CN102656517B - Photosensitive composition, partition wall, color filter and organic EL element - Google Patents

Photosensitive composition, partition wall, color filter and organic EL element Download PDF

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Publication number
CN102656517B
CN102656517B CN201080057676.4A CN201080057676A CN102656517B CN 102656517 B CN102656517 B CN 102656517B CN 201080057676 A CN201080057676 A CN 201080057676A CN 102656517 B CN102656517 B CN 102656517B
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group
polymkeric substance
photosensitive composite
spaced walls
side chain
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CN102656517A (en
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高桥秀幸
石关健二
川岛正行
山田光太郎
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AGC Inc
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Asahi Glass Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

Disclosed is a photosensitive composition containing an ink-repellent component, which is capable of imparting a partition wall obtained therefrom with good ink repellency at the upper part thereof, developer resistance sufficient for preventing corrosion by a liquid developer, properties of preventing the occurrence of film remaining, and good wettability and spreadability of an ink over an opening portion between partition walls, although the ink-repellent component does not have an ethylenic double bond. Specifically disclosed is a photosensitive composition which contains: a polymer that has a mass average molecular weight (Mw) of larger than 2.6*104 and no greater than 4 and contains a side chain having a group represented by general formula (1) and a side chain having a polyoxyalkylene group but no side chain having an ethylenic double bond; a photocuring initiator; and a binder resin. -CFXRf (1) (In the formula, X represents a hydrogen atom, a fluorine atom or a trifluoromethyl group; and Rf represents a fluorine atom or a fluoroalkyl group having 1-20 carbon atoms and optionally having an ether oxygen atom.)

Description

Photosensitive composite, spaced walls, colored filter and organic EL
Technical field
The present invention relates to photosensitive composite, use the spaced walls of said composition and there is colored filter and the organic EL of this spaced walls.
Background technology
In recent years, as the formation material of permanent film of spaced walls, the spaced walls of wiring substrate etc. of ITO electrode of spaced walls, liquid crystal display cells of dividing each TFT in the spaced walls between the pixel of the spaced walls between the pixel of colored filter, organic EL (electroluminescence (Electro-Luminescence)) display element, organic tft (ThinFilm Transistor: thin film transistor (TFT)) array, photosensitive composite is attracted attention.For example, while manufacturing colored filter, use photoetching process to form after spaced walls pattern (also playing the effect of black matrix"), the peristome that uses ink-jet method that the ink of R (red), G (green) and B (indigo plant) is coated between spaced walls forms pixel.In addition, while manufacturing organic EL, use photoetching process to form after spaced walls pattern, by ink-jet method, by the solution coat of hole mobile material, luminescent material etc., the peristome between spaced walls forms the pixel with hole transmission layer, luminescent layer etc.
In order to prevent, between the neighbor of such colored filter and organic EL, colour mixture occurs, the upper surface of spaced walls must have and rejects the character of ink, i.e. so-called liquid-repellant.In addition, white in order to prevent the leakage of colored filter and organic EL, the peristome between spaced walls must have the character, the i.e. so-called lyophily that infiltrate for ink.
In order to obtain desired these characteristics of spaced walls, put forward to form with adding the scheme of refusing ink composition in photosensitive composite in spaced walls.For example, in patent documentation 1, recorded to be at least included in side chain and there is the repetitive of fluorine atom and there is the repetitive of polyether structure as the photosensitive polymer combination of feature at side chain.The matter average molecular weight of the fluorochemicals of recording in the embodiment of patent documentation 1 is 26000 to the maximum.
In patent documentation 2, recorded comprise optical polymerism compound, as at least make fluorochemical monomer with containing have etheric oxygen atom alkylidene monomer copolymerization and the photosensitive composition of refusing ink compound, Photoepolymerizationinitiater initiater, colorant of multipolymer.The matter average molecular weight of the fluorinated copolymer of recording in the embodiment of patent documentation 2 is 10900 to the maximum.
But, at present for the existing ink composition of refusing, use in the situation of the fluorine resin that contains the two keys of ethene, the spaced walls of gained can fully obtain above-mentioned desired performance, be that spaced walls top good refused ink, is not developed the performance such as developer solution tolerance, the good ink invasion to peristome between spaced walls that liquid corrodes, but use in the situation of the fluorine resin that does not contain the two keys of ethene, cannot obtain the spaced walls that fully meets all these performances.
In addition, fully possess above-mentioned conduct refuse the fluorine resin containing the two keys of ethene of the desired performance of ink composition exist for will containing the group of the two keys of ethene introduce fluorine resin and process number increase etc. in the disadvantageous place of manufacture view.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2008-33229 communique
Patent documentation 2: Japanese Patent Laid-Open 2009-168948 communique
The summary of invention
Invent technical matters to be solved
The present invention is the invention completing in order to solve the existing problem of prior art, its object is to provide and comprises the photosensitive composite of refusing ink composition, the described ink composition of refusing is the ink composition of refusing containing the two keys of ethene not, but the spaced walls that can give gained is refused ink, is not developed developer solution tolerance that liquid corrodes, is suppressed not to be developed and character that residual residual film produces and the good ink invasion to peristome between spaced walls with spaced walls top good.The present invention also aims to provide the well behaved spaced walls obtaining with the favourable material in economy aspect and colored filter and the organic EL with this spaced walls.
The technical scheme that technical solution problem adopts
The invention provides photosensitive composite, spaced walls, colored filter and the organic EL with following formation.
[1] photosensitive composite, it is to comprise to have containing the side chain of the group that represents with following general formula (1) with containing the side chain of polyoxyalkylenes and do not have the photosensitive composite containing the polymkeric substance (A) of the side chain of ethene pair keys, trigger for optical solidification (B), adhesive resin (C)
The matter average molecular weight (Mw (A)) of described polymkeric substance (A) meets 2.6 × 10 4< Mw (A)≤20 × 10 4;
-CFXR f …(1)
In formula, X represents hydrogen atom, fluorine atom or trifluoromethyl, R fexpression can be more than 1 fluoro-alkyl below 20 or fluorine atom containing the carbon number of etheric oxygen atom.
[2] photosensitive composite as described in [1], the polyoxyalkylenes in described polymkeric substance (A) containing proportional be 5～60 quality %.
[3] photosensitive composite as described in [1] or [2], described polymkeric substance (A) is containing acidic-group.
[4] photosensitive composite as described in any one in [1]～[3], it is 20～50 quality % that the fluorine atom in described polymkeric substance (A) contains proportional.
[5] photosensitive composite as described in any one in [1]～[4], the ratio of the described polymkeric substance (A) in all solids composition of described photosensitive composite is 0.07～1 quality %.
[6] photosensitive composite as described in any one in [1]～[5], described polymkeric substance (A) is also containing the a kind of above group that is selected from epoxy radicals, sulfydryl and hydroxyl.
[7] photosensitive composite as described in any one in [1]～[6], described polymkeric substance (A) also has the side chain containing the group representing with following general formula (2);
[changing 1]
In formula, R 1and R 2represent independently respectively hydrogen atom or the alkyl that can be replaced by fluorine atom, naphthenic base or aryl, R 3represent that hydrogen atom or carbon number are more than 1 organic group below 10, n represents more than 1 integer below 200.
[8] photosensitive composite as described in any one in [1]～[7], also comprise polymkeric substance (A) ', described polymkeric substance (A) ' have containing the side chain of the group that represents with above-mentioned general formula (2) and contain the side chain of polyoxyalkylenes, and do not have containing the side chain of the group representing with described general formula (1) with containing the either party in the side chain of the two keys of ethene, and its matter average molecular weight (Mw (A) ') meet 2.6 × 10 4< Mw (A) '≤20 × 10 4.
[9] photosensitive composite as described in any one in [1]～[8], described trigger for optical solidification (B) is Photoepolymerizationinitiater initiater, described adhesive resin (C) is the photoresist containing acidic-group and the two keys of ethene.
[10] photosensitive composite as described in [9], also comprises the crosslinking chemical (D) with 2 two keys of above ethene.
[11] photosensitive composite as described in any one in [1]～[10], also comprises black colorant (E).
[12] spaced walls, it is the spaced walls that is formed as the form of the multiple blocks that are partitioned into pixel formation use on substrate, it is characterized in that, is formed by the coating film cured product thereof of the photosensitive composite described in any one in [1]～[11].
[13] colored filter, it is the colored filter that has multiple pixels and be positioned at the spaced walls between the pixel of adjacency on substrate, it is characterized in that, and described spaced walls is formed by the spaced walls [12] Suo Shu, and described pixel forms by ink-jet method.
[14] organic EL, it is the organic EL that has multiple pixels and be positioned at the spaced walls between the pixel of adjacency on substrate, it is characterized in that, and described spaced walls is formed by the spaced walls [12] Suo Shu, and described pixel forms by ink-jet method.
In this instructions, term " trigger for optical solidification " is as the general name that is produced spike and caused the compound of the curing reaction of above-mentioned adhesive resin (C) by illumination.
In addition, in this instructions, polyoxyalkylenes refer to-(RO) pthe divalent group of-expression, R represents alkylidene, p represents more than 2 integers.Be combined with end group in one end of polyoxyalkylenes, the other end is the key of being combined with the main chain side of polymkeric substance.
The effect of invention
If adopt photosensitive composite of the present invention, what its usage economy aspect was favourable refuses ink composition, and the spaced walls that can give gained is refused ink, is not developed developer solution tolerance that liquid corrodes, is suppressed not to be developed and character that residual residual film produces and the good ink invasion to peristome between spaced walls with spaced walls top good.If employing the present invention, uses the photosensitive composite of the invention described above, can obtain the favourable and well behaved spaced walls in economy aspect and there is colored filter and the organic EL of this spaced walls.
The mode carrying out an invention
Below, describe implementing mode of the present invention, but the present invention is not limited in following embodiment.
In this instructions, unless otherwise specified, % represents quality %.In addition, (methyl) acryloyl group is as representing that the two general name of acryloyl group and methacryl is used.(methyl) acrylate is as representing that the two general name of acrylate and methacrylate is used.(methyl) acrylic acid is as representing that the two general name of acrylic acid and methacrylic acid is used.(methyl) acrylamide is as representing that the two general name of acrylamide and Methacrylamide is used.(methyl) allyl is as representing that the two general name of allyl and methacrylic is used.The group representing with general formula (1) is called to group (1).Other group too.
<1> photosensitive composite
Photosensitive composite of the present invention is to comprise to have contain the side chain of the group representing with following general formula (1) and contain the side chain of polyoxyalkylenes and do not have the matter average molecular weight (Mw (A)) satisfied 2.6 × 10 containing the side chain of the two keys of ethene 4< Mw (A)≤20 × 10 4polymkeric substance (A), trigger for optical solidification (B), the photosensitive composite of adhesive resin (C).
-CFXR f …(1)
In formula, X represents hydrogen atom, fluorine atom or trifluoromethyl, R fexpression can be more than 1 fluoro-alkyl below 20 or fluorine atom containing the carbon number of etheric oxygen atom.
Photosensitive composite of the present invention is the photosensitive composite that comprises above-mentioned polymkeric substance (A), trigger for optical solidification (B) and adhesive resin (C), while being the exposure in photoetching process etc. the adhesive resin (C) of illumination part by the effect of trigger for optical solidification (B) curing negative photosensitive composition.In photoetching process etc., when the alkali not carried out after exposure by the part of illumination (unexposed portion) develops, optionally removed, formed thus the spaced walls being formed by the solidfied material of above-mentioned photosensitive composite.
Negative-type photosensitive compound is divided into the such as several type such as radical-curable, acid cure type according to curing kind, selects the combination of trigger for optical solidification used (B) and adhesive resin (C) according to its curing kind.If photosensitive composite of the present invention is negative photosensitive composition, applicable to curing type arbitrarily, be particularly suitable for the photosensitive composite of radical-curable.Below, for the embodiment of photosensitive composite of the present invention, describe as an example of radical-curable photosensitive composite and acid cure type photosensitive composite example.
(1) radical-curable photosensitive composite
Photosensitive composite of the present invention is in the situation of radical-curable, and photosensitive composite comprises polymkeric substance (A), as the Photoepolymerizationinitiater initiater (B1) of trigger for optical solidification (B) with as the photoresist (C1) containing the two keys of acidic-group and ethene of adhesive resin (C).For such radical-curable photosensitive composite, when exposure in photoetching process etc., there is free radical polymerization by Photoepolymerizationinitiater initiater (B1) in the photoresist (C1) of illumination part, curing being promoted and form coating film cured product thereof.
Below, the contained each composition of radical-curable photosensitive composite of the present invention is described.(1-1) polymkeric substance (A)
Polymkeric substance (A) is to have containing the side chain of the group that represents with above-mentioned general formula (1), comprise polyoxyalkylenes and do not have the fluoropolymer containing the side chain of the two keys of ethene, its matter average molecular weight (Mw (A)) satisfied 2.6 × 10 4< Mw (A)≤20 × 10 4.
It is the high molecular as shown in above-mentioned scope that polymkeric substance (A) has containing side chain and the matter average molecular weight of the group (1) of above-mentioned contain fluorine atoms, therefore to photosensitive composite of the present invention being coated on substrate and the film forming while being dried easily travels to the near surface of film.In addition, polymkeric substance (A) does not contain the two keys of ethene in side chain, but there is the high molecular as shown in above-mentioned matter average molecular weight scope, even so in the time that photosensitive composite curing carried out in the exposure by after dried coating film, also near the film coated surface travelling to while resting on above-mentioned dried coating film, easily in this position immobilization.In addition, for polymkeric substance (A), by making matter average molecular weight in above-mentioned scope, developing solution dissolution is also fully guaranteed.Consequently, can bring into play liquid-repellant in upper surface in the spaced walls that the painting film development after exposure is formed, the peristome between spaced walls is also brought into play lyophily.In addition, after development, even if heat (baking afterwards), polymkeric substance (A) can not migrate to peristome yet, and the peristome between spaced walls, can maintain lyophily.
In addition, polymkeric substance (A) has the side chain containing polyoxyalkylenes, also can keep liquid-repellant even if therefore use after developing procedure the spray operation of water under high pressure.The reason that shows described phenomenon is also unclear, but is presumed as follows.
Based on the interaction of polyoxyalkylenes and other composition, for example adhesive resin (C), i.e. so-called anchoring effect, polymkeric substance (A) is considered to have and is difficult for the effect that departs from from film coated surface.After developing procedure, use the spray operation of water under high pressure, polymkeric substance (A) especially easily departs from from top layer.But because polymkeric substance (A) has the side chain containing polyoxyalkylenes, therefore based on described anchoring effect, polymkeric substance (A) easily residues in film coated surface, film easily manifests liquid-repellant.Therefore, use ink-jet method that ink is coated while being spaced apart the peristome that wall impales, can suppress the leakage that the colour mixture that occurs between the peristome of adjacency and peristome occur white.In addition,, by making polymkeric substance (A) there is the side chain containing polyoxyalkylenes, can suppress the generation of the residual film of following explanation.
The phenomenon that, produces residual film is considered to following phenomenon.During by manufacture spaced walls such as photoetching process etc., alkaline developer used generally comprises surfactant, therefore in development treatment, easily produces bubble.In addition, this bubble is attached in the situation on liquid-repellant surface and is difficult to remove.Therefore, originally should dissolve the part of removing due to bubbles attached by alkaline developer, what photosensitive composite was contained refuse ink composition is easily membranaceous remaining.The polymkeric substance (A) with the side chain that contains polyoxyalkylenes can suppress the appearance of the residual film producing like this.
Polyoxyalkylene chain suppresses mechanism that residual film produces unclear, even but think that the bubble in developer solution is temporarily attached to film, because surface exists polyoxyalkylene chain, bubble is easily removed, or bubble is at least difficult for resting on same place.
The matter average molecular weight (Mw (A)) of the polymkeric substance (A) using in the present invention meets 2.6 × 10 4< Mw (A)≤20 × 10 4, be better 3.0 × 10 4< Mw (A)≤12 × 10 4, be more preferably 3.5 × 10 4≤ Mw (A)≤12 × 10 4, particularly preferably 4.0 × 10 4≤ Mw (A)≤10 × 10 4.
