The film according to claim 16 or 17, wherein the film thickness of the cured layer is 3 to 100% with respect to the film thickness of the film-like substrate.