KR101051228B1 - Metal Oxide Compositions, Cured Films, and Laminates - Google Patents

Abstract

Metal oxide composition characterized by containing the dispersing agent (A) represented by following General formula (1), and a metal oxide whose average primary particle diameter is 5-100 nm;

General formula (1):

[Formula 1]

(Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom or a methyl group, and R ⁵ to R ⁸ each independently represent an unsubstituted or substituted, straight or branched alkylene group or alkyleneoxyalkylene group. , R ⁹ represents a tetravalent aromatic group or an aliphatic group.) And a cured film formed by curing this metal oxide composition and a laminate thereof.

Dispersant, metal oxide, composition, cured film, laminate, semiconductor element sealing material, dispersion

Description

Metal Oxide Compositions, Cured Films, and Laminates {METAL OXIDE COMPOSITION, CURED FILM AND LAMINATE}

The present invention relates to a metal oxide composition having hard coating properties, a cured film using the same, and a laminate thereof.

In the aspect of securing performance and safety measures of conventional information and communication equipment, using a photometal oxide composition on the surface of the device to form a hard coating film or an antistatic coating film having scratch resistance, adhesion, high refractive index, etc. have.

Recently, due to the development and generalization of dazzling information and communication devices, the performance improvement and productivity of the hard coat coating film, the antistatic coating film, and the like are further demanded, and various proposals using photocurable materials have been made.

For example, the following technical proposals are mentioned (refer patent document 1-3). In patent document 1, the method of mixing electroconductive powder, such as a tin oxide, and some monomer component using the ball mill etc. in an organic solvent, and producing a conductive coating is disclosed. In patent document 2, the method of mixing the antimony dope tin oxide and an ultraviolet curable silane coupling agent using the ball mill in the organic solvent, and creating the dispersion for electrically conductive coatings is disclosed. Moreover, in patent document 3, the method of disperse | distributing an electroconductive oxide fine powder in the mixed solvent of a dispersible low boiling point solvent and a hardly dispersible high boiling point solvent is disclosed, and the method of producing electroconductive paint is disclosed.

(Patent Document 1) Japanese Unexamined Patent Publication No. 04-172634

(Patent Document 2) Japanese Unexamined Patent Publication No. 06-264009

(Patent Document 3) Japanese Unexamined Patent Publication No. 2001-131485

However, by the above method, even when it is possible to prepare a metal oxide composition having good physical properties in high refractive index, hard coating property, antistatic property, light resistance, and the like, the average primary degree is high for a medium having high hydrophobicity such as an organic solvent. Since the metal oxide having a particle diameter of 100 nm or less cannot be stably dispersed and stabilized at the primary particle level, problems are easily caused in view of transparency of the coating film and stability over time of the photocurable paint.

Thus, the present invention is capable of forming a coating film having excellent physical properties in all of high refractive index, antistatic property, hard coating property, transparency and light resistance while containing a metal oxide having an average primary particle diameter of 100 nm or less. It is an object to provide a stable metal oxide composition, a cured film using the same, and a laminate thereof.

This invention relates to the metal oxide composition containing the dispersing agent (A) represented by following General formula (1), and the metal oxide whose average primary particle diameter is 5-100 nm.

General formula (1):

[Formula 1]

(Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom or a methyl group, and R ⁵ to R ⁸ each independently represent an unsubstituted or substituted, straight or branched alkylene group or alkyleneoxyalkylene group. , R ⁹ represents a tetravalent aromatic or aliphatic group.)

Another invention relates to the cured film formed by hardening | curing the said metal oxide composition.

Another invention is related with the laminated body containing a base material and the said cured film.

Another invention relates to an optical semiconductor device encapsulant comprising the metal oxide composition.

Another invention is a method for producing a metal oxide dispersion comprising dispersing a metal oxide having an average primary particle size of 5 to 100 nm in the presence of an organic solvent, using a dispersant (A) represented by the following general formula (1). It is about.

General formula (1):

[Formula 2]

(Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom or a methyl group, and R ⁵ to R ⁸ each independently represent an unsubstituted or substituted, straight or branched alkylene group or alkyleneoxyalkylene group. , R ⁹ represents a tetravalent aromatic or aliphatic group.)

 Another invention relates to the manufacturing method of the cured film containing apply | coating the said metal oxide composition to a base material, and hardening a metal oxide composition by irradiating an active energy ray.

The metal oxide composition which concerns on this invention contains the dispersing agent (A) represented by following General formula (1), and a metal oxide whose average primary particle diameter is 5-100 nm, A 2 or more types of metal oxide and 2 or more types of dispersing agent You may also include (A), respectively.

General formula (1):

(3)

(Wherein, R ¹ to R ⁴ each independently represent a hydrogen atom or a methyl group, and R ⁵ to R ⁸ each independently represent an unsubstituted or substituted, straight or branched alkylene group or alkyleneoxyalkylene group. , R ⁹ represents a tetravalent aromatic or aliphatic group.)

This dispersant (A) has high dispersibility and photocurability with respect to a metal oxide. The dispersant (A) increases the dispersibility of the metal oxide having an average primary particle diameter of 5 to 100 nm and also increases the photocurability, whereby the metal oxide composition of the present invention is excellent in curability, hard coating property, transparency, light resistance, and high refractive index. It is possible to form a cured film excellent in the properties and antistatic properties and a laminate thereof. Therefore, in particular, it can be suitably used for plastic optical parts, optical disks, antireflection films, touch panels, and film-type liquid crystal elements, and can also be suitably used as hard coating agents for various plastic laminates.

When this metal oxide composition can form the cured film with a high refractive index, and when apply | coating this to the base material about the same refractive index, the obtained laminated body does not produce a reflective interference fringe, and is used suitably for an optical use. Moreover, since the refractive index of hardened | cured material containing a metal oxide can be controlled high, it is suitable also as an optical semiconductor element sealing material.

In said Formula (1), as a tetravalent aromatic group of R <^9> , specifically, a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenyl ether skeleton, a diphenyl sulfone skeleton, a diphenyl sulfide skeleton, a perylene skeleton, a flu Orene skeleton, tetrahydronaphthalene skeleton, naphthalene skeleton and the like. Especially, it is preferable that R <^9> is at least 1 sort (s) chosen from the group which consists of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and a tetrahydro naphthalene skeleton.

As a tetravalent aliphatic skeleton of R <^9> , a tetravalent aliphatic group which is a C4-10 alkyl skeleton is a suitable example, Specifically, a butane skeleton, a cyclobutane skeleton, a hexane skeleton, a cyclohexane skeleton, a decalin skeleton, etc. are mentioned. .

In said Formula (1), as an unsubstituted or substituted linear or branched alkylene group of R <^5> -R <^8> , For example, alkylene groups, such as a methylene group, an ethylene group, C3-C10 polymethylene group, etc. It can be illustrated. Moreover, a C3 alkylene-oxy-C3 alkylene group can be illustrated as an unsubstituted or substituted linear or branched alkylene oxyalkylene group. These alkylene groups or alkyleneoxyalkylene groups are derived from the following 1st and 2nd hydroxyl group containing (meth) acrylate compound used as a raw material. As a substituent which an alkylene group or an alkylene oxyalkylene group can take, an alkyl group, such as a methyl group and an ethyl group, a hydroxyl group, acryloyloxymethyl group, acryloyloxyethyl group, a phenoxy group, etc. can be illustrated.

The dispersing agent (A) represented by General formula (1) is a functional group which can react with the compound (x1) which has an aromatic skeleton or an aliphatic skeleton, and two or more carboxylic anhydride groups, and a carboxylic anhydride group, for example. It is obtained by making compound (X) which has a carboxyl group formed by making compound (x2) which reacts, and compound (Y) which has a functional group which can react with a carboxyl group react. Here, from the viewpoint of photocurability and hard coating property, it is preferable that at least a part of the compound (x2) and the compound (Y) have a polymerizable unsaturated double bond group.