If the matter average molecular weight of polymkeric substance (A) is 2.6 × 10 4below, the lyophily deficiency of peristome between spaced walls, while using ink-jet method coating ink, ink cannot be at the abundant invasion of peristome.In addition, if matter average molecular weight higher than 20 × 10 4, alkali solubility, developability deficiency.
If matter average molecular weight (Mw) is higher than 3.0 × 10 4and 12 × 10 4in following scope, be not subject to the impact of the kind of alkali and concentration, spray condition, easily keep high liquid-repellant, the scope of application of manufacture expands, so preferably.In addition be also preferred from the manufacture difficulty of polymkeric substance (A).
In addition, the number-average molecular weight of polymkeric substance (A) (Mn (A)) is better 1.0 × 10 4≤ Mn (A)≤15.0 × 10 4, be more preferably 1.5 × 10 4≤ Mn (A)≤12.0 × 10 4, particularly preferably 2.0 × 10 4≤ Mn (A)≤10.0 × 10 4.If the number-average molecular weight of polymkeric substance (A) is lower than 1.0 × 10 4, the lyophily deficiency of peristome between spaced walls, while using ink-jet method coating ink, ink may be at the abundant invasion of peristome; If number-average molecular weight is higher than 15 × 10 4, alkali solubility, developability may be not enough.
In this instructions, matter average molecular weight (Mw) and number-average molecular weight (Mn) refer to the value of measuring take polystyrene as standard substance by gel permeation chromatography.
The relation of the lyophily of the peristome between matter average molecular weight and number-average molecular weight and the spaced walls of polymkeric substance (A) is also indefinite.Generally, photosensitive composite, particularly comprise black colorant photosensitive composite in the situation that when exposure in,, curing reaction did not fully carry out, when exposure not immobilized polymkeric substance (A) may be in exposure, conventionally carry out after developing be known as after travel to the side of spaced walls or flow out to the peristome between spaced walls when the heat treated (aftermentioned) of baking.If the matter average molecular weight of polymkeric substance (A) is higher than 2.6 × 10 4, be more preferably number-average molecular weight 1.0 × 10 4the phenomenon of dividing a word with a hyphen at the end of a line, flow out of the polymkeric substance (A) above, can think above-mentioned rear baking time is inhibited.
The molecular weight distribution representing with matter average molecular weight (Mw (A))/number-average molecular weight (Mn (A)) of the polymkeric substance (A) using in the present invention is better more than 1.2 below 8, is more preferably more than 1.3 below 4.Favourable aspect economy if the molecular weight distribution of polymkeric substance (A) within the scope of this, can be simplified polymkeric substance (A) production process, and developability is also good.
The polymkeric substance (A) using in the present invention has the group (1) of the contain fluorine atoms representing with above-mentioned general formula (1) at side chain.In group (1), R fin the situation of the fluoro-alkyl that can be 1～20 containing the carbon number of etheric oxygen atom, R fcan contain the halogen atom except fluorine atom.As such halogen atom, it is better chlorine atom.In addition, as the structure of this fluoro-alkyl, being not particularly limited, can exemplifying linear chain structure, branched structure, ring structure, partly have the structure of ring etc., is better linear chain structure.In addition, R fbe to contain in the situation of fluoro-alkyl of etheric oxygen atom, etheric oxygen atom may reside between the carbon-carbon bond of fluoro-alkyl, also may reside in the end of fluoro-alkyl.
As the R of group (1) f, be better the above-mentioned fluoro-alkyl that is 1～20 containing the carbon number of etheric oxygen atom.In addition particularly preferably fluorine atom of X.
In above-mentioned group (1), R ffor the carbon number that can contain etheric oxygen atom be in the situation of more than 1 fluoro-alkyl below 20, R fthere is this structure, be not particularly limited.As R f, specifically can exemplify-CF 3,-CF 2cF 3,-CF 2cHF 2,-(CF 2) 2cF 3,-(CF 2) 3cF 3,-(CF 2) 4cF 3,-(CF 2) 5cF 3,-(CF 2) 6cF 3,-(CF 2) 7cF 3,-(CF 2) 8cF 3,-(CF 2) 9cF 3,-(CF 2) 11cF 3,-(CF 2) 15cF 3,-CF (CF 3) O (CF 2) 5cF 3,-CF 2o (CF 2cF 2o) pcF 3,-CF (CF 3) O (CF 2cF (CF 3) O) qc 6f 13,-CF (CF 3) O (CF 2cF (CF 3) O) rc 3f 7deng, the integer that p is 1～8, the integer that q is 1～4, the integer that r is 1～5.
R ffor the carbon number that can contain etheric oxygen atom be in the situation of more than 1 fluoro-alkyl below 20, R fbe better not contain the perfluoroalkyl of etheric oxygen atom and the perfluoroalkyl containing etheric oxygen atom, be more preferably the not perfluoroalkyl containing etheric oxygen atom.Its carbon number is better 1～11, particularly preferably 3～5.
In these groups (1), in the present invention, be better perfluoroalkyl or the Polyfluoroalkyl containing 1 hydrogen atom, particularly preferably perfluoroalkyl.Perfluoroalkyl and Polyfluoroalkyl comprise the group containing etheric oxygen atom.In addition as the above-mentioned Polyfluoroalkyl containing 1 hydrogen atom, be better that X is the compound of hydrogen atom.By this, use the liquid-repellant of upper surface of the spaced walls that photosensitive composite of the present invention forms good.
In addition, group (1) is better that carbon number is 4～6.As such group (1), specifically can exemplify-(CF 2) 3cF 3,-(CF 2) 4cF 3,-(CF 2) 5cF 3,-CF 2o (CF 2) 2oCF 3,-CF 2o (CF 2) 2o (CF 2) 2oCF 3deng.If the carbon number of the group (1) that polymkeric substance (A) has at side chain is 4～6, can make polymkeric substance (A) and the intermiscibility of other composition that forms photosensitive composite improve.Take this, can suppress to be coated with photosensitive composite and the aggegation of polymkeric substance (A) in the film that forms, thereby can form the good spaced walls of outward appearance.
In polymkeric substance (A), the call number with the group (1) in the side chain of group (1) is 1.In each side chain with group (1) of polymkeric substance (A), group (1) can be identical, also can be different.That is, the group (1) that polymkeric substance (A) has at side chain can be only a kind, can be also combination of more than two kinds.In the polymkeric substance (A) that the present invention uses, can in all side chains, introduce group (1), but be better that the condition of the fluorine atom content that reaches following is suitably adjusted the ratio of the side chain of introducing group (1) in polymkeric substance (A) entirety.Specifically, while manufacturing polymkeric substance (A) by the polymerization of starting monomer as described later, adjust and there is the monomer of group (1) with respect to the incorporation of whole starting monomers.
In addition, the introducing position of the side chain with group (1) in polymkeric substance (A) is not particularly limited, better to reach the condition of following fluorine atom content, uniformly-spaced on the main chain that forms polymkeric substance (A), to introduce the side chain with group (1) with block or random mode regularly.Thus, as long as in the scope of the matter average molecular weight of the invention described above, having the side chain of group (1), can introduce with any form in alternating copolymer, segmented copolymer, random copolymers in polymkeric substance (A).As polymkeric substance (A), from manufacture homogeneity in the molecule of efficiency and liquid repellent composition, with liquid repellent composition beyond the angle of intermiscibility etc. of composition, be better random copolymers.For the side chain with various groups of any introducing of following explanation, with same with the introducing of side chain with group (1), be better to introduce with random fashion by random copolymerization.
In the polymkeric substance (A) that the present invention uses, mainly because the fluorine atom content having in the polymkeric substance (A) producing containing the side chain of group (1) is better 20～50 quality %, be more preferably 25～42 quality %, particularly preferably 25～35 quality %.If lower than 20 quality %, there is the tendency that cannot obtain enough development tolerances in the fluorine atom content in this polymkeric substance (A), thereby the liquid-repellant of the upper surface of spaced walls may be not enough.In addition, if the fluorine atom content in polymkeric substance (A) higher than 50 quality %, exists the tendency of mutual aggegation between polymkeric substance (A), thereby the liquid-repellant of the upper surface of spaced walls may be not enough.In addition, the adaptation of spaced walls and substrate may decline.
Fluorine atom content in polymkeric substance (A) is the content that is mainly derived from the contained fluorine atom of above-mentioned group (1) that polymkeric substance (A) has at side chain.But, such as polymkeric substance (A) containing as directly with in the situation of the non-fluorine atom that derives from above-mentioned group (1) such as fluorine atom that the carbon of main chain is combined, the fluorine atom content in polymkeric substance (A) refers to fluorine atom that above-mentioned group (1) is contained and the contained fluorine atom addition of polymkeric substance (A) and the fluorine atom total content that obtains except group (1).
In addition in the polymkeric substance (A) that, the present invention uses, there is the side chain containing polyoxyalkylenes.This polyoxyalkylenes is the polyoxyalkylenes take the oxyalkylene group of carbon number 2～4 as repetitive.
The content of the polyoxyalkylenes in the polymkeric substance (A) that the present invention uses is better 5～60 quality %, is more preferably 10～55 quality %, particularly preferably 15～50 quality %.If the content of the polyoxyalkylenes in polymkeric substance (A), lower than 5 quality %, uses the spray operation of water under high pressure after developing procedure, liquid-repellant may significantly decline.In addition, may form the spaced walls that finally obtains or spaced walls peristome and exist the state of a large amount of residual films.In addition, if the content of polyoxyalkylenes higher than 60 quality %, liquid-repellant may decline.
The polyoxyalkylenes using in the present invention is specially the group (also claiming below group (11)) representing with following general formula (11).
-(R 11O) m(R 12O) jR 13…(11)
In formula (11), R 11represent ethylidene, R 12represent the alkylidene of carbon number 3 or 4, R 13represent that hydrogen atom maybe can have the alkyl of substituent carbon number 1～10, m represents 4～100 integer, and j represents 0～100 integer, and m+j is 4～100.
In above-mentioned group (11), R 11represent ethylidene (CH 2cH 2-), R 12represent the alkylidene of carbon number 3 or 4.The structure of the alkylidene of carbon number 3 or 4 can be linear chain structure, can be also branched structure.R 12there is 1,2-propylidene (CH 2cH (CH 3)-), 1,3-propylidene (CH 2cH 2cH 2-), ethyl ethylidene (CH 2cH (CH 2cH 3)-), 1,2-dimethyl ethylidene (CH (CH 3) CH (CH 3)-), Isosorbide-5-Nitrae-butylidene ((CH 2) 4-) etc., be better 1,2-propylidene or Isosorbide-5-Nitrae-butylidene.
In formula (11), m represents 4～100 integer, and j represents 0～100 integer, is better respectively below 50, is more preferably below 30.In addition the R in polyoxyalkylenes, 11quantitative proportion m/ (m+j) be better 50～100%, be more preferably 80～100%, be particularly preferably essentially 100%.
In addition, m+j is 4～100, is better 6～50, is more preferably 8～30.If m+j below 3, uses the spray operation of water under high pressure after developing procedure, liquid-repellant easily declines.In addition, there is the tendency that produces a large amount of residual films.If m+j is more than 101, polymkeric substance while baking afterwards (A) migrates to peristome, the lyophily deficiency of peristome between spaced walls, and while using ink-jet method coating ink, ink may be fully at peristome invasion.In above-mentioned general formula (11), (R 11o) m(R 12o) jto represent that group (11) has m (R 11o) unit and j (R 12o) unit, to (R 11o) unit and (R 12o) binding sequence of unit is not particularly limited.That is, in group (11), m (R 11o) unit and j (R 12o) unit can for example replace or be random or with block fashion combination.
In above-mentioned group (11), R 13for can have the alkyl of substituent carbon number 1～10 time, its structure can be linear chain structure, branched structure, ring structure, the part structure with ring etc.In addition,, as substituting group, specifically can exemplify the alkoxy of carboxyl, hydroxyl, carbon number 1～5 etc.In the present invention, as the R in group (11) 13, be better the straight chain of carbon number 1～5, the alkyl that nothing replaces, be more preferably methyl, ethyl.
The polyoxyalkylenes of the above-mentioned group (11) that polymkeric substance (A) has at side chain etc. can be used alone a kind, and also two or more kinds may be used.In addition, containing the side chain of group (11) to the introducing of polymkeric substance (A) as described later, in the time that polymkeric substance (A) is manufactured in the polymerization by starting monomer, in the scope of not destroying effect of the present invention, suitably adjust the monomer that contains group (11) with respect to the incorporation of whole starting monomers, can give polymkeric substance (A) effect that above-mentioned developability improves to reach.
Except above-mentioned, containing the side chain of group (1), the contained polymkeric substance (A) of photosensitive composite of the present invention also can have the side chain containing the functional group corresponding to various objects in the scope of not destroying effect of the present invention.Introduce the example of functional group as such to polymkeric substance (A) side chain, for example, in order to improve tumbling property of ink and the ozone of resistance to UV, can in the side chain of above-mentioned polymkeric substance (A), introduce the group (also claiming below group (2)) of the silicone-containing key representing with following general formula (2).
[changing 2]
Figure BDA00001779313400111
In formula, R 1and R 2represent independently respectively hydrogen atom or the alkyl that can be replaced by fluorine atom, naphthenic base or aryl, R 3represent that hydrogen atom or carbon number are more than 1 organic group below 10, n represents more than 1 integer below 200.
In above-mentioned group (2), the R in each Component units 1and R 2can be identical or different.R 1, R 2during for alkyl, carbon number is better 1～10, is more preferably 1～6.They can be linear chain structure, can be also branched structures.R 1, R 2during for naphthenic base, carbon number is better 3～10, is more preferably 5 or 6.R 1, R 2during for aryl, carbon number is better 6～15, is more preferably 6～10.R 1, R 2part or all of hydrogen atom can be replaced by fluorine atom.
In addition, using the liquid-repellant of the spaced walls of the photosensitive composite formation that comprises polymkeric substance (A) if consider, is better R 1and R 2represent independently respectively hydrogen atom, methyl, trifluoromethyl or phenyl, particularly preferably the R of all siloxane units 1and R 2it is all methyl.
In addition R, 3during for more than 1 organic group below 10 of carbon number, R 3can nitrogen atom, oxygen atom, fluorine atom etc.In the present invention, R 3be better the alkyl of hydrogen atom, the carbon number alkyl that is 1～5 or the carbon number 1～5 that replaced by fluorine atom, be more preferably trifluoromethyl or methyl.In addition, in group (2), n is better 2～100 integer.
When polymkeric substance (A) has containing the side chain of group (2), group (2) can be used alone a kind, and also two or more kinds may be used.In addition, the silicon atom content that derives from group (2) in polymkeric substance (A) is better 0.1～25 quality %, is more preferably 0.5～20 quality %.If silicon atom content within the scope of this, can be given polymkeric substance (A) with above-mentioned effect in the situation that not destroying effect of the present invention.The adjustment nationality of the silicon atom content in polymkeric substance (A) is by suitably adjusting containing the monomer of group (2) and carry out with respect to the incorporation of whole starting monomers in the time that polymkeric substance (A) being manufactured in the polymerization by starting monomer as described later.
Polymkeric substance (A) is better the side chain also having containing acidic-group.The introducing of the side chain containing acidic-group in polymkeric substance (A) is the raising for developability.Development photosensitive composite developer solution used is generally alkaline-based developer, and by introducing acidic-group, the developing solution dissolution of polymkeric substance (A) is good.The contained polymkeric substance (A) of the unexposed portion of film is removed by developer solution.Polymkeric substance (A) has in the situation containing the side chain of acidic-group, and alkali favorable solubility, so that polymkeric substance (A) is attached to the possibility of peristome is again minimum.Therefore, the lyophily of peristome is good.The acidic-group that polymkeric substance (A) has at side chain can be a kind, can be also two or more.
As the acidic-group of introducing polymkeric substance (A), be not particularly limited, can exemplify carboxyl, phenol hydroxyl, sulfonic group etc.Here, can be by the end group R to above-mentioned polyoxyalkylenes (11) to the introducing of the acidic-group of the side chain of polymkeric substance (A) 13introduce and carry out.The polymkeric substance (A) that the present invention uses, in the time that polymkeric substance (A) is manufactured in the polymerization by starting monomer as described later, suitably adjust the monomer that contains acidic-group with respect to the incorporation of whole starting monomers, make the polymkeric substance (A) of gained there is following preferred acid number.
