CN105319849A - Photosensitive composition for forming shading board, shading board and display device - Google Patents

Photosensitive composition for forming shading board, shading board and display device Download PDF

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Publication number
CN105319849A
CN105319849A CN201510354198.8A CN201510354198A CN105319849A CN 105319849 A CN105319849 A CN 105319849A CN 201510354198 A CN201510354198 A CN 201510354198A CN 105319849 A CN105319849 A CN 105319849A
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China
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methyl
shadow shield
photosensitive composite
antioxidant
mass parts
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白土香织
新美优嗣
森下聪
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JSR Corp
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JSR Corp
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Abstract

The invention relates to a photosensitive composition for forming a shading board, the shading board and a display device. The photosensitive composition is white, is well designed, has high solvent resistance, and is suitable for forming the shading board. The photosensitive composition for forming the shading board contains a white pigment (A), a binding resin (B), a polymerized compound (C) and a photopolymerization initiator (D), wherein the photopolymerization initiator (D) contains at least one photopolymerization initiator selected from an O-acyl-oxime photopolymerization initiator, an alpha-amino-alkyl-benzophenone photopolymerization initiator, an acyl-phosphine-oxide photopolymerization initiator and a titanocene photopolymerization initiator.

Description

Shadow shield is formed by photosensitive composite, shadow shield and display device
Technical field
The present invention relates to shadow shield formation photosensitive composite, shadow shield and display device, more specifically, relate to for the formation of the photosensitive composite of the middle shadow shields used such as portable digital terminal, the shadow shield using this photosensitive composite to be formed and the display device possessing this shadow shield.
Background technology
In recent years, in the various portable digital display device such as smart mobile phone, tablet terminal, touch panel is popularized rapidly as location input device, and the capacitive multi-point touch display that mainly can carry out multiple multi-point touch operations becomes main flow.For capacitive touch panel, in order to can't see wiring lead from user side, have studied the technology (for example, referring to patent documentation 1) be hidden in by wiring lead after light shield layer.
But the nowadays miniaturization of desired display device, lightness, therefore have studied the width of constriction light shield layer (also referred to as shadow shield).Now, light shield layer is mainly formed with screen printing mode, but because following reason, forms the pattern difficulty of fine.That is, easily occur when method for printing screen has that spreading and sinking in of distribution is oozed, friction etc. or form distribution row (joining Line ラ イ Application) time between distribution row, produce bubble and become that display frame is etched, the problem of the reason of corrosion wire breakage and so on.
Therefore, have studied use photosensitive composite and form light shield layer by photoetching.Such as, in patent documentation 2 ~ 3, propose the technology using the photosensitive composite being dispersed with black pigment to form black light shield layer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 5199913 instructions
Patent documentation 2: Japanese Unexamined Patent Publication 2012-145699 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2013-205474 publication
Summary of the invention
In the past, from the viewpoint of light-proofness, light shield layer is generally black, but in recent years along with the change of hobby, the light shield layer of demand white sometimes.In order to present white, Chinese white such as, is used to replace black pigment to prepare photosensitive composite in patent documentation 2 ~ 3, but when using this photosensitive composite to form white light shield layer, due to the xanthochromia of the resinous principle that thermal conductance causes, whiteness (whiteness) is declined.In recent years in order to make touch panel part integration; sometimes transparency electrode, the diaphragm of touch panel is formed on the upper strata of light shield layer; but through the heating of more than 250 DEG C when forming transparency electrode, cause the obvious xanthochromia of resinous principle, the white light shield layer therefore making whiteness high is more and more difficult.
In addition, need to etch etc. metal film after forming light shield layer, therefore also require that the material of light shield layer has chemical resistance.
Urgent expectation provides a kind of and meets the photosensitive composite as above all requiring characteristic.
Therefore, problem of the present invention is to provide a kind of whiteness high and chemical resistance and light-proofness excellence, the applicable photosensitive composite forming shadow shield.Further, problem of the present invention is to provide a kind of shadow shield using this photosensitive composite to be formed and the display device possessing this shadow shield.
The present inventor etc., through further investigation, found that by using specific Photoepolymerizationinitiater initiater, can solve above-mentioned problem.
That is, the invention provides a kind of shadow shield formation photosensitive composite, wherein, containing (A) Chinese white, (B) resin glue, (C) polymerizable compound and (D) Photoepolymerizationinitiater initiater,
(D) Photoepolymerizationinitiater initiater contains at least a kind of Photoepolymerizationinitiater initiater be selected from O-acyl oxime system Photoepolymerizationinitiater initiater, alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters.
In addition, the invention provides a kind of shadow shield using this photosensitive composite to be formed and the display device possessing this shadow shield.
Use photosensitive composite of the present invention, the high and shadow shield of chemical resistance and light-proofness excellence of whiteness can be formed.
Therefore, photosensitive composite of the present invention is suitable for making the display device being representative with the portable digital such as smart mobile phone, tablet terminal display device very much.
Embodiment
First, the main term used in the present invention is described.
(light shield layer (shadow shield))
Light shield layer has following function, distribution, control circuit etc. that the peripheral part being namely hidden in the position surveyed area (touch panel portion) of display device central authorities has, makes it can not be in sight, does not damage the outward appearance of display device thus.Therefore, light shield layer is required to the light-proofness being used for hiding unwanted parts.
(white)
In the present invention, white is defined as CIELAB (L *a *b *colour system) in, lightness index (L *) be more than 80 and chromaticity index (a *, b *) be greater than ﹣ 5 respectively and be less than 5 color.L *a *b *above-mentioned three attributes of colour system can utilize the commercially available mensuration such as spectral photometric colour measuring meter, spectrophotometer.
(xanthochromia)
Xanthochromia refers to that object absorbs the light of a large amount of wavelength 380 ~ 550nm, especially wavelength 400 ~ 450nm in roughly visible region, and result causes being included in a large number in object color as the yellow component of its complementary color.L *a *b *in colour system, if b *be more than 5, then can identify xanthochromia by visualization.Should illustrate, a *represent redness or the green of object, irrelevant with the degree of xanthochromia.
Next, the present invention is described in detail.
Shadow shield formation photosensitive composite
-(A) Chinese white-
As the Chinese white used in photosensitive composite of the present invention, such as, can select from calcium carbonate, ceruse, barium carbonate, barium sulphate, lead sulfate, lead phosphate, trbasic zinc phosphate, titanium dioxide, aluminium oxide, silicon dioxide, zinc paste, antimony oxide, zirconia, tin oxide, zinc sulphide, strontium sulfide, strontium titanates, barium tungstate, metasilicic acid lead, talcum, porcelain earth, clay, bismoclite, calcium hydroxide, hollow silica etc.
As Chinese white, such as, can enumerate color index (C.I.; TheSocietyofDyersandColourists corporation issues) in be classified as the compound of pigment, be namely endowed the compound that following color index (C.I.) is numbered.
C.I. Pigment white 1, C.I. Pigment white 2, C.I. Pigment white 3, C.I. Pigment white 4, C.I. Pigment white 5, C.I. Pigment white 6, C.I. Pigment white 6:1, C.I. Pigment white 7, C.I. Pigment white 8, C.I. Pigment white 10, C.I. Pigment white 11, C.I. Pigment white 12, C.I. Pigment white 13, C.I. Pigment white 14, C.I. Pigment white 15, C.I. Pigment white 16, C.I. Pigment white 17, C.I. Pigment white 18, C.I. Pigment white 18:1, C.I. Pigment white 19, C.I. Pigment white 20, C.I. Pigment white 21, C.I. Pigment white 22, C.I. Pigment white 23, C.I. Pigment white 24, C.I. Pigment white 25, C.I. Pigment white 26, C.I. Pigment white 27, C.I. Pigment white 28, C.I. Pigment white 30, C.I. Pigment white 32, C.I. Pigment white 33.
These Chinese whites also can use after other the metal process of its surface aluminium oxide, siloxane etc.
In these Chinese whites, from the viewpoint of obtaining the high light shield layer of light-proofness, preferably containing at least a kind that is selected from titanium dioxide and strontium titanates.The crystal formation of titanium dioxide is preferably rutile-type.
The mean grain size of Chinese white is generally 100 ~ 700nm, from the viewpoint of the storage stability of light-proofness and photosensitive composite, is preferably 180 ~ 500nm, is more preferably 200 ~ 400nm, more preferably 250 ~ 400nm.Here, " mean grain size " refers to the major diameter being determined at 100 primary particles existed in the observation visual field of transmission electron microscope, calculates their mean value and the value obtained.
Do not depart from the scope of purport of the present invention, in photosensitive composite of the present invention, also can be used together other the colorant beyond Chinese white.As other such colorant, red pigment, yellow uitramarine, blue pigment, viridine green, violet pigment, black pigment etc. can be enumerated.
In the present invention, also other pigment of Chinese white and mixing arbitrarily can be carried out refining rear use by recrystallization method, reprecipitation method, solvent cleaning method, sublimed method, vaccum heating method or their combination.In addition, these pigment can use after its improving particle surface with resin as required.As the resin of the improving particle surface by pigment, such as, can enumerate the resin of vector resin or the commercially available various pigment dispersions recorded in Japanese Unexamined Patent Publication 2001-108817 publication.In addition, organic pigment uses after so-called salt mill can be utilized to make primary particle miniaturization.As the method for salt mill, such as, method disclosed in Japanese Unexamined Patent Publication 08-179111 publication can be adopted.
