CN106167634B

CN106167634B - Metal oxide composition, its cured film and the component with the cured film

Info

Publication number: CN106167634B
Application number: CN201610329904.8A
Authority: CN
Inventors: 伊藤光人
Original assignee: Toyo Ink SC Holdings Co Ltd; Toyochem Co Ltd
Current assignee: Toyochem Co Ltd; Artience Co Ltd
Priority date: 2015-05-18
Filing date: 2016-05-18
Publication date: 2018-04-27
Anticipated expiration: 2036-05-18
Also published as: KR20160135667A; TWI561598B; JP5910781B1; CN106167634A; JP2016216563A; TW201641616A; KR101725786B1

Abstract

The present invention provides a kind of metal oxide composition, its cured film and the component with the cured film, its metal oxide composition includes compound (A), metal oxide (B) and the solvent of the compound (A1) with the acryloyl group of more than 6 represented by the following general formula (1).It may also provide the cured film using it and component with the cured film according to the present invention.(in general formula (1), R₁Represent specific tetravalence organic residue；R₂、R₃Represent specific monovalence organic residue) metal oxide composition provided by the invention, contain metal oxide using its cured film and the component with the cured film and may be formed in hard painting propert, the transparency film that has excellent physical property concurrently.

Description

Metal oxide composition, its cured film and the component with the cured film

Technical field

The present invention relates to a kind of metal oxide composition with hard painting propert, its cured film and with the cured film Component.

Background technology

In the past, thus it is ensured that for the performance of information communication device and the aspect of Security Countermeasures, gold is used on the surface of equipment Belong to oxide composition and form hard painting propert film or antistatic property painting with marresistance, adhesion, high index of refraction etc. Film.

In recent years, there is particularly pertinent achievement in the development and generalization of information communication device, it is desirable to hard painting propert film, The further performance of antistatic property film etc. improves and productive raising, and proposes have using the various of photo-hardening material Motion.

For example, can enumerate it is following as technology motion (with reference to patent document 1~patent document 3).Disclosed in patent document 1 Have and mixed antimony doped tin oxide in organic solvent with the silane coupling agent with UV cured property using ball mill, to make The method of the dispersion of conductive coating paint.And then having disclosed in patent document 2 makes electroconductive oxide micropowder be scattered in easily The in the mixed solvent of dispersed low boiling point solvent and difficult dispersed high boiling solvent, to make the method for conductive coating paint.In addition, Having disclosed in patent document 3 makes inorganic oxide be scattered in the compound with polymerism unsaturated double-bond in organic solvent, To prepare the method for metal oxide composition.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 06-264009 publications

[patent document 2] Japanese Patent Laid-Open 2001-131485 publications

[patent document 3] WO2007/138946 publications

The content of the invention

The subject that the invention solves

However, in patent document 1 or patent document 2, i.e., can be produced on simultaneous in hard painting propert, antistatic property, light resistance etc. Have the metal oxide composition of good physical property, can not also make the metal oxygen of particulate of the average primary particle diameter as hundreds of below nm Compound is stably disperseed and is stabilized with primary particle level relative to the high medium of the hydrophobicitys such as organic solvent, therefore with regard to film The transparency or photo-hardening coating the viewpoint such as ageing stability for easily produce problem.

In addition, in the technology that patent document 3 is recorded, in order to make the gold of particulate of the average primary particle diameter as hundreds of below nm Belong to oxide and stably disperse and stabilize with primary particle level, and there is polymerism unsaturated double-bond used in increasing The usage amount of compound, therefore have the problem for the ratio that can not improve metal oxide.

Therefore, it is an object of the invention to provide one kind containing metal oxide and may be formed in hard painting propert, the transparency Have the metal oxide composition, the cured film using it and component with the cured film of the film of excellent physical property concurrently.

Solve the technological means of problem

The form of the present invention is related to a kind of metal oxide composition, it contains：With the acryloyl groups of more than 6 Compound (A), metal oxide (B) and solvent,

The compound (A) includes the chemical combination that the compound (X) for making to have carboxyl is formed with the reaction of biphenyl glycidol ether Thing,

The compound (X) is the one kind made in pentaerythritol triacrylate and Dipentaerythritol Pentaacrylate Or two kinds of compounds (x2) and selected from by 1,2,4,5- benzene tertacarbonic acids dianhydride, 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides, 9,9- Double (3,4- dicarboxyphenyis) fluorenes dicarboxylic anhydrides (9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride), And one or more kinds of compound (x1) reactions forms in the group that is formed of 1,2,3,4- butane tetracarboxylic acid dianhydrides.

Another form of the present invention is related to a kind of metal oxide composition, it contains：With more than 6 acryloyl groups Compound (A), metal oxide (B) and solvent,

The compound (A) includes the compound with the acryloyl group of more than 6 represented by the following general formula (1) (A1),

General formula (1)

[changing 1]

(in general formula (1), R₁Represent following arbitrary tetravalence organic residues；

[changing 2]

R1

In general formula (1), R₂Represent following arbitrary monovalence organic residues；

[changing 3]

R2

In general formula (1), R₃Represent following monovalence organic residues)

[changing 4]

R3

The another form of the present invention is related to the metal oxide composition, wherein R₁To be organic residual comprising aromatic rings Base.

The another form of the present invention is related to the metal oxide composition, and wherein aromatic rings is cyclohexyl biphenyl.

The another form of the present invention is related to the metal oxide composition, wherein metal oxide (B) contain be selected from by At least one of the group that titanium, zinc, zirconium, indium, tin, aluminium, silicon and phosphorus are formed element.

The another form of the present invention is related to the metal oxide composition, and the D50 particle diameters of wherein metal oxide (B) are 0.005 μm~0.200 μm.

Another form of the present invention is related to a kind of cured film, it is to form the metal oxide composition hardening.

Another form of the present invention is related to a kind of component with cured film, it is that institute is set at least a portion of base material Cured film is stated to form.

The effect of invention

According to the present invention, it is possible to provide one kind containing metal oxide and may be formed at hard painting propert, the transparency in have concurrently it is excellent The metal oxide composition of the film of physical property, the cured film using it and component with the cured film.

Embodiment

Hereinafter, embodiments of the present invention are illustrated.Furthermore embodiments described below is the implementation of the present invention The example of mode, the present invention and from the limitation of implementation below.

The metal oxide composition of the present invention contains：Include the chemical combination of the compound (A1) represented by the following general formula (1) Thing (A), metal oxide (B) and solvent.Metal oxide composition can also include two or more metal oxides respectively (B), two or more compound (A) and two or more solvents.

General formula (1)：

[changing 1]

[changing 2]

R1

In general formula (1), R₂Separately represent following arbitrary monovalence organic residues；

[changing 3]

R2

In general formula (1), R₃Separately represent following monovalence organic residues)

[changing 4]

R3

Compound (A) mainly includes the compound (A1), but in addition to compound (A1), as described later, can include The high molecular weight body of compound (A1) etc..The compound (A) has high dispersiveness and light for metal oxide Hardening.The compound (A) improves the dispersiveness of metal oxide (B) and improves photo-hardening, thus, metal of the invention Oxide composition can form excellent hardening and hard painting propert, the transparent excellent cured film and structure with the cured film Part.Therefore, in addition to it can be suitable for plastics optics parts, CD, anti-reflective film, touch-screen, film-type liquid crystal elements, especially The hard paint of various plastic layer stacks can be also suitable for use as.

The metal oxide composition can form the cured film of high refractive index, be equal journey being coated on refractive index In the case of on the base material of degree, the layered product obtained will not produce reflection interference striped, be suitable for optical applications.And then Can the refractive index of the hardening thing comprising metal oxide be controlled high, therefore be also suitable for as optical semiconductor sealing material Material.

In the general formula (1), R₁For tetravalence organic residue, phenyl skeleton, xenyl skeleton, fluorene skeleton or Asia are included Butyl.In these, phenyl skeleton, xenyl skeleton or fluorene skeleton more preferably as the organic residue comprising aromatic rings.

In addition, the compound (A1) that compound (A) is included may be, for example, by the compound (X) for making to have carboxyl and connection The compound that benzene glycidol ether is reacted and obtained, the compound (X) are make tetrabasic carboxylic acid represented by the following general formula (2) two Acid anhydride (x1), be selected from one or both of pentaerythritol triacrylate and Dipentaerythritol Pentaacrylate compound (x2) Reaction forms.Herein, for the viewpoint of photo-hardening and hard painting propert, the compound (x2) is preferably three propylene of pentaerythrite Acid esters and/or Dipentaerythritol Pentaacrylate.

General formula (2)

[changing 5]

As the tetracarboxylic dianhydride (x1) represented by the general formula (2), can enumerate：1,2,4,5- benzene tertacarbonic acids dianhydride, tool There are the 3,3' of xenyl skeleton, 4,4'- biphenyl tetracarboxylic dianhydrides, double (3,4- dicarboxyphenyis) fluorenes two of 9,9- with fluorene skeleton Acid anhydrides (9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride) or double [4- (the 3,4- dicarboxyls of 9,9- Phenoxy group) phenyl] fluorenes dicarboxylic anhydride (9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene Dianhydride), 1,2,3,4- butane tetracarboxylics acid dianhydride etc..

In general formula (2), R₁R preferably defined in general formula (1)₁。

In these tetracarboxylic dianhydrides, 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides have xenyl skeleton, and can be by xenyl The skeleton efficiency good intramolecular for being directed into compound (A), and then the hard painting propert and metal oxide of cured film can be had concurrently Good dispersiveness, therefore particularly preferably.

As compound (x2) pentaerythritol triacrylate and Dipentaerythritol Pentaacrylate it is specific commercially available Product can be enumerated：Than this gram (Viscoat) #300 (Osaka Organic Chemical Industry (stock) manufacture), card Asia ladd (KYARAD) PET30 (Japanese chemical drug (stock) manufacture), group's patch (PETIA) (Daicel (Daicel) UCB (stock) manufactures), sieve Ah Nice (Aronix) M305 (East Asia synthesis (stock) manufacture), NK esters (NK ester) A-TMM-3LMN (Xin Zhong villages chemical industry (stock) manufacture), Lai Te Acrylate (Light Acrylate) PE-3A (common prosperity society chemistry (stock) manufacture), SR-444 (Sartomers (Sartomer) (stock) Manufacture), Lay spy acrylate (Light Acrylate) DPE-6A (common prosperity society chemistry (stock) manufacture), the sub- ladd (KYARAD) of card DPHA (Japanese chemical drug (stock) manufacture), sieve Ah Nice (Aronix) M402 (East Asia synthesis (stock) manufacture) etc..