The acid number of polymkeric substance (A) is better below 100mgKOH/g, is more preferably 10～50mgKOH/g.If acid number, within the scope of this, can carry out the development of unexposed portion well, the liquid-repellant on the spaced walls top of exposure portion is also good.Further, acid number be in and the quality [mg] of the required potassium hydroxide of 1g sample, in this instructions, unit is designated as mgKOH/g.
Polymkeric substance (A) is better also to have the side chain that the functional group of cross-linking reaction can occur by the contained functional group of the matrix of heat or light and formation spaced walls containing epoxy radicals, sulfydryl, hydroxyl etc.These functional groups that introduce polymkeric substance (A) can be used alone or two or more kinds may be used.In addition, introducing these functional groups to the side chain of polymkeric substance (A) can be by the end group R having to above-mentioned polyoxyalkylenes (11) 13introduce and carry out.For the introducing of hydroxyl, also can pass through R 13being converted into hydrogen atom carries out.
Except polymkeric substance (A), photosensitive composite of the present invention comprises trigger for optical solidification (B) and adhesive resin (C).This adhesive resin (C) utilizes the effect of trigger for optical solidification (B) to solidify by exposing.Make in the situation of spaced walls of photosensitive composite, the unexposed portion by pattern exposure beyond curing part utilizes developer solution to be removed.With as the negative photosensitive composition such as photosensitive composite of the present invention while implementing photoetching process, conventionally use containing the adhesive resin (C) of acidic-group and the combination of alkaline-based developer.
Polymkeric substance (A) containing epoxy radicals, hydroxyl etc. can with the situation of the functional group of acidic-group heat cross-linking under, by the rear baking processing after exposure, development, the acidic-group heat cross-linking of what these functional groups of polymkeric substance (A) and spaced walls matrix had derive from adhesive resin (C), polymkeric substance (A) is fully fixed on spaced walls.In addition, polymkeric substance (A) simultaneously containing above-mentioned can with the situation of the functional group of acidic-group heat cross-linking and acidic-group under, heat cross-linking reaction occurs mutually and producing high-molecular between the partial polymer (A) particularly existing in polymkeric substance (A) high density of spaced walls upper surface, the state of spaced walls is fully fixed in formation.In addition, polymkeric substance (A), containing in the situation of sulfydryl, similarly operates with above-mentioned, processes by rear baking, crosslinked with the ethene unsaturated double-bond group that derives from adhesive resin (C), is fully fixed on spaced walls.Take this, can prevent thereafter outflow or the stripping from spaced walls to ink of the polymkeric substance (A) worried by ink-jet in the time that spaced walls peristome injects ink.
Introduce containing the functional group that can have with spaced walls matrix and carry out in the situation of side chain of crosslinked functional group to polymkeric substance (A), in the time that polymkeric substance (A) is manufactured in the polymerization by starting monomer as described later, suitably adjust the monomer of the functional group crosslinked containing the functional group that can have with spaced walls with respect to the incorporation of whole starting monomers, make the incorporation of the effect of its outflow that reaches the polymkeric substance (A) can give polymkeric substance (A) inject to suppress above-mentioned ink in the situation that not destroying effect of the present invention time, stripping.
(manufacture of polymkeric substance (A))
The polymkeric substance (A) using for the present invention, there is the side chain that contains above-mentioned group (1) and the structure that contains the side chain of the polyoxyalkylenes such as above-mentioned group (11) in order to realize, further realization at random has containing the side chain of above-mentioned group (2), containing the side chain of acidic-group, containing the structure of the side chain of crosslinked functional group of the functional group that can have by heat or light and spaced walls matrix etc., can exemplify by polyreaction and directly form and contain the side chain of these groups or form the method containing the side chain of these groups by the chemical conversion after polyreaction.
For polymkeric substance (A), for must have by the direct formation of polyreaction containing the side chain of group (1) with containing the side chain of the polyoxyalkylenes such as group (11) and the side chain containing above-mentioned each group having arbitrarily, select felicity condition make containing the monomer of group (1), have containing the monomer of the side chain of the polyoxyalkylenes such as group (11) and adopt as required containing the monomer of group (2), containing the monomer of acidic-group, contain monomer and/or other monomer copolymerization of crosslinked functional group of the functional group that can have with spaced walls matrix.
As the kind of copolymerization, can exemplify alternating copolymerization, block copolymerization, random copolymerization etc., can implement by current known method respectively, but in the present invention, polymkeric substance (A) is better to carry out by random copolymerization the random copolymers that copolymerization obtains.
As the above-mentioned monomer containing group (1) for the manufacture of polymkeric substance (A), it is better the compound representing with following general formula (3).They can be used alone or two or more kinds may be used.
CH 2=CR 4-COO-Y-CFXR f…(3)
In formula (3), R 4the alkyl of the fluoro-alkyl that is hydrogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom, trifluoromethyl, can be 1～20 containing the carbon number of etheric oxygen atom, cyano group, carbon number 1～20, alkyl, the aryl of carbon number 6～20 or the naphthenic base of carbon number 3～20 being replaced by the aryl of carbon number 7～20.Y is that singly-bound or carbon number are the divalent organic group of 1～6 not contain fluorine atoms.-CFXR fit is the group corresponding to above-mentioned group (1)., X is hydrogen atom, fluorine atom or trifluoromethyl.R fcan be 1～20 containing the carbon number of etheric oxygen atom fluoro-alkyl or fluorine atom.
In above-claimed cpd (3)-CFXR fpreferred form identical with the form illustrating about above-mentioned group (1).
In above-mentioned formula (3), in the group shown in Y, the Y of the divalent organic group of the not contain fluorine atoms that is 1～6 as carbon number, can exemplify-R 5-,-R 5-NR 6-SO 2-,-R 5-NR 6-CO-,-CH 2cH (OH)-R 7-etc., R 5that carbon number is 1～6 alkylidene, R 6hydrogen atom or methyl, R 7that singly-bound or carbon number are 1～4 alkylidene, R 6during for methyl, with NR 6in conjunction with R 5carbon number be 1～5.As R 5, specifically can exemplify-CH 2-,-CH 2cH 2-,-CH (CH 3)-,-CH 2cH 2cH 2-,-C (CH 3) 2-,-CH (CH 2cH 3)-,-CH 2cH 2cH 2cH 2-,-CH (CH 2cH 2cH 3)-,-CH 2(CH 2) 3cH 2-,-CH (CH 2cH (CH 3) 2)-etc.As R 7, specifically can exemplify-CH 2-,-CH 2cH 2-,-CH (CH 3)-,-CH 2cH 2cH 2-,-C (CH 3) 2-,-CH (CH 2cH 3)-,-CH 2cH 2cH 2cH 2-,-CH (CH 2cH 2cH 3)-etc.
Wherein, as the Y in compound (3), considering from the complexity obtaining, is better that carbon number is 2～4 alkylidene.
Above-mentioned R in compound (3) 4in shown group, be better hydrogen atom, fluorine atom, chlorine atom, methyl, trifluoromethyl, phenyl, benzyl etc., be more preferably hydrogen atom, fluorine atom, chlorine atom, methyl or trifluoromethyl.As R 4, particularly preferably hydrogen atom or methyl., particularly preferably (methyl) acrylate of compound (3).
As the compound representing with general formula (3), particularly preferably-CFXR ffor perfluoroalkyl and the Y of carbon number 4～6 are (methyl) acrylate of the alkylidene of carbon number 2～4.Specifically, can exemplify (methyl) acrylic acid-2-(perfluoro hexyl) ethyl ester, (methyl) acrylic acid-2-(perfluoro butyl) ethyl ester etc.
As the above-mentioned monomer containing group (11) for the manufacture of polymkeric substance (A), it is better the compound representing with following general formula (12) or (13).They can be used alone or two or more kinds may be used.
CH 2=CR 14-COO-(W-O) q-(R 11O) m(R 12O) jR 13…(12)
CH 2=CR 14-O-(W-O) q-(R 11O) m(R 12O) jR 13…(13)
In formula (12) or (13), R 14the alkyl, the aryl of carbon number 6～20 or the naphthenic base of carbon number 3～20 that are the alkyl of hydrogen atom, chlorine atom, bromine atoms, iodine atom, cyano group, carbon number 1～20, replaced by the aryl of carbon number 7～20.W is that carbon number is the divalent organic group of 1～10 not contain fluorine atoms.Q is 0 or 1.-(R 11o) m(R 12o) jr 13it is the group corresponding to above-mentioned group (11).
In above-claimed cpd (12) and (13)-(R 11o) m(R 12o) jr 13preferred form identical with the form illustrating about above-mentioned group (11).
In compound (12) and (13)-(W-O) q-be to represent singly-bound at 0 o'clock at q.Q is 1 o'clock ,-(W-O) q-be at R 11side has the organic group of oxygen atom.Q is 1 o'clock, W is better the divalent alkyl of carbon number 2～10, preferably the cycloalkylidene of the alkylidene of carbon number 2～6, carbon number 5 or 6, in the both sides of the cycloalkylidene of carbon number 5 or 6 or a side there is the alkylidene containing cycloalkylidene of total carbon number 6～10 of the alkylidene of carbon number 1～2.Wherein, W is and R 11when identical alkylidene, also comprise q be not in 0 situation W for and R 12when identical alkylidene, q regards 0 as.
In addition, as the R in above-claimed cpd (12) and (13) 14, be better hydrogen atom, fluorine atom, chlorine atom, methyl or trifluoromethyl, particularly preferably hydrogen atom or methyl.
In above-mentioned formula (12) and (13), q is 1 o'clock ,-(W-O)-be better R 11o, R 12linear chain structure beyond O, branched structure, ring structure, part have the oxygen atom end alkyl that the carbon number of the structure of ring is 1～10.Be more preferably the oxygen atom end alkyl of carbon number 3～8.As this oxygen atom end alkyl, specifically can exemplify CH 2c 6h 10cH 2o (the C in formula 6h 10for cyclohexylidene), CH 2o, CH (CH 3) O, CH 2cH 2cH 2o, C (CH 3) 2o, CH (CH 2cH 3) O, CH 2cH 2cH 2cH 2o, CH (CH 2cH 2cH 3) O, CH 2(CH 2) 3cH 2o, CH (CH 2cH (CH 3) 2) O etc.Wherein, as the W in compound (12) and (13), from the difficulty obtaining, be better that carbon number is 3 or 4 oxyalkylene group, j is not 0 o'clock and R 12except the identical oxyalkylene group of O.
Above-mentioned R in compound (12) and (13) 14in shown group, be better hydrogen atom, chlorine atom, methyl, phenyl, benzyl etc., be more preferably hydrogen atom, chlorine atom or methyl.
As the compound representing with above-mentioned general formula (12), general formula (13), preferred compound can exemplify compound shown below.
(compound representing with general formula (12))
CH 2=CHOCH 2C 6H 10CH 2O(CH 2CH 2O) mR 13
CH 2=CHO(CH 2) 4O(CH 2CH 2O) mR 13
(compound representing with general formula (13))
CH 2=CHCOO(CH 2CH 2O) mR 13
CH 2=C(CH 3)COO(CH 2CH 2O) mR 13
CH 2=CHCOO(CH 2CH 2O) m(C 3H 6O) jR 13
CH 2=C(CH 3)COO(CH 2CH 2O) m(C 3H 6O) jR 13
CH 2=CHCOO(CH 2CH 2O) m(C 4H 8O) jR 13
In above-mentioned formula, m, j are as hereinbefore.C 6h 10for cyclohexylidene, C 3h 6for propylidene, C 4h 8for Isosorbide-5-Nitrae-butylidene.R in formula 13for the straight chain of carbon number 1～10, for example, without the alkyl replacing, methyl, hydrogen atom etc.
In the manufacture of polymkeric substance (A), as the above-claimed cpd (12) and (13) that use in order to introduce group (11) in side chain, can use commercially available product.As such commercially available product, can exemplify for example following product.
BLEMMER PME-400 (trade name, NOF Corp (Japanese grease society) system, CH 2=C (CH 3) COO (CH 2cH 2o) kcH 3: the k in formula represents intermolecular mean value, and the value of k is about 9.Below, k, the m in the molecular formula of each commercially available product, j all represent intermolecular mean value).
NK Ester M-230G:(trade name, chemical industry Co., Ltd. of Xin Zhong village (chemistry society of Xin Zhong village) system, CH 2=C (CH 3) COO (CH 2cH 2o) kcH 3: the k in formula represents intermolecular mean value, and the value of k is about 23).
New Frontier NFBisomer PEM6E (trade name, Di-ichi Kogyo Seiyaku Co., Ltd. (a Gong Yesystemyao society), CH 2=C (CH 3) COO (CH 2cH 2o) kh: in formula, k is about 6).
Light Ester 130A (trade name, Kyoeisha Chemical Co., Ltd. (Sakae society chemistry society altogether) system, CH 2=CHCOO (CH 2cH 2o) kcH 3: in formula, k is about 9).
BLEMMER AE-400 (trade name, NOF Corp's system, CH 2=CHCOO (CH 2cH 2o) kh: in formula, k is about 10).
BLEMMER PP-800 (trade name, NOF Corp's system, CH 2=C (CH 3) COO (C 3h 6o) kh: in formula, k is about 13).
BLEMMER AP-800 (trade name, NOF Corp's system, CH 2=CHCOO (C 3h 6o) kh: in formula, k is about 13).
BLEMMER 70PEP-350B (trade name, NOF Corp's system, CH 2=C (CH 3) COO (C 2h 4o) m(C 3h 6o) jh: in formula, m is about 5, j and is about 2).
BLEMMER 55PET-800 (trade name, NOF Corp's system, CH 2=C (CH 3) COO (C 2h 4o) m(C 4h 8o) jh: in formula, m is about 10, j and is about 5).
As the above-mentioned monomer containing group (2) using as required in the manufacture of polymkeric substance (A), it is better the compound representing with following general formula (4).They can be used alone or two or more kinds may be used.
[changing 3]
Figure BDA00001779313400171
In formula (4), R 8be hydrogen atom or methyl, Z is that singly-bound or carbon number are 1～6 divalent organic group.The group of the silicone-containing key of being combined with Z in addition, is the group corresponding to above-mentioned group (2)., R 1and R 2represent independently respectively hydrogen atom or the alkyl that can be replaced by fluorine atom, naphthenic base or aryl, R 3represent the organic group that hydrogen atom or carbon number are 1～10, n represents 1～200 integer.
R in above-claimed cpd (4) 1, R 2, R 3identical with the form illustrating about above-mentioned group (2) with the preferred form of n.
In group shown in above-mentioned Z, the Z having as compound (4), is better that carbon number is 1～6 divalent alkyl, specifically can exemplify-CH 2-,-CH 2cH 2-,-CH (CH 3)-,-CH 2cH 2cH 2-,-C (CH 3) 2-,-CH (CH 2cH 3)-,-CH 2cH 2cH 2cH 2-,-CH (CH 2cH 2cH 3)-,-CH 2(CH 2) 3cH 2-,-CH (CH 2cH (CH 3) 2)-etc.Particularly preferably-CH 2cH 2-,-CH 2cH 2cH 2-,-CH 2cH 2cH 2cH 2-.
As the above-mentioned monomer containing acidic-group using as required in the manufacture of polymkeric substance (A), containing acidic-group, be not particularly limited, can exemplify carboxylic monomer, containing the monomer of phenol hydroxyl, contain sulfonic monomer etc.They can be used alone or two or more kinds may be used.
As carboxylic monomer, can exemplified by acrylic, methacrylic acid, vinyl acetic acid, butenoic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt etc.
As the monomer containing phenol hydroxyl, can exemplify that o-hydroxy ethene, a hydroxy styrenes, 4-Vinyl phenol and their phenyl ring 1 above hydrogen atom is replaced by following group and compound etc.: the alkyl such as methyl, ethyl, normal-butyl, the alkoxys such as methoxyl, ethoxy, n-butoxy, halogen atom, containing the haloalkyl of 1 above halogen atom, nitro, cyano group, amide group.
As containing sulfonic monomer, can exemplify vinyl sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid, 2-hydroxyl-3-(methyl) allyloxy propane sulfonic acid, (methyl) acrylic acid-2-sulfo group ethyl ester, (methyl) acrylic acid-2-sulfo group propyl ester, 2-hydroxyl-3-(methyl) acryloxy propane sulfonic acid, 2-(methyl) acrylamide-2-methylpro panesulfonic acid etc.