As a "functional group which can react with a carboxylic anhydride group" in a compound (x2), a hydroxyl group, an amino group, glycidyl group, etc. are mentioned, A hydroxyl group is especially preferable at the control of reaction. Therefore, it is preferable that compound (x2) is an acrylate compound or methacrylate compound which has one or two hydroxyl groups.

As a "functional group which can react with a carboxyl group" in a compound (Y), an epoxy group, an oxazoline group, a hydroxyl group, an amino group, a carbodiimide group, an isocyanate group, an isothiocyanate group, a vinyl ether group, etc. are mentioned. Can be.

An example is further explained. The following general formula (2) which is a compound (x1) having an aromatic skeleton or an aliphatic skeleton and at least two carboxylic acid anhydride groups:

General formula (2)

[Formula 4]

(Wherein R ⁹ is as defined in formula (1))

The following general formula (3) which is a compound (x2) which has a functional group which can react the aromatic or aliphatic tetracarboxylic dianhydride represented by the following:

CH ₂ = C (R ¹ ) COOR ⁵ 0H General formula (3)

Where R ¹ and R ⁵ are as defined in equation (1).

The first hydroxyl group-containing acrylate compound or methacrylate compound represented by, and the following general formula (4):

CH ₂ = C (R ² ) COOR ⁶ 0H General formula (4)

Where R ² and R ⁶ are as defined in equation (1)

Reaction with the 2nd hydroxyl group containing acrylate compound or methacrylate compound represented by following General formula (5):

General formula (5)

[Chemical Formula 5]

Where R ¹ , R ² , R ⁵ , R ⁶ and R ⁹ are as defined in formula (1)

Compound (X) represented by can be obtained.

Here, a "acrylate group or a methacrylate group" is a concept containing both the acrylate group and the methacrylate group, or including the case where it is used. Hereinafter, acrylate and methacrylate may be referred to as "(meth) acrylate".

As aromatic tetracarboxylic dianhydride represented by the said General formula (2), a pyromellitic dianhydride, a benzophenone tetracarboxylic dianhydride, the biphenyl tetracarboxylic dianhydride which has a biphenyl skeleton, and oxydiphthalic acid Fluorine skeletons, such as a dianhydride, a diphenyl sulfontetracarboxylic dianhydride, a diphenyl sulfide tetracarboxylic dianhydride, a perylene tetracarboxylic dianhydride, and a naphthalene tetracarboxylic dianhydride which has a naphthalene skeleton, Branches have 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride or 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, tetrohydro Tetrahydronaphthalene carboxylic dianhydride which has a naphthalene frame | skeleton, ethylene glycol bis (anhydro trimellitate), glycerin bis (anhydro trimellitate) monoacetate, etc. are mentioned. .

Commercially available products from Shin-Nihon Rica Co., Ltd. include RICACID TMTA-C, Ricaside MTA-10, Ricaside MTA-15, Ricaside TMEG Series, Ricaside TDA, Lycaside DSDA 'and the like.

Among these aromatic tetracarboxylic dianhydrides, the biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton can be efficiently introduced into the molecule of the compound represented by the formula (1), It is particularly preferable because it can combine hard coating properties and good dispersibility of a metal oxide.

Butanetetracarboxylic dianhydride is mentioned as aliphatic tetracarboxylic dianhydride represented by General formula (2).

The 1st and 2nd hydroxyl group containing (meth) acrylate compound may mutually be same or different. As an example of such a hydroxyl group containing (meth) acrylate compound, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, glycerol mono (meth) acrylate, 2-hydroxy Oxy-3-acryloyloxypropyl (meth) acrylate, dihydroxyacrylate, glycerol (meth) acrylate, isocyanuric acid EO modified diacrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (Meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) a Relate, and the like can be mentioned dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate. In the case of the use which raises hardness, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are preferable. .

As a specific commercial item, bis coat # 300 (product of Osaka Yuki Kagaku Kogyo Co., Ltd.), KAYARAD PET30 (product of Nihon Kayaku Co., Ltd.), PETIA (product of Daicel UCB Co., Ltd.), aronix (Aronix) M305 ( Toagosei Co., Ltd., NK ester A-TMM-3LMN (manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.), light acrylate PE-3A (manufactured by Kyoeisha Kagaku Co., Ltd.), SR-444 (Satoma) Co., Ltd.), light acrylate DPE-6A (manufactured by Kyoeisha Kagaku Co., Ltd.), KAYARAD DPHA (manufactured by Nihon Kayaku Co., Ltd.), aronix M402 (manufactured by Toagosei Co., Ltd.), and the like. have.

In particular, KAYARAD PET30 (manufactured by Nihon Kayaku Co., Ltd.), which contains pentaerythritol tri (meth) acrylate as a main component, is more preferable because of good dispersibility of metal oxides. In the case of a polyfunctional (meth) acrylate compound, the weight average molecular weight after hardening of the dispersing agent (A) obtained by containing about 5 to 15 weight% of polyfunctional (meth) acrylate which has two hydroxyl groups as an auxiliary component is high molecular weight. Since it tends to be, the dispersibility of a metal oxide is also preferable at the point which becomes more favorable.

The reaction of the aromatic or aliphatic tetracarboxylic dianhydride with the first and second hydroxyl group-containing (meth) acrylate compounds is two carboxylic anhydrides of the aromatic or aliphatic tetracarboxylic dianhydride. As reaction with group and the hydroxyl group which a 1st and 2nd hydroxyl group containing (meth) acrylate compound has, respectively, it is well known in the said field itself. For example, the aromatic tetracarboxylic dianhydride and the 1st and 2nd hydroxyl group containing (meth) acrylate compound are 1,8- diazabicyclo [5.4.0] in organic solvents, such as cyclohexanone. In the presence of a catalyst such as -7-undecene, the reaction can be carried out at a temperature of 50 to 120 ℃. In this case, a polymerization inhibitor such as metoquinone may be added to the reaction system.

After the above reaction, the reaction mixture comprising the compound (X) of formula (5) as a reaction product is not purified, for example, the following general formula (6) is compound (Y):

General formula (6)

[Formula 6]

Wherein R ⁰ is a CH ₂ = C (R ³ ) -C (O) O- group and a CH ₂ = C (R ⁴ ) -C (O) O- group; R ³ and R ⁴ are as defined above )

A phosphorus epoxy group-containing compound is added and reacted to obtain a compound represented by the general formula (1) (in this case, R ⁷ and R ⁸ are —CH ₂ CH (OH) CH ₂ — groups.).

Examples of the compound represented by the formula (6) include epoxy group-containing (meth) acrylates such as glycidyl methacrylate and glycidyl acrylate; o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, monostyrene phenol glycidyl ether, 4-cyano-4-hydroxybiphenylglycidyl ether, 4,4'-biphenol Aromatic glycidyl ether compounds such as monoglycidyl ether and 4,4'-biphenol diglycidyl ether.

Reaction of the compound represented by Formula (5) and the compound represented by Formula (6) is reaction with the carboxyl group which the compound represented by Formula (5) has, and the epoxy group which the compound represented by Formula (6) has, It is well known in the art itself. For example, this reaction can be performed at 50-120 degreeC in presence of an amine catalyst, such as dimethylbenzylamine.

These reactions may be performed without a solvent, or may be performed in a solvent inert to the reaction. As such a solvent, For example, Hydrocarbon type solvent, such as n-hexane, benzene, or toluene; Ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone; Ester solvents such as ethyl acetate or butyl acetate; Ether solvents such as diethyl ether, tetrahydrofuran or dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or tetrachloroethylene; And polar solvents such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-dimethylimidazolidinone. These solvents may be used in combination of two or more kinds.

Next, the metal oxide contained in the metal oxide composition is a metal oxide having an average primary particle diameter of 5 to 100 nm. The average primary particle diameter of the metal oxide can be measured by directly observing the particles themselves using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

In the case of the metal oxide having an average primary particle diameter of less than 5 nm, it is very difficult to disperse the primary particle level having high transparency because the cohesion force between the fine particles is very large. On the other hand, in the case of a metal oxide having an average primary particle diameter of more than 100 nm, it is easy to disperse to the primary particle level, but since the particle diameter is large, scattering is likely to occur in light such as visible light, which causes a problem of deteriorating transparency of the cured film. .