There is no particular restriction for the allotment of metal oxide (B) and compound (A) in metal oxide composition, relative to 100 mass parts of metal oxide (B), the content of compound (A1) is preferably more than 9 mass parts and 45 is below mass part.With regard to film forming Property viewpoint for, compound (A1) is preferably more than 9 mass parts, and for the viewpoints such as hard painting propert, compound (A1) is preferably 45 is below mass part.Relative to 100 mass parts of metal oxide (B), the content of compound (A1) be more preferably 12 mass parts with On, and then preferably more than 14 mass parts, in addition, more preferably 32 is below mass part, and then preferably 27 is below mass part.Separately Outside, in the gross mass of compound (A), the content of compound (A1) is preferably more than 85 mass %, more preferably 90 mass % with On, and then preferably more than 95 mass %.

Herein, for simplicity, also can be by metal oxide (B) and the allotment ratio of " reactant of inclusion compound (A) " It is set to metal oxide (B) and the index of the allotment of compound (A1).Its reason is：The commercially available product of compound (x2) is usually divided Not containing 5 mass %~15 mass % or so pentaerythritol diacrylate, the dipentaerythritol tetrapropylene with 2 hydroxyls Acid esters is obtained in the reaction of compound (A1) as accessory ingredient, in addition to generation compound (A1), also generates source at the same time Resin that the molecular weights such as reactant, compound (A1) from accessory ingredient form etc., thus in the presence of only to compound (A1) into Row, which calculates, becomes numerous and diverse situation.Relative to 100 mass parts of metal oxide (B), the reactant of inclusion compound (A) is preferably More than 10 mass parts and 50 is below mass part, and more preferably more than 10 mass parts and 35 is below mass part, and then preferably 15 matter Measure more than part and 30 is below mass part.It is more excellent caused by may refrain from organic principle amount less for the viewpoint of the deterioration of film forming Elect situations more than 10 mass parts as.The amount of the reactant of inclusion compound (A), can be by remembering in embodiment as be described hereinafter The method measure of load.

The tetracarboxylic dianhydride (x1) and the reaction of compound (x2) are two acid anhydrides possessed by tetracarboxylic dianhydride With compound (x2) possessed by hydroxyl reaction, its own is in the related art known to people.Such as tetrabasic carboxylic acid two can be made Acid anhydride (x1) is with compound (x2) in the organic solvent as cyclohexanone, as 1,8- diazabicyclos [5.4.0] -7- hendecenes With 50 DEG C~120 DEG C of thermotonus in the presence of catalyst.In the case of described, methyl can be added in reaction system to benzene two Polymerization inhibitor as phenol (2-METHYLHYDROQUINONE).The ratio of each component is not particularly limited, such as can be set to (x1): (x2) (molar ratio)=1:1.4~1:4.0, it is preferably 1:1.6~1：3.0, more preferably 1:1.8~1:2.6, and then be preferably 1:1.9~1:2.4 scope.Herein, the mole of (x2) is that the mole of the accessory ingredient with multiple hydroxyls is included in (x2).

After the reaction, essence is not carried out to the reactant for including the compound (X) with carboxyl as reaction product System ground makes it be reacted with the compound represented by the following general formula (3) as biphenyl glycidol ether.

General formula (3)

[changing 6]

Compound (X) and the reaction of the biphenyl glycidol ether represented by general formula (3) are carboxyl possessed by compound (X) With biphenyl glycidol ether possessed by epoxy group reaction, its own is in the related art known to people.It is for example, described anti- It is able to should be carried out in the presence of the amine catalyst as dimethyl benzyl amine etc. with 50 DEG C~120 DEG C of temperature.The ratio of each component It is not particularly limited, such as (x1) can be set to:Biphenyl glycidol ether (molar ratio)=1:1.4~1:5.0, it is preferably 1: 1.6~1:4.0, more preferably 1:1.8~1:3.0 scope.

These reactions can carry out under no solvent, or be to carry out in inert solvent for reaction.As institute Solvent is stated, such as can be enumerated：The hydrocarbon system solvent such as n-hexane, benzene or toluene；The ketone such as acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK) It is solvent；The ester such as ethyl acetate or butyl acetate system solvent；The ether system solvents such as Anaesthetie Ether, tetrahydrofuran Huo dioxanes；Dichloro The halogen system solvents such as methane, chloroform, carbon tetrachloride, 1,2- dichloroethanes or perchloroethylene (perchloroethylene)；Second Nitrile, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, N- methylimidazole alkanone isopolarity solvents etc..These solvents Can and with two or more.

Furthermore in the case where obtaining compound (A) by the reaction, the so-called " reaction of inclusion compound (A) Thing " refers to the reactant and general formula (3) institute table of inclusion compound (x1) and the reaction product i.e. compound (X) of compound (x2) Reactant in the solid constituent for the reaction product that the compound shown is reacted (removes unreacted component and unrelated with reaction Component).More than the 85% of " reactant of inclusion compound (A) " in one embodiment, is preferably more than 90 mass %, into And preferably more than 95 mass % reacted in a manner of becoming compound (A).

In the present embodiment, the acryloyl group of compound (A) is more than 6.In the present invention, acryloyl group can and be used Number be less than the compound of 6, it is but better by inclusion compound (A), the hardness of the cured film obtained.

Secondly, metal oxide (B) is illustrated.Metal oxide is preferably that D50 particle diameters (particle diameter after scattered) are 0.005 μm~0.200 μm.The day using dynamic light scattering method for example can be used in the D50 particle diameters (volume reference) of metal oxide Machine dress (stock) manufacture " nano Cui Ke (Nanotrac) UPA " etc. is measured.

In the case where D50 particle diameters are too small, the mutual cohesiveness of particulate is very big, therefore has the high once grain of the transparency The tendency that sub horizontal dispersiveness reduces, therefore for the viewpoint that the horizontal dispersiveness of primary particle improves, it is preferably D50 particle diameters For more than 0.005 μm.On the other hand, in the case where D50 particle diameters are excessive, particle diameter is big, therefore has and easily the light such as visible ray are produced The raw tendency scattered and muddiness is produced in cured film, therefore for further suppressing the muddy viewpoint of cured film, it is preferably D50 particle diameters are less than 0.200 μm.D50 particle diameters are more preferably more than 0.015 μm, and then preferably more than 0.025 μm, in addition, more Preferably less than 0.170 μm, and then preferably less than 0.150 μm, particularly preferably less than 0.120 μm.

As metal oxide (B), preferably contain and be selected from by titanium, zinc, zirconium, antimony, indium, tin, aluminium, silicon, phosphorus and fluorine institute group Into at least one of group element.Especially more preferably any containing titanium, zinc, zirconium, indium, tin, aluminium, silicon and phosphorus or two The metal oxide of the element of the kind above.

Specifically, can enumerate：Antimony pentaoxide, antimony doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO), p-doped tin oxide (PTO), zinc antimonates (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO coat titanium oxide, mix alumina Change zinc, titanium oxide, zinc oxide, zirconium oxide, silica, aluminium oxide etc..These metals are aoxidized using organic matter or inorganic matter The surface of thing is handled.In addition, these metal oxides can and with two or more.

As the commercially available product of metal oxide, can enumerate：

Nissan Chemical Industries (stock) manufacture：Sheng Ai pools section (San epoch) EFR-6N, Sheng Aibo section (San epoch) EFR-6NP (antimony pentaoxide)；

Stone originates in industry (stock) manufacture：SN-100P(ATO)、FS-10P(ATO)、SN-102P(ATO)、FS-12P(ATO)、 ET-300W (ATO coat 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 (oxidations Titanium), TTO-F-1 (iron content titanium oxide), TTO-F-2 (iron content titanium oxide), TTO-F-3 (iron content titanium oxide), TTO-F-11 (iron content Titanium oxide), ST-01 (titanium oxide), ST-21 (titanium oxide), ST-30L (titanium oxide), ST-31 (titanium oxide)；

Mitsubishi Materials (stock) manufacture：T-1 (ITO), S-1200 (tin oxide), EP SP-2 (p-doped tin oxide)；

Mitsui Metal Co., Ltd.'s industry (stock) manufacture：Paasche spy bright (Passtran) (ITO, ATO)；

Uncommon love chemical conversion (C.I.Kasei) (stock) manufacture：Nai Nuodake (Nanotec) ITO, Nai Nuodake (Nanotec) SnO₂, Nai Nuodake (Nanotec) TiO₂, Nai Nuodake (Nanotec) SiO₂, Nai Nuodake (Nanotec) Al₂O₃, Nai Nuoda Section (Nanotec) ZnO；

Catalyst chemical conversion industry (stock) manufactures：TL-20(ATO)、TL-30(ATO)、TL-30S(PTO)、TL-120(ITO)、 TL-130(ITO)；

Ha Kusi Tykes (Hakusui Tech) (stock) manufacture：To Be Protected from Heat Tyke (PazetCK) (Al-Doped ZnO)；

Sakai chemical industry (stock) manufactures：Phoenix (FINEX) -25 (zinc oxide), Phoenix (FINEX) -25LP (oxygen Change zinc), Phoenix (FINEX) -50 (zinc oxide), Phoenix (FINEX) -50LP (zinc oxide), Phoenix (FINEX) all (the NANOFINE) -50A (zinc oxide) of -75 (zinc oxide), nano, all (the NANOFINE) -50SD of nano (oxidations Zinc), 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 (Sumitomo Osaka Cement) (stock) manufactures：OZC-3YC (zirconium oxide), OZC-3YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide)；

Japanese Electric (stock) manufactures：PCS (zirconium oxide), PCS-60 (zirconium oxide), PCS-90 (zirconium oxide), T-01 (oxidations Zirconium)；

Supreme Beingization (Tayca) (stock) manufactures：MT-100S (titanium oxide), MT-100HD (titanium oxide), MT-100SA (oxidations Titanium), 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 (oxidations Zinc), MZ-505M (zinc oxide)；

Japanese Ai Luoxier (Aerosil) (stock) manufacture：Aluminium oxide (Aluminium Oxide) C (aluminium oxide), Ai Luoxi That (AEROSIL) 130 (silica), Ai Luoxier (AEROSIL) 200 (silica), Ai Luoxier (AEROSIL) 200V (oxygen SiClx), Ai Luoxier (AEROSIL) 200CF (silica), Ai Luoxier (AEROSIL) 200FA (silica), Ai Luoxier (AEROSIL) 300 (silica), Ai Luoxier (AEROSIL) 300CF (silica), (oxidations of Ai Luoxier (AEROSIL) 380 Silicon), Ai Luoxier (AEROSIL) R972 (silica), Ai Luoxier (AEROSIL) R974 (silica), Ai Luoxier (AEROSIL) R976 (silica), Ai Luoxier (AEROSIL) R202 (silica), Ai Luoxier (AEROSIL) R805 (oxygen SiClx), Ai Luoxier (AEROSIL) R812 (silica), Ai Luoxier (AEROSIL) R812S (silica), Ai Luoxier (AEROSIL) MOX50 (silica), Ai Luoxier (AEROSIL) TT600 (silica), Ai Luoxier (AEROSIL) MOX80 (silica/alumina), Ai Luoxier (AEROSIL) MOX170 (silica/alumina), Ai Luoxier (AEROSIL) COX84 (silica/alumina) etc..

