JP4692630B2 - Method for producing metal oxide dispersion, laminate and dispersant - Google Patents

Description

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

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a hard coat coating film having scratch resistance, adhesion, high refractive index, etc., using a photometal oxide composition on the surface of the equipment, An antistatic coating film is formed.
In recent years, there has been remarkable progress in the development and generalization of information and communication equipment, and there has been a demand for further improvements in performance and productivity such as hard coat coatings and antistatic coatings. Various proposals used have been made.

For example, the following technical proposals can be cited (see Patent Documents 1 to 3). Patent Document 1 discloses a method of preparing a conductive paint by mixing conductive powder such as tin oxide and a plurality of monomer components in an organic solvent using a ball mill or the like. Patent Document 2 discloses a method of preparing a dispersion for conductive paint by mixing antimony-doped tin oxide and an ultraviolet curable silane coupling agent in an organic solvent using a ball mill. Further, Patent Document 3 discloses a method of preparing a conductive coating material by dispersing conductive oxide fine powder in a mixed solvent of an easily dispersible low boiling point solvent and a hardly dispersible high boiling point solvent.
(Patent Document 1) Japanese Patent Application Laid-Open No. 04-172634 (Patent Document 2) Japanese Patent Application Laid-Open No. 06-264209 (Patent Document 3) Japanese Patent Application Laid-Open No. 2001-131485

However, even if it is possible to produce a metal oxide composition having good physical properties in terms of high refractive index, hard coat properties, antistatic properties, light resistance, etc. by the above method, hydrophobicity such as organic solvents. Since it is impossible to stably disperse and stabilize metal oxides with an average primary particle size of 100 nm or less at the primary particle level for a high medium, the transparency of the coating film and the temporal stability of the photocurable paint, etc. Prone to problems from the viewpoint of
Accordingly, the present invention provides a coating film having excellent physical properties in all of high refractive index properties, antistatic properties, hard coat properties, transparency and light resistance while containing a metal oxide having an average primary particle size of 100 nm or less. It is an object to provide a metal oxide composition that is stable over time, a cured film using the same, and a laminate thereof.

（式中、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子またはメチル基を示し、Ｒ^５〜Ｒ^８は、それぞれ独立に非置換もしくは置換の、直鎖もしくは分岐鎖のアルキレン基またはアルキレンオキシアルキレン基を示し、Ｒ^９は、４価の芳香族基または脂肪族基を示す。）The present invention relates to a dispersant (A) represented by the following general formula (1) and a metal oxide composition containing a metal oxide having an average primary particle size of 5 to 100 nm.
General formula (1):

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

Another aspect of the present invention relates to a cured film formed by curing the metal oxide composition.
Another aspect of the present invention relates to a laminate including a base material and the cured film.
Another aspect of the present invention relates to an optical semiconductor element sealing material containing the metal oxide composition.

（式中、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子またはメチル基を示し、Ｒ^５〜Ｒ^８は、それぞれ独立に非置換もしくは置換の、直鎖もしくは分岐鎖のアルキレン基またはアルキレンオキシアルキレン基を示し、Ｒ^９は、４価の芳香族基または脂肪族基を示す。）Another present invention uses a dispersant (A) represented by the following general formula (1), and includes dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in the presence of an organic solvent. The present invention relates to a method for producing an oxide dispersion.
General formula (1):

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

  Yet another aspect of the present invention relates to a method for producing a cured film, comprising: applying the metal oxide composition to a substrate; and irradiating active energy rays to cure the metal oxide composition.

（式中、Ｒ^１〜Ｒ^４は、それぞれ独立に水素原子またはメチル基を示し、Ｒ^５〜Ｒ^８は、それぞれ独立に非置換もしくは置換の、直鎖もしくは分岐鎖のアルキレン基またはアルキレンオキシアルキレン基を示し、Ｒ^９は、４価の芳香族基または脂肪族基を示す。）The metal oxide composition according to the present invention contains a dispersant (A) represented by the following general formula (1) and a metal oxide having an average primary particle diameter of 5 to 100 nm, and two or more kinds thereof. The metal oxide and two or more kinds of dispersants (A) may be included.
General formula (1):

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

This dispersant (A) has high dispersibility and photocurability with respect to the metal oxide. When the dispersant (A) increases the dispersibility of the metal oxide having an average primary particle diameter of 5 to 100 nm and enhances the photocurability, the metal oxide composition of the present invention is excellent in curability and hard coat. It is possible to form a cured film and a laminate thereof having excellent properties, transparency, light resistance, high refractive index, and antistatic properties. Therefore, it can be suitably used particularly for plastic optical parts, optical disks, antireflection films, touch panels, film-type liquid crystal elements, and can also be suitably used as a hard coat agent for various plastic laminates.
This metal oxide composition can form a cured film having a high refractive index. When this metal oxide composition is applied to a base material having the same refractive index, the resulting laminate does not produce reflection interference fringes, and is optical. It is suitably used for applications. Furthermore, since the refractive index of the hardened | cured material containing a metal oxide is controllable highly, it is suitable also as an optical semiconductor element sealing material.

In the above formula (1), the tetravalent aromatic group of R ⁹ specifically includes phenyl skeleton, benzophenone skeleton, biphenyl skeleton, phenyl ether skeleton, diphenyl sulfone skeleton, diphenyl sulfide skeleton, perylene skeleton, fluorene skeleton, tetrahydro A naphthalene skeleton, a naphthalene skeleton, etc. are mentioned. Among these, it is preferable that R ⁹ is at least one selected from the group consisting of a biphenyl skeleton, a naphthalene skeleton, a fluorene skeleton, and a tetrahydronaphthalene skeleton.

As the tetravalent aliphatic skeleton of R ^9, a tetravalent aliphatic group which is an alkyl skeleton having 4 to 10 carbon chains is a preferred example, specifically, a butane skeleton, a cyclobutane skeleton, a hexane skeleton, a cyclohexane skeleton. And decalin skeleton.

