CN105911818A

CN105911818A - Photoresist composition, hardening film making method, hardening film and application thereof

Info

Publication number: CN105911818A
Application number: CN201610091143.7A
Authority: CN
Inventors: 米泽裕之
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2015-02-20
Filing date: 2016-02-18
Publication date: 2016-08-31
Also published as: JP6385853B2; JP2016153835A

Abstract

The objective of the invention is to provide a photoresist composition, a hardening film making method, a hardening film, a touch screen, a touch screen display device, a liquid display device and an organic EL display device. The photoresist composition includes a polymerized monomer with more than three (methyl) acryloyl groups and more than one carboxyl, a polymerized monomer with more than three (methyl) acryloyl groups and without carboxyl, a polymerization initiator, a compound with phosphate structure and ethylene unsaturation group (having D element) and a polymerization inhibitor, wherein the content of the polymerization inhibitor relative to the total organic solid components is more than 0.01 mass% and less than 0.5 mass%, and the content of the D elements relative to the total organic solid in the compound is more than 0.01 mass% and less than 5 mass%. A photoresist composition capable of obtaining hardening film with reprocessability, good rolling feature at development and small film thickness at development is provided.

Description

Photosensitive composite, the manufacture method of cured film, cured film and application thereof

Technical field

The present invention relates to a kind of photosensitive composite, the manufacture method of cured film, cured film, touch-screen, touch panel display device, Liquid crystal indicator and organic electroluminescent (Electroluminescence, EL) display device.

Background technology

The flat-panel monitor such as liquid crystal indicator, organic EL display (flat panel display) is widely used.It addition, In recent years, universal along with smart mobile phone (smartphone) or flat board (tablet) terminal, capacitive touch screen is looked steadily Mesh.The sensor base plate of capacitive touch screen is usually following structure: have tin indium oxide (Indium Tin on glass Oxide, ITO) or the patterned distribution of metal (silver, aluminium, aluminium etc.), the cross part of this external distribution has insulation Film, the diaphragm that ITO and metal are protected.

As existing touch-screen distribution diaphragm, it is known to diaphragm described in patent document 1 and patent document 2.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2013-200891 publication

[patent document 2] Japanese Patent Laid-Open 2010-27033 publication

Summary of the invention

Invent problem to be solved

The inventors have found that the key property required by touch-screen distribution diaphragm has " re-workability " and " crimping characteristic ".

So-called re-workability, refers to when using paste or sticker etc. to be fitted on diaphragm by Polarizer, because position alignment is bad Etc. reason, Polarizer could be peeled off and diaphragm surface is cleaned, and the characteristic of Polarizer of the most again fitting.

When Polarizer is peeled off, it is desirable to high density of access, so that diaphragm will not be peeled off from electrode base board.It addition, to protection When film surface is cleaned, carries out physical to remove paste or sticker etc. and/or chemically clean, therefore it is required that high rigidity And chemical-resistant.

The overall characteristic comprising these adhesions, hardness and chemical-resistant is re-workability.

So-called crimping, refers to when being exposed minus material, utilizing photoetching to pattern, and is not the most originally irradiated to photochemical The region of ray also produces the phenomenon of film hardening.If generation crimping, then cannot be properly formed the pattern of photomask, it is therefore preferable that It is not produce crimping.The minus material of hardness or good chemical resistance is high response, therefore, because of the light leak from photomask Deng and easily produce crimping, become mutually compromise performance.

Problem to be solved by this invention for provide a kind of obtain re-workability and development time crimping excellent and also develop Time the photosensitive composite of the few cured film of film thinning.

It addition, another problem to be solved by this invention is for providing the manufacturer of a kind of cured film using described photosensitive composite Method and cured film and use the touch-screen of described cured film, touch panel display device, liquid crystal indicator and organic EL to show Device.

The technological means of solution problem

The described problem of the present invention is by the means described in following<1>,<6>,<7>or<11>～<14> And solve.It is recorded in following together with<2>～<5>and<8>～<10>preferably.

<1>a kind of photosensitive composite, it is characterised in that contain the: there is (first of more than three as the intramolecular of composition A Base) polymerizable monomer of acryloyl group and more than one carboxyl；Intramolecular as composition B has (methyl) third of more than three Enoyl-and not there is the polymerizable monomer of carboxyl；Photoepolymerizationinitiater initiater as composition C；As components D, there is phosphate Structure and the compound of ethene unsaturated group；And the polymerization inhibitor as composition K；And composition K is relative in composition The content of total solid composition be 0.01 mass %～0.5 mass %, components D is relative to the total organic solid composition in composition Content is 0.01 mass %～5 mass %.

<2>according to photosensitive composite described in<1>, the wherein composition A total content relative to composition A and composition B Content is 10 mass %～50 mass %.

<3>according to photosensitive composite described in<1>or<2>, wherein total organic solid relative in composition of components D The content of body composition is 0.5 mass %～2 mass %.

<4>according to<1>to the photosensitive composite according to any one of<3>, wherein composition A and composition B is relative to group The total content of the total organic solid composition in compound is 70 mass %～95 mass %.

<5>according to<1>to the photosensitive composite according to any one of<4>, it is possibly together with inorganic particulate.

<6>manufacture method of a kind of cured film, it the most sequentially includes operation 1～operation 3:

Operation 1: the painting process being coated on substrate to the photosensitive composite according to any one of<5>according to<1>；

Operation 2: utilize the actinic ray exposure process being exposed at least partially to coated photosensitive composite；With And

Operation 3: utilize the developing procedure that exposed photosensitive composite is developed by aqueous developer solution.

<7>a kind of cured film, it is to make to form to the photosensitive composite hardening according to any one of<5>according to<1>.

<8>according to the cured film described in<7>, it is interlayer dielectric or diaphragm.

<9>according to the cured film described in<7>or<8>, it is touch-screen distribution diaphragm.

<10>according to<7>to the cured film according to any one of<9>, it is that the distribution in outer structure touch-screen is protected Cuticula.

<11>a kind of touch-screen, has according to<7>to the cured film according to any one of<10>.

<12>a kind of touch panel display device, has according to<7>to the cured film according to any one of<10>.

<13>a kind of liquid crystal indicator, has according to the cured film described in<7>or<8>.

<14>a kind of organic EL display, has according to the cured film described in<7>or<8>.

The effect of invention

According to the present invention can provide a kind of obtain re-workability and development time crimping excellent, development time film thinning few The photosensitive composite of cured film.

It addition, according to the present invention can provide the manufacture method of a kind of cured film using described photosensitive composite and cured film, with And use the touch-screen of described cured film, organic EL display, liquid crystal indicator and touch panel display device.

Accompanying drawing explanation

Fig. 1 represents the composition concept map of an example of organic EL display.And represent bottom-emission (bottom emission) type Organic EL display in the schematic sectional view of substrate, there is planarization film 4.

Fig. 2 represents the composition concept map of an example of liquid crystal indicator.And the active matrix (active in expression liquid crystal indicator Matrix) schematic sectional view of substrate, has the cured film 17 as interlayer dielectric.

Fig. 3 represents the composition concept map of an example of the liquid crystal indicator of the function with touch-screen.

Fig. 4 represents the composition concept map of another example of the liquid crystal indicator of the function with touch-screen.

[explanation of symbol]

1,16,440:TFT (thin film transistor (TFT))

2: distribution

3,8,280,420: dielectric film

4: planarization film

5: the first electrodes

6,14,15: glass substrate

7,18,282: contact hole

10: liquid crystal indicator

12: back light unit

17: cured film

19:ITO transparency electrode

20: liquid crystal

22,122,330: colored filter

110: pixel substrate

111,127: Polarizer

112,123: transparency carrier

113,370: common electrode

114: insulating barrier

115: pixel electrode

116,121,350: alignment films

120: substrate in opposite directions

124: phase retardation film

125: sensing detecting electrode

126: following layer

130: detecting means

140,400: liquid crystal layer

200: bottom display board

210: the 1 insulated substrates

220: gate electrode

240: gate insulating film

250: semiconductor layer

260,262: ohmic contact layer

270: source electrode

272: drain electrode

290: pixel electrode

300: top display board

310: the 2 insulated substrates

320: light obstructing member

410: sensing electrode

430: drive electrode

Detailed description of the invention

Hereinafter, present disclosure is described in detail.The explanation of constitutive requirements set forth below is sometimes according to the present invention Representative embodiment and carry out, but the present invention is not limited to this embodiment.Additionally, it is so-called in present specification "～" it is to use as lower limit and the connotation of higher limit comprising numerical value described before and after it.It addition, institute in the present invention Meaning organic EL element, refers to organic electroluminescent device.

In the statement of the group (atomic group) in this specification, do not record the statement being substituted and being unsubstituted and comprise not have and take The group (atomic group) of Dai Ji, and also comprise the group (atomic group) with substituent.Such as so-called " alkyl ", no Simply mean to the alkyl (alkyl being unsubstituted) without substituent, and comprise and there is the alkyl of substituent (be substituted Alkyl).

Additionally, in this specification, " (methyl) acrylate " represents acrylate and methacrylate, " (methyl) acrylic acid " Representing acrylic acid and methacrylic acid, " (methyl) acryloyl group " represents acryloyl group and methylacryloyl.

It addition, in the present invention, " quality % " and " weight % " are synonymous, and " mass parts " and " weight portion " are phase Same connotation.

It addition, in the present invention, plural preferred embodiment be combined as preferred embodiment.

In the present invention, about component of polymer, molecular weight be by with oxolane (Tetrahydrofuran, THF) as solvent The weight of polystyrene conversion that measured of the gel permeation chromatography (Gel Permeation Chromatography, GPC) of situation Amount mean molecule quantity.

(photosensitive composite)

The photosensitive composite (hereinafter also referred to as " composition ") of the present invention be characterised by containing: as composition A point There is in son the polymerizable monomer of (methyl) acryloyl group of more than three and more than one carboxyl, have as the intramolecular of composition B (methyl) acryloyl group having more than three and the polymerizable monomer without carboxyl, the Photoepolymerizationinitiater initiater as composition C, conduct The compound with phosphate ester structure and ethene unsaturated group of components D and the polymerization inhibitor as composition K, and become Dividing K is 0.01 mass %～0.5 mass % relative to the content of the total solid composition in composition, and components D is relative in composition The content of total organic solid composition be 0.01 mass %～5 mass %.

The photosensitive composite of the present invention also can contain other compositions such as inorganic particulate or alkoxysilane compound containing trialkylsilyl group in molecular structure.

The photosensitive composite of the present invention preferably can enter by utilizing the photoetching (photolithography) of alkaline-based developer Row patterning.Additionally, in the situation by utilizing the photoetching of alkaline-based developer that the photosensitive composite of the present invention is patterned Under, the pattern formed is the negative pattern that photographic department remains as pattern.

Additionally, in the present invention, " solid constituent " in so-called photosensitive composite refers to except the volatile ingredients such as solvent Composition.It addition, so-called " organic solid composition ", refer to the volatile ingredients such as solvent and inorganic grain from photosensitive composite Composition except the inorganic constituents such as son.

Specifically, the composition containing following component is illustrated as specific embodiment.

Present inventor has carried out making great efforts research, it was found that containing described composition A～components D and composition K, the containing of composition K Amount is specific scope relative to the content that total solid composition is specific scope and components D relative to total organic solid composition The few cured film of film thinning when crimping excellent when photosensitive composite can obtain re-workability and development, development, thus Complete the present invention.

The mechanism of action of the present invention is the most indefinite, but speculates as described below.It is inferred as by containing components D, during development Crimping excellent, it addition, be inferred as by containing composition A～components D and composition K, and the content of composition K is relative It is specific scope in the content that total solid composition is specific scope and components D relative to total organic solid composition, as bag Excellent at the re-workability of interior overall characteristic containing adhesion, hardness and chemical-resistant.

Hereinafter, each composition contained the photosensitive composite of the present invention is illustrated.

Composition A: intramolecular has (methyl) acryloyl group of more than three and the polymerizable monomer of more than one carboxyl

The photosensitive composite of the present invention contains intramolecular and has (methyl) acryloyl group of more than three and more than one carboxyl Polymerizable monomer is as composition A.

Composition A is that intramolecular has (methyl) acryloyl group of more than three and the compound of more than one carboxyl.

Composition A can be low molecular compound, it is possible to for oligomer, but and non-polymer.That is, from the sight of the hardness of cured film From the point of view of Dian, the molecular weight (for weight average molecular weight in the case of having molecular weight distribution) of composition A is 10, less than 000, Preferably 5, less than 000, and then preferably 3, less than 000.

Composition A has (methyl) acryloyl group of more than three in intramolecular.(methyl) that intramolecular (in a part) is had The number of acryloyl group preferably 3～15, more preferably 3～10, and then preferably 3～7.

The number of (if methyl) acryloyl group be described in the range of, then hardness and reactive excellent.

As long as composition A adds up to acryloyl group (-C (=the O)-CH=CH with more than three in a part₂) and methacryl Base (-C (=O)-C (CH₃)=CH₂), preferably add up to the acryloyl group epoxide with more than three (-O-C (=O)-CH=CH₂) and methylacryloyl epoxide (-O-C (=O)-C (CH₃)=CH₂).Additionally, it is preferable that have The acryloyl group of more than three, more preferably has the acryloyl group epoxide of more than three.

Compared with methylacryloyl, acryloyl group is preferred at the aspect that hardening (reactive) is excellent.It addition, (if methyl) Acryloyl group epoxide, then from reactive excellent, synthesize easy in terms of from the point of view of preferably.

Composition A has more than one carboxyl in intramolecular (in a part).The number of the carboxyl in a part preferably 1～6, More preferably 1～3, and then preferably 1 or 2, particularly preferred 1.

If the number of the carboxyl that composition A is had in a part be described in the range of, then developability and base material adhesion are excellent, The most preferred.

Additionally, the carboxyl that composition A has also can form salt.Form the cation preferred organic cation compound of salt, transition Metal coordination complex cation or metal cation.Organic cation compound can be enumerated: level Four ammonium cation, level Four Pyridylium, level Four quinoline cation, phosphorus cation, iodine cation, sulphur cation etc..Transition metal sun Ion can illustrate the compound described in No. 279143 publications of Japanese Patent No..Metal cation can illustrate: Na⁺、K⁺、Li⁺、 Ag⁺、Fe²⁺、Fe³⁺、Cu⁺、Cu²⁺、Zn²⁺、Al³⁺、Ca²⁺Deng.

