CN105223775A

CN105223775A - The manufacture method of curable adhensive compositions, cured film, cured film and touch-screen and display device

Info

Publication number: CN105223775A
Application number: CN201510382148.0A
Authority: CN
Inventors: 铃木成一; 河邉保雅; 伊藤寛晃; 柏木大助; 安藤豪
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2014-07-04
Filing date: 2015-07-02
Publication date: 2016-01-06
Anticipated expiration: 2035-07-02
Also published as: CN105223775B; JP6165805B2; JP2016027154A

Abstract

The invention provides a kind of curable adhensive compositions, the manufacture method of cured film, cured film and touch-screen and display device.Curable adhensive compositions of the present invention contains: as the hydrolytic condensation titanium compound of the specified quantitative of composition A and/or zirconium compounds, the multifunctional polymerizable component that can be the coordinating composition of titanium and/or the coordinating composition of zirconium and the compound identical with described coordinating composition, the Photoepolymerizationinitiater initiater as composition C and the solvent as components D as the specified quantitative of composition B, and relative to content 100 mass parts of composition A, the content of the coordinating composition of described titanium and/or the coordinating composition of zirconium is 15 mass parts ~ 140 mass parts.Curable adhensive compositions provided by the invention can have the refractive index of the cured film of gained and chemical-resistant and excellent storage stability concurrently.

Description

The manufacture method of curable adhensive compositions, cured film, cured film and touch-screen and display device

Technical field

The present invention relates to a kind of curable adhensive compositions, the manufacture method of cured film, cured film and use touch-screen, liquid crystal indicator, the various display device such as organic electroluminescent (Electroluminescence, EL) display device and touch panel display device of described cured film.

Background technology

Transparent material is used as the multiple part-structure of various display device, camera head, solar cell etc. with the form of dielectric film, diaphragm, light removing layer, distance piece (spacer), lenticule (microlens) etc.

In addition, as the purposes of transparent material, known in order to the performance of improved device with the material adjusting refractive index.

As refractive index adjustment transparent material, the composition (such as with reference to patent documentation 1 and patent documentation 2) of known use metal alkoxide.

In addition, as the composition of use metal alkoxide there is pattern being formed (patterning) performance, the composition recorded in known patent document 3 and patent documentation 4.

[prior art document]

[patent documentation]

No. 2010/050580th, [patent documentation 1] International Publication

[patent documentation 2] Japanese Patent Laid-Open 2002-6104 publication

[patent documentation 3] Japanese Patent Laid-Open 2012-203061 publication

[patent documentation 4] Japanese Patent Laid-Open 2011-178587 publication

Summary of the invention

[inventing problem to be solved]

In recent years, the high-precision refinement of display device or camera head is advanced, in the process manufactured, use various chemicals.But the chemical-resistant of the composition recorded in patent documentation 1 and patent documentation 2 is also insufficient.

In addition, the chemical-resistant of the composition recorded in patent documentation 3 and patent documentation 4 is also insufficient.

As mentioned above, the pattern forming material of existing use metal alkoxide cannot meet refractive index, chemical-resistant and storage stability.

Problem to be solved by this invention be to provide a kind of have the cured film of gained concurrently refractive index and the curable adhensive compositions of chemical-resistant and excellent storage stability, the cured film that described curable adhensive compositions is hardened and manufacture method thereof and there is the organic EL display of described cured film, liquid crystal indicator, touch-screen and touch panel display device.

[technological means of dealing with problems]

Described problem of the present invention is solved by the means described in following <1>, <7>, <8> and <11> ~ <14>.Below <2> ~ <6>, <9> and <10> is preferably recorded in the lump.

<1> curable adhensive compositions, it contains: as at least one be selected from the cohort be made up of following a1 and a2 of composition A, as at least one be selected from the cohort be made up of following b1 and b2 of composition B, as the Photoepolymerizationinitiater initiater of composition C, and as the solvent of components D, and relative to the total solid composition of curable adhensive compositions, the content of composition A is 40 quality % ~ 90 quality %, relative to the total solid composition of curable adhensive compositions, the content of composition B is 5 quality % ~ 59 quality %, relative to content 100 mass parts of composition A, the following compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group, be 15 mass parts ~ 140 mass parts with the following total content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium,

A1: titanium compound and/or the zirconium compounds with alkoxy,

A2: there is the titanoxane of the alkoxy of at least one direct bond on titanium atom or zirconium atom, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product,

B1: the compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group,

B2: there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and there is the compound of plural ethene unsaturated group.

The curable adhensive compositions of <2> described in <1>, the coordinating base of wherein said titanium and/or the coordinating base of zirconium are the group of coordination on titanium atom and/or zirconium atom by oxygen atom.

The curable adhensive compositions of <3> described in <1> or <2>, the coordinating base of wherein said titanium and/or the coordinating base of zirconium are for having the group of at least one structure in the cohort that is selected from and is made up of following structure: 1, 2-diketone structure, 1, 3-diketone structure, 1, 4-diketone structure, alpha-alcohol ketone structure, alpha-hydroxy esters structure, α-one base ester structure, beta-keto esters structure, diester malonate structure, dimethyl ester structure and ditridecyl phthalate structure.

The curable adhensive compositions that <4> is described any one of <1> to <3>, wherein said a2 is the water by being 0.5 times ~ 1.9 times of molar equivalents relative to the integral molar quantity 1.0 moles of titanium atom and zirconium atom, make to be selected from the titanium compound by having alkoxy, there is the zirconium compounds of alkoxy, there is the titanium compound of halogen radical, and at least one in the cohort that forms of the zirconium compounds with halogen radical is hydrolyzed the titanoxane of condensation gained, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product.

The curable adhensive compositions that <5> is described any one of <1> to <4>, wherein composition A comprises described a2.

The curable adhensive compositions that <6> is described any one of <1> to <5>, wherein when composition B contains described b2, when the content that the content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium of the total solid composition relative to curable adhensive compositions is set to BW1 quality %, have the compound of plural ethene unsaturated group is set to BW2 quality %, BW1: BW2 is 2: 8 ~ 8: 2.

The manufacture method of a <7> cured film, it comprises operation 1 ~ operation 5 at least successively,

Operation 1: painting process, is coated on substrate by curable adhensive compositions described any one of <1> to <6>;

Operation 2: solvent removal step, except desolventizing from be coated with curable adhensive compositions;

Operation 3: exposure process, utilizes actinic ray to the exposing at least partially of curable adhensive compositions eliminating solvent;

Operation 4: developing procedure, utilizes aqueous developer solution to develop to the curable adhensive compositions through exposure;

Operation 5: heat treatment step, heat-treats the curable adhensive compositions through development.

<8> cured film, it is that curable adhensive compositions sclerosis described any one of <1> to <6> is formed.

The cured film of <9> described in <8>, it is interlayer dielectric or outer film.

The cured film of <10> described in <8> or <9>, the refractive index under its medium wavelength 550nm is 1.78 ~ 2.40.

<11> liquid crystal indicator, has cured film described any one of <8> to <10>.

<12> organic EL display, has cured film described any one of <8> to <10>.

<13> touch-screen, has cured film described any one of <8> to <10>.

<14> touch panel display device, has cured film described any one of <8> to <10>.

[effect of invention]

According to the present invention, can provide a kind of have the cured film of gained concurrently refractive index and the curable adhensive compositions of chemical-resistant and excellent storage stability, the cured film that described curable adhensive compositions is hardened and manufacture method thereof and there is the organic EL display of described cured film, liquid crystal indicator, touch-screen and touch panel display device.

Accompanying drawing explanation

Fig. 1 represents the formation concept map of an example of liquid crystal indicator, represents the schematic cross sectional view of the active-matrix substrate in liquid crystal indicator, has the cured film 17 as interlayer dielectric.

Fig. 2 represents the formation concept map of an example of organic EL display, represents the schematic cross sectional view of the substrate in the organic EL display of bottom emission type, has planarization film 4.

Fig. 3 is the planimetric map of the electrode pattern represented with the touch-screen in an example of the display device of touch-screen.

Fig. 4 is the sectional view of the cross-section structure represented along the A-A ' line shown in Fig. 3.

Fig. 5 is the sectional view of the cross-section structure represented along the B-B ' line shown in Fig. 3.

[explanation of symbol]

1:TFT (thin film transistor (TFT))

2: distribution

3: dielectric film

4: planarization film

5: the first electrodes

6: glass substrate

7: contact hole

8: dielectric film

10: liquid crystal indicator

12: back light unit

14,15: glass substrate

16：TFT

17: cured film

18: contact hole

19:ITO transparency electrode

20: liquid crystal

22: colored filter

101a, 102a: cross part

101b, 102b: electrode section

The electrode in 101X:X direction

The electrode in 102:Y direction

111: substrate

112: dielectric film

112a: contact hole

113: diaphragm

W: insulation course (pedestal layer)

X, Y: electrode

Embodiment

Below, content of the present invention is described in detail.The explanation of the constitutive requirements below recorded is carry out according to representative embodiment of the present invention sometimes, but the present invention is not limited to this kind of embodiment.In addition, in this case instructions, so-called " ~ " comprises numerical value described before and after it to use as the implication of lower limit and higher limit.In addition, so-called organic EL of the present invention, refers to organic electroluminescent device.

In the statement of group (atomic group) in this manual, do not record the statement being substituted and being unsubstituted not only to comprise not there is substituent group (atomic group), and comprise yet there is substituent group (atomic group).Such as so-called " alkyl ", not only comprises and does not have substituent alkyl (alkyl be unsubstituted), and comprises and have substituent alkyl (alkyl be substituted).

In addition, the chemical structural formula in this instructions is also recorded with the schematic arrangement formula omitting hydrogen atom sometimes.

In addition; in this instructions; " (methyl) acrylate " represents acrylate and methacrylate, and " (methyl) acrylic acid " represents acrylic acid and methacrylic acid, and " (methyl) acryloyl group " represents acryloyl group and methacryl.

In the present invention, also " at least one in the cohort be made up of a1 and a2 will be selected from " etc. referred to as " composition A " etc.

In addition, in the present invention, " quality % " and " % by weight " are identical meanings, and " mass parts " and " weight portion " are identical meanings.

In addition, in the present invention, the combination of preferred implementation more preferably.

Weight average molecular weight in titanoxane of the present invention, zirconium oxygen alkane and titanoxane-zirconium oxygen alkane condensation product and number average molecular weight utilize gel permeation chromatography (GelPermeationChromatography, GPC) method to measure.

Curable adhensive compositions of the present invention (hereinafter also referred to as " composition ") contains: as at least one be selected from the cohort be made up of following a1 and a2 of composition A, as at least one be selected from the cohort be made up of following b1 and b2 of composition B, as the Photoepolymerizationinitiater initiater of composition C, and as the solvent of components D, and relative to the total solid composition of curable adhensive compositions, the content of composition A is 40 quality % ~ 90 quality %, relative to the total solid composition of curable adhensive compositions, the content of composition B is 5 quality % ~ 59 quality %, relative to content 100 mass parts of composition A, the following compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group, be 15 mass parts ~ 140 mass parts with the following total content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium.

A1: titanium compound and/or the zirconium compounds with alkoxy,

The people such as the present inventor have repeatedly carried out effort in view of described viewpoint and have studied, found that, by being set as containing composition A ~ components D and be the curable adhensive compositions of the certain content shown in above, the refractive index of the hardening thing of gained and developability and excellent storage stability can be had concurrently, thus complete the present invention.

Can infer, by the coordinating base of the titanium in composition B and/or the coordinating polymerization of olefin using catalyst of zirconium on the titanium atom and/or zirconium atom of composition A, the homogeneity of curable adhensive compositions or the compatibility of composition A and other compositions improve, can have the refractive index of the hardening thing of gained and developability and excellent storage stability concurrently, but the performance mechanism of detailed impression is indefinite.

Curable adhensive compositions of the present invention, preferably after the polymerization utilizing light, heat-treated, and the intensity of hardening thing is become higher composition by hardening things such as the cured films to gained.

In addition, curable adhensive compositions preferably clear hardening thing manufacture curable adhensive compositions of the present invention, more preferably transparent hardened film manufacture curable adhensive compositions.

And then, the refractive index of hardening thing under wavelength 550nm of curable adhensive compositions of the present invention preferably gained is the curable adhensive compositions of more than 1.78, more preferably the refractive index of the hardening thing of gained under wavelength 550nm is the curable adhensive compositions of more than 1.80, and then the refractive index of hardening thing under wavelength 550nm of preferably gained is the curable adhensive compositions of more than 1.83.In addition, the upper limit of the refractive index of hardening thing is not particularly limited, from the viewpoint of visibility improvement, and the refractive index under wavelength 550nm preferably less than 2.40, more preferably less than 2.30, and then preferably less than 2.20.

In addition, curable adhensive compositions of the present invention can be suitably used as interlayer dielectric with or outer film curable adhensive compositions.

Composition A: be selected from least one in the cohort be made up of a1 and a2

Curable adhensive compositions of the present invention contains at least one in the cohort being selected from and being made up of following a1 and a2 as composition A, and relative to the total solid composition of curable adhensive compositions, the content of composition A is 40 quality % ~ 90 quality %.

A1: titanium compound and/or the zirconium compounds with alkoxy,

A2: there is the titanoxane of the alkoxy of at least one direct bond on titanium atom or zirconium atom, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product.

