CN105404094A - Hardening composition, hardening film and method for manufacturing the same, touch screen and display device - Google Patents

Hardening composition, hardening film and method for manufacturing the same, touch screen and display device Download PDF

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Publication number
CN105404094A
CN105404094A CN201510564456.5A CN201510564456A CN105404094A CN 105404094 A CN105404094 A CN 105404094A CN 201510564456 A CN201510564456 A CN 201510564456A CN 105404094 A CN105404094 A CN 105404094A
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composition
compound
curable adhensive
adhensive compositions
methyl
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中村秀之
柏木大助
藤盛淳一
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Fujifilm Corp
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Fujifilm Corp
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Abstract

The invention provides a hardening composition capable of obtaining a hardening film with high transparency and high in-plane uniformity, the hardening film and a method for manufacturing the same, a touch screen and a display device. The hardening composition of the invention contains: a component A which is a specific titanium-containing compound and/or a zirconic compound; a component B which is a hardening compound; and a component C which is a solvent and contains a component C-1, namely at least an organic solvent with the viscosity of 50mPa*s-200mPa*s at the 20 DEG C and the surface tension of 30mN/m-41mN/m, and a component C-2, namely at least one organic solvent with the viscosity of less than 50mPa*s at the 20 DEG C. Compared with the total mass of the component C, the content of the component C-1 is 20mass%-95mass%, and the viscosity of the hardening composition at the 20 DEG C is 1mPa*s-30mPa*s.

Description

Curable adhensive compositions, cured film and manufacture method thereof, 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
In recent years, transparent hard composition is used in order to form interlayer dielectric, diaphragm, light removing layer, distance piece (spacer) component, lenticule (microlens) component etc.The hardening thing of transparent hard composition gained is used to can be used as the component of the multiple electron devices such as the various display device such as liquid crystal indicator or organic EL display, touch-screen, camera head, solar cell.
In addition, known light extraction efficiency in order to improve organic EL display further or prevent is had an X-rayed the touch detection electrodes of touch-screen etc. and is adjusted the refractive index of transparent hard composition.
As the transparent hard composition of adjusted refractive index, the known composition (such as with reference to patent documentation 1) employing oxidized metal or metal alkoxide.
In addition, as the transparent hard composition of adjusted refractive index there is pattern being formed (patterning) performance, the composition recorded in known patent document 2.
[prior art document]
[patent documentation]
No. 2010/050580th, [patent documentation 1] International Publication
[patent documentation 2] Japanese Patent Laid-Open 2012-203061 publication
Summary of the invention
[inventing problem to be solved]
In recent years, from the viewpoint of province's fluidity, appropriately can be coated with various substrate, seek the composition used when being coated on manufacturing the electron device such as display device or touch-screen by print process.There is the problems such as inner evenness is insufficient in the composition recorded in known patent documentation 1 and patent documentation 2.
Problem to be solved by this invention is to provide a kind of organic EL display, liquid crystal indicator, touch-screen and the touch panel display device that obtain the curable adhensive compositions of the cured film that the transparency is high, inner evenness is high, the cured film that described curable adhensive compositions is hardened and manufacture method thereof and have described cured film.
[technological means of dealing with problems]
Described problem of the present invention is solved by the means described in following <1>, <9> ~ <11> or <14> ~ <17>.Below <2> ~ <8>, <12> and <13> is preferably recorded in the lump.
<1> curable adhensive compositions, wherein contains: be selected from least one in the cohort be made up of following a1 ~ a3, as the hardening compound of composition B and the solvent as composition C as composition A; And composition C contains: be more than 50mPas as the viscosity at 20 DEG C of composition C-1 and below 200mPas and surface tension are more than 30mN/m and at least one organic solvent of below 41mN/m and be less than at least one organic solvent of 50mPas as the viscosity at 20 DEG C of composition C-2, relative to the gross mass of composition C, the content of composition C-1 is 20 quality % ~ 95 quality %, and the viscosity at 20 DEG C of curable adhensive compositions is more than 1mPas and below 30mPas;
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,
A3: the metal oxide containing titanium atom and/or zirconium atom.
The curable adhensive compositions of <2> described in <1>, wherein composition B is polymerizable compound.
The curable adhensive compositions of <3> described in <1> or <2>, wherein composition C-1 contains and is selected from by terpilenol (terpineol), dihydro-terpineol (dihydroterpineol), 4-(acetoxyl group)-α, at least one in the cohort that α, 4-trimethyl-cyclohexane methanol acetic acid ester and 2-[1-methyl isophthalic acid-(4-methyl-3-cyclohexene-1-base) ethoxy] ethanol form.
The curable adhensive compositions that <4> is described any one of <1> to <3>, wherein relative to the gross mass of curable adhensive compositions, the total amount of the solid constituent in described curable adhensive compositions is 2 quality % ~ 15 quality %.
The curable adhensive compositions that <5> is described any one of <1> to <4>, wherein composition B contains the polymerizable compound of more than six senses.
The curable adhensive compositions that <6> is described any one of <1> to <5>, 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, at least one in the cohort that the zirconium compounds with alkoxy and the titanium compound with halogen radical and the zirconium compounds with halogen radical form is hydrolyzed the titanoxane of condensation gained, zirconium oxygen alkane and/or titanoxane-zirconium oxygen alkane condensation product.
The curable adhensive compositions that <7> is described any one of <1> to <6>, wherein composition A comprises described a2.
The curable adhensive compositions that <8> is described any one of <1> to <7>, it contains Photoepolymerizationinitiater initiater as components D.
The manufacture method of a <9> cured film, it comprises operation a ~ operation d at least successively,
Operation a: painting process, is coated on substrate by curable adhensive compositions described any one of <1> to <8>;
Operation b: solvent removal step, except desolventizing from be coated with curable adhensive compositions;
Operation c: exposure process, utilizes actinic ray to the exposing at least partially of curable adhensive compositions eliminating solvent;
Operation d: heat treatment step, heat-treats curable adhensive compositions.
The manufacture method of a <10> 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 <8>;
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.
<11> cured film, it is that curable adhensive compositions sclerosis described any one of <1> to <8> is formed.
The cured film of <12> described in <11>, it is interlayer dielectric or outer film.
The cured film of <13> described in <11> or <12>, the refractive index under its wavelength 550nm is 1.6 ~ 1.9.
<14> liquid crystal indicator, has cured film described any one of <11> to <13>.
<15> organic EL display, has cured film described any one of <11> to <13>.
<16> touch-screen, has cured film described any one of <11> to <13>.
<17> touch panel display device, has cured film described any one of <11> to <13>.
[effect of invention]
According to the present invention, a kind of organic EL display, liquid crystal indicator, touch-screen and the touch panel display device that obtain the curable adhensive compositions of the cured film that the transparency is high, inner evenness is high, the cured film that described curable adhensive compositions is hardened and manufacture method thereof and there is described cured film can be provided.
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 A1-A2 line shown in Fig. 3.
Fig. 5 is the sectional view of the cross-section structure represented along the B1-B2 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
102a: electrode
111: substrate
112: insulation course
113: protective seam
W: insulation course (pedestal layer)
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 connotation 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 ~ a3 will be selected from " etc. referred to as " composition A " etc.
In addition, in the present invention, " quality % " and " % by weight " are synonymous, and " mass parts " and " weight portion " are synonymous.
In addition, in the present invention, preferred implementation be combined as preferred embodiment.
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)
Curable adhensive compositions of the present invention (hereinafter also referred to as " composition ") contains: be selected from least one in the cohort be made up of following a1 ~ a3, as the hardening compound of composition B and the solvent as composition C as composition A; And composition C contains: be more than 50mPas as the viscosity at 20 DEG C of composition C-1 and below 200mPas and surface tension are more than 30mN/m and at least one organic solvent of below 41mN/m and be less than at least one organic solvent of 50mPas as the viscosity at 20 DEG C of composition C-2, relative to the gross mass of composition C, the content of composition C-1 is 20 quality % ~ 95 quality %, and the viscosity at 20 DEG C of curable adhensive compositions is more than 1mPas and below 30mPas.
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,
A3: the metal oxide containing titanium atom and/or zirconium atom.
Curable adhensive compositions of the present invention be suitable for improveing visibility refractive index adjustment layer (index-matched (IndexMatching) layer) or in order to prevent in the purposes such as refractive index adjustment dielectric film or external coating etc. of having an X-rayed.
In touch-screen field, the distributions visible (so-called perspective) such as the visible or tin indium oxide (IndiumTinOxide, ITO) of polymer insulator (insulator) become problem.Refractive index adjustment layer (index matching layer) is used in order to head it off.
In the past, use the index matching layer of sputtering type as index matching layer always, the sputter evaporation layer etc. of such as niobium oxide, but due to material or make expense, therefore studying metal oxides such as giving the titanium dioxide of high index of refraction or zirconia or the metal alkoxide such as alkyl dioxide or alkoxide zirconium or be used as coating fluid and cambial coated form as the titanoxane of these condensation product or zirconium oxygen alkane etc.
The people such as inventor have carried out making great efforts research, result is known, if use the coating fluid of common solvent then can produce following problem: become surface state or the transparency deterioration of gonorrhoea time dry or produce depression fault or distribute in generation face when utilizing flexographic printing or ink jet printing is given.
The people such as the present inventor find, can obtain the curable adhensive compositions that can obtain the cured film that the transparency is high, inner evenness is high, thus complete the present invention by combinationally using specific solvent.
In addition, the performance of detailed impression mechanism is also indefinite, if but obtain the viscosity being suitable for flexographic printing or ink jet printing and the high viscosity solvent using alcohol system, then have because of high viscosity solvent that typically surface tension is high and produces the problem caved in.In addition, if use the high solvent of surface tension, then also exist because of during drying or dry after and substrate phasic property and produce the problem of pin hole (pinhole).And then, also exist with the compatibility of composition A and composition B low, be separated and gonorrhoea when drying, the problem of transparency deterioration.Can inferring, in the present invention, being used as solvent by combinationally using specific solvent, the viscosity of composition improves, and surface tension reduces, and then the generation of the gonorrhoea being separated and occurring thereupon when suppressing dry, but the performance mechanism of detailed impression is indefinite.
The preferred photosensitive composite of curable adhensive compositions of the present invention, can be positive light sensitivity composition, also can be negative photosensitive composition, preferred negative photosensitive composition.
When curable adhensive compositions of the present invention is negative photosensitive composition, preferably composition B is polymerizable compound.
When curable adhensive compositions of the present invention is positive light sensitivity composition, preferably containing, for example lower polymkeric substance and light acid producing agent, described polymkeric substance comprises the structural unit with the group that acidic group is protected by sour decomposability base.In addition, when curable adhensive compositions of the present invention is positive light sensitivity composition, the positive light sensitivity composition (chemically amplified positive photosensitive composite) of preferred chemical amplification type, in addition, also can be the positive light sensitivity composition of use 1,2-quinone di-azido compound as the non-chemically amplification type of the photoactinic smooth acid producing agent of induction.With regard to high sensitivity and the excellent aspect of the transparency, preferred chemically amplified positive photosensitive composite.
In addition, when curable adhensive compositions of the present invention is negative photosensitive composition, preferably after utilizing photoactinic polymerization, heat-treated by hardening things such as the cured films to gained, and the intensity of hardening thing becomes higher composition.
And then, when curable adhensive compositions of the present invention is positive light sensitivity composition, preferably after exposure portion is removed, by heating unexposed portion, and produces cross-linking reaction and harden.
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, refractive index under the wavelength 550nm of the curable adhensive compositions of the present invention preferably hardening thing of gained is the curable adhensive compositions of more than 1.60, and the refractive index under the wavelength 550nm of the more preferably hardening thing of gained is the curable adhensive compositions of more than 1.62.In addition, the refractive index under the wavelength 550nm of the hardening thing of gained preferably less than 1.90, more preferably less than 1.85.
In addition, when without special instruction, refractive index of the present invention is the refractive index of the light of wavelength 550nm at 25 DEG C.
In addition, curable adhensive compositions of the present invention can be suitably used as interlayer dielectric with or outer film curable adhensive compositions.