The metal oxide preferably contains at least one element selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, aluminum, silicon, phosphorus and fluorine. In particular, the metal oxide containing any one element of antimony, indium, and tin is more preferable because of its good conductivity.

Specifically, antimony pentaoxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), zinc antimonate (AZO), indium-doped oxide Zinc (IZO), tin oxide, ATO coated titanium oxide, aluminum dope zinc oxide, titanium oxide, zinc oxide, zirconium oxide, silicon oxide, aluminum oxide and the like. These metal oxides are safe even if they use two or more types together.

As a commercial item of a metal oxide,

Nissan Kagaku Kogyo Co., Ltd. products: Sun Epoch EFR-6N, Sun Epoch EFR-6NP (antimony pentoxide),

Ishihara Industries Co., Ltd. products: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO coated titanium oxide), TT0-55 (A ) (Titanium oxide), TT0-55 (B) (titanium oxide), TT0-55 (C) (titanium oxide), TT0-55 (D) (titanium oxide), TT0-55 (S) (titanium oxide), TT0-55 (N) (titanium oxide), TT0-51 (A) (titanium oxide), TT0-51 (C) (titanium oxide), TTO-S-1 (titanium oxide), TTO-S-2 (oxidized) Titanium), TTO-S-3 (titanium oxide), TTO-S-4 (titanium oxide), TTO-F-1 (iron-containing titanium oxide), TTO-F-2 (iron-containing titanium oxide), TTO-F -3 (titanium oxide with iron), TTO-F-11 (titanium oxide with iron), ST-01 (titanium oxide), ST-21 (titanium oxide), ST-30L (titanium oxide), ST-31 (oxidation) titanium),

Mitsubishi Material Co., Ltd. products: T-1 (ITO), S-1200 (tin oxide), EP SP-2 (phosphorus tin oxide),

Mitsui Kinzoku Kogyo Co., Ltd. products: Pastran (ITO, ATO),

CIKAISEI Co., Ltd. Products: Nanotech ITO, Nanotech SnO ₂ , Nanotech TiO ₂ , Nanotech SiO ₂ , Nanotech Al ₂ O ₂ , Nanotech ZnO,

Shokubaika Seigo Bridge Co., Ltd. products: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-130 (ITO),

Hakusui Tech Co., Ltd. product: Pazet CK (aluminum dope zinc oxide),

Sakai Kagaku Kogyo Co., Ltd. products: FINEX-25 (zinc oxide), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP (zinc oxide), FINEX-75 (zinc oxide), NANOFINE -50A (zinc oxide), NANOFINE-50SD (zinc oxide), EZ-1 (zinc oxide), STR-60C (titanium oxide), STR-60C-LP (titanium oxide), STR-100C (titanium oxide), STR -100C-LP (titanium oxide), STR-100A-LP (titanium oxide), STR-100W (titanium oxide),

Sumitomo Osaka Cement Products: OZC-3YC (zirconium oxide), OZC-3YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide),

Nihon Denko Co., Ltd. products: PCS (zirconium oxide), PCS-60 (zirconium oxide), PCS-90 (zirconium oxide), T-01 (zirconium oxide),

Takeka Co., Ltd. products: MT-100S (titanium oxide), MT-100HD (titanium oxide), MT-100SA (titanium oxide), MT-500HD (titanium oxide), MT-500SA (titanium oxide), MT-600SA (Titanium oxide), MT-700HD (titanium oxide), MZ-303S (zinc oxide), MZY-303S (zinc oxide), MZ-303M (zinc oxide), MZ-505S (zinc oxide), MZY-505S (oxidation) Zinc), MZ-505M (zinc oxide),

Nihon Aerosil Co., Ltd. Products: Aluminum Oxide C (aluminum oxide), AEROSIL 130 (silicon oxide), AEROSIL 200 (silicon oxide), AEROSIL 200V (silicon oxide), AEROSIL 200CF (silicon oxide), AEROSIL 200FA (oxidation) Silicon), AEROSIL 300 (silicon oxide), AEROSIL 300CF (silicon oxide), AEROSIL 380 (silicon oxide), AEROSIL R972 (silicon oxide), AEROSIL R974 (silicon oxide), AEROSIL R976 (silicon oxide), AEROSIL R202 (silicon oxide) ), AEROSIL R805 (silicon oxide), AEROSIL R812 (silicon oxide), AEROSIL R812S (silicon oxide), AEROSIL MOX50 (silicon oxide), AEROSIL TT600 (silicon oxide), AEROSIL MOX80 (silicon oxide / aluminum oxide), AEROSIL MOX170 ( Silicon oxide / aluminum oxide), AEROSIL COX84 (silicon oxide / aluminum oxide),

Etc. can be mentioned.

Although the addition amount of the metal oxide in a metal oxide composition is not restrict | limited, Preferably it is 1-80 weight part, More preferably, it is 10-70 weight part among 100 weight part of solid content of a dispersing agent (A) and a metal oxide. If the added amount of the metal oxide is less than 1 part by weight, the antistatic property derived from the metal oxide may be inferior, and if it exceeds 80 parts by weight, the film formation may be inferior due to the small amount of organic components.

Even if the metal oxide composition of the present invention is prepared by simply mixing the dispersant (A) and the metal oxide powder, a sufficiently desired effect can be obtained. However, it is mechanically mixed by a kneader, a roll, an attritor, a super mill, a dry grinding machine, or the like, or a solution containing a dispersing agent (A) is added to a suspension system made of metal oxide powder and an organic solvent, and the like on the surface of the metal oxide. When performed in a close mixing system such as depositing the dispersant (A), better results can be obtained.

This metal oxide composition is preferably a metal oxide dispersion in which metal oxide powder is uniformly dispersed. The metal oxide dispersion can be preferably produced by dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in the presence of an organic solvent using a dispersant (A).

As a degree of dispersion, when measured by Nikki Corporation "Nano Track UPA" using the dynamic light scattering method, the dispersed particle diameter D99 is preferably less than 300 nm, more preferably less than 200 nm.

For dispersing or dissolving the dispersant (A), the metal oxide, or the metal oxide composition in a non-aqueous vehicle such as an organic solvent, or mixing them, a paint conditioner (manufactured by Red Devil Co.), a ball mill, a sand mill (new floor) Enterprise's Dino Mill, etc.), Artwriter, Pearl Mill (Ahirich's 'DCP Mill,' etc.), COBOL Mill, Homo Mixer, Homogenizer (M, Technic's 'Clear Mix', etc.) , Dispersers such as wet jet mills (Genus PY), nanomizers (Nanomizer), and micro bead mills (Kotobuki Kogyo Co., Ltd. 'Super Apex Mill', 'Ultra Apex Mill') Can be used. When using a medium for the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads and the like. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes are used, respectively, so that they can be used step by step.

The metal oxide composition of this invention contains a dispersing agent (A) and a metal oxide at least, and can also contain a solvent and various additives in the range which does not impair the objective and effect of this invention. Specifically, solvents, photoinitiators, photocurable compounds, polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive polymers , Conductive surfactants, inorganic fillers, pigments, dyes and the like.

The method for producing a metal oxide composition containing a dispersant (A) and a component other than a metal oxide is not particularly limited and several methods may be mentioned. Specifically, a method of firstly mixing and dispersing a dispersant (A) and a metal oxide in an organic solvent to obtain a stable metal oxide dispersion, and then adding and adjusting various additives to produce the dispersant (A), The metal oxide, the organic solvent, and other additives are all mixed, and the method of making it disperse | distribute etc. are mentioned.

When adding a solvent, it is preferable to perform hardening process after making a solvent volatilize. It does not restrict | limit especially as a solvent, Various well-known organic solvent can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol , Ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipic acid, dimethyl succinate, glutamate Dimethyl tartarate, tetrahydrofuran, methylpyrrolidone and the like. These organic solvents do not interfere even if they use two or more types together.

