KR20160135667A - Metal oxide composition, cured film thereof, and member with cured film attached thereto - Google Patents

Abstract

The present invention relates to a metal oxide composition comprising: a compound (A) containing a compound (A1) having at least 6 acryloyl groups displayed as chemical formula (1), a metal oxide (B) and a solvent. According to the present invention, a metal oxide composition, a cured film thereof and a member with the cured film attached thereto capable of forming a film containing a metal oxide while having excellent physical properties such as high refractivity, hard-coating properties and transparency, and having temporal stability are able to be provided. In chemical formula (1), R1 represents a specific tetravalent organic residue; and R2 and R3 represent a specific monovalent organic residue.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal oxide composition, a cured film thereof, and a member to which the cured film is adhered,

The present invention relates to a metal oxide composition having hard coat properties, a cured film thereof, and a member to which the cured film is adhered.

Conventionally, in view of securing the performance of information communication equipment and safety measures, a hardcoat-based coating film having scratch resistance, abrasion resistance, high refractive index and the like by using a metal oxide composition on the surface of the device, Thereby forming an anticorrosive coating film.

In recent years, development and commercialization of information communication devices have surprisingly been required to improve the performance and productivity of a hard coat film and an antistatic film, and various proposals have been made using photocurable materials.

For example, the following technical proposals can be cited (see Patent Documents 1 to 3). Patent Document 1 discloses a method of producing a dispersion for electrically conductive paint by mixing a antimony doped tin oxide and a silane coupling agent having an ultraviolet curable property in an organic solvent using a ball mill. Further, Patent Document 2 discloses a method for producing a conductive paint by dispersing a conductive oxide fine powder in a mixed solvent of a dysprosium low boiling point solvent and an oily dispersion high boiling point agent. Patent Document 3 discloses a method of preparing a metal oxide composition by dispersing a compound having an inorganic oxide and a polymerizable unsaturated double bond in an organic solvent.

Japanese Patent Application Laid-Open No. H06-264009 Japanese Patent Application Laid-Open No. 2001-131485 WO2007 / 138946

However, in Patent Documents 1 and 2, even if it is possible to produce a metal oxide composition having good physical properties such as high refractive index, hard coat property, antistatic property, light resistance, and the like, , It is impossible to stably disperse and stabilize the fine metal oxide having an average primary particle diameter of several hundred nanometers or less at a primary particle level. Therefore, from the viewpoints of transparency of the coating film and stability of the photo- It is easy to cause problems.

In the technique described in Patent Document 3, in order to stably disperse and stabilize the fine metal oxide having an average primary particle size of several hundred nm or less at the primary particle level, the amount of the polymerizable unsaturated double bond- The problem is that the ratio of metal oxides can not be increased.

Accordingly, an object of the present invention is to provide a metal oxide composition capable of forming a coating film having a good hard coat property and transparency while containing a metal oxide, a cured film using the same, and a member to which the cured film is attached .

According to an aspect of the present invention,

(A) having at least 6 acryloyl groups, a metal oxide (B), and a solvent,

The compound (A)

Pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and at least one compound selected from the group consisting of 1,2,4,5-benzene tetracarboxylic acid dianhydride, 3,3 ', 4,4'- Selected from the group consisting of 4'-biphenyltetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, and 1,2,3,4-butanetetracarboxylic dianhydride A compound (X) having a carboxyl group, which is obtained by reacting one or more compounds (x1)

Biphenyl glycidyl ether

To a metal oxide composition.

Another aspect of the present invention is a process for producing a photosensitive resin composition comprising a compound (A) having at least 6 acryloyl groups, a metal oxide (B)

The present invention relates to a metal oxide composition, wherein the compound (A) comprises a compound (A1) having at least 6 acryloyl groups represented by the following general formula (1).

In general formula (1)

[Chemical Formula 1]

(In the general formula (1), R ₁ represents any one of the tetravalent organic moieties shown below.

(2)

In the general formula (1), R ₂ represents any one of the following monovalent organic residue.

(3)

In the general formula (1), R ₃ represents the following monovalent organic residue.)

[Chemical Formula 4]

A further aspect of the present invention relates to the above metal oxide composition, wherein R < _{1 >} is an organic moiety comprising an aromatic ring.

A further aspect of the present invention relates to the above metal oxide composition, wherein the aromatic ring is a biphenyl ring.

A further embodiment of the present invention is a metal oxide composition comprising the metal oxide (B) containing at least one element selected from the group consisting of titanium, zinc, zirconium, indium, tin, aluminum, .

A further embodiment of the present invention relates to the above metal oxide composition, wherein the D50 particle diameter of the metal oxide (B) is 0.005 to 0.200 m.

Another aspect of the present invention relates to a cured film obtained by curing the metal oxide composition.

Another aspect of the present invention relates to a member to which a cured film is attached, wherein the cured film is provided on at least a part of the base.

According to the present invention, it is possible to provide a metal oxide composition containing a metal oxide and capable of forming a coating film having excellent hard coat properties and transparency, a cured film using the metal oxide composition, and a member to which the cured film is adhered.

Hereinafter, embodiments of the present invention will be described. The embodiments described below are examples of the present invention, and the present invention is not limited to the following embodiments.

The metal oxide composition according to the present invention contains a compound (A) containing a compound (A1) represented by the following general formula (1), a metal oxide (B) and a solvent. The metal oxide composition may contain two or more metal oxides (B), two or more kinds of compounds (A), and two or more kinds of solvents, respectively.

In general formula (1):

[Chemical Formula 1]

(In the general formula (1), R ₁ represents any one of the tetravalent organic moieties shown below.

(2)

In the general formula (1), R ₂ independently represents any one of the following monovalent organic residues.

(3)

In the general formula (1), R ₃ independently represents a monovalent organic residue shown below.)

[Chemical Formula 4]

The compound (A) mainly includes the compound (A1), but in addition to the compound (A1), as described later, the compound (A) may include a high molecular weight compound such as the compound (A1). This compound (A) has high dispersibility and photo-curability against metal oxides. By increasing the dispersibility of the metal oxide (B) and increasing the photo-curability of the metal oxide (A), the metal oxide composition of the present invention is excellent in hardenability, hard coat property and transparency, It is possible to form an attached member. Therefore, it can be used suitably for plastic optical parts, optical disk, antireflection film, touch panel, film type liquid crystal device, and also as hard coat agent for various plastic laminate.

This metal oxide composition can form a cured film having a high refractive index. When the metal oxide composition is applied to a substrate having the same refractive index, the obtained laminate does not generate reflection interference fringes and is used for optical applications do. Furthermore, since the refractive index of the cured product containing the metal oxide can be controlled to a high level, it is also suitable as an optical semiconductor element encapsulant.

In the above general formula (1), R ₁ is a tetravalent organic residue and includes a phenyl skeleton, a biphenyl skeleton, a fluorene skeleton, or a butylene group. Among them, a phenyl skeleton, a biphenyl skeleton, or a fluorene skeleton, which is an organic residue including an aromatic ring, is more preferable.

The compound (A1) contained in the compound (A) can be obtained, for example, by reacting the dianhydride (x1) of the tetracarboxylic acid represented by the following formula (2) with pentaerythritol triacrylate and dipentaerythritol pentaacrylate (X) having a carboxyl group formed by reacting one or two compounds (x2) selected from the group consisting of a hydroxyl group and a hydroxyl group, and biphenyl glycidyl ether. From the viewpoints of photocurability and hard coatability, it is preferable that the compound (x2) is pentaerythritol triacrylate and / or dipentaerythritol pentaacrylate.

