JP2011157436A - Inorganic particle dispersion and cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersion producing a cured film having high hardness and excellent film surface scratch resistance, and a cured film obtained by curing the dispersion. <P>SOLUTION: In the dispersion, surface-treated inorganic particles are dispersed in a polymerizable organic component, and the surface-treated inorganic particles are obtained by treating the surfaces of inorganic particles with an organosilane compound having a group for starting polymerization reaction by active energy. The polymerizable organic component is a reaction product prepared by addition reaction of a monomer (b) having a (meth)acryloyl group and a carboxy group to a (meth)acrylic polymer (a1) having an epoxy group, or a reaction product prepared by addition reaction of a monomer (c) having a (meth)acryloyl group and an epoxy group to a (meth)acrylic polymer (a2) having a carboxy group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a dispersion suitably used for production of a cured film, and particularly to a dispersion obtained by dispersing inorganic particles in a polymerizable organic component.

UV curable hard coat materials (HC materials) have been widely used for automobile parts, cosmetic containers, electronic device cases, and the like for the purpose of providing surface protection from scratches and dirt and imparting design properties. In recent years, it is frequently used for the purpose of preventing damage to the display screen in applications such as a display screen of a mobile device such as a mobile phone or a PDA, a touch panel for screen display input such as ATM or car navigation. As the display device itself is used in a mobile environment from a conventional stationary type, a demand for a material that can be preferably used for surface protection is increasing. Under such circumstances, a material with higher hardness is desired in order to improve the scratch resistance of the HC material.

  In the UV curable organic HC material, the hardness and scratch resistance can be improved to some extent by increasing the crosslinking density. However, since the crosslinking reaction is polymerization of acrylic groups, shrinkage of the coat itself due to curing cannot be avoided, and the shrinkage due to curing causes problems such as a decrease in adhesion to the substrate and distortion.

  In addition, inorganic HC materials represented by polysiloxane and the like have advantages such as high hardness and high scratch resistance as well as excellent heat resistance and weather resistance compared to organic materials, but a heating process close to 100 ° C. Since it is necessary and passes through a polycondensation reaction, shrinkage occurs due to elimination of the organic group during curing, and it has a disadvantage that it is difficult to increase the film thickness, so that the range of use is limited.

Under such circumstances, organic and inorganic components are mixed at the nanoscale level, so it is possible to create materials that have the advantages of both. . Examples of the material include fumed silica powder as a nanomaterial that can be obtained at a relatively low cost. However, conventionally, there has been no simple method for solving strong secondary aggregation, so that sufficient physical properties could not be exhibited.

As a prior art, for example, in Patent Document 1, silica fine particles having a photopolymerization initiator on the surface thereof are disclosed in regard to silica fine particles having a photopolymerization initiator on the surface and a film forming method using the silica fine particles. Silica fine particles in which a photopolymerization initiator is introduced on the surface of the present invention can be formed into a film excellent in durability and transparency by being added to a radical polymerizable polyfunctional monomer and irradiated with actinic rays Describes that it has a great advantage in that a film excellent in durability and transparency can be obtained only by irradiation with the actinic ray without requiring other steps. Although the evaluation result is described about the base-material adhesiveness, wiping resistance, and scratch resistance of the film obtained by the invention, it is unclear whether a film that achieves the above target is obtained.

Patent Document 2 discloses a film pencil obtained from a coating composition containing at least one inorganic fine particle surface-treated with a hydrolyzate of an organosilane compound and / or a partial condensate thereof. In the steel wool resistance test in which the hardness is in the range of 3H to 4H and a load of 500 g / cm ² is applied to steel wool of # 0000, it is described that a product having no scratches is obtained.

JP-A-9-328522 JP2008-121011

An object of the present invention is to provide a dispersion capable of obtaining a cured film having high hardness and excellent scratch resistance on the film surface, and a cured film obtained by curing the dispersion.