In addition in the present invention, also can contain known spreading agent and dispersing aid with Chinese white further together with any other pigment mixed.
As known spreading agent, such as, can enumerate carbamate system spreading agent, polyethyleneimine system spreading agent, polyoxyethylene alkyl ether system spreading agent, polyoxyethylene alkyl phenyl ether system spreading agent, polyethylene glycol di system spreading agent, sorbitan fatty acid ester system spreading agent, Polyester spreading agent, (methyl) dispersant containing acrylic, phosphate system spreading agent etc.As commercially available product, such as, Disperbyk-2000 can be used, Disperbyk-2001, Disperbyk-182, Disperbyk-184, BYK-LPN6919, BYK-LPN21116, (methyl) dispersant containing acrylics such as BYK-LPN21324 (being BYK-Chemie (BYK) Inc. above), Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (being BYK-Chemie (BYK) Inc. above), the carbamate system spreading agents such as Solsperse76500 (Lubrizol Co., Ltd. system), the polyethyleneimine system spreading agents such as Solsperse24000 (Lubrizol Co., Ltd. system), AdisperPB821, AdisperPB822, AdisperPB880, the Polyester spreading agents such as AdisperPB881 (being AjinomotoFine-Techno Co., Ltd. system above), Disperbyk-110, the phosphate system spreading agents such as Disperbyk-180.
Wherein, as spreading agent, from the viewpoint of raising storage stability, be preferably selected from least a kind in (methyl) dispersant containing acrylic, phosphate system spreading agent, carbamate system spreading agent and Polyester spreading agent, be more preferably selected from least a kind in (methyl) dispersant containing acrylic and phosphate system spreading agent.
In addition, from the viewpoint of raising storage stability, spreading agent or the amine value of preferred dispersants to be acid number be 10 ~ 200mgKOH/g are the spreading agent of 20 ~ 200mgKOH/g.Acid number is more preferably 50 ~ 180mgKOH/g, more preferably 60 ~ 180mgKOH/g, is further preferably 80 ~ 150mgKOH/g.From the viewpoint of the storage stability of dispersible pigment dispersion and solidification compound, amine value is more preferably 40 ~ 200mgKOH/g, more preferably 60 ~ 180mgKOH/g, is further preferably 70 ~ 150mgKOH/g.On the other hand, from the viewpoint of forming the high shadow shield of whiteness, amine value is preferably 20 ~ 150mgKOH/g, is more preferably 20 ~ 80mgKOH/g.Here, the mg number of the KOH during " acid number " represents in the present invention and needed for 1g spreading agent solid constituent, the mg number of the HCl during " amine value " represents and needed for 1g spreading agent solid constituent and the KOH of equivalent.
In the present invention, spreading agent may be used singly or as a mixture of two or more.When mixing two or more use, preferably at least containing (methyl) dispersant containing acrylic, containing of (methyl) dispersant containing acrylic is proportional relative to spreading agent entirety preferably more than 50 quality %, is more preferably more than 70 quality %.By becoming such mode, easily obtain the photosensitive composite that storage stability is more excellent.
In the present invention, the content of spreading agent, relative to Chinese white and other total 100 mass parts of colorant arbitrarily used, is generally 0.5 ~ 50 mass parts, is preferably 2 ~ 30 mass parts, is more preferably 3 ~ 20 mass parts.By becoming such mode, the photosensitive composite of excellent storage stability can be formed.
In addition as above-mentioned dispersing aid, pigment derivative etc. can be enumerated.As pigment derivative, specifically, the sulfonic acid etc. of copper phthalocyanine, diketopyrrolopyrrolecocrystals, quinophthalone can be enumerated.
From the viewpoint of the shadow shield forming light-proofness excellence, Chinese white and other the total content of colorant arbitrarily used are 10 ~ 80 quality % usually in the solid constituent of photosensitive composite, be preferably 30 ~ 75 quality %, be more preferably 40 ~ 70 quality %, be particularly preferably 50 ~ 70 quality %.Here solid constituent refers to the composition beyond solvent described later.
During colorant together with Chinese white and with other, other colorant be preferably below 20 mass parts containing proportional relative to Chinese white 100 mass parts, be more preferably below 10 mass parts, more preferably below 5 mass parts.
-(B) resin glue-
As (B) resin glue in the present invention, be not particularly limited, preferably there is the resin of at least a kind of functional group be selected from acidic functionality and cyclic ether group.As acidic functionality, such as, can enumerate sulfo group, carboxyl, phosphate, phenolic hydroxyl group etc.In addition, as cyclic ether group, preferably having oxygen atom as the heteroatomic saturated heterocyclyl forming heterocycle forms the saturated heterocyclyl that the atomicity of ring is 3 ~ 7, such as, can enumerate epoxy ethyl, oxetanylmethoxy, ester ring type epoxy radicals, tetrahydrofuran base etc.Here, the epoxy radicals that " ester ring type epoxy radicals " refers to bonding 1 oxygen atom between 2 carbon atoms adjacent in the carbon atom forming ester ring type structure and formed, such as, can enumerate 3,4-epoxycyclohexyls, 3,4-epoxy three ring [5.2.1.0 2,6] decane-8-base, 3,4-epoxy three ring [5.2.1.0 2,6] decane-9-base etc.
Wherein, as (B) resin glue, preferably there is the polymkeric substance of carboxyl, there is the polymkeric substance of carboxyl and cyclic ether group.
It is (following that the polymkeric substance with carboxyl such as can enumerate the ethylenically unsaturated monomers of the carboxyl with more than 1, also referred to as " unsaturated monomer (b1) ") with other can multipolymer, the hydrolytic condensate of silane compound that makes to comprise polymkeric substance that the ethylenically unsaturated monomers with hydroxyl reacts as polymkeric substance and the multi-anhydride of monomeric unit and obtain, comprise the silane monomer with carboxyl of ethylenically unsaturated monomers (hereinafter also referred to as " unsaturated monomer (b2) ") of copolymerization.
As unsaturated monomer (b1), such as can enumerate (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate (2-(methyl) acrylyl oxy-ethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc.
Unsaturated monomer (b1) may be used singly or as a mixture of two or more.
In addition, as unsaturated monomer (b2), such as, can enumerate:
As the N-position substituted maleimide amine of N-phenylmaleimide, N-N-cyclohexylmaleimide and so on;
As styrene, α-methyl styrene, 4-Vinyl phenol, aromatic ethenyl compound to hydroxy-alpha-methyl styrene, acenaphthylene and so on;
As (methyl) alkyl acrylate of (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA and so on;
As hydroxy alkyl (methyl) acrylate of (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester and so on;
As (methyl) acrylate of the unsaturated alcohol of (methyl) vinyl acrylate, (methyl) allyl acrylate and so on;
As (methyl) benzyl acrylate of (methyl) phenyl acrylate, (methyl) benzyl acrylate and so on;
As (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate and so on (methyl) acrylate with ester ring type alkyl;
As (methyl) acrylate of the polyvalent alcohol of polyglycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, single (methyl) acrylate of polyglycol (degree of polymerization 2 ~ 10), single (methyl) acrylate of polypropylene glycol (degree of polymerization 2 ~ 10), glycerine list (methyl) acrylate and so on;
As cyclohexyl vinyl ether, isoborneol vinyl ether, three ring [5.2.1.0 2,6] decane-8-base vinyl ether, pentacyclopentadecandimethanol base vinyl ether, 3-(ethyleneoxy methyl)-3-Ethyloxetane and so on vinyl ether;
As fragrant and mellow (methyl) acrylate of ethylene-oxide-modified (methyl) acrylate and so on of (methyl) acrylic acid 4-hydroxylphenyl ester, p-cumylphenol;
As the macromonomer at the end of polymer molecular chain with list (methyl) acryloyl group of polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane and so on.
In addition as above-mentioned multi-anhydride, the acid anhydrides of the dibasic acid such as maleic anhydride, fumaric acid anhydride, itaconic anhydride, THPA, methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride, NA acid anhydrides can be enumerated; One acid anhydride of the polyprotonic acid more than ternary acids such as trimellitic anhydride; The dianhydride of the polyprotonic acid more than tetra-atomic acids such as cyclopentanetetracarboxylic's dianhydride, pyromellitic acid anhydride.
Wherein, as the polymkeric substance with carboxyl, the multipolymer of preferred unsaturated monomer (b1) and unsaturated monomer (b2), in this situation, as unsaturated monomer (b2), preferably containing (methyl) benzyl acrylate.Should illustrate, unsaturated monomer (b2) may be used singly or as a mixture of two or more.
In addition, as the polymkeric substance with carboxyl and cyclic ether group, such as can enumerate the ethylenically unsaturated monomers (hereinafter also referred to as " unsaturated monomer (b3) ") that comprises unsaturated monomer (b1) and the there is cyclic ether group multipolymer as unit cell; The part making to comprise the epoxy ethyl that the ethylenically unsaturated monomers with epoxy ethyl has as this multipolymer in the multipolymer of unit cell is reacted with unsaturated monomer (b1), then the multipolymer reacting with multi-anhydride and obtain; Comprise the hydrolytic condensate of the silane compound of the silane monomer with carboxyl and the silane monomer with cyclic ether group, above-mentioned multipolymer can have unsaturated monomer (b2) further as unit cell.As cyclic ether group, preferred epoxy ethyl, oxetanylmethoxy, ester ring type epoxy radicals, more preferably epoxy ethyl, oxetanylmethoxy.