Additionally, composition A does not the most have the acidic group beyond described carboxyl.Acidic group beyond carboxyl can illustrate sulfonic group, phosphorus Acidic group etc..By not having the acidic group beyond carboxyl, base material adhesion improves.

Composition A is the ester of polyol and unsaturated carboxylic acid, and preferably makes the most anti-of carboxylic acid anhydrides and polyol The hydroxyl reaction answered and the polymerizable monomer with acidic group (carboxyl), particularly preferably polyol be pentaerythrite and/ Or dipentaerythritol.

Composition A such as can be by the compound (hereinafter also referred to " hydroxyl to (methyl) acryloyl group Yu hydroxyl with more than three Quito official can (methyl) acrylate ") addition acid anhydrides and obtain.

Hydroxyl multifunctional (methyl) acrylate can illustrate polyol and (methyl) acrylic acid of the hydroxyl with more than four Ester.

There is the polyol preferred aliphat polyol of the hydroxyl of more than four, specifically can illustrate: two glycerine, Two-trimethylolethane, two-trimethylolpropane, two-tri hydroxy methyl butane, two-Trimethylolhexane, pentaerythrite, two seasons Penta tetrol, tripentaerythritol etc..In these compounds, preferably pentaerythrite, dipentaerythritol.

It addition, polyol is used as the alkylene oxide addition product of the polyol of described illustration, alkylene oxide can illustrate Oxirane, expoxy propane etc..

Hydroxyl multifunctional (methyl), as long as the manufacture method of acrylate suitably uses well-known method, there is no limit especially Fixed.Specifically can illustrate: the method under acidic catalyst, polyol and (methyl) acrylic acid being added thermal agitation.Acidic catalyst Agent can enumerate sulfuric acid, p-methyl benzenesulfonic acid and methanesulfonic acid etc..As long as it addition, reaction temperature is according to the compound used and purpose Suitably set, preferably 70 DEG C～140 DEG C.If in described temperature range, then reaction is fast, and stably reacts and press down The generation of impurity processed or gelation.

During reaction, it is preferred to use the organic solvent low with the solubility of the water generated in esterification, simultaneously azeotrope with water one Face promotes dehydration.Preferably organic solvent such as can be enumerated: the aromatic hydrocarbons such as toluene, benzene and dimethylbenzene, the fat such as hexane and heptane Fat race hydrocarbon, and the ketone such as methyl ethyl ketone and cyclohexanone etc..It addition, organic solvent can distill removal by decompression after the reaction.

It addition, the polymerization of (methyl) acrylate in order to prevent gained, polymerization inhibitor can be added in reactant liquor.This poly- Close inhibitor such as can enumerate: hydroquinones, hydroquinone monomethyl ether, BHT and phenthazine etc..

Composition A is to be obtained with the reaction of acid anhydrides by described hydroxyl multifunctional (methyl) acrylate.

Acid anhydrides can be enumerated: succinyl oxide, 1-dodecenylsuccinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, adjacent benzene Dicarboxylic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrochysene O-phthalic Acid anhydrides, methyl tetrahydrophthalic anhydride, Nadic anhydride (endo methylene-tetra-hydro phthalic Anhydride), methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, tetrachlorophthalic tetrachlorophthalic anhydrid, tetrabromophthalic anhydride and partially Benzenetricarboxylic acid acid anhydrides etc. have the compound of an anhydride group, and pyromellitic dianhydride, phthalic anhydride two in same intramolecular Polymers, diphenyl ether tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and 1,2,3,4-butane tetracarboxylics (commercially available product such as can enumerate new Japan Chemical (stock) for acid dianhydride, diphenyl ether tetracarboxylic anhydride and double (trimellitic anhydride) glycol ester The trade name manufactured keeps house moral (Rikacid) TMEG-100) etc. there is the compound of two anhydride group in same intramolecular.

In these compounds, preferably there is in same intramolecular the compound of an anhydride group.

As long as the manufacture method of composition A is conventionally.

Such as can enumerate: make hydroxyl multifunctional (methyl) acrylate and carboxylic acid anhydrides in the presence of a catalyst, at 60 DEG C～110 DEG C Lower reaction 1 hour～the method etc. of 20 hours.The catalyst of this situation can be enumerated: N, N-dimethyl benzyl amine, triethylamine, three Butylamine, triethylenediamine, zephiran chloride trimethyl ammonium, bromination benzyl triethyl ammonium, tetramethylammonium bromide, Cetyl front three Base ammonium and zinc oxide etc..

Compound represented by composition A preferred formula A-1 or the compound represented by formula A-2.

[changing 1]

In formula A-1, X¹Separately represent acryloyl group epoxide or methylacryloyl epoxide, W¹Represent carbon number 1～6 Alkylidene, the alkenylene of carbon number 2～6 or phenylene.

In formula A-2, X²Separately represent hydrogen atom, hydroxyl, the alkyl of carbon number 1～6, acryloyl group epoxide or methyl , there is the X of five in acryloyl group epoxide²In, at least three is acryloyl group epoxide or methylacryloyl epoxide, W²Represent carbon Alkylidene, the alkenylene of carbon number 2～6 or the phenylene of several 1～6.

In formula A-1, X¹Preferably acryloyl group epoxide.

In formula A-1, W¹Represent the alkylidene of carbon number 1～6, the alkenylene of carbon number 2～6 or phenylene, carbon number 1～6 Alkylidene can be straight-chain, branch-like, ring-type any one.The preferred carbon number of described alkylidene 2～6, can illustrate ethylidene, Asia Propyl group, butylidene, pentylidene, hexylidene, cyclohexylidene.

In formula A-1, W¹The preferably alkylidene of carbon number 1～6, the more preferably alkylidene of carbon number 2～6, and then preferably carbon number 2 Or the alkylidene of 3, particularly preferred ethylidene.

In formula A-2, there is the X of five²In, at least three represents acryloyl group epoxide or methylacryloyl epoxide, preferably Acryloyl group epoxide.Additionally, there are the X of five²In, three～five is acryloyl group epoxide or methylacryloyl epoxide, Preferably four～five is acryloyl group epoxide or methylacryloyl epoxide, and more preferably five is acryloyl group epoxide Or methylacryloyl epoxide.

It addition, the X beyond acryloyl group epoxide or methylacryloyl epoxide²Represent hydrogen atom, hydroxyl or carbon number 1～6 Alkyl.The alkyl of carbon number 1～6 can be straight-chain, branch-like, ring-type arbitrary alkyl.In these groups, (methyl) acryloyl X beyond base epoxide²Preferably hydrogen atom or the alkyl of carbon number 1～4, more preferably hydrogen atom, methyl or ethyl, and then preferably hydrogen Atom.

In formula A-2, W²With the W in formula A-1¹The most identical for synonymous, preferably scope.

Composition A be used as listing product, such as can enumerate East Asia synthesis (stock) manufacture as modified by polyacid acrylic acid It is M-510, M-520, TO-2349, TO-2359 etc. of sub-Luo Nisi (Aronix) (registration mark) series of oligomer.

Composition A can be used alone one, it is possible to and with two or more.

Relative to the total organic solid composition of photosensitive composite, the content of composition A preferably 3 mass %～60 mass %, more excellent Select 3 mass %～50 mass %, and then preferably 5 mass %～40 mass %, most preferably 10 mass %～35 mass %.

Additionally, in the present invention, " solid constituent " in so-called photosensitive composite, refer to volatile ingredients such as organic solvents Except composition.It addition, so-called " organic solid composition ", refer to the volatility such as organic solvent be become from photosensitive composite Point and the inorganic constituents such as inorganic particulate except composition.

It addition, in the photosensitive composite of the present invention, containing of the composition A total content relative to composition A and composition B described later Measure preferably 10 mass %～75 mass %, more preferably 10 mass %～50 mass %, and then preferably 15 mass %～40 mass %. If described scope, then crimping characteristic when developing is more excellent, and film thinning when can suppress development further.

Composition B: intramolecular has (methyl) acryloyl group of more than three and does not have the polymerizable monomer of carboxyl

The photosensitive composite of the present invention contains intramolecular to be had (methyl) acryloyl group of more than three and not to have the polymerization of carboxyl Property monomer is as composition B.

Composition B is to have the polymerization different from composition A of (methyl) acryloyl group of more than three in intramolecular (in a part) Property monomer.Composition B does not have carboxyl in intramolecular, does not the most have other acidic groups, other acidic groups can illustrate sulfonic group, Phosphate etc..

Composition B can be low molecular compound, it is possible to for oligomer, but and non-polymer.That is, from the sight of the hardness of cured film From the point of view of Dian, the molecular weight (for weight average molecular weight in the case of having molecular weight distribution) of composition B is 10, less than 000, Preferably 5, less than 000, and then preferably 3, less than 000.

The number of (methyl) acryloyl group that composition B is had is more than three, preferably 3～15, more preferably 3～10, most preferably 3～6.If described scope, then re-workability is excellent with crimping inhibition.

Composition B can suitably select the compound applied in this composition to use, such as, can enumerate Japanese Patent Laid-Open The composition described in paragraph 0011 of 2006-23696 publication or the paragraph 0031 of Japanese Patent Laid-Open 2006-64921 publication～ In composition described in paragraph 0047, there is in intramolecular the composition of (methyl) acryloyl group of more than three, these are recorded also Enter in present specification.

Composition B preferably illustrates (methyl) acrylate of polyol, specifically can enumerate: pentaerythrite three (methyl) Acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) Acrylate, three ((methyl) acryloyl group epoxide ethyl) isocyanuric acid ester, trimethylolpropane tris (methyl) acrylate, season penta Tetrol four (methyl) acrylated epoxy ethane (EO) modified body, dipentaerythritol six (methyl) acrylate EO modification body etc..

Composition B is used as the product of listing, such as, can enumerate: sub-Luo Nisi (Aronix) (registration mark) M-309, Sub-Luo Nisi (Aronix) M-400, sub-Luo Nisi (Aronix) M-405, sub-Luo Nisi (Aronix) M-450, Ya Luoni This (Aronix) M-7100, sub-Luo Nisi (Aronix) M-8030, sub-Luo Nisi (Aronix) M-8060, sub-Luo Nisi (Aronix) TO-1382, sub-Luo Nisi (Aronix) TO-1450 (East Asia synthesis (stock) manufactures), Ka Yala get (KAYARAD) TMPTA, Ka Yala get (KAYARAD) DPHA, Ka Yala get (KAYARAD) DPCA-20, Ka Yala get (KAYARAD) DPCA-30, Ka Yala get (KAYARAD) DPCA-60, Ka Yala get (KAYARAD) DPCA-120 (Japan's chemical drug (stock) manufactures), than this gram (Biscoat) 295, than this gram (Biscoat) 300, than this gram (Biscoat) 360, than this gram (Biscoat) GPT, than this gram (Biscoat) 3PA, than this gram (Biscoat) 400 (Osaka organic chemistry Industry (stock) manufactures) etc..

Even if additionally, be the compound being equivalent to composition B, the compound being equivalent to aftermentioned alkoxysilane compound containing trialkylsilyl group in molecular structure is also regarded as Alkoxysilane compound containing trialkylsilyl group in molecular structure.

<(methyl) propenoic methyl carbamate>

In the present invention, it is possible to use (methyl) propenoic methyl carbamate is as composition B.

In the present invention, spendable (methyl) propenoic methyl carbamate can illustrate use isocyanates and the addition reaction of hydroxyl and make The carbamate addition polymerization compound made, can illustrate Japanese Patent Laid-Open No. Sho 51-37193 publication, Japan Patent spy public affairs Such propenoic methyl carbamate class described in flat 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication, by this A little record is incorporated in present specification.

From the viewpoint of cured film hardness, the molecular weight preferably 500～10,000 of (methyl) propenoic methyl carbamate, more preferably 650～6,000, and then preferably 800～3,000.

By being set to this composition, and more effectively play the effect of the present invention.

(methyl) acryloxy in (methyl) propenoic methyl carbamate can be acryloxy, methacryloxy arbitrary Person, it is possible to for both, preferably acryloxy.

The number preferably more than 3, more preferably more than 6 of (methyl) acryloxy in (methyl) propenoic methyl carbamate, and then Preferably more than 10.If described embodiment, the most more effectively play the effect of the present invention.

It addition, the upper limit of the number of described (methyl) acryloxy there is no particular restriction, preferably less than 50, more preferably 30 with Under, and then preferably less than 20.

The photosensitive composite of the present invention can contain only one (methyl) propenoic methyl carbamate, it is possible to containing two or more.

There is no particular restriction for the number of the amino-formate bond in (methyl) propenoic methyl carbamate, preferably 1～30, more preferably 1～ 20, and then preferably 2～10, particularly preferred 2～5, most preferably 2 or 3.

(methyl) propenoic methyl carbamate preferably aliphatic (methyl) propenoic methyl carbamate.

It addition, (methyl) propenoic methyl carbamate preferably has isocyanuric acid ring (isocyanuric ring) structure.

It addition, (methyl) propenoic methyl carbamate preferably comprise have more than one amino-formate bond core part, And it is bonded in core part and has the compound of end section of more than one (methyl) acryloxy, more preferably in institute State the compound being bonded with plural described end section in core part, and then be preferably bonded with in described core part The compound of two～five described end sections, is particularly preferably bonded with two or three described ends in described core part The compound of end portion.

(methyl) propenoic methyl carbamate preferably at least has the chemical combination of the group represented by following formula Ae-1 or formula Ae-2 Thing, more preferably at least has the compound of group represented by following formula Ae-1.It addition, (methyl) Acrylic Ester more preferably has plural choosing group represented by free following formula Ae-1 and the institute of the group represented by formula Ae-2 group The compound of the group in the group become.

It addition, preferred following formula Ae-1 of described end section of (methyl) propenoic methyl carbamate or the base represented by formula Ae-2 Group.

[changing 2]

In formula Ae-1 and formula Ae-2, R separately represents that acrylic or methacrylic acid group, swash part represent and it The bonding position of his structure.