The content of metal oxide (B) is not particularly limited, and is preferably 5 matter of the gross mass of metal oxide composition Measure more than % and below 50 mass %.For the viewpoints such as hard painting propert, the content of metal oxide (B) is more preferably 5 mass % More than, for the viewpoints such as the dispersiveness of metal oxide, the content of metal oxide (B) is more preferably below 50 mass %. The content of metal oxide (B) is not particularly limited, more preferably metal oxide composition gross mass 7 mass % with On, and then preferably more than 10 mass %, in addition, more preferably below 40 mass %, and then preferably below 35 mass %.

According to the embodiment of the present invention, the metal oxide (B) of particulate can be made stably horizontal scattered with primary particle. As the metal oxide (B) of particulate, average grain diameter can be enumerated as below 100nm, preferably below 70nm, more preferably 50nm Following person.Furthermore if the characteristic of dispersion particle diameter or cured film can be maintained suitable scope, average grain diameter can also be used to surpass Cross the metal oxide (B) of 100nm.

In the case where adding solvent, preferably cure process is carried out after solvent is volatilized.There is no particular restriction for solvent, can Using in association area by the various organic solvents known to people.Specifically, such as can enumerate：Cyclohexanone, methyl-isobutyl Ketone, methyl ethyl ketone, acetone, pentanedione, toluene, dimethylbenzene, n-butanol, isobutanol, the tert-butyl alcohol, normal propyl alcohol, isopropanol, Ethanol, methanol, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -2- butanol, glycol monoethyl ether, ethylene glycol mono-n-butyl ether, 2- ethoxies Base ethanol, 1- methoxy-2-propanols, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether second Acid esters, propylene glycol methyl ether acetate, 2- ethoxyethyl acetates, butylacetic acid ester, isoamyl acetic acid ester, adipic acid diformazan Ester, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, methyl pyrrolidone etc..These organic solvents can and with two kinds with On.

Wherein, hydroxyl-bearing solvent is good to the wetability of the metal oxide with the high particle surface physical property of hydrophily It is good, therefore, in containing being formed in solvent, improving the dispersiveness and its coating (oxide-metal combinations of metal oxide Thing) ageing stability in terms of highly effective fruit, and the levelability of applying step is also improved, so it is preferred that.All solvents The content of hydroxyl-bearing solvent in composition is preferably the mass % of 10 mass %~100.Specifically, as containing the molten of hydroxyl Agent, can enumerate：N-butanol, isobutanol, the tert-butyl alcohol, normal propyl alcohol, isopropanol, ethanol, methanol, 3- methoxyl groups-n-butyl alcohol, 3- methoxies Base -2- butanol, glycol monoethyl ether, ethylene glycol mono-n-butyl ether, cellosolvo, 1- methoxy-2-propanols, diacetone alcohol, Ethyl lactate, butyl lactate, propylene glycol monomethyl ether etc..It is especially better with regard to the dispersiveness and dispersion stabilization of metal oxide It is preferably 3- methoxyl groups-n-butyl alcohol, propylene glycol monomethyl ether, glycol monoethyl ether, ethylene glycol mono-n-butyl ether for aspect.

The content of solvent is not particularly limited, and is preferably more than the 30 mass % of the gross mass of metal oxide composition, Additionally, it is preferred that it is below 95 mass %.If the content of solvent is in the scope, for the viewpoints such as screening characteristics more preferably. The content of solvent is more preferably more than 35 mass % of the gross mass of metal oxide composition, and then more preferably 40 mass % More than, in addition, more preferably below 90 mass %, and then more preferably below 85 mass %.Herein, solvent is contained in use In the case that reaction product is as the resin varnish containing compound (A), the content of the solvent is also comprising in reaction product Solvent including value.

Even if the metal oxide composition of the present invention mixes to prepare only by compound (A) with metal oxide powder, Also target effect can fully be obtained.Wherein, if utilizing kneader, roller, grater (attritor), super grinding machine (super Mill), dry grinding processor etc. carries out mechanical mixture, or the solution of inclusion compound (A) is added to metal oxide powder In suspension (suspension) system of formation such as end and organic solvent, and so that compound (A) sinks in metal oxide table The close mixed system in face etc. is mixed, then can further obtain good effect.

The metal oxide composition is preferably to make the metal oxide that metal oxide powder is uniformly dispersed Dispersion.Metal oxide dispersion by using compound (A) and can be such that metal oxide (B) divides in the presence of an organic Dissipate and preferably manufacture.

As degree of scatter, in " the nano Cui Ke of day machine dress (stock) manufacture by using dynamic light scattering method (Nanotrac) in the case that UPA " is measured, dispersion particle diameter D50 is preferably less than 200nm, more preferably less than 150nm.

Into the non-water system matchmaker liquid (vehicle) such as organic solvent disperse, dissolved compound (A), metal oxide (B), Or metal oxide composition and when mixing these etc., it can be used：Paint regulator (paint conditioner) (Red Devil (Red Devil) company manufactures), ball mill, sand mill be (manufacture of Xin Wan enterprises (Shinmaru Enterprises) company " Dai Nuomo (Dyno-Mill) "), grater, pearl grinding machine (the Pearl Mill) (vertical " DCP for being permitted the manufacture of (eirich) company of love Grinding machine " etc.), Double-cone sanding machine (CoBall Mill), homogeneous mixer, homogenizer (M technologies (M-technique) company system " Clare's mixer (clearmix) " for making etc.), (Jenas (Genus) company manufactures wet shotcrete technology grinding machine (Jet mill) " Jenas (Genus) PY "), " nano Mai Ze (Nanomizer) " of the manufacture of nano Mai Ze (Nanomizer) company is small Ball mill (beads mill) (" Si Paaipaikusi grinding machines (Super Apex Mill) ", " Wu Lu of longevity industry (stock) manufacture Ai Paikusi grinding machines (Ultra Apex Mill) ") etc. dispersion machine.It is excellent in the case of using medium (media) in dispersion machine Choosing uses glass beads, zirconium oxide (zirconia) bead, aluminium oxide (alumina) bead, magnetic beads, styrene beads Deng.On disperseing, two or more dispersion machines or two or more media of different sizes can be used respectively, and periodically make Disperseed with these.

The metal oxide composition of the present invention at least contains compound (A), metal oxide (B) and solvent, and can In the range of the purpose of the present invention and effect is not undermined and then comprising various additives.Specifically, can enumerate：Photopolymerization is drawn Send out agent, photo-hardening compound, polymerization inhibitor, light sensitizer, levelling agent, surfactant, antiseptic, antiblocking agent, modeling Agent, ultra-violet absorber, infrared absorbent, antioxidant, silane coupling agent, electric conductive polymer, conductive surface live Property agent, inorganic filler, pigment, dyestuff etc..

As the metal oxide group for including the component in addition to compound (A), metal oxide (B) and solvent The manufacture method of compound, there is no particular restriction, can enumerate several methods.Specifically, can enumerate：Initially, compound (A) is made And metal oxide (B) mixes metal oxide dispersion that is scattered, and obtaining stable in organic solvent, then adds other The method that various additives are prepared to manufacture；From most from the beginning of just by compound (A), metal oxide (B), organic solvent And in the state of other additives all mix, method for being disperseed to manufacture etc..

The metal oxide composition of the present invention and then can include Photoepolymerizationinitiater initiater.

As Photoepolymerizationinitiater initiater, the vinyl of the acrylic of compound (A) can be made as long as there is by light excitation Start the function of polymerization, be then not particularly limited, such as can be used：Monocarbonyl compound, dicarbonyl compound, acetophenone chemical combination Thing, benzoin ether compound, acylphosphine oxide compound, aminocarboxyl compound etc..

Specifically, as monocarbonyl compound, can enumerate：Benzophenone, 4- methyl-benzophenones, 2,4,6- front threes Base benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl benzophenones, 4- (4- methylphenyl-sulfanyls) phenyl-ethyl ketone, 3, 3'- dimethyl -4- methoxy benzophenones, 4- (1,3- acryloyl group -1,3,3'- dimethyl -4- methoxyl groups) benzophenone, 4- (five oxo tridecyls of 1,3- acryloyl groups -1,4,7,10,13-) benzophenone, (the tert-butyl hydroperoxide carbonyl of 3,3', 4,4'- tetra- Base) benzophenone, 4- benzoyl-Ns, N, N- trimethyl -1- propylamin hydrochlorides, 4- benzoyl-Ns, N- dimethyl-N -s 2- (1- oxo -2- acrylic epoxides ethyl) partially oxalic acid ammonium salt, 2-/4- i-propyls thioxanthone, 2,4- diethyl thioxanthones, The chloro- 4- propoxyl group thioxanthone of bis- chlorothiaxanthenones of 2,4-, 1-, 2- hydroxyls -3- (3,4- dimethyl -9- oxo -9H thioxanthenes Ketone -2- bases epoxide)-N, N, N- trimethyl -1- propylamin hydrochlorides, benzoyl methylene -3- methyl naphtho- (1,2-d) thiazoline Deng.

As dicarbonyl compound, can enumerate：1,2,2- trimethyl-bicyclos [2.1.1] heptane -2,3- diketone, benzil (benzyl, alias：Dibenzoyl), 2- ethyl hydrazine, 9,10- phenanthrenequione, alpha-oxo methyl phenylacetate, 4- phenyl benzils (4- Phenyl-benzil) etc..

As acetophenone compound, can enumerate：2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 1- (4- cumenes Base) -2- hydroxy-2-methyl -1- phenyl-propane -1- ketone,-two -2- methyl isophthalic acids of 1- (4- isopropyl phenyls) -2- hydroxyls-phenyl third Alkane -1- ketone, 1- hydroxy-cyciohexyls phenyl ketone, 2- hydroxy-2-methyl -1- styryl propane -1- ketone polymers, diethoxy Acetophenone, dibutoxy acetophenone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 2,2- diethoxy -1,2- hexichol Base ethane -1- ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinopropane -1- ketone, 2- benzyl -2- dimethylaminos - 1- (4- morpholino phenyls) butane -1- ketone, 1- phenyl -1,2- propanedione -2- (adjacent ethoxy carbonyl) oxime, 3,6- pairs (2- methyl - 2- morpholinyls-propiono) -9- butyl carbazoles etc..