In general formula (2)

[Chemical Formula 5]

Examples of the tetracarboxylic acid dianhydride (x1) represented by the general formula (2) include 1,2,4,5-benzenetetracarboxylic acid dianhydride, 3,3 ', 4,4'- 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride having 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride having an anhydride of phenyltetracarboxylic acid and fluorene skeleton, or 9,9- Bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9, , 4-butanetetracarboxylic acid dianhydride, and the like.

In the general formula (2), R ₁ is preferably as defined in the general formula (1).

Among these tetracarboxylic acid dianhydrides, the 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton can be efficiently introduced into the molecule of the compound (A) And further it is possible to combine the hard coat property of the cured film and the good dispersibility of the metal oxide.

Specific examples of commercial products of pentaerythritol triacrylate and dipentaerythritol pentaacrylate which are compounds (x2) include VISCOAT # 300 (manufactured by Osaka Organic Chemical Industry Ltd.) and KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) , PETIA (manufactured by Daicel-UCB Company, Ltd.), ARONIX M305 (manufactured by Toagosei Company, Limited), NK Ester A-TMM-3LMN (manufactured by Shin- Nakamura Chemical Co., Ltd.), LIGHTACRYLATE PE- (Manufactured by Sartomer, Inc.), LIGHTACRYLATE DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), ARONIX M402 Manufactured by Toagosei Company, Limited).

The content of the compound (A1) is not less than 9 parts by mass and not more than 45 parts by mass based on 100 parts by mass of the metal oxide (B), although the compounding of the metal oxide (B) . When the amount of the compound (A1) is 9 parts by mass or more, it is preferable from the viewpoint of film forming property, and when it is 45 parts by mass or less, it is preferable from the viewpoint of hard coatability and the like. The content of the compound (A1) is more preferably 12 parts by mass or more, more preferably 14 parts by mass or more, further preferably 32 parts by mass or less, and more preferably 27 parts by mass or more per 100 parts by mass of the metal oxide (B) Or less. The content of the compound (A1) is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, in the total mass of the compound (A).

Here, simply, the compounding ratio of the metal oxide (B) and the "reactant containing the compound (A)" may be used as an index of the compounding of the metal oxide (B) and the compound (A1). This is because commercially available products of the compound (x2) generally contain about 5 to 15 mass% of pentaerythritol diacrylate and dipentaerythritol tetraacrylate each having two hydroxyl groups as subcomponents. Thus, in the reaction for obtaining the compound (A1), a reaction product derived from the subcomponent, a resin obtained by high-molecular weight compound (A1), etc., are simultaneously produced in addition to the compound (A1) It is because. The amount of the reactant containing the compound (A) is preferably 10 parts by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 35 parts by mass or less, and still more preferably 15 parts by mass or more with respect to 100 parts by mass of the metal oxide (B) More preferably 30 parts by mass or less. When the amount is 10 parts by mass or more, it is more preferable from the viewpoint of suppressing the deterioration of the film formability due to the small organic content. The content of the reactant containing the compound (A) can be measured by the method described in the later Examples.

The reaction of the tetracarboxylic acid dianhydride (x1) with the compound (x2) is a reaction between the two carboxylic anhydride groups of the tetracarboxylic acid anhydride and the hydroxyl group of the compound (x2) Are well known in the art. For example, the tetracarboxylic acid dianhydride (x1) and the compound (x2) are reacted in the presence of a catalyst such as 1,8-diazabicyclo [5.4.0] -7-undecene in an organic solvent such as cyclohexanone , And 50 to 120 ° C. In this case, a polymerization inhibitor such as methylhydroquinone (2-METHYLHYDROQUINONE) may be added to the reaction system. For example, the ratio of (x1) :( x2) (molar ratio) = 1: 1.4 to 1: 4.0, preferably 1: 1.6 to 1: 3.0, more preferably 1: 1.8 to 1: 2.6, and more preferably from 1: 1.9 to 1: 2.4. Here, it is assumed that the molar amount of (x2) also includes the molar amount of the subcomponent having a plurality of hydroxyl groups in (x2).

After the above reaction, a compound represented by the following general formula (3), which is a biphenyl glycidyl ether, can be reacted to a reaction product containing a compound (X) having a carboxyl group as a reaction product without purification thereof.

In general formula (3)

[Chemical Formula 6]

The reaction of the compound (X) and the biphenyl glycidyl ether represented by the general formula (3) is a reaction between the carboxyl group of the compound (X) and the epoxy group of the biphenyl glycidyl ether, Lt; / RTI > For example, this reaction can be carried out at a temperature of 50 to 120 ° C in the presence of an amine catalyst such as dimethylbenzylamine or the like. For example, the above-mentioned (x1): biphenyl glycidyl ether (molar ratio) is 1: 1.4 to 1: 5.0, preferably 1: 1.6 to 1: 4.0, And more preferably in the range of 1: 1.8 to 1: 3.0.

These reactions may be carried out in the absence of a solvent or in a solvent inert to the reaction. Such a solvent includes, for example, hydrocarbon solvents 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-based solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or perchlorethylene; 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.

When the compound (A) is obtained by the above-mentioned reaction, the "reactant containing the compound (A)" means a reactant containing the compound (X) which is the reaction product of the compound (x1) and the compound , And the reaction product of the compound represented by the general formula (3) in the solid content (excluding unreacted components and components not involved in the reaction). In one embodiment, the reaction is preferably carried out so that 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more of the "reactant containing the compound (A)" is the compound (A) .

In the present embodiment, the number of acryloyl groups of the compound (A) is 6 or more. In the present invention, a compound having less than 6 acryloyl groups can be used in combination. However, when the compound (A) is included, the hardness of the resulting cured film becomes better.

Next, the metal oxide (B) will be described. The metal oxide preferably has a D50 particle size (particle diameter after dispersion) of 0.005 to 0.200 m. The D50 particle size (volume basis) of the metal oxide can be measured using, for example, "NANOTRAC UPA" manufactured by Nikkiso Co., Ltd. using a dynamic light scattering method.

When the D50 particle size is too small, the cohesive force between the fine particles is very large. From the viewpoint of improving the dispersibility at the primary particle level, the D50 particle size is 0.005 μm or more. On the other hand, when the D50 particle size is too large, scattering tends to occur in light such as visible light in the point that the particle diameter is large, and fogging tends to occur in the cured film. From the viewpoint of further suppressing the fogging of the cured film, And is preferably 0.200 m or less. The D50 particle size is more preferably 0.015 mu m or more, more preferably 0.025 mu m or more, further preferably 0.170 mu m or less, further preferably 0.150 mu m or less, particularly preferably 0.120 mu m or less.

The metal oxide (B) preferably contains at least one element selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, aluminum, silicon, phosphorus and fluorine. Particularly, metal oxides containing at least one element selected from the group consisting of titanium, zinc, zirconium, indium, tin, aluminum, silicon and phosphorus are more preferable.

Specific examples thereof include antimony pentoxide, antimony doped tin oxide (ATO), tin doped indium oxide (ITO), fluorine doped tin oxide (FTO), indium tin oxide (PTO), zinc antimonide (AZO) (IZO), tin oxide, ATO-coated titanium oxide, aluminum-doped zinc oxide, titanium oxide, zinc oxide, zirconium oxide, silicon oxide and aluminum oxide. These metal oxides may be treated with an organic or inorganic material. These metal oxides may be used in combination of two or more.

