CN101454351A - Metal oxide composition, cured film and laminate - Google Patents

Abstract

Disclosed is a metal oxide composition containing a dispersing agent (A) represented by the general formula (1) below and a metal oxide having an average primary particle diameter of 5-100 nm. [chemical formula 1] (1) (In the formula, R1-R4 independently represent a hydrogen atom or a methyl group; R5-R<8> independently represent an unsubstituted or substituted straight or branched chain alkyl group or alkylene oxyalkylene group; and R<9> represents a tetravalent aromatic group or aliphatic group).

Description

Metal oxide composition, cured film and duplexer

Technical field

The present invention relates to have being coated with property firmly metal oxide composition, use the cured film and the duplexer thereof of said composition.

Background technology

Consider from the angle of the performance of guaranteeing information communication device and reply safety in the past, make on the surface of equipment form with the light metal oxide composition have scuff resistance, the being coated with property firmly of adaptation, high refractive index etc. is filmed, static resistance is filmed.

The development of information communication device and universalization in recent years is significant, and the performance and the productivity that require further raising being coated with property is filmed firmly, static resistance is filmed etc. have proposed to adopt the various schemes of light solidified material.

For example can be listed below described technical scheme (with reference to patent documentation 1～3).The method of using electroconductive powder such as mixed oxidization tin and multiple monomer component in organic solvent such as ball mill to make conductive coating paint is disclosed in patent documentation 1.In patent documentation 2, disclose to use ball mill in organic solvent, to mix antimony doped tin oxide and have ultra-violet solidified silane coupling agent and made the method for conductive coating paint with dispersion.And then, the method that dispersed electro-conductive oxide micropowder end makes conductive coating paint in the mixed solvent of easily disperse low boiling point solvent and difficult dispersed high boiling solvent is disclosed in patent documentation 3.

(patent documentation 1) spy opens flat 04-172634 communique

(patent documentation 2) spy opens flat 06-264009 communique

(patent documentation 3) spy opens the 2001-131485 communique

Summary of the invention

But, even can be produced on high refractive index, aspects such as being coated with property, static resistance, the photostabilization metal oxide composition that has good rerum natura simultaneously firmly by aforesaid method, can not be for the high medium of hydrophobicitys such as organic solvent, be the metal oxide stability ground below the 100nm with average primary particle diameter and disperse and stabilization, thereby be easy to generate problem at the aspects such as ageing stability of the transparency of filming, light solidified coating with the primary particle level.

Therefore, the object of the present invention is to provide the cured film and the duplexer thereof of a kind of metal oxide composition, use said composition, it is the following metal oxide of 100nm that described metal oxide composition contains average primary particle diameter, can be formed in high refractive index, static resistance, being coated with property, the transparency and sunproof all aspects all have filming of excellent rerum natura firmly, and have ageing stability.

The present invention relates to a kind of metal oxide composition, it contains the dispersion agent (A) shown in the following general formula (1) and average primary particle diameter is the metal oxide of 5～100nm.

General formula (1):

(in the formula, R ¹～R ⁴Represent hydrogen atom or methyl independently of one another, R ⁵～R ⁸Alkylidene group or the alkylidene group oxyalkylene of representing the straight or branched of non-replacement or replacement independently of one another, R ⁹Aromatic group or the aliphatic group of representing 4 valencys.)

In addition, the present invention relates to above-mentioned metal oxide composition is solidified the cured film that forms.

In addition, the present invention relates to comprise the duplexer of base material and above-mentioned cured film.

In addition, the present invention relates to comprise the optical semiconductor sealing material of above-mentioned metal oxide composition.

In addition, the present invention relates to the manufacture method of metal oxide dispersion, it comprises: in the presence of organic solvent, use the dispersion agent (A) shown in the following general formula (1), making average primary particle diameter is the metal oxide dispersive step of 5～100nm.

General formula (1):

(in the formula, R ¹～R ⁴Represent hydrogen atom or methyl independently of one another, R ⁵～R ⁸Alkylidene group or the alkylidene group oxyalkylene of representing the straight or branched of non-replacement or replacement independently of one another, R ⁹Aromatic group or the aliphatic group of representing 4 valencys.)

Moreover, the present invention relates to the manufacture method of cured film, it comprises: above-mentioned metal oxide composition is coated on step on the base material; And the irradiation active energy beam, make the metal oxide composition step of curing.

Embodiment

The metal oxide composition that the present invention relates to contains the dispersion agent (A) shown in the following general formula (1) and average primary particle diameter is the metal oxide of 5～100nm, also can contain two or more metal oxides and two or more dispersion agent (A) separately.

General formula (1)

(in the formula, R ¹～R ⁴Represent hydrogen atom or methyl independently of one another, R ⁵～R ⁸Alkylidene group or the alkylidene group oxyalkylene of representing the straight or branched of non-replacement or replacement independently of one another, R ⁹Aromatic group or the aliphatic group of representing 4 valencys.)

This dispersion agent (A) has high dispersiveness and light solidified to metal oxide.Because this dispersion agent (A) improves the dispersed and raising light solidified that average primary particle diameter is the metal oxide of 5～100nm, therefore the solidified nature excellence of metal oxide composition of the present invention can form the cured film and the duplexer thereof of being coated with property, the transparency, photostabilization, high refractive index, excellent antistatic property firmly.Thereby, being suitable for plastic optical members, CD, antireflection film, touch-screen, film-type liquid crystal cell especially, can suit in addition as the hard paint of various plastic lamination bodies.

This metal oxide composition can form the high cured film of specific refractory power, and when being applied to it on base material of equal extent specific refractory power, the duplexer that obtains can not produce the reflection interference striped, is suitable for optical applications.And then, owing to the specific refractory power that contains the cured article of metal oxide can be controlled to be higher, therefore also suitable as the optical semiconductor sealing material.

In the above-mentioned formula (1), as R ⁹4 valency aromatic groups, specifically can enumerate benzene skeleton, benzophenone skeleton, biphenyl backbone, phenyl ether skeleton, sulfobenzide skeleton, diphenyl sulfoxide skeleton, perylene (perylene) skeleton, fluorene skeleton, naphthane skeleton and naphthalene skeleton etc.Wherein, R ⁹That preferably selects from the group of being made up of biphenyl backbone, naphthalene skeleton, fluorene skeleton and naphthane skeleton is at least a.

As R ⁹4 valency aliphatics skeletons, are suitable examples as the aliphatic group of 4 valencys of the alkyl skeleton of carbonatoms 4～10, can enumerate butane skeleton, tetramethylene skeleton, hexane skeleton, hexanaphthene skeleton, naphthalane skeleton etc. specifically.

In the above-mentioned formula (1), as R ⁵～R ⁸Non-replacement or the alkylidene group of the straight or branched of replacement, can for example alkylidene groups such as polymethylene of methylene radical, ethylidene, C3～C10 be shown example.In addition, the alkylidene group oxyalkylene as the straight or branched of non-replacement or replacement can example illustrate C3 alkylidene group-oxygen-C3 alkylidene group.These alkylidene groups or alkylidene group oxyalkylene derive from (methyl) acrylic compound that contains hydroxyl of the 1st and the 2nd as raw material.Substituting group as alkylidene group or alkylidene group oxyalkylene can have can example illustrate alkyl such as methyl, ethyl, hydroxyl, acryloyl-oxy methyl, acrylyl oxy-ethyl, phenoxy group etc.

Dispersion agent (A) shown in the general formula (1) can obtain with compound (Y) reaction of the functional group of carboxyl reaction by making the compound (X) with carboxyl and having, and described compound (X) with carboxyl is by making compound (x1) with aromatic series skeleton or aliphatics skeleton and 2 above carboxylic acid anhydride groups and having and can obtain with compound (x2) reaction of the functional group of carboxylic acid anhydride group's reaction.Here, from light solidified and the viewpoint consideration of being coated with property firmly, at least a portion of above-claimed cpd (x2) and compound (Y) preferably has the polymerizability unsaturated double-bond.

" can with the functional group of carboxylic acid anhydride group reaction " as in the compound (x2) can enumerate hydroxyl, amino, glycidyl etc., considers preferred especially hydroxyl from the complexity of control reaction.So compound (x2) preferably has the acrylic compound or the methacrylate compound of 1 or 2 hydroxyl.

" can with the functional group of carboxyl reaction " as in the compound (Y) can enumerate epoxy group(ing), oxazolinyl, hydroxyl, amino, carbodiimide-based, isocyanate group, isothiocyanate group, vinyl ether group etc.

And then giving one example illustrates.Make as aromatic series or aliphatics the tetracarboxylic dianhydride compound (x1) with aromatic series skeleton or aliphatics skeleton and 2 above carboxylic acid anhydride groups, shown in the following general formula (2), with as have can with the compound (x2) of the functional group of carboxylic acid anhydride reaction, the 1st shown in the following general formula (3) contain the acrylic compound or the methacrylate compound of hydroxyl, shown in the following general formula (4) the 2nd contains the acrylic compound or the methacrylate compound reaction of hydroxyl, just can obtain the compound (X) shown in the following general formula (5).