As benzoin ether compound, can enumerate：Styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin isobutyl ether, styrax n-butyl ether etc..

As acylphosphine oxide compound, can enumerate：2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 4- n-propyls Phenyl-two (2,6- dichloro-benzoyls base) phosphine oxide etc..

As aminocarboxyl compound, can enumerate：4- (dimethoxy amino) methyl benzoate, 4- (dimethylamino) benzene Ethyl formate, 4- (dimethylamino) benzoic acid -2- n-butoxies ethyl ester, 4- (dimethylamino) isoamyl benzoate, benzene first Double -4- the dimethylamino benzophenones of acid -2- (dimethylamino) ethyl ester, 4,4'-, the double -4- diethylamino hexichol first of 4,4'- Double (4- diethylaminos benzal) cyclopentanone of ketone, 2,5'- etc..

As the commercially available product of Photoepolymerizationinitiater initiater, can enumerate：Ciba (Ciba specialty chemicals) Gorgeous good solid (Irgacure) 184,651,500,907,127,369,784,2959 of (stock) manufacture, BASF (BASF) company system Road XiLin (LUCIRIN) TPO made, the prosperous (Esacure of Chinese mugwort Sa Gu of Japanese Waja (Nihon Siber Hegner) (stock) manufacture ONE) etc..

Photoepolymerizationinitiater initiater is not limited to the compound, as long as there is the energy for starting polymerization using ultraviolet Power, then can be any compound.One kind can be used in these Photoepolymerizationinitiater initiaters, in addition, can be used in mixed way two or more.

On the usage amount of Photoepolymerizationinitiater initiater, there is no particular restriction, and preferably the light relative to inclusion compound (A) is hard The total amount of the property changed compound (is compound (A) and change in the case of the photo-hardening compound beyond inclusion compound (A) The total amount of photo-hardening compound beyond compound (A)) 100 mass parts, and make in the range of the mass parts of 1 mass parts~20 With.

Also it can add and be used as sensitizer by various organic amines known to people etc. in the related technical field.

And then in addition to the radical polymerization shares initiator, can also and with the initiator of cationic polymerization.

Metal oxide composition can also include other adhesive resins or chemical combination in addition to inclusion compound (A) Photo-hardening compound beyond thing (A).

As adhesive resin, such as can enumerate：Polyurethane resin, carbamide resin, polyurethanes urea tree Fat, polyester resin (except compound (A)), polyether resin, polycarbonate resin, epoxy resin, amino resins, styrene resin Fat, acrylic resin, melmac, polyamide, phenolic resin, vinylite etc..These resins can be used one Kind, it can also be used in mixed way two or more.Preferably with the solid constituent (component beyond solvent of metal oxide composition.With Under, it is identical) total amount on the basis of (100 mass parts) adhesive resin is used in 20 scopes below mass part.

As photo-hardening compound, such as (methyl) acrylic compounds, fatty acid vinyl esterification can be used to close Thing, alkyl vinyl ether compound, alpha-olefin compound, vinyl compound, acetylene compound etc. have polymerism insatiable hunger With the compound of double bond base.These compounds with polymerism unsaturated double-bond base can so that with hydroxyl, alkoxy, carboxylic The functional groups such as base, amide groups, silanol group.(100 matter preferably on the basis of the total amount of the solid constituent of metal oxide composition Amount part) in the range of less than 50 mass parts, in the range of the mass parts of especially 5 mass parts~40 use the photo-hardening chemical combination Thing.

(methyl) acrylic compounds have (methyl) benzyl acrylate, alkyl system (methyl) acrylate, alkane glycol It is (methyl) acrylate, the compound with carboxyl and polymerism unsaturated double-bond, (methyl) acrylic acid series with hydroxyl Compound, nitrogenous (methyl) acrylic compounds etc..In addition, it can suitably use monofunctional compound, polyfunctional compound (except compound (A)).With regard to photo-hardening, the hard painting propert of film aspect for, be preferably polyfunctional compound.

As (methyl) acrylic compounds of simple function, specifically, alkyl system (methyl) acrylate can be enumerated： (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) third Olefin(e) acid pentyl ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) heptylacrylate, (methyl) Hexyl 2-propenoate, (methyl) propylene Misery ester, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) acrylic acid Dodecyl ester, (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecyl Ester, (methyl) aliphatic acrylate, (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate, (first Base) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester, (methyl) acrylic acid heneicosane base ester, (methyl) third (methyl) alkyl acrylate of the carbon numbers 1~22 such as olefin(e) acid docosane base ester.It is excellent in the case where being adjusted to target with polarity Choosing uses (methyl) acrylate containing alkyl with the alkyl of carbon number 2~10 and then preferred carbon number 2~8.In addition, In the case that adjusting with levelability etc. is target, preferably using (methyl) acrylic acid alkyl of the alkyl with carbon number more than 6 Ester.

Alkane glycol system (methyl) acrylate can be enumerated：Diethylene glycol list (methyl) acrylate, triethylene glycol list (first Base) acrylate, tetraethylene glycol list (methyl) acrylate, six ethylene glycol list (methyl) acrylate, polyethyleneglycol (first Base) acrylate, dipropylene glycol list (methyl) acrylate, tripropylene glycol list (methyl) acrylate, four propane diols list (first Base) acrylate, polytetramethylene glycol (methyl) acrylate etc. in end with hydroxyl and with polyoxy alkylidene chain Single (methyl) acrylate；Methoxy ethyl glycol (methyl) acrylate, methoxyl group diethylene glycol (methyl) acrylate, methoxy Base triethylene glycol (methyl) acrylate, methoxyl group tetraethylene glycol (methyl) acrylate, ethyoxyl tetraethylene glycol (methyl) third Olefin(e) acid ester, propoxyl group tetraethylene glycol (methyl) acrylate, n-butoxy tetraethylene glycol (methyl) acrylate, n-pentyloxy four Ethylene glycol (methyl) acrylate, tripropylene glycol (methyl) acrylate, four propane diols (methyl) acrylate, methoxyl group 3 third Glycol (methyl) acrylate, four propane diols of methoxyl group (methyl) acrylate, four propane diols of ethyoxyl (methyl) acrylate, Four propane diols of propoxyl group (methyl) acrylate, four propane diols of n-butoxy (methyl) acrylate, four propane diols of n-pentyloxy (methyl) acrylate, methoxyl group polytetramethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylic acid Ester, ethyoxyl polyethylene glycol (methyl) acrylate etc. are in list (methyl) of the end with alkoxy and with polyoxy alkylidene chain Acrylate；Phenoxy group diethylene glycol (methyl) acrylate, phenoxy group ethylene glycol (methyl) acrylate, three second two of phenoxy group Alcohol (methyl) acrylate, phenoxy group tetraethylene glycol (methyl) acrylate, six ethylene glycol of phenoxy group (methyl) acrylate, benzene Epoxide polyethylene glycol (methyl) acrylate, phenoxy group four propylidene ethylene glycol (methyl) acrylate etc. have benzene oxygen in end Poly (oxyalkylene) base system (methyl) acrylate of base or aryloxy.

Compound with carboxyl and polymerism unsaturated double-bond can be enumerated：Maleic acid, fumaric acid, itaconic acid, citraconic acid, Or these alkyl monoester or alkenyl monoesters, phthalic acid β-(methyl) acryloyl-oxyethyl monoesters, M-phthalic acid β-(methyl) acryloyl-oxyethyl monoesters, succinic acid β-(methyl) acryloyl-oxyethyl monoesters, acrylic acid, metering system Acid, butenoic acid, cinnamic acid etc..

(methyl) acrylic compounds containing hydroxyl can be enumerated：(methyl) 2-Hydroxy ethyl acrylate, (methyl) third Olefin(e) acid -2- hydroxy propyl esters, (methyl) acrylic acid -4- hydroxybutyls, single (methyl) glycerol acrylate, 4- hydroxyvinyls benzene, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyls etc..

Nitrogenous (methyl) acrylic compounds have：(methyl) acrylamide, N- methylols (methyl) acrylamide, N- Methoxy-(methyl) acrylamide, N- ethoxyl methyls-(methyl) acrylamide, N- propoxy methyls-(methyl) propylene The monohydroxyalkyl groups (methyl) such as acid amides, N- butoxymethyls-(methyl) acrylamide, N- amoxys methyl-(methyl) acrylamide Acrylamide, N, N- bis- (methylol) acrylamide, N- methylol-N- methoxies (methyl) acrylamide, N- ethyoxyls Methyl-N-methoxy methyl methacrylamide, N, N- bis- (ethoxyl methyl) acrylamide, N- ethoxyl methyls the third oxygen of-N- Ylmethyl Methacrylamide, N, N- bis- (propoxy methyl) acrylamide, N- butoxymethyls-N- (propoxy methyl) methyl Acrylamide, N, N- bis- (butoxymethyl) acrylamide, N- butoxymethyls-N- (methoxy) Methacrylamide, The dihydroxyalkyls such as N, N- bis- (amoxy methyl) acrylamide, N- methoxies-N- (amoxy methyl) Methacrylamide The acrylamide unsaturated compounds such as (methyl) acrylamide；(methyl) acrylate, (methyl) propylene Sour diethylamino ethyl ester, (methyl) acrylic acid methylethylamine ethyl ester, dimethylaminostyrene, diethylamino benzene second Alkene etc. has the unsaturated compound of dialkyl amido；And there is Cl^-、Br^-、I^-Deng halide ion or QSO₃ ^-(Q：Carbon number 1~20 Alkyl) quarternary ammonium salt of the unsaturated compound containing dialkyl amido as gegenion etc..

Other unsaturated compounds can be enumerated：(methyl) perfluoroethyl methyl formate, (methyl) perfluoroethyl ethyl Methyl esters, (methyl) acrylic acid -2- perfluoro butyls ethyl ester, (methyl) acrylic acid -2- perfluoro hexyls ethyl ester, (methyl) acrylic acid -2- Perfluorooctylethyl, (methyl) acrylic acid -2- perfluor isononyls ethyl ester, (methyl) acrylic acid -2- perfluor nonyls ethyl ester, (methyl) Acrylic acid -2- perfluoro decyls ethyl ester, (methyl) perfluoroethyl propyl group propyl ester, (methyl) perfluoroethyl octyl group propyl ester, (first Base) perfluoroethyl octyl group pentyl ester, (methyl) perfluoroethyl octyl group hendecane base ester etc. have the perfluoroalkyl of carbon number 1~20 (methyl) perfluoroethyl alkyl-alkyl esters.