And then curable adhensive compositions of the present invention can be used as refractive index adjustment layer curable adhensive compositions suitably.
Composition A: be selected from least one in the cohort be made up of a1 ~ a3
Curable adhensive compositions of the present invention contains at least one in the cohort being selected from and being made up of following a1 ~ a3 as composition A, and relative to the total solid composition of curable adhensive compositions, the content of composition A is 40 quality % ~ 80 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,
A3: the metal oxide containing titanium atom and/or zirconium atom.
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 synonymous, described a2 with " there is the titanoxane of the alkoxy of at least one direct bond on titanium atom, there is the 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 of the alkoxy of at least one direct bond on titanium atom or zirconium atom " be synonymous, described a3 is synonymous with " metal oxide containing titanium atom and/or the metal oxide containing zirconium atom ".
Relative to the total solid composition of curable adhensive compositions, the content preferably 15 quality % ~ 90 quality % of composition A.When the refractive index of hardening thing (cured film) is set to 1.60 ~ 1.90, from the viewpoint of refractive index adjustment, more preferably 15 quality % ~ 60 quality %, and then preferably 17.5 quality % ~ 45 quality %, particularly preferably 20 quality % ~ 35 quality %.In addition, when being used as high-index material, from the viewpoint of refractive index adjustment, preferably 40 quality % ~ 90 quality %, more preferably 50 quality % ~ 85 quality %, and then preferred 60 quality % ~ 80 quality %.In addition, " solid constituent " of so-called curable adhensive compositions, represents the composition removing the volatile ingredient gained such as solvent.In addition, described solid constituent also can be and non-solid liquid-like constituents certainly.
Composition A can be the potpourri of independent a1, separately a2, separately a3, a1 and a2, the potpourri of a1 and a3, the potpourri of a2 and a3, the potpourri of a1 and a2 and a3 any one, from the viewpoint of the storage stability of composition, the preferably potpourri of independent a2, separately a3 or a1 and a2, 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, composition A is preferably selected from the cohort be made up of titanium compound, titanoxane and titanium dioxide, in addition, from the viewpoint of hardening at subcritical temerature, setting rate and stability, be preferably selected from the cohort be made up of zirconium compounds, zirconium oxygen alkane and zirconia.
A1: titanium compound and/or the zirconium compounds with alkoxy,
As a1: there is the titanium compound of alkoxy and there is the zirconium compounds of alkoxy, 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 alkyl 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, diisopropoxy two positive fourth 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, diisopropoxy two positive fourth zirconia, 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.
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
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, at least one in the cohort that the titanium compound with halogen radical and the zirconium compounds with halogen radical form 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., its form is not particularly limited, and preferably has titanoxane or the zirconium oxygen alkane of 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.
A3: the metal oxide containing titanium atom and/or zirconium atom
As a3, titanium dioxide, zirconia can be illustrated and comprise the composite oxides of titanium atom and/or zirconium atom.
As the composite oxides comprising titanium atom and/or zirconium atom, preferential oxidation titanium, titanium composite oxide, zirconia or zirconium mixed oxide, more preferably titanium dioxide, titanium composite oxide or zirconia, and then preferential oxidation titanium or zirconia, particularly 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.
As composite oxides, stannic oxide-titanium oxide composite particle, silica-titania composite particle, tin oxide-zirconia composite particle etc. can be illustrated.
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.
A3 also can use commercially available product, such as, can enumerate: the stone as Titanium particles originates in the TTO series (TTO-51 (A), TTO-51 (C) etc.) that industry (stock) manufactures, TTO-S, TTO-V series (TTO-S-1, TTO-S-2, TTO-V-3 etc.), the MT series (MT-01, MT-05 etc.) that Supreme Beingization (Tayca) (stock) manufactures; Ao Pu as stannic oxide-titanium oxide composite particle opens up Rec (Optolake) TR-502, Ao Pu and opens up Rec (Optolake) TR-504; Ao Pu as silica-titania composite particle opens up Rec (Optolake) TR-503, Ao Pu and opens up Rec (Optolake) TR-513, Ao Pu and open up Rec (Optolake) TR-520, Ao Pu and open up Rec (Optolake) TR-521, Ao Pu and open up Rec (Optolake) TR-527 (above change into industry (stock) manufacture for waving catalyzer day); Zirconia particles (high-purity chemical research institute (stock) manufacture); Tin oxide-zirconia composite particle (wave catalyzer day and change into industry (stock) manufacture) etc.
From the viewpoint of the transparency of curable adhensive compositions, the preferred 1nm ~ 200nm of average primary particle diameter of a3, 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, a3 can be also prepare by using the mixing arrangement such as bowl mill, rod mill mix in suitable spreading agent and solvent by a3 to disperse for, described dispersion liquid with the form of dispersion liquid.
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: hardening compound
Curable adhensive compositions of the present invention contains hardening compound as composition B.
Hardening compound is at least any one and the compound hardened by heating, free radical activity kind, cationic species and anion active kind.
Wherein, the compound preferably with epoxy radicals, the compound with oxetanylmethoxy and/or following illustrated polymerizable compound.
< has the compound > of epoxy radicals or oxetanylmethoxy
When curable adhensive compositions of the present invention is positive light sensitivity composition, hardening compound, preferably containing having the compound of epoxy radicals and/or having the compound of oxetanylmethoxy, more preferably contains the compound in the compound in molecule with plural epoxy radicals and/or molecule with plural oxetanylmethoxy.
In addition, when curable adhensive compositions of the present invention is negative photosensitive composition and is hardened by cationic species, polymerizable compound, preferably containing having the compound of epoxy radicals and/or having the compound of oxetanylmethoxy, more preferably contains the compound in the compound in molecule with plural epoxy radicals and/or molecule with plural oxetanylmethoxy.
By heating, there is in molecule the epoxy radicals of the compound of epoxy radicals or oxetanylmethoxy or oxetanylmethoxy reacts each other or react with the acid (carboxylic acid etc.) in composition.In addition, by making itself and cationic species and depositing, and cationic polymerization is caused.
The concrete example in molecule with the compound of epoxy radicals can be enumerated: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin, have the acrylic resin etc. of epoxy radicals at side chain.
So-called acrylic resin, refers to that more than 70 % by mole of structural unit is the polymkeric substance comprising following structural unit.The weight average molecular weight of acrylic resin preferably 3,000 ~ 300,000, more preferably 7,000 ~ 50,000.
[changing 2]
In formula, R 1represent hydrogen atom or methyl, R 2represent hydrogen atom or any monovalent organic radical.
In formula, R 2represent hydrogen atom or any monovalent organic radical, any monovalent organic radical preferably comprises any one of hydrogen atom, carbon atom, oxygen atom and nitrogen-atoms.
The carbon number of described organic group preferably 1 ~ 25, more preferably 1 ~ 15.
These compounds can be used as commercially available product and obtain.Such as can enumerate: JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (holding (MitsubishiChemicalHoldings) (stock) of Mitsubishi Chemical manufactures) etc., the commercially available product etc. recorded in the paragraph 0189 of Japanese Patent Laid-Open 2011-221494 publication, in addition, also can enumerate: for that Cauer (Denacol) EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (changing into (NagaseChemteX) (stock) manufacture for length is rapids above), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above for aurification (stock) manufacture is lived by Nippon Steel) etc.These compounds can be used alone one or combinationally use two or more.
In these, more preferably enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, there is at side chain acrylic resin and the aliphatic epoxy resin of epoxy radicals, particularly preferably enumerate bisphenol A type epoxy resin, alicyclic epoxy resin and there is at side chain the acrylic resin of epoxy radicals.
As the concrete example of compound with oxetanylmethoxy, can use: sub-imperial oxetanes (AronOxetane) OXT-121, OXT-221, OX-SQ, PNOX (above for East Asia synthesis (stock) manufactures), have the acrylic resin of oxetanylmethoxy at side chain.
In addition, the compound of oxygen heterocycle butyl is preferably used alone or mixes with the compound containing epoxy radicals and use.
The preferred concrete example at side chain with the acrylic resin of epoxy radicals or oxetanylmethoxy can illustrate the acrylic resin with following structural unit.In addition, in following structural unit, R represents hydrogen atom or methyl.
[changing 3]
< polymerizable compound >
Curable adhensive compositions of the present invention preferably contains following polymerizable compound as composition B.
Polymerizable compound is not particularly limited, and can use free-radical polymerised compound, cationically polymerizable compound any one, from the preferred free-radical polymerised compound of indurative viewpoint.From the viewpoint preferred cationic polymerizable compound of the transparency.
As long as free-radical polymerised compound has the compound of at least one ethene unsaturated group, preferably terminal ethylene unsaturated group, be then not particularly limited, selection can be suitable in known ethene unsaturated compound and use.
In these, composition B preferably comprises the polymerizable compound of more than six senses, more preferably comprise the ethene unsaturated compound of more than composition B-1: six sense, and then preferably comprise (methyl) propenoic methyl carbamate of more than six senses.
Ethene unsaturated compound more than composition B-1: six sense
Curable adhensive compositions of the present invention preferably contains the ethene unsaturated compound of more than composition B-1: six sense as composition B.Ethene unsaturated compounds more than six senses can illustrate: (methyl) propenoic methyl carbamate more than composition B-1-1: six sense, composition B-1-2: ethene unsaturated compounds more than other six senses.In these, preferably contain composition B-1-1 as composition B.
Below, composition B-1-1 and composition B-1-2 is illustrated.
(methyl) propenoic methyl carbamate more than composition B-1-1: six sense
Curable adhensive compositions of the present invention preferably contains (methyl) propenoic methyl carbamate of more than composition B-1-1: six sense as composition B.
The number of (methyl) acryloxy in (methyl) propenoic methyl carbamates more than six senses preferably more than 8, more preferably more than 10, most preferably more than 12.By being set to such formation, can more effectively play effect of the present invention.
In addition, there is no particular restriction for the upper limit of the number of described (methyl) acryloxy, when not macromolecular structure, and preferably less than 50, more preferably less than 30, and then preferably less than 20.
Curable adhensive compositions of the present invention only can comprise (methyl) propenoic methyl carbamate of more than a kind of six senses, also can comprise two or more.When comprising two or more, total amount is preferably described scope.
(methyl) propenoic methyl carbamate in the present invention more than spendable six senses can illustrate the carbamate addition polymerization compound manufactured by the addition reaction utilizing isocyanates and hydroxyl, can illustrate in Japanese Patent Laid-Open No. Sho 51-37193 publication, Japanese Patent Laid-fair 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication and record such propenoic methyl carbamate class, these records are incorporated in instructions of the present invention.
From the viewpoint of cured film hardness, the molecular weight of (methyl) propenoic methyl carbamates more than six senses preferably 500 ~ 20,000, more preferably 650 ~ 6,000, and then preferably 800 ~ 3,000.
By being set to such formation, can more effectively play effect of the present invention.
(methyl) acryloxy in (methyl) propenoic methyl carbamates more than six senses can be acryloxy, methacryloxy any one, also can be two kinds, from indurative viewpoint, preferred acryloxy.
There is no particular restriction for the number of the amino-formate bond in (methyl) propenoic methyl carbamates more than six senses, and preferably 1 ~ 30, more preferably 1 ~ 20, and then preferably 2 ~ 10, particularly preferably 2 ~ 5, most preferably 2 or 3.
Aliphatics (methyl) propenoic methyl carbamate of (methyl) propenoic methyl carbamates more than six senses preferably more than six senses.
In addition, (methyl) propenoic methyl carbamate more than six senses preferably has isocyanuric acid ring (isocyanuricring) structure.
In addition, (methyl) propenoic methyl carbamates more than six senses preferably comprise there is more than one amino-formate bond core part, be binding on core part and there is the compound of the end section of more than one (methyl) acryloxy, more preferably in described core part, bond has the compound of the described end section of more than 2, and then preferably in described core part bond have the compound of 2 ~ 5 described end sections, particularly preferably being bond in described core part has the compound of 2 or 3 described end sections.
(methyl) propenoic methyl carbamates more than six senses preferably at least has the compound of the group represented by following formula Be-1 or formula Be-2, more preferably at least has the compound of the group represented by following formula Be-1.In addition, (methyl) propenoic methyl carbamate more than six senses more preferably has the compound of the plural group be selected from the cohort that the group represented by following formula Be-1 and the group represented by formula Be-2 form.