General formula (2):

(here, as for R ⁹, with defined the same in the general formula (1))

CH ₂=C (R ¹) COOR ⁵OH general formula (3)

(here, as for R ¹And R ⁵, with defined the same in the general formula (1))

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

(here, as for R ²And R ⁶, with defined the same in the general formula (1))

General formula (5)

(here, as for R ¹, R ², R ⁵, R ⁶And R ⁹, with defined the same in the general formula (1))

Here, the notion of " acrylate-based or methacrylate based " is to comprise containing or using acrylate-based and methacrylate based both situation.Below, sometimes acrylate and methacrylic ester summary are recited as " (methyl) acrylate ".

As the aromatic tetracarboxylic acid's dianhydride shown in the above-mentioned general formula (2), can enumerate pyromellitic acid dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride with biphenyl backbone, oxygen two phthalandione dianhydrides, the sulfobenzide tetracarboxylic dianhydride, the diphenyl sulfoxide tetracarboxylic dianhydride, the perylene tetracarboxylic dianhydride, has the naphthalene tetracarboxylic acid dianhydride of naphthalene skeleton etc., has 9 of fluorene skeleton, 9-two (3,4-dicarboxyl phenyl) fluorenes dianhydride or 9, two (4-(3, the 4-di carboxyl phenyloxy) phenyl) the fluorenes dianhydrides of 9-, naphthane carboxylic acid dianhydride with naphthane skeleton, ethylene glycol bis (trimellitic acid 1,2-anhydride ester), two (trimellitic acid 1,2-anhydride ester) monoacetates of glycerine etc.

As commercially available product, can enumerate " physics and chemistry is (リ カ シ Star De) TMTA-C ", " physics and chemistry is MTA-10 ", " physics and chemistry is MTA-15 " that New Japan Chem Co., Ltd makes, " physics and chemistry is TMEG series ", " physics and chemistry is TDA ", " physics and chemistry is DSDA " etc.

Among these aromatic tetracarboxylic acid's dianhydrides, biphenyl tetracarboxylic dianhydride has biphenyl backbone, can be efficiently with the intramolecularly of the compound shown in the biphenyl backbone introducing-type (1), and then have the being coated with property firmly of cured film and the good dispersiveness of metal oxide concurrently, be particularly preferred therefore.

Aliphatics tetracarboxylic dianhydride as shown in the general formula (2) can enumerate the butane tetracarboxylic acid dianhydride.

(methyl) acrylic compound that contains hydroxyl of the 1st and the 2nd can be the same or different each other.As the example of such (methyl) acrylic compound that contains hydroxyl, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, 2-acrylyl oxy-ethyl-2-hydroxyethyl phthalandione, single (methyl) vinylformic acid glyceryl ester, (methyl) vinylformic acid 2-hydroxyl-3-acryloxy propyl ester, the dihydroxyl acrylate, (methyl) vinylformic acid glyceryl ester, tricarbimide EO modification diacrylate, tetramethylolmethane list (methyl) acrylate, Dipentaerythritol list (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, Dipentaerythritol two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc.Under the situation of the purposes of raising hardness, be preferably tetramethylolmethane three (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate etc.

As concrete commercially available product, can enumerate the BISCOAT (#300 (Osaka Organic Chemical Industry Co., Ltd.'s manufacturing) of PVC ス コ-ト), KAYARAD PET30 (Nippon Kayaku K. K's manufacturing), PETIA (manufacturing of Daicel (Daicel) UCB Co., Ltd.), sieve Knicks (ア ロ ニ Star Network ス) M305 (Toagosei Co., Ltd's manufacturing) difficult to understand, NK ester A-TMM-3LMN (manufacturing of Xin Zhong village chemical industry Co., Ltd.), light acrylate (the PE-3A (Kyoeisha Chemical Co., Ltd.'s manufacturing) of ラ イ ト ア Network リ レ-ト), SR-444 (manufacturing of Sartomer (サ-ト マ-) Co., Ltd.), light acrylate DPE-6A (Kyoeisha Chemical Co., Ltd.'s manufacturing), KAYARAD DPHA (Nippon Kayaku K. K's manufacturing), sieve Knicks M402 difficult to understand (Toagosei Co., Ltd's manufacturing) etc.

Particularly be the KAYARAD PET30 (Nippon Kayaku K. K's manufacturing) of principal constituent, because the favorable dispersity of metal oxide is therefore preferred with tetramethylolmethane three (methyl) acrylate.Under the situation of multifunctional (methyl) acrylic compound, by containing multifunctional (methyl) acrylate about 5～15 weight % as minor component with 2 hydroxyls, the tendency that weight-average molecular weight after the curing of the dispersion agent that obtains (A) has polymer to quantize, it is better that the dispersiveness of metal oxide also becomes, therefore preferred.

Reaction between above-mentioned aromatic series or aliphatics tetracarboxylic dianhydride and (methyl) acrylic compound that contains hydroxyl of the 1st and the 2nd is, reaction between the hydroxyl that 2 carboxylic acid anhydride groups that aromatic series or aliphatics tetracarboxylic dianhydride have and (methyl) acrylic compound that contains hydroxyl of the 1st and the 2nd have is separately known in the field of himself.For example, can be in the such organic solvent of pimelinketone, 1, under the existence of the catalyzer that 8-diazacyclo [5.4.0]-7-undecylene is such, in 50～120 ℃ temperature, make (methyl) acrylic compound reaction that contains hydroxyl of aromatic tetracarboxylic acid's dianhydride and the 1st and the 2nd.At this moment, can in reaction system, add the such stopper of first quinone (methoquinone).

After the above-mentioned reaction, for the reaction mixture that comprises the compound that resultant of reaction is formula (5) (X), needn't make with extra care, to wherein for example adding as the compound that contains epoxy group(ing) shown in the following general formula (6) of compound (Y), make its reaction, just can obtain the compound (R in this case, shown in the general formula (1) ⁷And R ⁸Be-CH ₂CH (OH) CH ₂-Ji.)

General formula (6)

(R here, ⁰Be CH ₂=C (R ³)-C (O) O-base and CH ₂=C (R ⁴)-C (O) O-base; R ³And R ⁴Then the same) with above-mentioned definition

The example of the compound shown in the formula (6) comprises glycidyl methacrylate, such (methyl) acrylate that contains epoxy group(ing) of glycidyl acrylate, orthoxenol glycidyl ether, p-phenyl phenol glycidyl ether, single styrenated phenol glycidyl ether, 4-cyano group-4-xenol glycidyl ether, 4,4 '-xenol monoglycidyl ether, 4, the aromatic glycidyl ether compound that 4 '-xenol diglycidylether is such etc.

Reaction between the compound shown in compound shown in the formula (5) and the formula (6) is the reaction between the epoxy group(ing) that has of the carboxyl that has of the compound shown in the formula (5) and the compound shown in the formula (6), knows in the field of himself.For example, this reaction can be carried out in 50～120 ℃ temperature in the presence of amine catalysts such as dimethyl benzylamine.

These reactions can be carried out under condition of no solvent, can be to carry out in the inert solvent to reaction perhaps.As such solvent, can enumerate for example hydrocarbon system solvents such as normal hexane, benzene or toluene, ketone series solvents such as acetone, methyl ethyl ketone or mibk, ester series solvents such as vinyl acetic monomer or N-BUTYL ACETATE, ether series solvents such as Anaesthetie Ether, tetrahydrofuran (THF) Huo diox, methylene dichloride, chloroform, tetracol phenixin, 1, halogen series solvents such as 2-ethylene dichloride or tetrachloroethylene, acetonitrile, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-methylimidazole alkane ketone isopolarity solvent etc.Two or more kinds may be used for these solvents.

Then, contained metal oxide is that average primary particle diameter is the metal oxide of 5～100nm in the metal oxide composition.The average primary particle diameter of metal oxide can itself be measured by for example using transmission electron microscope (TEM) or scanning electronic microscope direct viewing particles such as (SEM).

Average primary particle diameter is less than the situation of the metal oxide of 5nm, and the cohesive force between particulate is very big, therefore is difficult to carry out the dispersion of the high primary particle level of the transparency.On the other hand, average primary particle diameter surpasses the situation of the metal oxide of 100nm, disperses with the primary particle level easily, but because particle diameter is big, for light such as visible lights scattering takes place easily, produces the problem of the transparency deterioration of cured film.

As metal oxide, preferably contain at least a element that is selected from the group that forms by titanium, zinc, zirconium, antimony, indium, tin, aluminium, silicon, phosphorus and fluorine.Particularly contain the metal oxide of any element in antimony, indium and the tin because electroconductibility is also good, therefore more preferred.

Can enumerate antimony pentaoxide, antimony doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO) particularly, mix phosphorus oxidation tin (PTO), zinc antimonates (AZO), mix indium zinc oxide (IZO), stannic oxide, ATO lining titanium oxide, Al-Doped ZnO, titanium oxide, zinc oxide, zirconium white, silicon oxide, aluminum oxide etc.Two or more kinds may be used for these metal oxides.

