WO2007138946A1 - Metal oxide composition, cured film and laminate - Google Patents

Abstract

Disclosed is a metal oxide composition containing a dispersing agent (A) represented by the general formula (1) below and a metal oxide having an average primary particle diameter of 5-100 nm. [chemical formula 1] (1) (In the formula, R1-R4 independently represent a hydrogen atom or a methyl group; R5-R8 independently represent an unsubstituted or substituted straight or branched chain alkyl group or alkylene oxyalkylene group; and R9 represents a tetravalent aromatic group or aliphatic group.) Also disclosed are a cured film obtained by curing this metal oxide composition, and a laminate thereof.

Description

 Specification

 Metal oxide composition, cured film and laminate

 Technical field

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

 Background art

 [0002] Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a hard coat property having a scratch resistance, adhesion, high refractive index, etc., using a photometal oxide composition on the surface of the equipment. Forming a coating film or an antistatic coating film is performed.

 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 of hard coat coatings and antistatic coatings. Various proposals have been made using

 [0003] 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 for producing a conductive coating material by dispersing a conductive oxide fine powder in a mixed solvent of an easily dispersible low boiling solvent and a hardly dispersible high boiling solvent.

 (Patent Document 1) Japanese Patent Application Laid-Open No. 04-172634

 (Patent Document 2) Japanese Patent Laid-Open No. 06-2644009

 (Patent Document 3) JP 2001-131485 A

 Disclosure of the invention

However, even if it is possible to create 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. Metals with an average primary particle size of lOOnm or less against highly hydrophobic media such as organic solvents Since the oxides cannot be stably dispersed and stabilized at the primary particle level, problems are likely to occur in terms of the transparency of the coating film and the temporal stability of the photocurable coating.

 Therefore, the present invention has excellent physical properties in all of high refractive index property, antistatic property, hard coat property, transparency and light resistance while containing a metal oxide having an average primary particle size of lOOnm or less. An object of the present invention is to provide a metal oxide composition capable of forming a coating film and stable over time, a cured film using the composition, and a laminate thereof.

The present invention relates to a metal oxide composition containing a dispersant (A) represented by the following general formula (1) and a metal oxide having an average primary particle size of 5 to 10 Onm.

 General formula (1):

 [Chemical 1]

(In the formula, I ^ to R ⁴ each independently represents a hydrogen atom or a methyl group, and R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group or Represents an alkylenoxyalkylene group, and R ⁹ represents a tetravalent aromatic group or an aliphatic group.) [0006] Another aspect of the present invention is a curing formed by curing the above metal oxide composition. Relates to the membrane.

 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 comprising the metal oxide composition.

[0007] Another aspect of the present invention is to disperse a metal oxide having an average primary particle size of 5 to LOONm in the presence of an organic solvent, using a dispersant (A) represented by the following general formula (1). The present invention relates to a method for producing a metal oxide dispersion.

General formula (1): [Chemical 2]

(In the formula, I ^ to R ⁴ each independently represents a hydrogen atom or a methyl group, and R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group or Represents an alkyleneoxyalkylene group, and R ⁹ represents a tetravalent aromatic group or an aliphatic group.) [0008] Still another aspect of the present invention is to apply the metal oxide composition to a substrate. And curing a metal oxide composition by irradiating active energy rays.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0009] 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 size of 5 to LOONm. Two or more kinds of metal oxides and two or more kinds of dispersants (A) may be included respectively.

 General formula (1):

(In the formula, I ^ to R ⁴ each independently represents a hydrogen atom or a methyl group, and R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group or Represents an alkyleneoxyalkylene group, and R ⁹ represents a tetravalent aromatic group or an aliphatic group.

[0010] The dispersant (A) has high dispersibility and photocurability with respect to the metal oxide. The dispersant (A) has an average primary particle diameter of 5 to 5: The metal oxide composition of the present invention is excellent in curability by enhancing the dispersibility of the metal oxide of LOOnm and enhancing the photocurability. Further, it is possible to form a cured film and a laminate thereof excellent in hard coat property, transparency, light resistance, high refractive index property and antistatic property. 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 substrate having the same refractive index, the resulting laminate does not produce reflection interference fringes, and optical It is suitably used for applications. Furthermore, since the refractive index of a cured product containing a metal oxyde can be controlled to be high, it is also suitable as an optical semiconductor element sealing material.

In the above formula (1), the tetravalent aromatic group of R ⁹ specifically includes a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenyl ether skeleton, a diphenylsulfone skeleton, a diphenyl skeleton, -Rusulfide skeleton, perylene skeleton, fluorene skeleton, tetrahydronaphthalene skeleton, naphthalene skeleton and the like. In particular, it is preferable that R ⁹ is at least one kind selected from the group force including biphenyl skeleton, naphthalene skeleton, fluorene skeleton, and tetrahydronaphthalene skeleton power! /.

[0012] As the tetravalent aliphatic skeleton of R ^9, a tetravalent aliphatic group which is an alkyl skeleton having 4 to 4 carbon chains is a preferred example, specifically, a butane skeleton, a cyclobutane skeleton, Examples include a hexane skeleton, a cyclohexane skeleton, and a decalin skeleton.

In the above formula (1), the unsubstituted or substituted linear or branched alkylene group of R ^{5 to} R ⁸ is, for example, an alkylene such as a methylene group, an ethylene group, or a C3-C10 polymethylene group. Examples are groups. Examples of the unsubstituted or substituted linear or branched alkyloxyalkylene group include C3 alkyleneoxy C3 alkylene group. These alkylene groups or alkyleneoxyalkylene groups It is derived from the following first and second hydroxyl group-containing (meth) ataretoy compound. Examples of the substituent that can be taken by the alkylene group or alkyleneoxyalkylene group include an alkyl group such as a methyl group and an ethyl group, a hydroxyl group, an attayloxymethyl group, an acryloyloxychetyl group, and a phenoxy group. .

[0014] The dispersant (A) represented by the general formula (1) includes, for example, a compound (xl) having an aromatic skeleton or an aliphatic skeleton, and two or more carboxylic anhydride groups, and a carboxylic acid. A compound (X) having a carboxyl group obtained by reacting a compound (x2) having a functional group capable of reacting with an anhydride group, and a compound (Y) having a functional group capable of reacting with the carboxyl group; Can be obtained by reacting. Here, from the viewpoint of photocurability and hard coat properties, it is preferable that the compound (x2) and the compound (Y) have at least a partially polymerizable polymerizable double bond group.

 [0015] The "functional group capable of reacting with a carboxylic acid anhydride group" in the compound (x2) includes a hydroxy group, an amino group, a glycidyl group, and the like. Is particularly preferred. 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 carpositimide group, an isocyanate group, an isothiocyanate group, and a butyl ether group.

 [0016] Further, an example will be described. The following general formula (2), which is a compound (xl) having an aromatic skeleton or an aliphatic skeleton and two or more carboxylic anhydride groups:

 General formula (2)

 [Chemical 4]

(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 = C (R ¹ ) COOR ⁵ OH Formula (3)

 2

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

 And a first hydroxyl group-containing ataretoy compound or a metatalylate compound represented by the following general formula (4):

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

 2

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

 By reacting with a second hydroxyl group-containing atalytoyl compound or methacrylate compound represented by the following general formula (5):

 General formula (5)

 [Chemical 5]

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

 The compound (X) shown by can be obtained.