In the above formula (1), examples of the unsubstituted or substituted linear or branched alkylene group represented by R ^{5 to} R ⁸ include alkylene groups such as a methylene group, an ethylene group, and a C3 to C10 polymethylene group. . Examples of the unsubstituted or substituted linear or branched alkyleneoxyalkylene group include a C3 alkylene-oxy-C3 alkylene group. These alkylene groups or alkyleneoxyalkylene groups are derived from the following first and second hydroxyl group-containing (meth) acrylate compounds as raw materials. Examples of the substituent that can be taken by the alkylene group or the alkyleneoxyalkylene group include alkyl groups such as methyl group and ethyl group, hydroxyl group, acryloyloxymethyl group, acryloyloxyethyl group, and phenoxy group.

  The dispersant (A) represented by the general formula (1) includes, for example, an aromatic skeleton or an aliphatic skeleton, and a compound (x1) having two or more carboxylic anhydride groups, a carboxylic anhydride group, It can be obtained by reacting a compound (X) having a carboxyl group obtained by reacting a compound (x2) having a functional group capable of reacting with a compound (Y) having a functional group capable of reacting with a carboxyl group. Here, from the viewpoint of photocurability and hard coat properties, it is preferable that at least a part of the compound (x2) and the compound (Y) have a polymerizable unsaturated double bond group.

Examples of the “functional group capable of reacting with a carboxylic anhydride group” in the compound (x2) include a hydroxy group, an amino group, and a glycidyl group, and a hydroxy group is particularly preferable because of easy control of the reaction. Therefore, the compound (x2) is preferably an acrylate compound or a methacrylate compound having one or two hydroxyl groups.
Examples of the “functional group capable of reacting with a carboxyl group” in the compound (Y) include an epoxy group, an oxazoline group, a hydroxy group, an amino group, a carbodiimide group, an isocyanate group, an isothiocyanate group, and a vinyl ether group.

（ここで、Ｒ^９は、一般式（１）で定義した通り）
で示される芳香族または脂肪族テトラカルボン酸二無水物を、カルボン酸無水物基と反応しうる官能基を有する化合物（ｘ２）である、下記一般式（３）：
ＣＨ_２＝Ｃ（Ｒ^１）ＣＯＯＲ^５ＯＨ 一般式（３）
（ここで、Ｒ^１およびＲ^５は、式（１）で定義した通り）
で示される第１のヒドロキシル基含有アクリレート化合物またはメタクリレート化合物、および下記一般式（４）：
ＣＨ_２＝Ｃ（Ｒ^２）ＣＯＯＲ^６ＯＨ 一般式（４）
（ここで、Ｒ^２およびＲ^６は、式（１）で定義した通り）
で示される第２のヒドロキシル基含有アクリレート化合物またはメタクリレート化合物と反応させて、下記一般式（５）：
一般式（５）

（ここで、Ｒ^１、Ｒ^２、Ｒ^５、Ｒ^６およびＲ^９は、式（１）で定義した通り）
で示される化合物（Ｘ）を得ることができる。Furthermore, an example is given and demonstrated. The following general formula (2), which is a compound (x1) having an aromatic skeleton or an aliphatic skeleton and two or more carboxylic anhydride groups:
General formula (2)

(Where R ⁹ is as defined in general formula (1))
A compound (x2) having a functional group capable of reacting an aromatic or aliphatic tetracarboxylic dianhydride represented by the following general formula (3):
^{_{CH 2 = C (R 1)}} COOR 5 OH Formula (3)
(Where R ¹ and R ⁵ are as defined in formula (1))
And a first hydroxyl group-containing acrylate compound or methacrylate compound represented by the following general formula (4):
^{_{CH 2 = C (R 2)}} COOR 6 OH Formula (4)
(Where R ² and R ⁶ are as defined in Formula (1))
Is reacted with a second hydroxyl group-containing acrylate compound or methacrylate compound represented by the following general formula (5):
General formula (5)

(Where R ¹ , R ² , R ⁵ , R ⁶ and R ⁹ are as defined in formula (1))
The compound (X) shown by can be obtained.

  Here, the “acrylate group or methacrylate group” is a concept that includes or includes both an acrylate group and a methacrylate group. Hereinafter, acrylate and methacrylate may be collectively referred to as “(meth) acrylate”.

  Examples of the aromatic tetracarboxylic dianhydride represented by the above general formula (2) include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride having a biphenyl skeleton, and oxydiphthalic acid dianhydride. 9,9- having a fluorene skeleton, such as an anhydride, diphenylsulfone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride having a naphthalene skeleton Bis (3,4-dicarboxyphenyl) fluorene dianhydride, or 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, tetrahydronaphthalenecarboxyl having a tetrohydronaphthalene skeleton Acid dianhydride, ethylene glycol Bis (anhydrotrimellitate), glycerin bis (anhydrotrimellitate) monoacetate, and the like.

Commercially available products include “Ricacid TMTA-C”, “Ricacid MTA-10”, “Ricacid MTA-15”, “Ricacid TMEG series”, “Ricacid TDA”, “Ricacid DSDA”, etc. Can be mentioned.
Among these aromatic tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton can be efficiently introduced into the molecule of the compound represented by formula (1). This is particularly preferable because it can have both hard coat properties of the cured film and good dispersibility of the metal oxide.

  Examples of the aliphatic tetracarboxylic dianhydride represented by the general formula (2) include butanetetracarboxylic dianhydride.

  The first and second hydroxyl group-containing (meth) acrylate compounds may be the same or different from each other. Examples of such hydroxyl group-containing (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxybutyl (meth). Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic 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 Ritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Is mentioned. In the case of increasing the hardness, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

Specific commercial products include Biscoat # 300 (manufactured by Osaka Organic Chemical Co., Ltd.), KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.), PETIA (manufactured by Daicel UCB Co., Ltd.), Aronix M305 (Toagosei Co., Ltd.) NK ester A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-444 (manufactured by Sartomer Co.), light acrylate Examples include DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), Aronix M402 (manufactured by Toagosei Co., Ltd.), and the like.
In particular, KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) containing pentaerythritol tri (meth) acrylate as a main component is more preferable because the dispersibility of the metal oxide is good. In the case of a polyfunctional (meth) acrylate compound, by containing about 5 to 15% by weight of a polyfunctional (meth) acrylate having two hydroxyl groups as an accessory component, the weight average molecular weight after curing of the resulting dispersant (A) Is preferred because it tends to increase the molecular weight and the dispersibility of the metal oxide becomes better.