As the ethylenically unsaturated monomers with epoxy ethyl, such as can enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate glycidol ether, (methyl) acrylic acid 2-hydroxy propyl ester glycidol ether, (methyl) acrylic acid 3-hydroxy propyl ester glycidol ether, (methyl) acrylic acid 4-hydroxybutyl glycidol ether, polyethylene glycol-propylene glycol (methyl) acrylate glycidol ether etc. has (methyl) acrylate of glycidyl, vinylbenzyl glycidyl ether etc. is had to the aromatic ethenyl compound of glycidyl.
As the ethylenically unsaturated monomers with ester ring type epoxy radicals, such as, can enumerate compound that following general formula (1) represents, (methyl) acrylate that compound etc. that compound that following general formula (2) represents, following general formula (3) represent has ester ring type epoxy radicals.
As the ethylenically unsaturated monomers with oxetanylmethoxy, such as, can enumerate 3-((methyl) acryloyloxymethyl) oxetanes, (methyl) acrylate that 3-((methyl) acryloyloxymethyl)-3-Ethyloxetane etc. has oxetanylmethoxy.
As the ethylenically unsaturated monomers with tetrahydrofuran base, such as, can enumerate (methyl) acrylate that base (methyl) acrylic acid tetrahydro furfuryl ester etc. has tetrahydrofuran base.
Unsaturated monomer (b3) may be used singly or as a mixture of two or more.
(in formula (1),
R 1represent hydrogen atom or methyl,
X 1represent singly-bound or can containing alkane two base of heteroatomic carbon number 1 ~ 6.〕
(in formula (2) and formula (3),
R 2represent hydrogen atom or methyl independently of each other,
X 2represent singly-bound or can containing alkane two base of heteroatomic carbon number 1 ~ 6 independently of each other.〕
X 1and X 2in alkane two base of carbon number 1 ~ 6 can be straight-chain also can be branched.As concrete example, such as, can enumerate methylene, ethylidene, ethane-1,1-bis-base, propane-1,1-bis-base, propane-1,2-bis-base, propane-1,3-bis-base, propane-2,2-bis-base, butane-1,2-bis-base, butane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,4-bis-base, pentane-1,5-bis-base, hexane-1,5-bis-base, hexane-1,6-bis-base etc.Wherein, alkane two base of preferred carbon number 1 ~ 4, more preferably alkane two base of carbon number 1 or 2.
Alkane two base of above-mentioned carbon number 1 ~ 6 can contain heteroatoms.As heteroatoms, such as, can enumerate oxygen atom, sulphur atom, nitrogen-atoms etc., as containing so heteroatomic alkane two base, (*)-CH can be enumerated 2cH 2-O-, (*)-CH 2-O-CH 2-, (*)-CH 2cH 2-S-, (*)-CH 2-S-CH 2-, (*)-CH 2cH 2-NH-, (*)-CH 2-NH-CH 2-etc.Wherein (*) represents the binding site with-COO-.
As the compound that formula (1) represents, methacrylic acid 3,4-epoxycyclohexanecarboxylate (trade name CyclomerM100, DAICEL chemical industry Co., Ltd. system can be enumerated; R in formula (1) 1for methyl, X 1compound for methylene), acrylic acid 3,4-epoxycyclohexanecarboxylate (trade name CyclomerA400, DAICEL chemical industry Co., Ltd. system; R in formula (1) 1for hydrogen atom, X 1compound for methylene).
As the compound that formula (2) represents, the compound etc. that formula (2-1) ~ (2-8) represents can be enumerated.
As the compound that formula (3) represents, the compound etc. that formula (3-1) ~ (3-8) represents can be enumerated.
Wherein, as unsaturated monomer (b3), consider from chemical-resistant viewpoint, (methyl) acrylate preferably with glycidyl, (methyl) acrylate with ester ring type epoxy radicals, there is (methyl) acrylate of oxetanylmethoxy, more preferably the compound that (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, formula (2-1) represent compound, formula (3-1) represent.
In the multipolymer of unsaturated monomer (b1) with unsaturated monomer (b2), the copolymerization ratios of the unsaturated monomer (b1) in this multipolymer is preferably 5 ~ 50 quality %, is more preferably 10 ~ 40 quality %.By making unsaturated monomer (b1) copolymerization with such scope, the photosensitive composite of alkali development and excellent storage stability can be obtained.
As the concrete example of unsaturated monomer (b1) with the multipolymer of unsaturated monomer (b2), such as, can enumerate multipolymer disclosed in Japanese Unexamined Patent Publication 7-140654 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-31308 publication, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 11-258415 publication, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2004-101728 publication etc.
In the present invention; such as; as open in Japanese Unexamined Patent Publication 5-19467 publication, Japanese Unexamined Patent Publication 6-230212 publication, Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 9-325494 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 2008-181095 publication etc., also can be used in side chain and there is the carboxylic polymkeric substance of the polymerism unsaturated links such as (methyl) acryloyl group as resin glue.
In addition, there is unsaturated monomer (b1) and unsaturated monomer (b3) as in the multipolymer of unit cell, the copolymerization ratios of the unsaturated monomer (b1) in this multipolymer is preferably 5 ~ 40 quality %, be more preferably 10 ~ 25 quality %, unsaturated monomer (b1) is preferably 1/9 ~ 7/3 by quality ratio with the copolymerization ratios (b1/b3) of unsaturated monomer (b3), is more preferably 3/7 ~ 6/4.By making unsaturated monomer (b1) and unsaturated monomer (b3) copolymerization with such ratio, on the basis of improving alkali development and storage stability, light-proofness, chemical resistance can be improved.
(B) resin glue in the present invention utilizes gel permeation chromatography (following, economize slightly GPC) (stripping solvent: tetrahydrofuran) weight-average molecular weight (Mw) of polystyrene conversion of measuring is generally 1000 ~ 100000, is preferably 3000 ~ 50000.By becoming such mode, residual film ratio, pattern form, thermotolerance, electrical characteristics, the resolution of tunicle can be improved further, the generation of dry foreign matter when being coated with can be suppressed in addition with high level.
In addition, the weight-average molecular weight (Mw) of (B) resin glue in the present invention is preferably 1.0 ~ 5.0 with the ratio (Mw/Mn) of number-average molecular weight (Mn), is more preferably 1.0 ~ 3.0.Should illustrate, the Mn mentioned here refers to the number-average molecular weight of the polystyrene conversion measured with GPC (stripping solvent: tetrahydrofuran).
(B) resin glue in the present invention can utilize known method manufacture, such as, also method disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, International Publication No. 2007/029871 pamphlet etc. be can utilize, its structure, Mw, Mw/Mn controlled.
In the present invention, (B) resin glue may be used singly or as a mixture of two or more.
In the present invention, the content of (B) resin glue, relative to Chinese white and other total 100 mass parts of colorant arbitrarily used, is generally 5 ~ 300 mass parts, is preferably 10 ~ 200 mass parts, is more preferably 20 ~ 100 mass parts.By becoming such mode, the shadow shield of light-proofness, thermotolerance, chemical resistance excellence can be formed.
-(C) polymerizable compound-
In the present invention, polymerizable compound refers to the compound of the polymerisable group with more than 2.Wherein, (B) resin glue is not comprised.As polymerisable group, such as, can enumerate ethylenic unsaturated group, epoxy ethyl, oxetanylmethoxy, N-alkoxy methyl amino etc.In the present invention, as polymerizable compound, preferably there is the compound of (methyl) acryloyl group of more than 2, or there is the compound of N-alkoxy methyl amino of more than 2.
As the concrete example of compound of (methyl) acryloyl group with more than 2, aliphatic polyhydroxy compound and (methyl) acrylic acid can be enumerated react and multifunctional (methyl) acrylate of obtaining, by multifunctional (methyl) acrylate of caprolactone modification, by multifunctional (methyl) acrylate of epoxyalkane modification, there is polyfunctional carbamate (methyl) acrylate that (methyl) acrylate of hydroxyl and polyfunctional isocyanate react and obtain, there is (methyl) acrylate of hydroxyl and anhydride reaction and multifunctional (methyl) acrylate etc. with carboxyl obtained.
Here, as aliphatic polyhydroxy compound, such as, the aliphatic polyhydroxy compound of 2 yuan as ethylene glycol, propylene glycol, polyglycol, polypropylene glycol and so on can be enumerated; As the aliphatic polyhydroxy compound of more than 3 yuan of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol and so on.As above-mentioned (methyl) acrylate with hydroxyl, such as, can enumerate (methyl) acrylic acid 2-hydroxy methacrylate, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerol dimethacrylate etc.As above-mentioned polyfunctional isocyanate, such as, can enumerate toluene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc.As acid anhydrides, such as can enumerate the acid anhydrides of the dibasic acid as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, HHPA and so on, the tetra-atomic acid dianhydride of Pyromellitic Acid, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and so on.