[0017] Here, "atallylate group or metatalylate group" is a concept that includes or includes both an acrylate group and a metatalylate group. Hereinafter, attalate and metatarrate may be collectively referred to as “(meta) aterate”.

[0018] Examples of the aromatic tetracarboxylic dianhydride represented by the general formula (2) include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyl tetra having a biphenyl skeleton. Carboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfonate 9, 9 Bis (3, 4) having a fluorene skeleton such as lacarboxylic dianhydride, diphenylsulfide tetracarboxylic dianhydride, perylene tetra carboxylic dianhydride, naphthalene tetracarboxylic dianhydride having a naphthalene skeleton —Dicarboxyphenyl) fluorene dianhydride or 9, 9 bis [4— (3,4-dicarboxyphenoxy) phenol] fluorene dianhydride, tetrahydronaphthalene with tetrohydronaphthalene skeleton Examples thereof include carboxylic acid dianhydride, ethylene glycol bis (anhydrotrimellitate), glycerin bis (anhydrotrimellitate) monoacetate and the like.

 [0019] Commercially available products include “Rikacid TMTA-C” and “Rikacid MTA-10” manufactured by Shin Nippon Rika Co., Ltd.

”,“ Licacid MTA-15 ”,“ Licacid TMEG Series ”,“ Licacid TDA ”,“ Licacid DSDA ”, and the like.

 Of these aromatic tetracarboxylic dianhydrides, biphenyl tetracarboxylic dianhydride has a biphenyl skeleton, and the biphenyl skeleton is efficiently introduced into the molecule of the compound represented by the formula (1). It is particularly preferred because it can have both hard coat properties of the cured film and good dispersibility of the metal oxide.

[0020] Examples of the aliphatic tetracarboxylic dianhydride represented by the general formula (2) include butanetetracarboxylic dianhydride.

[0021] The first and second hydroxyl group-containing (meth) ataretoy compound may be the same or different! /! /. Examples of such hydroxyl group-containing (meth) atalytoi compounds and salts, 4-hydroxybutyl (meth) atarylate, 2-hydroxybutyl (meth) atalylate, 2-hydroxy-3-phenoxypropyl (Meth) Atalylate, 2-Atalyloylochetiru 2-Hydroxyethyl phthalic acid, Glycerol mono (meth) atarylate, 2-Hydroxy —3-Ataliloyloxypropyl (meth) Atalylate, Dihydroxy Atari Rate, Glycerol (Meth) Atalylate, Isocyanuric Acid EO Modified Diatalylate, Pentaerythritol Mono (Meth) Atylate, Dipentaerythritol Mono (Meth) Atalylate, Pentaerythritol Di (meth) Atarylate, Dipenta Erythritol di (meth) attalylate, pentaerythritol Tri (meth) Atari rate, dipentaerythritol tri (meth) Atari rate, Jipentaerisuri tall tetra (meth) Atari rate, dipentaerythritol penta (meth) Atari rate etc. ani I can get lost. For the purpose of increasing hardness, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. are preferred. .

 [0022] Specific commercial products include Biscoat # 300 (Osaka Organic Chemical Co., Ltd.), KAYA RAD PET30 (Nippon Kayaku Co., Ltd.), PETIA (Daicel UCB Co., Ltd.), Aronix M 305 (manufactured by Toagosei Co., Ltd.), NK Ester A—TMM—3LMN (manufactured by Shin-Nakamura Chemical Co., Ltd.), Light Attalate PE—3A (manufactured by Kyoeisha Engineering Co., Ltd.), SR—444 (Cartoma) 1), Light Atarylate DPE-6A (Kyoeisha Igaku Co., Ltd.), KAYARAD DPHA (Nippon Kayaku Co., Ltd.), Aronix M402 (Toagosei Co., Ltd.), etc. .

 In particular, KAYARAD PET 30 (manufactured by Nippon Yakuyaku Co., Ltd.), which is mainly composed of pentaerythritol tri (meth) acrylate, is more preferable because of its good dispersibility of metal oxides. In the case of a polyfunctional (meth) atari toy compound, curing of the resulting dispersant (A) by containing about 5 to 15% by weight of polyfunctional (meth) atalylate having two hydroxyl groups as accessory components The weight average molecular weight tends to increase later, and the dispersibility of the metal acid compound is also preferable.

 [0023] The reaction of the aromatic or aliphatic tetracarboxylic dianhydride with the first and second hydroxyl group-containing (meth) acrylate compounds is carried out by the reaction of the aromatic or aliphatic tetracarboxylic dianhydride. This is a reaction between the two carboxylic anhydride groups possessed by the hydroxyl groups possessed by the first and second hydroxyl group-containing (meth) acrylate compounds, and is well known in the art. For example, an aromatic tetracarboxylic dianhydride and a first and second hydroxyl group-containing (meth) atalytoi compound are mixed in an organic solvent such as cyclohexanone with 1,8-diazabicyclo [5. 4. The reaction can be carried out at a temperature of 50 to 120 ° C in the presence of a catalyst such as 0] -7-undecene. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.

[0024] After the reaction, the reaction product containing the compound (X) of the formula (5), which is a reaction product, is purified without any purification. For example, the following general formula (6), which is the compound (Y):

 General formula (6)

[Chemical 6]

(Where R. is CH = C (R ³ ) — C (0) 0— group and CH = C (R ⁴ ) — C (0) 0— group; R

 twenty two

³ and R ⁴ are as defined above)

The compound represented by the general formula (1) can be obtained by adding an epoxy group-containing compound which is: (in this case, R ⁷ and R ⁸ are —CH 2 CH 2 (OH) 2 CH— groups ;).

 twenty two

 [0025] Examples of the compound represented by the formula (6) include epoxy group-containing (meth) acrylate, such as glycidyl methacrylate and glycidyl acrylate; o phenol glycidyl ether, p-phenol Flavors such as phenol glycidyl ether, monostyrenated phenol glycidyl ether, 4-ciano 4-hydroxybiphenol glycidyl ether, 4, 4'-biphenol monoglycidyl ether, 4, 4'-biphenol diglycidyl ether Group glycidyl ether compounds and the like.

 [0026] The reaction between the compound represented by formula (5) and the compound represented by formula (6) is carried out by the compound represented by formula (5) and the compound represented by formula (6). It is a reaction with an epoxy group and as such is well known in the art. 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.

 [0027] These reactions may be carried out without solvent or in a solvent inert to the reaction. Examples of powerful 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. Solvents; ether solvents such as jetyl, tetrahydrofuran, dioxane, etc .; halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene; acetonitrile, N, N-dimethylformamide, N, N Examples thereof include polar solvents such as dimethylacetamide and N, N-dimethylimidazolidinone. These solvents may be used in combination of two or more.

[0028] Next, the metal oxide contained in the metal oxide composition has an average primary particle size of 5 to: LOOn m metal oxide. The average primary particle diameter of the metal oxide can be determined 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 the primary particle level with high transparency. On the other hand, in the case of metal oxides having an average primary particle size exceeding lOOnm, it is easy to disperse at the primary particle level. Because of the large particle size, scattering is likely to occur for light such as visible light. There arises a problem of deteriorating the transparency of the cured film.