  The reaction of the aromatic or aliphatic tetracarboxylic dianhydride with the first and second hydroxyl group-containing (meth) acrylate compounds is carried out by using two carboxylic acids possessed by the aromatic or aliphatic tetracarboxylic dianhydride. This is a reaction between an anhydride group and a hydroxyl group contained in each of the first and second hydroxyl group-containing (meth) acrylate compounds, and as such is well known in the art. For example, the aromatic tetracarboxylic dianhydride and the first and second hydroxyl group-containing (meth) acrylate compounds are mixed with 1,8-diazabicyclo [5.4.0] -7 in an organic solvent such as cyclohexanone. The reaction can be carried out at a temperature of 50 to 120 ° C. in the presence of a catalyst such as undecene. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.

（ここで、Ｒ^０は、ＣＨ_２＝Ｃ（Ｒ^３）−Ｃ（Ｏ）Ｏ−基およびＣＨ_２＝Ｃ（Ｒ^４）−Ｃ（Ｏ）Ｏ−基；Ｒ^３およびＲ^４は、上記定義の通り）
であるエポキシ基含有化合物を添加し、反応させて一般式（１）で示される化合物を得ることができる（この場合、Ｒ^７およびＲ^８は、−ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−基である。）。After the reaction, the reaction product containing the compound (X) of the formula (5), which is a reaction product, is purified without purification, for example, the following general formula (6), which is the compound (Y):
General formula (6)

(Where 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)
And a compound represented by the general formula (1) can be obtained (in this case, R ⁷ and R ⁸ are —CH ₂ CH (OH) CH ₂ — groups). is there.).

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

  The reaction between the compound represented by formula (5) and the compound represented by formula (6) is a reaction between the carboxyl group possessed by the compound represented by formula (5) and the epoxy group possessed by the compound represented by formula (6). As such, it is well known in the art. For example, this reaction can be performed at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.

  These reactions may be carried out without solvent or in a solvent inert to the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene and toluene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; diethyl ether, tetrahydrofuran or Ether solvents such as dioxane; Halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazo Examples include polar solvents such as lysinone. Two or more of these solvents may be used in combination.

Next, the metal oxide contained in the metal oxide composition is a metal oxide having an average primary particle size 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 a metal oxide having an average primary particle diameter of less than 5 nm, the cohesive force between the fine particles is very large, so that it is very difficult to disperse at a primary particle level with high transparency. On the other hand, in the case of a metal oxide having an average primary particle size of more than 100 nm, it is easy to disperse at the primary particle level, but since the particle size is large, scattering is likely to occur with respect to light such as visible light. There arises a problem that deteriorates the transparency.

The metal oxide is preferably one containing at least one element selected from the group consisting of titanium, zinc, zirconium, antimony, indium, tin, aluminum, silicon, phosphorus and fluorine. In particular, a metal oxide containing any one element of antimony, indium, and tin is more preferable because of its good conductivity.
Specifically, antimony pentoxide, 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 zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, aluminum-doped zinc oxide, titanium oxide, zinc oxide, zirconium oxide, silicon oxide, aluminum oxide and the like. These metal oxides may be used in combination of two or more.

As a commercial product of metal oxide,
NISSAN CHEMICAL INDUSTRY CO., LTD .: Sanepoch EFR-6N, Sanepoch EFR-6NP (antimony pentoxide),
Ishihara Sangyo Co., Ltd .: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO-coated titanium oxide), TTO-55 (A ) (Titanium oxide), TTO-55 (B) (titanium oxide), TTO-55 (C) (titanium oxide), TTO-55 (D) (titanium oxide), TTO-55 (S) (titanium oxide), TTO-55 (N) (titanium oxide), TTO-51 (A) (titanium oxide), TTO-51 (C) (titanium oxide), TTO-S-1 (titanium oxide), TTO-S-2 (oxidation) 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 (iron-containing titanium oxide), TTO- 11 (iron-containing titanium oxide), ST-01 (titanium oxide), ST-21 (titanium oxide), ST-30L (titanium oxide), ST-31 (titanium oxide),
Mitsubishi Materials Corporation: T-1 (ITO), S-1200 (tin oxide), EP SP-2 (phosphorus-doped tin oxide),
Mitsui Kinzoku Kogyo Co., Ltd .: Pastoran (ITO, ATO),
CI Kasei Co., Ltd.: NANOTEC ITO, NANOTEC SnO _2, NANOTEC TiO _2, NANOTEC SiO _2, Nanotech _Al 2 _{O 3,} NANOTEC ZnO,
Catalyst Chemical Industry Co., Ltd .: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-130 (ITO),
Hakusuitec Co., Ltd .: PazetCK (aluminum-doped zinc oxide),
Sakai Chemical Industry Co., Ltd .: 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 Co., Ltd .: OZC-3YC (zirconium oxide), OZC-3YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide),
NIPPON Denko Co., Ltd .: PCS (zirconium oxide), PCS-60 (zirconium oxide), PCS-90 (zirconium oxide), T-01 (zirconium oxide),
Made by Teika Co., Ltd .: 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 (zinc oxide) ), MZ-505M (zinc oxide),
Made by Nippon Aerosil Co., Ltd .: Aluminum Oxide C (aluminum oxide), AEROSIL130 (silicon oxide), AEROSIL200 (silicon oxide), AEROSIL200V (silicon oxide), AEROSIL200CF (silicon oxide), AEROSIL200FA (silicon oxide), AEROSIL300 (silicon oxide) , AEROSIL300CF (silicon oxide), AEROSIL380 (silicon oxide), AEROSILR972 (silicon oxide), AEROSILR974 (silicon oxide), AEROSILR976 (silicon oxide), AEROSILR202 (silicon oxide), AEROSILR805 (silicon oxide), AEROSILR812 (ILO), 8ER (Silicon oxide), AEROSILMO 50 (silicon oxide), AEROSILTT600 (silicon oxide), AEROSILMOX80 (silicon oxide / aluminum oxide), AEROSILMOX170 (silicon oxide / aluminum oxide), AEROSILCOX84 (silicon oxide / aluminum oxide),
Etc.