In addition, as by multifunctional (methyl) acrylate of caprolactone modification, such as, the compound recorded in (0015) ~ (0018) section of Japanese Unexamined Patent Publication 11-44955 publication can be enumerated.As above-mentioned by multifunctional (methyl) acrylate of epoxyalkane modification, bisphenol-A two (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane can be enumerated, be selected from isocyanuric acid three (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from trimethylolpropane tris (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from pentaerythrite three (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from pentaerythrite four (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from dipentaerythritol five (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from dipentaerythritol six (methyl) acrylate etc. of at least a kind of modification in oxirane and epoxypropane.
In addition, as the compound of N-alkoxy methyl amino with more than 2, such as, the compound etc. with melamine structure, benzoguanamine structure, urea structure can be enumerated.Should illustrate, it is the chemical constitution of basic framework that melamine structure, benzoguanamine structure refer to that the triazine ring with more than 1 or phenyl replace triazine ring, is the concept also comprising melamine, benzoguanamine or their condensation product.As the concrete example of compound of N-alkoxy methyl amino with more than 2, N can be enumerated, N, N ', N ', N ", N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine, N, N, N ', N '-four (alkoxy methyl) glycoluril etc.
In these polymerizable compounds, preferably aliphatic polyhydroxy compound and (methyl) acrylic acid of more than 3 yuan react and obtain multifunctional (methyl) acrylate, by multifunctional (methyl) acrylate, polyfunctional carbamate (methyl) acrylate, the N of caprolactone modification, N, N ', N ', N "; N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine.In multifunctional (methyl) acrylate that aliphatic polyhydroxy compound more than 3 yuan and (methyl) acrylic acid react and obtains, surface smoothness that is high from the viewpoint of the intensity of dyed layer, dyed layer is excellent and unexposed portion not easily produces scum on substrate and on light shield layer, film remains, particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate.
In the present invention, (C) polymerizable compound may be used singly or as a mixture of two or more.
In the present invention, the content of (C) polymerizable compound, relative to Chinese white and other total 100 mass parts of colorant arbitrarily used, is generally 3 ~ 200 mass parts, is preferably 5 ~ 100 mass parts, is more preferably 10 ~ 50 mass parts.In addition, the content of (C) polymerizable compound, relative to resin glue 100 mass parts, is generally 20 ~ 150 mass parts, is preferably 30 ~ 120 mass parts, is more preferably 40 ~ 90 mass parts.By becoming such mode, the shadow shield of light-proofness, thermotolerance, chemical resistance excellence can be formed.
-(D) Photoepolymerizationinitiater initiater-
In coloured composition of the present invention; as (D) Photoepolymerizationinitiater initiater, comprise at least a kind that is selected from O-acyl oxime system Photoepolymerizationinitiater initiater, alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters.Being selected from Photoepolymerizationinitiater initiater in O-acyl oxime system Photoepolymerizationinitiater initiater, alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters can combination in any and and use two or more.
As O-acyl oxime system Photoepolymerizationinitiater initiater, such as can enumerate 1-(4-(thiophenyl) phenyl)-1, 2-octanedione 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethyl ketone 1-(O-acetyl oxime), 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-base)-ethyl ketone 1-(O-acetyl oxime), 1-(9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolyl) methoxybenzoyl base }-9H-carbazole-3-base)-ethyl ketone 1-(O-acetyl oxime), 1-[4-[3-[4-[[2-(acetoxyl group) ethyl] sulfonyl]-2-methyl benzoyl]-6-[1-[(acetoxyl group) imino group] ethyl]-9H-carbazole]-9-base] phenyl-1-octanone 1-(O-acetyl oxime) etc.As the commercially available product of O-acyl oxime compound, NCI-700, NCI-730, NCI-831, NCI-930 (above is Inc. of ADEKA Corp.), DFI-020, DFI-091 (above is Daitochemix Co., Ltd. system), IrgacureOXE-03, IrgacureOXE-04 (above is BASF AG's system) etc. can be used.
In these O-acyl oxime system Photoepolymerizationinitiater initiaters, preferred 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethyl ketone 1-(O-acetyl oxime), 1-[4-[3-[4-[[2-(acetoxyl group) ethyl] sulfonyl]-2-methyl benzoyl]-6-[1-[(acetoxyl group) imino group] ethyl]-9H-carbazole]-9-base] phenyl-1-octanone 1-(O-acetyl oxime).
O-acyl oxime system Photoepolymerizationinitiater initiater can be used alone or combines two or more and uses.
As alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, such as, can enumerate 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morphlinophenyl) butane-1-ketone etc.
In these alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiaters, preferred 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone.
Alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater can be used alone or combines two or more and uses.
As acylphosphine oxide system Photoepolymerizationinitiater initiater, such as, can enumerate:
Isobutyryl methyl-phosphinic acid methyl esters, isobutyryl phenyl phosphinic acid methyl esters, valeryl phenyl phosphinic acid methyl esters, 2-ethyl hexyl acyl group phenyl phosphinic acid methyl esters, valeryl phenyl phosphinic acid isopropyl ester, to toluyl groups phenyl phosphinic acid methyl esters, adjacent toluyl groups phenyl phosphinic acid methyl esters, 2,4-dimethylbenzoyl phenyl phosphinic acid methyl esters, to tert-butyl-benzoyl phenyl phosphinic acid isopropyl ester, acryloyl group phenyl phosphinic acid methyl esters, isobutyryl diphenyl phosphine oxide, 2-ethyl hexyl acyl group diphenyl phosphine oxide, adjacent toluyl groups diphenyl phosphine oxide, to tert-butyl-benzoyl diphenyl phosphine oxide, 3-picolinoyl diphenyl phosphine oxide, acryloyl group-diphenyl phosphine oxide, benzoyl diphenyl phosphine oxide, valeryl phenyl phosphinic acid vinyl esters, the two diphenyl phosphine oxide of adipyl base, valeryl diphenyl phosphine oxide, to toluyl groups diphenyl phosphine oxide, 4-(tert-butyl group) benzoyl diphenyl phosphine oxide, the two diphenyl phosphine oxide of paraphenylene terephthalamide, 2-methyl benzoyl diphenyl phosphine oxide, new capryl diphenyl phosphine oxide (バ ー サ ト イ Le ジ Off ェ ニ Le ホ ス Off ィ Application オ キ サ イ De), 2-methyl-2-ethyl hexyl acyl group diphenyl phosphine oxide, 1-methyl-cyclohexyl acyl group diphenyl phosphine oxide, valeryl phenyl phosphinic acid methyl esters, valeryl phenyl phosphinic acid isopropyl ester, the monoacylphosphine oxides such as TMDPO,
Two (2,6-dichloro-benzoyl base) phenyl phosphine oxide, two (2,6-dichloro-benzoyl base)-2,5-3,5-dimethylphenyl phosphine oxides, two (2,6-dichloro-benzoyl base)-4-ethoxyl phenenyl phosphine oxide, two (2,6-dichloro-benzoyl base)-4-propylphenylphosphine oxide, two (2,6-dichloro-benzoyl base)-2-naphthyl phosphine oxide, two (2,6-dichloro-benzoyl base)-1-naphthyl phosphine oxide, two (2,6-dichloro-benzoyl base)-4-chlorphenyl phosphine oxide, two (2,6-dichloro-benzoyl base)-2,4-Dimethoxyphenyl phosphine oxides, two (2,6-dichloro-benzoyl base) decyl phosphine oxide, two (2,6-dichloro-benzoyl base)-4-octyl phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, two (2,4,6-trimethylbenzoyl)-2,5-3,5-dimethylphenyl phosphine oxide, two (2,6-dichloro 3,4,5-trimethoxybenzoy)-2,5-3,5-dimethylphenyl phosphine oxides, two (chloro-3,4, the 5-trimethoxybenzoy of 2,6-bis-)-4-ethoxyl phenenyl phosphine oxide, two (2-methyl isophthalic acid-naphthoyl)-2,5-3,5-dimethylphenyl phosphine oxides, two (2-methyl isophthalic acid-naphthoyl)-4-ethoxyl phenenyl phosphine oxide, two (2-methyl isophthalic acid-naphthoyl)-2-naphthyl phosphine oxide, two (2-methyl isophthalic acid-naphthoyl)-4-propylphenylphosphine oxide, two (2-methyl isophthalic acid-naphthoyl)-2,5-3,5-dimethylphenyl phosphine oxides, two (2-methoxyl-1-naphthoyl)-4-ethoxyl phenenyl phosphine oxide, two (the chloro-1-naphthoyl of 2-)-2,5-3,5-dimethylphenyl phosphine oxides, two acylphosphine oxides such as two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide etc.
In addition, the acylphosphine compounds recorded in Japanese Unexamined Patent Publication 3-101686 publication, Japanese Unexamined Patent Publication 5-345790 publication, Japanese Unexamined Patent Publication 6-298818 publication can also be used.
In these acylphosphine oxide system Photoepolymerizationinitiater initiaters, as monoacylphosphine oxides, preferably 2, 4, 6-trimethyl benzoyl diphenyl base phosphine oxide (such as, BASF AG's system, DarocurTPO), as two acylphosphine oxide, preferred two (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide is (such as, BASF AG's system, Irgacure819), two (2, 6-Dimethoxybenzoyl)-2, 4, 4-tri-methyl-amyl phenyl phosphine oxide (such as, BASF AG's system, Irgacure1700), more preferably two (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide.