Above all, the hydroxyl group-containing solvent has good wettability with respect to metal oxides having high hydrophilic particle surface properties. Therefore, the hydroxyl group-containing solvent is contained in the solvent composition to improve the dispersibility of the metal oxide and the stability of the paint (metal oxide composition) over time. Since it is very effective and also improves the leveling property of a coating process, it is preferable. It is preferable that the hydroxyl-containing solvent content in all solvent compositions is 10 to 100 weight%. Specifically, as the hydroxyl group-containing solvent, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol Monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, and the like. In particular, 3-methoxy-1-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol mono n-butyl ether are preferable because the dispersibility and dispersion stability of a metal oxide become more favorable.

The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetphenone compound, a benzoin ether compound, an acylphosphine oxide Compounds, aminocarbonyl compounds and the like can be used.

Specifically, as a monocarbonyl compound, benzophenone, 4-methyl- benzophenone, 2,4,6-trimethyl benzophenone, methyl-o- benzoyl benzoate, 4-phenyl benzophenone, 4- (4-methylphenyl Thio) phenyl-ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1-propanamine hydrochloride, 4-benzoyl-N, N-dimethyl-N-2- (1-oxo-2-propenyloxyethyl) methammonium oxalate, 2 -/ 4-iso-propyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycyxanthone, 2-hydroxy-3- ( 3,4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphth (1,2-d) thia Sleepy etc. are mentioned.

Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone and methyl-α- Oxobenzene acetate, 4-phenylbenzyl, and the like.

As an acetphenone compound, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-1-one , 1- (4-isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2-hydroxy-2-methyl- 1-styrylpropane-1-one polymer, diethoxyacetphenone, dibutoxyacetphenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2 -Diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino- Propanoyl) -9-butylcarbazole and the like.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

Examples of the aminocarbonyl compounds include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate and isoamyl-4 -(Dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5 '-Bis (4-diethylaminobenzal) cyclopentanone and the like.

As a commercial item of a photoinitiator, Chiba Specialty Chemical Co., Ltd. product Irugacure 184, 651, 500, 907, 127, 369, 784, 2959, BASF company Lucirin TPO, Nihonshi Berghegner, Inc. Cure one, etc. are mentioned.

A photoinitiator is not limited to the said compound, Any thing may be used as long as it has the ability to start superposition | polymerization by ultraviolet-ray. These photoinitiators may be used by one type but may mix and use two or more types.

The amount of the photopolymerization initiator used is not particularly limited, but the total amount of the photocurable compound containing the dispersant (A) (when the optional photocurable compound is optionally included, the total amount of the dispersant (A) and the photocurable compound) 100 It is preferable to use within the range of 1-20 weight part with respect to a weight part.

A well-known organic amine etc. can also be added as a sensitizer.

Moreover, you may use together the initiator for cation polymerization other than the said initiator for radical polymerization.

The metal oxide composition may contain other binder resins and photocurable compounds in addition to the dispersing agent (A).

As the binder resin, for example, polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide Resins, phenol resins, vinyl resins and the like. These resins may be used by one type, or may mix and use two or more types. It is preferable to use binder resin within 20 weight part or less on the basis of the whole quantity of solid content (components other than a solvent. Hereafter, the same.) Of a metal oxide composition as a reference | standard (100 weight part).

As a photocurable compound, the compound which has a polymerizable unsaturated double bond group, such as a (meth) acrylic-type compound, a fatty acid vinyl compound, an alkyl vinyl ether compound, the (alpha)-olefin compound, a vinyl compound, an ethynyl compound, can be used, for example. The compound which has such a polymerizable unsaturated double bond group may also have functional groups, such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, and a silanol group. It is preferable to use this photocurable compound within the range of less than 50 weight part, especially the range of 5-40 weight part on the basis of whole quantity of solid content of a metal oxide composition (100 weight part).

Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol-based (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, and a (meth) acrylic type having a hydroxyl group. Compounds, nitrogen-containing (meth) acrylic compounds, and the like. Moreover, a monofunctional and polyfunctional compound can be used suitably. In the point of photocurability and the hard-coating property of a coating film, a polyfunctional thing is preferable.

As a monofunctional (meth) acrylic-type compound, specifically, as alkyl type (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acryl Laterate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, Heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, Henacyl (meth) acrylate, docosyl (meth) acrylate, etc. 1 to 22 carbon atoms And alkylene (meth) acrylates. When adjusting the polarity, it is preferable to use an alkyl group-containing (meth) acrylate having an alkyl group of 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. In addition, when adjusting the leveling property, etc., it is preferable to use the alkyl (meth) acrylate which has a C6 or more alkyl group.

Examples of the alkylene glycol-based (meth) acrylates include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and hexaethylene glycol mono (meth) acrylate. , Polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, etc. Mono (meth) acrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain; Methoxyethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tetraethylene glycol (meth) acrylate, ethoxy tetraethylene glycol (meth) Acrylate, propoxytetraethyleneglycol (meth) acrylate, n-butoxytetraethyleneglycol (meth) acrylate, n-pentaxitetraethyleneglycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetra Propylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy tetrapropylene glycol (meth) acrylate, ethoxy tetrapropylene glycol (meth) acrylate, propoxy tetrapropylene glycol (meth ) Acrylate, n-butoxy tetrapropylene glycol (meth) acrylate, n-pentaxite propylene glycol (meth) ) Terminals such as acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, and ethoxy polyethylene glycol (meth) acrylate Mono (meth) acrylates having an alkoxy group and having a polyoxyalkylene chain; Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxy tetraethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) Polyoxyalkylene type (meth) acrylate which has a phenoxy or an aryloxy group at the terminal, such as an acrylate, a phenoxy polyethyleneglycol (meth) acrylate, a phenoxy tetrapropylene ethylene glycol (meth) acrylate, is mentioned.

Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester and isophthalic acid. (beta)-(meth) acryloxyethyl monoester, succinic acid (beta)-(meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. are mentioned.

As a hydroxyl-containing (meth) acrylic-type compound, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3- phenoxypropyl (meth) acrylate, etc. are mentioned.

As a nitrogen-containing (meth) acrylic-type compound, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N Monoalkylol (meth) acrylamides such as -propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (Methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- ( Propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide , N-methoxymethyl-N- (pentoxy Butyl) acrylamide-based unsaturated compounds, such as methacrylic amide, such as di-alkylol (meth) acrylamide; Unsaturated compounds having dialkylamino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene and diethylaminostyrene; And quaternary ammonium salts of dialkylamino group-containing unsaturated compounds having halogen ions such as Cl ⁻ , Br ⁻ , I ⁻ , or QSO 3 ⁻ (Q: an alkyl group having 1 to 12 carbon atoms) as a pair ion.

As other unsaturated compounds, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) Acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (Meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate Perfluoro alkyl alkyl (meth) acrylates, such as a C1-C20 perfluoroalkyl group, are mentioned.

Furthermore, perfluoroalkyl group containing vinyl monomers, such as perfluoroalkyl, such as perfluoro butylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene, alkylene; Alkoxy silyl group-containing vinyl compounds and derivatives thereof such as vinyl trichlorsilane, vinyl tris (β-methoxyethoxy) silane, vinyltriethoxysilane and γ- (meth) acryloxypropyltrimethoxysilane; And glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate.

Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl crotonate, vinyl caprylate, vinyl laurate, vinyl chloracetate, vinyl oleate, and vinyl stearate.

Butyl vinyl ether, ethyl vinyl ether, etc. are mentioned as an alkyl vinyl ether compound.

Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

Examples of the vinyl compound include allyl compounds such as allyl acetic acid, allyl alcohol, allyl benzene and allyl cyanide, vinyl cyanide, vinyl cyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, and chloro styrene. .

Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyl toluene, 1-ethynyl-1-cyclohexanol and the like.

These may be used by one type and may mix and use two or more types.