And then it can enumerate：Perfluorobutyl ethylene, perfluorohexyl ethylene, perfluorooctyl ethylene, perfluoro decyl ethene etc. contain The vinyl monomer of the perfluoroalkyl of perfluoroalkyl, alkylene base class etc.；Vinyl trichlorosilane, (the 'beta '-methoxy second of vinyl three Epoxide) silane, vinyltriethoxysilane, γ-(methyl) acryloxypropyl trimethoxy silane etc. contain alkoxy The vinyl compound and its derivative of silylation；Glycidyl acrylate, acrylic acid -3,4- epoxycyclohexyethylSiOi esters etc. contain The acrylate of glycidyl.

Fatty acid ethylene ester compounds can be enumerated：Vinyl acetate, vinyl butyrate, vinyl crotonate, sad ethene Ester, vinyl laurate, vinyl chloroacetate, oleic acid vinyl acetate, stearic acid vinyl ester etc..

Alkyl vinyl ether compound can be enumerated：Butyl vinyl ether, ethyl vinyl ether etc..

Alpha-olefin compound can be enumerated：1- hexenes, 1- octenes, 1- decene, 1- laurylenes, 1-tetradecylene, 1- hexadecylenes etc..

Vinyl compound can be enumerated：The allylations such as allyl acetate, allyl alcohol, allyl benzene, cyaniding pi-allyl Compound, vinyl cyanide base, vinyl cyclohexane, ethenyl methyl ketone, styrene, α-methylstyrene, 2-methyl styrene, chlorine Styrene etc..

Acetylene compound can be enumerated：Acetylene, acetylenylbenzene, acetenyl toluene, 1- acetenyl -1- cyclohexanol etc..

One kind can be used in these, can also be used in mixed way two or more.

In these, with regard to coating strength, marresistance viewpoint for, can be suitably using at least having three functional groups' Poly- (methyl) esters of acrylic acid, the intramoleculars such as poly- (methyl) acrylic acid polyurethanes, the poly- epoxy-ester of poly- (methyl) acrylic acid Multifunctional acrylates with the acryloyl group of more than 3.

The poly- epoxy-ester of poly- (methyl) acrylic acid is that the epoxy group of epoxy resin is esterified and is incited somebody to action with (methyl) acrylic acid Functional group is set to (methyl) acryloyl group and forms, and has (methyl) acrylic acid adduct to bisphenol A type epoxy resin, to phenolic aldehyde (methyl) acrylic acid adduct of type epoxy resin etc..

Poly- (methyl) acrylic acid polyurethanes for example has：Make diisocyanate and (methyl) acrylic acid with hydroxyl Obtained by ester reaction, make polyalcohol and polyisocyanate reacted under conditions of isocyanate group surplus form contain isocyanic acid The carbamate prepolymer of ester group, with hydroxyl (methyl) esters of acrylic acid reaction obtained by.Alternatively, it can also make polynary Alcohol and polyisocyanate reacted under conditions of hydroxyl surplus the carbamate prepolymer containing hydroxyl formed, with different (methyl) esters of acrylic acid of cyanic acid ester group is reacted and obtained.

As polyalcohol, can enumerate：Ethylene glycol, propane diols, diethylene glycol, dipropylene glycol, butanediol, 1,6-HD, 3- methyl isophthalic acids, 5- pentanediols, neopentyl glycol, hexanetriol, trimethylolpropane, polytetramethylene glycol, adipic acid and ethylene glycol Condensation polymer etc..

As polyisocyanate, can enumerate：Toluene di-isocyanate(TDI), isophorone diisocyanate, hexa-methylene two are different Cyanate etc..

As (methyl) esters of acrylic acid with hydroxyl, can enumerate：(methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyls, pentaerythrite three (methyl) acrylate, dipentaerythritol Five (methyl) acrylate, two-trimethylolpropane four (methyl) acrylate etc..

As (methyl) esters of acrylic acid with isocyanate group, can enumerate：2- (methyl) acryloyl group epoxide ethyl Isocyanates, (methyl) propenoyl isocyanate etc..

As the commercially available product of photo-hardening compound, following product can be illustrated.

East Asia synthesis (stock) manufacture：Sieve Ah Nice (Aronix) M-400, sieve Ah Nice (Aronix) M-402, sieve Ah Nice (Aronix) M-408, sieve Ah Nice (Aronix) M-450, sieve Ah Nice (Aronix) M-7100, sieve Ah Nice (Aronix) M- 8030th, sieve Ah Nice (Aronix) M-8060；

Osaka Organic Chemical Industry (stock) manufactures：Than this gram (Viscoat) #400；

Chemical drug Sartomer (Sartomer) (stock) manufactures：SR-295；

Daicel (Daicel) UCB (stock) is manufactured：DPHA, Chinese mugwort Ba Keli (Ebecryl) 220, Chinese mugwort Ba Keli (Ebecryl) 1290K, Chinese mugwort Ba Keli (Ebecryl) 5129, Chinese mugwort Ba Keli (Ebecryl) 2220, Chinese mugwort Ba Keli (Ebecryl) 6602；

Xin Zhong villages chemical industry (stock) manufactures：NK esters (NK ester) A-TMMT, NK ester (NK ester) A-BPEF, NK is few Poly- (NK oligo) EA-1020, NK oligomerization (NK oligo) EMA-1020, NK oligomerization (NK oligo) EA-6310, NK oligomerization (NK oligo) EA-6320, NK oligomerization (NK oligo) EA-6340, NK oligomerization (NK oligo) MA-6, NK oligomerization (NK Oligo) U-4HA, NK oligomerization (NK oligo) U-6HA, NK oligomerization (NK oligo) U-324A；

BASF (BASF) company manufactures：La Lumo (Laromer) EA81；

Sheng Nuopuke (Sannopco) company manufactures：Fu Tuoma (Photomer) 3016；

Arakawa Chemical Industries (stock) manufacture：Than wooden Saite (Beam set) 371, than wooden Saite (Beam set) 575, than wood Saite (Beam set) 577, than wooden Saite (Beam set) 700, than wooden Saite (beam set) 710；

Industrial (stock) manufacture on root：Ya Telaijin (Art resin) UN-3320HA, Asia Te Laijin (Art resin) UN- 3320HB, Asia Te Laijin (Art resin) UN-3320HC, Asia Te Laijin (Art resin) UN-3320HS, Asia Te Laijin (Art Resin) UN-9000H, Asia Te Laijin (Art resin) UN-901T, Asia Te Laijin (Art resin) HDP, Asia Te Laijin (Art Resin) HDP-3, Asia Te Laijin (Art resin) H61；

Japanese synthetic chemical industry (stock) manufacture：Purple light UV-7600B, purple light UV-7610B, purple light UV-7620EA, purple light UV-7630B, purple light UV-1400B, purple light UV-1700B, purple light UV-6300B；

Common prosperity society chemistry (stock) manufacture：Lay spy acrylate (Light Acrylate) PE-4A, Lay spy's acrylate (Light Acrylate)DPE-6A、UA-306H、UA-306T、UA-306I；

Japanese chemical drug (stock) manufacture：Block Asia ladd (KAYARAD) DPHA, card Asia ladd (KAYARAD) DPHA2C, Ka Yala Moral (KAYARAD) DPHA-40H, card Asia ladd (KAYARAD) D-310, card Asia ladd (KAYARAD) D-330；

Osaka aerochemistry (stock) manufactures：Suo Lu (OGSOL) EA-2000 difficult to understand, Austria Suo Lu (OGSOL) EA-3000, Austria Suo Lu (OGSOL)GA-5000。

Secondly, cured film and the component with the cured film are illustrated.

Cured film is the film for forming the metal oxide composition hardening of the present invention.Its manufacture method for example may include： Metal oxide composition is coated on arbitrary base material and irradiates active energy ray and makes the metal oxide group on base material Compound hardens.

More specifically, can be formed in the following manner：By the metal oxide composition with dried thickness into For be preferably 0.03 μm~30 μm, more preferably 0.03 μm~20 μm of mode coated on after on arbitrary base material, hardened Processing.

Formed when, cured film can be applied directly on base material, also can between cured film and base material there are one layer with On bottom.

As the base material, metal, ceramics, glass, plastics, timber, slate (slate), paper etc. can be enumerated, is had no especially Limitation.As the species of specific plastics, can enumerate：Polyester, polyolefin, makrolon, polystyrene, poly-methyl methacrylate Ester, triacetyl cellulose resin, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS trees Fat), polyamide, epoxy resin, melmac etc..In addition, the shape of base material can enumerate film sheet, plate-like panel, lens Shape, disc-shape, the base material of threadiness, there is no particular restriction.

Optionally part or all of base material can be surface-treated or be formed functional layer (adhesion coating or information record Layer etc.).

It as coating method, can be used in correlative technology field by the various methods known to people, such as can be used and utilize The various coating methods such as method, nick version, intaglio plate, mould, heavy curtain, lip, slit or the rotation of bar or bar etc..

Cure process can be used by the various technologies known to people in correlative technology field, such as can be ultraviolet by irradiating Line, electron beam, the luminous ray isoreactivity energy line of wavelength 400nm~500nm carry out.Ultraviolet and wavelength 400nm~ High-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, gallium for example can be used in the line source (light source) of the luminous ray of 500nm Lamp, xenon lamp, carbon arc lamp etc..Thermionic emission rifle, electrolysis radiation rifle etc. can be used in electron beam source.

The active energy ray amount irradiated is preferably 5mJ/cm²~2000mJ/cm²In the range of, and then with regard to holding in terms of engineering It is preferably 50mJ/cm for manageable aspect²~1000mJ/cm²In the range of.

When irradiating these active energy rays can and with the heat using infrared ray, far infrared, hot wind, high-frequency heating etc. Reason.

Cured film can carry out hard after metal oxide composition is coated on base material and is subject to nature or force drying Change is handled to be formed, and also can be subject to nature or strong after metal oxide composition is coated on base material and carries out cure process Drying processed, but cure process is carried out more preferably after nature or force drying is subject to.

Especially in the case where being hardened with electron beam, in order to prevent hardening caused by water hinder or organic solvent it is residual The hardness of film reduces caused by staying, and cure process is carried out more preferably after nature or force drying is subject to.

The sequential of cure process can be with coating at the same time, or after coating.

Hard painting propert, the transparency, the high index of refraction of the cured film obtained are excellent, therefore can suitably be used as optics material Material.Therefore, cured film can also be used for cathode-ray tube, flat-panel display panel (liquid crystal display, plasma as layered product Body display, electrochromic display device (ECD), light emitting diode indicator etc.) etc. the front panel of various display devices or these input Device.

In addition, the cured film can be widely used in optics lens, eyeglass lens, optical recording CD (compact disk (compact disc), DVD disc, Blu-ray Disc (blu ray disc) etc.), in lamp box etc..

The sheet resistance value of cured film is preferably 1 × 10¹²Ω/below.

