CN106610565A - Photosensitive composition and application thereof - Google Patents

Photosensitive composition and application thereof Download PDF

Info

Publication number
CN106610565A
CN106610565A CN201610915919.2A CN201610915919A CN106610565A CN 106610565 A CN106610565 A CN 106610565A CN 201610915919 A CN201610915919 A CN 201610915919A CN 106610565 A CN106610565 A CN 106610565A
Authority
CN
China
Prior art keywords
phenyl
methyl
acid
compound
double
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201610915919.2A
Other languages
Chinese (zh)
Inventor
近藤学
龟井佑典
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JNC Corp
Original Assignee
JNC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JNC Corp filed Critical JNC Corp
Publication of CN106610565A publication Critical patent/CN106610565A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2012—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image using liquid photohardening compositions, e.g. for the production of reliefs such as flexographic plates or stamps
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Optical Filters (AREA)

Abstract

The invention relate to a photosensitive composition and applications thereof. The photosensitive composition contains polyesteramide acid, compounds with polymerized double bonds, a light polymerization initiator, epoxy compounds, an epoxy hardening agent, and a molecular weight regulator. The polyesteramide acid is a reaction product of a raw material which contains tetracarboxylic acid dianhydride, diamine, and polyols hydroxyl compounds as necessary components. Through using the photosensitive composition, a hard coated film whose heat resistance, flatness, transparency, and resolvability are excellent can be obtained.

Description

Photosensitive composite and its application
Technical field
The present invention relates to it is a kind of for forming electronic component in insulant, semiconductor device in passivating film, buffering The sense of interlayer dielectric or colored filter protecting film in film, interlayer dielectric or planarization film, or display element etc. Photosensitiveness compositionss, the hyaline membrane using the photosensitive composite and the electronic component comprising the film.
Background technology
In the manufacturing process of the elements such as display element, carry out sometimes at the various chemicals such as organic solvent, acid, aqueous slkali Reason, or when by sputtering (sputtering) and film forming wired electric pole, surface is locally heated by as high temperature.Therefore, have When in order to prevent the deterioration on the surface of various elements, damage, rotten and arrange surface protection film.For these protecting film, it is desirable to Each characteristic of the various process in manufacturing process as above can be tolerated.Specifically, it is desirable to thermostability, solvent resistance/ It is the chemical-resistants such as acid resistance/alkali resistance, resistance to water, the adhesion to basal substrates such as glass, the transparency, scratch resistance, flat Smooth property, light resistance etc..And, in showing for the high performance-baseds such as high visual angle, high-speed response, the High precision for advancing display element Under shape, in the case of as protective films of color filters, the material that the transparency, thermostability and planarization characteristics are improved is expected Material.
Photosensitive composite, thermmohardening can be substantially distinguished as to the species for forming the curable adhensive compositions of these protecting film Property compositionss.Make thermosetting compositionss fully hardened by high-temperature heating when film is formed, therefore, even if operation behind In there are the situation for being heated to high temperature, the volatile ingredient of generation is also few, and thermostability is also excellent.Heat with the excellent specific property is hard The Protective coatings of the property changed there are polyesteramide acid composition (for example, referring to patent documentation 1).However, thermosetting combination Thing cannot form score line (scribe line) and produce the fines of protecting film in large quantities in manufacture screen segmentation, therefore at it The screen for carrying out height is needed to clean operation afterwards.
On the other hand, photosensitive composite gathers comprising the polymer with optical polymerism base or oligomer or monomer with light Initiator is closed, and causes chemical reaction because of the energy of the light with ultraviolet as representative, and hardened.Photosensitive composite example The advantages of being such as readily formed for score line during manufacture screen segmentation, therefore there are the fines for not producing protecting film, phase Anti-, compared with the protecting film formed by thermosetting compositionss, the protecting film formed by common photosensitive composite Thermostability it is insufficient.
In recent years, needing the demand of the protecting film of thermostability gradually increases, and then needs the protecting film of fine pattern shape Demand also gradually increase.Thus, seek the protecting film that can form excellent heat resistance and the photonasty group of fine pattern can be formed Compound.
The photosensitive composite that the protecting film with very excellent thermostability can be formed there are polyimide precursor group Compound (for example, referring to patent documentation 2), soluble polyimide compositionss (for example, referring to patent documentation 3).Even if however, In any photosensitive composite, the polyimide precursor composition or soluble polyimide compositionss dissolving of gained can be made Organic solvent is also defined, it is also desirable to the very high organic solvent of polarity.
The organic solvent that the polarity of dissolving polyimide precursor composition, soluble polyimide compositionss etc. is high can be arranged Lift：Ketopyrrolidine system, sulfoxide system, formyl amine system, acetyl amine system, phenol system, tetrahydrofuran, diox, gamma-butyrolacton etc..
Particularly in the case where these photosensitive composites are used as into protective films of color filters, if containing these poles Property high organic solvent, then penetrate into the color filter layers of substrate, such as the coloring such as contained pigment or dyestuff material in pixel Material dissolution, therefore, it is difficult to making high-quality display element.
The example that photosensitive composite is used in the protecting film of colored filter be there are into patent documentation 4 and patent documentation 5, but the human desires such as the present inventor forms protecting film using photosensitive composite described in these patent documentations, as a result institute's shape Into pattern not make us abundant satisfaction, and expect further improvement.