Among these, as photocurable compounds other than a dispersing agent (A), from a viewpoint of coating film strength and abrasion resistance, poly (such as polyurethane poly (meth) acrylate and polyepoxy poly (meth) acrylate which have at least 3 functional group) Meta) acrylates and polyfunctional acrylates having three or more acryloyl groups in the molecule can be suitably used.

Polyepoxy poly (meth) acrylate esterified the epoxy group of an epoxy resin with (meth) acrylic acid, and made the functional group a (meth) acryloyl group, The (meth) acrylic acid addition product to a bisphenol-A epoxy resin, And (meth) acrylic acid adducts to novolak type epoxy resins.

Polyurethane poly (meth) acrylate is obtained by, for example, reacting (meth) acrylates having a diisocyanate with a hydroxyl group, and an isocyanate group-containing urethane formed by reacting a polyol and a polyisocyanate under conditions of excess isocyanate groups. There are some obtained by making a prepolymer react with (meth) acrylates which have a hydroxyl group. Alternatively, the hydroxyl group-containing urethane prepolymer obtained by reacting polyol and polyisocyanate under conditions of excessive hydroxyl group may be obtained by reacting with (meth) acrylates having an isocyanate group.

Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexane triol and trimerol Propane, polytetramethylene glycol, the polycondensation product of adipic acid and ethylene glycol, etc. are mentioned.

As polyisocyanate, tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc. are mentioned.

As (meth) acrylate which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.

As (meth) acrylate which has an isocyanate group, 2- (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, etc. are mentioned.

As a commercial item of a photocurable compound, the following can be illustrated.

Toagosei Co., Ltd. products: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060,

Osaka Yuki Kagaku Kogyo Co., Ltd. products: bis coat # 400,

Kayaku Satoma Co., Ltd. product: SR-295,

Daicel UCB Co., Ltd. products: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,

Shin-Nakamura Kagaku Kogyo Co., Ltd. products: NK ester A-TMMT, NK oligo EA-1020, NK oligo EMA-1020, NK oligo EA-6310, NK oligo EA-6320, NK oligo EA-6340, NK oligo MA- 6, NK oligo U-4HA, NK oligo U-6HA, NK oligo U-324A,

BASF products: Laromer EA81,

Sanofko Corporation product: photomer 3016,

Arakawa Kagaku Kogyo Co., Ltd. products: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;

Nagami Kogyo Co., Ltd. products: Art resin UN-3320HA, art resin UN-3320HB, art resin UN-3320HC, art resin UN-3320HS, art resin UN-9000H, art resin UN-901T, art resin HDP, art resin HDP-3, Atresin H61,

Nippon Kosei Kagaku Kogyo Co., Ltd. products: Light UV-7600B, Light UV-7610B, Light UV-7620EA, Light UV-7630B, Light UV-1400B, Light UV-1700B, Light UV-6300B,

Kyoeisha Kagaku Co., Ltd. products: light acrylate PE-4A, light acrylate DPE-6A, UA-306H, UA-306T, UA-306I,

Nihon Kayaku Co., Ltd. products: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.

Next, the cured film of this invention and its laminated body are demonstrated.

The cured film of this invention is a film | membrane formed by hardening the metal oxide composition of this invention. The manufacturing method includes, for example, applying a metal oxide composition to an arbitrary substrate, and irradiating active energy rays to cure the metal oxide composition on the substrate.

More specifically, this metal oxide composition can be formed by hardening | curing after apply | coating so that the film thickness after drying may be 0.1-30 micrometers, More preferably, it is 0.1-20 micrometers on arbitrary base materials.

At the time of formation, a cured film may be directly apply | coated to a base material, and one or more lower layers may exist between a cured film and a base material.

Examples of the substrate include metals, ceramics, glass, plastics, wood, slate, and the like, and are not particularly limited. Specific types of plastics include polyesters, polyolefins, polycarbonates, polystyrenes, polymethyl methacrylates, triacetylcellulose resins, ABS resins, AS resins, polyamides, epoxy resins, melamine resins, and the like. Moreover, although the thing of a film sheet, a plate-shaped panel, a lens shape, a disk shape, and a fiber shape is mentioned as a shape of a base material, It does not restrict | limit especially.

As a coating method, a well-known method can be used, For example, the method using a lot or a wire bar, etc., and various coating methods, such as a micro gravure, a gravure, a die, a curtain, a lip, a slot, or a spin, can be used.

Hardening process can be performed by irradiating active energy rays, such as an ultraviolet-ray, an electron beam, visible light of wavelength 400-500 nm, using a well-known technique. As a source (light source) of ultraviolet rays and visible rays having a wavelength of 400 to 500 nm, for example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. As the electron source, a thermoelectron radiation gun, an electrolytic radiation gun, or the like can be used.

The active energy dose to be irradiated is preferably in the range of 5 to 2000 mJ / cm 2, and more preferably in the range of 50 to 1000 mJ / cm 2 from the viewpoint of easy management in the process.

The heat treatment by infrared rays, far infrared rays, hot air, high frequency heating, etc. can be used together with these active energy ray irradiation.

The cured film may be formed by coating a substrate with a metal oxide composition, followed by natural or forced drying, followed by hardening treatment, or after coating and hardening treatment, followed by natural or forced drying. This is more preferable.

When hardening with an electron beam especially, in order to prevent the inhibition of hardening by water, or the fall of the strength of the coating film by the residual of the organic solvent, it is more preferable to perform hardening processing after natural or forced drying.

The timing of the curing treatment may be simultaneous with coating or after coating.

Since the cured film obtained is excellent in hard coating property, transparency, light resistance, high refractive index, and antistatic property, it can use suitably as an optical material. Therefore, the cured film of this invention can be used also as a front panel of various display apparatuses, such as a cathode ray tube, a flat display panel (liquid crystal display, a plasma display, an electroluminescent display, a light emitting diode display, etc.) as a laminated body, or these input devices. Can be.

In addition, the cured film can be widely used for optical lenses, spectacle lenses, optical recording discs (compact discs, DVD discs, Blu-ray discs, etc.), light cases and the like.

It is preferable that the surface resistance value of a cured film is 1 * 10 <^{12> (} ohm) / square or less.

It is preferable that the thickness of a cured film is 0.1-30 micrometers.

Moreover, it is preferable that it is the range of 1.4-2.0, and, as for the refractive index of a cured film, it is more preferable that it is the range of 1.5-1.8.

The laminated body of this invention contains the cured film and base material of this invention. As a base material, the thing of the said illustration can be used arbitrarily, It is especially preferable that it is a plastic base material. It is preferable that the shape of a base material is a film shape, a lens shape, or a disk shape.

In addition to these, it is preferable that the laminate contains at least one layer having a different refractive index, an adhesive layer, an information recording layer, or the like.

The laminate including the film M, the adhesive layer M, or the information recording layer M having different refractive indices can be, for example, a layer structure such as the following (I) to (iii).

(I) base material / (M) / hardened film

(II) Substrate / Cured Film / (M)

(III) Substrate / (M) / Cured Film / (M)

(IV) (M) / base material / cured film

(Ⅴ) (m) / base / (m) / cured film

(VI) (M) / base material / cured film / (M)

(Ⅶ) (M) / Material / (M) / Cured Film / (M)

(Ⅷ) (M) / cured film / substrate / cured film

(Iii) Cured film / (M) / base material / cured film

The films or information recording layers having different refractive indices have functions other than those of the cured product of the present invention. The formation method is not specifically limited, It is formed by a well-known method. For example, a dry coating method such as vapor deposition or sputtering, a method using a lot or a wire bar, or a wet coating method such as micro gravure, gravure, die, curtain, lip, slot, or spin can be used. The material to be used is also not limited, and if necessary, one of the following functions: information recording function, anti-glare function, Newton's ring prevention function, adhesion function, blocking of specific wavelengths, adhesion improvement, color tone correction, etc. Any material which can provide more than a kind to a laminated body can be used.