Commercially available product as metal oxide can be enumerated:

Nissan Chemical Ind Ltd makes: Sang Aipo gram (サ Application エ Port Star Network) EFR-6N, Sang Aipo restrains EFR-6NP (antimony pentaoxide);

Ishihara Sangyo Kaisha, Ltd. makes: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO be covered titanium oxide), TTO-55 (A) (titanium oxide), TTO-55 (B) (titanium oxide), TTO-55 (C) (titanium oxide), TTO-55 (D) (titanium oxide), TTO-55 (S) (titanium oxide), TTO-55 (N) (titanium oxide), TTO-51 (A) (titanium oxide), TTO-51 (C) (titanium oxide), TTO-S-1 (titanium oxide), TTO-S-2 (titanium oxide), TTO-S-3 (titanium oxide), TTO-S-4 (titanium oxide), 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);

Mitsubshi Materials Corp makes: T-1 (ITO), S-1200 (stannic oxide), EP SP-2 (mixing phosphorus oxidation tin);

Industrial Co., Ltd of Mitsui Metal Co., Ltd. makes: Paasche holder bright (パ ス ト ラ Application) (ITO, ATO);

CI changes into Co., Ltd. and makes: NanoTek ITO, NanoTek SnO ₂, NanoTek TiO ₂, NanoTek SiO ₂, NanoTek Al ₂O ₃, NanoTek ZnO;

Catalysts ﹠ Chem Ind Co makes: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-130 (ITO);

Japan plain boiled water science and technology (HAKUSUI TECH) Co., Ltd. makes: Pazet CK (Al-Doped ZnO);

Sakai Chemical Industry Co., Ltd. makes: FINEX-25 (zinc oxide), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP (zinc oxide), FINEX-75 (zinc oxide), NANOFINE-50A (zinc oxide), NANOFINE-50SD (zinc oxide), EZ-1 (zinc oxide), STR-60C (titanium oxide), STR-60C-LP (titanium oxide), STR-100C (titanium oxide), STR-100C-LP (titanium oxide), STR-100A-LP (titanium oxide), STR-100W (titanium oxide);

Sumitomo Osaka Cement Co., Ltd. makes: OZC-3YC (zirconium white), OZC-3YD (zirconium white), OZC-3YFA (zirconium white), OZC-8YC (zirconium white), OZC-0S100 (zirconium white);

Nitto Denko Corp makes: PCS (zirconium white), PCS-60 (zirconium white), PCS-90 (zirconium white), T-01 (zirconium white);

Japan Chemical Co., Ltd of kingdom makes: MT-100S (titanium oxide), MT-100HD (titanium oxide), MT-100SA (titanium oxide), MT-500HD (titanium oxide), MT-500SA (titanium oxide), MT-600SA (titanium oxide), MT-700HD (titanium oxide), MZ-303S (zinc oxide), MZY-303S (zinc oxide), MZ-303M (zinc oxide), MZ-505S (zinc oxide), MZY-505S (zinc oxide), MZ-505M (zinc oxide);

Japan AEROSIL Co., Ltd. makes Aluminium Oxide C (aluminum oxide), AEROSIL130 (silicon oxide), AEROSIL200 (silicon oxide), AEROSIL200V (silicon oxide), AEROSIL200CF (silicon oxide), AEROSIL200FA (silicon oxide), AEROSIL300 (silicon oxide), AEROSIL300CF (silicon oxide), AEROSIL380 (silicon oxide), AEROSILR972 (silicon oxide), AEROSILR974 (silicon oxide), AEROSILR976 (silicon oxide), AEROSILR202 (silicon oxide), AEROSILR805 (silicon oxide), AEROSILR812 (silicon oxide), AEROSILR812S (silicon oxide), AEROSILMOX50 (silicon oxide), AEROSILTT600 (silicon oxide), AEROSILMOX80 (silica), AEROSILMOX170 (silica), AEROSILCOX84 (silica) etc.

The addition of the metal oxide in the metal oxide composition is not particularly limited, but measures in 100 weight parts in the solids component total of dispersion agent (A) and metal oxide, is preferably 1～80 weight part, more preferably 10～70 weight parts.The addition of metal oxide is during less than 1 weight part, and the static resistance that is derived from metal oxide sometimes is relatively poor; When surpassing 80 weight parts, because the organic composition amount is few, film-forming properties is relatively poor sometimes.

Metal oxide composition of the present invention even mixed dispersant (A) and metal oxide are modulated simply, also can fully obtain desired effects.But, carry out mechanically mixing by kneader, cylinder, stirring ball mill (Attritor), super grinding machine, dry type pulverization process machine etc., perhaps at the solution that comprises dispersion agent (A) by interpolation in the suspension system of formation such as metal oxide powder and organic solvent, carry out in the so tight mixed system of metal oxide surface and dispersion agent (A) is deposited to, can obtain better effect.

This metal oxide composition preferably the metal oxide powder homodisperse metal oxide dispersion.By using dispersion agent (A), disperseing average primary particle diameter in the presence of organic solvent is the metal oxide of 5～100nm, just can make metal oxide dispersion aptly.

As for the dispersive degree, " the Nanotrac UPA " that make with the Nikkiso Company Limited that utilizes dynamic light scattering method disperses particle diameter D99 to be preferably less than 300nm when measuring, and is more preferably less than 200nm.

Dispersion agent (A), during metal oxide or metal oxide composition dispersing or dissolving and their mix are waited in non-water system vehicles such as organic solvent, can use paint regulator (manufacturing of red magic company), ball mill, sand mill (Shinmaru Enterprises company makes and wears promise mill (Dyno-mill) etc.), stirring ball mill, ball mill (liking that the upright company that permitted makes DCP shredder etc.), biconical sand mill (Coball mill), high-speed mixer, homogenizer (M Technology Co.'s manufacturing " CLEARMIX " etc.), (Ji Nasi company (Genus) makes " Genus PY " to the wet shotcrete technology grinding machine, Nanomizer company makes " Nanomizer "), small ball mill (" the SUPER Abbe lattice mills (ス-パ-ア ペ Star Network ミ Le) " of longevity Industrial Co., Ltd's manufacturing, " ULTRA Abbe lattice mill (ウ Le ト ラ ア ペ Star Network ミ Le) ") etc. dispersion machine.In dispersion machine, during working medium, preferably use granulated glass sphere, zirconium oxide bead, alumina bead, magnetic beads, vinylbenzene pearl etc.About dispersion, also the medium more than 2 kinds that can adopt the dispersion machine more than 2 kinds separately or vary in size uses by stages.

Metal oxide composition of the present invention contains dispersion agent (A) and metal oxide at least, can also contain solvent and various additive in the scope of not damaging purpose of the present invention and effect.Can enumerate solvent, Photoepolymerizationinitiater initiater, photocurable compound, stopper, photosensitizers, flow agent, tensio-active agent, antiseptic-germicide, anti-caking agent, softening agent, UV light absorber, infrared absorbent, antioxidant, silane coupling agent, electric conductive polymer, conductive surface's promoting agent, inorganic filler, pigment, dyestuff etc. particularly.

Manufacture method as the metal oxide composition that contains the composition except that dispersion agent (A) and metal oxide is not particularly limited, and can enumerate several method.Can enumerate particularly: earlier blending dispersion dispersion agent (A) and metal oxide in organic solvent, obtain stable metal oxide dispersion after, add and adjust the method that other various additives are made; The state that has just all mixed with dispersion agent (A), metal oxide, organic solvent and other additives from beginning disperses the method made etc.

Add the situation of solvent, preferably after solvent evaporates, carry out solidification treatment.Be not particularly limited as solvent, can use various known organic solvents.Can enumerate for example pimelinketone particularly; methyl iso-butyl ketone (MIBK); methyl ethyl ketone; acetone; Acetyl Acetone; toluene; dimethylbenzene; propyl carbinol; isopropylcarbinol; the trimethyl carbinol; n-propyl alcohol; Virahol; ethanol; methyl alcohol; 3-methoxyl group-1-butanols; 3-methoxyl group-2-butanols; ethylene glycol monomethyl ether; the glycol monomethyl n-butyl ether; cellosolvo; 1-methoxyl group-2-propyl alcohol; diacetone alcohol; ethyl lactate; n-Butyl lactate; propylene glycol monomethyl ether; ethylene glycol butyl ether acetate; propylene glycol monomethyl ether acetate; 2-ethoxyethyl group acetic ester; N-BUTYL ACETATE; isoamyl acetate; dimethyl adipate; Succinic acid dimethylester; Methyl glutarate; tetrahydrofuran (THF); methyl-2-pyrrolidone etc.Two or more kinds may be used for these organic solvents.

Wherein, the hydroxyl solvent, because the wettability to the metal oxide of the high particle surface rerum natura of possess hydrophilic property is good, by in solvent composition, containing this solvent, very effective aspect the ageing stability of dispersiveness that improves metal oxide and coating (metal oxide composition) thereof, and the levelling property of painting process also improves, and is therefore preferred.All the hydroxyl solvent in the solvent composition is preferably 10～100 weight %.Particularly, can enumerate propyl carbinol, isopropylcarbinol, the trimethyl carbinol, n-propyl alcohol, Virahol, ethanol, methyl alcohol, 3-methoxyl group-1-butanols, 3-methoxyl group-2-butanols, ethylene glycol monomethyl ether, glycol monomethyl n-butyl ether, cellosolvo, 1-methoxyl group-2-propyl alcohol, diacetone alcohol, ethyl lactate, n-Butyl lactate, propylene glycol monomethyl ether etc. as the hydroxyl solvent.Consider preferred especially 3-methoxyl group-1-butanols, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-butyl ether from the dispersiveness and the better angle of dispersion stabilization of metal oxide.