In addition, if those skilled in the art then know perfectly well certainly, described a1 and " have the titanium compound of alkoxy and/or have the zirconium compounds of alkoxy " are identical meanings, and described a2 is identical meanings with " have the titanoxane of the alkoxy of at least one direct bond on titanium atom, have the zirconium oxygen alkane of the alkoxy of at least one direct bond on zirconium atom or have the titanoxane-zirconium oxygen alkane condensation product of the alkoxy of at least one direct bond on titanium atom or zirconium atom ".

In addition, yes containing rutile (rutile) type or the Titanium particles of anatase (anatase) type or the composition of Zirconia particles for composition A.

Relative to the total solid composition of curable adhensive compositions, the content of composition A is 40 quality % ~ 90 quality %, from the viewpoint having refractive index and patternability (developability) concurrently, preferably 50 quality % ~ 90 quality %, more preferably 55 quality % ~ 85 quality %, and then preferred 60 quality % ~ 85 quality %.In addition, " solid constituent " of so-called curable adhensive compositions, represent the composition removing the volatile ingredient gained such as solvent, in addition, also a part of low-boiling compound is comprised in composition B, because losing volatility by coordination on titanium or zirconium, so composition B of the present invention is considered as being included in solid constituent.In addition, described solid constituent also can be and non-solid liquid-like constituents certainly.

Composition A can be any one of potpourri of independent a1, separately a2, a1 and a2, from the viewpoint of the storage stability of composition, and the preferably potpourri of a2 or a1 and a2 separately, more preferably independent a2.

In addition, also can also use titanium compound and zirconium compounds as a1.

In addition, from the viewpoint of refractive index and storage stability, composition A preferably at least comprises a2.

From the viewpoint of refractive index and developability, the preferred titanium compound of composition A and/or titanoxane, in addition, from the viewpoint of hardening at subcritical temerature, setting rate and stability, preferred zirconium compounds and/or zirconium oxygen alkane.

As a1, can enumerate: single alkyl dioxide, dioxane titanium dioxide, three alkyl dioxides, four alkyl dioxides, single alkoxide zirconium, dioxane zirconia, three alkoxide zirconiums and four alkoxide zirconiums, from the viewpoint of film physical property, preferably four alkyl dioxides and four alkoxide zirconiums, more preferably four alkyl dioxides.

In addition, as long as a1 has at least one alkoxy, other groups such as halogen radical or alkoxy can also be had.

From the viewpoint of film physical property, four alkyl dioxides represented by the preferred following formula a1-1 of four alkyl dioxides.

In addition, from the viewpoint of film physical property, four alkoxide zirconiums represented by the preferred following formula a1-2 of four alkoxide zirconiums.

[changing 1]

In formula a1-1 and formula a1-2, R ¹~ R ⁴separately represent the aralkyl of the alkyl of carbon number 1 ~ 18, the aryl of carbon number 6 ~ 18 or carbon number 7 ~ 18.

From the viewpoint of film physical property, the R in formula a1-1 and formula a1-2 ¹~ R ⁴the separately alkyl of preferred carbon number 1 ~ 18, the more preferably alkyl of carbon number 1 ~ 8, the particularly preferably alkyl of carbon number 1 ~ 5.

Four alkyl dioxides represented by formula a1-1 are not limited to following concrete example, such as, can enumerate: tetramethyl titanium dioxide, tetrem titanium dioxide, four positive third titanium dioxide, four titanium isopropoxide, four positive fourth titanium dioxide, four isobutyl titanium dioxide, two n-butoxy diisopropyl titanium dioxide, two tert-butoxy diisopropyl titanium dioxide, four tertiary fourth titanium dioxide, four different pungent titanium dioxide, four stearyl alkyl dioxides etc.

Four alkoxide zirconiums represented by formula a1-2 are not limited to following concrete example, such as, can enumerate: tetramethyl zirconia, tetrem zirconia, four positive third zirconias, four isopropyl zirconias, four positive fourth zirconias, four isobutyl zirconias, two n-butoxy diisopropyl zirconias, two tert-butoxy diisopropyl zirconias, four tertiary fourth zirconias, four different pungent zirconias, four stearyl alkoxide zirconiums etc.

These compounds can be used alone a kind of or used in combination two or more.

Titanoxane is also referred to as poly-titanoxane, for having the compound of plural Ti-O-Ti key.Its manufacture method such as can be enumerated: use water that four alkyl dioxides represented by described formula a1-1 are hydrolyzed condensation and obtain the method for titanoxane.In addition, the halogenated titaniums such as titanium tetrachloride also can be made to be hydrolyzed condensation.Wherein, from the easiness of synthesis, preferred alkyl dioxide, titanium chloride, more preferably alkyl dioxide.

Zirconium oxygen alkane is also referred to as poly-zirconium oxygen alkane, for having the compound of plural Zr-O-Zr key.In addition, its manufacture method can be enumerated: except being changed to by raw material except the zirconium compoundss such as alkoxide zirconium or zirconium halide, the method identical with the manufacture method of described titanoxane.

Titanoxane-zirconium oxygen alkane condensation product to be hydrolyzed the condensation product of condensation for using described titanium compound and described both zirconium compoundss.In addition, its manufacture method can be enumerated: except also using titanium compound and zirconium compounds as except raw material, the method identical with described manufacture method.

Described a2 is the water of 0.5 times ~ 1.9 times of molar equivalents preferably by the integral molar quantity 1.0 moles relative to titanium atom and zirconium atom, make to be selected from the titanium compound by having alkoxy, there is the zirconium compounds of alkoxy, there is the titanium compound of halogen radical, and at least one in the cohort that forms of the zirconium compounds with halogen radical is hydrolyzed the titanoxane of condensation gained, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product, more preferably by the water that the integral molar quantity 1.0 moles relative to titanium atom and zirconium atom is 0.5 times ~ 1.9 times of molar equivalents, the at least one making to be selected from the cohort be made up of the titanium compound with alkoxy and the zirconium compounds with alkoxy is hydrolyzed the titanoxane of condensation gained, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product.

When using the titanium compound with halogen radical and/or the zirconium compounds with halogen radical, preferably with there is the titanium compound of alkoxy and/or there is the zirconium compounds of alkoxy and use, or use the titanium compound for having halogen radical and there is the zirconium compounds of halogen radical and at least there is the compound of more than one alkoxy, or to add in water and add alcoholic compound and to be hydrolyzed condensation.

The titanium compound with halogen radical and the zirconium compounds with halogen radical can be enumerated: single halogenated titanium, dihalide titanium, three halogenated titaniums, titanium tetrahalide, single zirconium halide, dihalide zirconium, three zirconium halides and four zirconium halide, from the viewpoint of film physical property, can preferably enumerate titanium tetrahalide and four zirconium halide, more preferably titanium tetrahalide.These compounds can be used alone a kind of or used in combination two or more.

In addition, during described hydrolytic condensation, not only use water, also can use solvent etc., alcoholic compound also can be used as adjuvant.In addition, solvent can enumerate alcoholic compound suitably.

From the viewpoint of the physical strength of the film of gained, relative to the titanium atom of raw material and the integral molar quantity 1.0 moles of zirconium atom, amount preferably 0.5 molar equivalent ~ 1.9 molar equivalent of water used during described hydrolytic condensation, from the viewpoint of film strength, lower limit is preferably more than 0.9 molar equivalent, more preferably more than 1.2 molar equivalents, in addition, from the viewpoint of film flexibility, the upper limit is preferably below 1.8 molar equivalents, more preferably below 1.7 molar equivalents.

From the storage stability of composition and the viewpoint of film physical property, composition A preferably comprises the titanoxane (hereinafter also referred to as " titanoxane ") with the alkoxy of at least one direct bond on titanium atom, there is the zirconium oxygen alkane (hereinafter also referred to as " zirconium oxygen alkane ") of the alkoxy of at least one direct bond on zirconium atom, or there is the titanoxane-zirconium oxygen alkane condensation product (hereinafter also referred to as " titanoxane-zirconium oxygen alkane condensation product ") of the alkoxy of at least one direct bond on titanium atom or zirconium atom, more preferably comprise titanoxane or zirconium oxygen alkane, and then preferably comprise titanoxane.

Titanoxane, zirconium oxygen alkane and titanoxane-zirconium oxygen alkane condensation product can be arbitrary polymer morphology of straight-chain, branch-like, three-dimensional netted, cantilever-shaped, scalariform, caged etc., and its form is not particularly limited, and preferably has compatibility with composition B.In addition, titanoxane and zirconium oxygen alkane can be solid and also can be liquid under normal temperature (25 DEG C).

There is no particular restriction for the weight average molecular weight of titanoxane, zirconium oxygen alkane and titanoxane-zirconium oxygen alkane condensation product, and preferably 500 ~ 50,000, more preferably 1,000 ~ 20,000.

From the viewpoint of film physical property, the titanoxane represented by the preferred following formula a2-1 of described titanoxane.

In addition, from the viewpoint of film physical property, the zirconium oxygen alkane represented by the preferred following formula a2-2 of described zirconium oxygen alkane.

Ti _αO _β(OR) _γ(a2-1)

Zr _αO _β(OR) _γ(a2-2)

In formula a2-1 and formula a2-2, R separately represents the aralkyl of the alkyl of hydrogen atom, carbon number 1 ~ 18, the aryl of carbon number 6 ~ 18 or carbon number 7 ~ 18, and α, β and γ meet following condition a ' ~ condition c ', α and represent positive integer, β and γ represents positive number.

a′：200≥α≥2、

b′：1.9α≥β≥1.0α、

c′：γ＝4α-2β

The titanoxane of described a2, zirconium oxygen alkane and titanoxane-zirconium oxygen alkane condensation product can be single composition, also can be two or more potpourris.

In addition, from the viewpoint of high index of refraction and film physical property, relative to the total solid composition of curable adhensive compositions of the present invention, the total content preferably 5 quality % ~ 60 quality % of titanium atom and zirconium atom, more preferably 10 quality % ~ 50 quality %, and then preferred 15 quality % ~ 40 quality %.

Composition B: be selected from least one in the cohort be made up of b1 and b2

Curable adhensive compositions of the present invention contains at least one in the cohort being selected from and being made up of following b1 and b2 as composition B, relative to the total solid composition of curable adhensive compositions, the content of composition B is 5 quality % ~ 59 quality %, relative to content 100 mass parts of composition A, following there is the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group compound, be 15 mass parts ~ 140 mass parts with the following total content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium.

Relative to the atomicity sum of the titanium atom contained by composition A and zirconium atom, the ratio of the number of the coordinating base of titanium and/or the coordinating base of zirconium preferably 20% ~ 500%, more preferably 40% ~ 400%.

Curable adhensive compositions of the present invention at least containing there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group as composition B, or at least containing the compound with the coordinating base of titanium and/or the coordinating base of zirconium and there is plural ethene unsaturated group both compounds as composition B.

In addition, in the present invention, the compound being equivalent to composition B is the compound having the coordinating base of more than one titanium and/or the coordinating base of zirconium or have plural ethene unsaturated group or have both this.

In curable adhensive compositions of the present invention, from the viewpoint of the refractive index and developability that have cured film concurrently, relative to the total solid composition of curable adhensive compositions, the content of composition B is 5 quality % ~ 59 quality %, preferably 10 quality % ~ 55 quality %, more preferably 15 quality % ~ 50 quality %, and then preferred 25 quality % ~ 45 quality %.

In addition, in curable adhensive compositions of the present invention, from the refractive index and the viewpoint such as developability and storage stability that have cured film concurrently, relative to content 100 mass parts of composition A, described there is the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group compound, be 15 mass parts ~ 140 mass parts with the described total content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium, preferably 15 mass parts ~ 80 mass parts, more preferably 20 mass parts ~ 60 mass parts.

" the coordinating base of titanium and/or the coordinating base of zirconium " in so-called the present invention, refer to and can form the group of coordination bond with titanium atom and/or zirconium atom, can with titanium atom or zirconium atom only any one forms coordination bond, also can form coordination bond with titanium atom and zirconium atom.

In addition, the coordination formed by the coordinating base of titanium and/or the coordinating base of zirconium can be any one of the coordination of more than single tooth coordination (a tooth coordination), two tooth coordinations, three tooth coordinations and four teeth, the coordinating base of the preferred single tooth coordination of described coordinating base or two tooth coordinations, the coordinating base of more preferably two tooth coordinations.

And then the coordinating base of titanium and/or the coordinating base of zirconium preferably coordination become the group of the neutral ligand on titanium atom and/or zirconium atom on titanium atom and/or zirconium atom.

When the compound coordination at least with the coordinating base of titanium and/or the coordinating base of zirconium is on composition A, the titanium atom through coordination in composition A or the d track of zirconium atom can rank division.Therefore, the presence or absence of coordination is known by the division on observation energy rank.

Be confirmed whether that the method for the coordinating base of titanium and/or the coordinating base of zirconium can enumerate method with presence or absence of observation coordination.With presence or absence of concrete coordination, observation procedure can use well-known observation procedure, such as, can enumerate spectroscopic method or electron spin resonance (ElectronSpinResonance, ESR) etc.

From the stability of composition or the viewpoint of film physical property, the coordinating base of titanium in the present invention and/or the coordinating base of zirconium preferably have the group of oxygen atom, more preferably there is the group of plural oxygen atom, and then preferably at least have 2 oxygen atoms centre be situated between every other atoms of 2 atom ~ 4 atoms the group of the structure of bond, particularly preferably be at least have 2 oxygen atoms centre be situated between every 3 atoms or other atoms of 4 atoms the group of the structure of bond.In addition, the oxygen atom of at least one of described oxygen atom carbonyl preferably in carbonyl or ester structure.