  The addition amount of the metal oxide in the metal oxide composition is not particularly limited, but is preferably 1 to 80 parts by weight, more preferably 10 parts in 100 parts by weight of the total solid content of the dispersant (A) and the metal oxide. -70 parts by weight. When the addition amount of the metal oxide is less than 1 part by weight, the antistatic property derived from the metal oxide may be inferior, and when it exceeds 80 parts by weight, the film forming property may be inferior due to the small amount of the organic component.

  Even if the metal oxide composition of the present invention is prepared by simply mixing the dispersant (A) and the metal oxide powder, the intended effect can be obtained sufficiently. However, it can be mixed mechanically with a kneader, roll, attritor, super mill, dry pulverizer, etc., or a suspension containing a metal oxide powder and an organic solvent can be added to a suspension containing a dispersant (A) to Even better results can be obtained if the reaction is carried out in a close mixing system such as depositing the dispersant (A) on the oxide surface.

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 using a dispersant (A) and dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in the presence of an organic solvent.
As the degree of dispersion, when measured with “Nanotrack UPA” manufactured by Nikkiso Co., Ltd. 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 dispersing agent (A), metal oxide or metal oxide composition in a non-aqueous vehicle such as an organic solvent, and mixing thereof, a paint conditioner (manufactured by Red Devil), a ball mill, Sand mill (Shinmaru Enterprises "Dynomill", etc.), Attritor, Pearl Mill (Eirich "DCP Mill", etc.), Coball Mill, Homomixer, Homogenizer (M Technique Co., Ltd. "Clearmix", etc.), wet jet A disperser such as a mill (“Genus PY” manufactured by Genus Co., Ltd., “Nanomizer” manufactured by Nanomizer Co., Ltd.), a micro bead mill (“Super Apec Mill”, “Ultra Apec Mill” manufactured by Kotobuki Industries Co., Ltd.), etc. can be used. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and used in stages.

  The metal oxide composition of the present invention contains at least the dispersant (A) and the metal oxide, and further contains a solvent and various additives within a range that does not impair the object and effect of the present invention. it can. Specifically, solvents, photopolymerization initiators, photocurable compounds, polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared rays Examples include absorbents, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments, and dyes.

  It does not restrict | limit especially as a manufacturing method of the metal oxide composition containing components other than a dispersing agent (A) and a metal oxide, Several methods are mentioned. Specifically, the dispersant (A) and the metal oxide are first mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and then various other additives are added and adjusted to produce. Method: A method of dispersing and producing from the beginning in a state where all of the dispersant (A), metal oxide, organic solvent and other additives are mixed.

  When adding a solvent, it is preferable to perform a curing treatment after volatilizing the solvent. The solvent is not particularly limited, and various known organic solvents 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 adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, and methyl pyrrolidone. These organic solvents may be used in combination of two or more.

  Among them, the hydroxyl group-containing solvent has good wettability with respect to a metal oxide having a highly hydrophilic particle surface property. Therefore, when it is contained in the solvent composition, the dispersibility of the metal oxide and its paint ( This is preferable because it is very effective in improving the temporal stability of the metal oxide composition) and the leveling property of the coating process is also improved. The hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to 100% by 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 Examples thereof include monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, and propylene glycol monomethyl ether. 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 the metal oxide become better.

  The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl compounds. Etc. can be used.

  Specifically, as the monocarbonyl compound, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) 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) ) Metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3 4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline, and the like.

Examples of dicarbonyl compounds include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.
Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one Polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla Mino-1- (4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino -Propanonyl) -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 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) cyclopenta Non etc. are mentioned.
Commercially available photopolymerization initiators include Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, manufactured by Ciba Specialty Chemicals Co., Ltd., Lucilin TPO manufactured by BASF, Esacure One manufactured by Nippon Sibel Hegner, Inc. can give.

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 alone or in combination of two or more.
The amount of the photopolymerization initiator used is not particularly limited, but the total amount of the photocurable compound including the dispersant (A) (when the following photocurable compound is optionally included, the dispersant (A) and the light The total amount of the curable compound) is preferably used within a range of 1 to 20 parts by weight per 100 parts by weight.
A known organic amine or the like can be added as a sensitizer.
Furthermore, in addition to the radical polymerization initiator, a cationic polymerization initiator may be used in combination.

The metal oxide composition may contain other binder resin and a photocurable compound in addition to the dispersant (A).
Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, vinyl resin. Etc. These resins may be used alone or in combination of two or more. The binder resin is preferably used within a range of 20 parts by weight or less based on the total amount of solids (components other than the solvent; hereinafter the same) of the metal oxide composition (100 parts by weight).

  As a photocurable compound, for example, a compound having a polymerizable unsaturated double bond group such as a (meth) acrylic compound, a fatty acid vinyl compound, an alkyl vinyl ether compound, an α-olefin compound, a vinyl compound, and an ethynyl compound is used. Can do. These compounds 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, or a silanol group. This photocurable compound is preferably used in a range of less than 50 parts by weight, particularly in a range of 5 to 40 parts by weight, based on the total solid content of the metal oxide composition (100 parts by weight).

  Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, and a hydroxyl group (meta ) Acrylic compounds, nitrogen-containing (meth) acrylic compounds, and the like. Moreover, a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.

  Specific examples of monofunctional (meth) acrylic compounds include 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) acrylate, undecyl (meth) acrylate, dodecyl ( (Meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (medium) ) Acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkylene (meth) acrylate having 1 to 22 carbon atoms such as docosyl (meth) acrylate. In the case of adjusting 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. For the purpose of adjusting the leveling property, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms.

  Examples of alkylene glycol (meth) acrylates include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth). A polyoxyalkylene chain having a hydroxyl group at the terminal, such as acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, etc. (Meth) acrylate having methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate , Methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n- Pentaxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) ) Acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxy Tetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol Mono (meth) acrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain, such as (meth) acrylate; phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, Phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylic Examples thereof include polyoxyalkylene (meth) acrylates having a phenoxy or aryloxy group at the terminal, such as rate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene ethylene glycol (meth) acrylate.

  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 , Isophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like.