The thickness of cured film is preferably more than 0.03 μm, more preferably 0.1 μm~30 μm, and then preferably less than 20 μm.

And then the refractive index of cured film is preferably 1.4~2.0 scope, more preferably 1.5~1.9 scope.

The component with cured film of the present invention includes cured film and base material.Base material can arbitrarily use the base of the illustration Material, especially preferably plastic basis material.Base material is preferably shaped to film shape, lens shape or disc-shape.

In addition to these, the component with cured film preferably comprises more than one layer of the different film of refractive index, adhesion Layer or information recording layer etc..

Layer of the component with cured film such as can be set to following (I)~(IX) is formed.

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

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

(III) base material/(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/base material/cured film

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

Wherein, (M) includes the different film of refractive index, any layer of adhesive film or information recording layer or more than two layers, preferably Include any layer.

The different film of refractive index or information recording layer have the function of the present invention hardening thing possessed by beyond function.Its Forming method is not particularly limited, and can be formed using known method.Such as it can be used：The dry coating methods such as evaporation, sputtering, Utilize bar, the method for bar, or the wet coating method such as nick version, intaglio plate, mould, heavy curtain, lip, slit or rotation.Made Material is also not limited, and optionally can be used can assign information record function, anti-glazing function, Newton's ring to layered product (Newton's rings) prevent function, adhesion function, the blocking of specific wavelength, contiguity raising, tonal correction etc. more than one The arbitrary material of function.

As long as using laser light etc. some chemical changes occur for information recording layer and according to the change record information , material is not particularly limited.For example, the material as organic system, can enumerate polymethine pigment, naphthalene phthalocyanine system, phthalein Cyanines system, sour inner salt system of side, anthraquinone system, xanthene system, triphenyl methane system metal complex compounds, can be used the dyestuff One kind or be used in combination of two or more.As the recording layer of inorganic system, can be used Te, Ge, Se, In, Sb, Sn, Zn, Au, The metals such as Al, Cu, Pt, semimetallic one kind use two or more compositions.Information recording layer can be layered product etc., photochemical Learn change form can be phase change, bubble, opening-type it is any.And then can be based on the optomagnetic note of Fe, Tb, Co Record layer, or spiro-pyrans, the photochromic material of fulgide system.

For the viewpoint of antireflection, the cured film of high index of refraction is it is also preferred that set the cladding hardening of low-refraction on top layer Film and as imparting the component with cured film of anti-reflection function.That is, cured film preferably is formed on the base materials such as film, and then Cladding cured film is preferably formed as on its top layer and the component with cured film obtained is used as anti-reflective film.

In the component with cured film that reflection interference striped becomes problem, the metal oxide of the present invention is preferably adjusted The blending amount of metal oxide in composition, and by the difference of the cured film and the refractive index of base material or in cured film and base Between material there are random layer in the case of for cured film with and the difference of the refractive index of bottom that connects of cured film be set to ± 0.02 with It is interior.

The metal oxide composition of the present invention can be used as by the species or additive amount for controlling metal oxide to manufacture The cured film of the hardening thing of high index of refraction.Therefore, in order to improve the light emission efficiency of optical semiconductor, it is preferable to as will Seek the optical semiconductor sealing material for the refractive index that cured film is sequentially reduced from the lateral outermost layer of optical semiconductor.

As optical semiconductor, gallium nitride (GaN can be enumerated：Refractive index be 2.5), gallium phosphorus (GaP：Refractive index be 2.9), Gallium arsenic (GaAs：3.5) etc. it, is the very high raw material of refractive index that refractive index, which is,.Therefore, just improve light emission efficiency viewpoint and Speech, the refractive index for becoming the hardening thing of optical semiconductor sealing material is preferably more than 1.5, and more preferably 1.5~2.1, into And preferably 1.7~2.1.

As the method for the most preferred refractive index for reaching hardening thing, preferably using titanium oxide (refractive index for 2.5~ 2.7), zirconium oxide (refractive index 2.4), zinc oxide (refractive index 1.95) etc. are used as metal oxide.In addition, to dispersant It is required that high index of refraction, therefore preferably using the compound (A) with aromatic backbone.

The present invention also relates to following item.

[1] a kind of metal oxide composition, it contains：Compound (A) with the acryloyl group of more than 6, metal Oxide (B) and solvent,

The compound (X) is the one kind made in pentaerythritol triacrylate and Dipentaerythritol Pentaacrylate Or two kinds of compounds (x2) and selected from 1,2,4,5- benzene tertacarbonic acids dianhydride, 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides, 9,9- are double Compound (x1) reaction in (3,4- dicarboxyphenyis) fluorenes dicarboxylic anhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides forms.

[2] a kind of metal oxide composition, it contains：Compound (A) with the acryloyl group of more than 6, metal Oxide (B) and solvent,

General formula (1)

[changing 1]

[changing 2]

R1

[changing 3]

R2

In general formula (1), R₃Represent following monovalence organic residues)

[changing 4]

R3

[3] metal oxide composition according to described in [1] or [2], wherein R₁To be organic residual comprising aromatic rings Base.

[4] metal oxide composition according to described in [3], wherein aromatic rings is cyclohexyl biphenyl.

[5] metal oxide composition according to any one of [1] to [4], wherein metal oxide (B) contain By selected from least one of the group being made of titanium, zinc, zirconium, indium, tin, aluminium, silicon and phosphorus element.

[6] metal oxide composition according to any one of [1] to [5], wherein metal oxide (B) D50 particle diameters are 0.005 μm~0.200 μm.

[7] a kind of cured film, it is to make the metal oxide composition according to any one of [1] to [6] hard Change forms.

[8] a kind of component with cured film, it is hard described in setting [7] according at least a portion of base material Change film to form.

The present invention is related to the theme of Japanese patent application numbering 2015-100973 filed in 18 days Mays in 2015, and It is incorporated to by referring to by the entire disclosure into this specification.

[embodiment]

Hereinafter, based on Production Example, embodiment and then the present invention is described in detail.In Production Example, embodiment, part and % Mass parts and quality % are represented respectively.

Used chemicals, as shown below.

(Mitsubishi Chemical's (stock) manufactures 3,3', 4,4'- biphenyl tetracarboxylic dianhydrides, trade name：BPDA)

9,9- double (3,4- dicarboxyphenyi) fluorenes dicarboxylic anhydride (JFE chemistry (stock) manufacture, trade names：BPAF)

1,2,3,4- butane tetracarboxylic acid dianhydride (new Japan Chemical (stock) manufacture, trade name：Li Ka West Germany (Rikacid) BT- 100)

(Daicel (Daicel) (stock) manufactures 1,2,4,5- benzene tertacarbonic acid's dianhydride, trade name：Pyromellitic acid anhydride, PMDA)

Phthalic anhydride (and Wako Pure Chemical Industries (stock) manufacture)

Pentaerythritol triacrylate (1) (Japanese chemical drug (stock) manufacture, trade name：Block Asia ladd (KAYARAD) PET- 30, also comprising tetramethylol methane tetraacrylate as accessory substance)

(Xin Zhong villages chemical industry (stock) manufactures pentaerythritol triacrylate (2), trade name：A-TMM-3LM-N (three esters 57%), also comprising tetramethylol methane tetraacrylate as accessory substance)

(Xin Zhong villages chemical industry (stock) manufactures Dipentaerythritol Pentaacrylate (DPPA), trade name：A-9570W, is also wrapped Containing dipentaerythritol acrylate as accessory substance)

2-Hydroxy ethyl acrylate (Japanese catalyst (stock) manufacture, HEA)

Methyl hydroquinone (and Wako Pure Chemical Industries (stock) manufacture)

1,8- diazabicyclos [5.4.0] -7- hendecenes (Tokyo chemical conversion industry (stock) manufacture)

Dimethyl benzyl amine (and Wako Pure Chemical Industries (stock) manufacture)

Epihydric alcohol methylpropenoic acid ester (Japanese DOW Chemical (DOW Chemical) (stock) manufacture, glycidyl Methacrylate, GMA)

4- hydroxybutyl acrylates glycidol ether (Japan's chemical conversion (stock) manufacture, trade name：4- hydroxybutyl acrylic acid Ester glycidol ether)

(three light (stock) manufacture biphenyl glycidol ether (2- phenyls glycidol ether), trade name：OPP-G)

(Production Example)

(synthesis example 1：Dispersant (1))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 250.0 parts of hydroxyl valency be 122mgKOH/g pentaerythritol triacrylate (1), 0.24 part of methyl hydroquinone, 217.8 parts of cyclohexanone, are warming up to 60 DEG C.Then, it is double that 1.65 parts of 1,8- diazas are added Ring [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm measuring and obtaining using IR for reactant Anhydride group peak value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Described Time point is measured the acid value of reactant using the titration of customary way, that is, JIS K0070 (1992), as a result for 94mgKOH/g。

Then, the biphenyl glycidol ether of 140.0 parts of addition, 91.0 parts of cyclohexanone into the solution, are then added 2.65 parts of dimethyl benzyl amine when stirring 6 is small at 100 DEG C, and makes its reaction as catalyst.The reaction was continued on one side on one side The acid value of results of regular determination reactant, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.Obtained Resin varnish is faint yellow and transparent, solid constituent 60%, and final acid value is 3.0mgKOH/g, therefore the tree obtained The reactant of inclusion compound (A) in the reactant solid constituent of fat varnish is 79%.

Furthermore in the present specification, in addition to the compound (A), the reactant of inclusion compound (A) is also represented by Include the reactant of the high molecular weight reactant from the accessory substance that multiple hydroxyls are included in compound (x2).As described above, bag The ratio of reactant containing compound (A) can utilize the final acid value of resin varnish to calculate.Remaining is to represent to be made in reaction Do not have the compound or unreacting material of hydroxyl in compound (x2).By the reactant letter of inclusion compound (A) in table 1 Referred to as " reactant ".Also it is identical in following 2~synthesis example of synthesis example 5.

(synthesis example 2：Dispersant (2))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 1,2,3,4- butane tetracarboxylics acid dianhydride, 402.0 parts of hydroxyl valency be 113mgKOH/g pentaerythritol triacrylate (2), 0.33 part of methyl hydroquinone, 318.0 parts of cyclohexanone, are warming up to 60 DEG C.Then, it is double that 2.41 parts of 1,8- diazas are added Ring [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm measuring and obtaining using IR for reactant Anhydride group peak value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Described Time point is measured the acid value of reactant using customary way, is as a result 95mgKOH/g.

Then, the biphenyl glycidol ether of 182.9 parts of addition, 118.0 parts of cyclohexanone into the solution, are then added 3.88 parts of dimethyl benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when.The reaction was continued on one side, and one side results of regular determination is anti- The acid value of thing is answered, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained is Faint yellow and transparent, solid constituent 60%, final acid value is 3.0mgKOH/g, therefore the reactant solid constituent obtained In inclusion compound (A) reactant be 73%.