In addition, from the stability of composition or the viewpoint of film physical property, the coordinating base of titanium of the present invention and/or the coordinating base of zirconium be the group of coordination on titanium atom and/or zirconium atom by oxygen atom preferably.

The coordinating base of titanium of the present invention and/or the coordinating base of zirconium preferably have and are selected from by 1, 2-diketone structure, 1, 3-diketone structure, 1, 4-diketone structure, alpha-alcohol ketone structure, alpha-hydroxy esters structure, α-one base ester structure, beta-keto esters structure, diester malonate structure, the group of at least one structure in the cohort that dimethyl ester structure and ditridecyl phthalate structure form, more preferably have and be selected from by 1, 2-diketone structure, 1, 3-diketone structure, alpha-alcohol ketone structure, alpha-hydroxy esters structure, α-one base ester structure, the group of at least one structure in the cohort that beta-keto esters structure and ditridecyl phthalate structure form, and then preferably have and be selected from by 1, 3-diketone structure, the group of at least one structure in the cohort that beta-keto esters structure and ditridecyl phthalate structure form, particularly preferably being to have is selected from by 1, the group of at least one structure in the cohort that 3-diketone structure and beta-keto esters structure form.If described embodiment, then the refractive index of the cured film of gained and anti-Fractured more excellent.

Titanium of the present invention or the coordinating base of zirconium preferably have the group of any one of the structure represented by following formula b-1 ~ formula b-5, more preferably there is the group of the structure represented by following formula b-1, formula b-2 or formula b-5, and then preferably there is the group of the structure represented by following formula b-1 or formula b-2.

[changing 2]

In formula b-1 ~ formula b-5, L ¹and L ²separately represent the alkylidene of singly-bound or carbon number 1 or 2, R ' separately represents alkyl, alkoxy, halogen atom, acyl group or alkoxy carbonyl, and nb represents the integer of 0 ~ 4, and wave line part divides the binding site represented with other structures.

L ¹and L ²preferred methylene.

The carbon number of R ' preferably 0 ~ 20.In addition, R ' separately preferred alkyl, alkoxy or halogen atom.

Nb preferably 0 or 1, more preferably 0.

The coordinating base of titanium or the coordinating base of zirconium specifically preferably can enumerate following shown group.In addition, wave line part divides the binding site represented with other structures.

[changing 3]

There is no particular restriction for ethene unsaturated group in composition B, preferably can enumerate (methyl) acryloxy, (methyl) acrylamido, allyl, styryl and ethyleneoxy, more preferably can enumerate (methyl) acryloxy and allyl, particularly preferably can enumerate (methyl) acryloxy.

B1: the compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group

From the viewpoint of developability, b1 preferably has 1, multifunctional (methyl) acrylate compounds of 3-diketone structure or beta-keto esters structure or have the multifunctional ethene unsaturated compound of ditridecyl phthalate structure, more preferably has the multifunctional ethene unsaturated compound of ditridecyl phthalate structure.

In addition, the compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group can be used alone one, also can and with two or more.

The described compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group can illustrate the compound represented by following formula.

[changing 4]

From the viewpoint of the chemical-resistant of cured film, preferably there is the multifunctional ethene unsaturated compound of ditridecyl phthalate structure, particularly preferably can illustrate the diallyl phthalate represented by described formula (b1-1).

B2: there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and there is the compound of plural ethene unsaturated group

The compound with the coordinating base of titanium and/or the coordinating base of zirconium of described b2 can be does not have ethene unsaturated group and the compound with the coordinating base of titanium and/or the coordinating base of zirconium, in addition, also can be and there is an ethene unsaturated group and the compound with the coordinating base of titanium and/or the coordinating base of zirconium.

In addition, the compound with the coordinating base of titanium and/or the coordinating base of zirconium can be used alone one, also can and with two or more.

Described do not have ethene unsaturated group and the compound with the coordinating base of titanium and/or the coordinating base of zirconium preferably 1, 2-dione compounds, 1, 3-dione compounds, 1, 4-dione compounds, alpha-hydroxyacetone compounds, alpha-hydroxyester compound, α-one base ester compounds, beta-keto esters compound, diester malonate compound, dimethyl ester compound or ditridecyl phthalate compound, more preferably 1, 2-dione compounds, 1, 3-dione compounds, alpha-hydroxyacetone compounds, α-one base ester compounds, beta-keto esters compound or ditridecyl phthalate compound, and then preferably 1, 3-dione compounds or beta-keto esters compound.

Described not there is ethene unsaturated group and the concrete example with the compound of the coordinating base of titanium and/or the coordinating base of zirconium can enumerate following shown in compound.

[changing 5]

In these compounds, preferred diacetone (2,4-pentanedione), ethyl acetoacetate (ethyl 3-oxobutanoate) or ethyl lactate, particularly preferably diacetone or ethyl acetoacetate.

From the viewpoint of developability, the compound with the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group preferably has simple function (methyl) acrylate compounds of 1,3-diketone structure or beta-keto esters structure.The compound with the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group can be used alone one, also can and with two or more.

From the viewpoint of the chemical-resistant of cured film, the described compound with the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group preferably has simple function (methyl) acrylate compounds of the coordinating base of titanium and/or the coordinating base of zirconium, more preferably following shown compound.

[changing 6]

In described b2, the molecular weight with the compound of the coordinating base of titanium and/or the coordinating base of zirconium preferably 550 ~ 5,000, more preferably 550 ~ 2,000.

In described b2, from the viewpoint of chemical-resistant, the compound with the coordinating base of titanium and/or the coordinating base of zirconium preferably has the coordinating base of titanium and/or the coordinating base of zirconium and does not have the compound of ethene unsaturated group, from the viewpoint of refractive index, preferably there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group.

As long as the compound with plural ethene unsaturated group of described b2 is for having the multifunctional ethene unsaturated compound of plural ethene unsaturated group, then there is no particular restriction, suitably can select according to object.Such as can enumerate ester compounds, amide compound, carbamate compounds and other compounds.

Described ester compounds such as can be enumerated: multifunctional (methyl) acrylate, itaconate, butenoate, methacrylate, maleate, other ester compounds etc.In these, preferably multifunctional (methyl) acrylate (multifunctional (methyl) acrylate compounds) etc.

Described multifunctional (methyl) acrylate compounds such as can be enumerated: polyglycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, triethylene glycol two (methyl) acrylate, 1,3-BDO two (methyl) acrylate, tetramethylene glycol two (methyl) acrylate, hexanediol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol two (methyl) acrylate, dipentaerythritol three (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, D-sorbite three (methyl) acrylate, D-sorbite four (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, hexanediol two (methyl) acrylate etc.Wherein, particularly preferably pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

Other examples of described multifunctional (methyl) acrylate can be enumerated: at glycerine or trimethylolethane, the compound of in addition (methyl) acroleic acid esterification after the upper addition of ethylene oxide of the polyfunctional alcohols such as bisphenol-A or epoxypropane, Jap.P. examined patent publication 48-41708 publication, Jap.P. examined patent publication 50-6034 publication, the propenoic methyl carbamate class recorded in Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-Open No. Sho 48-64183 publication, the polyester acrylate class recorded in Jap.P. examined patent publication 49-43191 publication and Jap.P. examined patent publication 52-30490 publication, as the Epoxy Acrylates of epoxy resin with (methyl) acrylic acid reaction product, (methyl) acrylate recorded in Japanese Patent Laid-Open No. Sho 60-258539 publication or (methyl) propenoic methyl carbamate or vinyl acetate etc.

Other multifunctional ethene unsaturated compounds such as can be enumerated: trimethylolpropane tris (acryloxypropyl) ether, isocyanuric acid three (acryloyl-oxyethyl) ester, " Japan is association's magazine then " (Vol.20, No.7, the 300th page ~ the 308th page) in the photo-hardening monomer recorded and oligomer etc.

In addition, described amide compound such as can enumerate the acid amides (monomer) etc. of unsaturated carboxylic acid and aliphatic polybasic amines, specifically can enumerate: di-2-ethylhexylphosphine oxide (methyl) acrylamide, 1, two (methyl) acrylamide of 6-hexa-methylene, Diethylenetriamine three (methyl) acrylamide, two (methyl) acrylamides of dimethylbenzene etc., in addition, (methyl) acrylic acid amides etc. recorded in Japanese Patent Laid-Open No. Sho 60-258539 publication can be enumerated.

In addition, described carbamate compounds can illustrate the carbamic acid ester chain polymerizable compound manufactured by addition reaction using isocyanates and hydroxyl, such as can enumerate: the carbamate compound of pentaerythritol triacrylate and hexamethylene diisocyanate, the carbamate compound of pentaerythritol triacrylate and toluene diisocyanate, the carbamate compound of pentaerythritol triacrylate and isophorone diisocyanate, the carbamate compound of Dipentaerythritol Pentaacrylate and hexamethylene diisocyanate, the carbamate compound of Dipentaerythritol Pentaacrylate and toluene diisocyanate, the carbamate compound etc. of Dipentaerythritol Pentaacrylate and isophorone diisocyanate.

Specifically can illustrate: in Japanese Patent Laid-Open 2011-126921 publication, Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-fair 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication, record such propenoic methyl carbamate class, these records are incorporated in this case instructions.

In addition, other multifunctional ethene unsaturated compounds can be enumerated: the allyl compound recorded in No. 2010/050580th, Japanese Patent Laid-Open No. Sho 60-258539 publication, International Publication or the compound etc. containing thiazolinyl.

Specifically can enumerate: 1, 2-divinylbenzene, 1, 4-divinylbenzene, 1, 2-diallyl benzene, 1, 3-diallyl benzene, 1, 4-diallyl benzene, 1, 3, 5-trivinylbenzene, 1, 3, 5-triallyl benzene, 1, 2, 4, 5-tetraallyl benzene, six allyl benzenes, divinyl toluene, tetrabutyl ammonium bromide, 1, 2-bis-allyloxy benzene, 1, 4-bis-allyloxy benzene, diallyl p phthalate, diallyl isophthalate, 1, two (dimethyl ethenyl silylation) benzene of 4-, divinylmethyl phenyl silane, divinyldiphenylsilane, diallyl diphenyl silane etc.

The number of the ethene unsaturated group in described multifunctional ethene unsaturated compound preferably 2 ~ 20, more preferably 2 ~ 16, and then preferably 3 ~ 10.

From the viewpoint of coating, the molecular weight of described multifunctional ethene unsaturated compound (being weight average molecular weight when having molecular weight distribution) preferably 100 ~ 2,000, more preferably 200 ~ 1,000.

Described multifunctional ethene unsaturated compound can be used alone one, also can and with two or more.Relative to the total solid composition of curable adhensive compositions, not there is the coordinating base of titanium and/or the coordinating base of zirconium and there is the content preferably 1 quality % ~ 50 quality % of the compound of plural ethene unsaturated group, more preferably 3 quality % ~ 40 quality %, and then preferred 5 quality % ~ 25 quality %.

The compound with plural ethene unsaturated group can be used alone one, also can and with two or more.

B2 is contained at curable adhensive compositions of the present invention, namely containing the compound with the coordinating base of titanium and/or the coordinating base of zirconium with when there is the compound of plural ethene unsaturated group, when the content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium of the total solid composition relative to curable adhensive compositions of the present invention is set to BW1 quality %, when the content with the compound of plural ethene unsaturated group is set to BW2 quality %, BW1: BW2 preferably 1: 20 ~ 20: 1, more preferably 1: 10 ~ 10: 1, and then preferably 2: 8 ~ 8: 2, particularly preferably 3: 7 ~ 7: 3.If BW1: BW2 is in described scope, then can obtain the hardening thing that hardening is excellent and refractive index is high, thus preferably.

B1 is contained at curable adhensive compositions of the present invention, namely containing when there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group, except b1, and then can and with there is the coordinating base of titanium and/or the coordinating base of zirconium and not there is the compound (compound hereinafter also referred to as having the coordinating base of titanium and/or the coordinating base of zirconium) of ethene unsaturated group, also can also with simple function or the multifunctional ethene unsaturated compound (hereinafter also referred to as simple function or multifunctional ethene unsaturated compound) without the coordinating base of titanium and/or the coordinating base of zirconium, in addition, also can and with the compound with the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group.In these, preferably and with there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium or there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group.

The described compound with the coordinating base of titanium and/or the coordinating base of zirconium can illustrate in b2 described do not had ethene unsaturated group and has the compound of the coordinating base of titanium and/or the coordinating base of zirconium, and preferred scope is also identical.

Described multifunctional ethene unsaturated compound (having the compound of plural ethene unsaturated group) can illustrate the compound with plural ethene unsaturated group described in b2, and preferred scope is also identical.

The described compound with the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group can illustrate the compound with the coordinating base of titanium and/or the coordinating base of zirconium and an ethene unsaturated group described in b2, and preferred scope is also identical.

As long as described monofunctional vinyl's property unsaturated compound is the compound not having the coordinating base of titanium and/or the coordinating base of zirconium and have an ethene unsaturated group, then be not particularly limited, can enumerate: the salt of the unsaturated carboxylic acid classes such as acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylate, maleic acid and these acid, (methyl) esters of acrylic acid, (methyl) acrylic amide, unsaturated compound such as property such as monofunctional vinyl such as (methyl) vinyl cyanide, phenylethylene etc.