 [0029] 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 Examples include zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, aluminum doped zinc oxide, titanium oxide, zinc oxide, zirconium oxide, silicon oxide, and aluminum oxide. Two or more of these metal oxides can be used in combination.

 [0030] Commercially available metal oxides include:

 NISSAN CHEMICAL INDUSTRY CO., LTD .: Sanepoch EFR—6N, Sanepoch EFR—6NP (pentanoic acid antimony),

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 (Titanium oxide), TTO—S—3 (titanium oxide), TTO—S—4 (titanium oxide), TT OF-l (iron-containing titanium oxide), TTO F—2 (iron-containing titanium oxide), TTO F— 3 ( Iron-containing titanium oxide), TTO F-11 (iron-containing titanium oxide), ST-01 (titanium oxide), s T21 (titanium oxide), ST-30L (titanium oxide), ST-31 (titanium oxide),

 Mitsubishi Materials Corporation: T—l (ITO), S—1200 (tin oxide), EP SP—2 (lind tin oxide),

 Mitsui Kinzoku Kogyo Co., Ltd .: Pastoran (ΙΤΟ, ΑΤΟ),

 Made by Shi Kasei Co., Ltd .: Nanotech Sakai, Nanotech SnO, Nanotech TiO, Nanotech

 twenty two

 SiO, Nanotech Al O, Nanotech ZnO,

 2 2 3

 Made by Catalytic Chemical Industry Co., Ltd .: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), T L-120 (ITO), TL 130 (ITO),

 No, made by Kusytec Co., Ltd .: PazetCK (aluminum doped acid zinc)

 Made by Sakai Chemical Industry Co., Ltd .: FINEX—25 (Zinc oxide), FINEX-25LP (Zinc oxide), FIN EX-50 (Zinc oxide), FINEX-50LP (Zinc oxide), FINEX-75 (Zinc oxide), NA NOFINE 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), S TR—100W (titanium oxide),

 Made by Sumitomo Osaka Cement Co., Ltd .: OZC-3YC (zirconium oxide), OZC-3 YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (oxidation) Zirconium),

 NIPPON DENKO CORPORATION: PCS (zirconium oxide), PCS-60 (zirconium oxide), PCS-90 (zirconium oxide), T-01 (zirconium oxide),

 Made by Tika Corporation: 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), M ZY-505S (Oxidation) Zinc), MZ—505M (zinc oxide),

Made by Nippon Aerosil Co., Ltd .: Aluminum Oxide C (aluminum oxide), AEROSIL 130 (silicon oxide), AEROSIL200 (silicon oxide), AEROSIL200V (silicon oxide), AEROSIL200CF (Chemical oxide), AEROSIL200FA (Chemical oxide), AEROSIL300 (Chemical oxide), AEROSIL300CF (Chemical oxide), AEROSIL380 (Chemical oxide), AEROSILR972 (Chemical oxide), AEROSILR974 (Chemical oxide), AEROSILR976 (Chemical oxide), AEROSILR202 (Chemical oxide), AEROSILR805 (Chemical oxide), A EROSILR812 (Chemical oxide), AEROSILR812S (Chemical oxide), AEROSILMOX 50 (Chemical oxide), AEROSILTT600 (Chemical oxide) AEROSILMOX80 (Chemical oxide / Aluminum oxide), AEROSILMOX170 (Chemical oxide / Aluminum oxide), AE ROSILCOX84 (Chemical oxide / Aluminum oxide),

 Etc.

 [0031] The addition amount of the metal oxide in the metal oxide composition is not particularly limited, but is preferably 1 in 100 parts by weight of the total solid content of the dispersant (A) and the metal oxide. -80 parts by weight, more preferably 10-70 parts by weight. If 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 if it exceeds 80 parts by weight, the film forming property may be inferior due to the small amount of the organic component. is there.

 [0032] 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 solution containing the dispersant (A) can be added to the suspension system using metal oxide powder and an organic solvent, etc. If a close mixing system such as deposition of the dispersant (A) on the surface of the oxide is performed, a better result can be obtained.

 [0033] The 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 size of ˜lOOnm 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 dispersion particle size D99 is preferably less than 300 nm, more preferably less than 200 nm.

[0034] Dispersant (A), metal oxide, or metal oxide in a non-aqueous vehicle such as an organic solvent For the dispersion or dissolution of the composition, and for mixing them, paint conditioners (manufactured by Red Devil), ball mills, sand mills (such as “Dynoichi Mill” manufactured by Shinmaru Enterprises), attritors, pearl mills (Eiritsu) "DCP mill" etc.), coball mill, homomixer, homogenizer (such as "Clairemix" manufactured by M'Technique), wet jet mill ("Genus PY" manufactured by Genus, "Nanomizer 1" manufactured by Nanomizer) Dispersers such as microbead mills (“Superapec Mill”, “Ultrapec Mill” manufactured by Kotobuki Industries Co., Ltd.) can be used. When using media in the disperser, it is preferable to use glass beads, zirconium beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, it is possible to use two or more types of dispersers or two or more types of media of different sizes, and use them in stages.

 [0035] The metal oxide composition of the present invention contains at least a dispersant (i) and a 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. Can be included. 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.

 [0036] The method for producing the metal oxide composition containing components other than the dispersant (i) and the metal oxide is not particularly limited, and several methods can be mentioned. Specifically, first, a dispersing agent (ii) and a metal oxide are 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: From the beginning, a method of dispersing and producing in a state where all of the dispersant (i), metal oxide, organic solvent and other additives are mixed.

[0037] When a solvent is added, it is preferable to perform a curing treatment after volatilizing the solvent. As the solvent, various known organic solvents that are not particularly limited can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetyl ethyl acetone, toluene, xylene, η-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy 1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ester One ether, ethylene glycol monobutyl _n - butyl ether, 2-ethoxy-ethanone no Honoré, 1 Meto carboxymethyl 2-propanol, diacetone alcohol, lactic Echiru, butyl lactate, propylene ranging Ricoh Honoré mono-methylol Honoré ether Honoré, ethylene glycol Honoré monobutyl Honoré Agent Tenole acetate

, Propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, methylpyrrolidone and the like. Two or more of these organic solvents may be used in combination.

[0038] 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 It is very effective in improving the aging stability of the paint (metal oxide composition), and the ability to improve the leveling property of the coating process is also preferable. The hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to: LOO% by weight. Specific examples of the hydroxyl group-containing solvent include n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy 1-butanol, 3-methoxy-2-butanol, and ethylene glycol. Examples include monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl acetate, butyl lactate, and propylene glycol monomethyl ether. In particular, ₃ -methoxy-1-butanol, propylene glycol monomethylenotenole, ethyleneglycolmonomethylenotenole, and ethyleneglycololemono- _n- butyl ether are the dispersibility and dispersion stability of metal oxides. Is preferable because it becomes better.

 [0039] The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation, for example, a monocarbonyl compound, a dicarbonyl compound, a acetophenone compound, a benzoin ether compound, a acylphosphine. Xoxide compounds and aminocarbo-Louis compounds can be used.