As a commercially available metal oxide,

Manufactured by Nissan Chemical Industries, Limited; Sun Epoch EFR-6N; Sun Epoch EFR-6NP (antimony pentoxide);

(ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO coated titanium oxide), TTO-55 (manufactured by Ishihara Sangyo Kaisha, Ltd.) (A) (titanium oxide), TTO-55 (B) (titanium oxide), TTO-55 (C) (titanium oxide), TTO-55 (D) (Titanium oxide), TTO-51 (A) (titanium oxide), TTO-51 (C) (titanium oxide), TTO-S-1 (Titanium oxide), TTO-S-3 (titanium oxide), TTO-S-4 (titanium oxide), TTO-F- F-3 (iron-containing titanium oxide), TTO-F-11 (iron-containing titanium oxide), ST-01 (titanium oxide), ST-21 (titanium oxide) Titanium oxide),

S-1200 (tin oxide), EP SP-2 (indium tin oxide), T-1 (ITO)

Mitsui Mining & Smelting Co., Ltd. Pastolan (ITO, ATO),

Nanotek ITO, Nanotek SnO 2, Nanotek TiO 2, Nanotek SiO 2, Nanotek Al 2 O 3, Nanotek ZnO,

Catalysts & Chemicals Industries Co., Ltd .; TL-20 (ATO), TL-30 (ATO), TL-30S (PTO)

Made by HakusuiTech Co., Ltd.: PazetCK (aluminum-doped zinc oxide),

FINEX-25 (zinc oxide), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP (zinc oxide) STR-60C-LP (titanium oxide), STR-100C (titanium oxide), NANOFINE-50A (zinc oxide), NANOFINE-50SD (zinc oxide), EZ- STR-100C-LP (titanium oxide), STR-100A-LP (titanium oxide), STR-100W

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

(Zirconium oxide), PCS-60 (zirconium oxide), PCS-90 (zirconium oxide), T-01 (zirconium oxide)

MT-100SA (titanium oxide), MT-100HD (titanium oxide), MT-100SA (titanium oxide), MT-500HD MZ-303S (zinc oxide), MZ-303S (zinc oxide), MZ-505S (zinc oxide), MZY-505S (zinc oxide) MZ-505M (zinc oxide),

AEROSIL200 (oxidized silicon), AEROSIL200 (oxidized silicon), AEROSIL200V (silicon oxide), AEROSIL200CF (silicon oxide), AEROSIL200FA (silicon oxide), AEROSIL300 (oxidized silicon) (Silicon oxide), AEROSIL300CF (silicon oxide), AEROSIL380 (silicon oxide), AEROSILR972 (silicon oxide), AEROSILR974 (silicon oxide), AEROSILR976 (silicon oxide), AEROSILR202 , AEROSILMOX50 (silicon oxide), AEROSILMOX50 (silicon oxide), AEROSILMOX80 (silicon oxide / aluminum oxide), AEROSILMOX170 (silicon oxide / aluminum oxide), AEROSILCOX84 (silicon oxide / aluminum oxide)

And the like.

The content of the metal oxide (B) is not particularly limited, but is preferably 5% by mass or more and 50% by mass or less based on the total mass of the metal oxide composition. When the content of the metal oxide (B) is 5 mass% or more, it is more preferable from the viewpoint of hard coatability or the like, and when it is 50 mass% or less, the dispersibility of the metal oxide is more preferable. The content of the metal oxide (B) is not particularly limited, but is more preferably 7% by mass or more, more preferably 10% by mass or more, further preferably 40% by mass or less, By mass or less.

According to the embodiment of the present invention, the fine metal oxide (B) can be stably dispersed at the primary particle level. The particulate metal oxide (B) has an average particle size of 100 nm or less, preferably 70 nm or less, and more preferably 50 nm or less. Further, the metal oxide (B) having an average particle size exceeding 100 nm may be used as long as the dispersion particle diameter and the properties of the cured film can be kept within a favorable range.

In the case of adding a solvent, it is preferable to perform the curing treatment after volatilizing the solvent. The solvent is not particularly limited and various organic solvents known in the art can be used. Specific examples thereof include alcohols such as cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, , 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxy ethanol, Propyleneglycol monobutylether acetate, propyleneglycol monomethylether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, propyleneglycol monomethyl ether, Dimethyl glutarate, tetrahydrofuran, methyl pyrrolidone and the like. These organic solvents may be used in combination of two or more.

Among them, the hydroxyl group-containing solvent is contained in the solvent composition in that it has good wettability with respect to the metal oxide having a high hydrophilicity and a surface property of the particles, and therefore the dispersion stability of the metal oxide and the stability And it is also preferable that the leveling property of the coating process is also improved. The content of the hydroxyl group-containing solvent in the total solvent composition is preferably 10 to 100% by mass. Specific examples of the hydroxyl group-containing solvent include n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3- 2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether and the like can be given as examples of the solvent. Particularly, 3-methoxy-1-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol mono-n-butyl ether are preferable from the viewpoint of better dispersibility and dispersion stability of the metal oxide.

The content of the solvent is not particularly limited, but is preferably 30 mass% or more, more preferably 95 mass% or less, of the total mass of the metal oxide composition. If the content of the solvent is within the above range, it is more preferable from the viewpoint of coatability and the like. The content of the solvent is more preferably 35 mass% or more of the total mass of the metal oxide composition, more preferably 40 mass% or more, further preferably 90 mass% or less, further preferably 85 mass% or less. Here, the content of the solvent is a value including the solvent in the reaction product when the reaction product containing the solvent is used as the resin varnish containing the compound (A).

In the metal oxide composition of the present invention, even if the compound (A) and the metal oxide powder are simply mixed and prepared, a desired effect can be sufficiently obtained. Alternatively, a solution containing the compound (A) may be added to the suspension system using a metal oxide powder, an organic solvent or the like mechanically by a kneader, a roll, an atrito, a super mill or a dry mill, (A) is deposited on the surface of the substrate, a more favorable result can be obtained.

The metal oxide composition is preferably a metal oxide dispersion in which the metal oxide powder is uniformly dispersed. The metal oxide dispersion can be preferably produced by using the compound (A) and dispersing the metal oxide (B) in the presence of an organic solvent.

When measured by "NANOTRAC UPA" manufactured by Nikkiso Co., Ltd. using the dynamic light scattering method, the dispersion particle diameter D50 is preferably less than 200 nm, and more preferably less than 150 nm.

(Manufactured by Red Devil), a ball mill, a sand mill (manufactured by Red Devil Co., Ltd.), and the like can be used for dispersing, dissolving, and mixing the compound (A), the metal oxide (B), or the metal oxide composition into a non- (Manufactured by Nippon Eirich Co., Ltd., "DCP Mill", etc.), a cob ball mill, a homomixer, and a homomixer manufactured by M Technique Co., Ltd. , "Super Appecks Mill", "Ultra Appecks Mill" (trade name, manufactured by Kotobuki Industries Co., Ltd.), " ) May be used. When a medium is used for the dispersing machine, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads or the like. As for the dispersion, two or more types of dispersion machines or two or more kinds of media of different sizes may be used respectively, and the dispersion may be performed by using them in a stepwise manner.

The metal oxide composition of the present invention contains at least a compound (A), a metal oxide (B) and a solvent, and may further contain various additives in a range that does not impair the objects and effects of the present invention have. Specifically, there may be mentioned a photopolymerization initiator, a photocurable compound, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an antibacterial agent, an antiblocking agent, a plasticizer, an ultraviolet absorber, an infrared absorber, an antioxidant, a silane coupling agent, Surfactants, inorganic fillers, pigments, dyes, and the like.

The method for producing the metal oxide composition including the compound (A), the metal oxide (B), and the components other than the solvent is not particularly limited and several methods can be used. Concretely, there are a method in which the compound (A) and the metal oxide (B) are mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and then various other additives are added and prepared; A method of dispersing and preparing all of the compound (A), the metal oxide (B), the organic solvent and other additives in a mixed state from the beginning; And the like.