As the monomer of crosslinked functional group of the above-mentioned functional group containing having by heat or light and spaced walls matrix using as required in the manufacture of polymkeric substance (A) (below also title " bridging property functional group "), as long as containing bridging property functional group, be not particularly limited.Specifically, can exemplify monomer, the monomer of hydroxyl etc. containing epoxy radicals.They can be used alone or two or more kinds may be used.Better in fact not containing group (1) and group (2) containing the monomer of bridging property functional group.
As the monomer containing epoxy radicals, can exemplify (methyl) glycidyl acrylate, acrylic acid-3,4-epoxycyclohexyl methyl esters etc.
As the monomer of hydroxyl, can exemplify (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid-3-hydroxy propyl ester, (methyl) acrylic acid-4-hydroxyl butyl ester, (methyl) acrylic acid-5-hydroxyl pentyl ester, the own ester of (methyl) acrylic acid-6-hydroxyl, (methyl) acrylic acid-4-hydroxyl cyclohexyl, single (methyl) acrylic acid DOPCP, (methyl) acrylic acid-3-chlorine-2-hydroxyl propyl ester, single (methyl) acrylic acid glycerine ester, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol mono vinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (methyl) acrylamide, N, N-bis-(hydroxymethyl) (methyl) acrylamide etc.
For the side chain containing the sulfydryl of aforementioned middle example as bridging property functional group, by using thiocarboxylic acid ester compounds as chain-transferring agent, can introduce carbothioic acid ester in polymer ends.By with acid or alkali, this polymkeric substance being processed, carbothioic acid ester decomposition can be obtained to the polymkeric substance endways with sulfydryl again.Thiocarboxylic acid ester compounds is by for example carboxyl of thioacetic acid, propane thioic acid, Thiobutyric acid, thiobenzoate be converted into-COSH base and the compound obtaining.
Disposable above-mentioned monomer in addition in manufacture as polymkeric substance (A), can exemplify hydrocarbon system olefines, vinyl ethers, isopropenyl ethers, allyl ether series, vinyl ester, allyl ester class, (methyl) esters of acrylic acid, (methyl) acrylic amide, aromatic ethenyl compound, chloro-alkenes class, conjugated diene etc., if consider the thermotolerance of spaced walls, be better (methyl) esters of acrylic acid or (methyl) acrylic amide.These compounds can contain the functional group such as carbonyl, alkoxy.
While manufacturing for polymkeric substance of the present invention (A), from the monomer of above-mentioned explanation, suitably select the monomer copolymerization in the proper ratio for polymerization.The optimum ratio of the various monomers that use while manufacturing polymkeric substance (A) is as follows.
With respect to the ratio of the monomer mass containing group (1) of the gross mass of the monomer of copolymerization be better adopt fluorine atom content in polymkeric substance (A) in above-mentioned preferable range, be specially 25～50 quality %, be more preferably 25～42 quality %, the ratio of 25～35 quality % particularly preferably.As this ratio, according to the kind containing the monomer of group (1) and difference is better specifically 20～80 quality %, be more preferably 30～70 quality %, particularly preferably 40～60 quality %.If this ratio is too low, can not guarantee enough fluorine atom contents, existence cannot obtain the tendency of enough development tolerances, and polymkeric substance (A) is difficult for travelling near the upper surface of the spaced walls that uses photosensitive composite formation of the present invention, thereby the liquid-repellant of the upper surface of spaced walls may be not enough.In addition, if this ratio is too high, fluorine atom content exceedes preferred scope, has the tendency of mutual aggegation between polymkeric substance (A), thereby the liquid-repellant of the upper surface of spaced walls may be not enough.In addition, the adaptation of spaced walls and substrate may decline.
While manufacturing polymkeric substance (A), use in the situation of the monomer that contains contain fluorine atoms the monomer of group (1) as starting monomer, suitably adjust the ratio of each starting monomer and make fluorine atom content in the polymkeric substance (A) of gained in above-mentioned preferable range.
With respect to the ratio of the monomer mass containing group (11) of the gross mass of the monomer of copolymerization be better adopt the content of the group (11) in polymkeric substance (A) to be 5～60 quality %, be more preferably 10～55 quality %, the ratio of 15～50 quality % particularly preferably.If within the scope of this, the content of the group (11) in polymkeric substance (A), roughly in above-mentioned preferable range, even if use after developing procedure the spray operation of water under high pressure, also can keep liquid-repellant.In addition, can also prevent the generation of residual film.
While manufacturing polymkeric substance (A), use as required in the situation containing the monomer of group (2), with respect to the ratio of the monomer mass containing group (2) of the gross mass of the monomer of copolymerization be better adopt silicon atom content in polymkeric substance (A) in above-mentioned preferable range, be specially 0.1～25 quality %, be more preferably the ratio of 0.5～20 quality %.As this ratio, according to the kind containing the monomer of group (2) and difference is better specifically 0.5～30 quality %, be more preferably 2～20 quality %.If the ratio of the monomer containing group (2) in whole monomers of copolymerization is within the scope of this, the silicon atom content in polymkeric substance (A) is roughly in above-mentioned preferable range, and tumbling property of ink and the ozone of resistance to UV etc. are good.
While manufacturing polymkeric substance (A), use as required in the situation containing the monomer of acidic-group, with respect to the ratio of the monomer mass containing acidic-group of the gross mass of the monomer of copolymerization be better adopt the acid number of polymkeric substance (A) in above-mentioned preferable range, be specially 100mgKOH/g, be more preferably the ratio of 10～50mgKOH/g.As this ratio, according to the kind containing the monomer of acidic-group and difference is better specifically 2～20 quality %, be more preferably 4～12 quality %.If the ratio of the monomer containing acidic-group in whole monomers of copolymerization, within the scope of this, can be implemented well the development of unexposed portion in the situation that not destroying effect of the present invention, can also make the lyophily of peristome improve.
While manufacturing polymkeric substance (A), use as required in the situation containing the monomer of above-mentioned bridging property functional group, ratio with respect to the monomer mass containing bridging property functional group of the gross mass of the monomer of copolymerization is better 1～40 quality %, is more preferably 5～20 quality %.If the ratio containing the monomer of bridging property functional group in whole monomers of copolymerization within the scope of this, can realize fixing to spaced walls of polymkeric substance (A) in the situation that not destroying effect of the present invention, and developability is good.
Manufacturing polymkeric substance when (A), use as required in the situation containing other monomer beyond above-mentioned, is better below 70 quality % with respect to the ratio of other monomer mass of the gross mass of the monomer of copolymerization, is more preferably below 50 quality %.If this mass ratio is higher than 70 quality %, alkali-developable may decline.
The polymkeric substance (A) that the present invention uses be have containing the side chain of above-mentioned group (1) and containing the side chain of the polyoxyalkylenes such as above-mentioned group (11) as essential structure and further there is arbitrarily the side chain that contains above-mentioned group (2), containing the side chain of acidic-group, containing the multipolymer of the side chain of heat cross-linking functional group etc., can be by making containing the monomer of group (1) with containing the monomer of the polyoxyalkylenes such as above-mentioned group (11) and the monomer containing group (2) adopting as required, containing the monomer of acidic-group, after being dissolved in solvent heating containing the monomer of heat cross-linking functional group and/or other monomer, add polymerization initiator that its copolymerization is synthesized.When copolymerization, be better to add as required chain-transferring agent.In addition, monomer, polymerization initiator, solvent and chain-transferring agent can add continuously.Here, the adjustment of the matter average molecular weight of polymkeric substance (A) can be undertaken by the adjustment of addition of the condition such as polymerization temperature, time and polymerization initiator amount, chain-transferring agent etc.
The polymkeric substance (A) of manufacturing like this be random copolymers, but also can manufacture segmented copolymer with changing according to the kind of monomer to usual ways such as times of copolymerization system importing starting monomer.
As the solvent of the polymerization for above-mentioned polymkeric substance (A), can exemplify for example ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, the alcohols such as ethylene glycol, acetone, methyl isobutyl ketone, the ketones such as cyclohexanone, 2-methyl cellosolve, cellosolvo, the cellosolve classes such as butoxy ethanol, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, the carbitol classes such as 2-(2-butoxy ethoxy) ethanol, methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, ethylene acetate, the ester classes such as glycerine triacetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether etc.
As polymerization initiator, can exemplify known organic peroxide, inorganic peroxide, azo-compound etc.Organic peroxide, inorganic peroxide also can use as redox class catalyzer with reductive agent combination.These polymerization initiators can use separately, and also two or more kinds may be used.
As organic peroxide, can exemplify benzoyl peroxide, lauroyl peroxide, peroxidating isobutyryl, t-butyl hydroperoxide, tert-butyl peroxide-α-isopropyl benzene etc.As inorganic peroxide, can exemplify ammonium persulfate, sodium peroxydisulfate, potassium persulfate, hydrogen peroxide, percarbonate etc.As azo-compound, can exemplify 2,2 '-azoisobutyronitrile, 1,1 '-azo two (hexamethylene-1-nitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo two (2-amidine propane) dihydrochloride etc.
As chain-transferring agent, can exemplify the thio-alcohols such as n-butyl mercaptan, n-dodecane mercaptan, tert-butyl mercaptan, ethyl thioglycolate, thioglycollic acid-2-ethyl hexyl ester, 2 mercapto ethanol, the alkyl halides such as chloroform, phenixin, carbon tetrabromide, the thiocarboxylic acid ester compounds exemplifying in the time that polymkeric substance (A) is introduced sulfydryl.
Here, side chain containing various groups of above-mentioned in the polymkeric substance (A) that the present invention uses, particularly also can form by the chemical conversion after polyreaction containing the side chain of acidic-group with containing the side chain of heat cross-linking functional group etc.For example, can there is the multipolymer containing the side chain of group (1) and the side chain of hydroxyl by above-mentioned polymerization manufacture, make the hydroxyl reaction of multi-anhydride (maleic anhydride etc.) and this multipolymer, thereby manufacture the polymkeric substance (A) having containing the side chain of the carboxyl as acidic-group.
In radical-curable photosensitive composite of the present invention, above-mentioned polymkeric substance (A) containing the proportional all solids composition with respect to composition be better 0.07～1 quality %, be more preferably 0.1～0.5 quality %.If this content is too low, use the liquid-repellant of the upper surface of the spaced walls that photosensitive composite of the present invention forms may be not enough; If too high levels, the adaptation of spaced walls and substrate may decline.
In addition,, in radical-curable photosensitive composite of the present invention, can comprise given spaced walls except above-mentioned polymkeric substance (A) composition with liquid repellent effect.As such composition, specifically can exemplary polymers (A) ', described polymkeric substance (A) ' have containing the side chain of the group that represents with above-mentioned general formula (2) and contain the side chain of polyoxyalkylenes, and do not have containing the side chain of the group representing with described general formula (1) with containing the either party in the side chain of the two keys of ethene, and its matter average molecular weight (Mw (A) ') meet 2.6 × 10 4< Mw (A) '≤20 × 10 4.
In other words, polymkeric substance (A) ' be in polymkeric substance (A), to there is side chain containing group (2) as must structure replacing the polymkeric substance containing the side chain of group (1).In addition, in above-mentioned polymkeric substance (A), to except having recorded structure containing the polymkeric substance (A) also having the side chain of group (1) containing the side chain of group (2), polymkeric substance (A) ' except not thering is the side chain containing group (1), can adopt the structure identical with its structure.
Specifically, polymkeric substance (A) ' in silicon atom content be better 0.1～25 quality %, be more preferably 0.5～20 quality %.If the content of silicon atom within the scope of this, can be given photosensitive composite of the present invention to improve the effect of the liquid-repellant that uses its spaced walls surface obtaining in the situation that not destroying effect of the present invention.
The ratio that the content of the group (11) of polymkeric substance (A) ' same with polymkeric substance (A), to be better with respect to polymkeric substance (A) ' is counted 5～60 % by weight has the side chain containing group (11).In addition, polymkeric substance (A) ' can at random have containing the side chain of acidic-group, pass through the side chain of the functional group of heat or photo-crosslinking etc. containing the functional group that can have with spaced walls matrix, for the polyreaction that is used to form the structure with such side chain, except not using containing the monomer of group (1) as starting monomer and using monomer containing group (2) as essential starting monomer, can similarly operate with above-mentioned polymkeric substance (A).
In radical-curable photosensitive composite of the present invention, use above-mentioned polymkeric substance (A) ' situation under, its containing the proportional all solids composition with respect to composition be better 0.5～30 quality %, be more preferably 2～20 quality %.By using with this content, can in the situation that not destroying effect of the present invention, give photosensitive composite of the present invention to improve the effect of the liquid-repellant that uses its spaced walls surface obtaining.In addition, use polymkeric substance (A) ' situation under, do not have containing the polymkeric substance (A) of the side chain of group (2) as with it and the polymkeric substance (A) of use even if use, also can bring into play effect similar to the above.
(1-2) trigger for optical solidification (B) (Photoepolymerizationinitiater initiater (B1))
Photosensitive composite of the present invention is in the situation of radical-curable, as trigger for optical solidification (B), can use the Photoepolymerizationinitiater initiater (B1) that produces free radical by illumination.
As Photoepolymerizationinitiater initiater (B1), as long as produce the compound of free radical by illumination, be not particularly limited.Specifically, can exemplify benzil, diacetyl, aminomethyl phenyl glyoxylic ester, α-the diones such as 9,10-phenanthrenequione, the acyloin classes such as benzoin, benzoin methyl ether, benzoin ethylether, the acyloin ethers such as benzoin isopropyl ether, thioxanthones, CTX, 2-methyl thioxanthones, 2,4-dimethyl thioxanthones, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-, bis-clopenthixal ketones, 2,4-diisopropyl thioxanthones, the thioxanthene ketones such as thioxanthones-4-sulfonic acid, benzophenone, 4,4 '-bis-(dimethylamino) benzophenone, the Benzophenones such as 4,4 '-bis-(lignocaine) benzophenone, acetophenone, 2-(4-tosyloxy)-2-phenyl acetophenone, to dimethylamino acetophenone, 2,2 '-dimethoxy-2-phenyl acetophenone, to *-methoxy acetophenone, 2-methyl-[4-(methyl mercapto) phenyl]-2-morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-acetophenone classes such as Ding-1-ketone, anthraquinone, 2-EAQ, camphorquinone, the quinones such as 1,4-naphthoquinone, 2-dimethyl ethyl aminobenzoate, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, the aminobenzoic acids such as 4-dimethylaminobenzoic acid 2-Octyl Nitrite, phenacyl chloride, the halogen compounds such as trihalomethyl group phenylsulfone, acylphosphine oxide class, the superoxide such as di-t-butyl peroxide, 1,2-acetyl caproyl, 1-[4-(phenyl sulfo-)-, 2-(O-benzoyl oxime)], ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] the oxime ester class such as-1-(O-acetyl oxime) etc., can and use two or more.
Wherein, the Photoepolymerizationinitiater initiater (B1) using as the present invention, is better the compound representing with following general formula (5).
[changing 4]
Figure BDA00001779313400231
In formula, R 21hydrogen atom, carbon number are 1～12 alkyl, carbon number is 3～8 naphthenic base, thiazolinyl, alkyl that carbon number is 2～5 replace or the phenyl that is 6～20 without the carbon number replacing or alkyl replaces or be 6～20 without the carbon number replacing phenoxy group, R 22the benzoyl that is that hydrogen atom, carbon number are 1～20 alkyl, carbon number is 3～8 naphthenic base, alkyl replace or the phenyl that is 6～20 without the carbon number replacing, alkanoyl, alkyl that carbon number is 2～20 replace or be 7～20 without the carbon number replacing, the alkoxy carbonyl that carbon number is 2～12 or alkyl replaces or be 7～20 without the carbon number replacing phenyloxycarbonyl, R 23that carbon number is 1～12 alkyl, R 24, R 25, R 26and R 27represent independently respectively hydrogen atom, carbon number is 1～12 alkyl, alkyl replacement or the naphthenic base that is 3～8 without the carbon number replacing, alkyl replacement or the phenyl that is 6～20 without the carbon number replacing, carbon number is 2～20 alkanoyl, alkyl replacement or the benzoyl that is 7～20 without the carbon number replacing, alkyl replacement or the benzyloxycarbonyl group that is 7～20 without the carbon number replacing, carbon number is 2～12 alkoxy carbonyl, alkyl replacement or the phenyloxycarbonyl that is 7～20 without the carbon number replacing, carbon number is 1～20 amide group or nitro.