It addition, (methyl) propenoic methyl carbamate preferably at least has the group represented by following formula Ac-1 or formula Ac-2 Compound, more preferably at least there is the compound of group represented by following formula Ac-1.

It addition, described preferred following formula Ac-1 of core part in (methyl) propenoic methyl carbamate or the base represented by formula Ac-2 Group.

[changing 3]

In formula Ac-1 and formula Ac-2, L¹～L⁴Separately represent carbon number 2～20 bivalent hydrocarbon radical, swash part represent with The bonding position of other structures.

L¹～L⁴The separately alkylidene of preferred carbon number 2～20, the more preferably alkylidene of carbon number 2～10, and then preferably carbon The alkylidene of several 4～8.It addition, described alkylidene also can have branched structure or ring structure, preferably straight-chain alkyl-sub.

It addition, (methyl) propenoic methyl carbamate is particularly preferably the group represented by formula Ac-1 or formula Ac-2 with choosing freely The compound of two or three group bondings in the group that the group represented by formula Ae-1 and formula Ae-2 is formed.

(methyl) propenoic methyl carbamate preferably used in the present invention illustrated below, but the present invention is not limited to this certainly A little compounds.

[changing 4]

[changing 5]

[changing 6]

Use isocyanates anti-with the addition of hydroxyl it addition, spendable in the present invention (methyl) propenoic methyl carbamate can illustrate The carbamate addition polymerization compound answered and manufacture, can illustrate Japanese Patent Laid-Open No. Sho 51-37193 publication, Japan specially Such propenoic methyl carbamate class described in profit JP 2-32293 publication, Japanese Patent Laid-fair 2-16765 publication, These records are incorporated in present specification.

The commercially available product of (methyl) propenoic methyl carbamate can illustrate: the NK ester that can obtain from Xin Zhong village chemical industry (stock) U-6HA, NK ester UA-1100H, NK ester U-6LPA, NK ester U-15HA, NK ester U-6H, NK ester U-10HA, NK ester U-10PA, NK ester UA-53H, NK ester UA-33H (being registration mark), or can be from common prosperity society chemistry (stock) UA-306H, UA-306T, UA-306I, the UA-510H obtained, the La Luomo that can obtain from BASF (BASF) company (Laromer) UA-9048, La Luomo (Laromer) UA-9050, La Luomo (Laromer) PR9052, can be from Daicel Ai Bai gram force (EBECRYL) 220 that-fine jade Knicks (Daicel-Allnex) (stock) difficult to understand obtains, Ai Bai gram force (EBECRYL) 5129, Ai Bai gram force (EBECRYL) 8301, Ai Bai gram force (EBECRYL) KRM8200, Ai Bai gram force (EBECRYL) 8200AE, Ai Bai gram force (EBECRYL) 8452 etc..

Composition B can be used alone one, it is possible to and with two or more.

Relative to the total organic solid composition of photosensitive composite, the content of composition B preferably 10 mass %～90 mass %, more Preferably 30 mass %～85 mass %, and then preferably 45 mass %～75 mass %.

In the photosensitive composite of the present invention, composition A and composition B is relative to the total content of the total organic solid composition in composition Preferably 30 mass %～99 mass %, more preferably 40 mass %～99 mass %, and then preferably 70 mass %～95 mass %. If described scope, then can suppress film thinning during development further.

Additionally, it is preferable that the content of the composition B in the photosensitive composite of the present invention in terms of mass conversion is more than containing of composition A Amount.If described scope, then can suppress film thinning during development further.

Composition C: Photoepolymerizationinitiater initiater

The photosensitive composite of the present invention contains Photoepolymerizationinitiater initiater as composition C.

Photoepolymerizationinitiater initiater preferably contains optical free radical polymerization initiator.

In the present invention, spendable Photoepolymerizationinitiater initiater is the compound that can be caused, promote polymerization by light.Wherein, more preferably Be optical free radical polymerization initiator.

So-called " light ", can be produced, as long as giving for being irradiated by it, the active energy ray causing the energy planted by composition C, Then there is no particular restriction, comprises alpha ray, gamma-rays, X-ray, ultraviolet (Ultra Violet, UV), visible widely Light, electron beam etc..In these, preferably at least bag light with violet rays.

Photoepolymerizationinitiater initiater such as can be enumerated: oxime ester compound, organic halogenation compound, epoxide diazole compounds, carbonyl compound Thing, ketal compound, styrax compound, acridine compounds, organic peroxy compound, azo-compound, cumarin Compound, azido compound, metallocene compound, six aryl united imidazoles, organic boric acid compounds, disulfonic acid compound, Salt compound, acylphosphanes (oxide) compound.In these compounds, in terms of sensitivity from the point of view of, preferably oxime ester compound, Six aryl united imidazole, more preferably oxime ester compounds.

Oxime ester compound can use: Japanese Patent Laid-Open 2000-80068 publication, Japanese Patent Laid-Open 2001-233842 public affairs Report, Japan Patent spy's table 2004-534797 publication, Japanese Patent Laid-Open 2007-231000 publication, Japanese Patent Laid-Open Described in the paragraph 0046 of the publication of 2009-134289 publication and International Publication the 2012/057165th～paragraph 0059 Compound.

The example of organic halogenation compound specifically can be enumerated: if " Japanization association publication (the Bull Chem.Soc. of woods et al. Japan) " (42,2924 (1969)), No. 3,905,815 specifications of U.S. Patent No., Japan Patent examined patent publication 46-4605 Number publication, Japanese Patent Laid-Open No. Sho 48-36281 publication, Japanese Patent Laid-Open No. Sho 55-32070 publication, Japanese Patent Laid-Open Clear 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 " the heterocycle of 63-70243 publication, Japanese Patent Laid-Open No. Sho 63-298339 publication, M.P. Hunter (M.P.Hutt) et al. Chemical periodical (Joumal of Heterocyclic Chemistry) " compound described in (7,511 (1970)) etc., especially Can enumerate through the three substituted azole compounds of halogenated methyl, s-triazine.

The example of six aryl united imidazoles such as can be enumerated: Japanese Patent Laid-fair 6-29285 publication, U.S. Patent No. No. 3,479,185, U.S. Patent No. 4,311,783, U.S. Patent No. 4,622,286 etc. each specification described in various Compound.

Acylphosphanes (oxide) compound can illustrate monoacylphosphine oxides compound and bisacylphosphine oxides compound, specifically comes Say, such as, can enumerate: gorgeous good solid (Irgacure) 819 that BASF (BASF) company manufactures, reach Luo Gu (Darocure) 4265, Luo Gu (Darocure) TPO etc. is reached.

Photoepolymerizationinitiater initiater can use one or be applied in combination two or more.

Relative to total solid composition 100 mass parts in composition, the Photoepolymerizationinitiater initiater in the photosensitive composite of the present invention Content preferably 0.5 mass parts～30 mass parts, more preferably 1 mass parts～20 mass parts, and then preferably 1 mass parts～10 mass Part, particularly preferred 1.5 mass parts～5 mass parts.

Components D: there is the compound of phosphate ester structure and ethene unsaturated group

The photosensitive composite of the present invention contains and has the compound of phosphate ester structure and ethene unsaturated group as components D, and And components D is 0.01 mass %～5 mass % relative to the content of the total organic solid composition in composition.

Phosphate ester structure in components D can be phosphate monoester structure, it is possible to for phosphodiester moieties, can be also phosphotriester structure, Preferably phosphoric acid monoesters structure or phosphodiester moieties.That is, components D preferably contains the compound with P-OH structure.

Ethene unsaturated group in components D can enumerate (methyl) acryloyl group, vinyl, pi-allyl, styryl, ethene Base ether, vinyl ester group etc., preferably (methyl) acryloyl group, more preferably (methyl) acryloyl group epoxide.If described embodiment party Formula, then hardening and reactive excellence, and re-workability is more excellent.

There is no particular restriction for the number of the ethene unsaturated group in components D, preferably 1～6, more preferably 1～3, particularly preferably 1 or 2.

The molecular weight of components D is preferably less than 1,000.

Compound represented by components D preferred formula D-1.

[changing 7]

In formula D-1, R^DSeparately represent hydrogen atom or methyl, L^DSeparately represent bivalence linking base, n represent 1～ 3。

R^DPreferably methyl.

L^DThe most separately for alkylidene or by two or more alkylidene and choosing freely more than one ehter bond and ester bond institute group The group of the key combination in the group become, is the most separately alkylidene, and then is the most separately sub-second Base.

L^DCarbon number preferably 2～40, more preferably 2～20, and then preferably 2～8, particularly preferred 2.

N preferably 1～2.Additionally, n non-integral situation represent that n takes two or more the mixing of described value with the form of mean value Compound.

The concrete example of components D can enumerate compound shown below, but is certainly not limited to these compounds.

[changing 8]

[changing 9]

[changing 10]

The commercially available product of these compounds can be enumerated: JPA-514 (north of the city chemical industry (stock) manufacture), Lay spy acrylate (Light Acrylate) P-1A (N), Lay spy's acrylate (LightAcrylate) P-1M, Lay spy's acrylate (LightAcrylate) P-2M (common prosperity society chemistry (stock) manufactures), Ka Yamei (KAYAMER) PM-2, Ka Yamei (KAYAMER) PM-21 (Japan's chemical drug (stock) manufactures), MR-200, MR-260 (manufacture of big eight chemical industry (stock)) etc..

Components D can individually contain one, it is possible to containing two or more.

In the photosensitive composite of the present invention, components D relative to the content of the total organic solid composition in photosensitive composite is 0.01 mass %～5 mass %, preferably 0.05 mass %～4.5 mass %, more preferably 0.1 mass %～4 mass %, Jin Eryou Select 0.3 mass %～3 mass %, particularly preferred 0.5 mass %～2 mass %.If described scope, then when can obtain development Crimping characteristic is more excellent and cured film that film thinning of when developing is less.

Composition K: polymerization inhibitor

The photosensitive composite of the present invention contains polymerization inhibitor as composition K, and total solid relative in composition of composition K The content of body composition is 0.01 mass %～0.5 mass %.If containing polymerization inhibitor in the range of described, then when can obtain development Crimping excellent and also the few cured film of film thinning when developing.

So-called polymerization inhibitor, refers to play the material of following effect: to by exposure or hot and by produced by polymerization initiator Polymerization initiation radical composition implements hydrogen supply (or awarding hydrogen), energy supply (or awarding energy), supplied for electronic (or awarding electronics) etc., makes to gather Close and cause free radical inactivation, suppression polymerization to cause.Such as can use the paragraph of Japanese Patent Laid-Open 2007-334322 publication 0154～paragraph 0173 described in compound etc..

The kind of polymerization inhibitor preferably uses compound that is hard and that do not reduce sensitivity.This polymerization inhibitor can be enumerated: Phenthazine, chlorpromazine (chlorpromazine), levomepromazine (1evomepromazine), fluphenazine (fluphenazine), The phenothiazine derivatives such as thioridazine (thioridazine), azophenlyene, 3,7-double (diethylamino) azophenlyene-5-perchlorate, 5-amino-9-(dimethylamino)-10-methyl benzo [a] azophenlyene-7-chlorate, 7-(amoxy)-3H-azophenlyene-3-ketone, 5,9-diamino The phenazene derivative such as base benzo [a] azophenlyene-7-acetate, 7-ethyoxyl-3H-azophenlyene-3-ketone, three-p-nitrophenyl ylmethyl, The stabilized radicals such as diphenyl bitter taste diazanyl (diphenyl picrylhydrazyl), jar (unit of capacitance) ten thousand epoxide (galvinoxyl), quinone, benzene Quinone, chloranil, 2,5-bis--chloranil, 2,6-bis--chloranil, 2,3-bis--methylbenzoquinone, 2,5-bis--methylbenzoquinone, methoxyl group benzoquinones, Methylbenzoquinone, tetrabromo-quinone, tetrachloroquinone, tetramethyl-benzoquinone, trichlorine benzoquinones, trimethylbenzoquinone, amyl group quinone, amoxy pair Benzenediol, 2,5-di-t-butyl hydroquinones, 2, the quinones such as 5-diphenyl 1,4-benzoquinone, alpha-Naphthol, 2-nitro-1-naphthols, betanaphthol, The aphthols such as 1-nitro-beta naphthal, 4-metoxyphenol, 4-thanatol, hydroquinones, phenol, tert-butyl catechol, Methyl hydroquinone, normal-butyl phenol, hydroquinones list propyl ether, tert-butyl group cresols, paracresol, 2,6-di-t-butyl paracresol, Catechol resorcinol, o-tert-butylphenol, 2,6-bis--p methoxy phenol, 2,6-di-t-butyl phenol, 2,4-di-t-butyl Phenol, 3,5-di-t-butyl phenol, 3,5-di-t-butyl-4-HBA, N, N '-bis--3-(3 ', 5 '-di-t-butyl-4-hydroxy benzenes Base) propiono hexamethylene diamine, 2,2 '-di-2-ethylhexylphosphine oxide (6-Butylated Hydroxytoluene), 3-(4-hydroxyl-3 ', 5 '-di-t-butyl phenyl) propionic acid N-octadecane base ester, (the 4-hydroxy-3-methyl-5-tert-butyl group) benzyl malonic acid distearyl ester, 2,4,6-tri--tert-butyl phenols, 1,6-oneself Double [the 3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) third of glycol double [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester], triethylene glycol Acid esters], 2,2-thiodiethylene double [3-(3,5-di-t-butyl-4-hydroxy phenyl) propionic ester], 3, double [1, the 1-dimethyl-2-[β-(3-of 9- Tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxyethyl-2,4,8,10-tetra-oxaspiro [5.5] hendecanes, 2,2 '-ethylidene-bis-(2,4-bis- -tert-butyl phenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-tri-(3,5-bis--tertiary fourths Base-4-hydroxybenzyl) benzene, three (3,5-di-t-butyl-4-hydroxybenzyl) isocyanates, three [2-(3 ', 5 '-di-t-butyl-, 4 '-hydroxyl phenylpropyl alcohols Acyloxy) ethyl] isocyanates, three (the 4-tert-butyl group-2,6-bis--methyl-3-hydroxybenzyl) isocyanates, four [methylene-3-(3 ', 5 '-two- The tert-butyl group-4 '-hydroxy phenyl) propionic ester] phenols such as methane, 2,4-DNP, o-nitrophenol, metanitrophenol, to nitro The nitrophenyl phenolics such as phenol, the gallic acid such as gallic acid, gallicin, propylgallate, isoamyl gallate Class, the pigment such as methylene blue, peacock green, betanaphthyl amine, N-nitroso cyclohexyl amine salt, two-to amines such as fluorophenyl amine, Pyrogallol, single benzyl oxide, benzoquinones, triphenylphosphine, stannous chloride, phenthazine, chloranil (chloranil), pyridine, nitrobenzene, Dinitro benzene, para-totuidine, picric acid, gaultherolin etc..