In addition, the group represented by described end section preferred following formula Be-1 or formula Be-2 in (methyl) propenoic methyl carbamate more than six senses.
[changing 4]
In formula Be-1 and formula Be-2, R separately represents acrylic or methacrylic acid group, and wave line part divides the binding site represented with other structures.
In addition, (methyl) propenoic methyl carbamates more than six senses preferably at least has the compound of the group represented by following formula Bc-1 or formula Bc-2, more preferably at least has the compound of the group represented by following formula Bc-1.
In addition, the group represented by described core part preferred following formula Bc-1 or formula Bc-2 in (methyl) propenoic methyl carbamate more than six senses.
[changing 5]
In formula Bc-1 and formula Bc-2, L 1~ L 4separately represent the bivalent hydrocanbon radical of carbon number 2 ~ 20, wave line part divides the binding site represented with other structures.
Preferred L 1~ L 4separately represent the alkylidene of carbon number 2 ~ 20, the more preferably alkylidene of carbon number 2 ~ 10, and then the alkylidene of preferred carbon number 4 ~ 8.In addition, described alkylidene also can branch or have ring structure, preferred straight-chain alkyl-sub-.
In addition, (methyl) propenoic methyl carbamate more than six senses particularly preferably is the group represented by formula Bc-1 or formula Bc-2, the compound with 2 or 3 group bonds in the cohort selecting the group represented by free style Be-1 and formula Be-2 to form.
Below, illustrate (methyl) propenoic methyl carbamate of more than six senses that can preferably use in the present invention, but the present invention is not limited to these compounds certainly.
[changing 6]
[changing 7]
[changing 8]
The commercially available product of (methyl) propenoic methyl carbamates more than six senses can illustrate: can Zi Xinzhong village chemical industry (stock) U-6HA, UA-1100H, U-6LPA, U-15HA, U-6H, U-10HA, U-10PA, UA-53H, UA-33H (being registered trademark) of obtaining; Or UA-306H, UA-306T, UA-306I, the UA-510H that can obtain from common prosperity society chemistry (stock); La Luomo (Laromer) UA-9048, UA-9050, the PR9052 that can obtain from BASF (BASF) company; Can from Daicel Austria Ai Bakeli (EBECRYL) how Coase (Daicel-Allnex) (stock) obtains 220,5129,8301, KRM8200,8200AE, 8452 etc.
Composition B-1-2: ethene unsaturated compounds more than other six senses
Also the composition B-1-2 beyond composition B-1-1 can be contained: ethene unsaturated compounds more than other six senses is as composition B in the present invention.Composition B-1-2 can be macromolecule (such as molecular weight is 2, more than 000), also can be and singly measures body (such as molecular weight is less than 2,000, and preferably molecular weight is more than 100 and is less than 2,000), preferably singly measure body.
Composition B-1-2 is (methyl) acrylate compounds preferably, such as, can illustrate dipentaerythritol six (methyl) acrylate.
Composition B-2: the ethene unsaturated compound being less than six senses
Curable adhensive compositions of the present invention not only comprises the ethene unsaturated compound of more than described six senses, also can comprise the ethene unsaturated compound being less than six senses
As long as described B-2 has the compound of the ethene unsaturated group being less than 6, then there is no particular restriction, can be suitable for selecting according to object.Such as can enumerate ester compounds, amide compound, carbamate compounds and other compounds.
The compound with ethene unsaturated group can be monofunctional vinyl's property unsaturated compound, two senses ~ face can any one of multifunctional ethene unsaturated compound, preferably comprise the multifunctional ethene unsaturated compound of two senses ~ face energy, the multifunctional ethene unsaturated compound of more preferably two senses ~ face energy.
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-butylene glycol 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, 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 and dipentaerythritol five (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 the addition reaction utilizing 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.
Monofunctional vinyl's property unsaturated compound can be enumerated: 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, the compound cohort replacing to unsaturated phosphonic acids, styrene, vinyl ether etc. also can be used to replace described unsaturated carboxylic acid.
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 curable adhensive compositions of the present invention, the content of the composition B-1 preferably for gross mass 100 mass parts of composition B is 70 mass parts ~ 100 mass parts, more preferably 75 mass parts ~ 100 mass parts, and then preferably 90 mass parts ~ 100 mass parts, particularly preferably 95 mass parts ~ 100 mass parts.If described embodiment, then more effectively play effect of the present invention.
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 preferably 5 quality % ~ 85 quality % of composition B, more preferably 10 quality % ~ 82.5 quality %, and then preferred 15 quality % ~ 80 quality %.
Composition C: solvent
Curable adhensive compositions of the present invention contains solvent as composition C, and composition C contains: be more than 50mPas as the viscosity at 20 DEG C of composition C-1 and below 200mPas and surface tension is more than 30mN/m and at least one organic solvent of below 41mN/m; And at least one organic solvent of 50mPas is less than as the viscosity at 20 DEG C of composition C-2, relative to the gross mass of composition C, the content of described composition C-1 is 20 quality % ~ 95 quality %.
Curable adhensive compositions of the present invention is preferably prepared into must composition and any component dissolves described later and/or the liquid that is scattered in solvent.
Below, composition C-1 and composition C-2 is illustrated.
Viscosity at composition C-1:20 DEG C is more than 50mPas and below 200mPas and surface tension is more than 30mN/m and at least one organic solvent of below 41mN/m
Curable adhensive compositions of the present invention contains composition C-1.Composition C-1 is the organic solvent that viscosity is higher and surface tension is low.By containing composition C-1, the low composition of surface tension can be obtained while the viscosity improving composition in its entirety.
The viscosity of composition C-1 at 20 DEG C is more than 50mPas and below 200mPas.If the viscosity at 20 DEG C is below 50mPas, then the viscosity of composition in its entirety is low, and inner evenness is poor.In addition, if the viscosity at 20 DEG C is more than 200mPas, then the viscosity of composition in its entirety is too high, inner evenness or depression failure restraint poor.
Preferred 80mPas ~ the 200mPas of the viscosity of composition C-1 at 20 DEG C.
The viscosity of composition C-1 is the value measuring at 20 DEG C and obtain, and specifically, is the RE85L type viscosity meter utilizing eastern machine industry (stock) to manufacture, and uses tapered (cone): 1 ° of 34 ' × R24, measure at liquid temperature 20 DEG C.
The surface tension of composition C-1 is more than 30mN/m and below 41mN/m.If the surface tension of composition C-1 is more than 41mN/m, then the surface tension of composition in its entirety uprises, and can cause depression.In addition, if surface tension is less than 30mN/m, then the too infiltration spread because surface tension is too low, thus produce oozing out of liquid at substrate.
Preferred 30mN/m ~ the 41mN/m of surface tension of composition C-1, more preferably 32mN/m ~ 36mN/m.
The surface tension of composition C-1 is according to Japanese Industrial Standards (JapaneseIndustrialStandards, JIS) K2241, at 20 DEG C, with the Zhang Du of steel wire for index, utilize Du Nuyi (Dunouy) surface tensiometer to measure the tension force of liquid level and platinum loop.
From the viewpoint of coating, the boiling point of composition C-1 preferably 100 DEG C ~ 300 DEG C, more preferably 120 DEG C ~ 250 DEG C, and then preferably 200 DEG C ~ 250 DEG C.
In curable adhensive compositions of the present invention, relative to the gross mass of composition C, the content of composition C-1 is 20 quality % ~ 95 quality %, if the content of composition C-1 is less than 20 quality % relative to the gross mass of composition C, then cannot obtain the viscosity needed for curable adhensive compositions, printability is poor.In addition, if the content of composition C-1 is more than 95 quality %, then viscosity becomes too high sometimes.
In addition, in curable adhensive compositions of the present invention, relative to the gross mass of composition C, the content preferably 30 quality % ~ 95 quality % of composition C-1, more preferably 50 quality % ~ 95 quality %.
In addition, composition C-1 can be used alone one, also can and with two or more.When and with two or more as composition C-1, as long as add up to described content.
As long as composition C-1 is for having described viscosity and capillary solvent is then not particularly limited, preferably there is terpenes (terpene) compound of hydroxyl and/or acetoxyl group (acetoxygroup), more preferably containing being selected from by terpilenol, dihydro-terpineol, 4-(acetoxyl group)-α, at least one in the cohort that α, 4-trimethyl-cyclohexane methanol acetic acid ester and 2-[1-methyl isophthalic acid-(4-methyl-3-cyclohexene-1-base) ethoxy] ethanol form.
Terpilenol exist following α-, β-, γ-isomeride, be by Japanese spices medicine (stock), Japanese terpinene chemistry (stock) commercially available (viscosity is 54mPas, and surface tension is 38mN/m).
[changing 9]
In addition, there are following two kinds of isomeride (1-hydroxyl-to terpane (1-hydroxy-p-menthane) and 8-hydroxyl-to terpane) in dihydro-terpineol, there is dihydro-terpineol by Japanese terpinene chemistry (stock) is commercially available (viscosity is 83mPas, surface tension is 36mN/m), Te Suobu (Terusolve) DTO-210 (viscosity is 72mPas, and surface tension is 36mN/m).
[changing 10]
4-(acetoxyl group)-α, α, 4-trimethyl-cyclohexane methanol acetic acid ester is the compound represented by following formula C-3, as the potpourri with the compound represented by formula C-1 and the compound represented by formula C-2, such as, by Japanese terpinene chemistry (stock) the commercially available Te Suobu of having (Terusolve) THA-90, (viscosity is 144mPas, surface tension is 32.8mN/m), Te Suobu (Terusolve) THA-70 (viscosity is 144mPas, and surface tension is 32.9mN/m).
[changing 11]
2-[1-methyl isophthalic acid-(4-methyl-3-cyclohexene-1-base) ethoxy] ethanol is the compound represented by following formula, such as, by Japanese terpinene chemistry (stock) the commercially available Te Suobu of having (Terusolve) TOE-100 (viscosity is 62mPas, and surface tension is 40.6mN/m).
[changing 12]
In these, composition C-1 of the present invention preferably comprise be selected from by terpilenol, dihydro-terpineol, formula C-1 ~ formula C-3 any one represented by compound and compound in the cohort that forms of 2-[1-methyl isophthalic acid-(4-methyl-3-cyclohexene-1-base) ethoxy] ethanol, more preferably comprise dihydro-terpineol and formula C-1 ~ formula C-3 any one represented by compound, and then the potpourri of compound preferably represented by formula C-1 and the compound represented by formula C-2 and the compound represented by formula C-3.
Viscosity at composition C-2:20 DEG C is less than the organic solvent of 50mPas
In the present invention, be less than the organic solvent of 50mPas containing the viscosity at 20 DEG C as composition C-2.If the viscosity of composition C-2 is more than 50mPas, then the viscosity of composition in its entirety is too high, and therefore inner evenness is poor.
Preferred below the 10mPas of the viscosity of composition C-2 at 20 DEG C, more preferably below 5mPas, and then preferred below 3mPas.In addition, its lower limit is not particularly limited, preferred more than 0.5mPas.
The composition C-2 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, diacetone, ethyl lactate, can particularly preferably illustrate: butanols, 1,3-BDO diacetate esters, diethylene glycol methyl ethyl ether, diacetone, ethyl lactate.
Composition C-2 can be used alone one, also can and with two or more.
From the viewpoint of coating, the boiling point of composition C-2 preferably 100 DEG C ~ 300 DEG C, more preferably 120 DEG C ~ 250 DEG C, and then preferably 120 DEG C ~ 200 DEG C.
From being adjusted to the viewpoint being suitable for the viscosity be coated with, the content of the solvent in curable adhensive compositions of the present invention preferably becomes the mode of 3 quality % ~ 30 quality % with the total solid component amount of curable adhensive compositions and contains.More preferably 5 quality % ~ 20 quality %, and then preferred 8 quality % ~ 15 quality %.That is, preferably total solid composition: total solvent (mass ratio)=8: 92 ~ 30: 70, more preferably 5: 95 ~ 20: 80, and then preferably 8: 92 ~ 15: 85.