Acylphosphine oxide system Photoepolymerizationinitiater initiater can be used alone or combines two or more and uses.
In addition, as two luxuriant titanium system Photoepolymerizationinitiater initiaters, such as, can enumerate two (cyclopentadienyl group) titanium chloride, two (cyclopentadienyl group) titanium of two phenyl, two (cyclopentadienyl group) titanium of two-2,3,4,5,6-pentafluorophenyl groups, two (cyclopentadienyl group) titanium of two-2,3,5,6-tetrafluoro phenyl, two (cyclopentadienyl group) titanium of two-2,4,6-trifluorophenyls, two (cyclopentadienyl group) titanium of two-2,6-difluorophenyls, two (cyclopentadienyl group) titanium of two-2,4-difluorophenyls, two (methyl cyclopentadienyl) titanium of two-2,3,4,5,6-pentafluorophenyl groups, two (methyl cyclopentadienyl) titanium of two-2,3,5,6-tetrafluoro phenyl, two (methyl cyclopentadienyl) titanium (such as BASF AG's system, Irgacure727L) of two-2,6-difluorophenyls, two (the fluoro-3-of 2,6-bis-(pyrroles-1-base) phenyl) two (cyclopentadienyl group) titanium (such as BASF AG's system, Irgacure784), two (the fluoro-3-of 2,4,6-tri-(pyrroles-1-base) phenyl) two (cyclopentadienyl group) titanium, two (the fluoro-3-of 2,4,6-tri-(2-5-dimethyl pyrrole-1-base) phenyl) two (cyclopentadienyl group) titanium, and Japanese Laid-Open Patent Publication 59-152396 publication, Japanese Laid-Open Patent Publication 61-151197 publication, Japanese Laid-Open Patent Publication 63-10602 publication, Japanese Laid-Open Patent Publication 63-41483 publication, Japanese Laid-Open Patent Publication 63-41484 publication, Japanese Unexamined Patent Publication 2-291 publication, Japanese Unexamined Patent Publication 3-12403 publication, Japanese Unexamined Patent Publication 3-20293 publication, Japanese Unexamined Patent Publication 3-27393 publication, Japanese Unexamined Patent Publication 3-52050 publication, Japanese Unexamined Patent Publication 4-219756 publication, the compound etc. recorded in Japanese Unexamined Patent Publication 4-221958 publication etc.
In these two luxuriant titanium systems Photoepolymerizationinitiater initiaters, preferably two (the fluoro-3-of 2,6-bis-(pyrroles-1-base) phenyl) two (cyclopentadienyl group) titanium.
Two luxuriant titanium system Photoepolymerizationinitiater initiaters can be used alone or combine two or more and use.
Wherein, as (D) Photoepolymerizationinitiater initiater, preferably containing at least a kind that is selected from acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters, more preferably containing acylphosphine oxide system Photoepolymerizationinitiater initiater.
In addition, do not departing from the scope of purport of the present invention, in photosensitive composite of the present invention, can be used together other Photoepolymerizationinitiater initiater.As such Photoepolymerizationinitiater initiater, such as, can enumerate thioxanthone compounds, Alpha-hydroxy alkyl phenones compound, united imidazole, triaizine compounds etc.As other such Photoepolymerizationinitiater initiater, such as, can enumerate illustrative Photoepolymerizationinitiater initiater in (0079) ~ (0095) section of Japanese Unexamined Patent Publication 2010-134419.
In the present invention, the content of (D) Photoepolymerizationinitiater initiater, relative to polymerizable compound 100 mass parts, is generally 5 ~ 200 mass parts, is preferably 10 ~ 100 mass parts, is more preferably 20 ~ 80 mass parts.By becoming such mode, the shadow shield of light-proofness, thermotolerance, chemical resistance, curability, tunicle excellent can be formed.
In addition; and during with at least a kind of Photoepolymerizationinitiater initiater be selected from O-acyl oxime system Photoepolymerizationinitiater initiater, alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters and other Photoepolymerizationinitiater initiater; the proportional total content relative to (D) Photoepolymerizationinitiater initiater that contains of other Photoepolymerizationinitiater initiater is preferably below 50 quality %; be more preferably below 30 quality %, more preferably below 20 quality %.
-(E) antioxidant-
From the viewpoint of forming the few shadow shield of xanthochromia, preferably containing antioxidant in photosensitive composite of the present invention.As such antioxidant, phenol system antioxidant, phosphorous antioxidant, sulphur system antioxidant, benzophenone series antioxidant can be enumerated.Antioxidant can be used alone or combines two or more and uses.
As phenol system antioxidant, such as, can enumerate:
2,4,6-tri-(3 ', 5 '-di-t-butyl-4 '-hydroxybenzyl)-1,3,5-trimethylbenzenes, 2,4-pair-(just pungent sulfenyl)-6-(4-hydroxyl-3,5-di-tert-butyl amido)-1,3,5-triazines, pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester (such as, BASF AG Irganox1010), 2,6-di-t-butyl-4-phenol in the ninth of the ten Heavenly Stems, thiodiethylene two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] (such as, BASF AG Irganox1035), 2,2 '-di-2-ethylhexylphosphine oxide-(6-(1-methylcyclohexyl) paracresol), N, N-hexa-methylene two (3,5-di-t-butyl-4-hydroxy-hydrocineamide), 2,5-di-tert-butyl hydroquinone, 2,5-bis-tertiary pentyl p-dihydroxy-benzene, 2,4-dimethyl-6-(1-methylcyclohexyl) phenol, 6-butyl o-cresol, the 6-tert-butyl group-2,4-xylenols, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol, two (octyl group sulfidomethyl) orthoresol of 2,4-, two (dodecylthiomethyl) orthoresol of 2,4-, ethylenebis (oxygen ethylidene) two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] (such as, BASF AG's system, Irganox245), two [2-(3-(tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1, the 1-dimethyl ethyl]-2 of 3,9-, 4,8,10-tetra-oxa-volution [5.5] undecane (such as, Sumitomo Chemical Co's system, SUMILIZERGA-80), two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester (such as, ADEKA Corp.'s system, ADKSTABAO-70) of triethylene glycol, 2-tert-amyl phenol, 2-TBP, 2,4-DTBP, 1,1,3-tri-(2 '-methyl-4 '-hydroxyl-5 '-tert-butyl-phenyl) butane, 4,4 '-butylidene-bis--(the 2-tert-butyl group-5-methylphenol), and as the ADKSTABAO-30 of commercially available product, ADKSTABAO-40, GPA-5001 (being ADEKA Corp.'s system above), SUMILIZERBBM, SUMILIZERGM (being Sumitomo Chemical Co's system above), TOPANOLCA (ICI Inc.).
As phosphorous antioxidant, such as, can enumerate tricresyl phosphite (isodecyl) ester, tricresyl phosphite (13 decyl) ester, the different monooctyl ester of phenyl, phenyl isodecyl ester, phenyl two (13 decyl) ester, the different monooctyl ester of phosphorous acid diphenyl, diphenylisodecyl ester, phosphorous acid diphenyl 13 decyl ester, triphenyl phosphite, tricresyl phosphite (nonyl phenyl) ester, phosphorous acid 4,4 '-isopropylidenediphenol Arrcostab, trisnonyl phenyl phosphite, tricresyl phosphite (dinonylphenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, tricresyl phosphite (xenyl) ester, distearyl pentaerythrityl diphosphite, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (nonyl phenyl) pentaerythritol diphosphites, phenyl bisphenol-A pentaerythritol diphosphites, four (13 decyl)-4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol) diphosphites, six (13 decyl)-1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane GW-540, 3,5-di-tert-butyl-4-hydroxyl benzyl phosphite ester diethylester, two (the two phenoxy group phosphonatos) benzene (1,3-PVC ス (ジ Off ェ ノ キ シ Off ォ ス Off ォ ニ ロ キ シ)-ベ Application ゼ Application) of 1,3-, two (2, the 4-di-t-butyl-6-aminomethyl phenyl) ester of phosphorous acid ethyl.As commercially available product, ADKSTAB1500, ADKSTAB2112, ADKSTABC, ADKSTAB135A, ADEKA1500 (above is Inc. of ADEKA Corp.), SUMILIZERGP (Sumitomo Chemical Co's system) etc. can be used.
As sulphur system antioxidant, such as, can enumerate the compound recorded in (0084) section of Japanese Unexamined Patent Publication 2009-122650 publication.
As benzophenone series antioxidant, such as, can enumerate the compound recorded in (0123) section of Japanese Unexamined Patent Publication 2014-026228 publication.
Wherein, from the viewpoint of the shadow shield forming lightness and light-proofness excellence, as antioxidant, preferably containing at least a kind that is selected from phenol system antioxidant and phosphorous antioxidant, more preferably at least containing phenol system antioxidant.In addition, phenol system antioxidant preferably has the phenolic hydroxyl group of more than 4, more preferably has the phenolic hydroxyl group of more than 6.
In the present invention, the content of antioxidant is relative to total content 100 mass parts of each composition except the solvent of photosensitive composite, is generally 0.01 ~ 10 mass parts, is preferably 0.05 ~ 5 mass parts, is more preferably 0.1 ~ 3 mass parts.By becoming such mode, the shadow shield that xanthochromia is few can be formed.