In the compound representing with general formula (5), as R 21, the alkyl that preferably carbon number is 1～10 or alkyl replace or the phenyl that is 6～12 without the carbon number replacing, can exemplified by methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, phenyl etc.Wherein, be better that carbon number is 1～4 alkyl, be more preferably carbon number and be 1 or 2 alkyl, particularly preferably methyl.
In the compound representing with general formula (5), as R 22, the alkoxy carbonyl that the alkyl that preferably carbon number is 1～10 or carbon number are 2～5, can exemplify such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl etc.Wherein, be better that carbon number is 1～6 alkyl, be more preferably carbon number and be 1～3 alkyl, particularly preferably methyl.
In the compound representing with general formula (5), as R 23shown carbon number is 1～12 alkyl, can exemplify such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc.Wherein, be better that carbon number is 1～8 alkyl, be more preferably carbon number and be 2～6 alkyl, particularly preferably ethyl.
In the compound representing with general formula (5), as R 24, R 26and R 27, preferably hydrogen atom.
In the compound representing with general formula (5), as R 25, preferred alkyl replaces or without the carbon number the replacing benzoyl that is 7～20 or alkyl replaces or be 7～20 without the carbon number replacing benzyloxycarbonyl group, particularly preferably 2-methyl benzoyl, benzyloxycarbonyl group or 1,3,5-trimethyl benzyl carbonyl.
As the compound representing with general formula (5) (O-acyl group oxime compound), be not particularly limited, can exemplify following compound: in general formula (5), R 21for phenyl, R 22for octyl group, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for the compound of benzoyl; R 21for methyl, R 22for butyl, heptyl or octyl group, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for the compound of benzoyl; R 21for phenyl, R 22for octyl group, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for the compound of 2-methyl benzoyl; R 21for methyl, R 22for methyl or octyl group, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for the compound of 2-methyl benzoyl; R 21and R 22for methyl, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for compound of 2-methyl-5-tetrahydrofuran base methoxybenzoyl base, 2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base or 2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base etc.
As Photoepolymerizationinitiater initiater (B1), can use commercially available product.As commercially available product; can exemplify for example OXE02 (trade name; Ciba company (チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ society) system; ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group oxime): in above-mentioned general formula (5), R 21and R 22for methyl, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for the compound of 2-methyl benzoyl).
The content of the Photoepolymerizationinitiater initiater (B1) in radical-curable photosensitive composite of the present invention is better 1～15 quality % with respect to all solids composition of composition, is more preferably 2～7 quality %.If the content of Photoepolymerizationinitiater initiater (B1) is 1～15 quality %, curability is good, can form pattern and live width close to mask pattern by exposure, development.
Further, if by 2-mercaptobenzimidazole, 2-sulfydryl benzo
Figure BDA00001779313400241
azoles, 2-mercaptobenzothiazole, 1, the mercaptan compounds such as 4-butanols two (3-sulfydryl butyric ester), three (2-sulfydryl propionyloxy ethyl) isocyanuric acid ester, pentaerythrite four (3-sulfydryl butyric ester) use together with Photoepolymerizationinitiater initiater (B1), may bring into play sensitization effect.
(1-3) adhesive resin (C) (photoresist (C1))
Photosensitive composite of the present invention is in the situation of radical-curable, as adhesive resin (C), can use the free radical producing by above-mentioned Photoepolymerizationinitiater initiater (B1) to carry out the photoresist (C1) containing acidic-group and the two keys of ethene of polymerization.
Photoresist (C1) relates to the two keys of above-mentioned photopolymerisable ethene and acidic-group owing to containing at 1 molecule, therefore can use alkaline developer optionally to remove the unexposed portion of uncured photosensitive composite, thereby can form spaced walls.Photoresist (C1) is better in fact not containing group (1) and group (2).
As the contained acidic-group of photoresist, be not particularly limited, can exemplify carboxyl, phenol hydroxyl, sulfonic group, phosphate etc., can and use two or more.
As the two keys of the contained ethene of photoresist (C1), be not particularly limited, can exemplify two keys that the addition polymerization groups such as (methyl) acryloyl group, allyl, vinyl, ethyleneoxy have, can and use two or more.Part or all of the hydrogen atom that these addition polymerization groups have can be by alkyl, be better methyl substituted.
As photoresist (C1), be not particularly limited, specifically can exemplify have containing the side chain of acidic-group and containing the resin (C1-1) of the side chain of the two keys of ethene, in epoxy resin, introduce the two keys of ethene and acidic-group and resin (C1-2) etc.They can be used alone or two or more kinds may be used.
Resin (C1-1) for example can synthesize as follows: by the monomer of hydroxyl, carboxyl, epoxy radicals isoreactivity group with containing the monomer copolymerization of acidic-group, what make gained has containing the side chain of reactive group with containing the multipolymer of the side chain of acidic-group with have the functional group that can be combined with reactive group and the compound of the two keys of ethene is dissolved in solvent and makes its reaction.Monomer as phosphorous acidic group as acidic-group, is not particularly limited, and can exemplify 2-(methyl) acryloxy ethane phosphoric acid etc.
Resin (C1-2) for example can synthesize as follows: after epoxy resin is reacted with containing the compound of carboxyl and the two keys of ethene, polybasic carboxylic acid or its acid anhydrides are reacted with it.Specifically, by making epoxy resin and react containing the compound of the two keys of carboxyl and ethene, thus the epoxy reaction of carboxyl and epoxy resin and introduce ethene pair keys.Then, by making polybasic carboxylic acid or its acid anhydrides and the hydroxyl reaction of resin of having introduced the two keys of ethene, thereby can introduce carboxyl.
As epoxy resin, be not particularly limited, can exemplify bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, tris-phenol type epoxy resin, there is the epoxy resin of naphthalene skeleton, the epoxy resin with biphenyl backbone representing with following general formula (6), the epoxy resin representing with following general formula (7), epoxy resin of representing with following general formula (8) etc.
[changing 5]
Figure BDA00001779313400261
In formula (6), s is 1～50, is better 2～10.In addition, the hydrogen atom of phenyl ring can be respectively independently by the alkyl of carbon number 1～12, halogen atom or can there is substituent phenyl and replace.
[changing 6]
In formula (7), R 31, R 32, R 33and R 34represent independently respectively the alkyl that hydrogen atom, chlorine atom or carbon number are 1～5, t is 0～10.
[changing 7]
In formula (8), the hydrogen atom of phenyl ring can be respectively independently by the alkyl of carbon number 1～12, halogen atom or can there is substituent phenyl and replace.U is 0～10.
After being reacted with containing the compound of carboxyl and the two keys of ethene, the epoxy resin that represents with general formula (6), general formula (7) or general formula (8) makes in situation that polybasic acid anhydride reacts with it, as polybasic acid anhydride, it is better the potpourri that uses dicarboxylic anhydride and tetracarboxylic dianhydride.At this moment,, by changing dicarboxylic anhydride and tetracarboxylic dianhydride's ratio, can control molecular weight.
The resin (C1-2) obtaining as introduce the two keys of acidic-group and ethene in epoxy resin, can use commercially available product.As such commercially available product, trade name can exemplify KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, CCR-1163H, CCR-1166H, CCR-1159H, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZFR-1122H, ZFR-1124H, ZFR-1185H, ZFR-1492H, ZCR-1571H, ZCR-1569H, ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1629H (being Nippon Kayaku K. K (Japanese chemical drug society) system above), EX1010 (Chang Lai Chemitec Co., Ltd. (Na ガ セ ケ system テ ッ Network ス society) system) etc.
As the resin (C1-2) of having introduced the two keys of acidic-group and ethene in epoxy resin, be better represents with formula (6) there is biphenyl backbone in introduced acidic-group and the two keys of ethene resin, in the epoxy resin representing with formula (7), introduced the resin of acidic-group and ethene pair keys or in the epoxy resin representing with formula (8), introduced acidic-group and the resin of ethene pair keys.By using this resin, can in composition, mix more black colorant, can improve light-proofness, optical density.In addition, film when development is peeled off and is inhibited, and can obtain the pattern that exploring degree is high.On the other hand, the rectilinearity of line is good, so preferably.In addition, the outward appearance after rear roasting procedure is maintained, and easily obtains level and smooth film coated surface, so preferably.
The matter average molecular weight of the above-mentioned photoresist (C1) that the present invention uses is better 1.5 × 10 3～30 × 10 3, be more preferably 2.0 × 10 3～15 × 10 3.If this matter average molecular weight is lower than 1.5 × 10 3, solidifying while exposure may be not enough; If higher than 30 × 10 3, developability may decline.
The quantity of the two keys of ethene that photoresist (C1) has is better that average out to 1 molecule is interior more than 3, is more preferably more than 6.If the quantity of the two keys of this ethene is more than 3, the alkali solubility of exposed portion and unexposed portion easily produces difference, can form fine pattern with exposure still less.
The acid number of photoresist (C1) is better 10～300mgKOH/g, is more preferably 30～150mgKOH/g.If the acid number of photoresist (C1) is 10～300mgKOH/g, the developability of photosensitive composite is good.
The content of the above-mentioned photoresist (C1) in radical-curable photosensitive composite of the present invention is better 5～80 quality % with respect to all solids composition of composition, is more preferably 10～60 quality %.If the content of photoresist (C1) is 5～80%, the developability of photosensitive composite is good.
(1-3) any composition
Radical-curable photosensitive composite of the present invention comprise above-mentioned polymkeric substance (A), as the Photoepolymerizationinitiater initiater (B1) of trigger for optical solidification (B) and as the photoresist (C1) containing the two keys of acidic-group and ethene of adhesive resin (C) as essential composition, but not destroying in the scope of effect of the present invention, any composition that also can comprise following explanation for objects such as the raisings of various functions.
(thering is the crosslinking chemical (D) of 2 two keys of above ethene)
Radical-curable photosensitive composite of the present invention is better the crosslinking chemical (D) with 2 two keys of above ethene comprising as promoting radical-cured any composition.By this, the curability of the above-mentioned photoresist (C1) when exposure improves, and can reduce the exposure while forming spaced walls.Above-mentioned crosslinking chemical (D) is better in fact not containing acidic-group.
As the crosslinking chemical (D) with 2 two keys of above ethene, be not particularly limited, be better the compound with 2～10 (methyl) acryloxies.Specifically, can exemplify two (methyl) acrylic acid binaryglycol ester, two (methyl) acrylic acid TEG ester, two (methyl) acrylic acid tripropylene glycol ester, two (methyl) acrylic acid DOPCP, two (methyl) acrylic acid 1, 9-nonanediol ester, three (methyl) acrylic acid trihydroxymethylpropanyl ester, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid two (trihydroxy methyl) propane ester, six (methyl) acrylic acid dipentaerythritol ester, epoxidation isocyanuric acid triacrylate, ammonia ester acrylate etc.They can be used alone or two or more kinds may be used.
In the present invention, as the crosslinking chemical (D) with 2 two keys of above ethene, can use commercially available product.As such commercially available product, can exemplify KAYARAD DPHA (trade name, Nippon Kayaku K. K's system, the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate), NK EsterA-9300 (trade name, chemical industry Co., Ltd. of Xin Zhong village system, epoxidation isocyanuric acid triacrylate), NK Ester A-9300-1CL (trade name, chemical industry Co., Ltd. of Xin Zhong village system, 6-caprolactone modification three (2-acryloxy ethyl) isocyanuric acid ester), BANI-M (trade name, Maruzen Petrochemical Co., Ltd. (Wan Shan petrochemistry society) system, two { 4-(allyl dicyclo [2.2.1] heptan-5-alkene-2, 3-dicarboximide) phenyl } methane), BANI-X (trade name, Maruzen Petrochemical Co., Ltd.'s system, N, two (allyl dicyclo [2.2.1] heptan-5-alkene-2 of a N '-xylylene, 3-dicarboximide)) etc.
As urethane acrylate, can exemplify the KAYARAD UX series of Nippon Kayaku K. K's system, concrete trade name can exemplify UX-3204, UX-6101, UX-0937, DPHA-40H, UX-5000, UX-5002D-P20 etc.
A-9300, BANI-M and BANI-X give film with hardness, preferred from suppressing the angle that heat hangs from above.A-9300-1CL is preferred with the angle of flexibility from giving film.Urethane acrylate can be realized appropriate development time, and developability is good, so preferably.
The content of the above-mentioned crosslinking chemical (D) in radical-curable photosensitive composite of the present invention is better 1～50 quality % with respect to all solids composition of composition, is more preferably 5～30 quality %.If the content of crosslinking chemical (D) is 1～50 quality %, the developability of photosensitive composite is good.
(black colorant (E))
Radical-curable photosensitive composite of the present invention, in the time that its solidfied material is used to require the purposes of light-proofness as black matrix" etc., is better to comprise black colorant (E) according to the optical density of desired spaced walls.
As black colorant (E), be not particularly limited, can exemplify metallics, perylene class black pigment of metal oxide, the silver-colored ashbury metals etc. such as carbon black, nigrosine, Anthraquinones black pigment, titanium be black etc.Specifically, can exemplify C.I. pigment black 1,6,7,12,20,31 etc.In addition, black colorant (E) can be the potpourri of the organic pigments such as red pigment, blue pigment, viridine green or inorganic pigment.Wherein, if consider the power of light-proofness, be better carbon black.Carbon black usable resins etc. was carried out surface treatment.In addition, in order to adjust the tone of black colorant (E), can and use carbon black and blue pigment or violet pigment.
In addition the carbon black using as black colorant (E), is better that the specific surface area being obtained by BET method is 50～200m 2/ g.If this specific surface area is too small, the shape that may cause spaced walls is deteriorated; If specific surface area is excessive, dispersing aid described later is excessively adsorbed in black colorant (E), may need to add a large amount of dispersing aiies.
In addition, if consider the exposure sensitivity of photosensitive composite, the carbon black using as black colorant (E) be better the oil absorption of dibutyl phthalate below 120cc/100g, more few better.
In addition the carbon black using as black colorant (E), is better that average primary particle diameter is 20～50nm.If this average primary particle diameter is too small, be difficult to make it to disperse with high concentration, may be difficult for obtaining the photosensitive composite that ageing stability is good; If average primary particle diameter is excessive, may cause that the shape of spaced walls is deteriorated.In addition, this carbon black is better that average aggregate particle size is 80～200nm.The particle diameter of carbon black can use determination of transmission electron microscopy.
In radical-curable photosensitive composite of the present invention, the content of the black colorant (E) while mixing black colorant (E) in order to give this such light-proofness of curing of coating image black matrix" is according to desired light-proofness, optical density and difference, better 15～60 quality % with respect to all solids composition of composition, be more preferably 20～50 quality %, particularly preferably 25～40 quality %.If this content is very few, make the optical density deficiency in black matrix" equal time next door; If content is too much, may cause the curability of photosensitive composite to decline, the degraded appearance of spaced walls, liquid-repellant declines.
(macromolecule dispersing agent dispersing aid)
Radical-curable photosensitive composite of the present invention is better to comprise macromolecule dispersing agent to improve its dispersiveness in the time comprising above-mentioned black colorant (E) isodispersity material.As macromolecule dispersing agent, be not particularly limited, can exemplify polyurethanes, polyimide, alcohol acids, epoxies, polyesters, melamine class, phenols, acrylic compounds, polyethers, polyvinyl chloride-base, vinyl chloride-vinyl-acetic ester based copolymer class, polyamide-based, polycarbonate-based etc.Wherein, be better polyurethanes or polyesters.In addition, macromolecule dispersing agent can have polyoxyethylene groups and/or polyoxypropylene base.
In situation by macromolecule dispersing agent for the dispersion of black colorant (E), be better to consider for the affinity of black colorant (E) to use the macromolecule dispersing agent with basic group.As basic group, be not particularly limited, can exemplify primary amino radical, secondary amino group or tertiary amino.
As such macromolecule dispersing agent, can use commercially available product; As commercially available product, can exemplify for example Supreme Being Si Balong DA-7301 (trade name, nanmu originally changes into Co., Ltd.'s (nanmu originally changes into society) system), BYK161, BYK162, BYK163, BYK182 (are trade name above, Bi Ke chemical company (BYK-Chemie society) system), Solspers 5000, Solspers 17000 (being above trade name, Ze Neika company (ゼ ネ カ society) system) etc.