Viscosity at 20 DEG C of curable adhensive compositions of the present invention is 1mPas ~ 30mPas.If the viscosity of curable adhensive compositions is less than 1mPas, then viscosity is low, printability is poor.In addition, if viscosity is more than 30mPas, then viscosity is too high, ink-jet ejection or inner evenness poor.
Preferred 5mPas ~ the 30mPas of viscosity at 20 DEG C of curable adhensive compositions of the present invention, more preferably 10mPas ~ 25mPas, and then preferred 10mPas ~ 20mPas.
The RE-80L type rotational viscosimeter that viscosity such as preferably uses eastern machine industry (stock) to manufacture measures at 20 DEG C ± 0.2 DEG C.About rotational speed when measuring, preferably with 1 when viscosity is less than 5mPas, 000rpm ~ 100rpm measures, 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, preferably measures with 10rpm when viscosity is more than 30mPas.
-have the compound of coordinating base-
In the present invention, when using a1 and/or a2, preferably containing there is the compound of the coordinating base of titanium and/or the coordinating base of zirconium as composition A.
" 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 a1 and/or a2, through the titanium atom of coordination 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, 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, the group of at least one structure in the cohort that dimethyl ester structure and ditridecyl phthalate structure form, more preferably has and is 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, alpha-alcohol ketone structure, the group of at least one structure in the cohort that beta-keto esters structure and ditridecyl phthalate structure form, particularly preferably is to have and is selected from by 1,3-diketone structure, the group of at least one structure in the cohort that alpha-alcohol ketone structure and beta-keto esters structure form, most preferably has the group of at least one structure in the cohort being selected from and being made up of 1,3-diketone structure and beta-keto esters structure.If described embodiment, then the refractive index of the cured film of gained and storage stability more excellent.
The coordinating base of 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, formula b-3 or formula b-5, and then preferably there is the group of the structure represented by following formula b-1, formula b-2 or formula b-3, particularly preferably be the group of the structure had represented by following formula b-1 or formula b-2.
[changing 13]
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 14]
In the present invention, the compound with the coordinating base of titanium and/or the coordinating base of zirconium also can be used as composition B and adds, and also can be used as composition C in addition and adds, being not particularly limited, and preferably adds as composition C, particularly preferably is as composition C-2 and adds.
When adding as composition B, there is no particular restriction for ethene unsaturated group, 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.
From the viewpoint of developability, the compound with the coordinating base of titanium and/or the coordinating base of zirconium and ethene unsaturated group preferably has 1, (methyl) acrylate compounds of 3-diketone structure or beta-keto esters structure or there is the ethene unsaturated compound of ditridecyl phthalate structure, more preferably there is (methyl) acrylate compounds of 1,3-diketone structure or beta-keto esters structure.
In addition, the compound with the coordinating base of titanium and/or the coordinating base of zirconium and 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 ethene unsaturated group preferably has (methyl) acrylate compounds of the coordinating base of titanium and/or the coordinating base of zirconium, more preferably there is simple function (methyl) acrylate compounds of the coordinating base of titanium and/or the coordinating base of zirconium, so preferably following shown in compound.
In addition, the ethene unsaturated compound described in ditridecyl phthalate structure preferably can illustrate diallyl phthalate third fat.
[changing 15]
In addition, not there is 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, alpha-hydroxyacetone compounds or beta-keto esters compound, particularly 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 16]
In these compounds, preferred diacetone (2,4-pentanedione), ethyl acetoacetate (ethyl 3-oxobutanoate) or ethyl lactate, particularly preferably diacetone or ethyl acetoacetate.These are applicable to composition C-2.
Relative to total content 100 mass parts of a1 and a2, these have content preferably 15 mass parts ~ 140 mass parts of the compound of coordinating base.
Components D: Photoepolymerizationinitiater initiater
Curable adhensive compositions of the present invention preferably contains Photoepolymerizationinitiater initiater as components D.When curable adhensive compositions of the present invention is negative photosensitive composition, particularly preferably containing Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater preferably comprises optical free radical polymerization initiator.
In the present invention, spendable Photoepolymerizationinitiater initiater is the compound that actinic ray can be utilized to cause, promote to have the polymerization of the polymerizable compounds such as the compound of ethene unsaturated group.
So-called " actinic ray ", as long as giving can produce by components D 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, oxygen base diazole compounds, carbonyls, ketal (ketal) 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 and/or six aryl united imidazole, more preferably oxime ester compounds.
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 D-1 or formula D-2.
[changing 17]
In formula D-1 or formula D-2, Ar represents aromatic series base or heteroaromatic base, R d1represent alkyl, aromatic series base or alkoxy, R d2represent hydrogen atom or alkyl, and then R d2also can tie with Ar base key and form ring.
Ar represents aromatic series base or heteroaromatic base, from phenyl ring, naphthalene nucleus or carbazole ring, preferably removes the group of a hydrogen atom gained, more preferably with R d2form 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 d1represent alkyl, aromatic series base or alkoxy, preferable methyl, ethyl, benzyl, phenyl, naphthyl, methoxy or ethoxy, more preferably methyl, ethyl, phenyl or methoxyl.
R d2represent 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 d1the group of preferred carbon number 1 ~ 30, in addition, R d2the group of preferred carbon number 1 ~ 50.
The compound of oxime ester compound more preferably represented by following formula D-3, formula D-4 or formula D-5, the compound particularly preferably represented by following formula D-5.
[changing 18]
In formula D-3 ~ formula D-5, R d1represent alkyl, aromatic series base or alkoxy, X represents-CH 2-,-C 2h 4-,-O-or-S-, R d3separately represent halogen atom, R d4the amino, arylthio, alkylthio group, alkoxy, aryloxy group or the halogen atom that separately represent alkyl, phenyl, replace through alkyl, R d5represent hydrogen atom, alkyl or aryl, R d6represent alkyl, n1 and n2 separately represents the integer of 0 ~ 6, and n3 represents the integer of 0 ~ 5.
R d1represent alkyl, aromatic series base or alkoxy, preferred R d11the group of-X '-alkylidene-represented.R d11represent alkyl or aryl, X ' expression sulphur atom or oxygen atom.R d11preferred aryl groups, more preferably phenyl.As R d11alkyl and aryl can replace through halogen atom (preferred fluorine atom, chlorine atom or bromine atoms) or alkyl.
The preferred sulphur atom of X.
R d3and R d4can bond on the optional position on aromatic rings.
R d4the 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 d4carbon number preferably 0 ~ 50, more preferably 0 ~ 20.
R d5represent 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 d6represent 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 D-3 or formula D-4 d3replacement number, the R on the aromatic rings of n3 expression D-5 d4replacement 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 19]
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 especially and replace oxazole compounds through trihalomethyl group, 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 AG's manufacture, reach Luo Gu (Darocure) 4265, reach Luo Gu (Darocure) TPO etc.
Acetophenone compound can illustrate gorgeous good solid (IRGACURE) 127 that BASF AG manufactures.
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.
-sensitizer-
In curable adhensive compositions of the present invention, except Photoepolymerizationinitiater initiater, smooth acid producing agent described later, also sensitizer can be added.
Sensitizer absorbs actinic ray or radioactive ray and becomes excited state.The sensitizer and the components D 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.
Composition E: sulfhydryl compound
Curable adhensive compositions of the present invention preferably also contains sulfhydryl compound as composition E.By containing sulfhydryl compound, the hardening thing that storage stability is more excellent, refractive index is higher can be obtained, in addition the good chemical resistance of hardening thing.
Sulfhydryl compound is for having the compound of at least one sulfydryl (-SH) in the molecule.
Sulfhydryl compound can enumerate monofunctional thiol's compound and multifunctional sulfhydryl compound, wherein, from the viewpoint of sensitivity, storage stability and film physical property, and preferred multifunctional sulfhydryl compound.
The sulfydryl of sulfhydryl compound can be one-level sulfydryl, also can be secondary sulfydryl, also can be three grades of sulfydryls, from the viewpoint of sensitivity and chemical-resistant, and preferred one-level sulfydryl or secondary sulfydryl, more preferably secondary sulfydryl.In addition, from the viewpoint of storage stability, preferred secondary sulfydryl or three grades of sulfydryls, more preferably secondary sulfydryl.
The molecular weight of spendable sulfhydryl compound preferably 100 ~ 2,000 in the present invention, more preferably 200 ~ 1,000.
In the present invention, there is no particular restriction for the number of the sulfydryl of spendable sulfhydryl compound, and preferably 1 ~ 20, more preferably 2 ~ 10, and then preferably 2 ~ 6.
-monofunctional thiol's compound-
From ageing stability, deliquescent viewpoint in a solvent, the preferred monofunctional thiol's compound of sulfhydryl compound.Monofunctional thiol's compound preferably molecular weight is the low molecular compound of more than 100, and specifically, preferably molecular weight is 80 ~ 1,000, more preferably 100 ~ 800.
In addition, from the viewpoint of sensitivity, monofunctional thiol's compound preferably has heterocycle, more preferably has thiazole structure.
Monofunctional thiol's compound can enumerate monofunctional aliphatic's sulfhydryl compound, monofunctional, aromatic's sulfhydryl compound etc., and concrete example can be enumerated: the sulfhydryl compound such as mercaptoethanol (mercaptoethanol), mercaprol, Mercaptobutanol, mercapto-propanediol, sulfydryl butylene glycol, hydroxy benzenes mercaptan (hydroxybenzenethiol) and derivant thereof, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 1-phenyl-1H-benzimidazolyl-2 radicals-mercaptan, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene.
In addition, the compound recorded in the paragraph 0086 ~ paragraph 0088 of the compound of record in the paragraph 0097 ~ paragraph 0098 of Japanese Patent Laid-Open 2011-65087 publication, Japanese Patent Laid-Open 2008-299211 publication can be enumerated.
-multifunctional sulfhydryl compound-
In addition, from the viewpoint of sensitivity, storage stability and film physical property, the preferred multifunctional sulfhydryl compound of sulfhydryl compound.Multifunctional sulfhydryl compound can enumerate multifunctional aliphatic sulfhydryl compound, multifunctional aromatic mercapto group compound etc.
In the present invention, so-called " multifunctional sulfhydryl compound ", refers to the compound in molecule with plural sulfydryl.Multi-functional thiol's compound preferably molecular weight is the low molecular compound of more than 100, and specifically, preferably molecular weight is 100 ~ 1,500, more preferably 150 ~ 1,000.
Multifunctional sulfhydryl compound preferably has 2 ~ 10 sulfydryls in molecule, more preferably has 2 ~ 6.
Aliphatics multi-functional thiol compound preferably has the compound of the group represented by plural following formula e-1.
[changing 20]
In formula e-1, R represents hydrogen atom or alkyl, and A represents-CO-or-CH 2-.
Multifunctional sulfhydryl compound preferably has more than 2 and the compound of the group represented by formula e-1 of less than 6, more preferably has more than 2 and the compound of less than 4.
The alkyl of the R in formula e-1 is the alkyl of straight chain, branch or ring-type, the scope of carbon number preferably 1 ~ 16, more preferably 1 ~ 10.The concrete example of alkyl is methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, 2-ethylhexyl etc., preferable methyl, ethyl, propyl group or isopropyl.
The preferred hydrogen atom of R, methyl, ethyl, propyl group or isopropyl, more preferably methyl or ethyl.
In the present invention, multifunctional sulfhydryl compound particularly preferably is the compound represented by following formula e-2 of the group had represented by multiple described formula e-1.
[changing 21]
In formula e-2, R represents hydrogen atom or alkyl, and A represents-CO-or-CH 2-.L represents n valency concatenating group, and n represents the integer of 2 ~ 6.
R in the alkyl of the R in formula e-2 and formula e-1 is synonymous, and preferred scope is also identical.N preferably 2 ~ 4.
The L as n valency concatenating group in formula e-2 such as can enumerate :-(CH 2) mthe bivalence linking bases such as-(m represents the integer of 2 ~ 6); Trimethylolpropane residue and there is three-(CH 2) pthe trivalent concatenating groups such as the isocyanuric acid ring (isocyanuricring) of-(p represents the integer of 2 ~ 6); Tetravalence concatenating group or the pentavalent concatenating groups such as pentaerythrite residue; And the sexavalence concatenating group such as dipentaerythritol residue.