And, no matter photosensitive composite, thermosetting compositionss, require these curable adhensive compositions in basal substrate On coating it is excellent.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2008-156546 publication
[patent documentation 2] Japanese Patent Laid-Open No. Sho 59-68332 publication
[patent documentation 3] Japanese Patent Laid-Open 2002-3516 publication
[patent documentation 4] Japanese Patent Laid-Open 2014-074787 publication
[patent documentation 5] Japanese Patent Laid-Open 2009-286904 publication
The content of the invention
[the invention problem to be solved]
The problem of the present invention is to provide a kind of organic solvent for not needing polarity high, and the transparency, thermostability, flatness And the especially excellent cured film of analyticity and provide the compositionss of the cured film.Further, there is provided a kind of with the cured film Electronic component.
[technological means of solve problem]
The present inventor et al. has carried out making great efforts research to solve the problem, as a result finds by following combination Thing and the cured film for hardening said composition and obtaining may achieve the purpose, so as to complete the present invention, the compositionss bag Containing polyesteramide acid, the compound with polymerism double bond, Photoepolymerizationinitiater initiater, epoxide, epoxy curing agent and molecule Amount regulator, the polyesteramide acid is by the reaction of the compound comprising tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound And obtain.
The present invention includes following composition.
[1] a kind of photosensitive composite, it is comprising polyesteramide acid, the compound with polymerism double bond, photopolymerization The compositionss of initiator, epoxide, epoxy curing agent and molecular weight regulator；The feature of the photosensitive composite exists In：
Polyesteramide acid is derived from the ratio set up with the relation of following formula (1) and formula (2) comprising X mole of tetrabasic carboxylic acid two The product of the raw material of acid anhydride, Y mole of diamidogen and Z mole of multi-hydroxy compound, with the knot represented by following formula (3) Construction unit represented by structure unit and formula (4)；
Compound with polymerism double bond includes plural polymerism double bond in each molecule；
Epoxide includes two～ten epoxy radicals in each molecule, and weight average molecular weight is less than 3,000；
Relative to polyesteramide 100 weight portions of acid, the total amount of the compound with polymerism double bond is 20 weight portion～300 Weight portion, the total amount of epoxide is 20 weight portion～200 weight portions, and the content of Photoepolymerizationinitiater initiater is more than molecular weight 5.0 times of the content of regulator, less than 30 times；
0.2≤Z/Y≤8.0 (1)
0.2≤(Y+Z)/X≤5.0 (2)
In formula (3) and formula (4), R1Be from tetracarboxylic dianhydride remove two-CO-O-CO- residue, R2It is from two Amine removes two-NH2Residue, R3It is the residue that two-OH are removed from multi-hydroxy compound.
[2] according to the photosensitive composite described in [1], its middle-molecular-weihydroxyethyl regulator be selected from mercaptan (mercaptan) class, One or more of xanthic acid (xanthogen) class, quinone (quinone) class, 2,4- diphenyl -4-methyl-1-pentene.
[3] photosensitive composite according to [1], its middle-molecular-weihydroxyethyl regulator is naphthoquinone (naphthoquinone) Class.
[4] photosensitive composite according to [1], its middle-molecular-weihydroxyethyl regulator is HNQ.
[5] photosensitive composite according to any one of [1] to [4], the material composition of wherein polyesteramide acid enters One step includes monohydroxy compound.
[6] photosensitive composite according to [5], wherein monohydroxy compound are selected from isopropanol, 1-propenol-3, benzyl One or more of alcohol, hydroxyethyl methacrylate, dihydroxypropane single-ether and 3- ethyl -3- hydroxymethyl oxetanes.
[7] photosensitive composite according to any one of [1] to [5], the wherein weight average point of polyesteramide acid Son amount is 1,000～200,000.
[8] according to the photosensitive composite any one of [1] to [5], wherein tetracarboxylic dianhydride is to be selected from 3,3 ', 4, 4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyphenyis)] six One or more of fluoro-propane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides and ethylene glycol double (dehydration trimellitates).
[9] according to the photosensitive composite any one of [1] to [5], wherein diamidogen is to be selected from 3,3 '-diaminourea two One or more of phenylsulfone and double [4- (3- amino-benzene oxygens) phenyl] sulfones.
[10] photosensitive composite according to any one of [1] to [5], wherein multi-hydroxy compound are selected from second Double (the 4- of glycol, Propylene Glycol, BDO, 1,5-PD, 1,6- hexanediol, 1,7- heptandiols, 1,8- ethohexadiols, 2,2- Hydroxy-cyclohexyl) propane, 4, one or more of 4 '-dihydroxyl dicyclohexyl and fulminuric acid three (2- hydroxyethyls) ester.
[11] photosensitive composite according to any one of [1] to [5], wherein relative to polymerism double bond The gross weight of compound, the compound with polymerism double bond contain it is more than 50 weight % selected from the acrylic acid of dipentaerythritol five Ester, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, fulminuric acid epoxy One or more of oxide-modified triacrylate and modified by polyacid (methyl) acrylate oligomers.