Polymerization inhibitor preferably selects the group that the derivative of free phenthazine, azophenlyene, hindered amine and these compounds is formed At least one in Qun, is more desirably selected from the group being made up of the derivative of phenthazine, azophenlyene and these compounds In at least one, particularly preferably select at least one in the group that free phenthazine and azophenlyene formed.

Phenthazine and derivative thereof can illustrate: phenthazine, double (α-methylbenzyl) phenthazine, 3,7-dioctyl phenthazine, double (α- Dimethyl benzyl) phenthazine, fluphenazine (fluphenazine), thioridazine (thioridazine), preferably phenthazine (phenothiazine)。

Azophenlyene and derivative thereof can illustrate: azophenlyene, 3,7-double (diethylamino) azophenlyene-5-perchlorate, 5-amino-9-(two Methylamino)-10-methyl benzo [a] azophenlyene-7-chlorate, 7-(amoxy)-3H-fen k piperazine-3-ketone, 5,9-diaminourea benzo [a] fen Piperazine-7-acetate, 7-ethyoxyl-3H-azophenlyene-3-ketone, preferably azophenlyene.

Hindered amine and derivative thereof can illustrate: intelligence Ma Suobu (CHIMASSORB) 2020FDL, slave refined (TINUVIN) 144, refined (TINUVIN) 765 of slave, slave refined (TINUVIN) 770 (being that BASF (BASF) company manufactures above), Preferably refined (TINUVIN) 144 of slave.

There is no particular restriction for the content of the polymerization inhibitor in the photosensitive composite of the present invention, total relative to photosensitive composite Solid constituent, is 0.01 mass %～0.5 mass %, preferably 0.05 mass %～0.5 mass %, more preferably 0.06 mass %～0.4 Quality %, particularly preferred 0.07 mass %～0.25 mass %.By adjusting the allotment amount of polymerization inhibitor, patterning can be improved And do not undermine sensitivity.

Composition E: inorganic particulate

The photosensitive composite of the present invention preferably contains inorganic particulate as composition E.By containing inorganic particulate, cured film Hardness become more excellent.

Preferred 1nm～200nm of average grain diameter, more preferably 5nm～100nm of inorganic particulate used in the present invention, and then Preferably 5nm～50nm.Average grain diameter refers to utilize the particle diameter of any 200 particles of determination of electron microscopy arithmetic average in addition The value of gained.It addition, in the case of the shape aspherical of particle, the longest limit is set to diameter.

It addition, from the viewpoint of the hardness of cured film, the voidage of inorganic particulate is preferably less than 10%, more preferably Less than 3%, most preferably tight.The voidage of particle is gap and the grain of the cross-sectional image by electron microscope gained The arithmetic average of 200 of the area ratio of subpopulation.

Inorganic particulate preferably contain beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), scandium (Sc), Yttrium (Y), lanthanum (La), cerium (Ce), gadolinium (Gd), terbium (Tb), dysprosium (Dy), ytterbium (Yb), lutetium (Lu), Titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), molybdenum (Mo), tungsten (W), zinc (Zn), boron (B), Aluminium (Al), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), tellurium (Te) etc. The metal oxide particle of atom, more preferably silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium/tin Oxide, antimony/tin-oxide, and then preferential oxidation silicon, titanium oxide, titanium composite oxide, zirconium oxide, from the stability of particle, From the point of view of obtaining the viewpoint such as easiness, the hardness of cured film, the transparency, refractive index adjustment, particularly preferred silica, titanium oxide, Zirconium oxide.

Silica preferably enumerates silica, it may be more preferable to silicon dioxide granule is enumerated on ground.

As long as the particle that silicon dioxide granule is the inorganic oxide containing silica, then there is no special problem, preferably contain There is silica or its hydrate particle as principal component (more than preferably 80 mass %).Described particle also can contain aluminate As a small amount of composition (e.g., less than 5 mass %).Sometimes the aluminate contained as a small amount of composition can enumerate sodium aluminate, aluminic acid Potassium etc..It addition, silicon dioxide granule also can contain the inorganic salts such as NaOH, potassium hydroxide, lithium hydroxide, ammonium hydroxide Or the organic salt such as tetramethyl ammonium hydroxide.The example of this compound can illustrate cataloid.

There is no particular restriction for the decentralized medium of cataloid, can be mixture arbitrary of water, organic solvent and these materials Kind.These decentralized media can be used alone one, it is possible to and with two or more.

In the present invention, particle also can with the form of dispersion liquid for, described dispersion liquid is by suitable dispersant and solvent The mixing arrangements such as middle use ball mill, rod mill carry out mixing dispersion and prepare.Additionally, in the photosensitive composite of the present invention, Cataloid is without existing with colloidal state.

About the content of inorganic particulate, in the case of allotment inorganic particulate, from the viewpoint of hardness, relative to photonasty group The total solid composition of compound, more than preferably 1 mass %, more than more preferably 5 mass %, and then more than preferably 10 mass %.Separately Outward, below preferably 80 mass %, below more preferably 50 mass %, and then below preferably 40 mass %, particularly preferred 30 mass Below %.

Inorganic particulate can contain only one, it is possible to containing two or more.Containing in the case of two or more, preferably it closes Metering becomes described scope.

Composition F: blocked isocyanate compound

The photosensitive composite of the present invention preferably contains blocked isocyanate compound as composition F.By containing composition F, Re-workability is more excellent.Its mechanism of action is the most indefinite, but heating after being considered because of photo-hardening and the closing of composition F is different Cyanic acid ester group deprotection.Be inferred as in cured film, by be derived from the effect of the NCO of composition F and with the contiguity of substrate Property improve, or re-workability is excellent by NCO and moisture, salt interaction.

As long as blocked isocyanate compound is the compound with blocked isocyanate base, then there is no particular restriction, from hardening From the viewpoint of, preferably there is in a part the compound of plural blocked isocyanate base.Blocked isocyanate The upper limit of the number of base not specially provided for, preferably less than 6.

It addition, about blocked isocyanate compound, its skeleton is not particularly limited, if different for having two in a part The compound of cyanic acid ester group, then can be arbitrary compound, can be aliphatic, alicyclic or aromatic PIC, example As used suitably: 2,4-toluene di-isocyanate(TDI)s, 2,6-toluene di-isocyanate(TDI), IPDI, 1,6-six is sub- Methyl diisocyanate, 1,3-trimethylene diisocyanate, Isosorbide-5-Nitrae-tetramethylene diisocyanate, 2,2,4-tri-methyl hexamethylenes Diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanates, 1,9-nine methylene diisocyanate, 1,10-decamethylene two Isocyanates, Isosorbide-5-Nitrae-cyclohexane diisocyanate, 2,2 '-Anaesthetie Ether diisocyanate, diphenyl methane-4,4 '-diisocyanate, Ortho-xylene diisocyanate, m xylene diisocyanate, paraxylene diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl isocyanic acid Ester), hexamethylene-1,3-dimethylene diisocyanate, hexamethylene-Isosorbide-5-Nitrae-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, 3,3 '-xylene-4,4 '-diisocyanate, 4,4 '-diphenyl ether diisocyanate, tetrachlorobenzene two are different Cyanate, norbornene alkyl diisocyanate, hydrogenation 1,3-XDI, hydrogenation Isosorbide-5-Nitrae-XDI etc. are different Cyanate esters and the polymer of these compounds and the compound of the skeleton of prepolymer type derived by these compounds. In these compounds, preferably will select free toluene di-isocyanate(TDI) (TDI) or methyl diphenylene diisocyanate (MDI), In the group that hexamethylene diisocyanate (HDI), IPDI (IPDI) and these polymer are formed The blocked isocyanate compound of compound protection, more preferably will choosing free hexamethylene diisocyanate, different Buddhist The blocked isocyanate compound of the compound protection in the group that ketone diisocyanate and these polymer are formed.

As long as the polymer that the polymer of isocyanate compound is more than dimer, then there is no particular restriction, can illustrate biuret (biuret) body, isocyanuric acid ester body, adduction object etc., preferably biuret body.

The parent structure of the blocked isocyanate compound in the photosensitive composite of the present invention can be enumerated: biuret type, isocyanuric acid Ester type, adduct type, two functional prepolymer types etc..

The sealer of the enclosed construction forming described blocked isocyanate compound can be enumerated: oxime compound, lactam compound, Phenolic compounds, alcoholic compound, amines, activity methene compound, pyrazole compound, mercaptan compound, imidazoles system Compound, imide series compound etc..In these compounds, preferably oxime compound, lactam compound, phenolic compounds, alcoholization Compound, amines, activity methene compound or pyrazole compound, more preferably oxime compound and lactam compound, And then preferably oxime compound, particularly preferred methyl ethyl ketone oxime.

Described oxime compound can enumerate oxime and ketoxime, can illustrate specifically: acetyl oxime, carbamoyl oxime, hexamethylene oxime, methyl Ethyl ketoxime, cyclohexanone oxime, diphenyl-ketoxime etc..

Described lactam compound can illustrate: epsilon-caprolactams, butyrolactam etc..

Described phenolic compounds can illustrate: phenol, naphthols, cresols, xylenol, through the phenol etc. of halogen substiuted.

Described alcoholic compound can illustrate: methyl alcohol, ethanol, propyl alcohol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propane diols list Alkyl ether, lactic acid alkyl ester etc..

Described amines can enumerate one-level amine and secondary amine, can be aromatic amine, aliphatic amine, cycloaliphatic amines any one, Can illustrate: aniline, diphenylamine, aziridine, ethylene imine etc..

Described activity methene compound can illustrate: diethyl malonate, dimethyl malenate, ethyl acetoacetate, acetyl second Acid methyl esters etc..

Described pyrazole compound can illustrate: pyrazoles, methylpyrazole, dimethyl pyrazole etc..

Described mercaptan compound can illustrate: alkyl hydrosulfide, aryl mercaptan etc..

In the photosensitive composite of the present invention, the form of the spendable commercially available product of blocked isocyanate compound obtains, and such as may be used It is preferably used: Crow Nat (Coronate) AP stable (Stable) M, Crow Nat (Coronate) 2503, Crow Nat (Coronate) 2515, Crow Nat (Coronate) 2507, Crow Nat (Coronate) 2513, Crow Nat (Coronate) 2555, rice Leo resistance to moral (Millionate) MS-50 (be that Japan's polyurethanes industry (stock) makes above Make), Plutarch Nat (Takenate) B-830, Plutarch Nat (Takenate) B-815N, Plutarch Nat (Takenate) B-820NSU, Plutarch Nat (Takenate) B-842N, Plutarch Nat (Takenate) B-846N, Plutarch Nat (Takenate) B-870N, Plutarch Nat (Takenate) B-874N, Plutarch Nat (Takenate) B-882N (being that Mitsui Chemicals (stock) manufactures above), Du draw Nat (Duranate) 17B-60P, Du draw Nat (Duranate) 17B-60PX, Du draw Nat (Duranate) TPA-B80X, Du draws Nat (Duranate) TPA-B80E, Du to draw Nat (Duranate) MF-B60X, Du to draw Nat (Duranate) MF-B60B, Du draw Nat (Duranate) MF-K60X, Du to draw Nat (Duranate) MF-K60B, Du to draw Nat (Duranate) E402-B80B, Du draw Nat (Duranate) SBN-70D, Du to draw Nat (Duranate) SBB-70P, Du to draw Nat (Duranate) K6000 (being that Asahi Chemical Industry's chemistry (stock) manufactures above), desmodur (Desmodur) BL1100, desmodur (Desmodur) BL1265, desmodur (Desmodur) MPA/X, desmodur (Desmodur) BL3575/1, desmodur (Desmodur) BL3272MPA, desmodur (Desmodur) BL3370MPA, desmodur (Desmodur) BL3475BA/SN, desmodur (Desmodur) BL5375MPA, desmodur (Desmodur) VPLS2078/2, Desmodur (Desmodur) BL4265SN, desmodur (Desmodur) PL340, desmodur (Desmodur) PL350, Soviet Union meter Du Er (Sumidur) BL3175 are (above for living to change Bayer carbamate (Sumika-Bayer Urethane) (stock) manufactures) etc..

Composition F can individually contain one, it is possible to containing two or more.

Relative to the total solid composition of photosensitive composite, the blocked isocyanate compound in the photosensitive composite of the present invention Content preferably 0.1 mass %～20 mass %, more preferably 0.5 mass %～10 mass %, and then preferably 1 mass %～5 mass %.

It addition, relative to the total organic solid composition of photosensitive composite, the closing isocyanic acid in the photosensitive composite of the present invention The content of ester compounds preferably 0.1 mass %～20 mass %, more preferably 0.5 mass %～10 mass %, and then preferably 1 mass %～5 mass %.

If the content of composition F be described in the range of, then can obtain cured film of excellent in reliability, the most preferably.

-other compositions-

The photosensitive composite of the present invention is in addition to described composition, it is possible to containing other compositions.Other compositions can use many institute's weeks The composition known, it is preferable to illustrate each composition of following presentation.

The photosensitive composite of the present invention also can contain solvent.The photosensitive composite of the present invention is preferably prepared as must Need composition A～the components D of composition and addressed any composition described later dissolving and/or dispersion composition in a solvent.

The preferred organic solvent of solvent.Organic solvent used in the photosensitive composite of the present invention can use well-known molten Agent, can illustrate: ethylene glycol monoalkyl ether class, glycol dialkyl ether class, ethylene glycol monoalkyl ether acetate class, propane diols list Alkyl ether, propane diols dialkyl ether, propylene-glycol monoalky lether acetate esters, diethylene glycol dialkyl ether class, diethylene glycol Monoalkyl ether acetate class, dipropylene glycol monoalkylether class, butanediol oxalic acid esters, DPG dialkyl ether, dipropyl Glycol monoalkyl ether acetate esters, alcohols, esters, ketone, amide-type, lactone etc..The concrete example of these organic solvents can Paragraph 0062 with reference to Japanese Patent Laid-Open 2009-098616 publication.