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

Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- ( Monoalkylol (meth) acrylamide such as (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-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylaminide, N-ethoxymethyl-N-propoxy Methyl methacrylate N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide-type unsaturated compounds such as acrylamide, N, N-di (pentoxymethyl) acrylamide, dialalkylol (meth) acrylamide such as N-methoxymethyl-N- (pentoxymethyl) methacrylamide; dimethylaminoethyl (meth) acrylate , diethylaminoethyl (meth) acrylate, methyl ethyl amino ethyl (meth) acrylate, dimethylamino styrene, the unsaturated compound having a dialkylamino group such as a diethylamino styrene; and, Cl as counterions ^-, Br @ -, I ^-, etc. Rogen'ion or QSO3 ^-: There are quaternary ammonium salts of dialkylamino group-containing unsaturated compound having a (Q alkyl group having 1 to 12 carbon atoms).

  Other unsaturated compounds include 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) Perfluoroalkanes having 1 to 20 carbon atoms such as acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate Can be mentioned perfluoroalkyl alkyl (meth) acrylates having an Le group.

  Furthermore, perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyl, alkylene, etc. such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene; vinyltrichlorosilane, vinyltris (β-methoxyethoxy) Examples include alkoxysilyl group-containing vinyl compounds such as silane, vinyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof; 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 crotonic acid, vinyl caprylate, 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 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, chlorostyrene, and the like. It is done.
Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like.
These may be used alone or in combination of two or more.

Among these, as photocurable compounds other than the dispersant (A), polyurethane poly (meth) acrylate and polyepoxypoly (meth) having at least three functional groups from the viewpoint of coating film strength and scratch resistance. Poly (meth) acrylates such as acrylate and polyfunctional acrylates having 3 or more acryloyl groups in the molecule can be suitably used.
Polyepoxy poly (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to a (meth) acryloyl group, and (meth) acrylic to a bisphenol A type epoxy resin. There are acid addition products, (meth) acrylic acid addition products to novolac type epoxy resins, and the like.

  Polyurethane poly (meth) acrylate is, for example, one obtained by reacting diisocyanate with (meth) acrylate having a hydroxyl group, or isocyanate group-containing urethane obtained by reacting polyol and polyisocyanate under the condition of excess isocyanate group. Some are obtained by reacting a prepolymer with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene 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 (meth) acrylates having a hydroxyl group include 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.
Examples of the (meth) acrylates having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate.

The following can be illustrated as a commercial item of a photocurable compound.
Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060,
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400
Kayaku Sartomer Co., Ltd .: SR-295,
Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,
Shin Nakamura Chemical Co., Ltd .: 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,
Manufactured by BASF: LaromerEA81,
Sannopco: Photomer 3016,
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: 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, Art resin H61,
Nippon Synthetic Chemical Industry Co., Ltd .: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1400B, Violet UV-1700B, Violet UV-6300B,
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I,
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.

Next, the cured film and laminated body of the present invention will be described.
The cured film of the present invention is a film formed by curing the metal oxide composition of the present invention. The manufacturing method includes, for example, applying the metal oxide composition to an arbitrary substrate, and irradiating active energy rays to cure the metal oxide composition on the substrate.
More specifically, after coating the metal oxide composition on an arbitrary base material so that the film thickness after drying is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, It can be formed by curing treatment.

At the time of formation, the cured film may be applied directly to the substrate, or one or more lower layers may exist between the cured film and the substrate.
Examples of the base material include metals, ceramics, glass, plastics, wood, slate and the like, and are not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

As a coating method, a known method can be used. For example, a method using a lot or a wire bar, or various coating methods such as microgravure, gravure, die, curtain, lip, slot or spin can be used. it can.
The curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm, using a known technique. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. As the electron beam source, a thermionic emission gun, an electrolytic emission 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.
These active energy rays can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.

The cured film may be formed by applying a metal oxide composition to a substrate and naturally or forcedly drying it, followed by curing treatment, or after coating and curing treatment, it may be natural or forced. Although it may be dried, it is more preferable to perform the curing treatment after natural or forced drying.
In particular, in the case of curing with an electron beam, it is more preferable to carry out the curing treatment after natural or forced drying in order to prevent the inhibition of curing by water or the decrease in strength of the coating film due to the remaining organic solvent.
The timing of the curing treatment may be simultaneous with coating or after coating.

The resulting cured film is excellent in hard coat properties, transparency, light resistance, high refractive index properties, and antistatic properties, and therefore can be suitably used as an optical material. Therefore, the cured film of the present invention can be used as a laminated body as a front plate of various display devices such as a cathode ray tube and a flat display panel (liquid crystal display, plasma display, electrochromic display, light emitting diode display, etc.) or an input device thereof. Available.
In addition, the cured film can be widely used for optical lenses, glasses lenses, optical recording disks (compact disks, DVD disks, Blu-ray disks, etc.), light cases, and the like.
The surface resistance value of the cured film is preferably 1 × 10 ¹² Ω / □ or less.
The thickness of the cured film is preferably 0.1 to 30 μm.
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 1.8.

The laminate of the present invention includes the cured film of the present invention and a substrate. As the substrate, those exemplified above can be arbitrarily used, and a plastic substrate is particularly preferable. The shape of the substrate is preferably a film shape, a lens shape, or a disk shape.
In addition to these, the laminate preferably contains one or more layers having different refractive indexes, adhesive layers, information recording layers, and the like.

The laminate including the film (M), the pressure-sensitive adhesive layer (M) or the information recording layer (M) having different refractive indexes can have a layer configuration such as the following (I) to (IX).
(I) Base material / (M) / cured film (II) Base material / cured film / (M)
(III) substrate / (M) / cured film / (M)
(IV) (M) / base material / cured film (V) (M) / base material / (M) / cured film (VI) (M) / base material / 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

  Films or information recording layers having different refractive indexes have functions other than the functions of the cured product of the present invention. The formation method is not particularly limited, and it is formed by a known method. For example, dry coating methods such as vapor deposition and sputtering, methods using lots and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used. There is no limitation on the material used, and if necessary, one or more functions such as information recording function, anti-glare function, Newton ring prevention function, adhesive function, blocking of specific wavelength, adhesion improvement, color correction, etc. are given to the laminate. Any material that can be used can be used.