The metal oxide composition of the present invention may further include a photopolymerization initiator.

The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization of the acrylic group of the compound (A) by photoexcitation, and examples thereof include monocarbonyl compounds, dicarbonyl compounds , Acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl compounds, and the like.

Specific examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4- Methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4,3'-dimethyl- - (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3 ', 4,4'-tetra (t- butylperoxycarbonyl) benzophenone N, N-dimethyl-N-2- (1-oxo-2-propenyloxyethyl) methaammonium oxalate, 4-benzoyl- Propyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d ) Thiazoline, and the like.

Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl (dibenzoyl) Phenanthrenequinone, methyl- alpha -oxobenzene acetate, 4-phenyl-benzyl, and the like.

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- Methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl -1-styrylpropane-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, -Morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6- -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 and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

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

Commercially available photopolymerization initiators include IRGACURE 184, 651, 500, 907, 127, 369, 784 and 2959 of Ciba Specialty Chemicals, Inc., Lucirin TPO of BASF Japan Ltd., and Esakyuawan of DKSH Japan KK.

The photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used singly or in combination of two or more.

The amount of the photopolymerization initiator to be used is not particularly limited, but the total amount of the photocurable compound containing the compound (A) (when the photopolymerizable compound other than the compound (A) ) Is preferably in the range of 1 to 20 parts by mass based on 100 parts by mass of the photo-curable compound.

As the sensitizer, various organic amines and the like known in the technical field may be added.

Further, in addition to the radical polymerization initiator, a cation polymerization initiator may be used in combination.

In addition to the compound (A), the metal oxide composition may contain other binder resins or photo-curable compounds other than the compound (A).

Examples of the binder resin include a polyurethane resin, a polyurea resin, a polyurethaneurea resin, a polyester resin (excluding the compound (A)), a polyether resin, a polycarbonate resin, an epoxy resin, A resin, an acrylic resin, a melamine resin, a polyamide resin, a phenol resin, and a vinyl resin. These resins may be used singly or in combination of two or more kinds. The binder resin is preferably used within a range of not more than 20 parts by mass based on the total amount of solid components (components other than the solvent, hereinafter the same) of the metal oxide composition as a reference (100 parts by mass).

As the photo-curing compound, for example, a compound having a polymerizable unsaturated double bond group such as a (meth) acrylic compound, an aliphatic vinyl compound, an alkyl vinyl ether compound, an -olefin compound, a vinyl compound or an ethynyl compound can be used . The compound having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, and a silanol group. The photocurable compound is preferably used in a range of less than 50 parts by mass, particularly in a range of 5 to 40 parts by mass based on the entire solid content of the metal oxide composition (100 parts by mass).

Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, compounds having a carboxyl group and a polymerizable unsaturated double bond, An acrylic compound, and a nitrogen-containing (meth) acrylic compound. Further, a monofunctional compound or a multifunctional compound (excluding the compound (A)) can be suitably used. In view of photocurability and hard coatability of the coating film, it is preferable that the film is polyfunctional.

Specific examples of the monofunctional (meth) acrylic compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (Meth) acrylate, octadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, icosyl Alkyl of 1 to 22 carbon atoms (Meth) acrylate. When it is intended to adjust the polarity, it is preferable to use an alkyl group-containing (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. Further, when it is intended to control the leveling property or the like, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms.

Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (Meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol Mono (meth) acrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain; (Meth) acrylates such as methoxyethylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxy tetraethylene glycol (Meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentoxy tetraethylene glycol (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy tetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxy tetrapropylene glycol N-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate and the like having an alkoxy group at the terminal and having a polyoxyalkylene chain Mono (meth) acrylate; (Meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxy triethylene glycol (Meth) acrylate having a phenoxy or aryloxy group at the terminal, such as phenoxypolyethylene glycol (meth) acrylate, phenoxy tetrapropylene ethylene glycol (meth) acrylate and the like.

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? - (meth) acryloxyethyl monoester, Phthalic acid? - (meth) acryloxyethyl monoester, succinic acid? - (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid.

Examples of the hydroxyl group-containing (meth) acrylic compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono , 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like.

Examples of the nitrogen-containing (meth) acrylic compound include (meth) acrylamide, N-methylol (meth) acrylamide, N- methoxymethyl- (meth) acrylamide, N- ethoxymethyl- (meth) (Meth) acrylamides such as N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide and N-pentoxymethyl- (meth) (Meth) acrylamide, N, N-di (ethoxymethyl) acrylamide, N, N-di Amide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl- N- (propoxymethyl) methacrylamide, N, N (Methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- Methoxymethyl) methacrylamide. Acrylamide-based unsaturated compounds such as alkylol (meth) acrylamide; Unsaturated compounds having dialkylamino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene and diethylaminostyrene; And a quaternary ammonium salt of a dialkylamino group-containing unsaturated compound having a halogen ion such as Cl ^- , Br ^- , I ^- or QSO ₃ ^- (Q: an alkyl group having 1 to 12 carbon atoms) as a counter ion.

Examples of the other unsaturated compound include perfluoromethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl Acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluorooctanoylethyl (meth) acrylate, 2-perfluorononylethyl Perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorooctyl (meth) And perfluoroalkylalkyl (meth) acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms, such as a perfluoroalkyl (meth) acrylate.

Also, perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyls such as perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene and perfluorodecyl ethylene, and alkylenes; Alkoxysilyl group-containing vinyl compounds such as vinylchlorosilane, vinyltris (? -Methoxyethoxy) silane, vinyltriethoxysilane and? - (meth) acryloxypropyltrimethoxysilane, and derivatives thereof; Glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate.

Examples of the aliphatic vinyl compound include vinyl acetate, vinyl butyrate, vinyl crotonate, vinyl caprate, vinyl laurate, vinyl chloroacetate, vinyl oleate and vinyl stearate.

Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

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

Examples of the vinyl compound include allyl compounds such as allylacetic acid, allyl alcohol, allylbenzene, and allyl cyanide; vinyl compounds such as vinylcyclohexane, vinylmethylketone, styrene,? -Methylstyrene, 2-methylstyrene, have.

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

These may be used singly or in combination of two or more.

Among them, photo-curable compounds other than the compound (A) are preferably a polyurethane poly (meth) acrylate having at least three functional groups and a poly (meth) acrylate such as polyepoxy poly (meth) acrylate in view of film strength and scratch resistance. (Meth) acrylates, and polyfunctional acrylates having three or more acryloyl groups in the molecule can be suitably used.

The polyepoxy poly (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid to give a (meth) acryloyl group as the functional group. The (meth) acrylic acid adduct, (Meth) acrylic acid adduct to novolak type epoxy resin, and the like.

The polyurethane poly (meth) acrylate can be obtained, for example, by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group, an isocyanate group-containing urethane obtained by reacting a polyol and a polyisocyanate under an isocyanate group- (Meth) acrylates having a hydroxyl group. Alternatively, it may be obtained by reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under an excess of hydroxyl group, with a (meth) acrylate 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-pentanediol, neopentyl glycol, hexanetriol, Propane, polytetramethylene glycol, and a condensation polymer of adipic acid and ethylene glycol.

Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

Examples of the (meth) acrylates having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri ) Acrylate, dipentaerythritol penta (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate.

Examples of the (meth) acrylates having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate.

As a commercially available product of the photo-curing compound, the following can be exemplified.