(synthesis example 3：Dispersant (3))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 1,2,4,5- benzene tertacarbonic acids dianhydride, 364.9 parts of hydroxyl valency are the pentaerythritol triacrylate (2) of 113mgKOH/g, 0.31 The methyl hydroquinone, 294.1 parts of cyclohexanone of part, are warming up to 60 DEG C.Then, 2.22 parts of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 93mgKOH/g.

Then, the biphenyl glycidol ether of 166.0 parts of addition, 107.1 parts of cyclohexanone into the solution, are then added 3.58 parts of dimethyl benzyl amine is as catalyst, and when stirring 6 is small at 100 DEG C, the reaction was continued on one side, and one side results of regular determination is anti- The acid value of thing is answered, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained is Faint yellow and transparent, solid constituent 60%, final acid value is 3.0mgKOH/g, therefore the reactant solid constituent obtained In inclusion compound (A) reactant be 74%.

(synthesis example 4：Dispersant (4))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 359.0 parts of hydroxyl valency be 85mgKOH/g Dipentaerythritol Pentaacrylate, 0.29 part of methyl hydroquinone, 290.1 parts of cyclohexanone, are warming up to 60 DEG C.Then, it is double that 2.19 parts of 1,8- diazas are added Ring [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm measuring and obtaining using IR for reactant Anhydride group peak value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Described Time point is measured the acid value of reactant using customary way, is as a result 74mgKOH/g.Thereafter, 123.1 parts are added Biphenyl glycidol ether, 78.5 parts of cyclohexanone, then the dimethyl benzyl amine of 3.53 parts of addition is as catalyst, at 100 DEG C When lower stirring 6 is small, the acid value of the reaction was continued one side results of regular determination reactant on one side, when acid value becomes below 5.0mgKOH/g, It is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent 60%, final acid value For 3.0mgKOH/g, therefore the reactant of the inclusion compound (A) in the solid constituent of the resin varnish obtained is 83%.

(synthesis example 5：Dispersant (5))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer Double (3,4- dicarboxyphenyis) the fluorenes dicarboxylic anhydrides of 9,9-, three acrylic acid of pentaerythrite that 160.2 parts of hydroxyl valency is 122mgKOH/g Ester (1), 0.16 part of methyl hydroquinone, 158.8 parts of cyclohexanone, are warming up to 60 DEG C.Then, 1.20 parts of 1,8- bis- is added Azabicyclo [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant And peak value, the i.e. 1780cm of the anhydride group obtained^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting. The acid value of reactant is measured using customary way at the time point, is as a result 82mgKOH/g.

Thereafter, 79.0 parts of biphenyl glycidol ether, the dimethyl of 50.7 parts of cyclohexanone, then 1.93 parts of addition is added Benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the acid value of the reaction was continued on one side one side results of regular determination reactant, in acid When valency becomes below 5.0mgKOH/g, it is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, Gu Body component is 60%, and final acid value is 3.0mgKOH/g, therefore includes change in the solid constituent of the resin varnish obtained The reactant of compound (A) is 79%.

(synthesis example 6：Dispersant (6))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 250.0 parts of hydroxyl valency be 122mgKOH/g pentaerythritol triacrylate (1), 0.24 part of methyl hydroquinone, 217.8 parts of cyclohexanone, are warming up to 60 DEG C.Then, it is double that 1.65 parts of 1,8- diazas are added Ring [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm measuring and obtaining using IR for reactant Anhydride group peak value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Described Time point is measured the acid value of reactant using customary way, is as a result 94mgKOH/g.

Thereafter, the epihydric alcohol methylpropenoic acid ester of 78.3 parts of addition, 54.0 parts of cyclohexanone, then add 2.65 parts Dimethyl benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the acid of the reaction was continued on one side one side results of regular determination reactant Valency, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained to be faint yellow and Transparent, solid constituent 60%, final acid value is 3.0mgKOH/g, therefore in the solid constituent of the resin varnish obtained Reactant is 76%.Furthermore reactant does not include compound (A).It is also identical in following 7~synthesis example of synthesis example 17.

(synthesis example 7：Dispersant (7))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 1,2,3,4- butane tetracarboxylics acid dianhydride, 402.0 parts of hydroxyl valency be 113mgKOH/g pentaerythritol triacrylate (2), 0.34 part of methyl hydroquinone, 203.8 parts of cyclohexanone, are warming up to 60 DEG C.Then, it is double that 1.75 parts of 1,8- diazas are added Ring [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm measuring and obtaining using IR for reactant Anhydride group peak value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Described Time point is measured the acid value of reactant using customary way, is as a result 95mgKOH/g.

Thereafter, the epihydric alcohol methylpropenoic acid ester of 116.4 parts of addition, 188.5 parts of cyclohexanone, then add 3.88 parts Dimethyl benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the reaction was continued on one side one side results of regular determination reactant Acid value, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow And transparent, solid constituent 60%, final acid value are 3.0mgKOH/g, therefore in the solid constituent of the resin varnish obtained Reactant be 71%.

(synthesis example 8：Dispersant (8))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer Phthalic anhydride, pentaerythritol triacrylate (2), 0.25 part of the methyl that 268.7 parts of hydroxyl valency is 113mgKOH/g Hydroquinone, 230.4 parts of cyclohexanone, are warming up to 60 DEG C.Then, 1.74 parts 1,8- diazabicyclos [5.4.0] -7- is added Hendecene as catalyst, stirred at 90 DEG C 8 it is small when.The peak for the anhydride group for confirming being measured using IR for reactant and obtaining Value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Utilized at the time point used Method is measured the acid value of reactant, is as a result 88mgKOH/g.

Thereafter, 122.2 parts of biphenyl glycidol ether, the diformazan of 78.7 parts of cyclohexanone, then 2.81 parts of addition is added Base benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the acid value of the reaction was continued on one side one side results of regular determination reactant, When acid value becomes below 5.0mgKOH/g, it is cooled to room temperature and stops reacting.The resin varnish obtained to be faint yellow and transparent, Solid constituent is 60%, and final acid value is 3.0mgKOH/g, therefore the reaction in the solid constituent of the resin varnish obtained Thing is 75%.

(synthesis example 9：Dispersant (9))

Thereafter, the epihydric alcohol methylpropenoic acid ester of 77.8 parts of addition, 49.1 parts of cyclohexanone, then add 2.80 parts Dimethyl benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the acid of the reaction was continued on one side one side results of regular determination reactant Valency, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained to be faint yellow and Transparent, solid constituent 60%, final acid value is 3.0mgKOH/g, therefore in the solid constituent of the resin varnish obtained Reactant is 72%.

(synthesis example 10：Dispersant (10))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 1,2,4,5- benzene tertacarbonic acids dianhydride, 364.9 parts of hydroxyl valency are the pentaerythritol triacrylate (2) of 113mgKOH/g, 0.31 The methyl hydroquinone, 293.9 parts of cyclohexanone of part, are warming up to 60 DEG C.Then, 2.22 parts of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 93mgKOH/g.

Thereafter, the epihydric alcohol methylpropenoic acid ester of 105.6 parts of addition, 66.9 parts of cyclohexanone, then add 3.58 parts Dimethyl benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the reaction was continued on one side one side results of regular determination reactant Acid value, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow And transparent, solid constituent 60%, final acid value are 3.0mgKOH/g, therefore in the solid constituent of the resin varnish obtained Reactant be 71%.

(synthesis example 11：Dispersant (11))

Thereafter, the epihydric alcohol methylpropenoic acid ester of 50.3 parts of addition, 31.6 parts of cyclohexanone, then add 1.94 parts Dimethyl benzyl amine as catalyst, stirred at 100 DEG C 6 it is small when, the acid of the reaction was continued on one side one side results of regular determination reactant Valency, when acid value becomes below 5.0mgKOH/g, is cooled to room temperature and stops reacting.The resin varnish obtained to be faint yellow and Transparent, solid constituent 60%, final acid value is 3.0mgKOH/g, therefore in the solid constituent of the resin varnish obtained Reactant is 75%.

(synthesis example 12：Dispersant (12))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 359.0 parts of hydroxyl valency be 85mgKOH/g Dipentaerythritol Pentaacrylate, 0.29 part of methyl hydroquinone, 290.1 parts of cyclohexanone, are warming up to 60 DEG C.Then, it is double that 2.19 parts of 1,8- diazas are added Ring [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm measuring and obtaining using IR for reactant Anhydride group peak value, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.Described Time point is measured the acid value of reactant using customary way, is as a result 74mgKOH/g.Thereafter, 78.3 parts are added Epihydric alcohol methylpropenoic acid ester, 48.7 parts of cyclohexanone, then add 3.53 parts of dimethyl benzyl amine as catalyst, When stirring 6 is small at 100 DEG C, the acid value of the reaction was continued one side results of regular determination reactant on one side, acid value become 5.0mgKOH/g with When lower, it is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent 60%, finally Acid value be 3.0mgKOH/g, therefore the reactant in the solid constituent of the resin varnish obtained is 69%.

(synthesis example 13：Dispersant (13))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 63.1 parts of hydroxyl valency be 483mgKOH/g 2-Hydroxy ethyl acrylate, 0.11 part Methyl hydroquinone, 94.6 parts of cyclohexanone, be warming up to 60 DEG C.Then, 0.72 part of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 215mgKOH/g.Thereafter, 78.3 parts of contracting is added Water glycerol methacrylate, 51.1 parts of cyclohexanone, then add 1.15 parts of dimethyl benzyl amine as catalyst, When stirring 6 is small at 100 DEG C, the acid value of the reaction was continued one side results of regular determination reactant on one side, acid value become 5.0mgKOH/g with When lower, it is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent 60%, finally Acid value be 3.0mgKOH/g, therefore the reactant in the solid constituent of the resin varnish obtained is 87%.

(synthesis example 14：Dispersant (14))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 1,2,3,4- butane tetracarboxylics acid dianhydride, 533.3 parts of hydroxyl valency are the Dipentaerythritol Pentaacrylate of 85mgKOH/g, 0.37 The methyl hydroquinone, 405.5 parts of cyclohexanone of part, are warming up to 60 DEG C.Then, 3.07 parts of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 75mgKOH/g.Thereafter, 116.4 parts of contracting is added Water glycerol methacrylate, 72.6 parts of cyclohexanone, then add 4.93 parts of dimethyl benzyl amine as catalyst, When stirring 6 is small at 100 DEG C, the acid value of the reaction was continued one side results of regular determination reactant on one side, acid value become 5.0mgKOH/g with When lower, it is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent 60%, finally Acid value be 3.0mgKOH/g, therefore the reactant in the solid constituent of the resin varnish obtained is 68%.