As the information recording layer, any chemical change may be caused by laser light or the like, and information may be recorded by the change, and the material is not particularly limited. For example, as an organic material, polymethine pigment | dye, naphthalocyanine type, phthalocyanine type, squarylium type, anthraquinone type, xanthene type, and triphenylmethane type metal complex compound are mentioned, The said dye is 1 type or 2 It can be used in combination of species or more. As the inorganic recording layer, metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, Pt, and semimetals can be used in one kind or a combination of two or more kinds. The information recording layer may be a laminate or the like, and the photochemical change may be any of phase change, bubble, or cavity type. Further, an optical magnetic recording layer mainly composed of Fe, Tb, and Co may be used, or a spiropy may be a fulgide-based photochromic material.

It is also preferable to use the high refractive index cured film as a laminated body which provided the low refractive index coating cured film in the surface layer from an antireflection viewpoint, and provided the antireflection function. That is, it is preferable to use the laminated body obtained by forming a cured film on base materials, such as a film, and more preferably forming a coating cured film as an antireflection film.

In the laminate in which the reflective interference fringe is a problem, the compounding amount of the metal oxide in the metal oxide composition of the present invention is adjusted so that the difference in refractive index between the cured film and the base material or an arbitrary layer between the cured film and the base material. When this exists, it is preferable to make it the difference of the refractive index between the cured film and the lower layer which the cured film contact | connects to be within +/- 0.02.

The metal oxide composition of this invention can manufacture the hardened | cured material of a high refractive index by controlling the kind and addition amount of a metal oxide. Therefore, in order to improve the light extraction efficiency of an optical semiconductor element, it can use suitably as an optical semiconductor element sealing material for which the refractive index of a resin layer is required to make it smaller sequentially from the optical semiconductor element side toward the outermost layer.

Examples of the optical semiconductor element include gallium nitride (GaN: refractive index 2.5), gallium phosphorus (GaP: refractive index 2.9), gallium arsenide (GaAs: refractive index 3.5), and the like. Therefore, it is preferable that the refractive index of the hardened | cured material used as an optical semiconductor element sealing material is 1.5 or more from a viewpoint of improving light extraction efficiency, More preferably, it is 1.5-2.1, More preferably, it is 1.7-2.1.

As a method of achieving the optimum refractive index of hardened | cured material, titanium oxide (refractive index 2.5-2.7), zirconium oxide (2.4 refractive index), zinc oxide (refractive index 1.95), etc. are preferable as a metal oxide to be used, and high refractive index is also required for a dispersing agent. In view of the above, a dispersant (A) having an aromatic skeleton is preferable.

<Examples>

Hereinafter, the present invention will be described in more detail based on Production Examples and Examples. In Production Examples and Examples, parts and percentages refer to parts by weight and% by weight, respectively.

The used drugs are as follows.

Biphenyl tetracarboxylic dianhydride (Mitsubishi Kagaku Co., Ltd. product)

9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd.,

Product name: BPAF)

Tetrahydronaphthalene dianhydride (Shin Nihon Rika Co., Ltd., brand name: ricaside TDA-100)

Naphthalene dianhydride (product of JFE Chemical Co., Ltd., brand name: NTCDA)

Butane tetracarboxylic dianhydride (Shin Nihon Rika Co., Ltd., brand name: Ricaside BT-100)

Pentaerythritol triacrylate (1) (product of Osaka Yukikagaku Kogyo Co., Ltd., a brand name: bis coat # 300)

Pentaerythritol triacrylate (2) (product of Nihon Kayaku Co., Ltd., brand name: KAYARAD PET-30)

Dipentaerythritol pentaacrylate (product of Nihon Kayaku Co., Ltd., brand name: KAYARAD DPHA)

2-hydroxyethyl acrylate (made by Nihon Shokubai Co., Ltd.)

Hydroquinone (product of Wako Pure Chemical Industries, Ltd.)

1,8-diazabicyclo [5.4.0] -7-undecene (Tokyo Kasei Kogyo Co., Ltd. product)

Glycidyl methacrylate (Dow Chemical Company)

Dimethylbenzylamine (product of Wako Pure Chemical Industries, Ltd.)

(Production Example 1: Dispersant (1))

80.0 parts of biphenyl tetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylate (1), 0.16 parts of hydroquinone, cyclohexanone 141.2 in the four neck flask equipped with the stirrer, the reflux cooling tube, the dry air introduction tube, and the thermometer. A part was put and heated up to 85 degreeC. Next, 1.65 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, followed by addition of 2.65 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was pale yellow transparent, 70% of solid content, the number average molecular weight (MN) 870, and the weight average molecular weight (MW) 2,830.

(Production Example 2: Dispersant (2))

80.0 parts of biphenyl tetracarboxylic dianhydride, 250.0 parts of pentaerythritol triacrylates (2), 0.16 parts of hydroquinone, cyclohexanone 141.2 in the four neck flask equipped with the stirrer, the reflux cooling tube, the dry air introduction tube, and the thermometer. A part was put and heated up to 85 degreeC. Next, 1.65 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Then, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, followed by adding 2.65 parts of dimethylbenzylamine as a catalyst, stirring at 85 degreeC for 6 hours, cooling to room temperature, and complete | finishing reaction. The obtained reaction solution was light yellowish transparent, 70% of solid content, the number average molecular weight 920, and the weight average molecular weight 3,130.

(Production Example 3: Dispersant (3))

80.0 parts of biphenyltetracarboxylic dianhydride, 124.8 parts of pentaerythritol triacrylate (1), 222.8 parts of dipentaerythritol pentaacrylate, in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer; 0.21 part of hydroquinone and 430.0 part of cyclohexanone were thrown in, and it heated up to 85 degreeC. Next, 2.14 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 80.7 parts of cyclohexanone were added, followed by addition of 3.42 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellow transparent, 50% of solid content, the number average molecular weight 1,050, and the weight average molecular weight 3,830.

(Production Example 4: Dispersant (4))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, 100.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride and pentaerythritol triacrylate (1) 200.2 parts 0.15 part of hydroquinone and 200.1 part of cyclohexanone were thrown in, and it heated up to 85 degreeC. Subsequently, 1.50 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 62.0 parts of glycidyl methacrylate and 42.4 parts of cyclohexanone were added, followed by adding 2.41 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The reaction solution obtained was pale yellow transparent, having a solid content of 60%, a number average molecular weight of 830, and a weight average molecular weight of 2,310.

(Production Example 5: Dispersant (5))

100.0 parts of tetrahydronaphthalene dianhydride, 305.7 parts of pentaerythritol triacrylate (2), 0.20 parts of hydroquinone, and 405.7 parts of cyclohexanone were charged into a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. It heated up to 85 degreeC. Next, 2.03 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 94.6 parts of glycidyl methacrylate and 96.9 parts of cyclohexanone were added, followed by 3.26 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C. for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellow transparent, 50% of solid content, the number average molecular weight 870, and the weight average molecular weight 3,150.

(Production Example 6: Dispersant (6))

100.0 parts of naphthalene dianhydride, 342.2 parts of pentaerythritol triacrylate (2), 0.22 parts of hydroquinone, 442.2 parts of cyclohexanone were put into a four necked flask equipped with a stirrer, a reflux cooling tube, a dry air inlet tube, and a thermometer. It heated up to. Next, 2.21 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 105.9 parts of glycidyl methacrylate and 108.4 parts of cyclohexanone were added, followed by addition of 3.56 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was pale yellow transparent, 50% of solid content, the number average molecular weight 820, and the weight average molecular weight 2,440.

(Production Example 7: Dispersant (7))

100.0 parts of biphenyltetracarboxylic dianhydride, 556.8 parts of dipentaerythritol pentaacrylate, 0.33 parts of hydroquinone, and 437.8 parts of cyclohexanone were charged into a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. And it heated up to 85 degreeC. Then, 3.28 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 96.6 parts of glycidyl methacrylate and 66.8 parts of cyclohexanone were added, followed by 5.28 parts of dimethylbenzylamine as a catalyst, which was stirred at 85 ° C for 6 hours, cooled to room temperature, and the reaction was completed. The obtained reaction solution was light yellowish transparent, 60% of solid content, the number average molecular weight 820, and the weight average molecular weight 2,660.