In order to solve the above-mentioned problems, the present inventors have studied a dispersion capable of producing a cured film cured film, and have completed the present invention. That is, the present invention
1. In a dispersion in which inorganic particles are dispersed in a polymerizable organic component,
1) Inorganic particles are surface-treated with an organosilane compound having a group that initiates a polymerization reaction by light or thermal energy,
2) A reaction product obtained by adding a monomer (b) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having a polysynthetic organic component having an epoxy group, or carboxyl It is a reaction product obtained by subjecting a (meth) acrylic polymer (a2) having a group to a monomer (c) having a (meth) acryloyl group and an epoxy group, and having a (meth) acryloyl equivalent of 200 to 600 (g / eq.) And a hydroxyl value of 90 to 280 (mgKOH / g),
2. A cured film obtained by curing the dispersion,
3. The present invention relates to a method for producing a cured film by forming a coating film on a substrate using the dispersion and then irradiating the coating film with light or heating the coating film.

  According to the present invention, it is possible to provide a dispersion that can be a cured film having high hardness and excellent scratch resistance on the film surface, and a cured film obtained by curing the dispersion.

(Dispersion)
The dispersion of the present invention is an organosilane compound in which a surface-treated inorganic particle has a group that initiates a polymerization reaction by light or heat energy in a dispersion in which surface-treated inorganic particles are dispersed in a polymerizable organic component. The surface of the inorganic particles is treated by
A reaction product obtained by adding a monomer (b) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having a polymerizable organic component having an epoxy group, or a carboxyl group The (meth) acrylic polymer (a2) having a (meth) acryloyl group and an epoxy group-containing monomer (c) is a reaction product, and has a (meth) acryloyl equivalent of 200 to 600 ( g / eq.) and a hydroxyl value of 90 to 280 (mg KOH / g).

  The inorganic particles of the present invention are not particularly limited as long as they are inorganic particles that can be surface treated with organosilane compounds such as silica particles, zirconia particles, alumina particles, cerium oxide particles, titanium particles, or barium titanate particles. Although there is no limitation, silica particles are particularly preferable. The preferable primary particle diameter of these particles can be in the range of 10 nm to 300 nm. If it is 10 nm or less, the dispersion of the inorganic particles in the dispersion becomes insufficient, and if it is 300 nm or more, it is not preferable because sufficient strength of the cured film cannot be maintained.

The organosilane compound of the present invention can be produced by a generally known method.
That is, for example, in order to obtain an organosilane compound (C) as represented by the general formula (1), it has an arbitrary group R ₁ capable of reacting and initiates a polymerization reaction by light energy or thermal energy. compounds having allowed to group with (a), an alkoxysilane compound having an R ₁ capable of reacting any group R ₂ with (B) may be reacted.

(In the formula, R ₁ and R ₂ represent any functional group capable of reacting, and R ₃ is an ester bond, a urethane bond, or the like obtained as a result of the reaction of R ₁ and R _2. )
However, the general formula (1) merely shows one embodiment of a method for producing an organosilane compound, and is not limited thereto.

  Furthermore, in order to obtain inorganic particles surface-treated with an organosilane compound, the inorganic particles may be reacted with an organosilane compound having a group that initiates a polymerization reaction by light energy or thermal energy. The inorganic particles must have a functional group capable of reacting with the organosilane compound on the surface. For example, in the case of silica particles, the silanol groups possessed on the surface of the silica particles and the alkoxysilyl groups of the organosilane compound. By carrying out the reaction, inorganic particles surface-treated with the target organosilane compound can be obtained.

  Even inorganic particles other than silica particles can be obtained in the same manner by using a generally known method, and similarly target inorganic particles surface-treated with the organosilane compound of the present invention.

The organosilane compound used in the present invention has a group that initiates a polymerization reaction by light energy or heat energy.
The group that initiates the polymerization reaction by light energy can be used without limitation as long as it is a generally known group that substantially initiates the radical photopolymerization reaction.

  Examples of such groups include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds, aromatic sulfoniums, active halogen compounds, and various compounds shown below.

  Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.

  Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone.

  Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of active esters include IRGACURE OXE01 (1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] by Chivas Specialty Chemicals), sulfonate esters, cyclic activity An ester compound is included.

  Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

  Examples of the borate salt are described in Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. And the organic borate compounds described.

As the thermal radical polymerization initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (propionitrile), 1,1'-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

  As the skeleton of the chemical structure of the preferred initiator, active halogen type, acetophenone type, oxazole type, oxadiazole type, phosphine oxide type, organic azo type are preferable, especially active halogen type, acetophenone type, oxazole type, oxadiazole. A system is preferred.

  Examples of the possible organosilane thus obtained include, but are not limited to, the following compounds.