The concrete example of multifunctional sulfhydryl compound such as can enumerate following compound as preferred multi-functional thiol's compound: trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), TEG two (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), pentaerythrite four (mercaptoacetate) (pentaerythritoltetrakis (2-thioglycollate)), pentaerythrite four (3-mercaptobutylate), butylene glycol two (3-mercaptobutylate), 1, two (the 3-sulfydryl butyryl acyloxy) butane of 4-, 1, two (the 3-mercaptobutyl oxygen base) butane of 4-, 1, 3, 5-tri-(3-sulfydryl butoxyethyl group)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone etc.
The commercially available product of multifunctional sulfhydryl compound can enumerate card Lenze MT (KarenzMT) (registered trademark) BD1, NR1 or PE1 (Showa electrician (stock) manufacture), special nurse pik (TEMPIC) (SC organic chemistry (stock) manufacture) etc.
[changing 22]
Other concrete examples can enumerate the compound recorded in the paragraph 0165 ~ paragraph 0167 of Japanese Patent Laid-Open 2012-14052 publication.
Aromatic mercapto group compound can enumerate the compound recorded in the paragraph 0021 ~ paragraph 0022 of No. 2010/050580th, International Publication.Wherein, preferably 4,4 '-thiobisbenzenethiol.
In addition, aromatic mercapto group compound preferably can enumerate the compound represented by formula e-3.
[changing 23]
In formula e-3, X erepresent atom N or C atom, Y erepresent atom N, C atom, S atom or O atom, L erepresent singly-bound or divalent organic base, A erepresent and X e=C-Y eform the atomic group of aromatic rings together.A ethe aromatic rings formed can have the substituting groups such as hydroxyl, ether, ester group, amino, amide group, nitro, cyano group, and then also can have and the different sulfydryl described in formula.
Aromatic mercapto group compound such as can be enumerated: benzenethiol, 4-acetamide benzenethiol, 4-tert-butylbenzenethiol, 2-naphthyl mercaptan, 2-aminobenzene mercaptan, 4-aminobenzene mercaptan, 4-(dimethylamino) benzenethiol, 2-thyroidan, 2-mercaptobenzothiazole, triphenyl methyl mercaptan (triphenylmethanthiol), 5-sulfydryl-1-phenyl-1H-TETRAZOLE, 2-mercaptopyridine, 2-sulfydryl-5-methyl isophthalic acid, 3,4-thiadiazoles, 2-sulfydryl-1,3,4-thiadiazoles, 2-amino-5-sulfydryl-1, monofunctional, aromatic's sulfhydryl compounds such as 3,4-thiadiazoles or
1,2-thioresorcin, 1,3-thioresorcin, Isosorbide-5-Nitrae-thioresorcin, two (mercapto methyl) benzene of 1,2-, two (mercapto methyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(mercapto methyl) benzene, two (mercaptoethyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(mercaptoethyl) benzene, two (sulfydryl methoxyl) benzene of 1,2-, two (sulfydryl methoxyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(sulfydryl methoxyl) benzene, two (sulfydryl ethoxy) benzene of 1,2-, two (sulfydryl ethoxy) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(sulfydryl ethoxy) benzene, 1,2,3-tri-thiol benzene, 1,2,4-tri-thiol benzene, 1,3,5-tri-thiol benzene, 1,2,3-tri-(mercapto methyl) benzene, 1,2,4-tri-(mercapto methyl) benzene, 1,3,5-tri-(mercapto methyl) benzene, 1,2,3-tri-(mercaptoethyl) benzene, 1,2,4-tri-(mercaptoethyl) benzene, 1,3,5-tri-(mercaptoethyl) benzene, 1,2,3-tri-(sulfydryl methoxyl) benzene, 1,2,4-tri-(sulfydryl methoxyl) benzene, 1,3,5-tri-(sulfydryl methoxyl) benzene, 1,2,3-tri-(sulfydryl ethoxy) benzene, 1,2,4-tri-(sulfydryl ethoxy) benzene, 1,3,5-tri-(sulfydryl ethoxy) benzene, 1,2,3,4-tetra-sulfydryl benzene, 1,2,3,5-tetra-sulfydryl benzene, 1,2,4,5-tetra-sulfydryl benzene, 1,2,3,4-tetra-(mercapto methyl) benzene, 1,2,3,5-tetra-(mercapto methyl) benzene, 1,2,4,5-tetra-(mercapto methyl) benzene, 1,2,3,4-tetra-(mercaptoethyl) benzene, 1,2,3,5-tetra-(mercaptoethyl) benzene, 1,2,4,5-tetra-(mercaptoethyl) benzene, 1,2,3,4-tetra-(sulfydryl methoxyl) benzene, 1,2,3,5-tetra-(sulfydryl methoxyl) benzene, 1,2,4,5-tetra-(sulfydryl methoxyl) benzene, 1,2,3,4-tetra-(sulfydryl ethoxy) benzene, 1,2,3,5-tetra-(sulfydryl ethoxy) benzene, 1,2,4,5-tetra-(sulfydryl ethoxy) benzene, 2,2 '-dimercapto biphenyl, 4,4 '-dimercapto biphenyl, 4,4 '-dimercapto bibenzyl, 2,5-first dimercaptobenzene, 3,4-first dimercaptobenzene, Isosorbide-5-Nitrae-naphthyl disulfide alcohol, 1,5-naphthyl disulfide alcohol, 2,6-naphthyl disulfide alcohol, 2,7-naphthyl disulfide alcohol, 2,4-dimethyl benzene-1,3-bis-mercaptan, 4,5-dimethyl benzene-1,3-bis-mercaptan, 9,10-anthracene diformazan mercaptan, 1,3-bis-(p-methoxyphenyl) propane-2,2-bis-mercaptan, 1,3-diphenyl propane-2,2-bis-mercaptan, phenylmethane-1,1-bis-mercaptan, 2,4-bis-(to mercaptophenyl) pentane, two (sulfydryl methyl mercapto) benzene of 1,2-, two (sulfydryl methyl mercapto) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(sulfydryl methyl mercapto) benzene, two (sulfydryl ethylmercapto group) benzene of 1,2-, two (sulfydryl ethylmercapto group) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(sulfydryl ethylmercapto group) benzene, 1,2,3-tri-(sulfydryl methyl mercapto) benzene, 1,2,4-tri-(sulfydryl methyl mercapto) benzene, 1,3,5-tri-(sulfydryl methyl mercapto) benzene, 1,2,3-tri-(sulfydryl ethylmercapto group) benzene, 1,2,4-tri-(sulfydryl ethylmercapto group) benzene, 1,3,5-tri-(sulfydryl ethylmercapto group) benzene, 1,2,3,4-tetra-(sulfydryl methyl mercapto) benzene, 1,2,3,5-tetra-(sulfydryl methyl mercapto) benzene, 1,2,4,5-tetra-(sulfydryl methyl mercapto) benzene, 1,2,3,4-tetra-(sulfydryl ethylmercapto group) benzene, 1,2,3,5-tetra-(sulfydryl ethylmercapto group) benzene, 1,2,4,5-tetra-(sulfydryl ethylmercapto group) benzene, 4,4 '-thiobisbenzenethiol (4,4 '-thiobisbenzenethiol), 2,5-dimercapto-1,3,4-thiadiazole, 2,6-dimercapto purine, the multifunctional aromatic mercapto group compounds such as 1,3,5-triazines-2,4,6-tri-mercaptan.
Sulfhydryl compound only can use one, also can and with two or more.
In addition, from the viewpoint of refractive index, sulfhydryl compound preferably has the sulfhydryl compound of aromatic rings.
And then from the viewpoint of developability, sulfhydryl compound preferably has ester group, thioester substrate (thioestergroup), hydroxyl, amide group, ether, thioether group (thioethergroup) isopolarity functional group in molecule.
From the viewpoint of film physical property, relative to the total solid composition of curable adhensive compositions, content preferably 0.1 mass parts ~ 20 mass parts of sulfhydryl compound, more preferably 0.5 mass parts ~ 15 mass parts, and then preferred 1 mass parts ~ 10 mass parts.
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 24]
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 25]
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 curable adhensive compositions of the present invention, or the cone angle (taperangle) of the film that formed by curable adhensive compositions of the present invention of adjustable and substrate.
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.In addition, be preferably 0.1 mass parts ~ 20 mass parts relative to composition B100 mass parts, more preferably 0.5 mass parts ~ 10 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 (above for BASF AG manufactures).
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: other metal oxide particles
Curable adhensive compositions of the present invention, in order to regulate refractive index or transmitance, can be free of titanium atom and zirconium atom and containing other metal oxide particles.In the metal of other metal oxide particles, also comprise the semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te).
Other metal oxide particles preferred preferably comprise 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), 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 zinc paste, indium/tin-oxide, antimony/tin-oxide.
From the viewpoint of the transparency of curable adhensive compositions, the preferred 1nm ~ 200nm of average primary particle diameter of other metal oxide particles, 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, other metal oxide particles can be used alone one, also can and with two or more.
As long as the content of other metal oxide particles 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 % ~ 50 quality %, more preferably be set as 1 quality % ~ 40 quality %, and then be preferably set as 2 quality % ~ 30 quality %.
In the present invention, other metal oxide particles can be also prepare by using the mixing arrangement such as bowl mill, rod mill mix in suitable spreading agent and solvent by other metal oxide particles 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, the polymkeric substance comprising the structural unit with the group that acidic group is protected by sour decomposability base, light acid producing agent, fluorenes (fluorene) compound, spreading agent, the heterogeneous ring compound with plural nitrogen-atoms.About these compositions, such as, can use composition, other well-known compositions of recording in the composition recorded in Japanese Patent Laid-Open 2009-98616 publication, Japanese Patent Laid-Open 2009-244801 publication, the composition recorded in Japanese Patent Laid-Open 2014-132292 publication paragraph 0203 ~ paragraph 0298, International Publication No. 2014/199967 publication paragraph 0025 ~ paragraph 0050.In addition, also the various ultraviolet light absorber recorded in " the new expansion (daily magazine industry newspaper office (stock)) of polymeric additive " or metal passivator etc. can be added 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 %.
< comprises the polymkeric substance > of the structural unit with the group that acidic group is protected by sour decomposability base
Curable adhensive compositions of the present invention also can contain following polymkeric substance, and described polymkeric substance comprises the structural unit with the group that acidic group is protected by sour decomposability base.
In addition, in the present invention, also " having the structural unit of the group that acidic group is protected by sour decomposability base " is called " structural unit that (a1) has the group that acidic group is protected by sour decomposability base ".
Curable adhensive compositions of the present invention can so that containing following polymkeric substance, described polymkeric substance be comprise the structural unit with the group that acidic group is protected by sour decomposability base polymkeric substance beyond polymkeric substance.
Curable adhensive compositions of the present invention is preferably containing the component of polymer comprising the polymkeric substance of at least one meeting following (1) and (2).
(1) comprise (a1) and there is the polymkeric substance that the structural unit of the group that acidic group is protected by sour decomposability base and (a2) have the structural unit of bridging property base
(2) comprise (a1) there is the polymkeric substance of the structural unit of the group that acidic group is protected by sour decomposability base and comprise the polymkeric substance that (a2) has the structural unit of bridging property base
The polymkeric substance that curable adhensive compositions of the present invention can and then contain beyond these.
From the viewpoint of residual film ratio in the transparency (mist degree) after sclerosis and unexposed portion, curable adhensive compositions of the present invention preferably comprises the composition meeting described (1).In addition, be that the polymkeric substance meeting comprising in the composition of described (1) or described (2) (a2) and have the structural unit of bridging property base is regarded as described composition B in the present invention.
" group that acidic group is protected by sour decomposability base " in the present invention can be used as acidic group and sour decomposability base and well-known group, is not particularly limited.Concrete acidic group can preferably enumerate carboxyl and phenolic hydroxyl group.In addition, sour decomposability base can use than the group being easier to decompose because of acid acetal system functional groups such as () ester structure of the group that such as formula a1-10 described later etc. are represented, oxinane ester group or tetrahydrofuran ester groups or compare group carbonic acid three grades of alkyl ester groups such as () such as three grades of alkyl such as tert-butyl ester base, t-butyl carbonate bases being difficult to decompose because of sour.