[12] photosensitive composite according to any one of [1] to [5], wherein epoxide are selected from 3,4- rings Oxygen cyclohexane-carboxylic acid -3 ', 4 '-epoxycyclohexanecarboxylate, 1- methyl -4- (2- methyl oxiranyls) -7- oxabicyclos [4.1.0] heptane, 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] second Base] phenyl] double [4- [1- [4- (2,3- glycidoxy) phenyl] -1- [4- [1- [4- (2,3- the third oxygen of epoxy of propane and 1,3- Base) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propanol mixture, 2- [4- (2,3- glycidoxy) benzene Base] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] ethyls] phenyl] propane, 1,1,1- tri- (4- hydroxy phenyls) second Double (oxiranyl methyl) -5- (2- acrylic) -1,3,5-triazines -2 of alkane triglycidyl ether, 1,3-, 4,6 (1H, 3H, In 1,2- epoxy radicals -4- (2- oxiranyls) the hexamethylene addition product of double (the hydroxymethyl)-n-butyl alcohols of 5H)-triketone, 2,2- More than one.
[13] photosensitive composite according to any one of [1] to [5], wherein Photoepolymerizationinitiater initiater are selected from α-ammonia One kind in base benzene alkyl ketone (α-aminoalkylphenone) system, acylphosphine oxide system, oxime ester system Photoepolymerizationinitiater initiater with On.
[14] photosensitive composite according to any one of [1] to [5], wherein epoxy curing agent are selected from inclined benzene three One or more of formic anhydride, hexahydro trimellitic anhydride and 2- undecyl imidazoles.
[15] according to the photosensitive composite any one of [1] to [5], wherein tetracarboxylic dianhydride is to be selected from 3,3 ', One or more of 4,4 '-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides；
Diamidogen is 3,3 '-diamino diphenyl sulfone；
Multi-hydroxy compound is BDO；
Monohydroxy compound is benzylalcohol；
Compound with polymerism double bond is selected from Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate One or more of and modified by polyacid (methyl) acrylate oligomers；
Relative to the gross weight of Photoepolymerizationinitiater initiater, Photoepolymerizationinitiater initiater contain it is more than 50 weight % selected from 1,2- pungent two Ketone -1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes), ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyls) -9- clicks Azoles -3- bases] -, 1- (O- acetyl group oximes) and 1,2- propanedione -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- One or more of acetyl group oxime)；
Epoxide is selected from 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- (2,3- epoxies third Epoxide) phenyl] ethyl] phenyl] propane and 1,3- it is double [4- [1- [4- (2,3- glycidoxy) phenyl] -1- [4- [1- [4- (2, 3- glycidoxies) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propanol mixture and 2- [4- (2,3- rings Oxygen propoxyl group) phenyl] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] ethyls] phenyl] and one kind in propane with On；
Epoxy curing agent is selected from one or more of trimellitic anhydride and 2- undecyl imidazoles；
Molecular weight regulator is HNQ, and is become more than molecular weight tune with the content of Photoepolymerizationinitiater initiater 5.0 times of whole dose of content, the mode less than 30 times contain molecular weight regulator；
Further contain selected from one or more of 3- methoxy methyl propionates and propylene glycol methyl ether acetate as molten Agent.
[16] a kind of cured film, it is by being obtained according to the photosensitive composite any one of [1] to [15].
[17] a kind of colored filter, it uses the cured film described in basis [16] as protecting film.
[18] a kind of display element, it uses the colored filter according to [17].
[19] a kind of solid-state imager, it uses the colored filter according to [17].
[20] a kind of display element, it is used according to the cured film described in [16] as being formed in thin film transistor (TFT) (Thin Film Transistor, TFT) transparent insulating film and transparency electrode between.
[21] a kind of display element, it is used according to the cured film described in [16] as being formed in transparency electrode and alignment films Between transparent insulating film.
[22] a kind of light emitting diode (Light Emitting Diode, LED) luminous body, it uses according to [16] Cured film as protecting film.
[The effect of invention]
The photosensitive composite of the preferred embodiment of the present invention is the organic solvent for not needing polarity high, and be may be formed at The material of especially excellent cured film in the transparency, thermostability, flatness and analyticity, in the colour as color display element In the case of optical filter protecting film, improve can display quality and reliability.In accordance with the above, practicality is very high, especially It is the protecting film for acting effectively as the colored filter manufactured using staining, pigment dispersion method, electrodeposition process and print process.And And, it is also used as the protecting film and transparent insulating film of various optical materials and uses.
Description of the drawings
Fig. 1 is that scanning electron obtained by the hole portion section to the glass substrate with pattern-like cured film shoots shows Micro mirror (scanning electron microscope) photo.
[explanation of reference]
AB：The bottom footpath of substrate surface
CD：In vertical direction the bottom surface away from substrate surface is the aperture at 0.5 μm of position
Specific embodiment
1. photosensitive composite
The present invention photosensitive composite be comprising polyesteramide acid, in each molecule include plural polymerism The compound of double bond, Photoepolymerizationinitiater initiater, in each molecule comprising two～ten epoxy radicals and weight average molecular weight not Foot 3,000 epoxide, epoxy curing agent and molecular weight regulator compositionss, the polyesteramide acid be derived from containing Tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound as the raw material of required composition product, the photosensitive composite It is characterised by：Relative to polyesteramide 100 weight portions of acid, the compound with polymerism double bond is 20 weight portion～300 weights Amount part, epoxide is 20 weight portion～200 weight portions, and the content of Photoepolymerizationinitiater initiater is containing more than molecular weight regulator Amount 5.0 times, less than 30 times.And, the photosensitive composite of the present invention can be with the range of the effect for obtaining the present invention Further containing the other compositions beyond described.