  The information recording layer may be any material as long as it causes some chemical change by laser light or the like and records information by the change, and the material is not particularly limited. Examples of organic materials include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, and triphenylmethane-based metal complex compounds, and one or a combination of two or more of the above dyes. Can be used. As the inorganic recording layer, metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, and Pt, and semimetals can be used singly or in combination of two or more. The information recording layer may be a laminate or the like, and the mode of photochemical change may be any of phase change, bubble, and punching type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb, or Co, or may be a spiropyran or a fluorinated photochromic material.

From the viewpoint of antireflection, the high refractive index cured film is also preferably used as a laminate provided with a low refractive index coating cured film on the surface layer to provide an antireflection function. That is, it is preferable to use a laminate obtained by forming a cured film on a substrate such as a film and more preferably forming a coated cured film as the antireflection film.
In a laminate in which reflection interference fringes are a problem, the blending amount of the metal oxide in the metal oxide composition of the present invention is adjusted, and the difference in the refractive index between the cured film and the substrate or the cured film When an arbitrary layer is present between the substrate and the substrate, the difference in refractive index between the cured film and the lower layer in contact with the cured film is preferably within ± 0.02.

The metal oxide composition of the present invention can produce a cured product having a high refractive index by controlling the type and addition amount of the metal oxide. Therefore, in order to improve the light extraction efficiency of the optical semiconductor element, it can be preferably used as an optical semiconductor element sealing material that requires that the refractive index of the resin layer be sequentially reduced 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 phosphide (GaP: refractive index 2.9), gallium arsenide (GaAs: refractive index 3.5), and the like. Is a high material. Therefore, the refractive index of the cured product that becomes the optical semiconductor element sealing material is preferably 1.5 or more, more preferably 1.5 to 2.1, and still more preferably 1 from the viewpoint of increasing the light extraction efficiency. .7 to 2.1.

  As a method of achieving the optimum refractive index of the cured product, titanium oxide (refractive index 2.5 to 2.7), zirconium oxide (refractive index 2.4), zinc oxide (refractive index 1) is used as a metal oxide to be used. .95) and the like are preferable, and the dispersant (A) having an aromatic skeleton is preferable because the dispersant is required to have high refractive index.

<Example>
Hereinafter, the present invention will be described in more detail based on production examples and examples. In Production Examples and Examples, parts and% represent parts by weight and% by weight, respectively.
The chemicals used are as follows.
Biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation)
9,9-bis (3,4-dicarboxyphenyl) fluorenedioic anhydride (manufactured by JFE Chemical Co., Ltd., trade name: BPAF)
Tetrahydronaphthalene dianhydride (manufactured by New Japan Chemical Co., Ltd., trade name: RIKACID TDA-100)
Naphthalene tetracarboxylic acid dianhydride (JFE Chemical Co., Ltd., trade name: NTCDA)
Butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd., trade name: Ricacid BT-100)
Pentaerythritol triacrylate (1) (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 300)
Pentaerythritol triacrylate (2) (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30)
Dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)
2-hydroxyethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.)
Hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.)
1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.)
Glycidyl methacrylate (Dow Chemical Japan Co., Ltd.)
Dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.)

(Production Example 1: Dispersant (1))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts biphenyltetracarboxylic dianhydride, 250.0 parts pentaerythritol triacrylate (1), 0.16 parts hydroquinone 141.2 parts of cyclohexanone was charged and the temperature was raised to 85 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent, and had a solid content of 70%, a number average molecular weight (MN) 870, and a weight average molecular weight (MW) 2,830.

(Production Example 2: Dispersant (2))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts biphenyltetracarboxylic dianhydride, 250.0 parts pentaerythritol triacrylate (2), 0.16 parts hydroquinone 141.2 parts of cyclohexanone was charged and the temperature was raised to 85 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent with a solid content of 70%, a number average molecular weight of 920, and a weight average molecular weight of 3,130.

(Production Example 3: Dispersant (3))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride, 124.8 parts of pentaerythritol triacrylate (1), dipentaerythritol pentaacrylate 222.8 parts, 0.21 part of hydroquinone and 430.0 parts of cyclohexanone were charged, and the temperature was raised to 85 ° C. Next, 2.14 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 77.3 parts of glycidyl methacrylate and 80.7 parts of cyclohexanone were added, and then 3.42 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 1,050, and a weight average molecular weight of 3,830.

(Production Example 4: Dispersant (4))
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 100.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, pentaerythritol triacrylate ( 1) 200.2 parts, 0.15 part of hydroquinone and 200.1 parts of cyclohexanone were charged, and the temperature was raised to 85 ° C. Next, 1.50 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 62.0 parts of glycidyl methacrylate and 42.4 parts of cyclohexanone were added, and then 2.41 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The obtained reaction solution was light yellow and transparent, and had 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))
Tetrahydronaphthalene dianhydride 100.0 parts, pentaerythritol triacrylate (2) 305.7 parts, hydroquinone 0.20 parts, cyclohexanone in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet pipe and thermometer 405.7 parts were charged and heated to 85 ° C. Next, 2.03 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 94.6 parts of glycidyl methacrylate and 96.9 parts of cyclohexanone were added, and then 3.26 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 870, and a weight average molecular weight of 3,150.

(Production Example 6: Dispersant (6))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 100.0 parts of naphthalene dianhydride, 342.2 parts of pentaerythritol triacrylate (2), 0.22 parts of hydroquinone, cyclohexanone 442 .2 parts were charged and the temperature was raised to 85 ° C. Next, 2.21 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 105.9 parts of glycidyl methacrylate and 108.4 parts of cyclohexanone were added, then 3.56 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 820, and a weight average molecular weight of 2,440.

(Production Example 7: Dispersant (7))
100.0 parts biphenyltetracarboxylic dianhydride, 556.8 parts dipentaerythritol pentaacrylate, 0.33 parts hydroquinone, cyclohexanone in a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet pipe and thermometer 437.8 parts were charged and the temperature was raised to 85 ° C. Next, 3.28 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 96.6 parts of glycidyl methacrylate and 66.8 parts of cyclohexanone were added, and then 5.28 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight of 820, and a weight average molecular weight of 2,660.

(Production Example 8: Dispersant (8))
In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 9,0.0 parts of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2-hydroxy acrylate 50.7 parts of ethyl, 0.08 parts of hydroquinone and 100.4 parts of cyclohexanone were charged and the temperature was raised to 85 ° C. Next, 1.51 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 5 hours. Thereafter, 62.0 parts of glycidyl methacrylate and 39.7 parts of cyclohexanone were added, followed by 1.21 parts of dimethylbenzylamine as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight of 890, and a weight average molecular weight of 1,200.