The polymerizable organic component of the present invention is not particularly limited as long as it is a component capable of dispersing inorganic particles, but the (meth) acrylic polymer (a1) having an epoxy group has a (meth) acryloyl group and a carboxyl group. Addition reaction of monomer (c) having (meth) acryloyl group and epoxy group to reaction product obtained by addition reaction of monomer (b) or (meth) acrylic polymer (a2) having carboxyl group Particularly preferred is a reaction product having a (meth) acryloyl equivalent of 200 to 600 (g / eq.) And a hydroxyl value of 90 to 280 (mg KOH / g).

Here, the (meth) acrylic polymer (a1) having an epoxy group includes, for example, a polymerizable monomer (b) having a (meth) acryloyl group and an epoxy group, and other polymerizable monomers as necessary. What is obtained by the copolymerization reaction of these can be mentioned. Examples of the monomer (b) 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. , Α-n-butyl (meth) acrylate glycidyl, (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 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) is obtained, for example, by a copolymerization reaction between a monomer having a (meth) acryloyl group and a carboxyl group and, if necessary, another polymerizable monomer. Examples of the monomer having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid, β-carboxyethyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethylphthalic acid, 2 -Unsaturated monocarboxylic acid, maleic acid, etc. having an ester bond such as acryloyloxyethyl hexahydrophthalic acid and modified lactones thereof. 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) or the (meth) acrylic polymer (a2) include the following monomers: Can be mentioned.
(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, (meth) acrylic acid 2- (Meth) acrylic acid esters having an aromatic ring such as hydroxy-3-phenopropyl;
(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, 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 ( (Meth) 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 a (per) fluoroalkyl group of 1 to 18 carbon atoms such as H-heptadecafluorodecyl (meth) acrylate or perfluoroethyloxyethyl (meth) acrylate Ethylenically unsaturated monomers;
(16) Silyl group-containing (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane;
(17) N, N-dialkylaminoalkyl (meth) acrylate such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate or N, N-diethylaminopropyl (meth) acrylate, etc. Is mentioned.

  Other 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. May be.

  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. For example, 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, typical solvents that can be used for solution polymerization and the like include, 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, ethyl 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 Ester solvents such as monomethyl 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 carry out the reaction of b) or the reaction of the carboxyl group-containing (meth) acrylic monomer (a2) and the epoxy group-containing monomer (c), the reaction is carried out 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.

  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 other azo compounds; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate 1,1'-bis- (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, organic peroxides such as t-hexylperoxy-2-ethylhexanoate, hydrogen peroxide, etc. Is mentioned.

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

  The reaction product obtained by adding the (meth) acryloyl group and the monomer (b) having a carboxyl group to the (meth) acrylic polymer (a1) having an epoxy group has an epoxy group as described above (meta ) The acrylic polymer (a1) is reacted with the monomer (b) having a (meth) acryloyl group and a carboxyl group. Examples of the monomer (b) having a (meth) acryloyl group and a carboxyl group include (meth) acrylic acid, β-carboxyethyl (meth) acrylate, 2-acryloyloxytyl succinic acid, and 2-acryloyloxyethylphthalate. Examples include acid, 2-acryloyloxyethylhexahydrophthalic acid, and unsaturated carboxylic acids having an ester bond such as lactone-modified products thereof and maleic acid.

  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 (b), a carboxyl group-containing polyfunctional (meth) An acrylate monomer may be used. These monomers (b) 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 (b) 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 (b) will not be specifically limited if the (meth) acryl equivalent of the obtained reaction product will be 200-600 (g / eq.), Usually The number of moles of the carboxyl group in the monomer (b) is preferably 0.4 to 1.1 mole per mole of the epoxy group.

  The reaction product obtained by addition reaction of the monomer (c) having a (meth) acryloyl group and an epoxy group to the (meth) acrylic polymer (a2) having a carboxyl group has a carboxyl group as described above (meta ) It can be obtained by reacting the acrylic polymer (a2) with the monomer (c) having a (meth) acryloyl group and an epoxy group. Examples of the monomer (c) 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 (c) 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 (c) will not be specifically limited if the (meth) acryl equivalent of the obtained reaction living organisms will be 200-600 (g / eq.), Usually The number of moles of the epoxy group in the monomer (c) is preferably 0.4 to 1.1 mole per mole of the carboxyl group.