The addition of macromolecule dispersing agent is better 5～30 quality % with respect to black colorant (E) isodispersity material, is more preferably 10～25 quality %.If this addition is very few, the effect that makes dispersiveness improve may be insufficient; If addition is too much, the developability of photosensitive composite may decline.
In addition, radical-curable photosensitive composite of the present invention can comprise phthalocyanine pigment derivant or the metal phthalocyanine sulfonamide compounds as dispersing aid.Dispersing aid is considered to have the function that is adsorbed in black colorant (E) isodispersity material and macromolecule dispersing agent and dispersion stabilization is improved.
(particulate)
Radical-curable photosensitive composite of the present invention can comprise particulate as required.By this, can in the time of rear baking described later, suppress the variation of spaced walls shape.
As particulate, be not particularly limited, can exemplified by silica, the mineral-type particulate such as zirconia, magnesium fluoride, tin-doped indium oxide (ITO), antimony doped tin oxide (ATO), the organic particulates such as tygon, polymethylmethacrylate (PMMA).As particulate, if consider thermotolerance, be better mineral-type particulate, if consider convenience and the dispersion stabilization of acquisition, be better silicon dioxide or zirconia.In addition, photosensitive composite comprises black colorant (E) and when improving its dispersed macromolecule dispersing agent, if consider the adsorptive power of this macromolecule dispersing agent, particulate is better electronegative.In addition, if consider the exposure sensitivity of photosensitive composite, particulate is better the light irradiating while not absorbing exposure, does not particularly preferably absorb i line (365nm), h line (405nm), g line (436nm) as the main light emission wavelength of ultrahigh pressure mercury lamp.
From the good angle of the surface smoothness of spaced walls, the mean grain size of particulate is better below 1 μ m, is more preferably below 200nm.
The content of the particulate in radical-curable photosensitive composite of the present invention is better 3～30 quality % with respect to all solids composition of composition, is more preferably 5～20 quality %.If this content is very few, variation that may origination interval wall shape while baking afterwards; If content is too much, the dispersion stabilization of photosensitive composite may decline.
(silane coupling agent)
Radical-curable photosensitive composite of the present invention can comprise silane coupling agent as required.By this, can make the adaptation of spaced walls and substrate improve.
As silane coupling agent, be not particularly limited.Specifically, can exemplify tetraethoxysilane, 3-glycidoxypropyltrime,hoxysilane, methyltrimethoxy silane, vinyltrimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, 17 fluorine octyl group ethyl trimethoxy silanes, N-phenyl-3-TSL 8330, polyoxyalkylene, imidazoles silane etc. containing triethoxysilyl, can and use two or more.
(thermal curing agents)
Radical-curable photosensitive composite of the present invention can comprise thermal curing agents as required.By this, can make the thermotolerance of spaced walls, resistance to water permeability improve.In addition, above-mentioned polymkeric substance (A) is containing in the situation of heat cross-linking functional group, and polymkeric substance (A) forms chemical bond with thermal curing agents, also can obtain thus the effect that polymkeric substance (A) is fixed on to spaced walls.
As thermal curing agents, be not particularly limited, can exemplify amino resins melamine compounds such as (etc.) hexa methoxy melamine methylols, containing the compound of 2 above epoxy radicals, the compound containing 2 above diazanyls, poly-carbodiimide compound, above containing 2
Figure BDA00001779313400311
the compound of azoles quinoline base, compound containing 2 above '-aziridinos, polyvalent metal class, containing compound, the polyisocyanate compound etc. of 2 above sulfydryls, can and use two or more.Wherein, if consider the chemical-resistant of spaced walls, be better amino resins, containing the compound of 2 above epoxy radicals or above containing 2
Figure BDA00001779313400312
the compound of azoles quinoline base.
(phosphate cpd)
Radical-curable photosensitive composite of the present invention can comprise phosphate cpd as required.Take this, can improve and the adaptation of substrate, so preferably.As phosphate cpd, can exemplify list (methyl) acryloxy ethyl phosphonic acid ester, two (methyl) acryloxy ethyl phosphonic acid ester, three (methyl) acryloxy ethyl phosphonic acid ester etc.
(other any composition)
In addition,, except above-mentioned various compositions, radical-curable photosensitive composite of the present invention can also comprise curing accelerator, thickening agent, plastifier, defoamer, levelling agent, anti-depression agent, ultraviolet light absorber etc. as required.
Radical-curable photosensitive composite of the present invention can be by must composition and add as required by above-mentioned explanation various any composition by above-mentioned incorporation proportioning and mix to prepare by conventional method.
(2) acid cure type photosensitive composite
Photosensitive composite of the present invention is in the situation of acid cure type, photosensitive composite comprise polymkeric substance (A), as the photoacid generator (B2) of trigger for optical solidification (B) and as adhesive resin (C) containing the alkali soluble resins (C21) of carboxyl and/or phenol hydroxyl and as containing 2 above can with the crosslinkable resin (C22) of the compound of the group of carboxyl and/or phenol hydroxyl reaction.Such acid cure type photosensitive composite forms coating film cured product thereof as follows: when exposure in photoetching process etc., produce acid in illumination part by photoacid generator (B2), containing the alkali soluble resins (C21) of carboxyl and/or phenol hydroxyl with as above carrying out cross-linking reaction with the crosslinkable resin (C22) of the compound of the group of carboxyl and/or phenol hydroxyl reaction containing 2.
Below, the contained each composition of acid cure type photosensitive composite of the present invention is described.
(2-1) polymkeric substance (A)
The contained polymkeric substance (A) of acid cure type photosensitive composite of the present invention is the characteristic chemical constituent in photosensitive composite of the present invention, including its preferred form, the polymkeric substance (A) illustrating in above-mentioned radical-curable photosensitive composite is applicable to acid cure type photosensitive composite.
In addition, the content of polymkeric substance (A) in photosensitive composite is also same as described above.In addition, can give in addition as above-mentioned polymkeric substance (A) polymkeric substance (A) that the composition of spaced walls liquid repellent effect illustrates hereinbefore ' can similarly use with the situation of radical-curable photosensitive composite.
(2-2) trigger for optical solidification (B) (photoacid generator (B2))
Photosensitive composite of the present invention is in the situation of acid cure type, as trigger for optical solidification (B), can be used as the photoacid generator (B2) of the acidic compound by light.As photoacid generator (B2), can exemplify for example diaryl iodine
Figure BDA00001779313400321
salt, triarylsulfonium salt, compound in triazine class, sulfonyl compound, sulfonic acid esters etc.
As diaryl iodine
Figure BDA00001779313400322
the object lesson of the cationic moiety of salt, can exemplify diphenyl iodine
Figure BDA00001779313400323
4-methoxyphenyl phenyl-iodide two (4-tert-butyl-phenyl) iodine
Figure BDA00001779313400325
deng.As diaryl iodine
Figure BDA00001779313400326
the object lesson of the anionicsite of salt, can exemplify fluoroform sulphonate, nine fluorine fourth sulfonate, tosilate, phenyl-pentafluoride sulfonate, hexafluoro sulfonate, tetrafluoroborate, hexafluoro antimonate, (R f) kpF (6-k) -deng; Wherein, the integer that k is 1～6.Diaryl iodine
Figure BDA00001779313400327
salt is by a kind of described cationic moiety and described anionicsite a kind be combined to form.For example, can exemplify two (4-tert-butyl-phenyl) iodine
Figure BDA00001779313400328
fluoroform sulphonate.
As the object lesson of the cationic moiety of triarylsulfonium salt, can exemplify triphenylsulfonium, diphenyl-4-aminomethyl phenyl sulfonium, diphenyl-2,4,6-trimethylphenyl sulfonium etc.As the object lesson of the anionicsite of triarylsulfonium salt, can exemplify described diaryl iodine
Figure BDA00001779313400331
the object lesson of the anionicsite of salt.Triarylsulfonium salt is by a kind of described cationic moiety and described anionicsite a kind be combined to form.For example, can exemplify triphenylsulfonium fluoroform sulphonate.
As the object lesson of compound in triazine class, can exemplify 2-methyl-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(4-methoxyphenyl)-4, two (trichloromethyl)-1 of 6-, 3,5-triazine, 2-(2-furyl) vinyl-bis-(trichloromethyl)-1,3,5-triazine, 2-(5-methyl-2-furyl) vinyl-bis-(trichloromethyl)-1,3,5-triazine, 2-(3,4-Dimethoxyphenyl) vinyl-bis-(trichloromethyl)-1,3,5-triazine etc.
As the object lesson of sulfonyl compound, can exemplify two (benzenesulfonyl) diazomethanes, two (tertiary fourth sulfonyl) diazomethane, two (hexamethylene sulfonyl) diazomethane, two (p-toluenesulfonyl) diazomethane etc.
As the object lesson of sulfonic acid esters, can exemplify 2-nitrobenzyl p-toluenesulfonic acid ester, α-(tolysulfonyl oxygen base imino group)-phenylacetonitrile etc.
The content of the photoacid generator (B2) in acid cure type photosensitive composite of the present invention is better 0.1～30 quality % with respect to all solids composition of composition, is more preferably 1～20 quality %.If within the scope of this, the developability of photosensitive composite is good.
(2-2) adhesive resin (C) (alkali soluble resins (C21) crosslinkable resin (C22))
Photosensitive composite of the present invention is in the situation of acid cure type, as adhesive resin (C), can exemplify the sour effect producing by above-mentioned photoacid generator (B2) carry out cross-linked polymeric containing the alkali soluble resins (C21) of carboxyl and/or phenol hydroxyl and as containing 2 above can with the combination of the crosslinkable resin (C22) of the compound of the group of carboxyl and/or phenol hydroxyl reaction.
(alkali soluble resins (C21))
Alkali soluble resins (C21) is containing carboxyl and/or phenol hydroxyl.By dissolving in alkaline solution containing carboxyl and/or phenol hydroxyl, and can with as containing 2 above can be crosslinked and form coating film cured product thereof with the crosslinkable resin (C22) of the compound of the group of carboxyl and/or phenol hydroxyl reaction.Alkali soluble resins (C21) is as long as the soluble resin of alkaline solution of the middle developer solutions that use such as the photoetching process for formation photosensitive composite, can use without any restrictionsly, for example can exemplify using the monomer containing carboxyl and the two keys of ethene and/or containing the monomer of phenol hydroxyl and the two keys of ethene and make its polymerization and the resin (C21-1), the phenolics etc. that obtain as essential composition.These resins are better in fact not containing group (1) and group (2).
Using the monomer containing the two keys of carboxyl and ethene and/or containing the monomer of phenol hydroxyl and the two keys of ethene as essential composition make its polymerization and resin (C21-1) can obtain with other monomer copolymerization of employing as required containing the monomer of carboxyl and the two keys of ethene and/or containing the monomer of phenol hydroxyl and the two keys of ethene by making.In addition,, in this alkali soluble resins (C21-1), the ratio of the monomeric unit based on other monomer is better below 30～95 quality %, is more preferably below 50～90 quality %.If within the scope of this, the alkali solubility of photosensitive composite and developability are good.
The monomer containing carboxyl and the two keys of ethene using when (C21-1) as the above-mentioned alkali soluble resins of preparation, can exemplified by acrylic, methacrylic acid, vinyl acetic acid, butenoic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and their salt etc.As the monomer containing phenol hydroxyl and the two keys of ethene, can exemplify o-hydroxy ethene, a hydroxy styrenes, 4-Vinyl phenol etc., the compound that 1 above hydrogen atom of their phenyl ring is obtained by following group replacement etc.: the alkyl such as methyl, ethyl, normal-butyl, the alkoxys such as methoxyl, ethoxy, n-butoxy, halogen atom, 1 haloalkyl that above hydrogen atom is replaced by halogen atom of alkyl, nitro, cyano group, amide group.As other monomer, can use the monomer same with other monomer using in the manufacture of above-mentioned polymkeric substance (A).
As phenolics, be using as be selected from that the aromatic hydroxy compounds such as phenol, cresols, xylenol, resorcinol, quinhydrones and their alkyl replace or the aldehyde compound polycondensation such as the phenols of at least a kind of halogen substituted aromatic compound and formaldehyde, acetaldehyde, benzaldehyde and must resin, can exemplify such as phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresols-formaldehyde cocondensation resin etc.
The acid number of alkali soluble resins (C21) is better 10～600mgKOH/g, is more preferably 50～300mgKOH/g.If within the scope of this, the developability of photosensitive composite is good.
The number-average molecular weight of alkali soluble resins (C21) is better 200～20000, is more preferably 2000～15000.If within the scope of this, alkali dissolubility, the developability of photosensitive composite are good.In addition, matter average molecular weight is better 1.5 × 10 3～30 × 10 3, be more preferably 2.0 × 10 3～15 × 10 3.If this matter average molecular weight is lower than 1.5 × 10 3, solidifying while exposure may be not enough; If higher than 30 × 10 3, developability may decline.
The content of the alkali soluble resins (C21) containing carboxyl and/or phenol hydroxyl in acid cure type photosensitive composite of the present invention is better 10～90 quality % with respect to all solids composition of composition, is more preferably 30～80 quality %.If within the scope of this, the alkali-developable of photosensitive composite of the present invention is good.
(crosslinkable resin (C22))
Crosslinkable resin (C22) be containing 2 above can with the compound of the group of carboxyl and/or phenol hydroxyl reaction.By containing 2 above can with the group of carboxyl and/or phenol hydroxyl reaction, can be with the alkali soluble resins (C21) containing carboxyl and/or phenol hydroxyl crosslinked and form coating film cured product thereof.In addition, in the situation of above-mentioned polymkeric substance (A) containing carboxyl and/or hydroxyl, also can be cross-linked and formation coating film cured product thereof with polymkeric substance (A).Crosslinkable resin (C22) is better the compound that does not contain in fact group (1) and group (2).
As crosslinkable resin (C22), be better selected from amino resins, epoxy compound,
Figure BDA00001779313400351
at least a kind of isoxazoline compound.They can be used alone, but also two or more is also used.
As amino resins, the compound that can exemplify part or all amino methylolation of melamine compounds, guanidine aminated compounds, carbamide compounds etc. and obtain, or such as, by part or all compound obtaining by etherificates such as methyl alcohol, ethanol, normal butyl alcohol, 2-methyl isophthalic acid-propyl alcohol of the hydroxyl of this methylolated compound, HMMM etc.
As epoxy compound, can exemplify bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, tris-phenol type epoxy resin, the glycidyl ethers such as brominated epoxy resin, 3, 4-epoxycyclohexyl methyl-3, 4-epoxycyclohexane carboxylate, two (2, 3-epoxide ring amyl group) cycloaliphatic epoxy resin such as ether, diglycidyl hexahydrobenzene dicarboxylic acid esters, diglycidyl tetrahydrochysene phthalic acid ester, the glycidyl esters classes such as diglycidyl phthalic acid ester, four glycidyl group diaminodiphenyl-methane, the glycidyl amines such as triglycidyl group para-aminophenol, the hetero ring type epoxy resin such as triglycidyl group isocyanuric acid ester etc.
As
Figure BDA00001779313400352
isoxazoline compound, can exemplify 2-vinyl-2-
Figure BDA00001779313400353
azoles quinoline, 2-vinyl-4-methyl-2-
Figure BDA00001779313400354
azoles quinoline, 2-vinyl-5-methyl-2- azoles quinoline, 2-isopropenyl-2-
Figure BDA00001779313400356
azoles quinoline, 2-isopropenyl-4-methyl-2- the multipolymer of the polymerizable monomers such as azoles quinoline.
In acid cure type photosensitive composite of the present invention as containing 2 above can be better 1～50 quality % with respect to all solids composition of composition with the content of the crosslinkable resin (C22) of the compound of the group of carboxyl and/or phenol hydroxyl reaction, be more preferably 5～30 quality %.If within the scope of this, the developability of photosensitive composite is good.
(2-3) any composition
Acid cure type photosensitive composite of the present invention comprise above-mentioned polymkeric substance (A), as the photoacid generator (B2) of trigger for optical solidification (B) and as adhesive resin (C) containing the alkali soluble resins (C21) of carboxyl and/or phenol hydroxyl and as containing 2 above can with the crosslinkable resin (C22) of the compound of the group of carboxyl and/or phenol hydroxyl reaction, but not destroying in the scope of effect of the present invention, can comprise various any compositions for object for raising of various functions etc.