[0040] Specifically, monocarbol compounds include benzophenone, 4-methyl-benzophenone, 2,4,6 trimethylbenzophenone, methylo-benzoylbenzoate, 4-phenylbenzophenone, 4 — (4-Methylphenol-thio) Hue-Luethanone, 3,3'-Dime 4-Cylbenzophenone, 4- (1, ₃ —Ataliloyl— 1, 3, 3 ′ Dimethyl 4 —Methoxybenzophenone, 4— (1,3-Ataliloyl 1,4,7, 10, 13 Pentaxotridecyl) benzophenone, 3, 3 ', 4,4'-tetra (t-butylperoxycarbol) benzazophenone, 4-benzoyl-N, N, N trimethyl-1-propanamine hydrochloride, 4-benzoyl N, N Dimethyl N— 2— (1-oxo 2-Proxelloxychetyl) Methaammuum oxalate, 2-Z4-iso-propyl thioxanthone, 2, 4 Jetylthioxanthone, 2, 4 Dichlorodithioxanthone, 1 Chloro-4 Propoxychio sandone, 2 Hydrokey 3— (3, 4 Dimethyl-9—Oxo 9H Thioxanthone 1—Iroxy— N, N, N Trimethyl-1-propanamine hydrochloride, Benzylmethylene—3 methyl Examples thereof include naphtho (1, 2-d) thiazoline.

 [0041] Dicarbol compounds include 1, 2, 2 trimethyl monobicyclo [2.1.1] heptane 1, 2, 3 dione, benzyl, 2 ethyl anthraquinone, 9, 10 phenanthrenequinone, methyl (X o Examples include xenobenzene acetate, 4-phenol penzyl, etc. Examples of the acetophenone compound include 2-hydroxy-1-2-methyl-1-phenolpropane-1-one, 1- (4-isopropylphenol) 2-hydroxy-2- Methyl 1-phenol Propanone 1-one, 1— (4-Isopropylphenol) 2 Hydroxy di-2-methyl —1-phenol propane mono-1-one, 1-hydroxy monocyclohexyl phenol ketone , 2-Hydroxy-2-methyl-1-styrylpropane 1-one polymer, methoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy 1,2-diphenylethane-1 1,2-diethoxy 1,2-diphenylethane 1-on, 2-methyl-1 [4 (methylthio) phenol] 2-morpholinopropane 1-on, 2-benzyl 2-dimethylaminoamino 1- (4-morpholinophenol ) Butane 1-one, 1-Ferro 1, 2—Puffed Pandione 2— (o Ethoxycarbol) oxime, 3, 6 Bis (2-methyl—2-morpholinopropanol) 9 Examples include butyl carbazole.

 [0042] 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 acyl phosphine oxide compounds include 2, 4, 6 trimethylbenzoyl diphenol. Examples thereof include phosphine oxide, 4-n-propylphenol (2, 6 dichlorobenzoyl) phosphine oxide, and the like.

[0043] The aminocarbol compounds include methyl-4- (dimethoxyamino) benzoate, ethyl 4- (dimethylamino) benzoate, 2-n-butoxetyl-4- (dimethylamino) benzoate, isoamiru 4 (dimethylamino) benzoate, 2 (Dimethylamino) ethyl benzoate, 4, 4'-bis 1-dimethylamino benzophenone, 4, 4'-bis 1 4 cetylamino benzophenone, 2, 5 'bis (4 jetylaminobenzal) cyclopentanone, etc. Is mentioned.

 Commercially available photopolymerization initiators include Ciba Specialty Chemicals Co., Ltd. Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, BASF's Lucillin TPO, Japan Siebel Hegner Co., Ltd. ) Made Esacure One.

[0044] 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 (Α) (if the following photocurable compound is optionally included, the dispersant (Α) (Total amount of curable compound) It is preferably used in the 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.

 [0045] The metal oxide composition may contain other binder resin and a photo-curable compound in addition to the dispersant (i).

Examples of the noinder resin include polyurethane resin, polyurethane resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, and melamine resin. Examples thereof include fat, polyamide resin, phenol resin, bull resin and the like. These coffins may be used alone or in combination of two or more. The binder resin is the solid content of the metal oxide composition. Outside ingredients. same as below. ) Based on the total amount (100 parts by weight), it is preferably used within the range of 20 parts by weight or less.

 [0046] Examples of the photocurable compound include polymerizable unsaturated double bond groups such as (meth) acrylic compounds, fatty acid vinyl compounds, alkyl butyl ether compounds, a-olefin compounds, bur compounds, and echul compounds. Can be used. 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 photo-curable compound is 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). It is preferable.

 [0047] The (meth) acrylic compound has benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, carboxyl group and polymerizable unsaturated double bond. Compounds, (meth) acrylic compounds having a hydroxyl group, nitrogen-containing (meth) acrylic compounds, and the like. Monofunctional and polyfunctional compounds can be used as appropriate. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.

[0048] Specific examples of monofunctional (meth) acrylic compounds include methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , Butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, no- (Meth) acrylate, Decyl (Meth) acrylate, Undecyl (Meth) acrylate, Dodecyl (Meth) atelate, Tridecyl (Meth) acrylate, Tetradecyl (meth) atelate, Pentadecyl (Meth) atelate Xadecyl (meth) atarylate, heptadecyl (meth) atalylate, octadecyl (meth) atarire And alkylene (meth) acrylates having 1 to 22 carbon atoms such as catechol, nonadecyl (meth) acrylate, icosyl (meth) acrylate, hencosyl (meth) acrylate and docosyl (meth) acrylate. For the purpose 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 leveling properties, it is preferable to use alkyl (meth) acrylate with an alkyl group having 6 or more carbon atoms! [0049] 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 (meta) ) Atalylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol Mono (meth) acrylate with a hydroxyl group at the end and a polyoxyalkylene chain, such as (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy diethylene 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-pentaxite tetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy tetra Propylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxy Tetrapropylene glycol (meth) atalylate, n-pentoxytetrapropylene glycol (meth) atalylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol ( (Meth) acrylate, ethoxy polyethylene glycol (Meth) acrylate, etc. Mono (meth) acrylate with an alkoxy group at the end and a polyoxyalkylene chain; Phenoxyethylene glycol (Meth) acrylate, Phenoxyethylene Glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate DOO, Fuenoki sheet polyethylene glycol (meth) Atari rate, such as phenoxyethanol tetrapropylene ethylene glycol (meth) Atari rate, polio Kishiarukiren system having a phenoxy or Ariruokishi group-terminated (meth) Atari rate and the like.

[0050] Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, and alkyl or alkmono monomers thereof. Esters, phthalic acid j8-(Meth) talarixetyl monoester, isophthalic acid j8-(Meth) talarixetyl monoester, succinic acid j8-(Meth) talarixetyl monoester, acrylic acid, methacrylic acid Examples include acids, crotonic acid, and cinnamic acid.

 [0051] Hydroxyl group-containing (meth) acrylic compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meta) ) Atalylate, 4-hydroxybutenebenzene, 2-hydroxy-1-3-phenoxypropyl (meth) acrylate, and the like.