  Reaction of the (meth) acrylic polymer (a1) having the epoxy group with the monomer (b) having a (meth) acryloyl group and a carboxyl group, and a (meth) acrylic polymer (a2) having a carboxyl group The reaction with the monomer (c) 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 the (meth) acrylic polymer (a1) is polymerized by a solution polymerization method, and the monomer (b) having a (meth) acryloyl group and a carboxyl group is added to the reaction system and reacted.

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

  The polymerizable organic component 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 polymer obtained by reacting the (meth) acrylic polymer (a1) having an epoxy group of the present invention with the monomer (b) having a (meth) acryloyl group and a carboxyl group is glycidyl. An acrylic polymer obtained by reacting an epoxy group-containing acrylic polymer obtained by polymerizing a polymerizable monomer containing (meth) acrylate and (meth) acrylic acid is preferred.

  The epoxy equivalent of the epoxy group-containing acrylic polymer (a1) is preferably 140 to 500 (g / eq.), And 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 by JIS-K-7236.

  The (meth) acryloyl equivalent of the polymerizable organic component of the present invention is preferably 200 to 600 (g / eq.), Particularly preferably 200 to 400 (g / eq.). The hydroxyl equivalent is preferably 90 to 280 (mgKOH / g), particularly preferably 140 to 280 (mgKOH / g).

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

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Corporation guard column HXL-H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
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 wt% tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 μL)

  The weight average molecular weight of the polymerizable organic component 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.

  The polymerizable organic component of the present invention may be reacted with a hydroxyl group of the polymerizable organic component, one isocyanate, and a monomer having a (meth) acryloyl group as long as the effects of the present invention are not impaired. 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 general formula (2) can be preferably exemplified.

In general formula (2), 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 polymerizable organic component of the present invention is not particularly limited, and a known method can be adopted. Specifically, for example, a monomer having one isocyanate and a (meth) acryloyl group is added dropwise to the polymerizable organic component of the present invention, and heated to 50 to 120 ° C., more preferably 60 to 90 ° C. And react. The amount of the polymerizable organic component, one isocyanate, and the monomer having a (meth) acryloyl group is not particularly limited. Usually, the hydroxyl group (mole) of the polymerizable organic component: 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 polymerizable organic component of the present invention can be suitably used as a dispersant for various inorganic particles. Examples of the inorganic particles include dry silica fine particles and wet silica fine particles. The dry silica fine particles are, for example, silica fine particles obtained by burning silicon tetrachloride in an oxygen or hydrogen flame. The wet silica fine particles are, for example, silica fine particles obtained by neutralizing sodium silicate with a mineral acid. The polymerizable organic component of the present invention has high dispersibility of inorganic particles. Therefore, the dispersion in which inorganic particles are dispersed in the polymerizable organic component of the present invention maintains good dispersion stability over a long period of time.

In addition, even when an active energy ray curable resin composition is prepared by adding the dispersion to an active energy ray curable oligomer such as urethane (meth) acrylate or epoxy (meth) acrylate or an active energy ray curable monomer, In the active energy ray-curable resin composition, the inorganic particles are stably dispersed over a long period of time. Thus, since the polymerizable organic component of the present invention has high dispersibility of inorganic particles, it is preferably used as a polymerizable organic component when dispersing inorganic particles having poor dispersibility stability in the composition. In addition, the polymerizable organic component of the present invention is preferably used as a dispersant used when dispersing inorganic particles in a compound having a (meth) acryloyl group.

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

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

In producing the reactive dispersion, the active energy ray-curable resin composition contains the polymerizable organic component of the present invention, inorganic particles, and a compound having a (meth) acryloyl group other than the polymerizable organic component. It can be. Examples of the compound having a (meth) acryloyl group other than the polymerizable organic component for inorganic particles include an active energy ray-curable monomer and / or an active energy ray-curable oligomer. The content of each component is not particularly limited, but the polymerizable organic component of the present invention and the active energy ray-curable monomer and / or the active energy ray-curable oligomer are selected from [(polymerizable organic component): (active energy ray-curable). 10 to 90 parts by weight: 90 to 10 parts by weight, and preferably 30 to 90 parts by weight: 70 to 10 parts by weight. It is more preferable to contain.

  Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate in addition to the polymerizable monomer that can be used in the preparation of the dispersant of the present invention. 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 Relate, 1,6-hexamethylene glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, hydroxypivalin Di (meth) acrylate of a compound obtained by adding caprolactone to acid neopentyl glycol, neopentyl glycol adipate di (meth) acrylate,

(Meth) acrylic to compounds having 3 or more hydroxyl groups such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tetramethylolmethane, and a hydroxyl group-containing compound 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, for example, selected from the group consisting of acrylic (meth) acrylate, urethane (meth) acrylate, ester (meth) acrylate, epoxy (meth) acrylate and the like other than the dispersant of the present invention. The (meth) acrylate compound more than a seed | species is 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 here 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. Moreover, when manufacturing this polyfunctional urethane (meth) acrylate, it superposes | polymerizes by substituting a part of hydroxyl-containing (meth) acrylate compound made to react with an isocyanate compound with a bivalent-tetravalent alcohol and / or a polyol compound. It may be good.

  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 represented by pyromellitic anhydride, etc. Meth) acrylate.

  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 (c) which has a (meth) acryloyl group and a carboxyl group. A reaction product having a (meth) acryloyl equivalent of 200 to 600 and a hydroxyl value of 90 to 280 mg / KOH, or a (meth) acrylic polymer (a2) having a carboxyl group and having a (meth) acryloyl group and an epoxy group. 10 to 90 parts by weight of a reaction product (hereinafter, polymerizable organic component for inorganic particles) 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 (d) And 90 to 10 parts by weight of silica fine particles so that the total concentration of the polymerizable organic component for inorganic particles and the inorganic particles is 1 to 50% by weight. Diluted with an organic solvent), 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 dioxola, and esters such as methyl acetate, ethyl acetate, and butyl acetate. , Aromatics such as toluene and xylene, and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and these can be used alone or in combination. Methyl ethyl ketone, which is a synthetic solvent for organic components, is preferred from the viewpoints of volatility during coating and solvent recovery.

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

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

(Synthesis example)
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), 1000 g of methyl isobutyl ketone (hereinafter referred to as MIBK) and t-butyl peroxyethyl hexanoate ( Then, 10 g of PO) was charged, and then the system temperature was raised to about 90 ° C. over about 1 hour under a nitrogen stream, and the temperature was kept for 1 hour. Next, the mixture was dropped into the system for about 2 hours under a nitrogen stream from a dropping funnel charged beforehand with a mixture consisting of 750 g of GMA and 30 g of PO, and kept at the same temperature for 3 hours. Then, it heated up at 120 degreeC and heat-retained for 2 hours. After cooling to 60 ° C., the nitrogen introduction tube was replaced with an air introduction tube, 507 g of acrylic acid (hereinafter referred to as AA), 2.3 g of methoquinone and 9.3 g of triphenylphosphine were charged and mixed, and then under air bubbling, The temperature was raised to 110 ° C. After incubating at the same temperature for 8 hours, 1.6 g of methoquinone was charged, cooled, and MIBK was added so that the non-volatile content was 50% to obtain a solution of a polymerizable organic component (A-1). The polymerizable organic component (A-1) had an acrylic equivalent of about 214 g / eq, a hydroxyl value of about 262 mgKOH / g, and a weight average molecular weight of about 30,000.

Example 1
In 80 mL of dehydrated ethyl acetate, 7.96 g (35.6 mmol) of 4 (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone (manufactured by Ciba Specialty, Irgacure 2959) was dissolved, and further 3-triethoxy 8.00 g (32.3 mmol) of silylpropyl isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd., KBE9007) was added, and the mixture was stirred at 80 ° C. for 20 hours. The obtained reaction solution was concentrated under reduced pressure, dissolved in a mixed solvent of ethyl acetate and hexane, purified with a silica gel column and then dried to obtain a purified powder of triethoxysilane having a photopolymerization initiator moiety at the end (B-1 )

<Synthesis of inorganic particles having a photoinitiator moiety introduced on the surface>
To 10 g of colloidal silica (Nissan Chemical, MIBK-ST) in solid content, 0.8 g of triethoxysilane (B-1) having the above photopolymerization initiator portion was added and stirred at 80 ° C. for 16 hours. A silica particle dispersion (C-1) into which a photo radical initiator was introduced was obtained.

<Preparation of photocurable composition>
1.0 g of polymerizable organic component (A-1) in solid content, 1.0 g of dipentaerythritol hexaacrylate (DPHA), and silica particle dispersion (C-1) having a photoradical initiator introduced on the surface thereof as solid content Then, 3 parts by weight of Irgacure 2959 was added to 100 parts of the nonvolatile content to obtain a photocurable composition.