In the group that acidic group is protected by sour decomposability base; from the basic physical properties of curable adhensive compositions; the particularly viewpoint of sensitivity or pattern form, the formative of contact hole, the storage stability of curable adhensive compositions, preferably carboxyl is the protection carboxyl protected by the form of acetal.And then, in the group that acidic group is protected by sour decomposability base, from the viewpoint of sensitivity, the protection carboxyl that the form that more preferably carboxyl is the acetal represented by following formula a1-10 is protected.In addition, when the protection carboxyl that the form that carboxyl is the acetal represented by following formula a1-10 is protected, the entirety of protection carboxyl becomes-(C=O)-O-CR 101r 102(OR 103) structure.
[changing 26]
(in formula a1-10, R 101and R 102separately represent hydrogen atom or alkyl, wherein, get rid of R 101with R 102be the situation of hydrogen atom.R 103represent alkyl.R 101or R 102with R 103can link and form cyclic ether)
In described formula a1-10, R 101~ R 103separately represent hydrogen atom or alkyl, described alkyl can be straight-chain, branched, ring-type any one.Here, there is not R 101and R 102both represent the situation of hydrogen atom, R 101and R 102at least one represent alkyl.
The preferred carbon number 1 ~ 12 of alkyl of described straight-chain or branched, more preferably carbon number 1 ~ 6, and then preferred carbon number 1 ~ 4.Specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl), n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl etc.
The preferred carbon number 3 ~ 12 of described cyclic alkyl, more preferably carbon number 4 ~ 8, and then preferred carbon number 4 ~ 6.Described cyclic alkyl such as can be enumerated: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group, norborny, isobornyl etc.
Described alkyl also can have substituting group, and substituting group can illustrate: halogen atom, aryl, alkoxy.When have halogen atom alternatively base, R 101, R 102, R 103become haloalkyl, when have aryl alternatively base, R 101, R 102, R 103become aralkyl.
Described halogen atom can illustrate: fluorine atom, chlorine atom, bromine atoms, atomic iodine, in these, and preferred fluorine atom or chlorine atom.
In addition, the aryl of the preferred carbon number 6 ~ 20 of described aryl, more preferably carbon number 6 ~ 12, specifically can illustrate: phenyl, Alpha-Methyl phenyl, naphthyl etc., as the alkyl entirety, the i.e. aralkyl that are replaced by aryl, benzyl, α-methylbenzyl, phenethyl, naphthyl methyl etc. can be illustrated.
The alkoxy of the preferred carbon number 1 ~ 6 of described alkoxy, more preferably carbon number 1 ~ 4, and then preferred methoxy or ethoxy.
In addition, when described alkyl is naphthenic base, described naphthenic base can have the straight-chain of carbon number 1 ~ 10 or the alkyl alternatively base of branched, when alkyl is the alkyl of straight-chain or branched, can have the naphthenic base alternatively base of carbon number 3 ~ 12.
These substituting groups also can be replaced by described substituting group further.
In described formula a1-10, at R 101, R 102and R 103when representing aryl, the preferred carbon number 6 ~ 12 of described aryl, more preferably carbon number 6 ~ 10.Described aryl can have substituting group, and described substituting group preferably can illustrate the alkyl of carbon number 1 ~ 6.Aryl such as can illustrate: phenyl, tolyl, xylyl, cumenyl, 1-naphthyl etc.
In addition, R 101, R 102and R 103can bond mutually, and together form ring with the carbon atom of these bonds.R 101with R 102, R 101with R 103, or R 102with R 103ring structure during bond such as can be enumerated: cyclobutyl, cyclopentyl, cyclohexyl, suberyl, tetrahydrofuran base, adamantyl and THP trtrahydropyranyl etc.
In addition, in described formula a1-10, preferably R 101and R 102any one be hydrogen atom or methyl.There is about other concrete comprising the polymkeric substance of the structural unit of the group that acidic group is protected by sour decomposability base, also preferably can use the polymkeric substance comprising the structural unit with the group that acidic group is protected by sour decomposability base recorded in Japanese Patent Laid-Open 2014-238438 publication paragraph 0037 ~ paragraph 0101.
< light acid producing agent >
Curable adhensive compositions of the present invention can contain light acid producing agent.When curable adhensive compositions of the present invention is positive light sensitivity composition, preferably containing light acid producing agent.
The light acid producing agent used in the present invention preferably responds to the actinic ray of more than wavelength 300nm, preferably wavelength 300nm ~ 450nm and acidic compound, but does not limit by its chemical constitution.In addition, about directly not responding to photoactinic smooth acid producing agent of more than wavelength 300nm, if by being used for responding to the actinic ray of more than wavelength 300nm and acidic compound with sensitizer, then preferably use after also can combining with sensitizer.As the light acid producing agent used in the present invention, preferably produce the light acid producing agent that pKa is the acid of less than 4, more preferably produce the light acid producing agent that pKa is the acid of less than 3, most preferably produce the light acid producing agent that pKa is the acid of less than 2.
The example of light acid producing agent can be enumerated: trichloromethyl-s-triazine, sulfonium salt Huo Iodonium salt, quarternary ammonium salt class, diazomethane compound, acid imide sulfonate compound and oxime sulfonate compounds etc.In these, from the viewpoint of sensitivity, preferably use acid imide sulfonate compound or oxime sulfonate compounds.These light acid producing agents can be used alone one or be used in combination of two or more.The concrete example of trichloromethyl-s-triazine, two fragrant base Iodonium salts, triaryl matte salt (such as following compound), quarternary ammonium salt class and diazomethane derivative can illustrate: in the paragraph 0083 ~ paragraph 0088 of Japanese Patent Laid-Open 2011-221494 publication record compound or Japanese Patent Laid-Open 2011-105645 publication paragraph 0013 ~ paragraph 0049 in record compound, described content is incorporated in instructions of the present invention.The concrete example of acid imide sulfonate compound can illustrate the compound recorded in the paragraph 0065 ~ paragraph 0075 of No. 2011/087011st, International Publication, described content is incorporated in instructions of the present invention.
The concrete example of oxime sulfonate compounds can illustrate: the compound recorded in the paragraph 0074 ~ paragraph 0102 of Japanese Patent Laid-Open 2014-122972 publication, the paragraph 0103 ~ paragraph 0133 of Japanese Patent Laid-Open 2014-238438 publication, is incorporated to described content in instructions of the present invention.
In curable adhensive compositions of the present invention, relative to total solid composition 100 mass parts in curable adhensive compositions, content preferably 0.1 mass parts ~ 20 mass parts of light acid producing agent, more preferably 0.5 mass parts ~ 10 mass parts, and then preferred 0.5 mass parts ~ 5 mass parts.Light acid producing agent only can use one, also can and with two or more.
The 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)
Hardening thing of the present invention is the hardening thing that curable adhensive compositions of the present invention is hardened.In addition, hardening thing of the present invention preferably cured film.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 a ~ operation d successively.
Operation a: curable adhensive compositions of the present invention is coated on the painting process on substrate
Operation b: except the solvent removal step of desolventizing from be coated with curable adhensive compositions
Operation c: utilize actinic ray to the exposure process exposed at least partially of curable adhensive compositions eliminating solvent
Operation d: the heat treatment step that curable adhensive compositions is heat-treated
In addition, the manufacture method of cured film of the present invention 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 the manufacture method of cured film comprising operation a ~ operation d, developing procedure becomes any operation, can illustrate the situation that the situation such as refractive index adjustment layer being located at the one side on base material etc. is formed without the need to pattern.
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, can enumerate and comprise following synthetic resin: 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, episulfide resin etc.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 slot coated method, spray-on process, rolling method, method of spin coating, cast coating method, slit and the method such as rotary process, print process (ink-jet, soft version, intaglio plate, half tone etc.).Print process can concentrate on necessary position to arrange composition, can realize province's liquefaction of composition, therefore preferably.
In these, curable adhensive compositions of the present invention is suitable for print process, is particularly suitable for flexographic printing process and ink jet printing method.
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.
When curable adhensive compositions is negative photosensitive composition, described exposure process preferably uses actinic ray, polymerization initiation kind is produced by Photoepolymerizationinitiater initiater, and carry out the polymerization of the polymerizable compounds such as the compound with ethene unsaturated group, make the operation of hardening at least partially of the curable adhensive compositions eliminating solvent.
In addition; when curable adhensive compositions is positive light sensitivity composition; utilize actinic ray and produce acid from light acid producing agent; thus the protecting group comprising the polymkeric substance of the structural unit with the group that acidic group is protected by sour decomposability base is decomposed; become the polymkeric substance comprising the structural unit with acidic group, the dissolubility thus in aqueous developer solution improves.
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/cm 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; The aqueous solution of sodium silicate, sodium metasilicate etc.In addition, also 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 can be used as 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 liquid method of covering (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 exposure process, comprises the operation of heat-treating curable adhensive compositions.By heat-treating after by curable adhensive compositions exposure 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 ~ 250 DEG C.If described embodiment, then estimate when using a1 and/or a2 as composition A, the condensation of composition A suitably occurs, 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 can before rear baking, after utilizing actinic ray to carry out exposing (post-exposure) again to the figuratum substrate of formation, carry out rear baking comprehensively, infer thus to be produced by composition A condensation reaction each other and/or the Photoepolymerizationinitiater initiater that remains in exposed portion because of thermal decomposition and to cause kind, and as promoting that the catalyzer of cross-linking process step plays function, thus can promote that film hardens.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.
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 display 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 as the interlayer dielectric in display device etc. or outer film suitable.
When for the interlayer dielectric between touch detection electrodes or diaphragm; from visibility improvement viewpoint, the refractive index of cured film preferably close to the refractive index of electrode, specifically; refractive index preferably under wavelength 550nm is 1.60 ~ 1.90, more preferably 1.62 ~ 1.85.
(liquid crystal indicator)
The feature of liquid crystal indicator of the present invention is to have 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 picture elements 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)
The feature of organic EL display of the present invention is to have 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, is formed with the state covering described TFT1 and comprise Si 3n 4dielectric film 3.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 Al, 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.
(capillary mensuration)
Surface tension is according to JISK2241, and utilizes Du Nuyi (Dunouy) surface tensiometer to measure at 20 DEG C.
(mensuration of viscosity)
RE85L type viscosity meter (the rotor title: tapered 1 ° of 34 ' × R24 measures utilizing eastern machine industry (stock) to manufacture.Liquid temperature is set to 20 DEG C.
The various compositions used in embodiment and comparative example are as described below.