Specifically, such as it is preferably selected from by propylene glycol methyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl Ether, propylene glycol monomethyl ether, 1,3-BDO diacetate esters, adnoral acetate, propylene-glycol diacetate and tetrahydrofurfuryl alcohol institute group At least one solvent in the group become.

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

In the present invention, spendable solvent can be used alone one or and with two or more.It is also preferred that by solvents different for boiling point And use.

About the content of the solvent in the photosensitive composite of the present invention, from the viewpoint of being adjusted to the viscosity being suitable to coating, phase For total solid composition 100 mass parts of composition, described content preferably 100 mass parts～3,000 mass parts, more preferably 200 Mass parts～2,000 mass parts, and then preferably 250 mass parts～1,000 mass parts.

The solid component concentration of photosensitive composite preferably 3 mass %～50 mass %, more preferably 20 mass %～40 mass %.

The viscosity preferred 1mPa s of photosensitive composite～200mPa s, more preferably 2mPa s～100mPa s, Jin Eryou Select 3mPa s～80mPa s.The RE-80L type rotation viscometer that viscosity such as manufactures preferably with east machine industry (stock) It is measured at 25 DEG C ± 0.2 DEG C.About measure time rotary speed, viscosity less than 5mPa s time preferably with 100rpm Rotary speed be measured, viscosity be 5mPa s less than during 10mPa s preferably with the rotary speed of 50rpm Be measured, viscosity be 10mPa s less than 30mPa s time be preferably measured with the rotary speed of 20rpm, When viscosity is more than 30mPa s, preferably rotary speed with 10rpm is measured.

From the point of view of improving the viewpoint such as distinguishing and epithelium characteristic, the photosensitive composite of the present invention preferably comprises binder polymer.

Described binder polymer preferred alkali-developable polymer.

So-called alkali-developable polymer refers to carry out the polymer of alkali development, and manifests in the case of contacting with alkaline aqueous solution Go out dissolubility and/or bloating tendency polymer.

There is no particular restriction for the alkali-developable group that alkali-developable polymer is had, it is preferable to enumerates carboxyl or hydroxyl, can be more Preferably enumerate carboxyl.

It addition, described binder polymer is preferably used threadlike organic polymers.This threadlike organic polymers can at random use Well-known threadlike organic polymers, preferably acrylic resin.Threadlike organic polymers is according to serving not only as epithelium formation Agent, and select as the purposes of the developer for the developer solution of water, alkalescent water or organic solvent system to use. If such as using water dissolvable organic polymer, water development can be carried out.This threadlike organic polymers can be enumerated: has on side chain There are the free radical polyalcohol of carboxylic acid group, such as Japanese Patent Laid-Open No. Sho 59-44615 publication, Japan Patent examined patent publication 54-34327 Number publication, Japan Patent examined patent publication 58-12577 publication, Japan Patent examined patent publication 54-25957 publication, Japanese Patent Laid-Open In clear 54-92723 publication, Japanese Patent Laid-Open No. Sho 59-53836 publication, Japanese Patent Laid-Open No. Sho 59-71048 publication The compound recorded, i.e. individually or the resin of combined polymerization, the monomer with acid anhydrides is independent by making to make to have the monomer of carboxyl Or the anhydride unit hydrolysis of combined polymerization or the half-esterification or resin of semi-amidation, with unsaturated monocarboxylic and acid anhydrides by ring The epoxy acrylate etc. of epoxy resins modification.

The monomer with carboxyl can be enumerated: acrylic acid, methacrylic acid, itaconic acid, butenoic acid, maleic acid, fumaric acid, 4- Carboxyl styrene etc..

The monomer with acid anhydrides can enumerate maleic anhydride etc..

It addition, the acid cellulose derivative similarly on side chain with carboxylic acid group can be enumerated.In addition, there is hydroxyl Polymer on the compound etc. of addition cyclic acid anhydride useful.

It addition, binder polymer preferably has bridging property base, more preferably contain the construction unit with bridging property base.

As long as described bridging property base is for causing the group of sclerous reaction by heating, then it is not particularly limited.

The preferred epoxy radicals of bridging property base, oxetanylmethoxy ,-NH-CH₂-O-R (R represents hydrogen atom or the alkyl of carbon number 1～20) Represented group or ethene unsaturated group, more preferably epoxy radicals or oxetanylmethoxy.

Such as can enumerate for forming the concrete example of the monomer of the construction unit with epoxy radicals: glycidyl acrylate, methyl Glycidyl acrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-n-butyl Ethylene oxidic ester, acrylic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, acrylic acid-3,4-epoxycyclohexanecarboxylate, Methacrylic acid-3,4-epoxycyclohexanecarboxylate, α-ethylacrylate-3,4-epoxycyclohexanecarboxylate, adjacent vinylbenzyl glycidyl Ether, a vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, the section of No. 4168443 publications of Japanese Patent No. Fall 0031～paragraph 0035 described in the compound etc. containing ester ring type epoxy skeleton.

Japanese Patent Laid-Open such as can be enumerated for forming the concrete example of the monomer of the construction unit with oxetanylmethoxy (methyl) acrylate etc. with oxetanylmethoxy described in the paragraph 0011 of 2001-330953 publication～paragraph 0016.

It addition, in the polymerization of binder polymer use monomer can enumerate specifically: styrene, t-butoxystyrene, Methyl styrene, AMS, acetoxy-styrene, methoxy styrene, ethoxystyrene, chlorostyrene, second Alkenyl benzene methyl formate, vinyl benzoic acid ethyl ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid N-propyl, (methyl) isopropyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate, acrylonitrile, ethylene glycol The construction unit of single acetyl acetic acid esters list (methyl) acrylate etc..In addition, Japanese Patent Laid-Open 2004-264623 can be enumerated Compound described in the paragraph 0021 of number publication～paragraph 0024.

It addition, from the viewpoint of electrical characteristics, binder polymer preferably comprises and is derived from phenylethylene or has aliphatic ring type bone The construction unit of the monomer of frame, more preferably contains the construction unit being derived from the monomer with aliphatic ring type skeleton.These monomers, Can enumerate specifically: styrene, t-butoxystyrene, methyl styrene, AMS, (methyl) acrylic acid two ring Pentyl ester, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) benzyl acrylate etc..

And then, about binder polymer, from the viewpoint of adhesion, preferably originate from the structure of (methyl) alkyl acrylate Unit.(methyl) alkyl acrylate specifically can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid third Ester, (methyl) n-butyl acrylate etc., more preferably (methyl) methyl acrylate.

Binder polymer can individually contain one, it is possible to containing two or more.

There is no particular restriction for the content of the binder polymer in the photosensitive composite of the present invention, relative to photosensitive composite For total solid composition, preferably 1 mass %～70 mass %, more preferably 5 mass %～60 mass %, and then preferably 10 mass %～55 mass %, particularly preferred 20 mass %～50 mass %.

The photosensitive composite of the present invention preferably contains alkoxysilane compound containing trialkylsilyl group in molecular structure.If use alkoxysilane compound containing trialkylsilyl group in molecular structure, then The adhesion of film and the substrate utilizing the photosensitive composite of the present invention and formed can be improved.

As long as alkoxysilane compound containing trialkylsilyl group in molecular structure is the compound with the group that at least one alkoxyl is directly binding on silicon atom, Then there is no particular restriction, preferably has dialkoxy silicane base and/or the compound of trialkoxy silane base, more preferably There is the compound of trialkoxy silane base.

In the present invention, spendable alkoxysilane compound containing trialkylsilyl group in molecular structure preferably makes the silication such as base material, such as silicon, silica, silicon nitride The compound that the adhesion of the metals such as compound, gold, copper, molybdenum, titanium, aluminium and cured film improves.Specifically, it is thus well known that Silane coupling agents etc. are the most effective.Preferably there is the silane coupling agent of ethene unsaturated bond.

Silane coupling agent such as can be enumerated: gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, γ-shrink are sweet Oil epoxide propyl trialkoxy silane, γ-glycidoxypropyl dialkoxy silicane, γ-methacryloxypropyl three alcoxyl Base silane, γ-methacryloxypropyl dialkoxy silicane, γ-chloropropyl trialkoxy silane, γ-mercaptopropyi tri-alkoxy Silane, β-(3,4-epoxycyclohexyl) ethyltrialkoxysilanes and vinyl trialkyl oxysilane.In these compounds, more excellent Select γ-methacryloxypropyl trialkoxy silane, γ-acryloxy propyl trialkoxy silane, vinyl tri-alkoxy silicon Alkane and/or γ-glycidyloxypropyl silane.These compounds can be used alone one or be applied in combination two kinds with On.

Commercially available product can illustrate KBM-403 or KBM-5103 that SHIN-ETSU HANTOTAI's chemical industry (stock) manufactures.

Relative to the total solid composition of photosensitive composite, containing of the alkoxysilane compound containing trialkylsilyl group in molecular structure in the photosensitive composite of the present invention Measure preferably 0.1 mass %～30 mass %, more preferably 2 mass %～20 mass %, and then preferably 3 mass %～10 mass %. Alkoxysilane compound containing trialkylsilyl group in molecular structure can only use one, it is possible to containing two or more.Containing in the case of two or more, preferably Total amount becomes described scope.

The photosensitive composite of the present invention also can contain surfactant.

Surfactant can use any one of anion system, cation system, nonionic system or both sexes, preferred surfactant For nonionic system surfactant.Surfactant preferred nonionic system surfactant, more preferably fluorine system surfactant.

In the present invention, spendable surfactant such as can be enumerated: as Mei Jiafa (Megafac) F142D, U.S. of commercially available product Good method (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) manufacture), Not rad (Fluorad) FC-135, Fu Lade (Fluorad) FC-170C, Fu Lade (Fluorad) FC-430, Fu Lade (Fluorad) FC-431, Nuo Beike (Novec) FC-4430 (Sumitomo 3M (stock) manufacture), rising sun Jiade (Asahi Guard) AG7105, rising sun Jiade (Asahi Guard) 7000, rising sun Jiade (Asahi Guard) 950, rising sun Jiade (Asahi Guard) 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) EF352, Ai Futuo (Eftop) EF801, Ai Futuo (Eftop) EF802 (Mitsubishi Materials electronics chemical conversion (stock) Manufacture), Fu Jite (Ftergent) 250 (Ni Aosi (Neos) (stock) manufacture).It addition, in addition to described, it is possible to Enumerate: KP (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), Bao Lifuluo (Polyflow) (common prosperity society chemistry (stock) manufactures), Ai Futuo (Eftop) (Mitsubishi Materials electronics chemical conversion (stock) manufactures), Mei Jiafa (Megafac) (Di Aisheng (DIC) (stock) Manufacture), Fu Lade (Fluorad) (Sumitomo 3M (stock) manufacture), rising sun Jiade (Asahi Guard), Sha Fulong (Surflon) (Asahi Glass (stock) manufacture), the precious each series managing Floex (PolyFox) (manufacture of Europe Nova (OMNOVA) company) etc..

It addition, surfactant also can enumerate paragraph 0119～the paragraph 0123 of Japanese Patent Laid-Open 2014-238438 publication Compound described in is as preference.

About the content of the surfactant in the photosensitive composite of the present invention, in the case of allocating, relative to combination For the total solid composition of thing, preferably 0.001 mass %～5.0 mass %, more preferably 0.01 mass %～2.0 mass %.

Surfactant can contain only one, it is possible to containing two or more.Containing in the case of two or more, preferably it adds up to Amount becomes described scope.

The photosensitive composite of the present invention is in addition to described composition, it is possible to containing antioxidant.

About antioxidant, well-known antioxidant can be contained.By add antioxidant, have can prevent cured film Look, maybe can reduce the advantage that thickness is thinning and heat resistant transparent is excellent caused by decomposing.

This antioxidant such as can be enumerated: phosphorous antioxidant, amide-type, hydrazides class, hindered phenol system antioxidant, anti-bad Hematic acid class, zinc sulfate, carbohydrate, nitrite, sulphite, thiosulfate, hydroxy amine derivatives etc..These compounds In, from the viewpoint of the coloring of cured film, thickness are thinning, particularly preferred hindered phenol system antioxidant, phosphorous antioxidant, Most preferably hindered phenol system antioxidant.These antioxidants can be used alone one, it is possible to mixes two or more.

Preferably commercially available product can be enumerated: Ai Di Coase tower ripple (Adekastab) AO-60, Ai Di Coase tower ripple (Adekastab) AO-80 (being that Ai Dike (ADEKA) (stock) manufactures above), gorgeous good promise (Irganox) 1098 (is BASF (BASF) above Company manufactures).

There is no particular restriction for the content of antioxidant, relative to the total solid composition of photosensitive composite, preferably 0.1 mass %～ 10 mass %, more preferably 0.2 mass %～5 mass %, and then preferably 0.5 mass %～4 mass %.

In the photosensitive composite of the present invention, it is possible to without departing from other changes contained in the range of the purport of the present invention beyond described Compound (such as contains the compound etc. of alkoxy methyl).Compound containing alkoxy methyl can enumerate Japanese Patent Laid-Open Compound described in the paragraph 0192 of 2011-221494 publication～paragraph 0194.

[other compositions]

In the photosensitive composite of the present invention, optionally in addition to described compound, it is possible to add sensitizer, there is epoxy radicals Compound, there are other compositions such as the compound of oxetanylmethoxy, plasticiser, thermal acid generator and acid proliferation generator.About These compositions, such as, can use paragraph 0102～paragraph 0104, the Japan Patent of Japanese Patent Laid-Open 2014-235216 publication The paragraph 0106 of JP 2014-235216 publication～paragraph 0108, Japanese Patent Laid-Open 2009-98616 publication, Japan are specially Profit compound described in JP 2009-244801 publication, other widely known compounds.Additionally, it is possible to by " macromolecule The new of additive launches (daily magazine Jndustrial News (stock)) " described in various ultra-violet absorbers or matal deactivator etc. add In the photosensitive composite of the present invention.