ARONIX M-8060, ARONIX M-8060, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-

Osaka Organic Chemical Industry Ltd., VISCOAT # 400,

Gunpowder Sartomer, Inc., SR-295,

Manufactured by Daicel-UCB Company, Ltd. DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,

Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Ester A-BPEF, NK Olygo EA-1020, NK Olygo EA-6310, NK Olygo EA- -6340, NK Olygo MA-6, NK Olygoi-4HA, NK Olygoi-6HA, NK Olygoi-324A,

Manufactured by BASF Japan Ltd., Laromer EA81,

Manufactured by San Nopco Limited: Photomer 3016,

Beam Set 371, Beam Set 575, Beam Set 577, Beam Set 700, Beam Set 710 manufactured by Arakawa Chemical Industries, Ltd.;

Art Resin UN-3320H, Art Resin UN-3320HC, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP-3, Art Resin H61,

Shiko UV-7600B, Shiko UV-7600B, Shiko UV-7600B, Shiko UV-7600B, Shiko UV-1400B, Shiko UV-

LIGHTACRYLATE PE-4A, LIGHTACRYLATE DPE-6A, UA-306H, UA-306T, UA-306I,

KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, KAYARAD DPHA, Nippon Kayaku Co.,

Osaka Gas Chemicals Co., Ltd., OGSOL EA-2000, OGSOL EA-3000, OGSOL GA-5000.

Next, the cured film and the member to which the cured film is attached will be described.

The cured film is a film formed by curing the metal oxide composition of the present invention. The preparation method can include, for example, applying a metal oxide composition to an arbitrary substrate, and irradiating an active energy ray to cure the metal oxide composition on the substrate.

More specifically, the metal oxide composition may be coated on an arbitrary substrate so that the film thickness after drying is preferably 0.03 to 30 탆, more preferably 0.03 to 20 탆, and then cured.

In forming, the cured film may be applied directly to the substrate, and there may be one or more underlying layers between the cured film and the substrate.

Examples of the substrate include metal, ceramics, glass, plastic, wood, slate, paper, and the like, but are not particularly limited. Specific examples of the plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetylcellulose resin, ABS resin, AS resin, polyamide, epoxy resin and melamine resin. The substrate may be in the form of a film sheet, a plate-like panel, a lens, a disk, or a fiber, but is not particularly limited.

A surface treatment or a functional layer (an adhesive layer or an information recording layer or the like) may be formed on a part or whole of the substrate, if necessary.

As the coating method, various methods known in the art can be used. For example, a method using a rod or a wire bar, or a method using a micro gravure, a gravure, a die, a curtain, a lip, Coating method can be used.

The curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, and visible rays having a wavelength of 400 to 500 nm, using various techniques known in the art. For example, a high-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, and the like can be used as a source of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. The electron source may be a thermionic emission gun, an electrolytic radiation gun, or the like.

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

These active energy rays can be used in combination with heat treatment by infrared rays, far-infrared rays, hot winds, high frequency heating or the like.

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

Particularly, in the case of curing with an electron beam, it is more preferable to carry out curing treatment after natural or forced drying in order to prevent hardening by water or decrease of strength of the coating film due to residual organic solvent.

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

The cured film obtained is excellent in hard coat property, transparency and high refractive index, and thus can be suitably used as an optical material. Therefore, the cured film can also be used as a front panel of various display devices such as a cathode ray tube, a flat display panel (liquid crystal display, plasma display, electrochromic display, light emitting diode display, etc.) or these input devices as a laminate.

In addition, the cured film can be widely used for an optical lens, a lens for a spectacle lens, an optical recording disk (compact disk, DVD disk, Blu-ray disk, etc.), a light case and the like.

The surface resistance value of the cured film is preferably 1 x 10 ¹² ? /? Or less.

The thickness of the cured film is preferably 0.03 m or more, more preferably 0.1 to 30 m, and further preferably 20 m or less.

Furthermore, the refractive index of the cured film is preferably in the range of 1.4 to 2.0, and more preferably in the range of 1.5 to 1.9.

The member to which the cured film of the present invention is attached includes a cured film and a substrate. As the substrate, any of the above examples may be used, and in particular, a plastic substrate is preferred. The shape of the substrate is preferably a film shape, a lens shape, or a disk shape.

It is preferable that the member to which the cured film is attached includes at least one film having a different refractive index, a pressure-sensitive adhesive layer, or an information recording layer.

The member to which the cured film is attached may have a layer structure such as the following (I) to (IX).

(I) substrate / (M) / curing membrane

(II) substrate / cured film / (M)

(III) substrate / (M) / cured film / (M)

(IV) (M) / substrate / curing membrane

(V) (M) / base material / (M) / curing film

(VI) (M) / substrate / cured film / (M)

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

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

(IX) cured film / (M) / substrate / cured film

Note that (M) includes any one or two or more layers, preferably any one layer, of a film having a different refractive index, a pressure-sensitive adhesive layer, or an information recording layer.

The film or information recording layer having a different refractive index has a function other than that of the cured product of the present invention. The forming method is not particularly limited and is formed by a known method. Wet coating methods such as a dry coating method such as vapor deposition and sputtering, a method using a rod or a wire bar, and a wet coating method such as a micro gravure, a gravure, a die, a curtain, a lip, a slot and a spin can be used. The material to be used is not limited, and if necessary, one or more kinds of functions such as information recording function, antiglare function, Newton ring function, adhesive function, blocking of specific wavelength, adhesion improvement, Can be used.

The information recording layer is not particularly limited as long as it can generate any chemical change by laser light or the like and record information by the change. Examples of organic materials include polymethine dyes, naphthalocyanine dyes, phthalocyanine dyes, squarylium dyes, anthraquinone dyes, xanthenes dyes, and triphenylmethane dyes. Two or more kinds of them can be used in combination. As the inorganic recording layer, metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu and Pt and semimetals may be used singly or in combination. The information recording layer may be a laminate or the like, and the mode of photochemical change may be any of a phase change, a bubble, and a hole type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb and Co, or a photochromic material based on spiropyran or a free-radical.

From the viewpoint of preventing reflection, it is also preferable that a cured film of high refractive index is used as a member provided with a cured film having a low refractive index and provided with an antireflection function. That is, it is preferable to use a member having a cured film formed by forming a cured film on a substrate such as a film and further forming a coated cured film on the surface layer, as the antireflection film.

It is preferable that the 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 substrate or between the cured film and the substrate It is preferable that the refractive index difference between the cured film and the lower layer in contact with the cured film is within ± 0.02.

The metal oxide composition of the present invention can produce a cured film as a cured product of high refractive index by controlling the kind and amount of the metal oxide to be added. As a result, it is preferable to use the optical semiconductor element encapsulant which is required to gradually decrease the refractive index of the cured film from the optical semiconductor element side toward the outermost layer in order to improve the light extraction efficiency of the optical semiconductor element.

Examples of the optical semiconductor element include gallium nitride (GaN: refractive index 2.5), gallium phosphor (GaP: refractive index 2.9), gallium arsenide (GaAs: refractive index 3.5) Accordingly, the refractive index of the cured product that becomes the optical semiconductor element encapsulant is preferably 1.5 or more, more preferably 1.5 to 2.1, and further preferably 1.7 to 2.1, from the viewpoint of increasing the light extraction efficiency.

As a method for achieving the optimum refractive index of the cured product, it is preferable to use titanium oxide (refractive index: 2.5 to 2.7), zirconium oxide (refractive index: 2.4), zinc oxide (refractive index: 1.95) Further, it is preferable to use the compound (A) having an aromatic skeleton because a high refractive index is required for the dispersing agent.

The present invention also relates to the following matters.