(composition A)
A-1: titanoxane, B-4, Japanese Cao Da (stock) manufacture, solid constituent is 98 quality %
A-2: four positive fourth titanium dioxide and the pure pharmaceutical worker's industry (stock) of light manufacture
A-3: originally refine (MatsumotoFineChemical) (stock) manufacture, solid constituent of zirconium oxygen alkane, ZA-65, pine is 87 quality % (butanols is 13 quality %)
(composition B)
B-1: propenoic methyl carbamate, 15 official's energy, U-15HA, Xin Zhong village chemical industry (stock) manufacture
B-2: propenoic methyl carbamate, 15 official's energy, UA-32P, Xinghe (Kowa) (stock) manufacture
B-3: dipentaerythritol acrylate, DPHA, Japanese chemical drug (stock) manufacture
B-4: tetramethylol methane tetraacrylate, A-TMMT, Xin Zhong village chemical industry (stock) manufacture
(composition C)
C-1-1: the terpilenol C potpourri of following three kinds (Japanese terpinene chemistry (stock) manufactures)
C-1-2: the dihydro-terpineol potpourri of following two kinds (Japanese terpinene chemistry (stock) manufactures)
C-1-3: Te Suobu (Terusolve) DTO-210 (Japanese terpinene chemistry (stock) manufactures, dihydro-terpineol (1-hydroxyl-potpourri) to terpane and 8-hydroxyl-to terpane)
C-1-4: Te Suobu (Terusolve) THA-90 potpourri of following three kinds (Japanese terpinene chemistry (stock) manufactures)
C-1-5: Te Suobu (Terusolve) THA-70 potpourri of following three kinds (Japanese terpinene chemistry (stock) manufactures)
C-1-6: Te Suobu (Terusolve) TOE-100 (Japanese terpinene chemistry (stock) manufacture, following compound)
[changing 27]
(comparative example)
C '-1-1:PGMEA (propylene glycol methyl ether acetate) (Daicel (Daicel) (stock) manufactures)
C '-1-2: Hai Suobu (Hisolve) EDE (diethylene glycol diethyl ether) (eastern nation chemical industry (stock) manufacture)
C '-1-3:MEDG (diethylene glycol ethyl methyl ether) (eastern nation chemical industry (stock) manufacture)
C '-1-4: Hai Suobu (Hisolve) EPH (ethyleneglycol monophenylether) (eastern nation chemical industry (stock) manufacture)
C '-1-5: tetrahydrofurfuryl alcohol (manufacturing with the pure pharmaceutical worker's industry (stock) of light)
C '-1-6: the dihydroterpinyl methyl ether potpourri of following two kinds (Japanese terpinene chemistry (stock) manufactures)
C '-1-7: Te Suobu (Terusolve) MTPH (isobornyl cyclohexanol) (Japanese terpinene chemistry (stock) manufactures)
(other)
C-2-1: Hai Suobu (Hisolve) EDE (diethylene glycol diethyl ether, viscosity at 20 DEG C: 1.47mPas, eastern nation chemical industry (stock) manufacture)
C-2-2: diacetone (viscosity at 20 DEG C: 0.6mPas and the pure pharmaceutical worker's industry (stock) of light manufacture)
[changing 28]
(components D)
D-1: gorgeous good solid (IRGACURE) CGI-242 (1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-ketoxime-O-acetic acid esters, Ciba (CibaSpecialtyChemicals) company manufacture)
(other)
KBM-5103:3-acryloxypropyl trimethoxy silane, SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture
(embodiment 1)
The making > of < curable adhensive compositions
As described belowly to be prepared.
A-1:B-4 (titanoxane, Japanese Cao Da (stock), solid constituent are 98 quality %): 2.60 parts
B-1: propenoic methyl carbamate (U-15HA, 15 officials' energy, Xin Zhong village chemical industry (stock) manufacture): 2.16 parts
B-2: propenoic methyl carbamate (UA-32P, 15 officials' energy, Xinghe (Kowa) (stock) manufacture): 2.16 parts
C-1-1: terpilenol C (Japanese terpinene chemistry (stock) manufactures): 80 parts
C-2-1: Hai Suobu (Hisolve) EDE (eastern nation chemical industry (stock) manufacture): 10 parts
C-2-2: diacetone (manufacturing with the pure pharmaceutical worker's industry (stock) of light): 2.86 parts
D-1: gorgeous good solid (IRGACURE) OXE-02 (BASF AG's manufacture): 0.30 part
F-1: Mei Jiafa (Megafac) F-554 (non-ionic surfactant, Di Aisheng (DIC) (stock) manufacture containing perfluoroalkyl): 0.004 part
Utilize magnetic stirring apparatus (magneticstirrer) that described composition is stirred 1 hour, utilize the teflon filtrator in 0.3 μm, aperture to filter, obtain the curable adhensive compositions of embodiment 1.
(embodiment 2 ~ embodiment 6 and comparative example 1 ~ comparative example 8)
The C-1-1 of embodiment 1 is changed to each solvent described in table 1, and change addition according to table 1, in addition, carry out similarly to Example 1 and obtain curable adhensive compositions.
(embodiment 7)
B-1 and B-2 of embodiment 2 is changed to B-3 respectively, in addition, carries out similarly to Example 2 and obtain curable adhensive compositions.
(embodiment 8)
The addition of A-1 in embodiment 4 is changed to 3.25 parts, in addition, carries out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 9)
The addition of Te Suobu (Terusolve) THA-90 is changed to 60 parts, in addition, carries out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 10)
A-1 is changed to A-2, in addition, carries out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 11)
A-1 is changed to A-3, and changes the amount of C-1 and C-2-1 added as was the case with table 1, in addition, carry out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 12)
Do not use C-2-2, and the addition of Te Suobu (Terusolve) THA-90 is changed to 90 parts, in addition, carry out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 13)
B-1 and B-2 of embodiment 4 is changed to B-4 respectively, in addition, carries out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 14)
The addition of terpilenol C in embodiment 1 is changed to 32 parts, and then, the addition of Hai Suobu (Hisolve) EDE is changed to 4 parts, in addition, carries out similarly to Example 1 and obtain curable adhensive compositions.
(embodiment 15)
The addition of Te Suobu (Terusolve) THA-90 in embodiment 4 is changed to 100 parts, and then, the addition of Hai Suobu (Hisolve) EDE is changed to 12.5 parts, in addition, carries out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 16)
Relative to composition total solid component amount and add the KBM-5103 of 1 quality %, in addition, carry out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 17)
The preparation > of < titanium dioxide dispersion liquid 1
Allocate the dispersion liquid of following composition, itself and zirconium oxide bead (0.3mm φ) 17,000 part are mixed, and uses the dispersion that coating vibrator (paintshaker) carries out 12 hours.Isolated by filtration zirconium oxide bead (0.3mm φ), obtains dispersion liquid.
Titania (stone originates in industry (stock) manufacture, trade name: TTO-51 (A), average primary particle diameter: 10nm ~ 30nm): 1,875 parts
Spreading agent (Di Sipabike (DISPERBYK)-111,100% product): 660 parts
Solvent (PGMEA, propylene glycol methyl ether acetate): 1,710 parts
In addition, the composition used is as described below.
TTO-51 (A): titania, stone originate in industry (stock) manufacture, average primary particle diameter is 10nm ~ 30nm, surface treatment kind: Al (OH) 3
Di Sipabike (DISPERBYK)-111: there is the macromolecule dispersing agent of more than one phosphate ester structure, Bi Ke chemistry (BYK-Chemie) company manufactures
Become the mode of same ratio with the content of content of titanium dioxide and A-1, A-1 is changed to described titanium dioxide dispersion liquid, and by the quantitative change of added C-2-1 more 6.47 parts, in addition, carry out similarly to Example 4 and obtain curable adhensive compositions.
(embodiment 18)
By the quantitative change of terpilenol C in embodiment 1 more 115 parts, and then, by the quantitative change more 115 parts of C-2-1 (Hai Suobu (Hisolve) EDE), in addition, carry out similarly to Example 1 and obtain curable adhensive compositions.
(embodiment 19)
By the quantitative change of dihydro-terpineol in embodiment 2 more 115 parts, and then, by the quantitative change more 115 parts of C-2-1 (Hai Suobu (Hisolve) EDE), in addition, carry out similarly to Example 2 and obtain curable adhensive compositions.
(embodiment 20)
By the quantitative change more 115 parts of Te Suobu (Terusolve) DTO-210 in embodiment 3, and then, by the quantitative change more 115 parts of C-2-1 (Hai Suobu (Hisolve) EDE), in addition, carry out similarly to Example 3 and obtain curable adhensive compositions.
(comparative example 9)
In example 4, the addition of Te Suobu (Terusolve) THA-90 is changed to 15 parts, and then, the addition of Hai Suobu (Hisolve) EDE is changed to 65 parts, in addition, carry out similarly to Example 4 and obtain curable adhensive compositions.
(comparative example 10)
In example 4, the addition of Te Suobu (Terusolve) THA-90 is changed to 90 parts, and then, do not add Hai Suobu (Hisolve) EDE, in addition, carry out similarly to Example 4 and obtain curable adhensive compositions.
[table 1]
(evaluation of curable adhensive compositions)
As described below made curable adhensive compositions to be evaluated.Evaluation result is gathered and is shown in Table 2.
In addition, when utilizing flexographic printing to be coated with, be use flexible printing machine (model A45, Na Kang (NAKAN) (stock) manufactures) as printing machine.On the glass substrate (trade name: XG, healthy and free from worry (Coming) company manufacture) of 300mm × 400mm, anilox roll (aniloxroll) #400 is used to carry out printed vulcanized property composition.In addition, when utilizing spin coater to be coated with, be use the glass substrate of 10cm × 10cm (trade name: XG, Corning Incorporated manufacture).
When ink jet printing, be use ink-jet printer (inkjetprinter) (manufacture of moral wheat Tekes (Dimatix) company, DMP-281 printer), the glass substrate (trade name: XG, Corning Incorporated manufacture) of 10cm × 10cm is coated with curable adhensive compositions.
< substrate gonorrhoea >
On the glass substrate (trade name: XG, Corning Incorporated manufacture) of 10cm × 10cm, become the mode spin coating curable adhensive compositions of 100nm with dry film thickness, utilize the oven drying (prebake conditions) 100 seconds of 90 DEG C.Film on the substrate of visual observations gained, evaluates by following benchmark.If gonorrhoea is less, then refers to and can obtain the more excellent film of the transparency.If be evaluated as 1 or 2, then practical upper and no problem, more preferably 1.
5: the desciccator diaphragm gonorrhoea of whole of substrate
4: the desciccator diaphragm that substrate is whole gonorrhoea slightly
3: the gonorrhoea slightly of the desciccator diaphragm about the half of substrate
2: the desciccator diaphragm gonorrhoea slightly of a part for substrate
1: desciccator diaphragm is without gonorrhoea
< caves in fault >
On the glass substrate (trade name: XG, Corning Incorporated manufacture) of 10cm × 10cm, become the mode spin coating curable adhensive compositions of 100nm with dry film thickness, utilize the oven drying (prebake conditions) 100 seconds of 90 DEG C.Film in the substrate entirety of visual observations gained on substrate, evaluates by following benchmark.If be evaluated as 1 or 2, then practical upper and no problem, more preferably 1.
1: do not produce depression
2: produce more than 1 and be less than the depression of 3
3: produce more than 3 and be less than the depression of 10
4: the depression producing more than 10
Film thickness uniformity > in < face
In glass substrate (trade name: XG, Corning Incorporated manufactures) on, the mode becoming 100nm with dry film thickness utilizes spin coating, flexographic printing, ink jet printing to be coated with curable adhensive compositions, utilizes the oven drying (prebake conditions) 100 seconds of 90 DEG C.Thereafter, use extra-high-pressure mercury vapour lamp, 150mJ/cm is carried out to whole face 2exposure (illumination is 24mW/cm 2), utilize thereafter baking oven to heat 30 minutes at 200 DEG C.
Measure of spread in the face of 64 places being carried out to thickness, as described belowly evaluates.
1: in face, be distributed as 100nm ± below 5nm
2: in face, distribution is more than 100nm ± 5nm and be 100nm ± below 10nm
3: in face, distribution is more than 100nm ± 10nm and be 100nm ± below 20nm
4: in face, distribution is more than 100nm ± 20nm
5: distribute without the need to measuring in face, and on substrate, there is coated portion and uncoated part
< chemical-resistant evaluates >
On the glass substrate (trade name: XG, Corning Incorporated manufacture) of 10om × 10cm, become the mode spin coating curable adhensive compositions of 100nm with dry film thickness, utilize the oven drying (prebake conditions) 100 seconds of 90 DEG C.Thereafter, use extra-high-pressure mercury vapour lamp, 150mJ/cm is carried out to whole face 2exposure (illumination is 24mW/cm 2), utilize thereafter baking oven to heat 30 minutes at 200 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.
5: survival rate is less than 80%
4: survival rate is more than 80% and is less than 90%
3: survival rate is more than 90% and is less than 95%
2: survival rate is more than 95% and is less than 98%
1: survival rate is more than 98% and less than 100%
< evaluating pencil hardness >
On the glass substrate (trade name: XG, Corning Incorporated manufacture) of 10cm × 10cm, become the mode spin coating curable adhensive compositions of 100nm with dry film thickness, utilize the oven drying (prebake conditions) 100 seconds of 90 DEG C.Thereafter, use extra-high-pressure mercury vapour lamp, 150mJ/cm is carried out to whole face 2exposure (illumination is 24mW/cm 2), utilize thereafter baking oven to heat 30 minutes at 200 DEG C.The pencil hardness of the cured film of gained is measured according to JISK5600-5-4:1999.