During containing phenol system antioxidant and phosphorous antioxidant, contain proportional (the phenol system antioxidant/phosphorous antioxidant) of phenol system antioxidant and phosphorous antioxidant is preferably 1/2 ~ 49/1 by quality ratio, be more preferably 1/1 ~ 19/1, more preferably 2/1 ~ 9/1, be further preferably 5/1 ~ 9/1.
-(F) solvent-
Other the composition that photosensitive composite of the present invention contains above-mentioned (A) ~ (D) composition and adds arbitrarily, usually coordinates organic solvent and is prepared into fluid composition.
As (F) solvent, form (A) ~ (D) composition, other the composition of photosensitive composite as long as can disperse or dissolve, and do not react with these compositions, and there is suitable volatility, just can suitably choice for use.
As organic solvent, such as, can enumerate:
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) the alkylene glycol monoalky lethers such as tripropylene glycol list ether,
The lactic acid alkyl ester such as methyl lactate, ethyl lactate;
(ring) alkylols such as methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutyl alcohol, the tert-butyl alcohol, octanol, 2-Ethylhexyl Alcohol, cyclohexanol;
The keto-alcohols such as diacetone alcohol;
(gathering) the alkylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, 3-methoxyacetic acid butyl ester, 3-methyl-3-methoxyacetic acid butyl ester;
The glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
The ketone such as MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone;
The diacetate esters such as propylene-glycol diacetate, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters;
The alkoxyl carboxylates such as 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxy propyl acid butyl ester;
The fatty acid alkyl esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester;
The aromatic hydrocarbon such as toluene, dimethylbenzene;
The acid amides of DMF, DMA, 1-METHYLPYRROLIDONE etc. or lactams etc.
In these organic solvents, from dissolubility, the dispersiveness of pigment, the viewpoints such as coating are considered, preferably (gather) alkylene glycol monoalky lether, lactic acid alkyl ester, (gathering) alkylene glycol monoalkyl ether acetate, glycol ether, ketone, diacetate esters, alkoxyl carboxylate, fatty acid alkyl esters, particularly preferably propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxyacetic acid butyl ester, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, cyclohexanone, 2-HEPTANONE, 3-heptanone, 1, 3-butylene glycol diacetate esters, 1, 6-hexanediol diacetate esters, ethyl lactate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-methyl-3-methoxy propyl acid butyl ester, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.
In the present invention, (F) solvent may be used singly or as a mixture of two or more.
(F) content of solvent is not particularly limited, and the total concentration of each composition except the solvent of photosensitive composite preferably becomes the amount of 10 ~ 70 quality %, more preferably becomes the amount of 30 ~ 60 quality %.By becoming such mode, coating, photosensitive composite that storage stability is good can be obtained.
-adjuvant-
Photosensitive composite of the present invention also can contain various adjuvant as required.
As adjuvant, such as, can enumerate the filling agent such as glass, aluminium oxide, the macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl) class, the surfactants such as fluorine system surfactant, silicon system surfactant, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, the closely sealed promoter such as 3-mercaptopropyi trimethoxy silane, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl) ultraviolet light absorber such as-5-chlorobenzotriazole, alkoxy benzophenone class, the deflocculants such as sodium polyacrylate, malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, the residue improver such as 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-PD, 2-amino-1,3-propanediol, amino-1, the 2-butylene glycol of 4-, the developability improvers etc. such as mono succinate (2-(methyl) acrylyl oxy-ethyl) ester, phthalic acid list (2-(methyl) acrylyl oxy-ethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate.
Coloured composition of the present invention can utilize suitable method preparation, as its preparation method, such as, (A) ~ (D) composition and (F) solvent, any other composition added can be mixed together and prepare.Wherein, be preferably as follows method, namely such as ball mill, roller mill etc. is used, in (F) solvent, under the existence of spreading agent, colorant containing Chinese white is according to circumstances carried out together with a part for (B) resin glue pulverize and mix disperseing and making dispersible pigment dispersion, then, in this dispersible pigment dispersion, add (C) polymerizable compound, add (B) resin glue, (D) Photoepolymerizationinitiater initiater, additional further (F) solvent, other composition as required, carry out mixing and preparing.
Shadow shield and manufacture method thereof
Shadow shield of the present invention uses photosensitive composite of the present invention to be formed, and more specifically, has the white solidified film using photosensitive composite of the present invention to be formed.
Below, the formation method of the white solidified film forming shadow shield is described.First, after being coated with the fluid composition of shadow shield formation photosensitive composite of the present invention on a surface of a substrate, carrying out preliminary drying and solvent is evaporated, form film.Then, via photomask, this film is exposed, use alkaline-based developer to develop afterwards, removing is dissolved in the unexposed portion of film.Thereafter, by rear baking, form white solidified film with the configuration specified.
As the substrate used when forming white solidified film, such as, can enumerate glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.
In addition, as required, also can implement to utilize the pre-treatment that the agent treated of silane coupling agent etc., Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. are suitable to these substrates.
When substrate is coated with shadow shield formation photosensitive composite, the rubbing method that spraying process, rolling method, method of spin coating (spin-coating method), slit mould rubbing method (slot coated method), excellent rubbing method etc. are suitable can be adopted, but particularly preferably adopt spin-coating method, slit mould rubbing method.
Preliminary drying usually and drying under reduced pressure and heat drying combine and carry out.Drying under reduced pressure usually proceeds to and reaches 50 ~ 200Pa.In addition, the condition of heat drying is generally 70 ~ 110 DEG C, about 1 ~ 10 minute.
Coating thickness, with dried film thickness gauge, is generally 1 ~ 50 μm, is preferably 2 ~ 30 μm, is more preferably 5 ~ 20 μm.
As the light source of the radioactive ray used when forming white solidified film, such as can enumerate the lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, the LASER Light Source etc. such as argon laser, YAG laser, XeCl excimer laser, N_2 laser.As exposure light source, also ultraviolet LED can be used.Optimal wavelength is at the radioactive ray of the scope of 190 ~ 450nm.
The exposure of radioactive ray is generally preferably 10 ~ 10000J/m 2.
In addition, as above-mentioned alkaline-based developer, such as, preferred sodium carbonate, sodium bicarbonate, NaOH, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1, the aqueous solution of 8-diazabicyclo-[5.4.0]-7-undecylene, 1,5-diazabicyclo-[4.3.0]-5-nonene etc.
Also the such as water-miscible organic solvent such as methyl alcohol, ethanol, surfactant etc. can be added in right amount in alkaline-based developer.Should illustrate, after alkaline development, usually wash.
As development treatment method, spray development method, spray development method, dipping (dip) development method can be adopted, soak and put (liquid pool) development method etc.Development conditions be preferably normal temperature, 5 ~ 300 seconds.
The condition of rear baking is generally 180 ~ 300 DEG C, about 10 ~ 90 minutes.Even if photosensitive composite of the present invention rear baking temperature be 200 ~ 300 DEG C, be further 230 ~ 300 DEG C, also can form the few white solidified film of xanthochromia under the condition that is further 250 ~ 300 DEG C.
The thickness of the white solidified film formed thus is generally 1 ~ 50 μm, is preferably 2 ~ 30 μm, is more preferably 5 ~ 20 μm.Even if the white solidified film using photosensitive composite of the present invention to be formed is the shadow shield that film also can be used as light-proofness excellence.In addition, when forming thicker thickness to improve light-proofness further, because the curability of photosensitive composite is excellent, so not only chemical resistance is excellent, also play the effect not making cured film surface produce fold and so on.
On the white solidified film obtained thus, nesa coating can be formed by sputtering as required, or form diaphragm.Even if photosensitive composite of the present invention is through forming the heating of more than 250 DEG C of transparency electrode, xanthochromia is also few, is therefore especially suitable for use as the photomask of white.
The shadow shield with the of the present invention white solidified film formed thus due to xanthochromia few, so be extremely suitable for the display device of the design sense needing white.Specifically, by making shadow shield of the present invention at CIELAB (L *a *b *colour system) in, lightness index (L *) be more than 80 and chromaticity index (a *, b *) be greater than ﹣ 5 respectively and be less than 5, thus the designability of the display device possessing this shadow shield can be made excellent.
Display device
Display device of the present invention possesses shadow shield of the present invention.As display device, the portable digital such as smart mobile phone, tablet terminal display device can be enumerated.
Embodiment
Below, enumerate embodiment, the present invention is specifically described further.Wherein, the invention is not restricted to following embodiment.
The synthesis of spreading agent
Synthesis example 1
In the flask possessing cooling tube and stirring machine, drop into propylene glycol methyl ether acetate (sometimes economizing slightly " PGMEA " below) 100 mass parts, and replace with nitrogen.Be heated to 80 DEG C, at such a temperature, PGMEA100 mass parts, succinic acid-2-acryloyloxyethyl ester 5 mass parts, methyl methacrylate 35 mass parts, butyl methacrylate 30 mass parts, 2-Ethylhexyl Methacrylate 20 mass parts, glycerol monomethacrylate 10 mass parts and 2 is dripped with 1 hour, 2 '-azo two (2,4-methyl pentane nitrile) mixed solution of 6 mass parts, keep this temperature to carry out polymerization in 2 hours.Thereafter, make the temperature to 90 DEG C of reaction solution, carry out polymerization in 1 hour further.After being cooled to room temperature, use PGMEA that solid component concentration is adjusted to 40 quality %.It can be used as spreading agent (1) solution (solid component concentration=40 quality %).The Mw=16000 of the spreading agent (1) obtained, Mn=8100, acid number is 13mgKOH/g.