The acid of 1-1. polyesteramides
Polyesteramide acid in the present invention is derived from containing tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound as required The product of the raw material of composition.More specifically, the polyesteramide acid is derived from the relation of following formula (1) and formula (2) The ratio of establishment contains the anti-of the raw material of X mole of tetracarboxylic dianhydride, Y mole of diamidogen and Z mole of multi-hydroxy compound Answer product.
0.2≤Z/Y≤8.0 (1)
0.2≤(Y+Z)/X≤5.0 (2)
Polyesteramide acid is with the construction unit and the construction unit represented by formula (4) represented by following formula (3).
In formula (3) and formula (4), R1It is the residue that two-CO-O-CO- are removed from tetracarboxylic dianhydride, preferably carbon The organic group of number 2～30.R2It is to remove two-NH from diamidogen2Residue, the preferably organic group of carbon number 2～30.R3It is The residue of two-OH, the preferably organic group of carbon number 2～20 are removed from multi-hydroxy compound.
The synthesis of polyesteramide acid at least needs solvent, and the solvent can be made directly to remain and make in view of operability etc. Liquid or gelatinous photosensitive composite, or the solvent can also be removed and make the solid in view of carrying property etc. The compositionss of shape.And, the synthesis of polyesteramide acid can also optionally comprising selected from monohydroxy compound and styrene-Malaysia The compound of one or more of acid anhydride copolymer as raw material, wherein, preferably comprise monohydroxy compound.And, polyester acyl The synthesis of amino acid optionally can also be made not undermining in the range of the purpose of the present invention comprising other compounds beyond described For raw material.The example of this kind of other raw materials can enumerate siliceous monoamine.
1-1-1. tetracarboxylic dianhydride
In the present invention, the materials'use tetracarboxylic dianhydride sour to obtain polyesteramide.Preferred tetracarboxylic dianhydride's Concrete example can be enumerated：3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,3, 3 ', 4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 2,2 ', 3,3 '-sulfobenzide. tetracarboxylic acid Acid dianhydride, 2,3,3 ', 4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3 '-two Phenyl ether tetracarboxylic dianhydride, 2,3,3 ', 4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyphenyis)] hexafluoro third Double (dehydration the trimellitate) (trade names of alkane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides, ethylene glycol；TMEG-100, new Japan Physics and chemistry limited company), Tetramethylene. tetracarboxylic dianhydride, methyl cyclobutane tetracarboxylic dianhydride, Pentamethylene. tetracarboxylic dianhydride, hexamethylene Alkane tetracarboxylic dianhydride, ethane tetracarboxylic dianhydride and butane tetracarboxylic acid dianhydride.Can use these tetracarboxylic dianhydrides in one kind with On.
In these tetracarboxylic dianhydrides, more preferably the 3,3 ', 4 of good transparency are given to cured film, 4 '-sulfobenzide. tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyphenyis)] hexafluoropropane dianhydride, 1,2, 3,4- butane tetracarboxylic acid dianhydrides and TMEG-100, particularly preferred 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '- Sulfobenzide. tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides.
1-1-2. diamidogen
In the present invention, the materials'use diamidogen sour to obtain polyesteramide.The concrete example of preferred diamidogen can be enumerated： 4,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, double [4- (4- aminobenzene oxygen Base) phenyl] sulfone, double [4- (3- amino-benzene oxygens) phenyl] sulfones, double [3- (4- amino-benzene oxygens) phenyl] sulfones, [4- (4- aminobenzenes Epoxide) phenyl] [3- (4- amino-benzene oxygens) phenyl] sulfone, [4- (3- amino-benzene oxygens) phenyl] [3- (4- amino-benzene oxygens) benzene Base] double [4- (4- amino-benzene oxygens) phenyl] HFC-236fa of sulfone and 2,2-.Can be using one or more of these diamidogen.
In these diamidogen, more preferably the 3 of good transparency are given to cured film, 3 '-diamino diphenyl sulfone and double [4- (3- amino-benzene oxygens) phenyl] sulfone, particularly preferred 3,3 '-diamino diphenyl sulfone.
1-1-3. multi-hydroxy compounds
In the present invention, the materials'use multi-hydroxy compound sour to obtain polyesteramide.Preferred multi-hydroxy The concrete example of compound can be enumerated：Ethylene glycol, diethylene glycol, triethylene glycol, TEG, weight average molecular weight are 1,000 Following Polyethylene Glycol, Propylene Glycol, dipropylene glycol, tripropylene glycol, four Propylene Glycol, weight average molecular weight are less than 1,000 Polypropylene glycol, 1,2- butanediols, 1,3 butylene glycol, BDO, 1,2- pentanediols, 1,5-PD, 2,4- pentanediols, 1, 2,5- penta triols, 1,2- hexanediol, 1,6- hexanediol, 2,5- hexanediol, 1,2,6- hexanetriols, 1,2- heptandiols, 1,7- heptan two Alcohol, 1,2,7- heptan triol, 1,2- ethohexadiols, 1,8- ethohexadiols, 3,6- ethohexadiols, 1,2,8- pungent triols, 1,2- nonanediols, 1,9- Nonanediol, 1,2,9- nonyl triols, 1,2- decanediols, decamethylene-glycol, 1,2,10- last of the ten Heavenly stems triols, 1,2- dodecanediols, 1,12- Dodecanediol, glycerol, trimethylolpropane, tetramethylolmethane, dipentaerythritol, fulminuric acid three (2- hydroxyethyls) ester, Bisphenol-A (2,2- double (4- hydroxy phenyls) propane), bisphenol S (double (4- hydroxy phenyls) sulfones), Bisphenol F (double (4- hydroxy phenyls) first Alkane), double (4- hydroxy-cyclohexyls) propane of 2,2-, 4,4 '-dihydroxyl dicyclohexyl, diethanolamine and triethanolamine.Can use One or more of these multi-hydroxy compounds.