In addition, also can use suitably there is the esters of unsaturated carboxylic acids of hydroxyl or the nucleophilic substitution such as amino, sulfydryl base or the addition reaction of amide-type and isocyanates or epoxies and the dehydration condensation thing etc. with simple function or polyfunctional carboxylic acid.

And then, following reactant is also suitable: the addition reaction with the substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group (isocyanate group) or epoxy radicals or amide-type and alcohols, amine, thio-alcohol, and then has the substituted reactant of the substituent esters of unsaturated carboxylic acids of the detachment such as halogen radical or tosyloxy or amide-type and alcohols, amine, thio-alcohol.

In addition, as other examples, also can use and replace described unsaturated carboxylic acid and replace to the compound cohort of unsaturated phosphonic acids, styrene, vinyl ether etc.

There is no particular restriction for monofunctional vinyl's property unsaturated compound, except described exemplary compounds, can use well-known various compound, such as, also can use the compound etc. recorded in Japanese Patent Laid-Open 2009-204962 publication.

And then, monofunctional vinyl's property unsaturated compound can preferably use: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, carbitol (methyl) acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid derivatives such as epoxy (methyl) acrylate, NVP, the N-vinyl compound classes such as N-caprolactam, the derivant of the allyl compounds such as allyl glycidyl ether.

In addition, b2 is contained, namely containing when there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium and there is the compound of plural ethene unsaturated group at curable adhensive compositions of the present invention, except b2, there is described in also can containing the compound of an ethene unsaturated group, i.e. monofunctional vinyl's property unsaturated compound.

In the present invention, with regard to the aspect of chemical-resistant, preferred b1, with regard to the aspect of refractive index, preferred b2.

Composition C: Photoepolymerizationinitiater initiater

Curable adhensive compositions of the present invention contains Photoepolymerizationinitiater initiater as composition C.

Photoepolymerizationinitiater initiater preferably comprises optical free radical polymerization initiator.

In the present invention, spendable Photoepolymerizationinitiater initiater is for can utilize actinic ray (hereinafter also referred to as " light "), causes, promotes to have the compound of the polymerization of the polymerizable compounds such as the compound of plural ethene unsaturated group.

So-called " actinic ray ", as long as giving can produce by composition C the active energy ray causing the energy of planting by its irradiation, then there is no particular restriction, comprises alpha ray, gamma-rays, X ray, ultraviolet (UV), luminous ray, electron beam etc. widely.In these, preferably at least bag light with violet rays.

Photoepolymerizationinitiater initiater such as can be enumerated: oxime ester compound, organic halogenation compound, oxadiazole compound, carbonyls, benzene alkyl ketone (alkylphenone) compound, styrax compound, acridine compounds, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, metallocene compound, six aryl united imidazoles, organic boric acid compounds, disulfonic acid compound, salt compound, acylphosphanes (oxide) compound.In these compounds, from the viewpoint of sensitivity, preferred oxime ester compound, six aryl united imidazoles, benzene alkyl ketone compound, more preferably oxime ester compound.

Oxime ester compound can use: the compound recorded in Japanese Patent Laid-Open 2000-80068 publication, Japanese Patent Laid-Open 2001-233842 publication, special table 2004-534797 publication, Japanese Patent Laid-Open 2007-231000 publication, Japanese Patent Laid-Open 2009-134289 publication.

Compound represented by oxime ester compound preferred following formula C-1 or formula C-2.

[changing 7]

In formula C-1 or formula C-2, Ar represents aromatic series base or heteroaromatic base, R ¹represent alkyl, aromatic series base or alkoxy, R ²represent hydrogen atom or alkyl, and then R ²also can tie with Ar base key and form ring.

Ar represents aromatic series base or heteroaromatic base, from benzene ring compound, naphthalene cycle compound or carbazole cyclic compound, preferably removes the group of a hydrogen atom gained on aromatic rings, more preferably with R ²form the naphthyl of ring, carbazyl together.Heteroatoms in heteroaromatic base can preferably enumerate nitrogen-atoms, oxygen atom and sulphur atom.Wherein, preferred nitrogen atom.

R ¹represent alkyl, aromatic series base or alkoxy, preferable methyl, ethyl, benzyl, phenyl, naphthyl, methoxy or ethoxy, more preferably methyl, ethyl, phenyl or methoxyl.

R ²represent hydrogen atom or alkyl, preferred hydrogen atom or the alkyl be substituted, more preferably hydrogen atom, the alkyl be substituted forming ring together with Ar or toluene sulfanyl.

In addition, the group of the preferred carbon number 4 ~ 20 of Ar, R ¹the group of preferred carbon number 1 ~ 30, in addition, R ²the group of preferred carbon number 1 ~ 50.

The compound of oxime ester compound more preferably represented by following formula C-3, formula C-4 or formula C-5, the compound particularly preferably represented by following formula C-5.

[changing 8]

In formula C-3 ~ formula C-5, R ¹represent alkyl, aromatic series base or alkoxy, X represents-CH ₂-,-C ₂h ₄-,-O-or-S-, R ³separately represent halogen atom, R ⁴the amino, arylthio, alkylthio group, alkoxy, aryloxy group or the halogen atom that separately represent alkyl, phenyl, replace through alkyl, R ⁵represent hydrogen atom, alkyl or aryl, R ⁶represent alkyl, n1 and n2 separately represents the integer of 0 ~ 6, and n3 represents the integer of 0 ~ 5.

R ¹represent alkyl, aromatic series base or alkoxy, preferred R ¹¹the group of-X '-alkylidene-represented.R ¹¹represent alkyl or aryl, X ' expression sulphur atom or oxygen atom.R ¹¹preferred aryl groups, more preferably phenyl.As R ¹¹alkyl and aryl can replace through halogen atom (preferred fluorine atom, chlorine atom or bromine atoms) or alkyl.

The preferred sulphur atom of X.

R ³and R ⁴can bond on the optional position on aromatic rings.

R ⁴the amino, arylthio, alkylthio group, alkoxy, aryloxy group or the halogen atom that represent alkyl, phenyl, replace through alkyl, preferred alkyl, phenyl, arylthio or halogen atom, more preferably alkyl, arylthio or halogen atom, and then preferred alkyl or halogen atom.The alkyl of the preferred carbon number 1 ~ 5 of alkyl, more preferably methyl or ethyl.The preferred chlorine atom of halogen atom, bromine atoms or fluorine atom.

In addition, R ⁴carbon number preferably 0 ~ 50, more preferably 0 ~ 20.

R ⁵represent hydrogen atom, alkyl or aryl, preferred alkyl.The alkyl of the preferred carbon number 1 ~ 5 of alkyl, more preferably methyl or ethyl.The aryl of the preferred carbon number 6 ~ 10 of aryl.

R ⁶represent alkyl, the alkyl of preferred carbon number 1 ~ 5, more preferably methyl or ethyl.

R on the aromatic rings of n1 and n2 difference expression C-3 or formula C-4 ³replacement number, the R on the aromatic rings of n3 expression C-5 ⁴replacement number.

N1 ~ n3 separately preferably 0 ~ 2 integer, more preferably 0 or 1.

The example of the oxime ester compound that can preferably use in the present invention is below shown.But oxime ester compound used in the present invention is not limited to these compounds certainly.In addition, Me represents methyl, and Ph represents phenyl.In addition, the Sys-trans isomerism of the double bond of the oxime in these compounds can be any one of EZ, also can be the potpourri of EZ.

[changing 9]

The example of organic halogenation compound specifically can be enumerated: if " Japanization association publication (BullChem.Soc.Japan) " (42 of Lin Dengren, 2924 (1969)), United States Patent (USP) the 3rd, 905, No. 815 instructionss, Jap.P. examined patent publication 46-4605 publication, Japanese Patent Laid-Open No. Sho 48-36281 publication, Japanese Patent Laid-Open No. Sho 55-32070 publication, Japanese Patent Laid-Open No. Sho 60-239736 publication, Japanese Patent Laid-Open No. Sho 61-169835 publication, Japanese Patent Laid-Open No. Sho 61-169837 publication, Japanese Patent Laid-Open No. Sho 62-58241 publication, Japanese Patent Laid-Open No. Sho 62-212401 publication, Japanese Patent Laid-Open No. Sho 63-70243 publication, Japanese Patent Laid-Open No. Sho 63-298339 publication, M.P. " heterocyclic chemistry magazine (JournalofHeterocyclicChemistry) " (1 (No3) of Hunter (M.P.Hutt),) etc. (1970) compound recorded in, can enumerate the oxazoline compound replaced through trihalomethyl group especially, s-triazine.

The example of six aryl united imidazoles such as can be enumerated: Japanese Patent Laid-fair 6-29285 publication, United States Patent (USP) the 3rd, 479, No. 185, United States Patent (USP) the 4th, 311, No. 783, the various compounds recorded in each instructions such as No. the 4th, 622,286, United States Patent (USP).

Acylphosphanes (oxide) compound can illustrate monoacylphosphine oxides compound and two acylphosphine oxide compound; specifically, such as can enumerate gorgeous good solid (IRGACURE) 819 of BASF (BASF) company manufacture, reach Luo Gu (Darocure) 4265, reach Luo Gu (Darocure) TPO etc.

Benzene alkyl ketone compound can illustrate benzil methyl ketal (benzilmethylketal) compound, Alpha-hydroxy benzene alkyl ketone compound, alpha-amido benzene alkyl ketone compound, specifically, gorgeous good solid (IRGACURE) 907, gorgeous good solid (IRGACURE) 127 that BASF (BASF) company manufactures can be illustrated.

Photoepolymerizationinitiater initiater can use one or combinationally use two or more.In addition, when use does not have the Photoepolymerizationinitiater initiater of absorption at the exposure wavelength, also sensitizer can be used.

Relative to total solid composition 100 mass parts in composition, total amount preferably 0.5 mass parts ~ 30 mass parts of the Photoepolymerizationinitiater initiater in curable adhensive compositions of the present invention, more preferably 1 mass parts ~ 20 mass parts, and then preferably 1 mass parts ~ 10 mass parts, particularly preferably 2 mass parts ~ 5 mass parts.

In addition, in the present invention, when Photoepolymerizationinitiater initiater has the coordinating base of titanium and/or the coordinating base of zirconium, the compound with the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group in b1 is not considered as yet, or the compound with the coordinating base of titanium and/or the coordinating base of zirconium in b2.

Sensitizer

In curable adhensive compositions of the present invention, except Photoepolymerizationinitiater initiater, also sensitizer can be added.

Sensitizer absorbs actinic ray or radioactive ray and becomes excited state.The sensitizer and the composition C that become excited state interact, and produce the effects such as electronics moves, energy moves, heating thus, can cause and promote polymerization.

The example of preferred sensitizer can be enumerated: belong to following compounds and within the scope of 350nm ~ 450nm, have the compound of absorbing wavelength.The polynuclear aromatic same clan (such as pyrene, perylene, triphenylene, anthracene, luxuriant and rich with fragrance), xanthene class (such as fluorescein, eosin, erythrosine, rhodamine B, rose-bengal), xanthene ketone (such as xanthone, thioxanthones, dimethyl thioxanthone, diethyl thioxanthone, isopropyl thioxanthone, CTX), cyanine class (such as thion cyanine, oxygen carbocyanine), merocyanine class (such as merocyanine, carbon merocyanine), if red cyanines class, oxonols class, thiazide (such as thionine, methylene blue, toluidine blue), acridine (such as acridine orange, chloroflavin, propylene flavine, benzoflavine), acridine ketone (such as acridone, 10-butyl-2-chloro-acridine ketone), Anthraquinones (such as anthraquinone, 9,10-dibutoxy anthracene), side's acid compound class (such as square acid compound), styrene base class, basicity styrene base class, Coumarins (such as 7-diethylamino-4-methylcoumarin, ketocoumarin), carbazoles (such as N-vinylcarbazole), camphor quinones, phenothiazines.

In addition, in the present invention, spendable typical sensitizer can enumerate sensitizer disclosed in Ke Liweiluo [J.V.Crivello, advanced polymkeric substance science and technology (Adv.inPolymerSci.), 62,1 (1984)].

The preferred concrete example of sensitizer can enumerate: Bi, perylene, acridine orange, thioxanthones, CTX, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy anthracenes, anthraquinone, cumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazines etc.Relative to polymerization initiator 100 mass parts, sensitizer preferably adds with the ratio of 30 mass parts ~ 200 mass parts.

Components D: solvent

Curable adhensive compositions of the present invention contains solvent as components D.In addition, solvent of the present invention is the compound beyond composition B, is considered as not included in solvent by the compound being equivalent to composition B.

Curable adhensive compositions of the present invention is preferably prepared into must composition and aftermentioned any component dissolves or the solution be scattered in solvent or dispersion liquid.

The solvent used in curable adhensive compositions of the present invention can use well-known solvent, can illustrate: alcohols, ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propylene-glycol monoalky lether class, propylene glycol dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol monoalkyl ether acetate class, dipropylene glycol monoalkylether class, butylene glycol diacetate esters class, dipropylene glycol dialkyl ether, dipropylene glycol monoalkylether acetate esters, ester class, ketone, amide-type, lactone etc.Other concrete examples can refer to the paragraph 0062 of Japanese Patent Laid-Open 2009-098616 publication.