The synthesis of resin glue
Synthesis example 2
In the flask possessing cooling tube and stirring machine, drop into PGMEA100 mass parts, and replace with nitrogen.Be heated to 80 DEG C, at such a temperature, drip PGMEA100 mass parts, methacrylic acid 10 mass parts, succinic acid-2-methacryloyloxyethyl 5 mass parts, benzyl methacrylate 35 mass parts, 2, the mixed solution of 2 '-azoisobutyronitrile 8.0 mass parts and α-methylstyrenedimer 8.0 mass parts also remains on 80 DEG C and carries out polymerization in 4 hours.Thereafter, by the temperature to 100 of reaction solution DEG C, carry out polymerization in 1 hour further.After being cooled to room temperature, use PGMEA that solid component concentration is adjusted to 40 quality %.It can be used as resin glue (B-1) solution.The Mw=8100 of the resin glue (B-1) obtained, Mn=5300.
Synthesis example 3
In the flask possessing cooling tube and stirring machine, drop into PGMEA100 mass parts, and replace with nitrogen.Be heated to 80 DEG C, at such a temperature, drip PGMEA100 mass parts, methacrylic acid 10 mass parts, succinic acid-2-methacryloyloxyethyl 5 mass parts, benzyl methacrylate 15 mass parts, glycidyl methacrylate 20 mass parts, 2, the mixed solution of 2 '-azoisobutyronitrile 8.0 mass parts and α-methylstyrenedimer 8.0 mass parts also remains on 80 DEG C and carries out polymerization in 4 hours.Thereafter, make the temperature to 100 DEG C of reaction solution, carry out polymerization in 1 hour further.After being cooled to room temperature, use PGMEA that solid component concentration is adjusted to 40 quality %.It can be used as resin glue (B-2) solution.The Mw=10600 of the resin glue (B-2) obtained, Mn=4900.
Synthesis example 4
In the flask possessing cooling tube and stirring machine, drop into PGMEA100 mass parts, and replace with nitrogen.Be heated to 80 DEG C, at such a temperature, drip PGMEA100 mass parts, methacrylic acid 10 mass parts, succinic acid-2-methacryloyloxyethyl 5 mass parts, benzyl methacrylate 15 mass parts, methacrylic acid 3-ethyl-3-oxetanylmethoxy methyl esters 20 mass parts, 2, the mixed solution of 2 '-azoisobutyronitrile 8.0 mass parts and α-methylstyrenedimer 8.0 mass parts also remains on 80 DEG C and carries out polymerization in 4 hours.Thereafter, by the temperature to 100 of reaction solution DEG C, carry out polymerization in 1 hour further.After being cooled to room temperature, use PGMEA that solid component concentration is adjusted to 40 quality %.It can be used as resin glue (B-3) solution.The Mw=6900 of the resin glue (B-3) obtained, Mn=4200.
Synthesis example 5
In the flask possessing cooling tube and stirring machine, drop into PGMEA100 mass parts, and replace with nitrogen.Be heated to 80 DEG C, at such a temperature, drip PGMEA100 mass parts, methacrylic acid 10 mass parts, succinic acid-2-methacryloyloxyethyl 5 mass parts, benzyl methacrylate 15 mass parts, methacrylic acid 3,4-epoxycyclohexanecarboxylate 20 mass parts, 2, the mixed solution of 2 '-azoisobutyronitrile 8.0 mass parts and α-methylstyrenedimer 8.0 mass parts also remains on 80 DEG C and carries out polymerization in 4 hours.Thereafter, by the temperature to 100 of reaction solution DEG C, carry out polymerization in 1 hour further.After being cooled to room temperature, use PGMEA that solid component concentration is adjusted to 40 quality %.It can be used as resin glue (B-4) solution.The Mw=8300 of the resin glue (B-4) obtained, Mn=4500.
Size-grade distribution particle diameter is evaluated
Utilize PGMEA that the dispersible pigment dispersion of following preparation is diluted 10 times, use size-grade distribution meter (HORIBA L-500), obtain the mean grain size of Chinese white.
The preparation of dispersible pigment dispersion
Preparation example 1
The mode becoming 65 quality % using solid component concentration uses 60.0 mass parts as the strontium titanates of (A) colorant, 6.2 mass parts as DISPERBYK-180 (BYK-Chemie (BYK) Inc. of spreading agent, phosphate system spreading agent, amine value 94mgKOH/g, acid number 94mgKOH/g, solid component concentration 81 quality %), as the PGMEA of solvent, utilize ball mill mixing dispersion 12 hours and make dispersible pigment dispersion (A-1).The mean grain size of Chinese white is 250nm.
Preparation example 2
The mode becoming 65 quality % using solid component concentration use 60.0 mass parts as (A) colorant, by the C.I. Pigment white 6:1 (titanium dioxide) on aluminium oxide modified surface, 12.5 mass parts as spreading agent (1) solution (the acid number 5.2mgKOH/g of spreading agent, solid component concentration 40 quality %), as the propylene glycol monomethyl ether (sometimes economizing slightly " PGME " below) of solvent, utilize ball mill mixing dispersion 12 hours and make dispersible pigment dispersion (A-2).The mean grain size of Chinese white is 480nm.
Preparation example 3
The mode becoming 65 quality % using solid component concentration use 60.0 mass parts as (A) colorant, by the C.I. Pigment white 6:1 on aluminium oxide modified surface, 9.6 mass parts as DISPERBYK-110 (BYK-Chemie (BYK) Inc. of spreading agent, phosphate system spreading agent, acid number 53mgKOH/g, solid component concentration 52 quality %), as the PGMEA of solvent, utilize ball mill mixing dispersion 12 hours and make dispersible pigment dispersion (A-3).The mean grain size of Chinese white is 320nm.
Preparation example 4
The mode becoming 65 quality % using solid component concentration use 60.0 mass parts as (A) colorant, by the C.I. Pigment white 6:1 on siloxane modified surface, 12.5 mass parts as BYK-LPN21116 (BYK-Chemie (BYK) Inc. of spreading agent, (methyl) dispersant containing acrylic, amine value 29mgKOH/g, solid component concentration 40 quality %), as the PGMEA of solvent, utilize ball mill mixing dispersion 12 hours and make dispersible pigment dispersion (A-4).The mean grain size of Chinese white is 280nm.
Preparation example 5
The mode becoming 65 quality % using solid component concentration uses 60.0 mass parts as the C.I. Pigment white 12 (zirconia) of (A) colorant, 9.6 mass parts as DISPERBYK-110 (BYK-Chemie (BYK) Inc. of spreading agent, phosphate system spreading agent, acid number 53mgKOH/g, solid component concentration 52 quality %), as the PGME of solvent, utilize ball mill mixing dispersion 12 hours and make dispersible pigment dispersion (A-5).The mean grain size of Chinese white is 120nm.
Preparation example 6
Use 60.0 mass parts as the C.I. Pigment white 4 (zinc paste) of (A) colorant, 9.6 mass parts as DISPERBYK-110 (BYK-Chemie (BYK) Inc. of spreading agent in the solid component concentration mode that is 65 quality %, phosphate system spreading agent, acid number 53mgKOH/g, solid component concentration 52 quality %), as the ethyl lactate of solvent, utilize ball mill mixing dispersion 12 hours and make dispersible pigment dispersion (A-6).The mean grain size of Chinese white is 180nm.
The preparation of photosensitive composite and evaluation
Embodiment 1
Dispersible pigment dispersion (A-1) 275 mass parts as (A) colorant and dispersible pigment dispersion (A-3) 275 mass parts is mixed in the solid component concentration mode that is 50 quality %, as resin glue (B-1) solution 250 mass parts of (B) resin glue, as KAYARADDPHA (Nippon Kayaku K. K's system) 50 mass parts of (C) polymerizable compound, as DAROCURTPO (BASF AG's system) 20 mass parts of (D) Photoepolymerizationinitiater initiater, as GPA-5001 (ADEKA system) 1 mass parts and ADKSTAB135A (ADEKA system) 0.2 mass parts of (E) antioxidant, as solvent PGMEA and make photosensitive composite (S-1).
Use spin coater to be coated on after on soda-lime glass substrate by white photosensitive composite (S-1), carry out 1 minute preliminary drying with hot plate at 100 DEG C, form the film of thickness 12 μm.Then, use high-pressure sodium lamp, not via photomask, will the radioactive ray of each wavelength of 365nm, 405nm and 436nm be comprised with 100J/m 2exposure film is exposed.Thereafter, with developer pressure 1kgf/cm 2(nozzle diameter 1mm) sprays 0.04% potassium hydroxide aqueous solution of 23 DEG C to film, carries out spray development thus, dries, substrate is formed the white solidified film of thickness 10 μm at 270 DEG C after carrying out 1 hour further afterwards.
Color evaluation
Use spectral photometric colour measuring meter (Konica Minolta CM-2600d), measure the reflected light of the white solidified film of above-mentioned formation, with CIELAB (L *a *b *colour system) quantized.