< refractive index evaluates >
On the Silicon Wafer of 10cm × 10cm, become the mode spin coating curable adhensive compositions of 500nm with dry film thickness, utilize the oven drying (prebake conditions) 100 seconds of 90 DEG C.Thereafter, use extra-high-pressure mercury vapour lamp, 150mJ/cm is carried out to whole face 2exposure (illumination is 24mW/cm 2), utilize thereafter baking oven to heat 30 minutes at 200 DEG C.
Use ellipsometer (ellipsometer) VUV-VASE (fertile blue (J.A.WoollamJapan) (stock) of Japanese J.A. manufactures), at 25 DEG C, measure the refractive index of the cured film under 550nm.
[table 2]
(embodiment 21)
The preparation > of < titanium dioxide dispersion liquid 2
Allocate the dispersion liquid of following composition, it is mixed with zirconium oxide bead (0.3mm φ) 100.0 parts, and uses coating vibrator to carry out the dispersion of 12 hours.Isolated by filtration zirconium oxide bead (0.3mm φ), obtains dispersion liquid.
Titania (stone originates in industry (stock) manufacture, trade name: TTO-51 (C), average primary particle diameter: 10nm ~ 30nm): 25.0 parts
Spreading agent: 25.0 parts
Solvent (PGMEA, propylene glycol methyl ether acetate): 50.0 parts
In addition, the composition used is as described below.
TTO-51 (C): titania, stone originate in industry (stock) manufacture, average primary particle diameter is 10nm ~ 30nm, surface treatment kind: Al (OH) 3, carry out stearic acid process
Spreading agent: use following compound 1 (molecular weight Mw=13,800, solid constituent be 30% PGMEA solution)
[changing 29]
In addition, in compound 1, with the sulphur atom of polymer chain bond can with the monomeric unit bond of P1, also can with the monomeric unit bond of P2.
< has the synthesis > of the polymkeric substance (polymkeric substance-1) of the group that acidic group is protected by sour decomposability base
In following synthesis example, following abbreviation represents following compound respectively.
V-601: dimethyl-2,2 '-azo two (propionic acid 2-methyl esters)
GMA: glycidyl methacrylate
PGMEA: propylene glycol methyl ether acetate
The synthesis > of < polymkeric substance-1 (K-1)
The mixed solution of following compositions is heated to 70 DEG C under nitrogen flowing:
Methacrylic acid tetrahydrofuran-2-base ester (63.2 parts (0.405 molar equivalent)),
Methacrylic acid (8.2 parts (0.095 molar equivalent)),
Methacrylic acid (3-Ethyloxetane-3-base) methyl esters (69 parts (0.375 molar equivalent)),
2-hydroxyethyl methacrylate (16.3 parts (0.125 molar equivalent)) and
Propylene glycol methyl ether acetate (PGMEA) (120 parts).One side stirs described mixed solution, the one side mixed solution dripping radical polymerization initiator (V-601: dimethyl-2,2 '-azo two (propionic acid 2-methyl esters) and pure pharmaceutical worker's industry (stock) manufacture of light, 12.0 parts) and PGMEA (80 parts) for 3.5 hours.After dropping terminates, react 2 hours at 70 DEG C, obtain the PGMEA solution of polymkeric substance-1 thus.And then, add PGMEA and solid component concentration is adjusted to 40 quality %.
The polymkeric substance-1 of gel permeation chromatography (GPC) to gained is utilized to measure and the weight average molecular weight (Mw) obtained is 15,000.
The synthesis > of < light acid producing agent 1
In the aaerosol solution of beta naphthal (10g), chlorobenzene (30mL), add aluminum chloride (10.6g), 2-chlorpromazine chloride (10.1g), react 2 hours after mixed liquor being heated to 40 DEG C.Under ice cooling, 4, in reactant liquor, drip the HCl aqueous solution (60mL) of 4N, then add ethyl acetate (50mL) to carry out separatory.Sal tartari (19.2g) is added in organic layer, react at 40 DEG C after 1 hour, the HCl aqueous solution (60mL) of adding 2N carries out separatory, after organic layer is concentrated, utilize diisopropyl ether (10mL) by crystallization more slurried (reslurry), then carry out filtering, dry and obtain ketonic compound (6.5g).
In the aaerosol solution of obtained ketonic compound (3.0g), methyl alcohol (30mL), add acetic acid (7.3g), 50 quality % aqueous hydroxylamine solutions (8.0g), and carry out heating backflow.After placing cooling, add water (50mL), separated out crystallization is filtered, after utilizing cold methanol to clean, in addition dry and obtain oxime compound (2.4g).
Obtained oxime compound (1.8g) is dissolved in acetone (20mL), adds triethylamine (1.5g), paratoluensulfonyl chloride (2.4g) under ice cooling, 4, react 1 hour after being warming up to room temperature.Water (50mL) is added in reactant liquor, after separated out crystallization is filtered, utilize methyl alcohol (20mL) slurried again, then carry out filtering, dry and obtain the compound (following structure) (2.3g) of B-1.
In addition, B-1 1h-NMR spectrum (300MHz, CDCl 3) be δ=8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).
[changing 30]
The making > of < curable adhensive compositions
As described belowly to be prepared.
A-3: described titanium dioxide dispersion liquid 2:3.0 part
K-1: described polymkeric substance-1 solution: 2.5 parts
C-1: terpilenol C (Japanese terpinene chemistry (stock) manufactures): 48.5 parts
C-2: propylene glycol methyl ether acetate (Daicel (stock) manufacture): 45.0 parts
L-1: described smooth acid producing agent 1:0.075 part
M-1:1-cyclohexyl-3-(2-morpholinyl ethyl) thiocarbamide (DSP five assists food and chemistry (DSPGOKYOFOOD & CHEMICAL) (stock)): 0.0007 part
O-1: ancient Sol (OGSOL) PG-100 difficult to understand (epoxy-fluorene derivative, Osaka aerochemistry (stock) manufacture): 0.37 part
O-2: ancient Sol (OGSOL) BPEF difficult to understand (two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9,9-, fluorenes system monomer, Osaka aerochemistry (stock) manufacture): 0.29 part
G-1: uncommon Qwest A-187 silane (SilquestA-187SILANE) (γ-glycidoxypropyltrimewasxysilane, figure new high-tech material (MomentivePerformanceMaterials) (stock) advanced in years manufacture): 0.065 part
G-2:KBE-846 (two (tri-ethoxy silylpropyl) four thioether, SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture): 0.12 part
B-1: Sai Luo West Germany (Celloxide) 2021P (3 ', 4 '-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, Daicel (stock) manufacture): 0.022 part
P-1:1,3-methylimidazole alkane-2-ketone (manufacturing with the pure pharmaceutical worker's industry (stock) of light): 0.056 part
F-1: Mei Jiafa (Megafac) F-554 (containing the non-ionic surfactant of perfluoroalkyl, Di Aisheng (DIC) (stock) manufactures): 0.0032 part
Utilize magnetic stirring apparatus that described composition is stirred 1 hour, utilize the teflon filtrator in 0.3 μm, aperture to filter, obtain the curable adhensive compositions of embodiment 21.
(embodiment 22 ~ embodiment 26, embodiment 29, embodiment 30 and comparative example 11 ~ comparative example 13)
C-1, C-2 of embodiment 21 are changed to each solvent described in table 3, and, change addition according to table 3, in addition, carry out similarly to Example 21 and obtain curable adhensive compositions.
(embodiment 27 and embodiment 28)
C-1 and C-2 of embodiment 21 is changed to each solvent described in table 3, and then, change the addition of solvent in the mode of the composition solid composition becoming table 3, in addition, carry out similarly to Example 21 and obtain curable adhensive compositions.
(embodiment 31)
C-1 and C-2 of embodiment 21 is changed to each solvent described in table 3, and then, titanium dioxide dispersion liquid 2 is changed to following Zirconium oxide dispersion liquid, in addition, carries out similarly to Example 21 and obtain curable adhensive compositions.
The preparation > of < Zirconium oxide dispersion liquid
The titanium dioxide of titanium dioxide dispersion liquid 2 described in embodiment 21 is changed to following zirconia (UPE-100, first rare element chemistry industry (stock) manufacture), in addition, carry out dispersion treatment in the same manner as titanium dioxide dispersion liquid 2 and obtain Zirconium oxide dispersion liquid.
For the curable adhensive compositions of gained, carry out similarly to Example 1 caving in, substrate gonorrhoea, the evaluation of film thickness uniformity, chemical-resistant, refractive index and pencil hardness in face.
In addition, about the evaluation of film thickness uniformity, chemical-resistant and pencil hardness in opposite, except not exposing, evaluate similarly to Example 1.
[table 4]
(embodiment 32)
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 the electrode Y (electrode 102a) 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 4 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 33)
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 (pedestal layer W) of the electrode Y (electrode 102a) of described Fig. 4, insulation course 112 and protective seam 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.
The formation of pedestal layer W, insulation course 112 and protective seam 113: by the curable adhensive compositions slot coated of embodiment 4 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.
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.

Claims (17)

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 ~ a3 of composition A,
As the hardening compound of composition B, and
As the solvent of composition C; And
Composition C contains: be more than 50mPas as the viscosity at 20 DEG C of composition C-1 and below 200mPas and surface tension are more than 30mN/m and at least one organic solvent of below 41mN/m and be less than at least one organic solvent of 50mPas as the viscosity at 20 DEG C of composition C-2
Relative to the gross mass of composition C, the content of composition C-1 is 20 quality % ~ 95 quality %,
Viscosity at 20 DEG C of curable adhensive compositions is more than 1mPas and below 30mPas;
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,
A3: the metal oxide containing titanium atom and/or zirconium atom.
2. curable adhensive compositions according to claim 1, wherein composition B is polymerizable compound.
3. curable adhensive compositions according to claim 1 and 2, wherein composition C-1 contains and is selected from by terpilenol, dihydro-terpineol, 4-(acetoxyl group)-α, at least one in the cohort that α, 4-trimethyl-cyclohexane methanol acetic acid ester and 2-[1-methyl isophthalic acid-(4-methyl-3-cyclohexene-1-base) ethoxy] ethanol form.
4. curable adhensive compositions according to claim 1 and 2, wherein relative to the gross mass of curable adhensive compositions, the total amount of the solid constituent in described curable adhensive compositions is 2 quality % ~ 15 quality %.
5. curable adhensive compositions according to claim 1 and 2, wherein composition B contains the polymerizable compound of more than six senses.
6. 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 and 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.
7. curable adhensive compositions according to claim 1 and 2, wherein composition A comprises described a2.
8. curable adhensive compositions according to claim 1 and 2, it contains Photoepolymerizationinitiater initiater as components D.
9. a manufacture method for cured film, it comprises operation a ~ operation d at least successively,
Operation a: painting process, is coated on substrate by curable adhensive compositions according to claim 1 and 2;
Operation b: solvent removal step, except desolventizing from be coated with curable adhensive compositions;
Operation c: exposure process, utilizes actinic ray to the exposing at least partially of curable adhensive compositions eliminating solvent; And
Operation d: heat treatment step, heat-treats curable adhensive compositions.
10. 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 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; And
Operation 5: heat treatment step, heat-treats the curable adhensive compositions through development.
11. 1 kinds of cured films, it curable adhensive compositions according to claim 1 and 2 is hardened form.
12. cured films according to claim 11, it is interlayer dielectric or outer film.
13. cured films according to claim 11, the refractive index under its wavelength 550nm is 1.6 ~ 1.9.
14. 1 kinds of liquid crystal indicators, have cured film according to claim 11.
15. 1 kinds of organic electroluminescence display device and method of manufacturing same, have cured film according to claim 11.
16. 1 kinds of touch-screens, have cured film according to claim 11.
17. 1 kinds of touch panel display devices, have cured film according to claim 11.
CN201510564456.5A 2014-09-09 2015-09-07 Hardening composition, hardening film and method for manufacturing the same, touch screen and display device Pending CN105404094A (en)

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