In these solvents, preferred concrete example can be enumerated: butanols, tetrahydrofurfuryl alcohol, phenoxetol, 1,3-butylene glycol diacetate esters, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, can more preferably enumerate: butanols, 1,3-BDO diacetate esters, diethylene glycol methyl ethyl ether.

From the viewpoint of coating, the boiling point of solvent preferably 100 DEG C ~ 300 DEG C, more preferably 120 DEG C ~ 250 DEG C.

In the present invention, spendable solvent can be used alone one or and with two or more.Also preferably also with the solvent that boiling point is different.

From being adjusted to the viewpoint such as viscosity being suitable for being coated with, relative to total solid composition 100 mass parts of curable adhensive compositions, content preferably 100 mass parts ~ 3 of the solvent in curable adhensive compositions of the present invention, 000 mass parts, more preferably 200 mass parts ~ 2,000 mass parts, and then preferred 250 mass parts ~ 1,000 mass parts.

Preferred 1mPas ~ the 200mPas of viscosity of curable adhensive compositions of the present invention, more preferably 2mPas ~ 100mPas, and then preferred 3mPas ~ 50mPas.

The RE-80L type rotational viscosimeter that viscosity such as preferably uses eastern machine industry (stock) to manufacture measures at 25 DEG C ± 0.2 DEG C.About rotational speed when measuring, viscosity preferably measures with 100rpm when being less than 5mPas, viscosity preferably measures with 50rpm when being more than 5mPas and being less than 10mPas, viscosity preferably measures with 20rpm when being more than 10mPas and being less than 30mPas, and viscosity is that the situation of more than 30mPas preferably measures with 10rpm.

Composition F: surfactant

Curable adhensive compositions of the present invention also can contain surfactant.

Surfactant can use negative ion system, kation system, nonionic system or both sexes any one, preferred surfactant is nonionic system surfactant.In addition, surfactant preferred fluorine system surfactant, more preferably fluorine system non-ionic surfactant.

In the present invention, spendable surfactant such as can be enumerated: as Mei Jiafa (Megafac) F142D of commercially available product, Mei Jiafa (Megafac) F172, Mei Jiafa (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F177, Mei Jiafa (Megafac) F183, Mei Jiafa (Megafac) F479, Mei Jiafa (Megafac) F482, Mei Jiafa (Megafac) F554, Mei Jiafa (Megafac) F780, Mei Jiafa (Megafac) F781, Mei Jiafa (Megafac) F781-F, Mei Jiafa (Megafac) R30, Mei Jiafa (Megafac) R08, Mei Jiafa (Megafac) F-472SF, Mei Jiafa (Megafac) BL20, Mei Jiafa (Megafac) R-61, Mei Jiafa (Megafac) R-90 (Di Aisheng (DIC) (stock) manufactures), Fu Lade (Fluorad) FC-135, not rad (Fluorad) FC-170C, not rad (Fluorad) FC-430, not rad (Fluorad) FC-431, promise Bake (Novec) FC-4430 (Sumitomo 3M (stock) manufacture), rising sun Jiade (Asahiguard) AG7105, 7000, 950, 7600, Sha Fulong (Surflon) S-112, Sha Fulong (Surflon) S-113, Sha Fulong (Surflon) S-131, Sha Fulong (Surflon) S-141, Sha Fulong (Surflon) S-145, Sha Fulong (Surflon) S-382, Sha Fulong (Surflon) SC-101, Sha Fulong (Surflon) SC-102, Sha Fulong (Surflon) SC-103, Sha Fulong (Surflon) SC-104, Sha Fulong (Surflon) SC-105, Sha Fulong (Surflon) SC-106 (Asahi Glass (stock) manufacture), Ai Futuo (Eftop) EF351, Ai Futuo (Eftop) 352, Ai Futuo (Eftop) 801, Ai Futuo (Eftop) 802 (Mitsubishi Materials electronics changes into (stock) and manufactures), Fu Jite (Ftergent) 250 (Ni Aosi (Neos) (stock) manufactures).In addition, except described, also can enumerate: KP (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Bao Lifuluo (Polyflow) (common prosperity society chemistry (stock) manufacture), Ai Futuo (Eftop) (Mitsubishi Materials electronics changes into (stock) and manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (stock) manufactures), not rad (Fluorad) (Sumitomo 3M (stock) manufacture), rising sun Jiade (Asahiguard), Sha Fulong (Surflon) (Asahi Glass (stock) manufacture), each series of precious reason Floex (PolyFox) (manufacture of Europe Nova (OMNOVA) company) etc.

In addition, surfactant can enumerate following multipolymer as preference: be 1 containing the structural unit A represented by following formula F-1 and structural unit B, the weight average molecular weight (Mw) of polystyrene conversion that measured by gel permeation chromatography using tetrahydrofuran as solvent, more than 000 and the multipolymer of 10, less than 000.

[changing 10]

Structural unit structural unit A B

In formula F-1, R ⁴⁰¹and R ⁴⁰³separately represent hydrogen atom or methyl, R ⁴⁰²represent carbon number more than 1 and the straight-chain alkyl-sub-of less than 4, R ⁴⁰⁴represent hydrogen atom or carbon number more than 1 and the alkyl of less than 4, L represents the alkylidene of carbon number more than 3 and less than 6, p and q is the quality percentage representing polymerization ratio, p represents more than 10 quality % and the numerical value of below 80 quality %, q represents more than 20 quality % and the numerical value of below 90 quality %, r represents more than 1 and the integer of less than 18, and s represents more than 1 and the integer of less than 10.

Branched alkylene groups represented by the preferred following formula F-2 of described L.R in formula F-2 ⁴⁰⁵represent carbon number more than 1 and the alkyl of less than 4, with regard to the aspect of compatibility and the wetting quality to applied, preferred carbon number more than 1 and the alkyl of less than 3, the more preferably alkyl of carbon number 2 or 3.

P and q sum (p+q) in formula F-1 is p+q=100, i.e. 100 quality % preferably.

[changing 11]

The weight average molecular weight (Mw) of described multipolymer more preferably 1, more than 500 and 5, less than 000.

These surfactants can be used alone a kind of or used in combination two or more.

When setup sheet surface-active agent, relative to total solid composition 100 mass parts of curable adhensive compositions, content preferably 0.001 mass parts ~ 5.0 mass parts of the surfactant in curable adhensive compositions of the present invention, more preferably 0.01 mass parts ~ 2.0 mass parts.

Composition G: alkoxysilane compound containing trialkylsilyl group in molecular structure

Composition of the present invention also can containing alkoxysilane compound containing trialkylsilyl group in molecular structure as contiguity modifying agent.If use alkoxysilane compound containing trialkylsilyl group in molecular structure, then can improve the adhesion of film and the substrate formed by composition of the present invention, or the character of film that adjustable is formed by composition of the present invention.

In composition of the present invention, spendable alkoxysilane compound containing trialkylsilyl group in molecular structure preferably makes the compound that the adhesion of the metal such as the silicon compound such as inorganics, such as silicon, monox, silicon nitride, gold, copper, molybdenum, titanium, aluminium and dielectric film becoming base material improves.Specifically, well-known silane coupling agent etc. are also effective.

Silane coupling agent preferably can enumerate the alkoxysilane compound containing trialkylsilyl group in molecular structure with epoxy radicals or (methyl) acryloxy.

Silane coupling agent such as can be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ-glycidyloxypropyl silane, γ-glycidoxypropyl dialkoxy silicane, γ-methacryloxypropyl trialkoxy silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi trialkoxy silane, β-(3, 4-epoxycyclohexyl) ethyltrialkoxysilanes, vinyl trialkyl oxysilane, 3-acryloxypropyl trimethoxy silane.In these, more preferably γ-glycidyloxypropyl silane or γ-methacryloxypropyl trialkoxy silane, 3-acryloxypropyl trimethoxy silane.

In curable adhensive compositions of the present invention, spendable alkoxysilane compound containing trialkylsilyl group in molecular structure is not particularly limited in these compounds, can use well-known compound.

Alkoxysilane compound containing trialkylsilyl group in molecular structure can be used alone one or combinationally use two or more.

When curable adhensive compositions of the present invention contains alkoxysilane compound containing trialkylsilyl group in molecular structure, relative to total solid composition 100 mass parts in curable adhensive compositions, content preferably 0.1 mass parts ~ 30 mass parts of alkoxysilane compound containing trialkylsilyl group in molecular structure, more preferably 0.5 mass parts ~ 20 mass parts.

Composition H: crosslinking chemical

Curable adhensive compositions of the present invention optionally also can contain crosslinking chemical.By adding crosslinking chemical, can make to become more firmly film by the cured film of curable adhensive compositions gained of the present invention.

As long as crosslinking chemical causes cross-linking reaction by heat, then also unrestricted (wherein, except each composition mentioned above), known crosslinking chemical can be used.

When curable adhensive compositions of the present invention contains crosslinking chemical, relative to total solid composition 100 mass parts in curable adhensive compositions, content preferably 0.1 mass parts ~ 50 mass parts of crosslinking chemical, more preferably 0.1 mass parts ~ 30 mass parts, and then preferred 0.5 mass parts ~ 20 mass parts.By adding in described scope, the cured film of physical strength and excellent solvent resistance can be obtained.Also by different types of crosslinking chemical and with multiple, now all crosslinking chemical phase Calais can be calculated content.

Composition I: antioxidant

Curable adhensive compositions of the present invention also can contain antioxidant.Antioxidant can contain well-known antioxidant.By adding antioxidant, the advantage such as have painted, that maybe can reduce the thickness caused by decomposing thinning, the in addition heat resistant transparent that can prevent cured film excellent.

This antioxidant such as can be enumerated: phosphorous antioxidant, amide-type, hydrazides class, hindered amine system antioxidant, sulphur system antioxidant, phenol system antioxidant, Vitamin C acids, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc.In these, from the viewpoint of the thinning of painted, the thickness of cured film, particularly preferably phenol system antioxidant (Hinered phenols), hindered amine system antioxidant, phosphorous antioxidant (alkyl phosphite class), sulphur system antioxidant (thioether class), most preferably phenol system antioxidant.These antioxidants can be used alone one, also can mix two or more.

Concrete example can be enumerated: these contents are incorporated in this case instructions by the compound recorded in the compound recorded in the paragraph 0026 ~ paragraph 0031 of Japanese Patent Laid-Open 2005-29515 publication, the paragraph 0106 ~ paragraph 0116 of Japanese Patent Laid-Open 2011-227106 publication.

Preferred commercially available product can be enumerated: Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-80 (above for Ai Dike (ADEKA) (stock) manufactures), this (Irganox) 1035 of gorgeous promise, this (Irganox) 1098 of gorgeous promise, this (Irganox) 1726 of gorgeous promise, gorgeous Floex (IRGAFOS) 168 (being that BASF (BASF) company manufactures above).

When curable adhensive compositions of the present invention contains antioxidant, relative to total solid composition 100 mass parts in curable adhensive compositions, content preferably 0.1 mass parts ~ 10 mass parts of antioxidant, more preferably 0.2 mass parts ~ 5 mass parts, and then preferred 0.5 mass parts ~ 4 mass parts.

Composition J: metal oxide particle

Curable adhensive compositions of the present invention, in order to regulate refractive index or transmitance, can contain metal oxide particle.In the metal of metal oxide particle, also comprise the semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te).

Preferred metal oxide particle is preferably containing beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), gadolinium (Gd), terbium (Tb), dysprosium (Dy), ytterbium (Yb), lutetium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), molybdenum (Mo), tungsten (W), zinc (Zn), boron (B), aluminium (Al), silicon (Si), germanium (Ge), tin (Sn), plumbous (Pb), antimony (Sb), bismuth (Bi), tellurium (Te) equiatomic oxide particle, more preferably titanium dioxide, titanium composite oxide, zinc paste, zirconia, indium/tin-oxide, antimony/tin-oxide, and then preferential oxidation titanium, titanium composite oxide, zirconia, particularly preferably titanium dioxide, zirconia, most preferably titanium dioxide.The titanium dioxide rutile-type that particularly preferably refractive index is high.These metal oxide particles also can utilize organic material effects on surface to process to give dispersion stabilization.

From the viewpoint of the transparency of curable adhensive compositions, the preferred 1nm ~ 200nm of average primary particle diameter of metal oxide particle, more preferably 3nm ~ 80nm, particularly preferably 5nm ~ 50nm.Here, the average primary particle diameter of particle refers to the particle diameter its arithmetic mean obtained that utilize any 200 particles of determination of electron microscopy.In addition, particle shape and in aspheric situation, longest edge is considered as particle diameter.

In addition, metal oxide particle can be used alone one, also can and with two or more.

As long as the content of the metal oxide particle in curable adhensive compositions of the present invention is considered, the refractive index required by the optical component by curable adhensive compositions gained or transmitance etc. are suitably determined, relative to the total solid composition of curable adhensive compositions of the present invention, preferably be set as 0 quality % ~ 40 quality %, more preferably be set as 1 quality % ~ 30 quality %, and then be preferably set as 2 quality % ~ 20 quality %.

In addition, the content of metal oxide particle is preferably less than the content of composition A, when the content of composition A is set to 100 mass parts, preferably below 80 mass parts, more preferably below 50 mass parts, and then preferably below 30 mass parts.

In the present invention, metal oxide particle can be also prepare by using the mixing arrangement such as bowl mill, rod mill mix in suitable spreading agent and solvent by metal oxide particle to disperse for, described dispersion liquid with the form of dispersion liquid.