<Method for producing cured coating film>
The active energy ray-curable resin composition is applied onto a triacetyl cellulose (TAC) film (film thickness 40 μm) with a bar coater (film thickness 10 μm), dried at 70 ° C. for 1 minute, and using a high-pressure mercury lamp under nitrogen. A test piece having a cured coating film was obtained by passing through and curing at an irradiation dose of 250 mJ / cm ² .

<Method for evaluating cured coating film (pencil hardness)>
The cured film of the test piece was evaluated by a pencil scratch test with a load of 500 g according to JIS K5600. The test was conducted five times, and a hardness scale in which no plastic deformation and cohesive failure were observed was obtained in all cases.

<Evaluation method of cured coating (steel wool resistance)>
Using a HEIDON reciprocating wear tester manufactured by Shinto Kagaku, the test piece was subjected to steel wool friction at a load of 1 kg and a speed of 100 mm / s. The haze change of the coating film before and after the test was evaluated according to JIS K7136.
The pencil hardness was 4H and the haze change was 0.2.

(Example 2)
<Preparation of photocurable composition>
1.0 g of polymerizable organic component (A-1) in solid content, 1.0 g of dipentaerythritol hexaacrylate (DPHA), and silica particle dispersion (C-1) having a photoradical initiator introduced on the surface thereof as solid content After mixing 2.0 g of Irgacure 184, 3 parts by weight of Irgacure 184 was added to 100 parts of the nonvolatile content to obtain a photocurable composition.

A cured coating film was prepared in the same manner as in Example 1, and pencil hardness and steel wool resistance were evaluated.
The pencil hardness was 4H and the haze change was 0.1.

(Comparative example 1) <Preparation of a photocurable composition>
After mixing 1.0 g of polymerizable organic component (A-1) in solid content, 1.0 g of dipentaerythritol hexaacrylate (DPHA), and 2.0 g in solid content of colloidal silica (Nissan Chemical, MIBK-ST) Irgacure 2959 was added in an amount of 5.2 parts by weight based on the total solid content to obtain a photocurable composition.

A cured coating film was prepared in the same manner as in Example 1, and pencil hardness and steel wool resistance were evaluated.
The pencil hardness was 3H and the haze change was 0.2.

The dispersion of the present invention can be made into a cured film by performing a polymerization reaction with light energy or thermal energy, and the cured film can be used as a high-strength surface cured film of various materials.

Claims (8)

In a dispersion in which inorganic particles are dispersed in a polymerizable organic component,
1) Inorganic particles are surface-treated with an organosilane compound having a group that initiates a polymerization reaction by light or thermal energy,
2) A reaction product obtained by adding a monomer (b) having a (meth) acryloyl group and a carboxyl group to a (meth) acrylic polymer (a1) having a polymerizable organic component having an epoxy group, or carboxyl It is a reaction product obtained by subjecting a (meth) acrylic polymer (a2) having a group to a monomer (c) having a (meth) acryloyl group and an epoxy group, and having a (meth) acryloyl equivalent of 200 to 600 (g / eq.) And a hydroxyl value of 90 to 280 (mgKOH / g).   The dispersion according to claim 1, wherein the polymerizable organic component is obtained by addition reaction of (meth) acrylic acid to a (meth) acrylic polymer having an epoxy group obtained by polymerizing glycidyl (meth) acrylate. body.   The dispersion according to claim 1 or 2, wherein the polymerizable organic component has a weight average molecular weight of 5,000 to 100,000.   The dispersion according to any one of claims 1 to 3, wherein the inorganic particles are silica particles or zirconia particles having a primary particle diameter of 10 nm to 300 nm.   The dispersion according to any one of claims 1 to 4, wherein the group that initiates the polymerization reaction by light energy is a group selected from an acetophenone group, a benzoin group, a benzophenone group, and an aromatic sulfonium salt.   The dispersion according to any one of claims 1 to 4, wherein the group that initiates the polymerization reaction by thermal energy is a group selected from a peroxide group, an azo group, and a diazo group.   A cured film obtained by curing the dispersion according to claim 1.   After forming a coating film on a base material using the dispersion according to any one of claims 1 to 6, the coating film is irradiated with light or heated to heat the coating film. A method for producing a cured film.