In these multi-hydroxy compounds, the ethylene glycol of the favorable solubility more preferably in reaction dissolvent, Propylene Glycol, 1, Double (the 4- hydroxy-cyclohexyls) third of 4- butanediols, 1,5-PD, 1,6- hexanediol, 1,7- heptandiols, 1,8- ethohexadiols, 2,2- Alkane, 4,4 '-dihydroxyl dicyclohexyl and fulminuric acid three (2- hydroxyethyls) ester, particularly preferred BDO, 1,5- penta Glycol and 1,6- hexanediol.
1-1-4. monohydroxy compound
In the present invention, the material to obtain polyesteramide acid can use monohydroxy compound.By using single hydroxyl Based compound, the storage stability that can make photosensitive composite is improved.The concrete example of preferred monohydroxy compound can be arranged Lift：Benzylalcohol, dihydroxypropane single-ether, propylene glycol monomethyl ether, DPE, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, hydroxyethyl methacrylate, terpineol (terpineol), 3- ethyls -3- hydroxymethyl oxetanes and dimethyl benzyl carbinol (dimethyl benzyl carbinol).Can be using one or more of these monohydroxy compounds.
More preferably benzylalcohol, hydroxyethyl methacrylate, dihydroxypropane single-ether and 3- second in these monohydroxy compounds Base -3- hydroxymethyl oxetanes.If it is considered that by the polyesteramide formed using these monohydroxy compounds acid with contain There is the compatibility in the case of polymer, epoxide and the epoxy curing agent mixing of epoxy radicals, or photosensitive composite exists Coating on colored filter, then monohydroxy compound is particularly preferably using benzylalcohol.
Relative to the weight portion of total amount 100 of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound, 0 weight is preferably comprised The monohydroxy compound of part～300 weight portions and reacted.More preferably 5 weight portion～200 weight portions.
1-1-5. styrene-maleic anhydride copolymer
And, the polyesteramide acid used in the present invention can have more than three anhydride with the addition in the raw material The compound of base and synthesize.Carry out as described above, the transparency that can make cured film is improved, therefore preferably.Have The example of the compound of more than three anhydride groups can be enumerated：Styrene-maleic anhydride copolymer.With regard to constituting styrene-Malaysia The ratio of each composition of acid anhydride copolymer, the mol ratio of phenylethylene/maleic anhydride is 0.5～4, preferably 1～3.Further and Speech, more preferably 1 or 2, particularly preferred 1.
The concrete example of styrene-maleic anhydride copolymer can be enumerated：SMA3000P, SMA2000P, SMA1000P (are business The name of an article；River crude oil limited company).The thermostability and alkali resistance that cured film is particularly preferably made in these commercially available products becomes good SMA1000P.
Contain 0 weight preferably with respect to the weight portion of total amount 100 of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound The styrene-maleic anhydride copolymer of amount part～500 weight portion.More preferably 10 weight portion～300 weight portions.
The siliceous monoamines of 1-1-6.
In the synthesis of polyesteramide acid, can be not undermine in the range of the purpose of the present invention, optionally comprising institute Used as raw material, the example of this kind of other raw materials can enumerate siliceous monoamine to other raw materials beyond stating.
The concrete example of the preferred siliceous monoamine used in the present invention can be enumerated：3- TSL 8330s, APTES, 3- amino propyl methyl dimethoxysilanes, 3-amino propyl methyl diethoxy silane, 4- aminobutyl trimethoxy silanes, 4- ammobutyltriethoxysilanes, 4- aminobutyl methyldiethoxysilanes, to ammonia Base phenyltrimethoxysila,e, p-aminophenyl triethoxysilane, p-aminophenyl methyl dimethoxysilane, p-aminophenyl Ylmethyl diethoxy silane, m-aminophenyl base trimethoxy silane and m-aminophenyl ylmethyl diethoxy silane.Can make With one or more of these siliceous monoamines.
In these siliceous monoamines, more preferably make cured film acid resistance become good APTES and P-aminophenyl trimethoxy silane, from from the viewpoint of acid resistance, the compatibility, particularly preferred 3- aminopropyls triethoxysilicane Alkane.
Preferably with respect to the weight portion of total amount 100 of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound, containing 0 weight The siliceous monoamine of part～300 weight portions.More preferably 5 weight portion～200 weight portions.
Solvent used in the synthetic reaction of 1-1-7. polyesteramides acid
Can enumerate to the concrete example of the solvent used in the synthetic reaction for obtaining polyesteramide acid：Diethylene glycol diformazan Ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetic acid esters, ethylene glycol monoethylether acetate, Propylene glycol methyl ether acetate, 3- methoxy methyl propionates, 3- ethoxyl ethyl propionates, ethyl lactate, Ketohexamethylene.These solvents In preferably propylene glycol methyl ether acetate, 3- methoxy methyl propionates or diethylene glycol methyl ethyl ether.