(other compositions)

In curable adhensive compositions of the present invention, optionally can add other compositions such as plasticiser, polymerization inhibitor, thermal acid generator, acid proliferation generator, binder polymer.About these compositions, such as, can use composition, other well-known compositions of recording in Japanese Patent Laid-Open 2009-98616 publication, Japanese Patent Laid-Open 2009-244801 publication.In addition, also can by the new expansion of < polymeric additive (daily magazine industry newspaper office (stock)) " in the various ultraviolet light absorber recorded or metal passivator etc. add in curable adhensive compositions of the present invention.

-polymerization inhibitor-

Curable adhensive compositions of the present invention can contain polymerization inhibitor.

So-called polymerization inhibitor, refer to the material playing following effect: hydrogen supply (or awarding hydrogen), energy supply (or awarding energy), supplied for electronic (or awarding electronics) etc. are implemented to the polymerization initiation radical composition produced by polymerization initiator, make polymerization initiation radical inactivation, suppress polymerization to cause.Such as can use the compound etc. recorded in the paragraph 0154 ~ paragraph 0173 of Japanese Patent Laid-Open 2007-334322 publication.

Preferred compound can be enumerated: phenothiazine, phenoxazine, p-dihydroxy-benzene, 3,5-dibutyl-4-hydroxy-methylbenzenes.

There is no particular restriction for the content of polymerization inhibitor, relative to the total solid composition of curable adhensive compositions, and preferably 0.0001 quality % ~ 5 quality %.

(preparation method of curable adhensive compositions)

There is no particular restriction for the preparation method of curable adhensive compositions of the present invention, can utilize well-known method to prepare, such as, arbitrary method can be utilized to be mixed by each composition with set ratio, stirring and dissolving and/or dispersion and prepare curable adhensive compositions.In addition, such as, after also each composition can being made the solution dissolved in advance respectively in a solvent, these solution are prepared curable adhensive compositions with the mixing of set ratio.Curable adhensive compositions prepared as above such as also can use the filtrator etc. in 0.2 μm, aperture to carry out filtering rear use.

(cured film and manufacture method thereof)

Cured film of the present invention is the cured film that curable adhensive compositions of the present invention is hardened.In addition, cured film of the present invention is preferably by the cured film of the manufacture method gained of cured film of the present invention.

As long as the manufacture method of cured film of the present invention makes curable adhensive compositions of the present invention harden and manufactures the method for cured film, then there is no particular restriction, preferably comprises following operation 1 ~ operation 5 successively.

Operation 1: curable adhensive compositions of the present invention is coated on the painting process on substrate

Operation 2: except the solvent removal step of desolventizing from be coated with curable adhensive compositions

Operation 3: utilize actinic ray to the exposure process exposed at least partially of curable adhensive compositions eliminating solvent

Operation 4: utilize the developing procedure that aqueous developer solution is developed to the curable adhensive compositions through exposure

Operation 5: the heat treatment step that the curable adhensive compositions through development is heat-treated

In described painting process, preferably curable adhensive compositions of the present invention is coated on moistening film substrate made containing solvent.Can go forward curable adhensive compositions is applied to substrate, carry out the cleaning of the substrates such as alkali cleaning or plasma clean.And then, can after base-plate cleaning, utilize hexamethyldisilazane etc. to process substrate surface.By carrying out described process, there is the tendency that curable adhensive compositions improves the adhesion of substrate.

Described substrate can enumerate inorganic substrate, resin, resin composite materials etc.

Inorganic substrate such as can be enumerated: glass, quartz, silicon, silicon nitride and on this substrate evaporation have the composite base plate of molybdenum, titanium, aluminium, copper etc.

About resin, following resin can be enumerated: polybutylene terephthalate, polyethylene terephthalate, Polyethylene Naphthalate, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, polycarbonate, polysulfones, polyethersulfone, polyarylate, allyl diglycolcarbonate resin, polyamide, polyimide, polyamidoimide, polyetherimide, poly-indoles, polyphenylene sulfide, polycyclic alkene, norbornene resin, the fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomeric resins, cyanate ester resin, crosslinked dimethyl ester, cyclic polyolefin, aromatic ether resin, maleimide-olefin copolymer, cellulose, the synthetic resin such as episulfide resin.These substrates seldom directly use with described form, are usually formed with the such multilayer laminated boards structure of such as thin film transistor (TFT) (ThinFilmTransistor, TFT) element according to the form of final products.

Curable adhensive compositions of the present invention is to by sputter, the contiguity of the metal film of masking or metal oxide is good, and therefore substrate preferably contains the metal film of the masking by sputter.The oxide of the preferred titanium of metal, copper, aluminium, indium, tin, manganese, nickel, cobalt, molybdenum, tungsten, chromium, silver, neodymium and these metals or alloy, the more preferably alloy of molybdenum, titanium, aluminium, copper and these metals.In addition, metal or metal oxide can be used alone one, also can and with multiple.

The coating process of substrate is not particularly limited, such as, can uses the methods such as slot coated method, spray-on process, rolling method, method of spin coating, cast coating method, slit and rotary process, ink-jet method, print process (soft version, intaglio plate, half tone etc.).Ink-jet method, print process can concentrate on necessary position to arrange composition, can realize province's liquefaction of composition, therefore preferably.

Moistening thickness during coating is not particularly limited, and can be coated with the thickness corresponding with purposes, the scope of preferably 0.05 μm ~ 10 μm.

And then, also before being coated on substrate by curable adhensive compositions of the present invention, in application Japanese Patent Laid-Open 2009-145395 publication, the pre-wet method of such what is called can be recorded.

In described solvent removal step, from be coated with described film, form dry coating except desolventizing at substrate by decompression (vacuum) and/or heating etc.The heating condition preferably 70 DEG C ~ 130 DEG C of solvent removal step and 30 second ~ 300 seconds about.

In addition, described painting process and described solvent removal step can be carried out successively, also can carry out simultaneously, also can carry out by alternate repetition.Such as after the ink-jet application in described painting process all terminates, described solvent removal step can be carried out, also can heated substrates in advance, the ejection of the curable adhensive compositions of the ink-jet application mode one side that utilizes that one side is carried out in described painting process carries out solvent removing.

Described exposure process uses actinic ray, produces polymerization initiation kind, carry out the polymerization of the compound with ethene unsaturated group, make the operation of hardening at least partially of the curable adhensive compositions eliminating solvent by Photoepolymerizationinitiater initiater.

In described exposure process, spendable exposure light source can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light-emittingdiode (LightEmittingDiode, LED) light source, excimer laser generation device etc., can preferably use i ray (365nm), h ray (405nm), g ray (436nm) etc. to have more than 300nm and the actinic ray of the wavelength of below 450nm.In addition, optionally also irradiation light is adjusted by point optical filter that long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter are such.

Exposure device can use: mirror surface projection aims at the exposure device of the various modes such as exposure machine, stepper, scanner, proximity exposure device, contact exposure device, microlens array, lens scan instrument, laser explosure.

In addition, the exposure in described exposure process is also not particularly limited, preferred 1mJ/cm ²~ 3,000mJ/em ², more preferably 1mJ/cm ²~ 500mJ/cm ².

From the viewpoint promoting sclerosis, the exposure in described exposure process is preferably carried out under the state blocked through oxygen.The method blocking oxygen can illustrate: expose in a nitrogen environment, or arrange oxygen barrier film.

In addition, as long as exposure in described exposure process is to the carrying out at least partially of curable adhensive compositions eliminating solvent, such as, can be blanket exposure, also can be pattern exposure.

In addition, after described exposure process, can carry out exposing rear heating: PostExposureBake (hereinafter also referred to " PEB ").Temperature when carrying out PEB preferably more than 30 DEG C and less than 130 DEG C, more preferably more than 40 DEG C and less than 120 DEG C, particularly preferably more than 50 DEG C and less than 110 DEG C.

The method of heating is not particularly limited, and can use well-known method.Such as can enumerate hot plate, baking oven, infrared heater etc.

In addition, about the heat time, when hot plate preferably 1 minute ~ about 30 minutes, when in addition preferably 20 minutes ~ about 120 minutes.In described scope, can when not causing when damage heat substrate, device.

The manufacture method of cured film of the present invention preferably also comprises: utilize the developing procedure that developer solution develops to the curable adhensive compositions through exposure.

In developing procedure, utilize solvent or alkaline-based developer to develop to the curable adhensive compositions exposing into pattern-like, form pattern.In the developer solution used in developing procedure, preferably containing alkali compounds.Alkali compounds such as can use: the alkali metal hydroxides such as lithium hydroxide, NaOH, potassium hydroxide; The alkali carbonate such as sodium carbonate, sal tartari class; The alkaline metal bicarbonate such as sodium bicarbonate, potassium bicarbonate class; The ammonium hydroxide classes such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide benzyltrimethylammon.um, bursine; Sodium silicate, sodium metasilicate etc.The aqueous solution of adding the water-miscible organic solvents such as the methyl alcohol of appropriate amount or ethanol or surfactant in the aqueous solution of described bases, preferably containing the aqueous solution of described alkali compounds, in addition, also can be used as developer solution by developer solution.

Preferred developer solution can enumerate 0.4 quality % ~ 2.5 quality % aqueous solution of tetramethyl ammonium hydroxide.

The pH value of developer solution preferably 10.0 ~ 14.0.Development time preferably 30 second ~ 500 seconds, in addition, the method for development can be fluid containing method (puddle formula development method), spray process, infusion process etc. any one.

After development, also drip washing operation can be carried out.In drip washing operation, utilize pure water etc. to clean the substrate after development, carry out the developer solution removing of adhering to, residue removing of developing.ELUTION METHOD can use well-known method.Such as can enumerate spray drip washing or dipping drip washing etc.

About pattern exposure and development, well-known method or well-known developer solution can be used.Such as can use the pattern exposure method recorded in Japanese Patent Laid-Open 2011-186398 publication, Japanese Patent Laid-Open 2013-83937 publication and developing method suitably.

The manufacture method of cured film of the present invention, preferably after described developing procedure, comprises the operation (after baking) to heat-treating through the curable adhensive compositions of development.By heat-treating after by curable adhensive compositions development of the present invention, the cured film that intensity is more excellent can be obtained.

Described heat treated temperature preferably 80 DEG C ~ 300 DEG C, more preferably 100 DEG C ~ 280 DEG C, particularly preferably 120 DEG C ~ 200 DEG C.If described embodiment, then suitably there is the condensation of composition A in presumption, and the physical property of cured film is more excellent.

In addition, the described heat treated time, there is no particular restriction, preferably 1 minute ~ 360 minutes, more preferably 5 minutes ~ 240 minutes, and then preferably 10 minutes ~ 120 minutes.

In addition, the sclerosis of light and/or heat that utilizes in the manufacture method of described cured film of the present invention can be carried out continuously, also can carry out successively.

In addition, when heat-treating, also improve the transparency further by carrying out in a nitrogen environment.

Before heat treatment step (afterwards toast), after also can toasting under relatively low temperature, carry out heat treatment step (in adding roasting procedure).When carrying out middle baking, preferably heat at 90 DEG C ~ 150 DEG C after 1 minute ~ 60 minutes, toast after carrying out under the high temperature more than 200 DEG C.In addition, also middle baking, rear baking can be divided into the multistage in three stages more than heats.By managing to carry out this middle baking, rear baking, the cone angle of adjustable pattern.These heating can use the well-known heating means such as hot plate, baking oven, infrared heater.

In addition, also before rear baking, rear baking can be carried out after utilizing actinic ray to carry out exposing (post-exposure) again to the figuratum substrate of formation comprehensively.By carrying out post-exposure, the sclerous reaction of film can be promoted further.Comprise the preferred 100mJ/cm of preferred exposure when post-exposure operation ²~ 3,000mJ/cm ², particularly preferably 100mJ/cm ²~ 500mJ/cm ².

(cured film)

Cured film of the present invention or hardening thing (hereinafter sometimes referred to cured film etc.) make curable adhensive compositions of the present invention harden and obtain.

Cured films of the present invention etc. can be as mentioned above through the cured film etc. of development, also can be undeveloped cured film etc., preferably can play the cured film etc. through development of effect of the present invention further.In addition, when for undeveloped cured film etc., except not comprising described developing procedure, identical method can be utilized obtain.

Cured films of the present invention etc. are the organic and inorganic mixed hardening films etc. formed by composition A, composition B etc., and the film of the crystallization of nonmetal oxide.Crystallised component preferably 30 below the volume % of the metal oxide in cured film etc., more preferably 10 below volume %, and then preferably not containing crystallised component.By being set to this embodiment, anti-Fractured improves.The content of crystallised component is evaluated by the X-ray diffraction etc. of cured film etc.

The refractive index of cured film of the present invention etc. is high, have high transparent, and the light that therefore can be used as lenticule, optical waveguide, anti-reflective film, solar cell or organic EL luminous element is suitably taken into/and extraction efficiency improves the diaphragm of the distribution electrode used in the diaphragm that uses in the display device such as optical component, organic EL display or liquid crystal indicator such as layer, LED encapsulant and LED chip Tu Cai or dielectric film, touch-screen.

In addition; liquid crystal layer also can be held in the structural elements etc. of certain thickness distance piece, MEMS (micro electro mechanical system) (MicroElectroMechanicalSystems, MEMS) device by cured film of the present invention suitably for being used in the diaphragm of the colored filter in liquid crystal indicator or organic el device etc., liquid crystal indicator.