About colourity, by b *average evaluation lower than 2 is "○", by b *be more than 2 and be " △ " lower than the average evaluation of 5, by b *be more than 5 and be " △ △ " lower than the average evaluation of 7, by b *be more than 7 average evaluation be "×".Show the result in table 1.
About lightness, by L *be more than 85 average evaluation be "○", by L *be more than 80 and be " △ " lower than the average evaluation of 85, by L *be more than 75 and be " △ △ " lower than the average evaluation of 80, by L *average evaluation lower than 75 is "×".Show the result in table 1.
In table 1, as long as colourity and lightness are "○" or a side be "○" and the opposing party is " △ ", just can say that this cured film xanthochromia does not occur.If at least one party in colourity and lightness is "×", then can think that this cured film there occurs xanthochromia.Other when, can think that this cured film there occurs some xanthochromias, be grade no problem in practicality.
Light-proofness is evaluated
Use optical concentration meter (Macbeth TD-904), measure the optical concentration (OD) of the white solidified film of above-mentioned formation.By OD be more than 0.8 average evaluation be "○", OD be more than 0.5 and be " △ " lower than the average evaluation of 0.8, by OD lower than 0.5 average evaluation be "×".OD is larger, can say that light-proofness is better.Show the result in table 1.
Chemical resistance is evaluated
Use spectral photometric colour measuring meter (Konica Minolta CM-2600d), measure the reflected light of the white solidified film of above-mentioned formation, with CIELAB (L *a *b *colour system) quantized.
Next, by white solidified film immersion, at TOK106, (chemical industry system is answered in Tokyo.The anticorrosive additive stripping liquid controlling be made up of monoethanolamine/dimethyl sulphoxide solution.) in 1 minute, after cleaning with ultrapure water, carry out curing for 1 minute at 100 DEG C.Measure the reflected light of this cured film, with CIELAB (L *a *b *colour system) quantized.
Obtain the b before and after dipping *variable quantity, by Δ b *average evaluation lower than 1 is "○", by Δ b *be more than 1 and be " △ " lower than the average evaluation of 2, by Δ b *be more than 2 average evaluation be "×".Δ b *less, can say that chemical resistance is better.Show the result in table 1.
Embodiment 2 ~ 33 and comparative example 1 ~ 4
In embodiment 1, the kind of each composition and amount are changed by table 1, in addition, carries out similarly to Example 1, prepare photosensitive composite (S-2) ~ (S-37).Next, use photosensitive composite (S-2) ~ (S-37) to replace photosensitive composite (S-1), in addition, evaluate similarly to Example 1.Show the result in table 1.
[table 1]
In table 1, each composition is as follows.
(polymerizable compound)
C-1:KAYARADDPHA (Nippon Kayaku K. K's system.The potpourri of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate.)
C-2:ARONIXM-450 (Toagosei Co., Ltd's system.The potpourri of pentaerythritol triacrylate and tetramethylol methane tetraacrylate.)
C-3:ARONIXM-315 (Toagosei Co., Ltd's system.The potpourri of the ethylene-oxide-modified diacrylate of isocyanuric acid and triacrylate.)
C-4:KAYARADDPHA-40H (Nippon Kayaku K. K's system.Polyfunctional carbamate acrylate.)
C-5:ARONIXTO-1382 (Toagosei Co., Ltd's system.The potpourri of the monoesters compound of Dipentaerythritol Pentaacrylate and succinic acid, dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate.)
(Photoepolymerizationinitiater initiater)
D-1:DarocurTPO (BASF system.2,4,6-trimethylbenzoy-dipheny-phosphine oxide.Monoacylphosphine oxides system Photoepolymerizationinitiater initiater)
D-2:Irgacure1700 (BASF system.Two (2,6-Dimethoxybenzoyl) (2,4,4-tri-methyl-amyl) phosphine oxide.Two acylphosphine oxide systems Photoepolymerizationinitiater initiater)
D-3:Irgacure819 (BASF system.Two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.Two acylphosphine oxide systems Photoepolymerizationinitiater initiater)
D-4:Irgacure784 (BASF system.Two [the fluoro-3-of 2,6-bis-(1-pyrrole radicals) phenyl] two (2,4-cyclopentadienyl group) titanium (IV).Two luxuriant titanium system Photoepolymerizationinitiater initiaters)
D-5:Irgacure907 (BASF system.2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone.Alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater)
D-6:Irgacure184 (BASF system.1-hydroxycyclohexylphenylketone.Other Photoepolymerizationinitiater initiater)
D-7:Irgacure127 (BASF system.2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl propiono) benzyl] phenyl }-2-methylpropane-1-ketone.Other Photoepolymerizationinitiater initiater)
D-8:Irgacure369 (BASF system.2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone.Alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater)
D-9:IrgacureOXE-02 (BASF system.1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethyl ketone 1-(O-acetyl oxime).O-acyl oxime system Photoepolymerizationinitiater initiater)
(phenol system antioxidant)
E-1:GPA-5001 (ADEKA system)
E-4:SUMILIZERGA-80 (Sumitomo Chemical Co's system)
E-5:Irganox1010 (BASF AG's system)
E-6:Irganox1035 (BASF AG's system)
E-8:2,5-di-tert-butyl hydroquinone
(phosphorous antioxidant)
E-2:ADKSTAB135A (ADEKA system.Alkyl allyl ester system)
E-3:SUMILIZERGP (Sumitomo Chemical Co's system.6-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propoxyl group]-2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] two phosphorus cycloheptane (6-[3-(3-t-Butyl-4-hydroxy-5-methylphenyl) propoxy]-2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphepin))
E-7:ADEKA1500 (ADEKA system.Four-C 12-15-alkyl propane-2,2-bis-base two (4,1-phenylene)) two (phosphite ester) Tetra-C 12-15-alkylpropane-2,2-diylbis (4,1-phenylene)) bis (phosphite))
(solvent)
PGMEA: propylene glycol methyl ether acetate
PGME: propylene glycol monomethyl ether

Claims (14)

1. a shadow shield formation photosensitive composite, wherein, containing (A) Chinese white, (B) resin glue, (C) polymerizable compound and (D) Photoepolymerizationinitiater initiater,
(D) Photoepolymerizationinitiater initiater contains at least a kind of Photoepolymerizationinitiater initiater be selected from O-acyl oxime system Photoepolymerizationinitiater initiater, alpha-aminoalkyl benzophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater and two luxuriant titanium system Photoepolymerizationinitiater initiaters.
2. shadow shield formation photosensitive composite according to claim 1, wherein, further containing (E) antioxidant.
3. shadow shield formation photosensitive composite according to claim 2, wherein, (E) antioxidant contains at least a kind that is selected from phenol system antioxidant and phosphorous antioxidant.
4. the shadow shield formation photosensitive composite according to Claims 2 or 3, wherein, (E) antioxidant contains phenol system antioxidant and phosphorous antioxidant, phenol system antioxidant and phosphorous antioxidant be 2/1 ~ 9/1 by quality ratio containing proportional i.e. phenol system antioxidant/phosphorous antioxidant.
5. shadow shield formation photosensitive composite according to claim 3, wherein, phenol system antioxidant has the phenolic hydroxyl group of more than 4.
6. shadow shield formation photosensitive composite according to claim 1 and 2, wherein, (B) resin glue is the resin with at least a kind of functional group be selected from acidic functionality and cyclic ether group.
7. shadow shield formation photosensitive composite according to claim 6, wherein, cyclic ether group is epoxy ethyl, oxetanylmethoxy or ester ring type epoxy radicals.
8. shadow shield formation photosensitive composite according to claim 1 and 2, wherein, (A) Chinese white contains at least a kind that is selected from titanium dioxide and strontium titanates.
9. shadow shield formation photosensitive composite according to claim 1 and 2, wherein, the mean grain size of (A) Chinese white is 200 ~ 400nm.
10. shadow shield formation photosensitive composite according to claim 1 and 2 wherein, be the spreading agent of 10 ~ 200mgKOH/g or amine value is further the spreading agent of 20 ~ 200mgKOH/g containing acid number.
11. 1 kinds of shadow shields use the shadow shield formation photosensitive composite according to any one of claim 1 ~ 10 to be formed.
12. shadow shield according to claim 11, wherein, thickness is 1 ~ 50 μm.
13. shadow shields according to claim 11 or 12, wherein, CIELAB and L *a *b *in colour system, lightness index L *be more than 80 and chromaticity index a *, b *be greater than ﹣ 5 respectively and be less than 5.
14. 1 kinds of display device, possess the shadow shield according to any one of claim 11 ~ 13.
CN201510354198.8A 2014-06-25 2015-06-24 Photosensitive composition for forming shading board, shading board and display device Pending CN105319849A (en)

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CN107870515A (en) * 2016-09-27 2018-04-03 东友精细化工有限公司 Blue cured property resin combination, colour filter and include its image display device
CN111886302A (en) * 2018-03-27 2020-11-03 富士胶片株式会社 Black ink composition for ink jet, light-shielding film, optical member, and image forming method
CN113759661A (en) * 2020-06-03 2021-12-07 新应材股份有限公司 Photosensitive resin composition, partition wall, light conversion layer, and light emitting device

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