(Production Example 9: Dispersant (9))
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, butanetetracarboxylic dianhydride 100.0 parts, pentaerythritol triacrylate (1) 463.2 parts, hydroquinone 0.28 parts Then, 563.2 parts of cyclohexanone was charged and the temperature was raised to 85 ° C. Next, 2.82 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 146.5 parts of cyclohexanone were added, and then 4.53 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 820, and a weight average molecular weight of 2,000.

(Production Example 10: Dispersant (10))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 100.0 parts butanetetracarboxylic dianhydride, 463.2 parts pentaerythritol triacrylate (2), 0.28 parts hydroquinone Then, 563.2 parts of cyclohexanone was charged and the temperature was raised to 85 ° C. Next, 2.82 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 146.5 parts of cyclohexanone were added, and then 4.53 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 920, and a weight average molecular weight of 2,200.

(Production Example 11: Dispersant (11))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, butanetetracarboxylic dianhydride 80.0 parts, pentaerythritol triacrylate (2) 185.3 parts, dipentaerythritol pentaacrylate 330.9 parts, hydroquinone 0.30 parts and cyclohexanone 599.5 parts were charged and heated to 85 ° C. Next, 2.98 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 114.8 parts of glycidyl methacrylate and 119.6 parts of cyclohexanone were added, and then 4.77 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 950, and a weight average molecular weight of 2,600.

(Production Example 12: Dispersant (12))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube and thermometer, 50.0 parts butanetetracarboxylic dianhydride, 413.4 parts dipentaerythritol pentaacrylate, 0.23 parts hydroquinone, cyclohexanone 463.4 parts were charged and heated to 85 ° C. Next, 2.32 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 8 hours. Thereafter, 71.7 parts of glycidyl methacrylate and 74.3 parts of cyclohexanone were added, and then 3.73 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight of 900, and a weight average molecular weight of 2,070.

(Production Example 13: Dispersant (13))
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 100.0 parts butanetetracarboxylic dianhydride, 117.2 parts 2-hydroxyethyl acrylate, 0.11 part hydroquinone, 144.8 parts of cyclohexanone was charged and heated to 85 ° C. Next, 2.17 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 85 ° C. for 5 hours. Thereafter, 143.4 parts of glycidyl methacrylate and 93.3 parts of cyclohexanone were added, and then 1.74 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, and cooled to room temperature to complete the reaction. The resulting reaction solution was light yellow and transparent and had a solid content of 60%, a number average molecular weight of 780, and a weight average molecular weight of 1,100.

(Production of metal oxide dispersion paste: Examples 1 to 22, Comparative Examples 1 to 3)
Using each dispersing agent (A) prepared by the above production example, metal oxide dispersion was carried out according to the formulation shown in Table 1 to prepare a metal oxide dispersion paste (the compounding amount indicates the solid content). Dispersion method is pre-dispersion (using zirconia beads (1.25 mm) as media and dispersing for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as media). (Dispersion with machine UAM-015).

In Table 1,
Sb ₂ O ₅ : “San-Epoch EFR-6N” manufactured by Nissan Chemical Industries, Ltd. (average primary particle size: 20 nm)
ATO: “SN-100P” manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20 nm)
ITO: “Nanotech ITO” manufactured by CI Kasei Co., Ltd. (average primary particle size: 30 nm)
PTO: “EP SP-2” manufactured by Mitsubishi Materials Corporation (average primary particle size: 15 nm)
ZrO ₂ : “PCS-60” manufactured by Nippon Electric Works Co., Ltd. (average primary particle size: 20 nm)
TiO ₂ : “TTO-51 (A)” manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20 nm)
ZnO: “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm)
SiO ₂ : “AEROSIL50” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 50 nm)
Al ₂ O ₅ : “Aluminium Oxide C” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 13 nm)
Commercially available dispersant: “Disperbyk-111” (100% solid content) manufactured by Big Chemie Japan Co., Ltd.
Commercially available polyfunctional monomer (1): “Biscoat # 400” (100% solid content) manufactured by Osaka Organic Chemical Co., Ltd.
Commercially available polyfunctional monomer (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd. (solid content: 100%)
MIBK: Methyl isobutyl ketone Metobuta: 3-methoxy-1-butanol

<Coating and evaluation of cured film: Examples 1 to 22, Comparative Examples 1 to 3>
Using the metal oxide dispersion paste prepared above, a metal oxide composition having the composition shown in Table 2 was prepared (the blending amount represents the solid content). The obtained metal oxide composition was applied to a 100 μm thick easy-adhesion-treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) with a bar coater so that the film thickness after drying was 5 μm. After the processing, ultraviolet rays of 400 mJ / cm ² were irradiated with a metal halide lamp to form a cured film (hard coat layer). The obtained cured film was evaluated for refractive index, scratch resistance, pencil hardness, transparency (haze), light resistance, and surface resistance by the following methods. The results are shown in Table 2.

In Table 2,
Photo-curable compound (1): “UA-306T” manufactured by Kyoeisha Chemical Co., Ltd.
Photo-curable compound (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Solvent: PGME (propylene glycol monomethyl ether)
* 1: Not measured because metal oxide paste was poorly dispersed

<Production and Evaluation of Laminate: Examples 23 to 27>
(Preparation of low refractive index coating liquid)
1,2,9,10-Tetraacryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane 50% by weight, silica sol 30% dispersion (MEK- manufactured by Nissan Chemical Industries, Ltd.) 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-nonadecafluoroundecyl 10 parts by weight, butyl alcohol 900 parts by weight, photopolymerization initiator (Nippon Kayaku Co., Ltd. KAYACURE BMS) 5 parts by weight, A low refractive index coating solution was prepared.