As Photoepolymerizationinitiater initiater; just be not particularly limited so long as have the material that can cause the function of vinyl polymerization, can use for example mono-carbonylation compound, dicarbonyl compound, acetophenone compound, benzoin ether compound, acylphosphine oxide compound, aminocarboxyl compound etc. by optical excitation.

Particularly; can enumerate benzophenone as the mono-carbonylation compound; 4-methyldiphenyl ketone; 2; 4; the 6-tri-methyl benzophenone; methyl o-benzoyl yl benzoic acid ester; the 4-phenyl benzophenone; 4-(4-aminomethyl phenyl sulfo-) Propiophenone; 3; 3 '-dimethyl-4-methoxy benzophenone; 4-(1; 3-acryl-1; 3; 3 '-dimethyl-4-methoxy benzophenone; 4-(1; 3-acryl-1; 4; 7; 10; 13-five oxygen tridecyls) benzophenone; 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone; the 4-benzoyl-N; N, N-trimethylammonium-1-propane amine hydrochlorate; the 4-benzoyl-N, N-dimethyl-N-2-(1-oxygen-2-propenyl oxygen ethyl) is ammonium oxalate partially; 2-/4-isopropyl thioxanthone; 2; the 4-diethyl thioxanthone; 2; 4-two clopenthixal ketones; 1-chloro-4-propoxy-thioxanthone; 2-hydroxyl-3-(3,4-dimethyl-9-oxygen-9H thioxanthone-2-base oxygen-N, N; N-trimethylammonium-1-propane amine hydrochlorate; benzoyl methylene radical-3-methylnaphthalene (1,2-d) thiazoline etc.

As dicarbonyl compound, can enumerate 1,2,2-trimethylammonium-dicyclo [2.1.1] heptane-2,3-diketone, benzil (ベ Application ザ イ Le), 2-ethyl-anthraquinone, 9,10-phenanthrenequione, methyl-alpha-oxo-benzene acetic ester, 4-phenyl benzil etc.

As acetophenone compound, can enumerate 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxyl-two-2-methyl isophthalic acid-phenyl-propane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styryl propane-1-ketone polymer, diethoxy acetophenone, the dibutoxy methyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, 2,2-diethoxy-1,2-diphenylethane-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 1-phenyl-1,2-propanedione-2-(adjacent ethoxy carbonyl) oxime, 3, two (2-methyl-2-morpholino the acetonyl)-9-butyl carbazoles of 6-etc.

As the benzoin ether compound, can enumerate st-yrax, benzoin methyl ether, Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, st-yrax n-butyl ether etc.

As the acylphosphine oxide compound, can enumerate 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 4-n-propyl phenyl-two (2,6-dichloro-benzoyl base) phosphine oxide etc.

As aminocarboxyl compound, can enumerate methyl-4-(dimethoxy amino) benzoic ether, ethyl-4-(dimethylamino) benzoic ether, 2-n-butoxy ethyl-4-(dimethylamino) benzoic ether, isopentyl-4-(dimethylamino) benzoic ether, 2-(dimethylamino) ethylamino benzonitrile acid esters, 4,4 '-two-4-dimethylamino benzophenone, 4,4 '-two-4-diethylamino benzophenone, 2,5 '-two (4-diethylamino Ben Yajiaji) cyclopentanone etc.

Commercially available product as Photoepolymerizationinitiater initiater, can enumerate the Irgacure184,651,500,907,127,369,784,2959 that Ciba company makes, the Ai Sakuerwan (エ サ キ ユ ア ワ Application) that the Lucirin TPO that BASF AG makes, Japanese Waja (シ イ ベ Le ヘ グ Na-) company make etc.

Photoepolymerizationinitiater initiater is not limited to above-claimed cpd, as long as the ability that has by ultraviolet-initiated polymerization then can be any material.These Photoepolymerizationinitiater initiaters can use a kind, also can be mixed with two or more.

Usage quantity about Photoepolymerizationinitiater initiater is not particularly limited, with respect to the total amount of the photocurable compound that contains dispersion agent (A) (when the situation that contains following photocurable compound arbitrarily, be the total amount of dispersion agent (A) and photocurable compound) 100 weight parts, preferably use in the scope of 1～20 weight part.

As sensitizing agent, can also add known organic amine etc.

And then, except above-mentioned radical polymerization share initiator, can also and with the cationoid polymerisation initiator.

Except dispersion agent (A), metal oxide composition can also comprise other adhesive resin, photocurable compound.

As adhesive resin, can enumerate for example urethane resin, carbamide resin, polyurethane urea resin, vibrin, polyether resin, polycarbonate resin, Resins, epoxy, aminoresin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resins, Vinylite etc.These resins can use a kind, also can be mixed with two or more.Total amount with the solids component of metal oxide composition (composition beyond the solvent, below same) is benchmark (100 weight part), and adhesive resin preferably uses in the scope below 20 weight parts.

As photocurable compound, for example can use (methyl) acrylic acid series compound, fatty acid ethylene ester cpds, alkyl vinyl ether compound, alpha-olefin compound, vinyl compound, acetylene compound etc. to have the compound of polymerizability unsaturated double-bond group.These compounds with polymerizability unsaturated double-bond group can further have functional groups such as hydroxyl, alkoxyl group, carboxyl, amide group, silanol group.Total amount with the solids component of metal oxide composition is benchmark (100 weight part), and this photocurable compound is preferably in the scope less than 50 weight parts, particularly use in the scope of 5～40 weight parts.

As (methyl) acrylic acid series compound, (methyl) benzyl acrylate, alkyl system (methyl) acrylate, aklylene glycol system (methyl) acrylate are arranged, have carboxyl and polymerizability unsaturated double-bond compound, have (methyl) acrylic acid series compound of hydroxyl, nitrogenous (methyl) acrylic acid series compound etc.In addition, can suit to use simple function, polyfunctional compound.Consider preferred polyfunctional compound from the angle of light solidified, the being coated with property firmly of filming.

(methyl) acrylic acid series compound as simple function, specifically, as alkyl system (methyl) acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) 2-EHA, (methyl) vinylformic acid heptyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid heptadecyl ester, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid nonadecyl ester, (methyl) vinylformic acid eicosyl ester, (methyl) vinylformic acid heneicosyl ester, (methyl) vinylformic acid alkylene ester of carbonatomss 1～22 such as (methyl) vinylformic acid docosyl ester.When being purpose to adjust polarity, preferred use have carbonatoms 2～10, more preferably carbonatoms 2～8 alkyl contain alkyl (methyl) acrylate.In addition, when be purpose to regulate levelling property etc., preferred use has (methyl) alkyl acrylate of the alkyl of carbonatoms more than 6.

As aklylene glycol system (methyl) acrylate, can enumerate list (methyl) acrylate that diglycol monotertiary (methyl) acrylate, triglycol list (methyl) acrylate, Tetraglycol 99 list (methyl) acrylate, hexaethylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, dipropylene glycol list (methyl) acrylate, tripropylene glycol list (methyl) acrylate, four propylene glycol list (methyl) acrylate, polytetramethylene glycol (methyl) acrylate etc. have hydroxyl endways and have polyoxyalkylene chain; Methoxyl group ethylene glycol (methyl) acrylate, methoxyl group glycol ether (methyl) acrylate, methoxyl group triglycol (methyl) acrylate, methoxyl group Tetraglycol 99 (methyl) acrylate, oxyethyl group Tetraglycol 99 (methyl) acrylate, propoxy-Tetraglycol 99 (methyl) acrylate, n-butoxy Tetraglycol 99 (methyl) acrylate, n-pentyloxy Tetraglycol 99 (methyl) acrylate, tripropylene glycol (methyl) acrylate, four propylene glycol (methyl) acrylate, methoxyl group tripropylene glycol (methyl) acrylate, methoxyl group four propylene glycol (methyl) acrylate, oxyethyl group four propylene glycol (methyl) acrylate, propoxy-four propylene glycol (methyl) acrylate, n-butoxy four propylene glycol (methyl) acrylate, n-pentyloxy four propylene glycol (methyl) acrylate, polytetramethylene glycol (methyl) acrylate, methoxyl group polytetramethylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, oxyethyl group polyoxyethylene glycol (methyl) acrylate etc. has alkoxyl group endways and has list (methyl) acrylate of polyoxyalkylene chain; Phenoxy group glycol ether (methyl) acrylate, phenoxy group ethylene glycol (methyl) acrylate, phenoxy group triglycol (methyl) acrylate, phenoxy group Tetraglycol 99 (methyl) acrylate, phenoxy group hexaethylene glycol (methyl) acrylate, phenoxy group polyoxyethylene glycol (methyl) acrylate, phenoxy group four propylidene ethylene glycol (methyl) acrylate etc. have polyoxyalkylene system (methyl) acrylate of phenoxy group or aryloxy endways.

As compound, can enumerate toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid or their alkyl or alkenyl monoesters, phthalic acid β-(methyl) acryloxy ethyl monoesters, m-phthalic acid β-(methyl) acryloxy ethyl monoesters, succsinic acid β-(methyl) acryloxy ethyl monoesters, vinylformic acid, methacrylic acid, Ba Dousuan, TRANSCINNAMIC ACID etc. with carboxyl and polymerizability unsaturated double-bond.