The synthetic method of 1-1-8. polyesteramides acid
Used in the present invention polyesteramide acid synthetic method be make in the solvent X mole of tetracarboxylic dianhydride, Y mole of diamidogen and multi-hydroxy compound Z molar reactives.Now, X, Y and Z are preferably set at following between these X, Y and Z The ratio that the relation of formula (1) and formula (2) is set up.If the scope, then polyesteramide acid dissolubility in a solvent is high, therefore The coating of compositionss is improved, and as a result can obtain the excellent cured film of flatness.
0.2≤Z/Y≤8.0 (1)
0.2≤(Y+Z)/X≤5.0 (2)
In formula (1), preferably 0.7≤Z/Y≤7.0, more preferably 1.0≤Z/Y≤5.0.And, in formula (2), preferably 0.5≤(Y+Z)/X≤4.0, more preferably 0.6≤(Y+Z)/X≤2.0.
It is believed that the polyesteramide acid used in the present invention is that under the cited reaction conditions, relative to Y+Z, surplus makes Under conditions of with X, the molecule than having amino or hydroxyl in end is generated superfluously has anhydride group (- CO-O- in end CO- molecule).It is right in order to react with the anhydride group of molecular end in the case where being reacted with the composition of this kind of monomer End is esterified, and can optionally add described monohydroxy compound.Reacted and institute by adding monohydroxy compound The polyesteramide acid for obtaining can improve the compatibility with epoxide and epoxy curing agent, and can improve comprising these compounds The coating of the photosensitive composite of the present invention.
And, in the case where being reacted with the composition of the monomer, in order to the anhydride group of molecular end reaction and Silylation is imported in end, siliceous monoamine can be added.If using containing polyesteramide acid, (the polyesteramide acid is by adding Plus siliceous monoamine is reacted and is obtained) photosensitive composite of the invention, then can improve gained cured film acid resistance. And, in the case where being reacted with the composition of the monomer, can also add monohydroxy compound and siliceous monoamine this two Person and reacted.
If using 100 weight relative to total 100 weight portions of tetracarboxylic dianhydride, diamidogen and multi-hydroxy compound Reaction dissolvent more than part, then reacting successfully is carried out, therefore preferably.Reaction with 40 DEG C～200 DEG C react 0.2 hour～ It is advisable within 20 hours.
Order reaction raw materials made an addition in response system is not particularly limited.I.e., it is possible to use any side below Method：Tetracarboxylic dianhydride and diamidogen and multi-hydroxy compound are added into reaction dissolvent simultaneously；Make diamidogen and multi-hydroxy After compound is dissolved in reaction dissolvent, add tetracarboxylic dianhydride；Tetracarboxylic dianhydride is set to react in advance with multi-hydroxy compound Afterwards, diamidogen is added in its product；Or after tetracarboxylic dianhydride is reacted in advance with diamidogen, add in its product Multi-hydroxy compound etc..
In the case where the siliceous monoamine is reacted, in the reaction of tetracarboxylic dianhydride and diamidogen and multi-hydroxy compound After end, after reactant liquor is cooled to into less than 40 DEG C, add siliceous monoamine, react 0.1 hour～6 hours at 10 DEG C～40 DEG C It is advisable.Furthermore, it is possible in the random time point addition monohydroxy compound of reaction.
The polyesteramide acid for synthesizing as mentioned above is represented comprising the construction unit and formula (4) represented by the formula (3) Construction unit, and its end is derived from tetracarboxylic dianhydride, the anhydride group of diamidogen or multi-hydroxy compound, the ammonia as raw material Additive beyond base or hydroxyl, or these compounds constitutes its end.By the way that comprising this kind of composition, hardening becomes good.
The weight average molecular weight of the polyesteramide acid of gained is preferably 1,000～200,000, more preferably 3,000～ 50,000.If being in these scopes, flatness and thermostability become good.
Weight average molecular weight in this specification is using gel permeation chromatography (Gel Permeation Chromatography, GPC) method (tubing string temperature：35 DEG C, flow velocity：The value of polystyrene conversion 1ml/min) obtained.Mark Accurate polystyrene uses polystyrene (for example, the Agilent Technologies (Agilent that molecular weight is 645～132,900 Technologies) polystyrene calibration set group (calibration kit) PL2010-0102 of limited company), tubing string Using PLgel MIXED-D (Agilent Technologies Co., Ltd.), it is possible to use tetrahydrofuran (Tetrahydrofuran, THF) it is measured as mobile phase.And, the weight average molecular weight of the commercially available product in this specification is catalogue (catalogue) record value.
1-2. has the compound of polymerism double bond
1-2-1. compounds with plural polymerism double bond in each molecule
The compound with polymerism double bond used in the present invention is not particularly limited, preferably in each molecule Compound with plural polymerism double bond.If the compound phase with polymerism double bond is for polyesteramide acid 100 weight portions and be 50 weight portion～300 weight portions, then develop after residual film ratio become it is good and preferred.