In addition, cured film of the present invention etc. can be used for the visibility lower layer of the distribution electrode used in touch-screen etc.In addition; the visibility lower layer of the distribution electrode used in so-called touch-screen; refer to reduce in touch-screen the distribution electrode that uses etc. visibility, namely, the layer that makes distribution electrode etc. not easily in sight, such as can enumerate the diaphragm (outer film) etc. of the interlayer dielectric between touch detection electrodes (such as tin indium oxide (ITO) system), electrode.In addition, index matching layer (sometimes also referred to as IM (IndexMatching) layer or refractive index adjustment layer) is also suitable for.So-called index matching layer, refers to the adjustment light reflectance of display device or the layer of transmissivity.About index matching layer, have a detailed description in Japanese Patent Laid-Open 2012-146217 publication, described content is incorporated in this instructions.By cured film of the present invention is used for visibility lower layer, can be made into the touch-screen of visibility excellence.

Wherein, cured film of the present invention is suitable as interlayer dielectric in display device etc. or outer film.

When for the interlayer dielectric between touch detection electrodes or diaphragm; from the viewpoint of visibility improvement; the refractive index of cured film is preferably close to the refractive index of electrode; specifically; refractive index under wavelength 550nm preferably 1.78 ~ 2.40; more preferably 1.80 ~ 2.30, and then preferably 1.83 ~ 2.20.

(liquid crystal indicator)

Liquid crystal indicator of the present invention there is cured film of the present invention.

Liquid crystal indicator of the present invention uses except the planarization film that formed of curable adhensive compositions of the present invention or interlayer dielectric except having, and there is no particular restriction, can enumerate the well-known liquid crystal indicator adopting various structure.

Thin film transistor (TFT) (the Thin-FilmTransistor that such as liquid crystal indicator of the present invention possesses, TFT) concrete example can be enumerated: amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT (such as indium gallium zinc oxide, so-called IGZO) etc.Cured film of the present invention, due to electrical characteristics excellence, therefore can be combined in these TFT and preferably uses.

In addition, the desirable liquid crystal drive mode of liquid crystal indicator of the present invention can be enumerated: twisted nematic (TwistedNematic, TN) mode, vertical orientated (VerticalAlignment, VA) (In-Plane-Switching is switched in mode, face, IPS) mode, fringing field switch (FringeFieldSwitching, FFS) mode, optical compensation curved (OpticallyCompensatedBend, OCB) mode etc.

In panel is formed, colorful optical filter array (ColorFilteronArray, also cured film of the present invention be can use in the liquid crystal indicator of COA) mode, such as, the organic insulating film (115) of Japanese Patent Laid-Open 2005-284291 publication or the organic insulating film (212) of Japanese Patent Laid-Open 2005-346054 publication can be used as.In addition, the specifically aligned of the liquid crystal orientation film that liquid crystal indicator of the present invention is desirable enumerates friction orientation method, optical alignment method etc.In addition, also the polymkeric substance by recording in Japanese Patent Laid-Open 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication supports that orientation (PolymerSustainedAlignment, PSA) technology is to carry out polymer orientation support.

In addition, curable adhensive compositions of the present invention and cured film of the present invention are not limited to described purposes, can be used for various uses.Such as except planarization film or interlayer dielectric, also can be used as being used in the diaphragm of colored filter or liquid crystal indicator suitably and liquid crystal layer is held in certain thickness distance piece or solid-state imager the lenticule etc. be arranged on colored filter.

Fig. 1 is the conceptual sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.Described color liquid crystal display arrangement 10 is the liquid crystal panel on the back side with back light unit 12, and be configured with the element of TFT16 in liquid crystal panel, the element of described TFT16 with to be pasted with all pixels configured between 2 sheet glass substrates 14 of light polarizing film, glass substrate 15 corresponding.For each element formed on the glass substrate, carried out the distribution of the ito transparent electrode 19 forming pixel electrode by the contact hole 18 be formed in cured film 17.On ito transparent electrode 19, the layer being provided with liquid crystal 20 and RGB (RedGreenBlue, the RGB) colored filter 22 being configured with black matrix".

The light source of backlight is not particularly limited, and can use well-known light source.Such as can enumerate: multi-colored led, fluorescent light (cold-cathode tube), organic EL etc. of White LED, blue red green etc.

In addition, liquid crystal indicator can be made into three-dimensional (Threedimension, 3D) (stereopsis) type, also can be made into touch screen type.And then also can be made into flexible type, can be used as the interlayer dielectric (520) recorded in the 2nd interlayer dielectric (48) recorded in Japanese Patent Laid-Open 2011-145686 publication or Japanese Patent Laid-Open 2009-258758 publication.

(organic EL display)

Organic EL display of the present invention has cured film of the present invention.

Organic EL display of the present invention uses except the planarization film that formed of curable adhensive compositions of the present invention or interlayer dielectric except having, there is no particular restriction, can enumerate the well-known various organic EL display or liquid crystal indicator of taking various structure.

The concrete example of the thin film transistor (TFT) (Thin-FilmTransistor, TFT) that such as organic EL display of the present invention possesses can enumerate amorphous silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc.Cured film of the present invention, due to electrical characteristics excellence, therefore can be combined in these TFT and preferably uses.

Fig. 2 is the formation concept map of an example of organic EL display, represents the schematic cross sectional view of the substrate in the organic EL display of bottom emission type, has planarization film 4.

Glass substrate 6 is formed the TFT1 of bottom gate type, forms with the state covering described TFT1 the dielectric film 3 comprising Si3N4.Formed after omitting illustrated contact hole in dielectric film 3 here, form the distribution 2 (height 1.0 μm) being connected to TFT1 through described contact hole on the insulating film 3.Distribution 2 is used to the distribution that will connect between TFT1 or be connected with TFT1 by the organic EL formed in subsequent handling.

And then, in order to make, because of the concavo-convex planarization formed caused by distribution 2, to form planarization film 4 on the insulating film 3 with the concavo-convex state of landfill caused by distribution 2.

Planarization film 4 is formed the organic EL of bottom emission type.That is, on planarization film 4, be connected to distribution 2 via contact hole 7 and form the first electrode 5 comprising ITO.In addition, the first electrode 5 is equivalent to the anode of organic EL.

Forming the dielectric film 8 of the shape at the edge of covering first electrode 5, by arranging described dielectric film 8, the short circuit between the second electrode of being formed in the first electrode 5 and its subsequent handling can be prevented.

And then, in Fig. 2 although not shown, but across required pattern mask successively evaporation, electric hole transport layer, organic luminous layer, electron transfer layer are set, then on whole of surface, form the second electrode comprising A1, glass for sealing plate and ultraviolet ray hardening type epoxy resin is used to fit, seal thus, obtain to connect each organic EL and be used for the organic EL display of active array type of the TFT1 driving described each organic EL.

(touch-screen and touch panel display device)

Touch-screen of the present invention is the touch-screen that all or part of of insulation course and/or protective seam comprises the hardening thing of curable adhensive compositions of the present invention.In addition, touch-screen of the present invention preferably at least has transparency carrier, electrode and insulation course and/or protective seam.

Touch panel display device of the present invention preferably has the touch panel display device of touch-screen of the present invention.Touch-screen of the present invention can be any one of the well-known modes such as resistive film mode, electrostatic capacitance mode, ultrasound wave mode, way of electromagnetic induction.Wherein, preferred electrostatic capacitance mode.

The touch-screen of electrostatic capacitance mode can enumerate touch-screen disclosed in touch-screen disclosed in Japanese Patent Laid-Open 2010-28115 publication or No. 2012/057165th, International Publication.As other touch-screens, can enumerate: so-called embedded (in-cell) type (such as Fig. 5, Fig. 6, Fig. 7, Fig. 8 of Jap.P. spy table 2012-517051 publication), so-called outer (on-cell) type (Fig. 2 (b) of Figure 14 of such as Japanese Patent Laid-Open 2012-43394 publication, No. 2012/141148th, International Publication), OGS type, TOL type, other form (such as Fig. 6 of Japanese Patent Laid-Open 2013-164871 publication).

[embodiment]

Below enumerate embodiment more specifically to be illustrated the present invention.Material shown in following embodiment, use amount, ratio, contents processing, processing sequence etc. only otherwise depart from purport of the present invention, then can suitably change.Therefore, scope of the present invention is not limited to concrete example shown below.In addition, as long as no special instructions, then " part ", " % " are quality criteria.

(synthesis example 1)

Four positive fourth titanium dioxide 34.0g (0.10 mole) are dissolved in after in normal butyl alcohol 12.0g, at room temperature drip the mixed liquor of water 2.7g (0.15 mole) and normal butyl alcohol 24.0g.After dropping terminates, at room temperature stir after 1 hour, and then at 110 DEG C, add hot reflux 1 hour, obtain titanoxane A-6.Solid component concentration is 20 quality %.

(synthesis example 2)

Four positive fourth titanium dioxide 34.0g (0.10 mole) are dissolved in after in normal butyl alcohol 12.0g, at room temperature drip the mixed liquor of water 1.8g (0.10 mole) and normal butyl alcohol 24.0g.After dropping terminates, at room temperature stir after 1 hour, and then at 110 DEG C, add hot reflux 1 hour, obtain titanoxane A-7.Solid component concentration is 29 quality %.

(synthesis example 3)

Four positive fourth titanium dioxide 34.0g (0.10 mole) are dissolved in after in normal butyl alcohol 12.0g, at room temperature drip the mixed liquor of water 1.35g (0.075 mole) and normal butyl alcohol 24.0g.After dropping terminates, at room temperature stir after 1 hour, and then] add hot reflux 1 hour at 10 DEG C, obtain titanoxane A-8.Solid component concentration is 34 quality %.

(synthesis example 4)

Four tertiary fourth titanium dioxide 34.0g (0.10 mole) are dissolved in after in tert-butyl alcohol 12.0g, at room temperature drip the mixed liquor of water 1.8g (0.10 mole) and tert-butyl alcohol 24.0g.After dropping terminates, at room temperature stir after 1 hour, and then at 100 DEG C, add hot reflux 1 hour, obtain titanoxane A-9.Solid component concentration is 29 quality %.

(synthesis example 5)

Four titanium isopropoxide 28.4g (0.10 mole) are dissolved in after in isopropyl alcohol 12.0g, at room temperature drip the mixed liquor of water 1.8g (0.10 mole) and isopropyl alcohol 24.0g.After dropping terminates, at room temperature stir after 1 hour, and then at 85 DEG C, add hot reflux 1 hour, obtain titanoxane A-10.Solid component concentration is 27 quality %.

(synthesis example 6)

Tetrem titanium dioxide 22.8g (0.10 mole) is dissolved in after in ethanol 12.0g, at room temperature drips the mixed liquor of water 1.8g (0.10 mole) and ethanol 24.0g.After dropping terminates, at room temperature stir after 1 hour, and then at 78 DEG C, add hot reflux 1 hour, obtain titanoxane A-11 solution.Solid component concentration is 25 quality %.

(synthesis example 7)

Stir while make titanium tetrachloride 5.0g (0.026 mole) be dissolved in after in isopropyl alcohol 100g, stir 2 hours under room temperature (25 DEG C).By carrying out bubbling (bubbling) to the mixed gas (1/1 volume ratio) of ammonia and nitrogen, make chloride precipitation.Described mixed liquor is filtered and removes ammonium chloride.And then solvent is removed under reduced pressure distillation, obtains target titanium isopropoxide.Thereafter, carry out the operation identical with synthesis example 1, obtain titanoxane A-12.Solid component concentration is 19 quality %.

(embodiment 1)

The making > of < curable adhensive compositions

Be prepared as described below.

Utilize and add solvent 1 (diethylene glycol methyl ethyl ether), in the mode becoming addition and the solid constituent recorded in table 1, following composition is adjusted, and utilize magnetic stirring apparatus (magneticstirrer) to stir 1 hour.

A-1:PC-200 (titanoxane, pine is originally refined (MatsumotoFineChemical) (stock) manufactures, and solid constituent is 31.0%)

R-1: diacetone (manufacturing with the pure pharmaceutical worker's industry (stock) of light)

M-1: multifunctional ethene unsaturated compound

C-1: gorgeous good solid (IRGACURE) CGI-124 (1-[4-(thiophenyl) phenyl]-1,2-octadione-2-(O-benzoyl oximes), BASF (BASF) company manufactures)

F-1: Mei Jiafa (Megafac) F-554 (containing the non-ionic surfactant of perfluoroalkyl, Di Aisheng (DIC) (stock) manufactures)

Then, utilize the membrane filter of 0.45 μm (membranefilter) to filter, make the curable adhensive compositions of embodiment 1.

(embodiment 2 ~ embodiment 57 and comparative example 1 ~ comparative example 21)

The making > of < curable adhensive compositions

Except changing to each composition and allotment amount and solid constituent amount recorded in following table 1 ~ table 4, carry out in the same manner as the making of the curable adhensive compositions of embodiment 1, make the curable adhensive compositions of embodiment 2 ~ embodiment 57 and comparative example 1 ~ comparative example 21 respectively.

In addition, in table 1 ~ table 4, the addition of each composition beyond the solid constituent amount of composition represents that the mass parts relative to total solid component amount 100 mass parts, "-" refer to not containing described composition.In addition, the addition of each composition is recorded with solid constituent amount.

In table 1 ~ table 4, " interpolation solvent " and " solvent " synonym.

The details of the abbreviation in the table 1 ~ table 4 except described are below shown.