 [0052] Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N —Propoxymethyl— (meth) acrylamide, N-butoxymethyl— (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, and other monoalkylol (meth) acrylamides, N, N—di (methylol) acrylamide, N-methylol — N— Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethyl Methacrylamide, N, N—di Propoxymethyl) acrylamide, N-butoxymethyl—N— (propoxymethyl) methatalamide, N, N—di (butoxymethyl) acrylamide, N-butoxymethyl—N— (methoxymethyl) methacrylamide, N, N—di Acrylamide-type unsaturated compounds such as (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dialalkylol (meth) acrylamide, etc .; dimethylaminoethyl (meth) acrylate, diethylamino Unsaturated compounds having a dialkylamino group such as ethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, and jetylaminostyrene; and Cl—, Br −, Γ as counter ions Halogen ion such as QS03_ (Q: carbon number 1 There quaternary Anmoniumu salts of dialkylamino group-containing unsaturated compound having an alkyl group) of 12.

[0053] Other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, monofluoroethyl methyl (meth) acrylate, 2-perfluorobutyl cetyl (meth) alkyl. Relate, 2-Perfluohexyl Hexylethyl (meth) atarylate, 2-Perfluoro Ota Tyrethyl (meth) acrylate, 2-Perfluoroisonoruethyl (meth) acrylate, 2-Perfluorono-rucetyl (meth) acrylate, 2-Perfluorodecyl cetyl (meth) acrylate, Per Carbon number such as fluoropropylpropyl (meth) acrylate, perfluoro oxypropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctyldecyl (meth) acrylate Mention may be made of perfluoroalkylalkyl (meth) acrylates having 1 to 20 perfluoroalkyl groups.

[0054] Furthermore, perfluoroalkyl groups such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene and the like, and perfluoroalkyl groups such as alkylenes. Bulle monomers; Bulle trichlorosilane, Buturis (methoxyethoxy) silane, Vinyltriethoxysilane, _Alkoxysilyl group-containing Bully compounds such as _Ύ- (meth) atyloxypropyltrimethoxysilane and derivatives thereof; Glycidyl acrylate, 3, 4 Examples include glycidyl group-containing acrylate, such as epoxycyclohexyl acrylate.

 [0055] Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl crotonate, butyrate caprylate, laurate, chloroacetate, oleate, and stearate.

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

 [0056] Examples of the a-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene.

 Examples of the bur compound include allylic compounds such as allylic acetic acid, allylic alcohol, allylic benzene, and cyano cyanide, cyano cyanide, biscyclohexane, butyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, chlorostyrene, and the like. Is mentioned. Examples of the ethul compound include acetylene, eth benzene, ethul toluene, 1 ethynyl-1-cyclohexanol, and the like.

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

[0057] Among these, as photocurable composites other than the dispersant (Α), the coating film strength, scratch resistance, etc. From the viewpoint of safety, poly (meth) acrylates such as polyurethane poly (meth) acrylate with at least three functional groups, poly epoxy poly (meth) acrylate, and three or more acryloyl groups in the molecule The polyfunctional attalylate possessed can be preferably used.

 Polyepoxy poly (meth) acrylate is an epoxy resin whose epoxy group is esterified with (meth) acrylic acid and the functional group is a (meth) taroloyl group. To bisphenol A type epoxy resin (Meth) acrylic acid adducts, and (meth) acrylic acid adducts to novolac epoxy resins.

[0058] Polyurethane poly (meth) acrylate is obtained, for example, by reacting diisocyanate and (meth) acrylate having a hydroxyl group, under the condition that polyol and polyisocyanate are excessive in isocyanate group. There are those obtained by reacting an isocyanate group-containing urethane preform made by reacting with (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 a hydroxyl group-excess condition with a (meth) acrylate having an isocyanate group.

 [0059] Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentandalol, neopentyl glycol, hexane. Examples include triol, trimellyl propane, polytetramethylene glycol, and a polycondensation product of adipic acid and ethylene glycol.

 [0060] Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like.

 Examples of (meth) atalylates having a hydroxyl group include 2-hydroxyethyl (meth) atalyl pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate. Etc.

 Examples of (meth) acrylates having an isocyanate group include 2- (meth) attalylooxyethylisocyanate, (meth) attalyloyl isocyanate, and the like.

[0061] Examples of commercially available photocurable composites include the following. Toa Gosei Co., Ltd .: Alonix M-400, Aguchi-X M-402, Aguchi-X M-408, Aguchi-X M-450, Aguchi-X M-7100, Aronix M-8030,口 口 -tuss M—8060,

 Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400,

 Kayaku Satomaichi Co., Ltd .: SR-295,

 Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 51 29, Ebecryl 2220, Ebecryl 6602,

 Shin-Nakamura Chemical Co., Ltd .: NK Ester A—TMMT, NK Oligo EA—1020, NK Odigo EMA—1020, NI U Go EA—6310, NI U Go EA—6320, NI U Go EA—6 340, NK Oligo MA-6, NK Oligo U— 4HA ゝ NK Oligo U— 6HA ゝ NK Oligo U— 3 24A,

 BASF: LaromerEA81,

 Made by San Nopco: Photomer 3016,

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

 Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN—9000 H, Art Resin UN—901T, Art Resin HDP, Art Resin HDP-3, Art Resin H61,

 Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV—7600B, Purple light UV—7610B, Purple light UV—7 620EA, Purple light UV—7630B, Purple light UV—1400B, Purple light UV—1700B, Purple light UV—6 300B,

 Kyoeisha Co., Ltd .: Light Attalate PE-4A, Light Attalate DPE-6A, UA-306H, UA-306T, UA-3061,

 Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARA D 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. Made of The production method includes, for example, applying the 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 is deposited on an arbitrary substrate so that the film thickness after drying is preferably 0.1 to 30 111, more preferably 0.1 to 20 m. It can be formed by applying a curing treatment after coating.

 [0063] At the time of formation, the cured film may be applied directly to the substrate, or one or more lower layers may be present between the cured film and the substrate.

 Examples of the substrate include metals, ceramics, glass, plastics, wood, slate and the like, and are not particularly limited. Specific plastic types include polyester, polyolefin, polycarbonate, polystyrene, polymethylmetatalylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, and melamine resin. It is done. In addition, the shape of the substrate is not particularly limited, and includes a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber-like material.

 [0064] As the coating method, a known method can be used, for example, a method using a lot or wire bar, and various coatings such as microgravure, gravure, die, curtain, lip, slot or spin. The method can be used.

 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 lamp clamp, or the like can be used as a source of ultraviolet light 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.

[0065] The active energy dose to be irradiated is preferably within the range of 5 to 2000 miZcm ² , and more preferably within the range of 50 to: LOOOmjZcm 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.

[0066] The cured film is formed by applying a metal oxide composition to a base material and naturally or forcedly drying it. It may be formed by curing treatment! After coating, curing and curing, it may be natural or forced drying, but it is more preferable to perform curing treatment after natural or forced drying. Better ,.

 In particular, in the case of curing with an electron beam, it is more preferable to perform the curing treatment after natural or forced drying in order to prevent the curing inhibition by water or the decrease in the 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.

 [0067] The obtained cured film is excellent in hard coat properties, transparency, light resistance, high refractive index properties, and antistatic properties, and thus can be suitably used as an optical material. Therefore, the cured film of the present invention is a laminated body, such as a cathode ray tube, a front panel of various display devices such as a flat display panel (liquid crystal display, plasma display, electoric chromic display, light emitting diode display, etc.) or an input thereof. It can also be used as a device.