[1] A photosensitive resin composition comprising a compound (A) having at least 6 acryloyl groups, a metal oxide (B)

The compound (A)

Pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and at least one compound selected from the group consisting of 1,2,4,5-benzene tetracarboxylic acid dianhydride, 3,3 ', 4,4'- Biphenyltetracarboxylic acid dianhydride, 4'-biphenyltetracarboxylic acid dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, and 1,2,3,4- (X) having a carboxyl group, which is obtained by reacting a compound (X1)

Biphenyl glycidyl ether

And reacting the metal oxide with the metal oxide.

[2] A photosensitive composition comprising a compound (A) having at least 6 acryloyl groups, a metal oxide (B) and a solvent,

Wherein the compound (A) comprises a compound (A1) having at least 6 acryloyl groups represented by the following general formula (1).

In general formula (1)

[Chemical Formula 1]

(In the general formula (1), R ₁ represents any one of the tetravalent organic moieties shown below.

(2)

In the general formula (1), R ₂ represents any one of the following monovalent organic residues.

(3)

In the general formula (1), R ₃ represents the following monovalent organic residue.)

[Chemical Formula 4]

[3] The metal oxide composition according to [1] or [2], wherein R ₁ is an organic residue containing an aromatic ring.

[4] The metal oxide composition according to [3], wherein the aromatic ring is a biphenyl ring.

[5] The method according to any one of [1] to [4], wherein the metal oxide (B) contains at least one element selected from the group consisting of titanium, zinc, zirconium, indium, tin, aluminum, 0.0 > 1, < / RTI >

[6] The metal oxide composition according to any one of [1] to [5], wherein the D50 particle size of the metal oxide (B) is 0.005 to 0.200 μm.

[7] A cured film obtained by curing the metal oxide composition according to any one of [1] to [6].

[8] A member to which a cured film is attached, wherein the cured film described in [7] is provided on at least a part of the base.

The present invention relates to the subject matter of Japanese Patent Application No. 2015-100973, filed on May 18, 2015, the entire disclosure of which is incorporated herein by reference.

[Example]

Hereinafter, the present invention will be described in more detail based on Preparation Examples and Examples. In Production Examples and Examples, "parts" and "%" represent "mass parts" and "mass%", respectively.

The drugs used are as follows.

≪ Carboxylic anhydride >

3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride (manufactured by Mitsubishi Chemical Corporation, trade name: BPDA)

(3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Corporation, trade name: BPAF)

1,2,3,4-butanetetracarboxylic acid anhydride (manufactured by New Japan Chemical Co., Ltd., trade name: RIKACID BT-100)

1,2,4,5-benzenetetracarboxylic acid dianhydride (manufactured by Daicel Corporation, trade name: pyromellitic dianhydride, PMDA)

Phthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)

≪ Compound (x2) >

Pentaerythritol triacrylate (1) (trade name: KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd., pentaerythritol tetraacrylate as a by-product)

Pentaerythritol triacrylate (2) (trade name: A-TMM-3LM-N (trisester 57%) manufactured by Shin-Nakamura Chemical Co., Ltd., and pentaerythritol tetraacrylate as a by-

Dipentaerythritol pentaacrylate (DPPA) (trade name: A-9570W, manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate as a by-product)

<Acrylate Compound>

2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd., HEA)

<Polymerization inhibitor>

Methyl hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.)

<Catalyst>

1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.)

Dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.)

&Lt; Epoxy flame retardant compound &

Glycidyl methacrylate (methacryloglycidyl ether) (GMA manufactured by The Dow Chemical Company)

4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Chemical Co., Ltd., trade name: 4 hydroxybutyl acrylate glycidyl ether)

Biphenyl glycidyl ether (2-phenylphenyl glycidyl ether) (trade name: OPP-G, manufactured by Sanko Co., Ltd.)

(Production example)

(Synthesis Example 1: Dispersant (1))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 122.0 parts by weight of pentaerythritol triacrylate having a hydroxyl value of 122 mgKOH / g 250.0 parts of the compound (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone, and the mixture was heated to 60 占 폚. Subsequently, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured according to the titration method according to JIS K0070 (1992), which is a generic method, and found to be 94 mgKOH / g.

Subsequently, 140.0 parts of biphenyl glycidyl ether and 91.0 parts of cyclohexanone were added to this solution. Then, 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was reacted at 100 DEG C for 6 hours with stirring. The acid value of the reaction product was periodically measured while continuing the reaction. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish is light yellow transparent, has a solid content of 60%, and a final acid value of 3.0 mgKOH / g. Therefore, the reactant including the compound (A) in the solid content of the resin varnish obtained is 79%.

In the present specification, the reactant containing the compound (A) refers to a reactant containing a high molecular weight reactant derived from a by-product containing a plurality of hydroxyl groups in the compound (x2) in addition to the above-mentioned compound (A1) . The proportion of the reactants containing the compound (A) can be calculated from the final acid value of the resin varnish as described above. The remainder represents a compound having no hydroxyl group or an unreacted raw material in the compound (x2) used in the reaction. In Table 1, the reactant containing the compound (A) is abbreviated as &quot; reactant &quot;. The same applies to the following Synthesis Examples 2 to 5.

(Synthesis Example 2: Dispersant (2))

To a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer was charged 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 100.0 parts by weight of pentaerythritol triacrylate (2) having a hydroxyl value of 113 mgKOH / , 0.33 part of methylhydroquinone and 318.0 parts of cyclohexanone were charged and the temperature was raised to 60 占 폚. Then 2.41 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 95 mgKOH / g.

Then, 182.9 parts of biphenyl glycidyl ether and 118.0 parts of cyclohexanone were added to this solution. Then, 3.88 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 占 폚 for 6 hours. The acid value of the reaction product was periodically measured while continuing the reaction. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resulting resin varnish was light yellow transparent, and had a solid content of 60% and a final acid value of 3.0 mgKOH / g. Therefore, the reactant containing the compound (A) in the resulting solid of reaction product was 73%.

(Synthesis Example 3: Dispersant (3))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer, 80.0 parts of 1,2,4,5-benzene tetracarboxylic dianhydride and 100.0 parts by weight of pentaerythritol triacrylate (2) having a hydroxyl value of 113 mgKOH / , 0.31 part of methylhydroquinone and 294.1 parts of cyclohexanone were charged, and the temperature was raised to 60 占 폚. Then, 2.22 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 93 mgKOH / g.

Subsequently, 166.0 parts of biphenyl glycidyl ether and 107.1 parts of cyclohexanone were added to this solution, followed by addition of 3.58 parts of dimethylbenzylamine as a catalyst. The mixture was stirred at 100 DEG C for 6 hours, and the reaction was carried out periodically The acid value of the reaction product was measured. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resulting resin varnish was light yellow transparent, having a solid content of 60% and a final acid value of 3.0 mgKOH / g, and thus the reactant containing the compound (A) in the solid content of the obtained reaction product was 74%.

(Synthesis Example 4: Dispersant (4))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 85.0 parts of dipentaerythritol pentaacrylate having a hydroxyl value of 85 mgKOH / g 359.0 parts of methyl methacrylate, 0.29 parts of methylhydroquinone and 290.1 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 74 mgKOH / g. Thereafter, 123.1 parts of biphenyl glycidyl ether and 78.5 parts of cyclohexanone were added. Then, 3.53 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resultant resin varnish is light yellow transparent, has a solid content of 60% and a final acid value of 3.0 mgKOH / g. Therefore, the reactant containing the compound (A) in the solid content of the obtained resin varnish is 83%.

(Synthesis Example 5: Dispersant (5))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride and 95.0 parts of pentaerythritol triacrylate having a hydroxyl value of 122 mgKOH / g 160.2 parts of RATE (1), 0.16 parts of methylhydroquinone and 158.8 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then 1.20 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was determined by a conventional method and found to be 82 mgKOH / g.