(synthesis example 15：Dispersant (15))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 1,2,3,4- butane tetracarboxylics acid dianhydride, 93.7 parts of hydroxyl valency be the 2-Hydroxy ethyl acrylate of 483mgKOH/g, 0.15 part Methyl hydroquinone, 114.8 parts of cyclohexanone, are warming up to 60 DEG C.Then, 0.87 part of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 264mgKOH/g.Thereafter, 116.4 parts are added Epihydric alcohol methylpropenoic acid ester, 76.2 parts of cyclohexanone, then add 1.4 parts of dimethyl benzyl amine as catalyst, When stirring 6 is small at 100 DEG C, the acid value of the reaction was continued one side results of regular determination reactant on one side, acid value become 5.0mgKOH/g with When lower, it is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent 60%, finally Acid value be 3.0mgKOH/g, therefore the reactant in the solid constituent of the resin varnish obtained is 86%.

(synthesis example 16：Dispersant (16))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 63.1 parts of hydroxyl valency be 483mgKOH/g 2-Hydroxy ethyl acrylate, 0.11 part Methyl hydroquinone, 94.6 parts of cyclohexanone, be warming up to 60 DEG C.Then, 0.72 part of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 215mgKOH/g.Thereafter, 123.1 parts are added Biphenyl glycidol ether, 80.9 parts of cyclohexanone, then the dimethyl benzyl amine of 1.15 parts of addition is as catalyst, at 100 DEG C When lower stirring 6 is small, the acid value of the reaction was continued one side results of regular determination reactant on one side, when acid value becomes below 5.0mgKOH/g, It is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent 60%, final acid value For 3.0mgKOH/g, therefore the reactant in the solid constituent of the resin varnish obtained is 89%.

(synthesis example 17：Dispersant (17))

80.0 parts of the input in the four-hole boiling flask for possessing mixer, reflux cooling tube, dry air ingress pipe, thermometer 3,3', 4,4'- biphenyl tetracarboxylic dianhydride, 63.1 parts of hydroxyl valency be 483mgKOH/g 2-Hydroxy ethyl acrylate, 0.11 part Methyl hydroquinone, 94.6 parts of cyclohexanone, be warming up to 60 DEG C.Then, 0.72 part of 1,8- diazabicyclos are added [5.4.0] -7- hendecenes as catalyst, stirred at 90 DEG C 8 it is small when.Confirm being measured using IR for reactant and obtain The peak value of anhydride group, i.e. 1780cm^-1And 1850cm^-1After neighbouring peak vanishes, cooled down and stop reacting.When described Between point the acid value of reactant is measured using customary way, be as a result 215mgKOH/g.Thereafter, 108.8 parts are added 4- hydroxybutyl acrylates glycidol ether, 71.4 parts of cyclohexanone, then add 1.15 parts of dimethyl benzyl amine conduct Catalyst, stirred at 100 DEG C 6 it is small when, the acid value of the reaction was continued one side results of regular determination reactant, becomes in acid value on one side During below 5.0mgKOH/g, it is cooled to room temperature and stops reacting.The resin varnish obtained is faint yellow and transparent, solid constituent For 60%, final acid value is 3.0mgKOH/g, therefore the reactant in the solid constituent of the resin varnish obtained is 89%.

Collecting for synthesis is represented in table 1.

The summary of the reactant obtained in synthesis example is represented in table 1.

[table 1]

(making of metal oxide paste)

Using the resin varnish for respectively containing compound (A) made by the Production Example, by the tune that number is shown in table 2 Match somebody with somebody, carry out the scattered of metal oxide (B), making metal oxide dispersion paste, (in table 2, reactant is relative to metal oxide (B) ratio of 100 parts by weight represents solid content).Process for dispersing is (to be made with pre-dispersed using zirconium oxide bead (0.5mm) For medium, and using paint mixer (paint shaker) scattered 1 it is small when), with formal scattered (use zirconium oxide bead (0.1mm) is used as medium, and is disperseed using the dispersion machine UAM-015 of longevity industrial (stock) manufacture) two stages carry out.

[table 2]

Metal oxide is had a guide look of

In table 2,

ZrO₂：" PCS-60 " (average primary particle diameter of Japanese Electric (stock) manufacture：20nm)

TiO₂：" MT-05 " (average primary particle diameter of Supreme Beingization (Tayca) (stock) manufacture：10nm)

Sb₂O₅：" Sheng Aibo sections (San epoch) EFR-6N " (average primary particle diameters of Nissan Chemical Industries (stock) manufacture： 20nm)

ATO：Stone originates in " SN-100P " (average primary particle diameter of industry (stock) manufacture：20nm)

ITO：" Nai Nuodake (Nanotec) ITO " (average primary particle diameters of uncommon love chemical conversion (C.I.Kasei) (stock) manufacture： 30nm)

PTO：" EP the SP-2 " (average primary particle diameters of Mitsubishi Materials (stock) manufacture：15nm)

ZnO：" Phoenix (FINEX) -50 " (average primary particle diameter of Sakai chemical industry (stock) manufacture：20nm)

SiO₂：" (the average once grains of Ai Luoxier (AEROSIL) 50 " of Japanese Ai Luoxier (Aerosil) (stock) manufacture Footpath：30nm)

Al₂O₅：" aluminium oxide (Aluminium Oxide) C " (average one of Japanese Ai Luoxier (Aerosil) (stock) manufacture Secondary particle diameter：13nm)

MEK：Methyl ethyl ketone

Wheat opens up portion's tower (Metobuta)：3- methoxyl groups-n-butyl alcohol

(evaluation method)

(1) it is dispersed

Visually to observe the state that obtained metal oxide dispersion is pasted.

A：With mobility.

B：Though it is cured, still confirm mobility but if tempestuously rocking.

C：It is cured.

" nano Cui Ke (Nanotrac) " manufactured using day machine dress (stock) measures the D50 of obtained metal oxide paste Particle diameter.It is preferably below 200nm in terms of practicality.

Using the metal oxide paste of the preparation, the metal oxide composition for the composition that number is shown in table 3 is prepared. The metal oxide composition obtained is coated on 100 μ m-thicks in a manner of dried thickness becomes 3 μm using bar coater Easily then handle PET film (Japan spin (stock) manufacture " Cowes not summer (cosmoshine) A-4100 ") on after, utilize high pressure Mercury light irradiation 400mJ/cm²Ultraviolet, formed cured film (hard conating).For the cured film obtained, with following methods Evaluate marresistance, pencil hardness, the transparency (mist degree).Will be evaluation result is shown in table in 3.

[table 3]

In table 3,

Photoepolymerizationinitiater initiater：Ciba (Ciba specialty chemicals) (stock) manufactures " gorgeous good solid (Irgacure)184”

Solvent：PGME (propylene glycol monomethyl ether)

*1：Metal oxide paste it is scattered bad, therefore be not measured

(evaluation method)

(1) it is transparent (Haze (mist degree) value)

The turbidity (Haze values) in the coating that is obtained is measured using Haze meters.It is preferably turbid in terms of practicality Spend for less than 1.0%.

(2) pencil hardness

According to JIS-K5600, pencil scratching tester (the scratch test machine that new east (HEIDON) company manufactures is used (Scratching Tester) new east (HEIDON) -14), and become the hardness of more kinds of pencil-leads, carried out 5 times with loading 750g Experiment.Also the hardness for the core not scratched for 1 time in 5 times or when only 1 time scratches is set to the pencil hardness of the cured film.Consider To the requirement physical property of practicality, the pencil hardness of cured film is determined as：

More than 2H：A

More than 1H：B

Less than 1H：D.

(3) marresistance

Coating is arranged to shake on testing machine, is shaken 10 times using the steel wool of No.0000 with loading 250g.For The coating of taking-up, judges scuffing situation with 5 following stages according to visual valuation.Numerical value is bigger, represents hardening The marresistance of film is the better.

5：There is no scar completely

4：It is slight to scratch

3：Though scratching, base material is not seen

2：Scratch, and a part of cured film is peeled off

1：Cured film has been peeled off, and is the state that base material exposes

Distinguished according to the result of table 3, on the curable adhensive compositions using 1~embodiment of embodiment 16 with cured film Component, transparent pencil hardness excellent scratch resistance and balance is good.Therefore, these components with hardened coating film can fit Preferably it is used for the purposes that display, touch-screen, construction material etc. need hard painting propert and the transparency.

In contrast, metal oxide paste (17) and metal oxide paste (20) using the different dispersant of resin structure ~metal oxide paste (23) can not make metal oxide paste, and comparative example 1 and 4~comparative example of comparative example 7 can not harden band The component of film is evaluated.

Use the comparative example 2 and comparative example 3, comparative example 9 of the metal oxide paste using the different dispersant of resin structure Curable adhensive compositions the component with cured film the transparency deficiency.

Use 10~comparative example of comparative example 8 and comparative example of the metal oxide paste using the different dispersant of resin structure The transparency and pencil hardness, marresistance of the component with cured film of 12 curable adhensive compositions are insufficient.

[industrial applicability]

The metal oxide composition of the present invention not only may be suitably used to optics film structural component, it can also be used to various plastics The glass pane of products formed, the lens in most surface portion of camera, the lens of glasses, building or vehicle etc. and various printed articles Respective surface assigns identical function.

Claims

1. a kind of metal oxide composition, it is characterised in that contain：Compound (A) with the acryloyl group of more than 6, D50 particle diameters are 0.005 μm~0.120 μm of metal oxide (B) and solvent,

The compound (A) includes the compound (A1) with the acryloyl group of more than 6 represented by the following general formula (1),

General formula (1)

In general formula (1), R₁Represent following arbitrary tetravalence organic residues；

In general formula (1), R₃Represent following monovalence organic residues；

2. metal oxide composition according to claim 1, it is characterised in that：R₁For the organic residue comprising aromatic rings.

3. metal oxide composition according to claim 2, it is characterised in that：Aromatic rings is cyclohexyl biphenyl.

4. metal oxide composition according to claim 1 or 2, it is characterised in that：Metal oxide (B), which contains, to be selected from At least one of the group being made of titanium, zinc, zirconium, indium, tin, aluminium, silicon and phosphorus element.

5. metal oxide composition according to claim 3, it is characterised in that：Metal oxide (B) contain be selected from by At least one of the group that titanium, zinc, zirconium, indium, tin, aluminium, silicon and phosphorus are formed element.

A kind of 6. cured film, it is characterised in that：It is to make metal oxide group according to any one of claim 1 to 5 Compound hardening forms.

A kind of 7. component with cured film, it is characterised in that：It is to be set at least a portion of base material according to claim 6 The cured film forms.