The hardening thing of the present invention is the hardening thing making the photosensitive composite of the present invention harden.Described hardening thing preferably hardens Film.It addition, the cured film of the present invention is preferably by cured film obtained by the manufacture method of the cured film of the present invention.

If the method that the manufacture method of the cured film of the present invention manufactures cured film for making the photosensitive composite of the present invention harden, Then there is no particular restriction, the most sequentially includes following operation 1～operation 3.

Operation 1: the painting process that the photosensitive composite of the present invention is coated on substrate

Operation 2: utilize the actinic ray exposure process being exposed at least partially to coated photosensitive composite

Operation 3: utilize the developing procedure that exposed photosensitive composite is developed by aqueous developer solution

It addition, the manufacture method of the cured film of the present invention more preferably includes following operation 4 after above operation 3.

Operation 4: the heat treatment step that developed photosensitive composite is heat-treated

And then, the manufacture method of the cured film of the present invention so preferably after above operation 3, include before operation 4 following Operation 3 '.

Operation 3 ': developed photosensitive composite is irradiated photoactinic operation further

In described painting process, preferably the photosensitive composite of the present invention is coated on substrate make containing solvent wet Profit film.The cleaning of the substrates such as alkali cleaning or plasma clean before being applied on substrate by photosensitive composite, can be carried out. And then can utilize HMDS etc. that substrate surface is processed after base-plate cleaning.By carrying out this process, have photosensitive Property composition tendency that the adhesion of substrate is improved.

Described substrate can be enumerated: inorganic substrate, resin, resin composite materials etc..

Inorganic substrate such as can be enumerated: glass, quartz, silicon, silicon nitride and evaporation molybdenum, titanium, aluminium, copper on as these substrates Etc. composite base plate.

About resin, the substrate comprising following resin can be enumerated: polybutylene terephthalate, PET, PEN, poly-naphthalenedicarboxylic acid fourth diester, polystyrene, Merlon, polysulfones, polyether sulfone, polyarylate, alkene Propyl group diglycol carbonates, polyamide, polyimides, polyamidoimide, PEI, polybenzoxazole, polyphenylene sulfide, The fluororesin such as polycyclic alkene, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, Silicone resin, ionomeric resins, cyanate ester resin, crosslinking dimethyl ester, cyclic polyolefin, aromatic polyether resin, The synthetic resin such as maleimide-olefin copolymer, cellulose, episulfide resin.

These substrates seldom directly use with described form, form such as thin film transistor (TFT) generally according to the form of final products Multilayer laminated boards structure as (Thin Film Transistor, TFT) element.

It addition, in the case of the touch-screen etc. of outer structure is such, it is possible at the liquid crystal display made for the time being as screen (Liquid Crystal Display, LCD) unit or Organic Light Emitting Diode (Organic Light Emitting Diode, OLED) On unit, the photosensitive composite of the application present invention.

The contiguity of the photosensitive composite of the present invention metal film to being manufactured by sputter or metal oxide is good, therefore base Plate preferably contains the metal film manufactured by sputter.The preferred titanium of metal, copper, aluminium, indium, tin, manganese, nickel, cobalt, The oxide of molybdenum, tungsten, chromium, silver, neodymium and these metals or alloy, and then preferably molybdenum, titanium, aluminium, copper and the conjunction of these metals Gold.The one additionally, metal or metal oxide can be used alone, it is possible to and with multiple.

The coating process of substrate is not particularly limited, such as can use ink-jet method, 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.

It addition, in the case of the photosensitive composite of the present invention contains solvent, the manufacture method of the cured film of the present invention preferably exists The solvent removing step removing solvent from coated photosensitive composite is comprised after operation 1, before operation 2.

In described solvent removing step, preferably by decompression (vacuum) and/or heating etc. from the described film being coated with On substrate, dry coating is formed except solvent.The heating condition of solvent removing step preferably 70 DEG C～130 DEG C and 30 seconds～300 About second.It addition, in described solvent removing step, it is not necessary to the solvent in photosensitive composite is removed completely, if near A few part is removed.

In described exposure process, preferably to the film of gained with more than set pattern-like illumination wavelength 300nm and 450nm Following actinic ray.In described operation, polymerizable monomer is polymerized hardening by the effect of Photoepolymerizationinitiater initiater.

Exposure light source can use Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, chemical lamp, light emitting diode (Light Emitting Diode, LED) light source, PRK generation device etc., it is preferable to use i ray (365nm), h to penetrate Line (405nm), g ray (436nm) etc. have the actinic ray of the wavelength of more than 300nm and below 450nm.It addition, The most also long wavelength cutoff wave filter, short wavelength's cut-off filter, bandpass filter (band pass filter) can be passed through like that Light splitting wave filter and adjust irradiation light.

Exposure device can use: mirror surface projection aligner (mirror projection aligner), stepper (stepper), sweeps Retouch instrument (scanner), close induction type (proximity), contact (contact), microlens array (microlens array), The exposure machine of the various modes such as lens scan instrument (lens scanner), laser explosure.

It addition, the light exposure in described exposure process is also not particularly limited, preferably 1mJ/cm²～3,000mJ/cm², more preferably 1 mJ/cm²～500mJ/cm²。

From the viewpoint of promoting hardening, the exposure in described exposure process was preferably carried out through oxygen blocks.Resistance The method of disconnected oxygen can illustrate and be exposed or arrange oxygen barrier film in a nitrogen environment.

If it addition, exposure the carrying out i.e. at least partially the photosensitive composite removed through solvent in described exposure process Can, can be such as blanket exposure, it is possible to for pattern exposure.In the present invention, exposure process preferred pattern expose, more preferably via The operation that photomask is exposed.

It addition, after described exposure process, can heat after being exposed (postexposure bake (Post Exposure Bake, with The most also referred to as " PEB ").Carry out the temperature preferably more than 30 DEG C and less than 130 DEG C of the situation of PEB, more preferably more than 40 DEG C And less than 120 DEG C, particularly preferred 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 heating plate, baking oven, infrared ray Heater etc..

It addition, about the heat time, in the case of heating plate preferably 1 minute～about 30 minutes, in addition in the case of excellent Select 20 minutes～about 120 minutes.In the range of described, substrate, device can not be added with causing damage (damage) Heat.

In developing procedure, use aqueous developer solution to be developed in the unhardened portion of the exposed photosensitive composite for pattern-like and remove, Form minus image.The aqueous developer solution of the developer solution used in developing procedure preferably alkalescence.

The aqueous solution of the preferred alkali compounds of developer solution used in developing procedure.Alkali compounds such as can use: lithium hydroxide, The alkali metal hydroxide such as NaOH, potassium hydroxide；The alkali carbonate classes such as sodium carbonate, potassium carbonate, cesium carbonate；Weight The alkaline metal bicarbonate class such as sodium carbonate, potassium bicarbonate；Tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide tetrapropyl The tetraalkylammonium hydroxide classes such as ammonium, tetrabutylammonium, diethyldimethylammonhydroxide hydroxide；The hydroxides such as choline (hydroxy alkyl) Trialkyl ammonium class；The silicates such as sodium metasilicate, sodium metasilicate；The alkyl amines such as ethamine, propylamine, diethylamine, triethylamine；Two The alcamines such as methylethanolamine, triethanolamine；1,8-diazabicyclo [5.4.0]-7-hendecene, 1,5-diazabicyclo [4.3.0]-5- The ester ring type amines such as nonene.

In these compounds, preferably NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, hydroxide Tetrapropyl ammonium, tetrabutylammonium, choline (hydroxide-2-hydroxyethyl trimethyl ammonium).

Additionally, it is possible to by be added with in the aqueous solution of described bases the water-miscible organic solvents such as methyl alcohol or the ethanol of appropriate amount or The aqueous solution of surfactant is used as developer solution.

Preferably developer solution can enumerate 0.4 mass %～the 2.5 mass % aqueous solution of tetramethyl ammonium hydroxide.

The pH value of developer solution preferably 10.0～14.0.

Developing time preferably 30 seconds～500 seconds, and, the method for development can be fluid containing method (covering liquid method), spray process, leaching Any one of stain method etc..

After developing procedure, it is possible to carry out drip washing operation.In drip washing operation, clean the substrate after development with pure water etc., thus carry out The removal of the developer solution of attachment, the removal of development residue.ELUTION METHOD can use well-known method.Such as can enumerate spray Drip washing (shower rinse) 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 suitably Pattern exposure method described in Japanese Patent Laid-Open 2011-186398 publication, Japanese Patent Laid-Open 2013-83937 publication And developing method.

It addition, from the viewpoint of improving film hardness, after developing procedure, before heat treatment step, preferably include through aobvious The photosensitive composite of shadow irradiates photoactinic operation (post-exposure) further.

In the case of described, carry out 50mJ/cm preferably with mercury vapor lamp or LED etc.²～3,000mJ/cm²The energy of left and right Amount exposure.It addition, post-exposure preferably carries out blanket exposure.

By carrying out post-exposure, can promote the sclerous reaction of film further, film hardness improves.

The manufacture method of the cured film of the present invention is preferably after described developing procedure, including to developed photosensitive composite Carry out the operation (baking afterwards) being heat-treated.By being heat-treated after the photosensitive composite of the present invention is developed, can Obtain the cured film that intensity is more excellent.

Heat treatment temperature preferably less than 180 DEG C, more preferably less than 150 DEG C, and then preferably less than 130 DEG C.Lower limit preferably 80 DEG C Above, more preferably more than 90 DEG C.The method of heating is not particularly limited, and can use well-known method.Such as can enumerate and add Hot plate, baking oven, infrared heater etc..

It addition, about the heat time, in the case of heating plate preferably 1 minute～about 30 minutes, in addition in the case of excellent Select 20 minutes～about 120 minutes.In the range of described, substrate, device can not be hardened with causing damage.

It addition, can be carried out continuously by the hardening caused by light and/or heat in the manufacture method of the cured film of the described present invention, it is possible to depend on Sequence is carried out.

It addition, when being heat-treated, by processing in a nitrogen environment, can further improve the transparency.

From the viewpoint of Adjusting Shape after heating, it is possible to before heat treatment step (baking afterwards), in relatively low temperature Heat treatment step (roasting procedure in adding) is carried out after toasting under degree.Such as can illustrate and first heat 30 minutes at 90 DEG C (middle baking), the afterwards method etc. of heating 30 minutes (baking afterwards) at 120 DEG C.Additionally, it is possible to by middle baking, dry afterwards Baking is divided into the multistage of more than three phases to heat.By arranging this middle baking, toasting afterwards, the cone of adjustable pattern Angle.These heating can use the well-known heating means such as heating plate, baking oven, infrared heater.

The cured film of the present invention is the cured film making the photosensitive composite hardening of the present invention obtain

The cured film of the present invention can suitably serve as outer film (diaphragm) or interlayer dielectric.It addition, the cured film of the present invention The cured film of manufacture method gained preferably by the cured film of the present invention.

By the photosensitive composite of the present invention, the cured film with abundant hardness also can be obtained even if hardening at low temperatures.Such as The cured film that pencil hardness is more than 2H can be obtained.The diaphragm that the photosensitive composite making the present invention hardens and formed is due to hardening Film physical properties excellent, therefore in the purposes of touch-screen, touch panel display device, organic EL display, liquid crystal indicator etc. Useful.Wherein, the cured film of the present invention preferably touch-screen distribution diaphragm, the most outer structure touch-screen In distribution diaphragm.

The photosensitive composite of the present invention, due to hardening and cured film excellent, is therefore as MEMS (Micro Electro Mechanical Systems, MEMS) with the structural elements of device, will make the present invention photosensitive composite hardening and The hardening thing become or Resist patterns are as dividing wall, or a part of group as Mechanical Driven part enters and use.This MEMS Such as can enumerate with device: surface acoustic wave (Surface Acoustic Wave, SAW) wave filter, bulk acoustic wave (Bulk Acoustic Wave, BAW) wave filter, gyrosensor (gyro sensor), display micro-shutter (microshutter), image The parts such as sensor (image sensor), Electronic Paper, ink gun, biochip (Bio-chip), sealant.More specifically Example is to be illustrated in Japan Patent spy's table 2007-522531 publication, Japanese Patent Laid-Open 2008-250200 publication, Japan specially In profit JP 2009-263544 publication etc..

The photosensitive composite of the present invention is excellent due to flatness or the transparency, therefore can also be used for forming such as Japanese Patent Laid-Open Bunding (bank) layer (16) described in Fig. 2 of 2011-107476 publication and planarization film (57), Japanese Patent Laid-Open Dividing wall (12) described in Fig. 4 (a) of 2010-9793 publication and planarization film (102), Japanese Patent Laid-Open 2010-27591 The bunding floor (221) described in Figure 10 of number publication and the 3rd interlayer dielectric (216b), Japanese Patent Laid-Open 2009-128577 The 2nd interlayer dielectric (125) described in Fig. 4 (a) of number publication and the 3rd interlayer dielectric (126), Japan Patent are special Open the planarization film (12) described in Fig. 3 of 2010-182638 publication and pixel separation dielectric film (14) etc..In addition, Also can be suitably used in liquid crystal indicator for liquid crystal layer being held in certain thickness distance piece (spacer), liquid crystal display Element etc. scooped up by the colored filter of device or protective films of color filters, facsimile machine (facsimile), electronic copier, solid Chip enamel the imaging optical system of optical filter (on-chip color filter) or the lenticule (microlens) of the joints of optical fibre.

The organic EL display of the present invention is characterized by the cured film of the present invention.

The organic EL display of the present invention is except having the planarization film using the photosensitive composite of the described present invention to be formed Or beyond interlayer dielectric, there is no particular restriction, the well-known various organic EL displays using various structures can be enumerated Or liquid crystal indicator.

Such as, the concrete example of the TFT (Thin-Film Transistor) that the organic EL display of the present invention is had can be enumerated: Non-crystalline silicon-TFT, low temperature polycrystalline silicon-TFT, oxide semiconductor TFT etc..The cured film of the present invention is excellent due to electrical characteristics, because of This can be combined to be preferably used in these TFT.

Fig. 1 is the composition concept map of an example of organic EL display.And represent in the organic EL display of bottom emission type The schematic sectional view of substrate, there is planarization film 4.