Thereafter, 79.0 parts of biphenyl glycidyl ether and 50.7 parts of cyclohexanone were added. Then, 1.93 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish is light yellow transparent, has a solid content of 60%, and a final acid value of 3.0 mgKOH / g. Therefore, the reactant containing the compound (A) in the solid content of the resin varnish obtained is 79%.

(Synthesis Example 6: Dispersant (6))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 122.0 parts by weight of pentaerythritol triacrylate having a hydroxyl value of 122 mgKOH / g 250.0 parts of the compound (1), 0.24 parts of methylhydroquinone and 217.8 parts of cyclohexanone, and the mixture was heated to 60 占 폚. Subsequently, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 94 mgKOH / g.

Thereafter, 78.3 parts of glycidyl methacrylate and 54.0 parts of cyclohexanone were added. Then, 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow transparent, had a solid content of 60%, and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish was 76%. In addition, the reactant does not contain the compound (A). The same is applied to the following Synthesis Examples 7 to 17.

(Synthesis Example 7: Dispersant (7))

To a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer was charged 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 100.0 parts by weight of pentaerythritol triacrylate (2) having a hydroxyl value of 113 mgKOH / , 0.34 parts of methylhydroquinone and 203.8 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then 1.75 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 95 mgKOH / g.

Thereafter, 116.4 parts of glycidyl methacrylate and 188.5 parts of cyclohexanone were added. Then, 3.88 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow transparent, had a solid content of 60% and a final acid value of 3.0 mgKOH / g, and thus the reactivity in the solid content of the obtained resin varnish was 71%.

(Synthesis Example 8: Dispersant (8))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of phthalic anhydride, 268.7 parts of pentaerythritol triacrylate (2) having a hydroxyl value of 113 mgKOH / g, 0.25 parts of methylhydroquinone, And the temperature was raised to 60 占 폚. Then 1.74 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 88 mgKOH / g.

Thereafter, 122.2 parts of biphenyl glycidyl ether and 78.7 parts of cyclohexanone were added. Then, 2.81 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resultant resin varnish is light yellow transparent, has a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish is 75%.

(Synthesis Example 9: Dispersant (9))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of phthalic anhydride, 268.7 parts of pentaerythritol triacrylate (2) having a hydroxyl value of 113 mgKOH / g, 0.25 parts of methylhydroquinone, And the temperature was raised to 60 占 폚. Then 1.74 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 88 mgKOH / g.

Thereafter, 77.8 parts of glycidyl methacrylate and 49.1 parts of cyclohexanone were added. Then, 2.80 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resulting resin varnish was light yellow transparent, having a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish was 72%.

(Synthesis Example 10: Dispersant (10))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer, 80.0 parts of 1,2,4,5-benzene tetracarboxylic dianhydride and 100.0 parts by weight of pentaerythritol triacrylate (2) having a hydroxyl value of 113 mgKOH / , 0.31 part of methylhydroquinone and 293.9 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then, 2.22 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 93 mgKOH / g.

Thereafter, 105.6 parts of glycidyl methacrylate and 66.9 parts of cyclohexanone were added. Then, 3.58 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The obtained resin varnish was light yellow transparent, had a solid content of 60% and a final acid value of 3.0 mgKOH / g, and thus the reactivity in the solid content of the obtained resin varnish was 71%.

(Synthesis Example 11: Dispersant (11))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride and 95.0 parts of pentaerythritol triacrylate having a hydroxyl value of 122 mgKOH / g 160.2 parts of RATE (1), 0.16 parts of methylhydroquinone and 158.8 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then 1.20 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was determined by a conventional method and found to be 82 mgKOH / g.

Thereafter, 50.3 parts of glycidyl methacrylate and 31.6 parts of cyclohexanone were added. Then, 1.94 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resultant resin varnish is light yellow transparent, has a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish is 75%.

(Synthesis Example 12: Dispersant (12))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 85.0 parts of dipentaerythritol pentaacrylate having a hydroxyl value of 85 mgKOH / g 359.0 parts of methyl methacrylate, 0.29 parts of methylhydroquinone and 290.1 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 74 mgKOH / g. Thereafter, 78.3 parts of glycidyl methacrylate and 48.7 parts of cyclohexanone were added. Then, 3.53 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resulting resin varnish was light yellow transparent, had a solid content of 60% and a final acid value of 3.0 mgKOH / g, and thus the reactivity in the solid content of the obtained resin varnish was 69%.

(Synthesis Example 13: Dispersant (13))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer, 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl 63.1 parts of acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 215 mgKOH / g. Thereafter, 78.3 parts of glycidyl methacrylate and 51.1 parts of cyclohexanone were added. Then, 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resultant resin varnish was light yellow transparent, had a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish was 87%.

(Synthesis Example 14: Dispersant (14))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 533.3 parts of dipentaerythritol pentaacrylate having a hydroxyl value of 85 mgKOH / g 0.37 parts of methylhydroquinone, and 405.5 parts of cyclohexanone were charged, and the temperature was raised to 60 占 폚. Then, 3.07 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 75 mgKOH / g. Thereafter, 116.4 parts of glycidyl methacrylate and 72.6 parts of cyclohexanone were added, and then 4.93 parts of dimethylbenzylamine was added as a catalyst. The mixture was stirred at 100 DEG C for 6 hours, and the acid value of the reaction product was measured periodically When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resultant resin varnish was light yellow transparent, had a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish was 68%.

(Synthesis Example 15: Dispersant (15))

A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube and a thermometer was charged with 80.0 parts of 1,2,3,4-butanetetracarboxylic dianhydride and 2 parts of 2-hydroxyethyl acrylate 93.7 having a hydroxyl value of 483 mgKOH / g , 0.15 part of methylhydroquinone and 114.8 parts of cyclohexanone were charged, and the temperature was raised to 60 占 폚. Then, 0.87 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 264 mgKOH / g. Thereafter, 116.4 parts of glycidyl methacrylate and 76.2 parts of cyclohexanone were added. Then, 1.4 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resulting resin varnish was light yellow transparent, had a solid content of 60% and a final acid value of 3.0 mgKOH / g, and thus the reactivity in the solid content of the obtained resin varnish was 86%.

(Synthesis Example 16: Dispersant (16))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer, 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl 63.1 parts of acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 215 mgKOH / g. Thereafter, 123.1 parts of biphenyl glycidyl ether and 80.9 parts of cyclohexanone were added. Then, 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 DEG C for 6 hours. While continuing the reaction, the acid value of the reaction product When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resin varnish thus obtained was light yellow transparent, having a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish was 89%.

(Synthesis Example 17: Dispersant (17))

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introducing tube, and a thermometer, 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl 63.1 parts of acrylate, 0.11 part of methylhydroquinone and 94.6 parts of cyclohexanone, and the temperature was raised to 60 占 폚. Then, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, followed by stirring at 90 占 폚 for 8 hours. After confirming that the peak of the acid anhydride group, that is, the peak near 1780 cm ^-1 and 1850 cm ^-1 , was cut by the IR measurement of the reactant, the reaction was stopped by cooling. At this point, the acid value of the reactant was measured by a conventional method and found to be 215 mgKOH / g. Thereafter, 108.8 parts of 4-hydroxybutyl acrylate glycidyl ether and 71.4 parts of cyclohexanone were added. Then, 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. While continuing the reaction, , The acid value of the reaction product was measured. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature. The resin varnish thus obtained was light yellow transparent, having a solid content of 60% and a final acid value of 3.0 mgKOH / g, so that the reactivity in the solid content of the obtained resin varnish was 89%.