In addition, this cured film can be widely used for optical lenses, eyeglass 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 0.1-30 / ζ πι.

 Furthermore, the refractive index of the cured film is preferably in the range of 1.4 to 2.0, more preferably in the range of 1.5 to 1.8.

[0068] 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 includes one or more films having different refractive indexes, an adhesive layer or an information recording layer.

[0069] For example, a laminate including a film (Μ), an adhesive layer (Μ) or an information recording layer (Μ) having different refractive indexes can have a layer configuration such as the following (I) to (IX). .

 (I) Substrate Ζ (Μ) Ζ Cured film

(II) Substrate Ζ Cured film Ζ (Μ) (III) Base material Z (M) Z cured film Z (M)

 (IV) (M) Z substrate Z cured film

 (v) ^) 7 substrate 7 ^) 7 cured film

 (vi) (M) Z substrate Z cured film Z (M)

 (VII) (M) Z substrate Z (M) Z cured film Z (M)

 (VIII) (M) Z cured film Z substrate Z cured film

 (IX) Cured film Z (M) Z substrate Z cured film

 [0070] 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 are no restrictions on the materials used, and 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 as necessary. Any material that can be used can be used.

 [0071] The information recording layer is not particularly limited as long as it is capable of causing some chemical change by laser light or the like and recording information by the change. Examples of organic materials include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, triphenylmethane-based metal complexes, and one or more of the above dyes. Two or more types 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 can be used alone or in combination of two or more. The information recording layer may be a laminate or the like. 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, and Co, or may be a spiropyran or fluorinated photochromic material.

[0072] From the viewpoint of antireflection, the cured film having a high refractive index is also preferably used as a laminate provided with a coated cured film having a low refractive index on the surface layer to provide an antireflection function. That is, a product obtained by forming a cured film on a substrate such as a film, and more preferably forming a coated cured film. The layer body is preferably used as an 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 base material is cured. When an arbitrary layer is present between the film and the substrate, it is preferable that the difference in refractive index between the cured film and the lower layer in contact with the cured film is within ± 0.02.

[0073] 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, as an optical semiconductor element sealing material that requires the refractive index of the resin layer to be gradually reduced from the optical semiconductor element side toward the outermost layer, Examples of optical semiconductor elements that can be preferably used include gallium nitride (GaN: refractive index 2.5), gallium phosphide (GaP: refractive index 2.9), gallium arsenide (GaAs: refractive index 3.5), etc. It is a material with a high refractive index. 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 more preferably from the viewpoint of increasing the light extraction efficiency. Preferably it is 1.7-7.

 [0074] As a method of achieving the optimum refractive index of the cured product, as the metal oxide to be used, titanium oxide (refractive index 2.5 to 2.7), zirconium oxide (refractive index 2.4), acid The dispersant (A) having an aromatic skeleton is preferred because a dispersant having a high refractive index is also required for a dispersant such as zinc oxide (refractive index 1.95).

 [0075] <Example>

 Hereinafter, the present invention will be described in more detail based on production examples and examples. In the 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-dicarboxyphenol) fluorenedioic anhydride (manufactured by JFE Chemical Co., Ltd., trade name: BPAF)

Tetrahydronaphthalene dianhydride (trade name: Ricacid TDA— 1 00) Naphthalene dianhydride (JFE Chemical Co., Ltd., trade name: NTCDA)

 Butanetetracarboxylic dianhydride (trade name: Ricacid BT—100, manufactured by Shin Nippon Riyaku Co., Ltd.)

 Pentaerythritol triatalylate (1) (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name: Biscote # 300)

 Pentaerythritol triatalylate (2) (Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30)

 Dipentaerythritol pentaatalylate (Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA)

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

 Hydroquinone (Wako Pure Chemical Industries, Ltd.)

 1, 8—Zazabicyclo [5. 4. 0] — 7—Undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) Glycidyl metatalylate (manufactured by Dow Chemical Japan Co., Ltd.)

 Dimethyl penzylamine (Wako Pure Chemical Industries, Ltd.)

[0076] (Production Example 1: Dispersant (1))

 In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, biphenyl tetracarboxylic dianhydride 80.0 parts, pentaerythritol tritalylate (1) 250.0 parts, hydroquinone 0 16 parts and 141.2 parts of cyclohexanone were charged and the temperature was raised to 85 ° C. Next, 1,8-diazabicyclo [5. 4. 0] -7-undecene 1.65 kg was added as an insect medium and stirred at 85 ° C for 8 hours. Then, add 77.3 parts of glycidyl metatalylate and 3.3.9 parts of cyclohexanone, then add 2.65 parts of dimethylbenzylamine as a catalyst, stir at 85 ° C for 6 hours, and cool to room temperature The reaction was terminated. The resulting reaction solution was light yellow and transparent with a solid content of 70%, a number average molecular weight (MN) of 870, and a weight average molecular weight (MW) of 2,830.

[0077] (Production Example 2: Dispersant (2))

A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, biphenyl tetracarboxylic dianhydride 80.0 parts, pentaerythritol-reactor relay (2) 250.0 parts, hydroquinone 0 16 parts and 141.2 parts of cyclohexanone were charged and the temperature was raised to 85 ° C. Next, 1,8-diazabicyclo [5. 4. 0] -7-undecene 1.65 kg was added as an insect medium and stirred at 85 ° C for 8 hours. Thereafter, 77.3 parts of glycidyl metatalylate and 3.3.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine as a catalyst were added and stirred at 85 ° C. for 6 hours. The reaction was terminated by cooling to room temperature. The resulting reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight of 920, and a weight average molecular weight of 3,130.

 [0078] (Production Example 3: Dispersant (3))

 In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, biphenyl tetracarboxylic dianhydride 80.0 parts, pentaerythritol tritalylate (1) 124.8 parts, dipenta Erythritol pentaatalylate 222.8 parts, hydroquinone 0.21 parts, cyclohexanone 430.0 parts 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 metatalylate and 80.7 parts of cyclohexanone were added, and then 3.42 parts of dimethylbenzylamine was added as a catalyst, followed by stirring at 85 ° C for 6 hours. The reaction was terminated by cooling to room temperature. 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.

 [0079] (Production Example 4: Dispersant (4))

 9, 9-bis (3, 4-dicarboxyphenol) fluorene dianhydride 100.0 parts, pentaerythris in a 4 neck flask equipped with stirrer, reflux condenser, dry air inlet tube, thermometer Triol tritalylate (1) 200.2 parts, hydroquinone 0.15 parts, cyclohexanone 200.1 parts 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. The reaction was terminated. The resulting 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.

 [0080] (Production Example 5: Dispersant (5))

A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, tetrahydronaphthalene dianhydride (10.0 parts), pentaerythritol tritalate (2) 305.7 parts, Hydroquinone (0.20 part) and cyclohexanone (405.7 part) were charged, and the temperature was raised 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 metatalylate and 96.9 parts of cyclohexanone were added, and then 3.26 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C for 6 hours and allowed to reach room temperature. The reaction was terminated by cooling. 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.