As hydroxyl (methyl) acrylic acid series compound, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, single (methyl) acrylate of glycerol, 4-hydroxyl vinyl benzene, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate etc.

As nitrogenous (methyl) acrylic acid series compound, (methyl) acrylamide is arranged, N-methylol (methyl) acrylamide, N-methoxymethyl-(methyl) acrylamide, N-ethoxyl methyl-(methyl) acrylamide, N-propoxy-methyl-(methyl) acrylamide, N-butoxymethyl-(methyl) acrylamide, N-pentyloxy methyl-single silane alcohol base (alkylol) (methyl) acrylamides such as (methyl) acrylamide, N, N-two (methylol) acrylamide, N-methylol-N-methoxymethyl (methyl) acrylamide, N, N-two (methylol) acrylamide, N-ethoxyl methyl-N-methoxymethyl Methacrylamide, N, N-two (ethoxyl methyl) acrylamide, N-ethoxyl methyl-N-propoxy-methyl acrylamide, N, N-two (propoxy-methyl) acrylamide, N-butoxymethyl-N-(propoxy-methyl) Methacrylamide, N, N-two (butoxymethyl) acrylamide, N-butoxymethyl-N-(methoxymethyl) Methacrylamide, N, N-two (pentyloxy methyl) acrylamide, acrylamide unsaturated compounds such as dioxane alcohol radical (methyl) acrylamide such as N-methoxymethyl-N-(pentyloxy methyl) Methacrylamide; (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid methylethyl amino ethyl ester, dimethylamino vinylbenzene, diethylamino vinylbenzene etc. have the unsaturated compound of dialkyl amido; And has a Cl ^-, Br ^-, I ^-Deng halogen ion or QSO3 ^-(Q: the alkyl of carbonatoms 1～12) as quaternary ammonium salt that contains the dialkyl amido unsaturated compound of counter ion etc.

As other unsaturated compounds, can enumerate (methyl) vinylformic acid perfluoro-methyl methyl esters, (methyl) vinylformic acid perfluor ethyl methyl esters, (methyl) vinylformic acid-2-perfluoro butyl ethyl ester, (methyl) vinylformic acid-2-perfluoro hexyl ethyl ester, (methyl) vinylformic acid-2-perfluoro capryl ethyl ester, the different nonyl ethyl ester of (methyl) vinylformic acid-2-perfluor, (methyl) vinylformic acid-2-perfluor nonyl ethyl ester, (methyl) vinylformic acid-2-perfluor decyl ethyl ester, (methyl) vinylformic acid perfluoro propyl propyl ester, (methyl) vinylformic acid perfluoro capryl propyl ester, (methyl) vinylformic acid perfluoro capryl pentyl ester, (methyl) vinylformic acid perfluoro capryl undecyl ester etc. has (methyl) vinylformic acid perfluoroalkyl alkyl esters of the perfluoroalkyl of carbonatoms 1～20.

And then, also can enumerate the vinyl monomer that perfluoroalkyls such as perfluorobutyl ethylene, perfluoro hexyl ethene, perfluoro capryl ethene, perfluor decyl ethylene, alkene class etc. contain perfluoroalkyl; Vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, γ-(methyl) acryloxy propyl trimethoxy silicane etc. contain the vinyl compound and the derivative thereof of alkoxysilyl; Glycidyl acrylate, vinylformic acid-3,4-epoxy cyclohexyl etc. contains the acrylate of glycidyl.

As the fatty acid ethylene ester cpds, can enumerate vinyl acetate, vinyl butyrate, Vinyl crotonate, sad vinyl acetate, vinyl laurate, vinyl chloroacetate, oleic acid vinyl acetate, stearic acid vinyl ester etc.

As the alkyl vinyl ether compound, can enumerate butyl vinyl ether, ethyl vinyl ether etc.

As the alpha-olefin compound, can enumerate 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene etc.

As vinyl compound, can enumerate allylic cpds such as allyl acetic acid, allyl alcohol, allyl benzene, allyl cyanide, vinyl cyanide, vinyl cyclohexane, ethenyl methyl ketone, vinylbenzene, alpha-methyl styrene, 2-methyl styrene, chloro-styrene etc.

As acetylene compound, can enumerate acetylene, acetylenylbenzene, ethynyl toluene, 1-ethynyl-1-hexalin etc.

These compounds can use a kind, also can be mixed with two or more.

Among these; as dispersion agent (A) photocurable compound in addition; consider from the angle of coating strength, scuff resistance; can suit to use poly-(methyl) esters of acrylic acids such as polyurethane polyureas (methyl) acrylate with at least three functional groups, poly-(methyl) acrylate of poly-epoxy, have the polyfunctional acrylic ester class of 3 above acryls at intramolecularly.

Poly-(methyl) acrylate of poly-epoxy; be with of the epoxy group(ing) esterification of (methyl) vinylformic acid with Resins, epoxy; make functional group become the compound of (methyl) acryl, have (methyl) vinylformic acid to the affixture of bisphenol A type epoxy resin, (methyl) vinylformic acid to affixture of phenolic resin varnish type epoxy resin etc.

Polyurethane polyureas (methyl) acrylate for example has: make compound that vulcabond obtains with (methyl) esters of acrylic acid reaction with hydroxyl, containing of polyvalent alcohol and polyisocyanates reacts form under the condition of isocyanate group surplus, the isocyanate group urethane prepolymer reacted with (methyl) esters of acrylic acid with hydroxyl and the compound that obtains.Perhaps, also can obtain with (methyl) esters of acrylic acid reaction by the hydroxyl urethane prepolymer that makes polyvalent alcohol and polyisocyanates under the condition of hydroxyl surplus, react formation with isocyanate group.

As polyvalent alcohol, can enumerate ethylene glycol, propylene glycol, glycol ether, dipropylene glycol, butyleneglycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, the polycondensate of 5-pentanediol, neopentyl glycol, hexanetriol, TriMethylolPropane(TMP), polytetramethylene glycol, hexanodioic acid and ethylene glycol etc.

As polyisocyanates, can enumerate tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate etc.

As (methyl) esters of acrylic acid, can enumerate (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-2-hydroxy propyl ester, (methyl) vinylformic acid-4-hydroxyl butyl ester, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate etc. with hydroxyl.

As (methyl) esters of acrylic acid, can enumerate 2-(methyl) acryloxy ethyl isocyanate, (methyl) acryl isocyanic ester etc. with isocyanate group.

Commercially available product as photocurable compound can the following material of illustration.

Toagosei Co., Ltd makes: sieve Knicks M-400 difficult to understand, sieve Knicks M-402 difficult to understand, sieve Knicks M-408 difficult to understand, sieve Knicks M-450 difficult to understand, sieve Knicks M-7100 difficult to understand, sieve Knicks M-8030 difficult to understand, sieve Knicks M-8060 difficult to understand;

Osaka Organic Chemical Industry Co., Ltd. makes: BISCOAT#400;

Chemical drug Sartomer Co., Ltd. makes: SR-295;

Daicel UCB Co., Ltd. makes: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl5129, Ebecryl 2220, Ebecryl 6602;

Xin Zhong village chemical industry Co., Ltd. makes: NK ester A-TMMT, the oligomeric EA-1020 of NK, the oligomeric EMA-1020 of NK, the oligomeric EA-6310 of NK, the oligomeric EA-6320 of NK, the oligomeric EA-6340 of NK, the oligomeric MA-6 of NK, the oligomeric U-4HA of NK, the oligomeric U-6HA of NK, the oligomeric U-324A of NK;

BASF AG makes: LaromerEA81;

Sheng Nuopuke (SANNOPCO) Co., Ltd. makes: Photomer 3016;

Arakawa Chemical Industries, Ltd. makes: finish nurse Saite (PVC-system セ Star ト) 371, finish nurse Saite 575, finish nurse Saite 577, finish nurse Saite 700, finish nurse Saite 710;

Industrial Co., Ltd makes on the root: atropic resin (ア-ト レ ジ Application) UN-3320HA, atropic resin UN-3320HB, atropic resin UN-3320HC, atropic resin UN-3320HS, atropic resin UN-9000H, atropic resin UN-901T, atropic resin HDP, atropic resin HDP-3, atropic resin H61;

The Nippon Synthetic Chemical Industry Co., Ltd makes: 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;

Kyoeisha Chemical Co., Ltd. makes: light acrylate PE-4A, light acrylate DPE-6A, UA-306H, UA-306T, UA-306I;

Nippon Kayaku K. K makes: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.

Then, cured film of the present invention and duplexer thereof are described.

Cured film of the present invention is to solidify metal oxide composition of the present invention and the film that forms.Its manufacture method for example comprises: to the step of any base material coating metal oxide composition, and the irradiation active energy beam makes the metal oxide composition step of curing on the base material.

More specifically, can be at this metal oxide composition of coating on any base material, make dried thickness be preferably 0.1～30 μ m, 0.1～20 μ m more preferably, be cured then and handle and form.

During formation, cured film can be coated directly onto on the base material, also can be at the bottom that exists between cured film and the base material more than 1 layer.