As so any composition, can be by the situation of the whole compositions except the crosslinking chemical (D) containing 2 two keys of above ethene and radical-curable photoresist in any composition illustrating in above-mentioned radical-curable photoresist similarly for acid cure type photoresist.
Acid cure type photosensitive composite of the present invention can be by must composition and add as required by above-mentioned explanation various any composition by above-mentioned incorporation proportioning and mix to prepare by conventional method.
[dilution solvent]
While stating in the use the photosensitive composite formation of the present invention such as bright radical-curable photosensitive composite and acid cure type photosensitive composite spaced walls, better to use the dilution obtaining with solvent dilution photosensitive composite to form after film (moistening film), solvent evaporates is removed, thereby form the film of photosensitive composite.
As the solvent of dilution photosensitive composite, be not particularly limited.Specifically, can exemplify ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, the alcohols such as ethylene glycol, acetone, methyl isobutyl ketone, the ketones such as cyclohexanone, 2-methyl cellosolve, cellosolvo, butoxy ethanol, the cellosolve classes such as 2-propoxyl group ethanol, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, the carbitol classes such as 2-(2-butoxy ethoxy) ethanol, methyl acetate, ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, butyl carbitol acetate, propylene glycol methyl ether acetate, ethylene acetate, propylene-glycol diacetate, 3-ethoxyl ethyl propionate, cyclohexyl acetate, ethyl lactate, n-butyl lactate, gamma-butyrolacton, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, the ester classes such as glycerine triacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, TRIGLYME, tetraethyleneglycol dimethyl ether, Propylene Glycol Dimethyl Ether, dipropylene glycol dimethyl ether, butyl ether, the ethers such as diethylene glycol methyl ethyl ether, cyclohexanone, 4-butyrolactone etc., can and use two or more.
By above-mentioned photosensitive composite with solvent dilution dilution be better adjusted to photosensitive composite concentration, solid component concentration reaches 5～40 quality %, is more preferably 10～25 quality %.
<2> spaced walls
Spaced walls of the present invention is to be formed as being partitioned into by the coating film cured product thereof of the photosensitive composite of the invention described above the spaced walls that form that pixel forms multiple blocks of use obtains on substrate, applicable to the black matrix" of colored filter and organic EL etc.
Below, as an example of method of manufacturing spaced walls of the present invention, the method that uses photoresist of the present invention to manufacture spaced walls by photo-mask process is described.
(painting process)
First, the dilution of photosensitive composite of the present invention is coated to substrate.As substrate, be not particularly limited, can exemplify various glass plates, the inorganic substrates such as SiC substrate, silicon, the inorganic oxide substrates such as ITO, the thermoplastic plastic sheet of polyester (polyethylene terephthalate etc.), polyolefin (tygon, polypropylene etc.), polycarbonate, polymethylmethacrylate, polysulfones, polyimide, poly-(methyl) acryl resin etc., the cured sheet of the thermoset resins such as epoxy resin, unsaturated polyester (UP) etc.If consider thermotolerance, as substrate, be better the heat-resistant resin such as glass plate and polyimide.In addition,, from the angle that can expose from the face of a side that does not form spaced walls of substrate, substrate is better transparent.In addition, substrate can be on the transparency carriers such as glass substrate, to be formed with organic film or TFT (Thin Film Transi stor: thin film transistor (TFT)), ITO, SiO 2deng inorganic oxide film substrate or form figuratum substrate, be formed with the substrate of the dielectric film of silicon nitride or polyimide etc., can be also these substrates stacked and laminated base plate.
As coating process, be not particularly limited, can exemplify spin-coating method, spraying process, slot coated method, rolling method, method of spin coating, excellent Tu Fa etc.
(drying process)
Then, the film that is formed at substrate is dried.By this, solvent evaporates, therefore can obtain the film without adhering photosensitive composite.As drying means, be not particularly limited, can exemplify vacuum drying, heat drying.In order to be dried efficiently appearance of film uneven in the case of not occurring, to be better and to use vacuum drying and heat drying.Drying condition is according to kind, the composition etc. of the contained composition of photosensitive composite and different, and vacuum drying is better to carry out 10～300 seconds under 10～500Pa (absolute pressure), and heat drying is better at 50～120 ℃, to carry out 10～2000 seconds.
(exposure process)
Then, across the mask of predetermined pattern, film is exposed.The light irradiating during as exposure, is not particularly limited, and can exemplify visible ray, ultraviolet ray, far ultraviolet, KrF excimer laser, ArF excimer laser, F 2excimer laser, Kr 2excimer laser, KrAr excimer laser, Ar 2the excimer laser such as excimer laser, X ray, electron ray etc.Be better that wavelength is the light of 100～600nm, be more preferably the light that wavelength is 300～500nm, particularly preferably i line (365nm), h line (405nm), g line (436nm).As light source, can adopt known ultrahigh pressure mercury lamp etc.
Exposure is 5～1000mJ/cm conventionally take i line as benchmark 2, be better 10～400mJ/cm 2, be more preferably 20～200mJ/cm 2, particularly preferably 50～100mJ/cm 2.If exposure is lower than 5mJ/cm 2, film is curing insufficient, and developability may decline; If higher than 1000mJ/cm 2, may obtain high-resolution.
(developing procedure)
Then, use developer solution that the unexposed portion of film is removed and developed.As developer solution, be not particularly limited, can exemplify the aqueous solution of the alkali such as inorganic base, amine, alkanol amine, quaternary ammonium salt.Development time, time of contacting with developer solution is better 5～180 seconds.As developing method, be not particularly limited, can exemplify immersion method (Japanese: liquid is contained り method), infusion process, spray process etc.
(spray operation)
Then be, better to spray.Spray refers to by hydraulic pressure contracting or by water and air compression, the operation of spraying to being formed with the substrate of spaced walls.Pressure is better 2～20MPa.By spraying, can remove undissolved residue in developing procedure and develop in the part of composition of lysed photosensitive composite be again attached to substrate and the residue that forms.
After spray, make it air-dry with pressurized air or compressed nitrogen, thereby can remove the moisture on substrate.
(post-exposure operation)
Then, can be to carrying out post-exposure through the spaced walls of developing.At this moment, can self-forming there be the face of a side of spaced walls and the arbitrary face not forming in the face of a side of spaced walls to expose, also can expose from two sides.The light irradiating when exposure is better ultraviolet ray.
As light source, can adopt known ultrahigh pressure mercury lamp, high-pressure sodium lamp etc.The general transmitting of these light sources impels the light below the curing wavelength 600nm of spaced walls, and the transmitting of the light of the wavelength of oxygenolysis that causes spaced walls below 200nm is few.In addition, light source quartz ampoule glass used is better the optical filter function with the light of shielding wavelength below 200nm.
Exposure is conventionally at 50mJ/cm 2above, be better at 200mJ/cm 2above, be more preferably at 1000mJ/cm 2above, particularly preferably at 2000mJ/cm 2above.
In addition, as light source, also can adopt low pressure mercury lamp, but the light of the wavelength of low pressure mercury lamp transmitting below 200nm is many, therefore exposure is better at 500mJ/cm 2below, be more preferably at 300mJ/cm 2below.
(rear roasting procedure)
After developing (after being post-exposure while carrying out post-exposure), be better that spaced walls is heated.Heating condition is better at 150～250 ℃ 5～90 minutes, and heating-up temperature is better more than 180 ℃.If heating-up temperature is too low, chemical-resistant may be not enough, when ink is coated to spaced walls, and may the swelling of origination interval wall or the situation of ink penetration.
On the other hand, if heating-up temperature is too high, may there is thermal decomposition in spaced walls.
As heating arrangement, can adopt heating plate, baking oven etc.
By make photosensitive composite of the present invention solidify through photo-mask process as above, thereby form spaced walls of the present invention.In spaced walls of the present invention, by mixing black colorant (E) at the photosensitive composite of preparing for it as required, can form the black matrix" that is black.In this situation, by using photosensitive composite to form spaced walls, can form black matrix".
The mean value of the width of spaced walls of the present invention is better below 100 μ m, is more preferably below 20 μ m.In addition, distance between the spaced walls of adjacency, the mean value of the width of peristome is better below 300 μ m, is more preferably below 100 μ m.In addition, the mean value of the height of spaced walls is better 0.05～50 μ m, is more preferably 0.2～10 μ m.
Conventionally, as the liquid-repellant (refusing ink) of the spaced walls being formed by the coating film cured product thereof of photosensitive composite, can exemplify water repellency and oil repellent, respectively can be by evaluating with the contact angle of water and PGMEA (propylene glycol methyl ether acetate: the organic solvent that is often used as the solvent of ink).The upper surface of spaced walls of the present invention and the contact angle of water are better 90 °～150 °, are more preferably 95 °～120 °.In addition, the upper surface of spaced walls and the contact angle of PGMEA are better 35 °～55 °, are more preferably 40 °～50 °.
<3> colored filter
Colored filter of the present invention is the colored filter that has multiple pixels and be positioned at the spaced walls between the pixel of adjacency on substrate, it is characterized in that, described spaced walls is formed by the spaced walls of the invention described above, and described pixel forms by ink-jet method.In colored filter of the present invention, spaced walls is better that optical density is the black matrix" of 2～7 left and right.
Colored filter of the present invention can be manufactured as follows: on substrate, form as previously mentioned after spaced walls, for example black matrix", form pixel with the peristome that spaced walls coated by ink by ink-jet method.
As ink-jet method, be not particularly limited, can exemplify spray continuously charged ink the method for controlling by magnetic field, with piezoelectric element off and on ink jet method, heating ink and utilize its method of spraying off and on of foaming etc.
As the arrangement of pixel, be not particularly limited, can exemplify the known arrangements such as stripe, mosaic type, triangular form, 4 pixel arrangement types.
Ink mainly comprises coloring components, adhesive resin composition, solvent, can be any in water color ink and oil-based ink.As coloring components, preferably use the good pigment such as thermotolerance, photostability and/or dyestuff.As adhesive resin composition, the resin that preferably clear and thermotolerance are good, can exemplified by acrylic resin, melamine resin, urethane resin etc.In water color ink, as solvent, the water-miscible organic solvent that comprises water and adopt as required, as adhesive resin composition, comprises water soluble resin and/or water-dispersed resin.In addition, in oil-based ink, as solvent, comprise organic solvent, as adhesive resin composition, comprise the resin that dissolves in organic solvent.
By using ink-jet method ink to be coated after the peristome of spaced walls, for example black matrix", can be dried as required, be heating and curing, ultraviolet curing etc., can form pixel.
In addition, form after pixel at the peristome of spaced walls, can form as required diaphragm.By this, can be when the surface smoothness that makes colored filter improve, stop from the leachable arrival of spaced walls or pixel and the liquid crystal layer of diaphragm adjacency.
At this moment, forming before diaphragm, be, better the liquid-repellant of removing the upper surface of spaced walls.The upper surface that by this, can suppress spaced walls is the repulsion with coating fluid to diaphragm.As the method for liquid-repellant of upper surface of removing spaced walls, be not particularly limited, can exemplify plasma ashing processing, light ashing processing etc.
In addition, in order to improve the quality of the liquid crystal panel that uses colored filter manufacture of the present invention, can on spaced walls, for example black matrix", form as required photonasty sept (photo-spacer).
<4> organic EL
Organic EL of the present invention is the organic EL that has multiple pixels and be positioned at the spaced walls between the pixel of adjacency on substrate, it is characterized in that, described spaced walls is formed by the spaced walls of the invention described above, and described pixel forms by ink-jet method.
Organic EL of the present invention can be manufactured as follows.First, use sputtering method etc. on the transparency carriers such as glass substrate, to form the transparency electrode of ITO etc., as required transparency electrode is etched into required pattern.Then, similarly operate with the situation of colored filter, on substrate, form after spaced walls, for example black matrix", use ink-jet method to be coated with successively the solution of hole mobile material and the solution of luminescent material dry as ink at the peristome of spaced walls (black matrix"), form hole transmission layer and luminescent layer.Then, use the electrode of the formations aluminium such as vapour deposition method etc. and form pixel, thus acquisition organic EL.
Embodiment
Below, based on embodiment, the present invention will be described, but the present invention is not limited to these embodiment.Part represents mass parts.
The abbreviation of the compound using in following each example is as follows.
[1] compound using in the manufacture of polymkeric substance (A) and polymkeric substance (R)
(monomer)
C6FMA:CH 2=C(CH 3)COOCH 2CH 2(CF 2) 6F
X-24-8201: containing the methacrylate X-24-8201 (Shin-Etsu Chemial Co., Ltd (chemical industry society of SHIN-ETSU HANTOTAI) system) of dimethyl siloxane chain (in general formula (4), R 8for methyl, Z is 1,3-propylidene, R 1, R 2, R 3be respectively methyl, n counts 24 compound with intermolecular mean value)
MAA: methacrylic acid
2-HEMA: methacrylic acid-2-hydroxy methacrylate
PME400:BLEMMER PME-400 (NOF Corp's system,
CH 2=C (CH 3) COO (CH 2cH 2o) kcH 3, the k in formula represents intermolecular mean value, the value of n is about 9)
PME1000:BLEMMER PME-1000 (NOF Corp's system,
CH 2=C (CH 3) COO (CH 2cH 2o) kcH 3, the k in formula represents intermolecular mean value, the value of n is about 23)
GMA: methyl propenoic acid glycidyl base ester
MMA: methyl methacrylate
(polymerization initiator)
V-65:V-65 (Wako Pure Chemical Industries, Ltd.'s (with light Pure medicine society) system, 2,2 '-azo two (2,4-methyl pentane nitrile))
(chain-transferring agent)
N-DM: n-dodecyl mercaptan
(solvent)
MEK:2-butanone
[2] photosensitive composite composition
(trigger for optical solidification (B): Photoepolymerizationinitiater initiater (B1))
OXE02:OXE02 (Ciba company system, ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group oxime); In general formula (5), R 21and R 22for methyl, R 23for ethyl, R 24, R 26and R 27for hydrogen atom, R 25for the compound of 2-methyl benzoyl)
(adhesive resin (C): photoresist (C1))
(Chang Lai Chemitec Co., Ltd. system has been introduced the solution of the resin of the two keys of ethene and acidic-group, solid constituent 70 quality %, matter average molecular weight: 3020) to EX1010:EX-1010 in the epoxy resin representing with general formula (7)
ZCR1569H:ZCR-1569H (Nippon Kayaku K. K's system, in the epoxy resin with biphenyl backbone representing with general formula (6), introduce the solution of the resin of the two keys of ethene and acidic-group, solid constituent 70 quality %, matter average molecular weight: 4710)
(crosslinking chemical (D))
DPHA:KAYARAD DPHA (Nippon Kayaku K. K's system, the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate)
A9300:NK Ester A-9300 (chemical industry Co., Ltd. of Xin Zhong village system, epoxidation isocyanuric acid triacrylate)
(solvent)
PGMEA: propylene glycol methyl ether acetate
(black colorant (E), particulate)
CB: carbon black dispersion liquid (average aggregate particle size 120nm, dispersion medium PGMEA, carbon black 20 quality %, the polyurethane class high molecular spreading agent 5 quality % that amine value is 18mgKOH/g)
Silicon dioxide: silica dispersions (mean grain size 20nm, dispersion medium PGMEA, solid constituent 30 quality %)
[synthesis example 1 of polymkeric substance (A)]
Add MEK (420.0g), C6FMA (90.0g), MAA (9.0g), PME1000 (81.0g) and polymerization initiator V-65 (0.5g) to possessing in the autoclave of internal volume 1L of stirring machine, in stirring under nitrogen atmosphere, make it 50 ℃ of polymerizations 24 hours, synthetic thick multipolymer.In the solution of the thick multipolymer of gained, add hexane to carry out after deposition and purification, vacuum drying, obtains corresponding to the polymkeric substance (A-1) of polymkeric substance (A) (162.4g) again.
The number-average molecular weight of polymkeric substance (A-1) is 37800, and matter average molecular weight is 58730.
[synthesis example 2～4 of polymkeric substance (A)]
In above-mentioned polymkeric substance (A-1) synthetic, by except the reaction according to same the proportioning of table 1 feed change, obtain polymkeric substance (A-2) corresponding to polymkeric substance (A)～(A-4).