 [0081] (Production Example 6: Dispersant (6))

 A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer. Naphthalene anhydride 100.0 parts, pentaerythritol retorali talilate (2) 342.2 parts, hydroquinone 0.22 parts Then, 442.2 parts of cyclohexanone was 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 metatalylate and 108.4 parts of cyclohexanone were added, and then 3.56 parts of dimethylbenzylamine was added as a catalyst. The mixture was stirred at 85 ° C for 6 hours and cooled to room temperature. The reaction was terminated. 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.

 [0082] (Production Example 7: Dispersant (7))

 In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, biphenyl tetracarboxylic dianhydride 100.0 parts, dipentaerythritol pentaatalylate 55 6.8 parts, hydroquinone 0. 33 parts, cyclohexanone 437. 8 parts are charged 85. The temperature was raised to 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. Then, 96.6 parts of glycidyl metatalylate and 66.8 parts of cyclohexanone were added, and then 5.28 parts of dimethylbenzylamine as a catalyst, stirred at 85 ° C for 6 hours, and cooled to room temperature. The reaction was terminated. 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.

 [0083] (Production Example 8: Dispersant (8))

9, 9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 100.0 parts, acrylic acid in a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer 2—Hydrochichechinole 50. 7, Hydroquinone 0.08 咅 ^ Cyclohexanone 100. 4 咅 The temperature was raised to 5 ° C. Next, 1.51 parts of 1,8-diazabicyclo [5.4.0] -7-undecene as a catalyst was added and stirred at 85 ° C. for 5 hours. Thereafter, 62.0 parts of glycidyl metatalylate 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. The reaction was terminated. The resulting reaction solution was light yellow and transparent with a solid content of 60%, a number average molecular weight of 890, and a weight average molecular weight of 1,200.

 [0084] (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 tritalylate (1) 463.2 parts, hydroquinone 0.28 Part, cyclohexanone 563.2 parts, 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 metatalylate 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. The reaction was terminated. 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.

 [0085] (Production Example 10: Dispersant (10))

 In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, butanetetracarboxylic dianhydride 100.0 parts, pentaerythritol tritalylate (2) 463.2 parts, hydroquinone 0.28 Part, cyclohexanone 563.2 parts, 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 metatalylate 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. The reaction was terminated. The obtained 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.

 [0086] (Production Example 11: Dispersant (11))

A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer. Butane teracarboxylic acid dianhydride 80.0 parts, pentaerythritol-reactor relay (2) 185.3 parts, dipentaerythritol penta Atalylate 330.9 parts, Hydroquinone 0.30 parts, Cyclohexyl The temperature was raised to 85 ° C with 599.5 parts of Sanon. Next, 2.98 parts of 1,8-diazabic mouth [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 daricidylmetatalylate 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. The reaction was terminated. 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.

 [0087] (Production Example 12: Dispersant (12))

 In a 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, butanetetracarboxylic dianhydride 50.0 parts, dipentaerythritol pentaatalylate 413.4 parts, hydroquinone 0.23 parts, Cyclohexanone 463. 4 parts were charged and the temperature was raised 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 metatalylate and 74.3 parts of cyclohexanone were added, and then 3.73 parts of dimethylbenzylamine as a catalyst were added and stirred at 85 ° C for 6 hours. The reaction was terminated by cooling to. The obtained 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.

 [0088] (Production Example 13: Dispersant (13))

 In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 10.0 parts of butantetracarboxylic dianhydride, 117.2 parts of 2-hydroxyethyl acrylate, 0.11 of hydroquinone And 144.8 parts of cyclohexanone were charged and the temperature was raised to 85 ° C. Next, add 1.17 parts of 1,8-diazabicyclo [5. 4. 0] —7-undecene as catalyst. Stir at C for 5 h. Then, 143.4 parts of glycidinoremetatalylate and 93.3 parts of cyclohexanone were added, followed by 1.74 parts of dimethylbenzylamine as a catalyst, stirred at 85 ° C for 6 hours, and cooled to room temperature. The reaction was terminated. 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.

 [0089] (Preparation of metal-acid dispersion paste: Examples 1 to 22, Comparative Examples 1 to 3)

Using each dispersant (A) prepared in the above production example, metal oxide dispersion was carried out according to the formulation shown in Table 1, and a metal oxide dispersion paste was prepared (the amount is a solid content). O Dispersion method is , Pre-dispersion (Zircon beads (1.25mm) 1 hour dispersion with Acre) and this dispersion (using Zirca beads (0.1 mm) as a medium and dispersion with UAM-015, a disperser manufactured by Kotobuki Industries Co., Ltd.).

[table 1]

Table Formulation of gold oxide dispersion paste

[0091] In Table 1,

 Sb O: “San-Epoque EFR-6N” manufactured by Nissan Chemical Industries, Ltd. (average primary particle size: 20η

twenty five

 m)

 ATO: “SN-100PJ (average primary particle size: 20nm) manufactured by Ishihara Sangyo Co., Ltd.

 ITO: "Nanotech ITO" manufactured by Shi Kasei Co., Ltd. (average primary particle size: 30nm) PTO: "EP SP-2" manufactured by Mitsubishi Materials Corporation (average primary particle size: 15nm) ZrO: manufactured by Nippon Electric Works Co., Ltd. "PCS-60" (average primary particle size: 20nm)

 2

 TiO: “TTO-51 (A)] manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 20nm)

 2

 ZnO: “FINEX-50” manufactured by Sakai Chemical Industry Co., Ltd. (average primary particle size: 20 nm) SiO: “AEROSIL50” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 50 nm)

 2

 Al O: Nippon Aerosil Co., Ltd. “Aluminium Oxide C” (average primary particle size: 13

twenty five

 nm)

Commercial dispersant: Big Chemie Japan Co., Ltd. “Di _S perbyk— 111” (100% solids) Commercial polyfunctional monomer (1): Osaka Organic Chemical Co., Ltd. “Biscoat # 400” (solid content 100

%)

 Commercially available multifunctional monomer (2): “KAYARAD DPHAj (solid content 100) manufactured by Nippon Kayaku Co., Ltd.

%)

 MIBK: Methinoreisobutinoleketone

 Methobuta: 3-Methoxy-1-butanol

<Coating and Cured Film Evaluation: 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 indicates the solid content). O The obtained metal oxide composition was Easy coating treatment with a thickness of 100 m PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) was coated with a bar coater so that the film thickness after drying would be 5 πι, and then a metal halide run A cured film (hard coat layer) was formed by irradiating with 400 mjZcm ² of ultraviolet rays. 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.

[0093] [Table 2] Table 2 Composition of metal oxide composition and evaluation of cured film

[0094] In Table 2,

 Photo-curable compound (1): “UA-306TJ” manufactured by Kyoeisha Chemical Co., Ltd.

 Photo-curing compound (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.

 Photopolymerization initiator: Ciba Specialty Chemicals "Irgacure 184" Solvent: PGME (propylene glycol monomethyl ether)

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

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

 (Preparation of low refractive index coating liquid)

 1,2,9,10—Tetraatalylooxy— 4, 4, 5, 5, 6, 6, 7, 7—Octafluorodecane 50 parts by weight, silica sol 30% dispersion (MEK manufactured by Nissan Chemical Industries, Ltd.) -ST) 120 weight

, 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, 5 parts by weight of a photopolymerization initiator (Nippon Kayaku Co., Ltd. KA YACURE BMS) was mixed to prepare a low refractive index coating solution.