Can enumerate metal, pottery, glass, plastics, timber, slabstone etc. as this base material, be not particularly limited.Can enumerate polyester, polyolefine, polycarbonate, polystyrene, polymethylmethacrylate, tri acetyl cellulose resin, ABS resin, AS resin, polymeric amide, Resins, epoxy, melamine resin etc. as the kind of concrete plastics.In addition, can enumerate diaphragm, plate-like panel, lens shape, discoid, fibrous material, be not particularly limited as the shape of base material.

Known method can be adopted as coating process, the various coating processes such as method, the coating of nick version, intaglio plate coating, die head coating, the coating of curtain formula, die lip coating, slot scraping coating or rotary coating that for example use scraper or line rod (wirebar) etc. can be adopted.

Solidification treatment can adopt known technology, and for example the visible rays isoreactivity energy-ray by irradiation ultraviolet radiation, electron rays, wavelength 400～500nm carries out.For example can use high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, gallium lamp, xenon lamp, carbon arc lamp etc. as the gamma ray source (light source) of the visible rays of ultraviolet ray and wavelength 400～500nm.Can use thermoelectronic emission rifle, electrolysis radiation rifle etc. as electronic radial source.

The active energy beam amount of irradiation is preferably 5～2000mJ/cm ²Scope in, and then manageable angle is considered on the operation, is preferably 50～1000mJ/cm ²Scope in.

Can will utilize the thermal treatment and the irradiation of these active energy beams of infrared rays, far infrared rays, hot blast, ratio-frequency heating etc. and use.

As for cured film, can be on base material the coating metal oxide composition, carry out carrying out solidification treatment after nature or the forced drying and form, also can be coated with and carry out carrying out nature or forced drying after the solidification treatment, but more preferably carry out carrying out after nature or the forced drying mode of solidification treatment.

Situation about being cured by electron rays is particularly solidified or is reduced because of organic solvent residual causes coating strength for anti-sealing hinders, and more preferably carries out carrying out after nature or the forced drying mode of solidification treatment.

Can be and the coating while, also can be after coating the opportunity of solidification treatment.

The cured film that obtains since being coated with property, the transparency, photostabilization, high refractive index, excellent antistatic property firmly therefore can suit as optical material.Therefore, cured film of the present invention can be used as duplexer and is used for cathode tube, the front panel of panel display screen various display unit such as (liquid-crystal display, plasma display, electrochromic display device, light emitting diode indicators etc.) or their input unit.

In addition, this cured film can extensively be used in optics lens, eyeglass lens, optical recording (compact disk, DVD dish, Blu-ray disc etc.), lamp box etc.

The sheet resistance value of cured film is preferably 1 * 10 ¹²Below Ω/sq..

The thickness of cured film is preferably 0.1～30 μ m.

And then the specific refractory power of cured film is preferably 1.4～2.0 scope, more preferably 1.5～1.8 scope.

Duplexer of the present invention comprises cured film of the present invention and base material.Can at random use above-mentioned illustrative base material as base material, be preferably plastic basis material especially.The shape of base material is preferably film shape, lens shape or disc-shape.

This duplexer except that these, preferably includes different film, adhesive coating or the information recording layers etc. of specific refractory power more than 1 layer.

Comprise that the duplexer of the different film of specific refractory power (M), adhesive coating (M) or information recording layer (M) can form the layer structure of for example following (I)～(IX) etc.

(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

Film that specific refractory power is different or information recording layer have the function function in addition that cured article of the present invention has.Its formation method is not particularly limited, and can be formed by known method.Can adopt for example dry type such as evaporation, sputter coating method, wet type coating methods such as the method for use scraper, line rod and the coating of nick version, intaglio plate coating, die head coating, the coating of curtain formula, die lip coating, slot scraping coating, rotary coating.The material that uses can use as required and can give information writing function, anti-dazzle function to duplexer, prevents the Newton's rings function, any materials of function more than a kind in the functions such as adhesion function, blocking-up specific wavelength, raising adaptation, revisal tone also without limits.

As information recording layer, so long as utilize laser etc. to produce some chemical transformation, get final product according to the layer of this change records information, material is not particularly limited.For example as the organic system material, can enumerate polymethine pigment, naphthalene cyanines system, phthalocyanine system, Si Kuli (Squalilium) and be, anthraquinone system, xanthene system, triphenyl methane be metal complex, above-mentioned dyestuff can use a kind or be used in combination more than 2 kinds.As inorganic be recording layer, can use a kind in metal, the semi-metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, Pt or be used in combination more than 2 kinds.Information recording layer can be a duplexer etc., and the mode of photochemical transformations can be any one of phase change, foaming, open cell type.And then, can be magneto-optical recorder layer based on Fe, Tb, Co, also can be spiro-pyrans, fulgide are photochromic material.

Consider that from the angle that prevents to reflect the also preferred lining cured film that low-refraction is set on the top layer of the cured film of high refractive index is utilized as the duplexer of having given anti-reflective function.That is, preferably use on base materials such as film, form cured film so that be preferably formed the lining cured film and the duplexer that obtains as antireflection film.

Become the duplexer of problem about the reflection interference striped, the preferred use level of adjusting the metal oxide in the metal oxide composition of the present invention, make its cured film and base material specific refractory power difference or when between cured film and base material, have random layer the difference of the specific refractory power of cured film and the bottom that joins with cured film be in ± 0.02.

Metal oxide composition of the present invention is by the kind of control metal oxide and the cured article that addition can be made high refractive index.Therefore, be preferably used as the optical semiconductor sealing material that requires to reduce successively the resin layer specific refractory power for the light extraction efficiency that improves optical semiconductor from optical semiconductor side direction outermost layer.

Specific refractory power 2.5), gallium phosphide (GaP, specific refractory power 2.9), gallium arsenide (GaAs: specific refractory power 3.5) etc., be the very high material of specific refractory power as optical semiconductor, can enumerate gan (GaN:.Therefore, consider that from the angle that improves light extraction efficiency the specific refractory power that becomes the cured article of optical semiconductor sealing material is preferably more than 1.5, more preferably 1.5～2.1, more preferably 1.7～2.1.

Method as the best specific refractory power that realizes cured article, the metal oxide that uses is preferably titanium oxide (specific refractory power 2.5～2.7), zirconium white (specific refractory power 2.4), zinc oxide (specific refractory power 1.95) etc., because dispersion agent also requires high refractive index, therefore preferably has the dispersion agent (A) of aromatic series skeleton.

＜embodiment 〉

Below illustrate in greater detail the present invention based on Production Example, embodiment.In Production Example, embodiment, part and % represent weight part and weight % respectively.

The pharmaceutical chemicals that uses is as follows.

Biphenyl tetracarboxylic dianhydride (Mitsubishi chemical Co., Ltd's manufacturing)

9, (JFE KCC makes two (3,4-dicarboxyl phenyl) the fluorenes dicarboxylic anhydrides of 9-, trade(brand)name: BPAF)

The naphthane dicarboxylic anhydride (New Japan Chem Co., Ltd makes, trade(brand)name: physics and chemistry be TDA-100)

(JFE KCC makes the naphthalene dicarboxylic anhydride, trade(brand)name: NTCDA)

The butane tetracarboxylic acid dianhydride (New Japan Chem Co., Ltd makes, trade(brand)name: physics and chemistry be BT-100)

(Osaka Organic Chemical Industry Co., Ltd. makes pentaerythritol triacrylate (1), trade(brand)name: BISCOAT#300)

(Nippon Kayaku K. K makes pentaerythritol triacrylate (2), trade(brand)name: KAYARADPET-30)

(Nippon Kayaku K. K makes Dipentaerythritol five acrylate, trade(brand)name: KAYARADDPHA)

Vinylformic acid 2-hydroxy methacrylate (Nippon Shokubai Co., Ltd's manufacturing)

Quinhydrones (Wako Pure Chemical Industries, Ltd.'s manufacturing)

1,8-diazabicyclo [5.4.0]-7-undecylene (Tokyo HuaCheng Industry Co., Ltd's manufacturing)

Glycidyl methacrylate (manufacturing of DOW Chemical Amada Co., Ltd.)

Dimethyl benzylamine (Wako Pure Chemical Industries, Ltd.'s manufacturing)

(Production Example 1: dispersion agent (1))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 80.0 parts of biphenyl tetracarboxylic dianhydrides, 250.0 parts of pentaerythritol triacrylates (1), 0.16 part of quinhydrones, 141.2 parts of pimelinketone, be warming up to 85 ℃.Then, add 1.65 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 77.3 parts of glycidyl methacrylate, 33.9 parts of pimelinketone, then, add 2.65 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 70%, and number-average molecular weight (MN) is 870, and weight-average molecular weight (MW) is 2830.

(Production Example 2: dispersion agent (2))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 80.0 parts of biphenyl tetracarboxylic dianhydrides, 250.0 parts of pentaerythritol triacrylates (2), 0.16 part of quinhydrones, 141.2 parts of pimelinketone, be warming up to 85 ℃.Then, add 1.65 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 77.3 parts of glycidyl methacrylate, 33.9 parts of pimelinketone, then, add 2.65 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 70%, and number-average molecular weight is 920, and weight-average molecular weight is 3130.