Glass substrate 6 is formed the TFT1 of bottom gate type, is formed comprise Si to cover the state of this TFT1₃N₄Exhausted Velum 3.Dielectric film 3 is formed after omitting the contact hole of diagram here, formed on the insulating film 3 and connect via this contact hole Distribution 2 (highly 1.0 μm) in TFT1.Distribution 2 is used to connect between TFT1 or by having of being formed in subsequent handling The distribution that machine EL element is connected with TFT1.

And then, in order to make because forming the concavo-convex planarization caused by distribution 2, to be embedded into by the concavo-convex state caused by distribution 2 absolutely Planarization film 4 is formed on velum 3.

On planarization film 4, it is formed with the organic EL element of bottom emission type.That is, on planarization film 4, via contact Hole 7 is connected with distribution 2 and forms the first electrode 5 of comprising ITO.It addition, the first electrode 5 is equivalent to the sun of organic EL element Pole.

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

And then, but can sequentially be deposited with across required pattern mask and hole transmission layer, organic light emission are set in Fig. 1 although not shown Layer, electron transfer layer, then formed on whole of surface and comprise second electrode of Al, use glass for sealing plate and Ultraviolet ray hardening type epoxy resin is fitted, and thus seals, it is thus achieved that connects each organic EL element and is used for driving this organic The active matrix organic EL display device of the TFT1 of EL element.

The liquid crystal indicator of the present invention is characterized by the cured film of the present invention.

The liquid crystal indicator of the present invention is except having the diaphragm, smooth using the photosensitive composite of the described present invention to be formed Changing beyond film or interlayer dielectric, there is no particular restriction, can enumerate the well-known liquid crystal indicator using various structures.

It addition, the desirable liquid crystal drive mode of the liquid crystal indicator of the present invention can be enumerated: twisted nematic (Twisted Nematic, TN) mode, (Vertical Alignment, VA) arranged vertically mode, in-plane switching (In-Plane-Switching, IPS) Mode, fringing field switching (Fringe Field Switching, FFS) mode, optical compensation curved (Optically Compensated Bend, OCB) mode etc..

In screen is constituted, in the liquid crystal indicator of colorful optical filter array (Color Filter on Array, COA) mode Be used as the cured film of the present invention, such as can be used as Japanese Patent Laid-Open 2005-284291 publication organic insulating film (115), Or the organic insulating film (212) of Japanese Patent Laid-Open 2005-346054 publication.It addition, the liquid crystal indicator of the present invention can The the most aligned of the liquid crystal orientation film taken enumerates friction orientation method, optical alignment method etc..Additionally, it is possible to pass through Japan Patent Polymer-supported described in JP 2003-149647 publication or Japanese Patent Laid-Open 2011-257734 publication capture to (Polymer Sustained Alignment, PSA) technology carries out polymer orientation support.

It addition, the cured film of the photosensitive composite of the present invention and the present invention is not limited to described purposes, can be used for various uses. Such as in addition to planarization film or interlayer dielectric, it is possible to be suitably used in diaphragm or liquid crystal indicator for by liquid Crystal layer is held in certain thickness distance piece or the lenticule etc. being arranged in element on colored filter scooped up by solid.

Fig. 2 is the conceptual sectional view of an example of the liquid crystal indicator 10 representing active matrix mode.This Color Liquid Crystal Display Device 10 is in the liquid crystal display on the back side with back light unit 12, and liquid crystal display, configures and attached to the 2 of light polarizing film The element of the TFT16 that all pixels of configuration are corresponding between sheet glass substrate 14, glass substrate 15.For being formed at glass Each element on substrate, by cured film 17 formed contact hole 18 and by formed pixel electrode ito transparent electrode 19 join Line.On ito transparent electrode 19, the layer being provided with liquid crystal 20 and the RGB being configured with black matrix" (Red Green Blue, RGB) colored filter 22.

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

It addition, liquid crystal indicator may be set to three-dimensional (three dimensional, 3D) (stereopsis) type, it is possible to be set as Touch screen type.And then also may be set to soft type, can be used as the 2nd described in Japanese Patent Laid-Open 2011-145686 publication Interlayer dielectric (520) described in interlayer dielectric (48) or Japanese Patent Laid-Open 2009-258758 publication.

<touch-screen and touch panel display device>

The touch-screen of the present invention is the hard of all or part of photosensitive composite comprising the present invention of insulating barrier and/or protective layer The touch-screen of compound.It addition, the touch-screen of the present invention preferably at least has transparency carrier, electrode and insulating barrier and/or protection Layer.

The touch panel display device of the present invention preferably has the touch panel display device of the touch-screen of the present invention.The present invention touches Touching screen can be the arbitrary of the well-known modes such as resistive film mode, electrostatic capacitance mode, ultrasonic wave mode, way of electromagnetic induction Kind.Wherein, preferred electrostatic capacitance mode.

The touch-screen of electrostatic capacitance mode can enumerate the touch-screen disclosed in Japanese Patent Laid-Open 2010-28115 publication or the world Touch-screen disclosed in No. 2012/057165 is disclosed.Other touch-screens can be enumerated: so-called embedded (in-cell) type (such as day Described person in Fig. 5, Fig. 6, Fig. 7, Fig. 8 of this patent spy's table 2012-517051 publication), so-called outer insert-type (such as Described person, the figure of Japanese Patent Laid-Open 2012-89102 publication in Figure 19 of Japanese Patent Laid-Open 2013-168125 publication Described person in 1 or Fig. 5), one chip glass touch screen (One Glass Solution, OGS) type or cover layer touch (Touch-on-Lens, TOL) type (person, Japan described in such as Fig. 2 of Japanese Patent Laid-Open 2013-54727 publication Described person in Fig. 2, Fig. 3, Fig. 4, Fig. 5 of open patent 2015-15042 publication), other are constituted, and (such as Japan is specially Described person in Fig. 6 of profit JP 2013-164871 publication), various plug-in (out-cell) type (so-called GG, G1 G2, GFF, GF2, GF1, G1F etc.).

It addition, Fig. 3 represents the composition concept map of an example of the liquid crystal indicator of the function with touch-screen.

Such as, the diaphragm between each layer that the cured film of the present invention is suitably applied in Fig. 3, and, it also is adapted for being applied to touch Touch the interlayer dielectric that the detecting electrode of screen is spaced apart.Additionally, the detecting electrode of touch-screen preferably silver, copper, aluminium, titanium, aluminium, And the alloy of these metals.

In Fig. 3,110 represent pixel substrate, and 140 represent liquid crystal layer, and 120 represent substrate in opposite directions, and 130 represent detecting means.Picture Element substrate 110 start from the downside of Fig. 3 sequentially to have Polarizer 111, transparency carrier 112, common electrode 113, insulating barrier 114, Pixel electrode 115, alignment films 116.Substrate 120 starts sequentially have alignment films 121, colorized optical filtering from the downside of Fig. 3 in opposite directions Sheet 122, transparency carrier 123.Detecting means 130 is respectively provided with phase retardation film 124, following layer 126, Polarizer 127.It addition, In Fig. 3,125 is sensing detecting electrode.The cured film of the present invention can be used for the insulating barrier (114) of pixel substrate part (also It is referred to as interlayer dielectric) or various diaphragm (not shown), the various diaphragms (not shown) of pixel substrate part, in opposite directions The various diaphragms (not shown) of substrate portion, the various diaphragms (not shown) etc. of transducing part.

Following layer 126 or Polarizer 127 can use well-known following layer composition.

The concrete example of Polarizer or following layer can be enumerated: the embodiment 1 of Japanese Patent Laid-Open 2014-152319 publication, enforcement The Polarizer of the band following layer described in example 7 or embodiment 13, the embodiment 1 of Japanese Patent Laid-Open 2014-191005 publication, The Polarizer of the band following layer described in embodiment 3 or embodiment 6, the embodiment of Japanese Patent Laid-Open 2013-100386 publication 1, embodiment 3, embodiment 6, embodiment 11 or the Polarizer of the band following layer described in embodiment 14, Japanese Patent Laid-Open The embodiment 1 of 2013-163783 publication, embodiment 2, embodiment 3 or the following layer described in embodiment 4.

In order to prevent electrostatic, following layer preferably contains antistatic additive.

Antistatic additive can use well-known antistatic additive.Metallic, metal oxide, electric conductivity such as can be used to be polymerized Thing, quarternary ammonium salt or lithium salts isoiony compound.

The concrete example of antistatic additive can be enumerated: the paragraph 0107 of Japanese Patent Laid-Open 2014-191005 publication～paragraph 0115 Described in antistatic additive, the paragraph 0046 of Japanese Patent Laid-Open 2013-100386 publication～anti-quiet described in paragraph 0054 Electricity agent and the paragraph 0027 of Japan Patent spy's table 2014-515046 publication～the antistatic additive described in paragraph 0047.

And then, even if in the liquid crystal indicator of static drive mode, it is possible to show that design is high by the application present invention Pattern.About its example, the present invention can be applied as polymer such described in Japanese Patent Laid-Open 2001-125086 publication The dielectric film of network type liquid crystal.

It addition, the composition concept map of another example of the liquid crystal indicator that Fig. 4 is the function with touch-screen.

Touch panel display device comprises: bottom display board 200, possesses thin film transistor (TFT) (TFT) 440, is equivalent to film crystal Pipe display board；Top display board 300, with bottom display board 200 in opposite directions, with bottom display board 200 face in opposite directions on possess many Individual colored filter 330, is equivalent to colored filter display board；And liquid crystal layer 400, it is formed at bottom display board 200 with upper Between portion's display board 300.Liquid crystal layer 400 is containing liquid crystal molecule (not shown).

Bottom display board 200 comprises the 1st insulated substrate 210, be arranged on the 1st insulated substrate 210 thin film transistor (TFT) (TFT), The dielectric film 280 being formed on the upper surface of thin film transistor (TFT) (TFT) and the pixel electrode 290 being arranged on dielectric film 280. Thin film transistor (TFT) (TFT) can contain gate electrode 220, cover the gate insulating film 240 of gate electrode 220, semiconductor layer 250, Ohmic contact layer 260, ohmic contact layer 262, source electrode 270 and drain electrode 272.

In dielectric film 280, in the way of the drain electrode 272 of thin film transistor (TFT) (TFT) exposes, it is formed with contact hole 282.

Top display board 300 comprises: be arranged on a face of the 2nd insulated substrate 310 and with the light obstructing member of rectangular arrangement 320, the colored filter 330 be arranged in the alignment films 350 on the 2nd insulated substrate 310, being arranged in alignment films and configuration On colored filter 330 and corresponding with the pixel electrode 290 of bottom display board 200 and liquid crystal layer 400 is executed alive Common electrode 370.

In the liquid crystal indicator shown in Fig. 4, the another side of the 2nd insulated substrate 310 configures sensing electrode 410, absolutely Velum 420, driving electrode 430 and diaphragm 280.Like this, in the manufacture of the liquid crystal indicator shown in Fig. 4, in shape When becoming top display board 300, the sensing electrode 410, absolutely of inscape as touch screen (touch screen) can be formed together Velum 420 and driving electrode 430 etc..The cured film especially making the photosensitive composite of the present invention harden can be suitably used for Dielectric film 280 or dielectric film 420.

Also the following layer in the Polarizer of the band following layer illustrated in described following layer 126 or Polarizer 127 can be fitted in protection On film 280.

[embodiment]

Hereinafter enumerate embodiment the present invention is more particularly described.Material shown in below example, usage amount, ratio, Process content, processing sequence etc. without departing from the purport of the present invention, then can suitably change.Therefore, the scope of the present invention does not limits Due to concrete example shown below.Additionally, as long as no special instructions, then " part ", " % " are quality criteria.

[synthesis of compound A]

Ethyl carbazole (100.0g, 0.512mol) is dissolved in the chlorobenzene of 260ml, after being cooled to 0 DEG C, adds aluminium chloride (70.3g, 0.527mol).Then, with dropping toluoyl chlorine (81.5g, 0.527mol) in 40 minutes, it is warmed up to room temperature (25 DEG C, the most identical) also stir 3 hours.Then, after being cooled to 0 DEG C, add aluminium chloride (75.1g, 0.563mol). With dropping 4-chlorobutanoylchloride (79.4g, 0.563mol) in 40 minutes, it is warmed up to room temperature and stirs 3 hours.By the 35 of 156ml The aqueous hydrochloric acid solution of quality % is cooled to 0 DEG C with the mixed solution of the distilled water of 392ml, dropwise reaction solution.The solid that will separate out After suction filtration, it is carried out with distilled water and methyl alcohol, after carrying out recrystallization with acetonitrile, it is thus achieved that the compound A of following structure (produces Amount 164.4g, productivity 77%).

[changing 11]

[synthesis of compound B]

The compound A (20.0g, 47.9mmol) of described acquisition is dissolved in the oxolane (THF) of 64ml, adds Add 4-chlorobenzenethiol (7.27g, 50.2mmol) and sodium iodide (0.7g, 4.79mmol).Then in reactant liquor, add hydrogen Sodium oxide molybdena (2.0g, 50.2mmol), refluxes 2 hours.Then after being cooled to 0 DEG C, with 20 minutes dropping SM-28 (11.1g, 57.4mmol, 28% methanol solution of first sodium oxide molybdena, and Wako Pure Chemical Industries (stock) manufacture), be warmed up to room temperature and to stir 2 little Time.Then, after being cooled to 0 DEG C, with dropping isoamyl nitrite (6.73g, 57.4mmol) in 20 minutes, it is warmed up to room temperature also Stir 3 hours.Reactant liquor is diluted in 120ml acetone, is added drop-wise to be cooled in the 0.1N aqueous hydrochloric acid solution of 0 DEG C.Will After the solid suction filtration separated out, clean with distilled water.Then recrystallization is carried out with acetonitrile, it is thus achieved that the compound B of following structure (yield 17.0g, productivity 64%).

[changing 12]

[synthesis of compound 1]

Compound B (18.0g, 32.4mmol) is dissolved in the 1-METHYLPYRROLIDONE (NMP) of 90ml, adds three Ethamine (Et₃N, 3.94g, 38.9mmol).Then after being cooled to 0 DEG C, with 20 minutes dropping chloroacetic chloride (AcCl, 3.05g, After 38.9mmol), it is warmed up to room temperature and stirs 2 hours.Reactant liquor is added drop-wise to the distilled water being cooled to 0 DEG C of 150ml In, after the solid suction filtration that will separate out, clean, in addition after drying with the isopropanol being cooled to 0 DEG C of 200ml, it is thus achieved that Compound 1 (yield 19.5g, productivity 99%).