[relatively synthesis example 1,2]: comparative example polymkeric substance (R) synthetic that does not meet polymkeric substance (A)
In above-mentioned polymkeric substance (A-1) synthetic, by except the reaction according to same the proportioning of table 1 feed change, obtain the polymkeric substance (R-1), (R-2) that do not meet the polymkeric substance (A) in the present invention.
For the each polymkeric substance (A) obtaining in above-mentioned and comparative example polymkeric substance (R), number-average molecular weight (Mn) that method by following is measured, matter average molecular weight (Mw), Mw/Mn, fluorine atom (F) content, polyoxyalkylenes be shown in table 1 containing proportional, silicon atom (Si) content, acid number, developing solution dissolution together with polymkeric substance receipts amount.
< molecular weight >
Number-average molecular weight (Mn) and matter average molecular weight (Mw) are measured take polystyrene as standard substance by gel permeation chromatography.As gel permeation chromatography, use HPLC-8220GPC ((East ソ ー society of TOSOH Co., Ltd) system).As post, use the post 3 shodex LF-604 being connected and obtain.As detecting device, use RI detecting device.As standard substance, use EasiCal PS1 (polymkeric substance laboratory company (Polymer Laboratories society) system).In addition, while measuring number-average molecular weight and matter average molecular weight, post is held in to 37 ℃, eluent uses tetrahydrofuran, and flow velocity is made as 0.2mL/ minute, injects 0.5 quality % tetrahydrofuran solution 40 μ L of working sample.
< fluorine atom content >
Fluorine atom content in polymkeric substance calculates according to the reinforced value of polyreaction.
< polyoxyalkylenes containing proportional >
Calculating containing the proportional reinforced value according to polyreaction of polyoxyalkylenes in polymkeric substance.
< silicon atom content >
Silicon atom content in polymkeric substance calculates according to the reinforced value of polyreaction.
< acid number >
Acid number is the theoretical value calculating according to the proportioning of the monomer as raw material.
< developing solution dissolution >
The each polymkeric substance obtaining in above-mentioned is added into 0.1% NaCO 3aqueous solution (pH11,23 ℃ of temperature), obtains the ratio (quality %) of the polymkeric substance dissolving when stirring condition is 50rpm, the deliquescent index as polymkeric substance for alkaline aqueous solution.
[table 1]
Figure BDA00001779313400441
[embodiment 1]
Using the polymkeric substance obtaining in above-mentioned synthesis example (A-1) (0.03 part), as the CB (31.6 parts) of the dispersion liquid of black colorant (E), as the OXE02 (0.76 part) of Photoepolymerizationinitiater initiater (B1), as the EX1010 (6.3 parts) of the dispersion liquid of photoresist (C1), mix as the DPHA (1.9 parts) of crosslinking chemical (D) with as PGMEA (34.4 parts), the cyclohexanone (25.0 parts) of solvent, obtain the dilution of photosensitive composite.The content of the polymkeric substance (A-1) in all solids composition of the dilution of photosensitive composite is 0.20 quality %.
After adopting rotary coating machine that the dilution of photosensitive composite is coated on glass substrate, be dried 2 minutes in 100 ℃ on heating plate, forming thickness is the film of the photosensitive composite of 2.0 μ m.Then, use ultrahigh pressure mercury lamp to see through mask film is irradiated to exposure take i line (365nm) as benchmark is as 100mJ/cm 2light expose.It is that 150 μ m × 400 μ m, light transmission part are the clathrate pattern of 20 μ m that mask is shading light part, and the volume of the peristome forming is 120pL.In addition, the area of pattern is 10cm 2.Then, use developing machine to develop.Developer solution uses 10 times of dilute aqueous solutions of Semi Clean DL-A4 (trade name, Yokohama oil prodution industry Co., Ltd. (Heng Bang oil prodution industry society) system).Nozzle uses the illumination angle of substrate is controlled to the nozzle below 8 degree, and the pressure that applies 0.15MPa spues developer solution to substrate, thereby produces bubble, carries out spin coating development.Then, water washes away unexposed portion, makes it dry.Then, in baking oven, in 220 ℃, glass plate is heated to (baking afterwards) 30 minutes, thereby obtain the glass substrate sample (1) of the embodiment 1 that is formed with spaced walls.
Except not using mask exposes, similarly operate with above-mentioned, obtain the glass substrate sample (2) of the embodiment 1 of the solidfied material of the film that is formed with photosensitive composite.In addition, carry out the spray of 10 seconds by the high pressure spray jetting of 4.0MPa, obtain the glass substrate sample (3) of embodiment 1.
[embodiment 2～5]
Except changing according to table 2 proportioning of each composition, operate similarly to Example 1, obtain the embodiment 2～5 that is formed with the spaced walls being formed by the coating film cured product thereof of photosensitive composite that comprises respectively the polymkeric substance (A-2) that obtains in above-mentioned synthesis example～(A-5) glass substrate sample (1), be formed with the solidfied material of the film of this photosensitive composite embodiment 2～5 glass substrate sample (2) and further carried out the glass substrate sample (3) spraying.
[comparative example 1,2]
Except changing according to table 2 proportioning of each composition, operate similarly to Example 1, obtain the comparative example 1,2 that is formed with the spaced walls being formed by the coating film cured product thereof of photosensitive composite that comprises respectively the polymkeric substance (R-1) that obtains in above-mentioned relatively synthesis example, (R-2) glass substrate sample (1), be formed with the solidfied material of the film of this photosensitive composite comparative example 1,2 glass substrate sample (2) and further carried out the glass substrate sample (3) spraying.
[table 2]
Figure BDA00001779313400451
[evaluation method and evaluation result]
By the method for following explanation, use glass substrate sample (2) and the glass substrate sample (3) in the various embodiments described above and comparative example, made to evaluate liquid-repellant.In addition, use the glass substrate sample (1) of making in the various embodiments described above and comparative example, evaluated the state of the invasion of the ink in peristome between spaced walls, the generation of residual film.Containing together with quality % of each composition in all solids composition of evaluation result and photosensitive composite is shown in table 3.
In table, ◎ represents optimum, and zero represents that well △ represents qualified, × represent defective.What the present invention was preferred whole is evaluated as ◎ or zero.
< liquid-repellant >
Evaluate liquid-repellant by the coating film cured product thereof surface of measuring glass substrate sample (2) with the contact angle of PGMEA.In addition, evaluate the tolerance for the liquid-repellant of spray by the coating film cured product thereof surface of measuring glass substrate sample (3) with the contact angle of PGMEA.
Contact angle refers to the angle that the tangent line for liquid surface on the point that solid contacts with liquid and solid surface form, and is defined as the angle of a side that comprises liquid.Therefore, contact angle is larger, means that the liquid-repellant of coating film cured product thereof is better.By being judged to be zero with contact angle sample below 50 ° more than 40 ° of PGMEA, more than 35 ° and lower than the sample of 40 °, be judged to be △, lower than the sample of 35 ° be judged to be ×.
The state > that the residual film of < produces
For glass substrate sample (1), count developing defect number by visual inspection, thereby the state that residual film is produced is evaluated.The sample that the developing defect number of unit area is less than to 100 is judged to be zero, and more than 100 and be less than the sample of 200 and be judged to be △, the sample more than 200 is judged to be ×.
The invasion > of the ink between < spaced walls in peristome
By liquid epoxy resin ME-562 (Japanese Peng Nuo Co., Ltd. (Japanese ペ Le ノ ッ Network ス society) system) (6.25g), hardening agent HV-562 (Japanese Peng Nuo Co., Ltd. system) (6.25g), diethylene adipate (12.5g) and diethyl malonate (25.0g) be uniformly mixed 1 hour with stirrer, makes ink.
Use ink-jet method the ink of about 10pL or the above-mentioned middle preparation of about 20pL to be coated to peristome between the spaced walls of glass substrate sample (1), to with super degree of depth measuring shape microscope VK-8500 (the (キ ー エ of Keyemce company Application ス society) system) shooting photo observe, thereby the invasion of the ink in peristome between evaluation intervals wall.
The part that in photo obtained above, peristome ink is arranged between 10 place's spaced walls is that the sample at 0 place is judged to be ◎, and the sample that the sample at 1～2 place is judged to be zero, 3～5 places is judged to be △, the sample at 5～10 places is judged to be ×.
[table 3]
As shown in Table 3, even in the situation that spraying, there is use and comprise respectively with matter average molecular weight (Mw (A)) 2.6 × 10 4< Mw (A)≤20 × 10 4scope in, the liquid-repellant of the glass substrate sample (3) of the embodiment 1～5 of the spaced walls that obtains containing the photosensitive composite of the present invention of polymkeric substance (A-1) corresponding to the polymkeric substance (A) of polyoxyalkylenes～(A-5) (polyoxyalkylenes in polymkeric substance containing proportional all in the present invention in the scope of preferred 5～60 quality %) is good.This shows to use in the spaced walls that the photosensitive composite of embodiment 1～5 obtains, even in the case of the high pressure water cleaning that is called spray, polymkeric substance (A) can be from surface layer peeling yet, and liquid-repellant is maintained.
Have in the glass substrate sample (1) of embodiment 1～5 of the spaced walls that photosensitive composite of the present invention that use comprises respectively the polymkeric substance (A-1) corresponding with polymkeric substance (A)～(A-5) obtains, the generation of residual film is few.This shows to use the surface of the spaced walls that the photosensitive composite of embodiment 1～5 obtains to have the polyoxyalkylenes of q.s, and therefore the generation of residual film is inhibited.
Between the spaced walls that is 120pL at volume, in peristome, be coated with the ink of about 20pL, be that the coating weight of ink is with respect in the less situation of the volume of peristome, have in the glass substrate sample (1) of embodiment 1～5 of the spaced walls that photosensitive composite of the present invention that use comprises respectively the polymkeric substance (A-1) corresponding with polymkeric substance (A)～(A-5) obtains, invasion in the peristome of ink between spaced walls is white without leaking.In this film that shows to be obtained by the photosensitive composite of embodiment 1～5, developability is good, also there is no the movement of polymkeric substance (A) composition from spaced walls surface to peristome between spaced walls.
In addition, even in the case of the ink of approximately 10pL still less of coating, the ink of the embodiment 1～4 of the matter average molecular weight of polymkeric substance (A) more than 40000 is invasion in the peristome between spaced walls also, white without leaking.
On the other hand, have and use the scope of the matter average molecular weight Mw (A) that is included in polymkeric substance of the present invention (A) outer, be specially matter average molecular weight Mw and be less than 2.6 × 10 4the glass substrate sample (3) of comparative example 1 of the spaced walls that obtains of the photosensitive composite of polymkeric substance (R-1), the liquid-repellant after its spray significantly declines.In addition, between the spaced walls that is 120pL at volume, peristome is coated with the ink of about 20pL, and the coating weight of ink, with respect in the less situation of the volume of peristome, exists the not part of invasion in peristome of ink.When this shows rear baking, polymkeric substance (R-1) migrates in peristome, and the lyophily of peristome declines.
Have in the glass substrate sample (1) that uses the comparative example 2 that comprises not the spaced walls obtaining containing the photosensitive composite of the polymkeric substance (R-2) of polyoxyalkylenes and produce a large amount of residual films.
The possibility of utilizing in industry
Photosensitive composite of the present invention is to comprise the photosensitive composite of refusing ink composition, the described ink composition of refusing is the ink composition of refusing containing the two keys of ethene not, but the spaced walls that can give gained is refused ink, is not developed developer solution tolerance that liquid corrodes, is suppressed not to be developed and character that residual residual film produces and the good ink invasion to peristome between spaced walls with spaced walls top good.
Photosensitive composite of the present invention has like this been applicable to for example utilize the formation of the spaced walls of the colored filter manufacture use of ink-vapor recording technology law, organic EL display element manufacture use.In addition, be also suitable as the material that the permanent film such as spaced walls, the spaced walls of wiring substrate of the ITO electrode of the spaced walls of each TFT of organic tft (Thin Film Transistor: thin film transistor (TFT)) array, liquid crystal display cells is separated in formation.
Here quote the full content of instructions, claims and summary of No. 2009-298961, the Japanese patent application of filing an application on Dec 28th, 2009 as the announcement of instructions of the present invention.

Claims (14)

1. photosensitive composite, it is to comprise to have containing the side chain of the group that represents with following general formula (1) with containing the side chain of polyoxyalkylenes and do not have the photosensitive composite containing the polymkeric substance (A) of the side chain of ethene pair keys, trigger for optical solidification (B), adhesive resin (C)
The matter average molecular weight (Mw (A)) of described polymkeric substance (A) meets 3.5 × 10 4≤ Mw (A)≤20 × 10 4;
-CFXR f…(1)
In formula, X represents hydrogen atom, fluorine atom or trifluoromethyl, R frepresent that carbon number is more than 1 fluoro-alkyl below 20 or fluorine atom,
Polyoxyalkylenes in described polymkeric substance (A) containing proportional be 15～50 quality %.
2. photosensitive composite as claimed in claim 1, is characterized in that, the matter average molecular weight (Mw (A)) of described polymkeric substance (A) meets 4.0 × 10 4≤ Mw (A)≤20 × 10 4.
3. photosensitive composite as claimed in claim 1 or 2, is characterized in that, described polymkeric substance (A) is containing acidic-group.
4. photosensitive composite as claimed in claim 1 or 2, is characterized in that, it is 20～50 quality % that the fluorine atom in described polymkeric substance (A) contains proportional.
5. photosensitive composite as claimed in claim 1 or 2, is characterized in that, the ratio of the described polymkeric substance (A) in all solids composition of described photosensitive composite is 0.07～1 quality %.
6. photosensitive composite as claimed in claim 1 or 2, is characterized in that, described polymkeric substance (A) is also containing the a kind of above group that is selected from epoxy radicals, sulfydryl and hydroxyl.
7. photosensitive composite as claimed in claim 1 or 2, is characterized in that, described polymkeric substance (A) also has the side chain containing the group representing with following general formula (2);
[changing 1]
Figure FDA0000394706780000011
In formula, R 1and R 2represent independently respectively hydrogen atom or the alkyl that can be replaced by fluorine atom, naphthenic base or aryl, R 3represent that hydrogen atom or carbon number are more than 1 organic group below 10, n represents more than 1 integer below 200.
8. photosensitive composite as claimed in claim 1 or 2, it is characterized in that, also comprise polymkeric substance (A) ', described polymkeric substance (A) ' have containing the side chain of the group that represents with following general formula (2) and contain the side chain of polyoxyalkylenes, and do not have containing the side chain of the group representing with described general formula (1) with containing the either party in the side chain of the two keys of ethene, and its matter average molecular weight (Mw (A) ') meet 2.6 × 10 4< Mw (A) '≤20 × 10 4;
[changing 2]
Figure FDA0000394706780000021
In formula, R 1and R 2represent independently respectively hydrogen atom or the alkyl that can be replaced by fluorine atom, naphthenic base or aryl, R 3represent that hydrogen atom or carbon number are more than 1 organic group below 10, n represents more than 1 integer below 200.
9. photosensitive composite as claimed in claim 1 or 2, is characterized in that, described trigger for optical solidification (B) is Photoepolymerizationinitiater initiater, and described adhesive resin (C) is the photoresist containing acidic-group and the two keys of ethene.
10. photosensitive composite as claimed in claim 9, is characterized in that, also comprises the crosslinking chemical (D) with 2 two keys of above ethene.
11. photosensitive composites as claimed in claim 1 or 2, is characterized in that, also comprise black colorant (E).
12. spaced walls, it is the spaced walls that is formed as the form of the multiple blocks that are partitioned into pixel formation use on substrate, it is characterized in that, is formed by the coating film cured product thereof of the photosensitive composite described in any one in claim 1～11.
13. colored filters, it is the colored filter that has multiple pixels and be positioned at the spaced walls between the pixel of adjacency on substrate, it is characterized in that, and described spaced walls is formed by the spaced walls described in claim 12, and described pixel forms by ink-jet method.
14. organic ELs, it is the organic EL that has multiple pixels and be positioned at the spaced walls between the pixel of adjacency on substrate, it is characterized in that, and described spaced walls is formed by the spaced walls described in claim 12, and described pixel forms by ink-jet method.
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