(Production Example 3: dispersion agent (3))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 80.0 parts of biphenyl tetracarboxylic dianhydrides, 124.8 parts of pentaerythritol triacrylates (1), 222.8 parts of Dipentaerythritol five acrylate, 0.21 part of quinhydrones, 430.0 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.14 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 77.3 parts of glycidyl methacrylate, 80.7 parts of pimelinketone, then, add 3.42 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 1050, and weight-average molecular weight is 3830.

(Production Example 4: dispersion agent (4))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 part 9,9-two (3,4-dicarboxyl phenyl) fluorenes dicarboxylic anhydride, 200.2 parts of pentaerythritol triacrylates (1), 0.15 part of quinhydrones, 200.1 parts of pimelinketone are warming up to 85 ℃.Then, add 1.50 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 62.0 parts of glycidyl methacrylate, 42.4 parts of pimelinketone, then, add 2.41 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 60%, and number-average molecular weight is 830, and weight-average molecular weight is 2310.

(Production Example 5: dispersion agent (5))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 parts of naphthane dicarboxylic anhydrides, 305.7 parts of pentaerythritol triacrylates (2), 0.20 part of quinhydrones, 405.7 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.03 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 94.6 parts of glycidyl methacrylate, 96.9 parts of pimelinketone, then, add 3.26 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 870, and weight-average molecular weight is 3150.

(Production Example 6: dispersion agent (6))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 parts of naphthalene dicarboxylic anhydrides, 342.2 parts of pentaerythritol triacrylates (2), 0.22 part of quinhydrones, 442.2 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.21 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 105.9 parts of glycidyl methacrylate, 108.4 parts of pimelinketone, then, add 3.56 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 820, and weight-average molecular weight is 2440.

(Production Example 7: dispersion agent (7))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 parts of biphenyl tetracarboxylic dianhydrides, 556.8 parts of Dipentaerythritol five acrylate, 0.33 part of quinhydrones, 437.8 parts of pimelinketone, be warming up to 85 ℃.Then, add 3.28 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 96.6 parts of glycidyl methacrylate, 66.8 parts of pimelinketone, then, add 5.28 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 60%, and number-average molecular weight is 820, and weight-average molecular weight is 2660.

(Production Example 8: dispersion agent (8))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 part 9,9-two (3,4-dicarboxyl phenyl) fluorenes dicarboxylic anhydride, 50.7 parts of vinylformic acid 2-hydroxy methacrylates, 0.08 part of quinhydrones, 100.4 parts of pimelinketone are warming up to 85 ℃.Then, add 1.51 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 5 hours at 85 ℃.Then, add 62.0 parts of glycidyl methacrylate, 39.7 parts of pimelinketone, then, add 1.21 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 60%, and number-average molecular weight is 890, and weight-average molecular weight is 1200.

(Production Example 9: dispersion agent (9))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 parts of butane tetracarboxylic acid dianhydrides, 463.2 parts of pentaerythritol triacrylates (1), 0.28 part of quinhydrones, 563.2 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.82 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 143.4 parts of glycidyl methacrylate, 146.5 parts of pimelinketone, then, add 4.53 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 820, and weight-average molecular weight is 2000.

(Production Example 10: dispersion agent (10))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 parts of butane tetracarboxylic acid dianhydrides, 463.2 parts of pentaerythritol triacrylates (2), 0.28 part of quinhydrones, 563.2 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.82 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 143.4 parts of glycidyl methacrylate, 146.5 parts of pimelinketone, then, add 4.53 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 920, and weight-average molecular weight is 2200.

(Production Example 11: dispersion agent (11))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 80.0 parts of butane tetracarboxylic acid dianhydrides, 185.3 parts of pentaerythritol triacrylates (2), 330.9 parts of Dipentaerythritol five acrylate, 0.30 part of quinhydrones, 599.5 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.98 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 114.8 parts of glycidyl methacrylate, 119.6 parts of pimelinketone, then, add 4.77 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 950, and weight-average molecular weight is 2600.

(Production Example 12: dispersion agent (12))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 50.0 parts of butane tetracarboxylic acid dianhydrides, 413.4 parts of Dipentaerythritol five acrylate, 0.23 part of quinhydrones, 463.4 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.32 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 8 hours at 85 ℃.Then, add 71.7 parts of glycidyl methacrylate, 74.3 parts of pimelinketone, then, add 3.73 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 50%, and number-average molecular weight is 900, and weight-average molecular weight is 2070.

(Production Example 13: dispersion agent (13))

In the four-hole boiling flask that stirrer, reflux condensing tube, dry air ingress pipe, thermometer are installed, add 100.0 parts of butane tetracarboxylic acid dianhydrides, 117.2 parts of vinylformic acid 2-hydroxy methacrylates, 0.11 part of quinhydrones, 144.8 parts of pimelinketone, be warming up to 85 ℃.Then, add 2.17 parts as 1 of catalyzer, 8-diazabicyclo [5.4.0]-7-undecylene stirred 5 hours at 85 ℃.Then, add 143.4 parts of glycidyl methacrylate, 93.3 parts of pimelinketone, then, add 1.74 parts of dimethyl benzylamines, stirred 6 hours, be cooled to room temperature, termination reaction at 85 ℃ as catalyzer.The reaction soln that obtains is faint yellow transparent, and solids component is 60%, and number-average molecular weight is 780, and weight-average molecular weight is 1100.

(metal oxide disperses the making of paste: embodiment 1～22, comparative example 1～3)

Each dispersion agent (A) that use is made by above-mentioned Production Example disperses according to the row metal oxide compound that fits into shown in the table 1, makes metal oxide and disperses to stick with paste (use level is represented the solids component amount).Dispersing method is divided into following 2 stages to carry out: pre-dispersedly (use zirconium oxide bead (1.25mm) as medium, disperseed 1 hour with paint mixer) and formal dispersion the (use zirconium oxide bead (0.1mm) as medium, the dispersion machine UAM-015 of Industrial Co., Ltd's manufacturing disperses with the longevity).

In table 1:

Sb ₂O ₅: Nissan Chemical Ind Ltd makes " Sang Aipo restrains EFR-6N " (average primary particle diameter: 20nm)

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

ITO:CI changes into Co., Ltd. and makes " NanoTek ITO " (average primary particle diameter: 30nm)

PTO: Mitsubshi Materials Corp makes " EP SP-2 " (average primary particle diameter: 15nm)

ZrO ₂: Nitto Denko Corp makes " PCS-60 " (average primary particle diameter: 20nm)

TiO ₂: Ishihara Sangyo Kaisha, Ltd. makes " TTO-51 (A) " (average primary particle diameter: 20nm)

ZnO: Sakai Chemical Industry Co., Ltd. makes " FINEX-50 " (average primary particle diameter: 20nm)

SiO ₂Japan AEROSIL Co., Ltd. makes " AEROSIL50 " (average primary particle diameter 50nm)

Al ₂O ₅: Japanese AEROSIL Co., Ltd. makes " Aluminium Oxide C " (average primary particle diameter: 13nm)

Commercial dispersants: Bi Ke chemistry Amada Co., Ltd. makes " Disperbyk-111 " (solids component 100%)

Commercially available polyfunctional monomer (1): organic chemistry Co., Ltd. in Osaka makes " BISCOAT#400 " (solids component 100%)

Commercially available polyfunctional monomer (2): Nippon Kayaku K. K makes " KAYARAD DPHA " (solids component 100%)

MIBK: methyl iso-butyl ketone (MIBK)

メ ト Block : 3-methoxyl group-1-butanols

(coatingization and cured film evaluation: embodiment 1～22, comparative example 1～3)

Use above-mentioned synthetic metal oxide to disperse to stick with paste the metal oxide composition of forming shown in the modulometer 2.Using rod to be coated with device is coated on the metal oxide composition that obtains on thick easy the to be bonding processing PET film of 100 μ m (Japan spins Co., Ltd. and makes " コ ス モ シ ヤ イ Application A-4100 "), make that dried thickness is 5 μ m, uses metal halide light irradiation 400mJ/cm then ²Ultraviolet ray, form cured film (hard coat).At the cured film that obtains, estimate specific refractory power, scuff resistance, pencil hardness, the transparency (mist degree), photostabilization and surface resistivity by following method.It the results are shown in the table 2.

In table 2:

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

Photocurable compound (2): Nippon Kayaku K. K makes " KAYARAD DPHA "

Photoepolymerizationinitiater initiater: Ciba company makes " Irgacure 184 "

Solvent: PGME (propylene glycol monomethyl ether)

* 1:, measure because metal oxide is stuck with paste and disperseed badly

(making of duplexer and evaluation: embodiment 23～27)

(making of low-refraction coating fluid)

Mix 50 weight parts 1,2,9,10-tetrapropylene acyloxy-4,4,5,5,6,6,7,7-octafluoro decane, 120 weight part silicon dioxide gels, 30% dispersion liquid (MEK-ST that Nissan Chemical Ind Ltd makes), 10 weight parts 2 ', 2 '-two ((methyl) acryloyl-oxy ylmethyl) propionic acid (2-hydroxyl)-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-19 fluorine undecyl esters, 900 weight part butanols, 5 weight part Photoepolymerizationinitiater initiaters (the KAYACURE BMS that Nippon Kayaku K. K makes), modulation low-refraction coating fluid.