Table 1 summarizes the synthesis.

Table 1 shows the outline of the reactants obtained in Synthesis Examples.

[Table 1]

(Preparation of Metal Oxide Paste)

A metal oxide dispersion paste was prepared by dispersing the metal oxide (B) by using the resin varnish containing the compound (A) prepared in the above Production Example and by adding the components shown in Table 2 together (see Table 2 , The ratio of the reactants to 100 parts by weight of the metal oxide indicates the solid content). The dispersion was carried out in the same manner as in Kotobuki Industries Co., Ltd. using zirconia beads (0.1 mm) as a medium, and the total dispersion (zirconia beads (0.5 mm) as a medium and dispersing with a paint shaker for 1 hour). Dispersed in a disperser UAM-015).

[Table 2]

In Table 2,

ZrO ₂ : "PCS-60" (average primary particle size: 20 nm) manufactured by Nihondenko Co.,

TiO ₂ : "MT-05" (average primary particle diameter: 10 nm) manufactured by Taica Corporation,

Sb ₂ O ₅ : "Sun Epoch EFR-6N" (average primary particle diameter: 20 nm) manufactured by Nissan Chemical Industries, Limited,

ATO: SN-100P (average primary particle diameter: 20 nm) manufactured by Ishihara Sangyo Kaisha, Ltd.

ITO: &quot; Nanotek ITO &quot; (average primary particle diameter: 30 nm) manufactured by CI Kasei Co.,

PTO: "EP SP-2" (average primary particle diameter: 15 nm) manufactured by Mitsubishi Materials Corporation,

ZnO: FINEX-50 (average primary particle diameter: 20 nm) manufactured by Sakai Chemical Industry Co.,

SiO ₂ : "AEROSIL 50" (average primary particle size: 50 nm) manufactured by Nippon Aerosil Co.,

Al ₂ O ₅ : "Aluminum Oxide C" (average primary particle diameter: 13 nm) manufactured by Nippon Aerosil Co., Ltd.

MEK: methyl ethyl ketone

Methoxybutanol: 3-methoxy-1-butanol

(Assessment Methods)

(1) Dispersibility

<State immediately after dispersion>

The state of the obtained metal oxide dispersion paste was visually observed.

A: There is liquidity.

B: It is solidified, but fluidity can be confirmed by gently shaking it.

C: It is solidified.

<D50 particle size>

The D50 particle diameter of the obtained metal oxide paste was measured using "NANOTRAC UPA" manufactured by Nikkiso Co., Ltd. Practically, it is preferably 200 nm or less.

&Lt; Painting and cured film evaluation: Examples 1 to 19, Comparative Examples 1 to 12 >

Using the metal oxide paste prepared above, a metal oxide composition having the composition shown in Table 3 was prepared. The resulting metal oxide composition was coated on this adhesive-treated PET film ("Cosmo Shine A-4100" manufactured by Toyobo Co., Ltd.) with a thickness of 3 μm by a bar coater to a thickness of 3 μm, And irradiated with ultraviolet rays of 400 mJ / cm ^{2 by} a lamp to form a cured film (hard coat layer). The scratch resistance, pencil hardness and transparency (haze) of the obtained cured film were evaluated by the following methods. The results are shown in Table 3.

[Table 3]

In Table 3,

Photopolymerization initiator: "IRGACURE 184" manufactured by Ciba Specialty Chemicals, Inc.

Solvent: PGME (propylene glycol monomethyl ether)

* 1: Since the metal oxide paste was poorly dispersed,

(Assessment Methods)

(1) Transparency (Haze value)

The haze value in the obtained coating material was measured using a haze meter. Practically, the turbidity is preferably 1.0% or less.

(2) Pencil hardness

In accordance with JIS-K5600, the pencil hardness tester (ScratchingTester HEIDON-14 manufactured by HEIDON Co., Ltd.) was used, and the hardness of the pencil core was varied in various ways. The hardness of the core when no scratches occurred or only one time of scratches occurred in 5 times was defined as the pencil hardness of the cured film. Considering practical requirements, the pencil hardness of the cured film is preferably in the range of,

2H or more: A

1H or more: B

Less than 1H: D

Respectively.

(3) Scratch resistance

The pottery was set in a gauge tester, and the sample was graded 10 times at a load of 250 g using No.0000 steel wool. The degree of occurrence of scratches was determined according to the following five-stage visual evaluation. The larger the value, the better the scratch resistance of the cured film.

5: No scratches

4: There is some scratches.

3: Scratches are formed, but no substrate is seen.

2: Scratches were formed, and some of the cured films were peeled off.

1: Cured film peeled off, substrate exposed

From the results shown in Table 3, it was found that the members to which the cured films were applied using the curable compositions of Examples 1 to 16 were excellent in balance of transparency, pencil hardness and scratch resistance. Therefore, the member to which the cured coating film is adhered can be suitably used for applications requiring hard coatability and transparency such as a display, a touch panel, and a building material.

On the contrary, the metal oxide paste 17 and the metal oxide pastes 20 to 23 using the dispersing agent having a different resin structure can not produce a metal oxide paste. In Comparative Example 1 and Comparative Examples 4 and 7, Evaluation of the attached member was not possible.

The metal oxide paste using the dispersing agent having a different resin structure and the cured film of Comparative Example 2 and Comparative Example 3 and Comparative Example 9 with a cured film had insufficient transparency.

The member having the cured film using the curable composition of Comparative Example 8 and Comparative Examples 10 to 12 of the metal oxide paste using the dispersing agent having a different resin structure had insufficient transparency, pencil hardness and scratch resistance.

The metal oxide composition according to the present invention can be used not only for optical film members, but also for various plastic molded articles, lenses on the outermost surface of a camera, lens for glasses, window glass for buildings and vehicles, It can also be used to give the same function.

Claims (8)

(A) having at least 6 acryloyl groups, a metal oxide (B), and a solvent,
The compound (A)
Pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and at least one compound selected from the group consisting of 1,2,4,5-benzene tetracarboxylic acid dianhydride, 3,3 ', 4,4'- (3,4-dicarboxyphenyl) fluorene dianhydride, and 1,2,3,4-butanetetracarboxylic acid dianhydride, from the group consisting of 4'-biphenyltetracarboxylic acid dianhydride, 9,9- A compound (X) having a carboxyl group, which is obtained by reacting one or more compounds (x1)
Biphenyl glycidyl ether
And reacting the metal oxide with the metal oxide.
(A) having at least 6 acryloyl groups, a metal oxide (B), and a solvent,
Wherein the compound (A) comprises a compound (A1) having at least 6 acryloyl groups represented by the following general formula (1).
In general formula (1)
[Chemical Formula 1]

(In the general formula (1), R ₁ represents any one of the tetravalent organic moieties shown below.
(2)

In the general formula (1), R ₂ represents any one of the following monovalent organic residue.
(3)

In the general formula (1), R ₃ represents the following monovalent organic residue.)
[Chemical Formula 4]

3. The method according to claim 1 or 2,
Wherein R &lt; _{1 &gt;} is an organic moiety comprising an aromatic ring.
The method of claim 3,
Wherein the aromatic ring is a biphenyl ring.
5. The method according to any one of claims 1 to 4,
Wherein the metal oxide (B) contains at least one element selected from the group consisting of titanium, zinc, zirconium, indium, tin, aluminum, silicon and phosphorus.
6. The method according to any one of claims 1 to 5,
Wherein the metal oxide (B) has a D50 particle diameter of 0.005 to 0.200 m.
A cured film obtained by curing the metal oxide composition according to any one of claims 1 to 6.
A member to which a cured film is attached, wherein the cured film according to claim 7 is provided on at least a part of the base.