(Production Example 8: Dispersant (8))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, 100.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 50.7 parts of 2-hydroxyethyl acrylate, hydro 0.08 part of quinones and 100.4 part of cyclohexanone were thrown in, and it heated up to 85 degreeC. Next, 1.51 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 5 hours. Thereafter, 62.0 parts of glycidyl methacrylate and 39.7 parts of cyclohexanone were added, followed by addition of 1.21 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellowish transparent, 60% of solid content, the number average molecular weight 890, and the weight average molecular weight 1,200.

(Production Example 9: Dispersant (9))

100.0 parts of butanetetracarboxylic dianhydride, 463.2 parts of pentaerythritol triacrylate (1), 0.28 parts of hydroquinone, 563.2 parts of cyclohexanone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. It put and heated up to 85 degreeC. Next, 2.82 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 146.5 parts of cyclohexanone were added, followed by addition of 4.53 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C. for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellow transparent, 50% of solid content, the number average molecular weight 820, and the weight average molecular weight 2,000.

(Production Example 10: Dispersant (10))

100.0 parts of butanetetracarboxylic dianhydride, 463.2 parts of pentaerythritol triacrylate (2), 0.28 parts of hydroquinone, 563.2 parts of cyclohexanone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. It put and heated up to 85 degreeC. Next, 2.82 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 146.5 parts of cyclohexanone were added, followed by addition of 4.53 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C. for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellow transparent, 50% of solid content, the number average molecular weight 920, and the weight average molecular weight 2,200.

(Production Example 11: Dispersant (11))

80.0 parts of butanetetracarboxylic dianhydride, 185.3 parts of pentaerythritol triacrylate (2), 330.9 parts of dipentaerythritol pentaacrylate, in a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube and a thermometer 0.30 part of quinones and 599.5 parts of cyclohexanone were thrown in, and it heated up to 85 degreeC. Then, 2.98 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 114.8 parts of glycidyl methacrylate and 119.6 parts of cyclohexanone were added, followed by addition of 4.77 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellow transparent, 50% of solid content, the number average molecular weight 950, and the weight average molecular weight 2,600.

(Manufacture example 12: Dispersant (12))

50.0 parts of butanetetracarboxylic dianhydride, 413.4 parts of dipentaerythritol pentaacrylate, 0.23 parts of hydroquinone, 463.4 parts of cyclohexanone were charged into a four-necked flask equipped with a stirrer, a reflux cooling tube, a dry air introduction tube, and a thermometer. It heated up to 85 degreeC. Next, 2.32 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 8 hours. Thereafter, 71.7 parts of glycidyl methacrylate and 74.3 parts of cyclohexanone were added, followed by 3.73 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C. for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellow transparent, 50% of solid content, the number average molecular weight 900, and the weight average molecular weight 2,070.

(Production Example 13: Dispersant (13))

Into a four-necked flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, 100.0 parts of butanetetracarboxylic dianhydride, 117.2 parts of 2-hydroxyethyl acrylate, 0.11 parts of hydroquinone, and 144.8 parts of cyclohexanone were charged. It heated up to 85 degreeC. Subsequently, 2.17 parts of 1,8- diazabicyclo [5.4.0] -7-undecene were added as a catalyst, and it stirred at 85 degreeC for 5 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 93.3 parts of cyclohexanone were added, followed by addition of 1.74 parts of dimethylbenzylamine as a catalyst, followed by stirring at 85 ° C for 6 hours, and cooling to room temperature to complete the reaction. The obtained reaction solution was light yellowish transparent, 60% of solid content, the number average molecular weight 780, and the weight average molecular weight 1,100.

(Creation of metal oxide dispersion paste: Examples 1 to 22, Comparative Examples 1 to 3)

The metal oxide dispersion paste was created by mix | blending shown in Table 1 using each dispersing agent (A) created by the said manufacturing example, and the metal oxide dispersion paste was produced (the compounding quantity shows solid amount). Dispersion method uses pre-dispersion (zirconia beads (1.25mm) as a medium, disperse 1 hour with a paint shaker) and bone dispersion (zirconia beads (0.1mm) as a medium, Kotobuki Dispersion by UAM Co., Ltd. product disperser UAM-015).

In Table 1,

Sb ₂ O ₅ : Nippon Kagaku Kogyo Co., Ltd.'Sun Epoch EFR-6N '(average primary particle size: 20nm)

ATO: SN-100P, Ishihara Sangyo Co., Ltd. (average primary particle size: 20nm)

ITO: `` Nanotech ITO '' manufactured by CIKAISEI Co., Ltd. (average primary particle size: 30nm)

PTO: Mitsubishi Material Co., Ltd. product 'EP SP-2' (average primary particle size: 15nm)

ZrO ₂ : Nippon Denco Co., Ltd. product 'PCS-60' (average primary particle size: 20nm)

TiO ₂ : 'TT0-51 (A)' manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20nm)

ZnO: Sakaikagaku Kogyo Co., Ltd. product 'FINEX-50' (average primary particle size: 20nm)

SiO ₂ : Nihon Aerosil Co., Ltd. product 'AEROSIL 50' (average primary particle size: 50nm)

Al ₂ O ₅ : Nippon Aerosil Co., Ltd. 'Aluminium Oxide C' (average primary particle size: 13nm)

Commercial dispersant: BYK-Chemi Japan Co., Ltd. 'Disperbyk-111' (100% solids)

Commercially available polyfunctional monomer (1): `` Bis Court # 400 '' manufactured by Osaka Yukikagaku Co., Ltd. (100% solids)

Commercially available polyfunctional monomers (2): Nihon Kayaku Co., Ltd.KAYARAD DPHA (100% solids)

MIBK: methyl isobutyl ketone

Metobuta: 3-methoxy-1-butanol

<Coating and Cured Film Evaluation: Examples 1 to 22, Comparative Examples 1 to 3>

Using the metal oxide dispersion paste adjusted above, the metal oxide composition of the composition shown in Table 2 was prepared (the compounding quantity shows the solid content.). The obtained metal oxide composition was coated on a 100 μm-thick two-bonded PET film (Cosmo Shine A-4100 manufactured by Toyobo Co., Ltd.) with a bar coder so that the film thickness after drying was 5 μm. Ultraviolet rays of 400 mJ / cm 2 were irradiated with a halide lamp to form a cured film (hard coating layer). About the obtained cured film, refractive index, abrasion resistance, pencil hardness, transparency (haze), light resistance, and surface resistance were evaluated by the following method. The results are shown in Table 2.

In Table 2,

Photocurable compound (1): UA-306T, manufactured by Kyoeisha Chemical Co., Ltd.

Photocurable compound (2): KAYARAD DPHA from Nihon Kayaku Co., Ltd.

Photopolymerization Initiator: `` Irugacure 184 '' from Chiba Specialty Chemical Co., Ltd.

Solvent: PGME (propylene glycol monomethyl ether)

* 1: Not measured because the metal oxide paste was poorly dispersed

<Production and Evaluation of Laminates: Examples 23 to 27>

(Production of Low Refractive Index Coatings)

1,2,9,10-tetraacryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane 50 parts by weight, silica sol 30% dispersion (Nissan Kagaku Kogyo Co., Ltd. ) MEK-ST) 120 parts by weight, 2 ', 2'-bis ((meth) acryloyloxymethyl) propionic acid (2-hydroxy) -4,4,5,5,6,6,7,7 , 8,8,9,9,10,10,11,11,11-nonadecafluorodecyl 10 parts by weight, butyl alcohol 900 parts by weight, photoinitiator (Nihon Kayaku Co., Ltd. KAYACURE BMS) 5 parts by weight The part was mixed and the low refractive index coating liquid was adjusted.