Use the metal oxide of embodiment 2 to disperse to stick with paste each metal oxide composition (use level is represented the solids component amount) that the cooperation shown in the modulometer 3 is formed.Use rod to be coated with device this metal oxide composition is applied on easy the to be bonding treated side of thick easy the to be bonding processing PET film (specific refractory power of easy bonding processing layer=1.60) of 100 μ m, make that dry film thickness is 6 μ m.The coating layer that obtains after 1 minute, is used metal halide light irradiation 400mJ/cm 100 ℃ of dryings ²Ultraviolet ray.Use spin coater, further be coated with above-mentioned low-refraction coating fluid on the cured film that obtains, the adjustment bed thickness makes represents that by dry film thickness the optical wavelength of λ/4 is about 550nm.At 100 ℃ to the coating layer that obtains after dry 1 minute, with metal halide light irradiation 400mJ/cm ²Ultraviolet ray, obtain duplexer.

At the duplexer that obtains, measure the specific refractory power of cured film by following method, and the scuff resistance of evaluate cure film, pencil hardness, the transparency (mist degree), specific refractory power, reflection interference striped.It the results are shown in the table 3.

The cooperation of table 3 metal oxide composition and the evaluation of cured film

(weight part)	Embodiment 23	Embodiment 24	Embodiment 25	Embodiment 26	Embodiment 27
						Metal oxide disperses to stick with paste	37.28	44.25	51.52	56.1	62.96
Photocurable compound (2)	41.36	31.91	25.37	20.2	15.63
						Photoepolymerizationinitiater initiater	2.38	1.91	1.56	1.35	1.14
Solvent (PGME)	68.98	71.93	71.55	72.35	70.27
						The specific refractory power of cured film	1.56	1.58	1.6	1.62	1.64
Scuff resistance	5	5	5	5	5
						Pencil hardness	A	A	A	A	A
The transparency (haze value)	0.58	0.62	0.65	0.68	0.75
						The refringence of cured film and base material	0.04	0.02	0	0.02	0.04
The reflection interference striped	D	A	A	A	D

In table 3:

Photocurable compound (2): Nippon Kayaku K. K makes " KAYARAD DPHA "

Photoepolymerizationinitiater initiater: Ciba company makes " Irgacure 184 "

Base material: easy the to be bonding processing PET film that 100 μ m are thick (Japan spins Co., Ltd. and makes " コ ス モ シ ヤ イ Application A-4100 ", is coated with at easy bonding treated side (specific refractory power 1.60))

Solvent: PGME (propylene glycol monomethyl ether)

(evaluation method)

(1) specific refractory power

Use Japan to like to open up (ATAGO) Co., Ltd. and make the specific refractory power that Abbe refractomecer is measured the cured film that obtains.

(2) scuff resistance

To be coated with thing and be fixed on and learn on the vibration shape frictional testing machines, and use Steel Wool No.0000 with load 250g reciprocating friction 10 times.At the coating thing that takes out, judge the situation of damage according to the visual assessment of following 5 grades.Numerical value is big more, shows that the scuff resistance of cured film is good more.

5: not damage fully

4: have damage a little

3: have damage, but can't see base material

2: have damage, partly solidified film peels off

1: cured film is peeled off, the state that base material exposes

(3) pencil hardness

According to JIS-K5600, use pencil scratching tester (HEIDON society makes Scratching TesterHEIDON-14), the hardness of pencil-lead is carried out various changes, carry out 5 tests with load 500g.1 damage does not have yet or only has the pencil hardness of the pencil-lead hardness in 1 when damage as this cured film in 5 times.Consider the rerum natura that needs on the practicality, the pencil hardness of cured film be judged to be:

More than the 2H: A

More than the 1H: B

Be lower than 1H:D

(4) transparency (haze value)

Use haze meter to measure the turbidity (haze value) of the coating thing that obtains.

(5) photostabilization

During the light Continuous irradiation through the time xanthochromia, be very disadvantageous for the expansion of purposes.Xanthochromia during therefore, to the light Continuous irradiation is confirmed.

At first, at light fastness test machine (light source: xenon lamp, illuminance: 100W/cm ², blackboard temperature: 60 ℃, 60%RH) in to coating thing exposure 24 hours.Subsequently, place the coating thing on blank sheet of paper, it is painted to use colour examining machine (ミ ノ Le CR-300) to measure.Measured color value is by L ^*a ^*b ^*Expression is with b ^*Value is judged the degree of the xanthochromia of cured film.b ^*Be worth more for a short time, the xanthochromia degree is more little, and the expression photostabilization is good more.The rerum natura that needs on the consideration practicality is with the b of cured film ^*Value is judged to be:

Situation less than 3.5: A

3.5 above situation: D

(6) surface resistivity

According to the surface resistivity of following benchmark evaluation cured film (Ω/sq.).

Surface resistivity is 1 * 10 ¹²Following situation: A

Surface resistivity is for being higher than 1 * 10 ¹²And 1 * 10 ¹⁴Following situation: B

Surface resistivity surpasses 1 * 10 ¹⁴Situation: D

(7) reflection interference striped

The reflection interference striped of the cured film that obtains according to following benchmark visual valuation.

Do not observe reflection interference striped: A

Can observe reflection interference striped: D

The spy of the disclosed content of the application and on May 29th, 2006 application is willing to 2006-148854 number and the spy of application on May 29th, 2006 is willing to that the theme of 2006-148855 number record is relevant, and their whole disclosures are incorporated in this.

Should be noted in the discussion above that except that foregoing do not breaking away under the of the present invention new and favourable feature condition in addition, above-mentioned embodiment can increase various modifications or change.Thereby so whole modification or change all are included in the application's the scope of claim.

Claims (19)

1. metal oxide composition, it contains the dispersion agent (A) shown in the following general formula (1) and average primary particle diameter is the metal oxide of 5～100nm,

General formula (1):

In the formula, R ¹～R ⁴Represent hydrogen atom or methyl independently of one another, R ⁵～R ⁸Alkylidene group or the alkylidene group oxyalkylene of representing the straight or branched of non-replacement or replacement independently of one another, R ⁹Aromatic group or the aliphatic group of representing 4 valencys.

2. metal oxide composition according to claim 1, wherein, in the general formula (1), R ⁹Be at least a 4 valency aromatic groups that are selected from the group of forming by biphenyl backbone, naphthalene skeleton, fluorene skeleton and naphthane skeleton, or as 4 valency aliphatic groups of the alkyl skeleton of carbonatoms 4～10.

3. metal oxide composition according to claim 1 and 2, wherein, dispersion agent (A) is to make the compound (X) with carboxyl and have to obtain with compound (Y) reaction of the functional group of carboxyl reaction, and described compound (X) with carboxyl is to make the compound (x1) with aromatic series skeleton or aliphatics skeleton and 2 above carboxylic acid anhydride groups and have to react with the compound (x2) of the functional group of carboxylic acid anhydride group's reaction to obtain;

At least a portion of compound (x2) and compound (Y) has polymerizability unsaturated double-bond group.

4. metal oxide composition according to claim 3, wherein, compound (x2) is acrylic compound or the methacrylate compound with 1 or 2 hydroxyl.

5. according to each described metal oxide composition in the claim 1～4, wherein, metal oxide contains at least a element that is selected from the group of being made up of titanium, zinc, zirconium, antimony, indium, tin, aluminium, silicon, phosphorus and fluorine.

6. according to each described metal oxide composition in the claim 1～5, wherein, further contain solvent, and it is the hydroxyl solvent of 10～100 weight % that solvent comprises with respect to total solvent.

7. cured film, it solidifies each described metal oxide composition in the claim 1～6 and forms.

8. cured film according to claim 7, its thickness are 0.1～30 μ m.

9. according to claim 7 or 8 described cured film, its specific refractory power is in 1.4～2.0 scope.

10. duplexer, it comprises each described cured film in base material and the claim 7～9.

11. duplexer according to claim 10, wherein, base material is a plastic basis material.

12. according to claim 10 or 11 described duplexers, wherein, base material is a lens shape.

13. according to each described duplexer of claim 10～12, wherein, cured film does not form on base material across other layers, the difference of the specific refractory power of cured film and base material is in ± 0.02.

14. according to each described duplexer of claim 10～12, wherein, further have the above bottom of one deck between cured film and the base material, the difference of the specific refractory power of the bottom that cured film is contacted with cured film is in ± 0.02.

15. according to each described duplexer of claim 10～14, it comprises information recording layer.

16. according to each described duplexer of claim 10～14, it is an antireflection film.

17. an optical semiconductor sealing material, it contains each described metal oxide composition of claim 1～6.

18. the manufacture method of a metal oxide dispersion, it comprises: in the presence of organic solvent, use the dispersion agent (A) shown in the following general formula (1), making average primary particle diameter is the metal oxide dispersive step of 5～100nm,

General formula (1):

In the formula, R ¹～R ⁴Represent hydrogen atom or methyl independently of one another, R ⁵～R ⁸Alkylidene group or the alkylidene group oxyalkylene of representing the straight or branched of non-replacement or replacement independently of one another, R ⁹Aromatic group or the aliphatic group of representing 4 valencys.

19. the manufacture method of a cured film, it comprises: each described metal oxide composition in the claim 1～6 is coated on step on the base material; And the irradiation active energy beam, make the metal oxide composition step of curing.