A-2: titanoxane (T-3072, pine is originally refined (MatsumotoFineChemical) (stock) manufactures)

A-3: titanoxane (B-2, Japanese Cao Da (stock) manufacture)

A-4: titanoxane (B-4, Japanese Cao Da (stock) manufacture)

A-5: zirconium oxygen alkane (ZA-65, pine is originally refined (MatsumotoFineChemical) (stock) manufactures)

A-6 ~ A-12: the titanoxane made in synthesis example 1 ~ synthesis example 7

A-13: utilize normal butyl alcohol to be the 30 quality % persons of forming by four positive fourth titanium dioxide (manufacturing with the pure pharmaceutical worker's industry (stock) of light) dilution

R-2: methyl acetoacetate (manufacturing with the pure pharmaceutical worker's industry (stock) of light)

R-3: ethyl lactate (Tokyo changes into industry (stock) manufacture)

R-4: methacrylic acid-2-acetoacetoxyethyl methacrylate (Tokyo changes into industry (stock) manufacture)

M-1: the mass ratio of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate is the potpourri (Japanese chemical drug (stock) manufactures) of 70: 30

M-2: the mass ratio of tetramethylol methane tetraacrylate and pentaerythritol triacrylate is the potpourri (East Asia is synthesized (stock) and manufactured) of 37 ~ 45: 63 ~ 55

M-3: ethylene-oxide-modified bisphenol a diacrylate (following compound, Xin Zhong village chemistry (stock) manufacture)

M-4: methyl methacrylate (Tokyo changes into industry (stock) manufacture)

M-5: benzyl methacrylate (Tokyo changes into industry (stock) manufacture)

M-6: diallyl phthalate (Tokyo changes into industry (stock) manufacture)

C-2: gorgeous good solid (IRGACURE) CGI-242 (1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-oxime-O-acetic acid esters, BASF (BASF) company manufactures)

C-3: gorgeous good solid (IRGACURE) 907 (2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropane-1, BASF (BASF) company manufactures)

C-4: oxime ester system Photoepolymerizationinitiater initiater (following compound, the synthetic method with reference to the specific compound 1 recorded in Japanese Patent Laid-Open 2009-134289 publication is synthesized)

Add solvent 2: the mixed solution of diethylene glycol methyl ethyl ether/1,3-BDO diacetate esters=9/1 (mass ratio)

C-5:2,2 '-bis-(chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline (hodogaya chemical industry (stock) manufacture)

C-6: diethylamino benzophenone (hodogaya chemical industry (stock) manufacture)

[changing 12]

[changing 13]

[changing 14]

(evaluation of curable adhensive compositions)

As described below made curable adhensive compositions is evaluated.Evaluation result is shown in table 1 ~ table 4.

< storage stability evaluates >

In the glass substrate (trade name: XG of 100mm × 100mm, healthy and free from worry (Corning) company manufactures) on, the mode becoming 1.0 μm with thickness is coated with curable adhensive compositions, utilizes the oven drying (prebake conditions) 100 seconds of 80 DEG C.Film on the substrate of visual observations gained, evaluates by following benchmark.

1: after coating, the whole colourless of substrate is turbid

2: after coating, the whole face of substrate gonorrhoea slightly

3: after coating, gonorrhoea slightly about the half of substrate

4: after coating, the part gonorrhoea slightly of substrate

5: after prebake conditions, without gonorrhoea

< refractive index evaluates >

Use spinner (spinner) to be coated on silicon wafer substrate by the curable adhensive compositions of gained, at 80 DEG C, drying 100 seconds, forms the film of thickness 0.5 μm thus.Use extra-high-pressure mercury vapour lamp, with 100mJ/cm ²(utilizing i ray to measure), to described base board to explosure, thereafter, utilizes baking oven to heat 30 minutes at 220 DEG C.

Use ellipsometer (ellipsometer) VUV-VASE (fertile blue (J.A.WoollamJapan) (stock) of Japanese J.A. manufactures) measures the refractive index of the cured film under 550nm.Refractive index gets over Gao Yuejia, and more preferably more than 1.78.Metewand is as described below.

1: be less than 1.75

2:1.75 above and be less than 1.78

3:1.78 above and be less than 1.80

4:1.80 above and be less than 1.83

5:1.83 more than

< developability evaluates (analyticity, nargin (margin) and rectilinearity) >

In the glass substrate (trade name: XG of 100mm × 100mm, healthy and free from worry (Corning) company manufactures) on, the mode becoming 1.0 μm with thickness is coated with curable adhensive compositions, utilizes the oven drying (prebake conditions) 100 seconds of 80 DEG C.Thereafter, line and gap (lineandspace) is utilized to be that the mask with the line of 1 μm ~ 100 μm of 1: 1 is to carry out 100mJ/cm ²exposure (illumination is 24mW/cm ²), use alkaline-based developer (aqueous solution of tetramethyl ammonium hydroxide 2.38 quality %), develop at 25 DEG C.

-analyticity evaluation-

For the substrate after development, utilize optical microscope to be confirmed whether formation pattern.Metewand is shown in following.

1: do not resolve

2: the pattern that can form more than 20 μm

3: more than 10 μm can be formed and be less than the pattern of 20 μm

4: more than 5 μm can be formed and be less than the pattern of 10 μm

5: the pattern being less than 5 μm can be formed

-nargin evaluation-

In developability is evaluated, change and use alkaline-based developer (aqueous solution of tetramethyl ammonium hydroxide 2.38 quality %) time of flooding at 25 DEG C, the drafting department evaluating 50 μm is without time of disconnecting of residue ground.The described time is longer, represents that development nargin is wider.Metewand is shown in following.

1: be less than 10 seconds

More than 2:10 second be less than 20 seconds

More than 3:20 second

-rectilinearity evaluation-

For the substrate after the development made with the line of 50 μm and gap, utilize optical microscope to confirm the rectilinearity of line edge part.Metewand is shown in following.

1: in the face of online edge part, there is many spaces

2: in the face of online edge part, there is a little space

3: online edge part almost can't see space

< chemical-resistant evaluates >

In the glass substrate (trade name: XG of 100mm × 100mm, healthy and free from worry (Corning) company manufactures) on, the mode becoming 1.0 μm with thickness is coated with curable adhensive compositions, utilizes the oven drying (prebake conditions) 100 seconds of 80 DEG C.Thereafter, use extra-high-pressure mercury vapour lamp, 100mJ/cm is carried out to whole face ²exposure (illumination is 24mW/cm ²), utilize thereafter baking oven to heat 30 minutes at 220 DEG C.

Then, flood 2 minutes in 1-METHYLPYRROLIDONE with 25 DEG C, measure the thickness before and after dipping, measure the survival rate of film.Metewand is shown in following.

1: survival rate is less than 80%

2: survival rate is more than 80% and is less than 90%

3: survival rate is more than 90% and is less than 95%

4: survival rate is more than 95% and is less than 98%

5: survival rate is more than 98% and less than 100%

In addition, " interpolation solvent " in following table 1 ~ table 4 is identical meanings with " solvent " as components D.

In comparative example 1 ~ comparative example 21, the analyticity of cured film is poor, cannot evaluate nargin and rectilinearity.

In addition, especially the refractive index of the cured film of embodiment 21 under wavelength 550nm is 1.94.

(embodiment 101)

In the touch-screen described in Fig. 3 ~ Fig. 5, formed as described below with substrate 111 in the lump around the insulation course W (hereinafter also referred to " pedestal layer W ") of Y (102a) electrode of described Fig. 4, in addition, formed in the same manner as method described in Japanese Patent Laid-Open 2013-97692 publication, obtain touch-screen of the present invention.And then, use described touch-screen, the display device obtained with touch-screen according to Japanese Patent Laid-Open 2013-97692 publication.

The formation of pedestal layer: the curable adhensive compositions of embodiment 11 is coated on substrate, after carrying out prebake conditions, use extra-high-pressure mercury vapour lamp to expose, utilize alkaline aqueous solution to carry out developing and forming pattern, at 200 DEG C, carry out the heating of 30 minutes, form pedestal layer W.In addition, described pedestal layer to have as touch detection electrodes between the function of interlayer dielectric.

Apply driving voltage to the display device of gained, result is known: show good display characteristic and touch control detection performance, is the device that reliability is high.

(embodiment 102 and embodiment 103)

In embodiment 101, the composition of embodiment 11 is replaced with respectively the composition of embodiment 45, embodiment 48, in addition, utilize the method identical with embodiment 101 to make display device with touch-screen.

(embodiment 201)

In the touch-screen described in Fig. 3 ~ Fig. 5; formed as described below with substrate 11 in the lump around the insulation course W (pedestal layer W) of Y (102a) electrode of described Fig. 4, dielectric film 112 and diaphragm 113; in addition; formed in the same manner as method described in Japanese Patent Laid-Open 2013-97692 publication, obtain touch-screen of the present invention.And then, use described touch-screen, the display device obtained with touch-screen according to Japanese Patent Laid-Open 2013-97692 publication.

In addition, in Fig. 3 ~ Fig. 5,101a and 102a represents cross part, 101b and 102b represents electrode section, and 101X represents the electrode of X-direction, and the electrode of 102 expression Y-directions, 112a represents contact hole, and X represents electrode.

The formation of pedestal layer W, dielectric film 112 and diaphragm 113: by the curable adhensive compositions slot coated of embodiment 11 on substrate; after carrying out prebake conditions; extra-high-pressure mercury vapour lamp is used to expose; alkaline aqueous solution is utilized to carry out developing and forming pattern; at 200 DEG C, carry out the heating of 30 minutes, form each layer.

(embodiment 202 and embodiment 203)

In embodiment 201, the composition of embodiment 11 is replaced with respectively the composition of embodiment 45, embodiment 48, in addition, utilize the method identical with embodiment 201 to make display device with touch-screen.

Claims

1. a curable adhensive compositions, is characterized in that containing:

As at least one be selected from the cohort be made up of following a1 and a2 of composition A,

As at least one be selected from the cohort be made up of following b1 and b2 of composition B,

As the Photoepolymerizationinitiater initiater of composition C, and

As the solvent of components D; And

Relative to the total solid composition of described curable adhensive compositions, the content of described composition A is 40 quality % ~ 90 quality %,

Relative to the total solid composition of described curable adhensive compositions, the content of described composition B is 5 quality % ~ 59 quality %,

Relative to content 100 mass parts of described composition A, following there is the coordinating base of titanium and/or the coordinating base of zirconium and plural ethene unsaturated group compound, be 15 mass parts ~ 140 mass parts with the following total content with the compound of the coordinating base of titanium and/or the coordinating base of zirconium;

A1: titanium compound and/or the zirconium compounds with alkoxy,

2. curable adhensive compositions according to claim 1, the coordinating base of wherein said titanium and/or the coordinating base of zirconium are the group of coordination on titanium atom and/or zirconium atom by oxygen atom.

3. curable adhensive compositions according to claim 1 and 2, the coordinating base of wherein said titanium and/or the coordinating base of zirconium are for having the group of at least one structure in the cohort that is selected from and is made up of following structure: 1,2-diketone structure, 1,3-diketone structure, Isosorbide-5-Nitrae-diketone structure, alpha-alcohol ketone structure, alpha-hydroxy esters structure, α-one base ester structure, beta-keto esters structure, diester malonate structure, dimethyl ester structure and ditridecyl phthalate structure.

4. curable adhensive compositions according to claim 1 and 2, wherein said a2 is the water by being 0.5 times ~ 1.9 times of molar equivalents relative to the integral molar quantity 1.0 moles of titanium atom and zirconium atom, and at least one making to be selected from the cohort be made up of the titanium compound with alkoxy, the zirconium compounds with alkoxy, the titanium compound with halogen radical and the zirconium compounds with halogen radical is hydrolyzed the titanoxane of condensation gained, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product.

5. curable adhensive compositions according to claim 1 and 2, wherein said composition A comprises described a2.

6. curable adhensive compositions according to claim 1 and 2, wherein when described composition B contains described b2, when the content described in the total solid composition relative to described curable adhensive compositions with the compound of the coordinating base of titanium and/or the coordinating base of zirconium is set to BW1 quality %, described in there is the compound of plural ethene unsaturated group content be set to BW2 quality % time, BW1: BW2 is 2: 8 ~ 8: 2.

7. a manufacture method for cured film, it comprises operation 1 ~ operation 5 at least successively,

Operation 1: painting process, is coated on substrate by curable adhensive compositions according to claim 1 and 2;

Operation 2: solvent removal step, except desolventizing from be coated with described curable adhensive compositions;

Operation 3: exposure process, utilizes actinic ray to the exposing at least partially of described curable adhensive compositions eliminating solvent;

Operation 4: developing procedure, utilizes aqueous developer solution to develop to the described curable adhensive compositions through exposure; And

Operation 5: heat treatment step, heat-treats the described curable adhensive compositions through development.

8. a cured film, it curable adhensive compositions according to claim 1 and 2 is hardened form.

9. cured film according to claim 8, it is interlayer dielectric or outer film.

10. cured film according to claim 8 or claim 9, the refractive index under its wavelength 550nm is 1.78 ~ 2.40.

11. 1 kinds of liquid crystal indicators, have cured film according to claim 8 or claim 9.

12. 1 kinds of organic electroluminescence display device and method of manufacturing same, have cured film according to claim 8 or claim 9.

13. 1 kinds of touch-screens, have cured film according to claim 8 or claim 9.

14. 1 kinds of touch panel display devices, have cured film according to claim 8 or claim 9.