Each metal oxide composition of the composition by the mixing | blending shown in Table 3 was adjusted using the metal oxide dispersion paste of Example 2 (the compounding quantity shows solid amount.). This metal oxide composition was applied to the easily adhesive treated surface of the 100 micrometer-thick easily adhesive PET film (refractive index of the easily adhesive layer = 1.60) so that it might become 6 micrometers by dry film thickness using a bar coater. After drying the obtained application layer at 100 degreeC for 1 minute, the ultraviolet-ray of 400mJ / cm <2> was irradiated with the metal halide lamp. On the obtained cured film, the thickness of the layer was adjusted and applied to the low refractive coating liquid so that the wavelength of light showing λ / 4 in the dry film thickness was about 550 nm with a spin coater. After drying the obtained application layer at 100 degreeC for 1 minute, the ultraviolet-ray of 400mJ / cm <2> was irradiated with the metal halide lamp, and the laminated body was obtained.

About the obtained laminated body, the refractive index of the cured film was measured by the following method, and the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflective interference fringe of the cured film were evaluated. The results are shown in Table 3.

 Formulation of Metal Oxide Composition and Evaluation of Cured Film (Parts by weight) Example 23 Example 24 Example 25 Example 26 Example 27 Metal Oxide Dispersion Paste 37.28 44.25 51.52 56.1 62.96 Photocurable Compounds (2) 41.36 31.91 25.37 20.2 15.63 Photopolymerization Initiator 2.38 1.91 1.56 1.35 1.14 Solvent (PGME) 68.98 71.93 71.55 72.35 70.27 Refractive Index of Cured Film 1.56 1.58 1.6  1.62 1.64 Scratch resistance 5 5 5 5 5 Pencil hardness A A A A A Transparency (Haze value) 0.58 0.62 0.65 0.68 0.75 Difference in Refractive Index between Cured Film and Substrate 0.04 0.02 0 0.02 0.04 Reflective interference stripes  D A A A  D

In Table 3

Photocurable compound (2): KAYARAD DPHA from Nihon Kayaku Co., Ltd.

Photopolymerization Initiator: `` Irugacure 184 '' from Chiba Specialty Chemical Co., Ltd.

Substrate: 100 μm thick adhesive PET film (Cosmo Shine A-4100, manufactured by Toyobo Co., Ltd., coated on the adhesive adhesive surface (refractive index of 1.60))

Solvent: PGME (propylene glycol monomethyl ether)

(Assessment Methods)

(1) refractive index

The refractive index of the obtained hardened film was measured using ABE Co., Ltd. product Abe refractive index meter.

(2) scratch resistance

The coated object was set in a school tester and shaken 10 times with a load of 250 g using No.0000 of steel wool. The state of a flaw was judged according to the visual evaluation of the following five steps about the extracted coating. The larger the numerical value, the better the scratch resistance of the cured film.

5: no scratch

4: there are some scratches

3: There is a flaw, but a mention is not seen

2: scratched, some cured film peeled off

1: the cured film is peeled off and the substrate is exposed

(3) pencil hardness

In accordance with JIS-K5600, a pencil hardness tester (scratching tester HEIDON-14 manufactured by HEIDON Co., Ltd.) was used five times at a load of 500 g by varying the hardness of the pencil lead. The hardness of the seam at the time of not scratching even once of 5 times, or a scratch only once was made into the pencil hardness of the cured film. In consideration of practical required physical properties, the pencil hardness of the cured film,

2H or more: A

1H or more: B

Lower than 1H: D

Was determined.

(4) Transparency (Haze value)

The turbidity (Haze value) in the obtained coating material was measured using the Haze meter.

(5) light resistance

Yellowing over time upon continuous light irradiation is very undesirable in terms of application development. Therefore, yellowing property at the time of light continuous irradiation was confirmed.

First, the coatings were exposed for 24 hours with a light resistance tester (light source: xenon lamp, illuminance: 100 W / cm 2, black panel temperature: 60 ° C., 60% RH). Thereafter, the coating was placed on white paper, and coloring was measured using a colorimeter (Minolta CR-300). The colorimetric value was expressed by L ^* a ^* b ^* , and the criterion of yellowing of the cured film was judged as b ^* value. The smaller the value of b ^* value, the smaller the degree of yellowing and the better the light resistance. In consideration of the practical required physical properties, the b ^* value of the cured film

Less than 3.5: A

3.5 or more: D

Was determined.

(6) surface resistance

The surface resistance (Ω / square) of the cured film was evaluated according to the following criteria.

When surface resistance is 1 × 10 ¹² or less: A

If surface resistance is higher than 1 × 10 ^{12 and} less than 1 × 10 ¹⁴ : B

If surface resistance exceeds 1 × 10 ¹⁴ : D

(7) reflective interference stripes

The reflective interference stripes of the obtained cured film were visually evaluated according to the following criteria.

Reflective interference stripes cannot be observed: A

Reflective interference fringes can be observed: D

The present disclosure relates to the subject matter disclosed in Japanese Patent Application No. 2006-148854, filed May 29, 2006, and Japanese Patent Application No. 2006-148855, filed May 29, 2006, and all of their disclosures. Is hereby incorporated by reference.

It should be noted that, in addition to those already described, various modifications and changes may be added to the above embodiments without departing from the novel and advantageous features of the present invention. Accordingly, all such modifications or changes are intended to be included in the appended claims.

Claims (19)

A method for producing a metal oxide dispersion comprising dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in an organic solvent using a dispersant (A), The dispersant (A), Formula: [Formula 4]

(Wherein R ⁹ is at least one tetravalent aromatic group selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and a tetrahydronaphthalene skeleton, or 4 which is an alkyl skeleton having 4 to 10 carbon chains) Dianhydride (x1) of tetracarboxylic acid represented by (). 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate , Dihydroxy acrylate, glycerol (meth) acrylate, isocyanuric acid EO modified diacrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate , Dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipenta Less erythritol penta (meth) alone or in combination of two or more compounds selected from acrylate (x2), To compound (X) having a carboxyl group, The manufacturing method of the metal oxide dispersion obtained by making it react with 1 type (s) or 2 or more types of compound (Y) which are epoxy group containing (meth) acrylates. The method of claim 1, The compound (x2) is pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( And a hydroxyl group-containing (meth) acrylate compound selected from the group consisting of meth) acrylate and dipentaerythritol penta (meth) acrylate, wherein the compound (Y) is a glycidyl (meth) acrylate. Method for producing a metal oxide dispersion comprising. The method of claim 2, The said dispersing agent (A) is tetracarboxylic dianhydride, a pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, a pentaerythritol tri (meth) acrylate, and a dipentaerythritol tree (meth) At least one hydroxyl group-containing (meth) acrylate compound selected from the group consisting of acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate, and glycidyl (meth) A method for producing a metal oxide dispersion, which is obtained by a reaction with an acrylate. The method according to any one of claims 1 to 3, And the metal oxide contains at least one element selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, aluminum, silicon, phosphorus and fluorine. delete delete delete delete As a dispersant for dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in an organic solvent, the following chemical formula: [Formula 4]

(Wherein R ⁹ is at least one tetravalent aromatic group selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and a tetrahydronaphthalene skeleton, or 4 which is an alkyl skeleton having 4 to 10 carbon chains) Dianhydride (x1) of tetracarboxylic acid represented by (). 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate , Dihydroxy acrylate, glycerol (meth) acrylate, isocyanuric acid EO modified diacrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate , Dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipenta Less erythritol penta (meth) alone or in combination of two or more compounds selected from the group consisting of acrylate (x2), Compound (X) having a carboxyl group formed by reacting The dispersing agent obtained by making it react with 1 type (s) or 2 or more types of compound (Y) which are epoxy group containing (meth) acrylates. 10. The method of claim 9, The compound (x2) is pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( And a hydroxyl group-containing (meth) acrylate compound selected from the group consisting of meth) acrylate and dipentaerythritol penta (meth) acrylate, wherein the compound (Y) is a glycidyl (meth) acrylate. Dispersant containing. The method of claim 10, Tetracarboxylic dianhydride, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra By the reaction of at least one hydroxyl group-containing (meth) acrylate compound selected from the group consisting of (meth) acrylate and dipentaerythritol penta (meth) acrylate with glycidyl (meth) acrylate Dispersant that is obtained. delete delete delete delete delete delete delete delete