[0096] 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). O This metal oxide composition was ,

Easy adhesion treatment of 100 m thick PET film (refractive index of the easy adhesion treatment layer = 1.60) was applied to the easy adhesion treatment surface using a bar coater to a dry film thickness of 6 m. 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. Further, the low refractive coating liquid was applied onto 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.

 Regarding the obtained laminate, the refractive index of the cured film was measured by the following method, and the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflection interference fringes of the cured film were evaluated. The results are shown in Table 3.

[0097] [Table 3] Table 3 Composition of metal oxide composition and evaluation of S

 (Parts by weight) Example 23 Example 24 Example 25 Example 26 Example 27 Metal oxide dispersion paste 37.28 44.25 51.52 56.1 62.96 Photocurable compound (2) 41.36 31.91 25.37 20.2 15.63

 2.38 1.91 1.56 1.35 1.14 Solvent (PGME) 68.98 71.93 71.55 72.35 70.27 Refractive index of cured film 1.56 1.58 1.6 1.62 1.64 Abrasion resistance 5 5 5 5 5 Pencil hardness AAAAA Transparency (Haze value) 0.58 0.62 0.65 0.68 0.75 Cured film and base Refractive index difference 0.04 0.02 0 0.02 0.04 Reflective interference fringe DAAAD

[0098] In Table 3

 Photo-curing compound (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.

 Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd. Base material: 100 m thick easily treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) (Coating to refractive index 1.60)

 Solvent: PGME (propylene glycol monomethyl ether)

[0099] (Evaluation method)

 (1) Refractive index

 The refractive index of the obtained cured film was measured using an Abbe refractometer manufactured by Atago Co., Ltd.

[0100] (2) Scratch resistance

 The coated product was set on a Gakushin Tester and shook 10 times with a load of 250g using steel wool No.0000. The removed coating was judged for scratching according to the following five-step visual evaluation. The larger the value, the better the scratch resistance of the cured film.

 5: No scratch

 4: There are slight scratches

3: Scratches are attached! Come on! You can see the base material! 2: Scratched and part of the cured film is peeled off

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

[0101] (3) Pencil hardness

 In accordance with JIS K5600, a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON) was used, and the test was performed five times at a load of 500 g with various changes in pencil core hardness. The pencil hardness of the hardened film was defined as the hardness of the core when the scratch was not scratched once or was scratched only once. In consideration of practical required physical properties, the pencil hardness of the cured film is 2H or more: A

 1H or more: B

 Lower than 1H: D

 It was determined.

[0102] (4) Transparency (Haze value)

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

[0103] (5) Light resistance

 Yellowing with the passage of time during continuous light irradiation is very 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 WZcm ² , black panel temperature: 60 ° C, 60% RH). Thereafter, the coated material was placed on white paper, and the color 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 b * value, the smaller the degree of yellowing and the better the light resistance. Considering the practical properties required, the b * value of the cured film is

 3. Less than 5: A

 3. More than 5: D

 It was determined.

[0104] (6) Surface resistance

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

If the surface resistance is 1 X 10 ¹² or less: A For surface resistance higher than 1 X 10 "and lower than 1 X 10 ¹⁴ : B

If the surface resistance exceeds 1 X 10 ¹⁴ : D

[0105] (7) Reflective interference fringes

 The reflected interference fringes of the obtained cured film were visually evaluated according to the following criteria.

 The reflection interference fringes cannot be observed ヽ: A

 Reflective interference fringes can be observed: D

[0106] This disclosure 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. All of which are hereby incorporated 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

Claims [1] A metal oxide composition comprising a dispersant (A) represented by the following general formula (1) and a metal oxide having an average primary particle diameter of 5 to LOONm. General formula (1):

 [Chemical 1]

(In the formula, I ^ to R ⁴ each independently represents a hydrogen atom or a methyl group, and R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group or Represents an alkyleneoxyalkylene group, and R ⁹ represents a tetravalent aromatic group or an aliphatic group.

[2] In the general formula (1), R ⁹ is at least one tetravalent aromatic group selected from the group force consisting of biphenyl skeleton, naphthalene skeleton, fluorene skeleton, and tetrahydronaphthalene skeleton, or carbon Claim 4: The metal oxide composition according to claim 1, wherein the metal oxide composition is a tetravalent aliphatic group that is an alkyl skeleton of L0.

 [3] Compound (xl) in which dispersant (A) has an aromatic skeleton or an aliphatic skeleton, and two or more carboxylic anhydride groups, and a compound having a functional group capable of reacting with a carboxylic anhydride group (X2) is obtained by reacting a compound (X) having a carboxyl group obtained by reacting with (x2) and a compound (Y) having a functional group capable of reacting with a carboxyl group,

 The metal oxide composition according to claim 1 or 2, wherein at least a part of the compound (x2) and the compound (Y) has a polymerizable unsaturated double bond group.

 [4] Compound (x2) force The metal oxide composition according to claim 3, wherein the compound is an attareito toy compound or a methacrylic toy compound having one or two hydroxyl groups.

[5] The metal oxide is titanium, zinc, zirconium, antimony, indium, tin, 5. The metal oxide composition according to any one of claims 1 to 4, which contains at least one element selected from the group force of lumium, silicon, phosphorus and fluorine.

[6] The metal oxide composition according to any one of claims 1 to 5, further comprising a solvent, wherein the solvent comprises 10 to LOO% by weight of a hydroxyl group-containing solvent with respect to the total solvent. object.

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

[8] The cured film according to claim 7, wherein the thickness is 0.1 to 30 μm.

[9] The cured film according to claim 7 or 8, wherein the refractive index is in the range of 1.4 to 2.0.

[10] A laminate comprising a base material and the cured film according to any one of claims 7 to 9.

11. The laminate according to claim 10, wherein the substrate is a plastic substrate.

12. The laminate according to claim 10 or 11, wherein the substrate has a lens shape.

[13] The cured film according to any one of claims 10 to 12, wherein the cured film is formed on the substrate without any other layer, and the difference in refractive index between the cured film and the substrate is within ± 0.02. The laminate according to any one of the above.

[14] The present invention further comprises one or more lower layers between the cured film and the substrate, and the difference in refractive index between the cured film and the lower layer in contact with the cured film is within ± 0.02. The laminate according to any one of 12 items 1.

 [15] The laminate according to any one of claims 10 to 14, comprising an information recording layer.

[16] The laminate according to any one of claims 10 to 14, which is an antireflection film.

[17] An optical semiconductor element sealing material comprising the metal oxide composition according to any one of claims 1 to 6.

 [18] Metal oxide including dispersing agent (A) represented by the following general formula (1) and dispersing a metal oxide having an average primary particle diameter of 5 to: LOOnm in the presence of an organic solvent A method of manufacturing a material dispersion.

 General formula (1):

[Chemical 2]

(In the formula, I ^ to R ⁴ each independently represents a hydrogen atom or a methyl group, and R ^{5 to} R ⁸ each independently represents an unsubstituted or substituted linear or branched alkylene group or 7 represents an alkylenealkylene group, and R ⁹ represents a tetravalent aromatic group or an aliphatic group.) The metal oxide composition according to any one of claims 1 to 6 is used as a base material. Applying; and

Irradiating active energy rays to cure the metal oxide composition;

The manufacturing method of the cured film containing this.