Each metal oxide composition having the composition shown in Table 3 was prepared using the metal oxide dispersion paste of Example 2 (the amount is a solid content). This metal oxide composition was applied to an easy-adhesion-treated surface of a 100-μm-thick easy-adhesion-treated PET film (refractive index of the easy-adhesion-treated layer = 1.60) to a dry film thickness of 6 μm using a bar coater. did. The obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 mJ / cm ² ultraviolet rays with a metal halide lamp. Further, the low refractive coating liquid was applied on the obtained cured film with a spin coater while adjusting the layer thickness so that the wavelength of light having a dry film thickness of λ / 4 was about 550 nm. The obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 mJ / cm ² of ultraviolet rays with a metal halide lamp to obtain a laminate.
About the obtained laminated body, while measuring the refractive index of the cured film by the following method, the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflection interference fringe of the cured film were evaluated. The results are shown in Table 3.

In Table 3, photocurable compound (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Base material: 100 μm thick easy-adhesion-treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd., coated on easy-adhesion-treated surface (refractive index 1.60))
Solvent: PGME (propylene glycol monomethyl ether)

(Evaluation methods)
(1) Refractive index The refractive index of the obtained cured film was measured using an Atago Co., Ltd. Abbe refractometer.

(2) Scratch resistance The coated material was set on a Gakushin tester, and was shaken 10 times with a load of 250 g using steel wool No. 0000. About the taken-out coating material, the degree of a crack was judged according to the following five-step visual evaluation. It shows that the abrasion resistance of a cured film is so favorable that a numerical value is large.
5: No scratches 4: Slight scratches 3: Scratches are observed, but the substrate is not visible 2: Scratches are present, and part of the cured film is peeled 1: The cured film is peeled off The base material is bare

(3) Pencil Hardness Based on JIS-K5600, a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON) was used, and the hardness of the pencil core was changed variously, and the test was performed five times at a load of 500 g. The hardness of the core when the scratch was not scratched or scratched only once in 5 times was defined as the pencil hardness of the cured film. Considering the practical properties required, the pencil hardness of the cured film is
2H or more: A
1H or more: B
Lower than 1H: D
It was determined.

(4) Transparency (Haze value)
Turbidity (Haze value) in the obtained coated product was measured using a Haze meter.

(5) Light resistance Yellowing with the passage of time during continuous light irradiation is extremely undesirable for application development. Therefore, yellowing during continuous light irradiation was confirmed.
First, the coated material was 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 coated material was placed on white paper, and coloring was measured using a colorimeter (Minolta CR-300). The colorimetric value was displayed as L ^* a ^* b ^* , and the guideline for yellowing of the cured film was judged from the b ^* value. The smaller the value of b ^* value, the smaller the degree of yellowing and the better the light resistance. In consideration of practical required physical properties, the b ^* value of the cured film is
Less than 3.5: A
3.5 or more: D
It was determined.

(6) Surface resistance The surface resistance (Ω / □) of the cured film was evaluated according to the following criteria.
When the surface resistance is 1 × 10 ¹² or less: A
When the surface resistance is higher than 1 × 10 ¹² and 1 × 10 ¹⁴ or less: B
When the surface resistance exceeds 1 × 10 ¹⁴ : D

(7) Reflective interference fringes The obtained interference interference fringes of the cured film were visually evaluated according to the following criteria.
Reflective interference fringes cannot be observed: A
Reflective interference fringes can be observed: D

The disclosure of the present application relates to the subject matter described in Japanese Patent Application No. 2006-148854 filed on May 29, 2006 and Japanese Patent Application No. 2006-148855 filed on May 29, 2006. The entire disclosure of which is incorporated herein by reference.
It should be noted that various modifications and changes may be made to the above-described embodiments without departing from the novel and advantageous features of the present invention other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.

Claims (9)

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) is
The following general formula:

(Here, R ⁹ has 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 an alkyl skeleton having 4 to 10 carbon chains. Represents a tetravalent aliphatic group.)
A tetracarboxylic dianhydride (x1) 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-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, dihydroxy acrylate, glycerol (meth) acrylate, isocyanuric acid EO-modified diacrylate, penta Erythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) a One or more selected from the group consisting of relate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate A compound (x2) of
A compound (X) having a carboxyl group obtained by reacting
It is obtained by reacting with one or more compounds (Y) which are epoxy group-containing (meth) acrylates,
A method for producing a metal oxide dispersion.   The compound (x2) is pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, And a hydroxyl group-containing (meth) acrylate compound selected from the group consisting of dipentaerythritol penta (meth) acrylate, wherein the compound (Y) contains glycidyl (meth) acrylate. Manufacturing method.   The dispersant (A) is tetracarboxylic dianhydride, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, What is obtained by reaction of at least one hydroxyl group-containing (meth) acrylate compound selected from the group consisting of dipentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate with glycidyl (meth) acrylate The method for producing a metal oxide dispersion according to claim 2, wherein   4. The metal oxide according to claim 1, wherein 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. 2. A method for producing a metal oxide dispersion according to item 1. A substrate, a cured film obtained by curing a metal oxide composition comprising a dispersion obtained by the production method of the metal oxide dispersion according to any one of claims 1 to 4, and an information recording layer including, product Sotai. The laminate according to claim 5 , wherein the substrate is a plastic substrate. A dispersant for dispersing a metal oxide having an average primary particle diameter of 5 to 100 nm in an organic solvent,
The following general formula:

(Here, R ⁹ has 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 an alkyl skeleton having 4 to 10 carbon chains. Represents a tetravalent aliphatic group.)
A tetracarboxylic dianhydride (x1) 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-hydroxyethylphthalic acid, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, dihydroxy acrylate, glycerol (meth) acrylate, isocyanuric acid EO-modified diacrylate, penta Erythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) a One or more selected from the group consisting of relate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate A compound (x2) of
A compound (X) having a carboxyl group obtained by reacting
It is obtained by reacting with one or more compounds (Y) which are epoxy group-containing (meth) acrylates,
Dispersant. The compound (x2) is pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and include dipentaerythritol penta (meth) hydroxyl group-containing selected from the group consisting of acrylates (meth) acrylate compound, said comprising the compound (Y) is glycidyl (meth) acrylate, dispersing agent according to claim 7. Tetracarboxylic dianhydride, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate , and dipentaerythritol penta (meth) one or more hydroxyl groups-containing selected from the group consisting of acrylates (meth) acrylate compound, is obtained by reaction with glycidyl (meth) acrylate, according to claim 8 Dispersant.