[changing 13]

It addition, the structure of the compound 1 of gained is to utilize nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) Identify.

¹H-NMR (400MHz, CDCl₃): δ=8.86 (s, 1H), 8.60 (s, 1H), 8.31 (d, 1H, J=8.0Hz), 8.81 (d, 1H, J=8.0Hz), 7.51-7.24 (m, 10H), 7.36 (q, 2H, 7.4Hz), 3.24-3.13 (m, 4H), 2.36 (s, 3H), 2.21 (s, 3H), 1.50 (t, 3H, 7.4Hz).

By 1 part 2,2 '-azo double (isobutyronitrile), 200 parts of PGMEA (propylene glycol methyl ether acetate) are put in flask.Afterwards, Put into 30 parts of methyl methacrylates, 20 parts of methacrylic acids, 30 parts of GMAs, 20 parts of styrene, It is stirred at room temperature a period of time, after bubbling to being sufficiently carried out nitrogen displacement in flask, at 70 DEG C, adds thermal agitation 5 little Time, it is thus achieved that copolymer p-1.

In addition to the kind changing the monomer used and/or addition, it is respectively synthesized altogether in the way of as the synthesis of P-1 Polymers P-2 and copolymer p-3.

Each composition used in embodiment and comparative example is as described below.

A-1: sub-Luo Nisi (Aronix) TO-2359 (East Asia synthesis (stock) manufactures), there are five functional acrylics of carboxyl Ester compounds, following compound a-1

A-2: sub-Luo Nisi (Aronix) M-510 (East Asia synthesis (stock) manufactures), there is the trifunctional acrylate of carboxyl Compound, following compound a-2

A-3: there is seven functional acrylic ester compounds of carboxyl, following compound a-3

A '-1: sub-Luo Nisi (Aronix) M-5300 (East Asia synthesis (stock) manufactures), ω-carboxyl-polycaprolactone Mono acrylic ester, a sense

[changing 14]

B-1: dipentaerythritol acrylate (Ka Yala get (KAYARAD) DPHA, Japan's chemical drug (stock) manufactures), Six senses

B-2: tetramethylol methane tetraacrylate (NK ester A-TMMT, Xin Zhong village chemical industry (stock) manufactures), four senses

B-3: trimethylolpropane trimethacrylate (M309, East Asia synthesis (stock) manufactures), trifunctional

B-4:NK oligomerization (NK OLIGO) U-15HA (Xin Zhong village chemical industry (stock) manufacture), 15 senses

B-5:UA-306H (common prosperity society chemistry (stock) manufactures), six senses

B '-1:1,9-nonanediol diacrylate (NK ester A-NOD-N, Xin Zhong village chemical industry (stock) manufactures), two officials Energy

C-1: compound 1 (composite, with reference to described), oxime ester compound

C-2: gorgeous good solid (IRGACURE) OXE-01 (manufacture of BASF (BASF) company), oxime ester compound, under State structure

C-3: gorgeous good solid (IRGACURE) OXE-02 (manufacture of BASF (BASF) company), oxime ester compound, under State structure

[changing 15]

D-1: Lay spy's ester (Light Ester) P-1M (common prosperity society chemistry (stock) manufacture, principal component is as following compound Phosphate compound)

D-2: Lay spy's ester (Light Ester) P-2M (common prosperity society chemistry (stock) manufacture, principal component is as following compound Phosphate compound)

D-3: Ka Yamei (KAYAMER) PM-21 (Japan's chemical drug (stock) manufactures, and meets the mixture of following composition)

D-4:JPA-514 (north of the city chemical industry (stock) manufactures, following two kinds of mixtures)

D-5:MR-260 (big eight chemical industry (stock) manufacture, following compound)

[table 1]

K-1: phenthazine (Tokyo chemical conversion industry (stock) manufactures)

K-2: azophenlyene (Tokyo chemical conversion industry (stock) manufactures)

E-1:PMA-ST (Nissan Chemical Industries (stock) manufacture), silicon dioxide granule, average grain diameter 10nm～15inm

E-2:MIBK-ST-L (Nissan Chemical Industries (stock) manufacture), silicon dioxide granule, average grain diameter 40inm～50nm

F-1: Plutarch Nat (Takenate) B870N (Mitsui Chemicals (stock) manufacture)

F-2: desmodur (Desmodur) BL3575/1PMA/SN (firmly changes Bayer carbamate (Sumika-Bayer Urethane) (stock) manufactures)

F-3: desmodur (Desmodur) BL4265 (firmly changes Bayer carbamate (Sumika-Bayer Urethane) (stock) manufactures)

F-4: Du draws Nat (Duranate) SBN-70D (Mitsui Chemicals (stock) manufacture)

P-1: methyl methacrylate (MMA)/methacrylic acid (MAA)/GMA (GMA) The copolymer of/styrene (St)=30/20/30/20 (mass ratio), weight average molecular weight (Mw)=12,000, quantity are average Molecular weight (Mn)=8,000, composite, with reference to described

P-2:MMA/MAA/GMA/St/ methacrylic acid two ring pentyl ester (DCPMA)=30/20/30/10/10 (mass ratio) Copolymer, Mw=13,000, Mn=8,500, composite, with reference to described

P-3:MMA/MAA/ acrylic acid (3-Ethyloxetane-3-base) methyl esters (OXE-10)/St=30/20/30/20 (quality Than) copolymer, Mw=11,000, Mn=7,500, composite, with reference to described

SC-1:KBM-403 (3-glycidoxypropyl triethoxysilane, SHIN-ETSU HANTOTAI's chemical industry (stock) manufactures)

SC-2:KBM-5103 (3-acryloxypropyl trimethoxy silane, SHIN-ETSU HANTOTAI's chemical industry (stock) manufactures)

W-1: Mei Jiafa (Megafac) F554 (Di Aisheng (DIC) (stock) manufactures, fluorine system surfactant)

J-1: Ai Di Coase tower ripple (Adekastab) AO-60 (hindered phenol system antioxidant, Ai Dike (ADEKA) (stock) Manufacture)

J-2: gorgeous good promise (Irganox) 1035 (hindered phenol system antioxidant, BASF (BASF) company manufactures)

J-3: card Lenze (Karenz) MT-PE-1 (mercaptan compound, Showa electrician (stock) manufactures)

Y-1: propylene glycol methyl ether acetate (Daicel (Daicel) (stock) manufacture)

Y-2: Methylethyl diethylene glycol (DEG) (Daicel (Daicel) (stock) manufacture)

Y-3:1,3-butanediol diacetate esters

(embodiment 1～embodiment 93 and comparative example 1～comparative example 13)

As described in table 2 below～table 5, solution and/or the dispersion liquid of solvent is made in the allotment of each composition and stirring, profit Filter with the polytetrafluoroethylene (PTFE) filter of aperture 0.3 μm, it is thus achieved that embodiment 1～embodiment 93 and comparative example 1～compare Each photosensitive composite of example 13.The unit of the addition of each composition of table 2 below～table 5 is mass parts.

The each photosensitive composite using gained carries out following evaluation.Evaluation result is shown in table 2～table 5.

By each photosensitive composite spin coating prepared in described on the glass substrate, at 90 DEG C, carry out the prebake conditions of 120 seconds, Obtain the coated film of thickness 2.0 μm.Then high-pressure mercury-vapor lamp is utilized to carry out 500mJ/cm²The light of (conversion of i ray) irradiates, and enters And utilize baking oven to carry out baking in 60 minutes at 120 DEG C, thus make cured film.

Then, inclined by the band acrylic acid series sticker that makes according to the embodiment 1 of Japanese Patent Laid-Open 7-331210 publication Tabula rasa is cut to width 20mm, length 100mm, utilizes 2kg roller with one in the environment of temperature 23 DEG C, humidity 50%RH Individual back and forth the sticker aspect of Polarizer is attached on cured film.

And then, after keeping 30 minutes in the environment of temperature 23 DEG C, humidity 50%RH, pinch evaluation with the hand of estimator and use The end of sample, with peel angle 100 °～120 °, draw speed 100mm/min～500 on the direction of length 100mm Mm/min peels off.

Finally, in order to cured film surface is cleaned, and use the adhesive-bonded fabric containing acetone, carry out wiping table with the hand of estimator Face.

Cured film after wiping is observed, judges as following.

5: without scratch on cured film, also do not produce Thickness Variation.

4: produce the slight scratch that display quality be there is no impact on cured film, or generate less than the Thickness Variation of 1%.

3: produce scratch the most influential on display quality on cured film, or produce the Thickness Variation that 1% less than 3%.

2: produce the obvious scratch that display quality is had big impact on cured film, or produce the Thickness Variation of more than 3%.

1: cured film is peeled off from base material.

By glass substrate (Iger (EAGLE) XG, 0.7mm are thick (manufacture of healthy and free from worry (Coming) company)) in pregnancy Expose 30 seconds under base disilazane (HMDS) steam, after each photosensitive composite of spin application, in heating plate at 90 DEG C Upper prebake conditions makes solvent volatilize in 120 seconds, forms the photosensitive composition layer of thickness 3.0 μm.

Then, the MPA 5500CF (high-pressure mercury-vapor lamp) that Canon's (Canon) (stock) manufactures is used, across having mask Footpath is that the photosensitive composition layer of gained is exposed by the mask of the sectional hole patterns of 50 μm.Then, alkaline-based developer (2.38% is utilized The tetramethyl ammonium hydroxide aqueous solution) at 23 DEG C to exposure after photosensitive composition layer carry out 60 seconds development after, with ultrapure Water wash 20 seconds.The hole of 10 μm at the point of 1.5 μm on film thickness direction will be differentiated from substrate-side by these operations Time the suitableeest i x ray exposure x amount (Eopt) as sensitivity.

About the sectional hole patterns that mask footpath is 50 μm, it is exposed with the suitableeest described i ray, aperture when making pattern is carried out Evaluate.In following evaluation, real sectional hole patterns footpath is that the size of the bottom (bottom surface) with resist specifies.Aperture and mask footpath Difference the least, i.e. crimping is the fewest, then screen design the easiest and preferred.

-metewand-

5: within the ratio in mask footpath and real sectional hole patterns footpath is ± 10%

4: the ratio in mask footpath and real sectional hole patterns footpath exceedes ± and 10% and within ± 20%

3: the ratio in mask footpath and real sectional hole patterns footpath exceedes ± and 20% and within ± 30%

2: the ratio in mask footpath and real sectional hole patterns footpath exceedes ± and 30% and within ± 40%

1: mask footpath exceedes ± 40% with the ratio in real sectional hole patterns footpath, or there is residual film and cannot differentiate bottom

Then, use high-pressure mercury-vapor lamp that the photosensitive composite of gained is carried out 100mJ/cm²The light of (conversion of i ray) irradiates. Then, utilize alkaline-based developer (the tetramethyl ammonium hydroxide aqueous solution of 2.38%) to the photosensitive composite after exposure at 23 DEG C After layer carries out development in 60 seconds, with ultra-pure water drip washing 20 seconds.

Measure the thickness before and after development treatment, development film thinning rate is evaluated.

-metewand-

5: film thinning rate is less than 3%

4: film thinning rate is 3% less than 8%

3: film thinning rate is 8% less than 15%

2: film thinning rate is 15% less than 30%

1: film thinning rate is more than 30%

In the display device shown in Fig. 4, it is used for the photosensitive composite of gained in various embodiments of the present invention touching detection electricity Pole diaphragm (dielectric film, 420), makes display device respectively.Specifically, diaphragm (420) is formed in the following manner: The photosensitive composite of gained in each embodiment of slot coated, carries out the prebake conditions of 120 seconds at 90 DEG C, utilizes high-pressure mercury Lamp carries out 500mJ/cm²The light of (conversion of i ray) irradiates, and then utilizes baking oven to carry out baking in 60 minutes at 120 DEG C.Display Other parts of device are to make according to the manufacture method recorded as Figure 19 in Japanese Patent Laid-Open 2013-168125 publication Make.The display performance of made display device, touch detection performance are the most excellent.

Claims

1. a photosensitive composite, it is characterised in that contain:

Intramolecular as composition A has (methyl) acryloyl group of more than three and the polymerizable monomer of more than one carboxyl；

Intramolecular as composition B has (methyl) acryloyl group of more than three and does not have the polymerizable monomer of carboxyl；

Photoepolymerizationinitiater initiater as composition C；

The compound with phosphate ester structure and ethene unsaturated group as components D；And

Polymerization inhibitor as composition K；And

Composition K is 0.01 mass %～0.5 mass % relative to the content of the total solid composition in composition,

Components D is 0.01 mass %～5 mass % relative to the content of the total organic solid composition in composition.

Photosensitive composite the most according to claim 1, wherein composition A is relative to composition A and the total content of composition B Content be 10 mass %～50 mass %.

Photosensitive composite the most according to claim 1 and 2, wherein total organic solid relative in composition of components D The content of body composition is 0.5 mass %～2 mass %.

Photosensitive composite the most according to claim 1 and 2, wherein composition A and composition B is relative in composition The total content of total organic solid composition is 70 mass %～95 mass %.

Photosensitive composite the most according to claim 1 and 2, it is possibly together with inorganic particulate.

6. a manufacture method for cured film, it the most sequentially includes operation 1～operation 3:

Operation 1: the painting process that photosensitive composite according to claim 1 and 2 is coated on substrate；

7. a cured film, it is to make photosensitive composite according to claim 1 and 2 hardening form.

Cured film the most according to claim 7, it is interlayer dielectric or diaphragm.

Cured film the most according to claim 7, it is touch-screen distribution diaphragm.

Cured film the most according to claim 7, it is the distribution diaphragm in outer structure touch-screen.

11. 1 kinds of touch-screens, it has cured film according to claim 7.

12. 1 kinds of touch panel display devices, it has cured film according to claim 7.

13. 1 kinds of liquid crystal indicators, it has cured film according to claim 7.

14. 1 kinds of organic electroluminescence display device and method of manufacturing same, it has cured film according to claim 7.