In the photosensitive composite of the present invention it is contained in each molecule with plural polymerism double bond Compound can be enumerated：Ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) Acrylate, TEG two (methyl) acrylate, Polyethylene Glycol two (methyl) acrylate, epichlorohydrin are modified ethylene glycol bisthioglycolate (methyl) acrylate, epichlorohydrin are modified the modified triethylene glycol two (methyl) of diethylene glycol two (methyl) acrylate, epichlorohydrin Acrylate, epichlorohydrin are modified TEG two (methyl) acrylate, epichlorohydrin modified poly (ethylene glycol) two (methyl) acrylic acid Ester, Propylene Glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, Four Propylene Glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, epichlorohydrin are modified Propylene Glycol two (methyl) third Olefin(e) acid ester, epichlorohydrin be modified modified tripropylene glycol two (methyl) acrylate of dipropylene glycol two (methyl) acrylate, epichlorohydrin, Epichlorohydrin is modified four Propylene Glycol two (methyl) acrylate, epichlorohydrin modified polypropylene glycol two (methyl) acrylate, three hydroxyl first Base propane three (methyl) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, epoxy pronane modification Trimethylolpropane tris (methyl) acrylate, epichlorohydrin are modified trimethylolpropane tris (methyl) acrylate, two-three hydroxyl first Base propane four (methyl) acrylate, glycerol (methyl) acrylate, glycerol two (methyl) acrylate, glycerol three (methyl) third Olefin(e) acid ester, epichlorohydrin modified glycerol three (methyl) acrylate, 1,6- hexanediol two (methyl) acrylate, epichlorohydrin modified 1, 6- hexanediol two (methyl) acrylate, two (methyl) methoxyethyl cyclohexyls, neopentyl glycol two (methyl) acrylic acid Ester, 3-hydroxypivalic acid neopentyl glycol two (methyl) acrylate, (methyl) third of caprolactone modification 3-hydroxypivalic acid neopentyl glycol two Olefin(e) acid ester, two glycerol four (methyl) acrylate, the oxide-modified acrylate of two glycerol epoxies, tetramethylolmethane three (methyl) propylene Acid esters, tetramethylolmethane four (methyl) acrylate, stearic acid modified tetramethylolmethane two (methyl) acrylate, dipentaerythritol five (methyl) acrylate, alkyl-modified dipentaerythritol five (methyl) acrylate, alkyl-modified dipentaerythritol four (methyl) Acrylate, alkyl-modified dipentaerythritol three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, caprolactone Modified dipentaerythritol six (methyl) acrylate, modified by polyacid (methyl) acrylate oligomers, two (methyl) acrylic acid alkene Propylated cyclohexyl, double [(methyl) acryloxy neopentyl glycol] adipate esters, bisphenol-A two (methyl) acrylate, epoxy Oxide-modified bisphenol-A two (methyl) acrylate, Bisphenol F two (methyl) acrylate, ethylene-oxide-modified Bisphenol F two (methyl) Acrylate, bisphenol S two (methyl) acrylate, ethylene-oxide-modified bisphenol S two (methyl) acrylate, BDO two It is (methyl) acrylate, 1,3 butylene glycol (methyl) acrylate, diacrylate bicyclopentyl ester, polyester diacrylate, poly- Ester triacrylate, polyester tetra acrylate, the acrylate of polyester five, polyester hexaacrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, ethylene-oxide-modified tricresyl phosphate (methyl) acrylate, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) propylene Acid esters, ethylene-oxide-modified tricresyl phosphate (methyl) acrylate, epichlorohydrin be modified phthalic acid two (methyl) acrylate, four Modified (the first of trimethylolpropane two of bromine bisphenol-A two (methyl) acrylate, triglycerin two (methyl) acrylate, neopentyl glycol Base) acrylate, the ethylene-oxide-modified diacrylate of fulminuric acid, ethylene-oxide-modified three acrylic acid of fulminuric acid Ester, caprolactone modification three [(methyl) acryloyl-oxyethyl] fulminuric acid ester, (methyl) acrylated fulminuric acid ester, Phenyl glycidyl ether acrylate/hexamethylene diisocyanate/carbamate prepolymer, phenyl glycidyl ether propylene Acid esters/toluene di-isocyanate(TDI)/carbamate prepolymer, pentaerythritol triacrylate/hexamethylene diisocyanate/ammonia Carbamate prepolymer, pentaerythritol triacrylate/toluene di-isocyanate(TDI)/carbamate prepolymer, tetramethylolmethane three Acrylate/isophorone diisocyanate/carbamate prepolymer, Dipentaerythritol Pentaacrylate/hexa-methylene two Isocyanates/carbamate prepolymer, the carbamate without xanthochromia type oligocarbamates acrylate and containing carboxylic acid Acrylate oligomer, epoxy acrylic oligomer ester etc..
The compound with plural polymerism double bond can be used alone the compound in each molecule, also may be used Mix two or more and use.
From the viewpoint of thermostability, the chemical-resistant of self-hardening film, there is plural polymerization in each molecule Preferably with trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylolmethane in the compound of property double bond Tetraacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, modified by polyacid (methyl) acrylic acid are few The ethylene-oxide-modified diacrylate of polymers, fulminuric acid, the ethylene-oxide-modified triacrylate of fulminuric acid, epoxy third Olefin(e) acid oligomer ester or these mixture.
Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, two seasons penta 4 The acrylate of alcohol five, dipentaerythritol acrylate, modified by polyacid (methyl) acrylate oligomers, fulminuric acid epoxy The ethylene-oxide-modified triacrylate of oxide-modified diacrylate, fulminuric acid, epoxy acrylic oligomer ester or these Mixture can use following etc commercially available products.The concrete example of trimethylolpropane trimethacrylate is Asia Luo Nisi (Aronix) M-309 (trade names；East Asia synthesizes limited company).Pentaerythritol triacrylate and tetramethylolmethane tetrapropylene The concrete example of the mixture of acid esters is Asia Luo Nisi (Aronix) M-306 (65 weight %～70 weight %), Asia Luo Nisi (Aronix) M-305 (55 weight %～63 weight %), Asia Luo Nisi (Aronix) M-303 (30 weight %～60 weight %), Sub- Luo Nisi (Aronix) M-452 (25 weight %～40 weight %) and Asia Luo Nisi (Aronix) M-450 are (less than 10 weights Measure %, be slightly designated as " M-450 " below) (it is trade name；Containing ratio in East Asia synthesis limited company, bracket is mixing The catalogue record value of the containing ratio of the pentaerythritol triacrylate in thing).Dipentaerythritol Pentaacrylate and two seasons penta 4 The concrete example of the mixture of the acrylate of alcohol six is Asia Luo Nisi (Aronix) M-403 (50 weight %～60 weight %), sub- sieve Nice (Aronix) M-400 (40 weight %～50 weight %), Asia Luo Nisi (Aronix) M-402 (30 weight %～40 weights Amount %, be slightly designated as " M-402 " below), Asia Luo Nisi (Aronix) M-404 (30 weight %～40 weight %), Asia Luo Nisi (Aronix) M-406 (25 weight %～35 weight %) and Asia Luo Nisi (Aronix) M-405 (10 weight %～20 weight %) (it is trade name；Containing ratio in East Asia synthesis limited company, bracket is the acrylic acid of dipentaerythritol five in mixture The catalogue record value of the containing ratio of ester).The concrete example of modified by polyacid (methyl) acrylate oligomers is Asia Luo Nisi (Aronix) M-510 and Asia Luo Nisi (Aronix) M-520 (are trade name；East Asia synthesizes limited company).Different trimerization The concrete example of the ethylene-oxide-modified diacrylate of cyanic acid is Asia Luo Nisi (Aronix) M-215 (trade names；East Asia synthesizes share Company limited).The ethylene-oxide-modified diacrylate of fulminuric acid and the ethylene-oxide-modified triacrylate of fulminuric acid The concrete example of mixture be Asia Luo Nisi (Aronix) M-313 (30 weight %～40 weight %) and Asia Luo Nisi (Aronix) M-315 (3 weight %～13 weight %, be slightly designated as " M-315 " below) (is trade name；East Asia synthesizes limited company, includes Containing ratio in number is that the catalogue of the containing ratio of the ethylene-oxide-modified diacrylate of fulminuric acid in mixture is recorded Value).The concrete example of epoxy acrylic oligomer ester is TEA-100 (trade names；KSM limited companies).
1-2-2. has a polymerism double bond in each molecule and has at least one to be selected from-OH in each molecule And the compound of the functional group in-COOH
From the viewpoint of self-analytic data, also can further contain in the photosensitive composite of the present invention and have in each molecule There is a polymerism double bond and there is the compound of at least one functional group in-OH and-COOH in each molecule.Such as Fruit has a polymerism double bond in each molecule and has at least one to be selected from-OH and-COOH in each molecule The compound phase of functional group is 1 weight portion～50 weight portion for polyesteramide 100 weight portions of acid, then analyticity become it is good and It is preferred that.
It is this kind of to there is a polymerism double bond in each molecule and have at least one to be selected from-OH in each molecule And the compound of the functional group in-COOH for example can be enumerated：(methyl) acrylic acid, (methyl) Hydroxyethyl Acrylate, (methyl) Hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate, (methyl) acrylic acid -2- hydroxyl -3- phenoxy-propyls, succinic acid - 2- (methyl) acryloyloxyethyl ester, hexahydrophthalic acid 2- (methyl) acryloyloxyethyl ester, phthalic acid -2- (first Base) acryloyloxyethyl ester, phthalic acid 2- (methyl) acryloyl-oxyethyl -2- hydroxy methacrylates, (methyl) acrylic acid -4- Hydroxy benzeness base ester, to hydroxyl (methyl) acrylic acid anilide, (methyl) acrylic acid -4- hydroxybutyls, Isosorbide-5-Nitrae-hexamethylene diformazan Alcohol list (methyl) acrylate, glycerol list (methyl) acrylate, acrylic acid -3- (2- hydroxy phenyls) esters and (methyl) propylene Acid-β-carboxyethyl.
In these compounds, (methyl) acrylic acid -4- hydroxy benzeness base ester and to hydroxyl (methyl) acrylic acid anilide Analyticity becomes good and preferred.
1-3. Photoepolymerizationinitiater initiater
As long as contained Photoepolymerizationinitiater initiater is can to make the polymerization of following compositionss in the photosensitive composite of the present invention Initiator, then be not particularly limited, and the compositionss contain polyesteramide acid, the compound with polymerism double bond, photopolymerization Initiator, epoxide, epoxy curing agent, molecular weight regulator.
Contained Photoepolymerizationinitiater initiater can be enumerated in the photosensitive composite of the present invention：Benzophenone, meter Qi Le ketone, 4, 4 '-bis- (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4- diethyl thioxanthenes Ketone, 2-ethyl-anthraquinone, 1-Phenylethanone., 2- hydroxy-2-methyl propiophenones, 2- hydroxy-2-methyls -4 '-cumene acetone, 1- hydroxyls Cyclohexyl-phenyl ketone, isopropyl benzoin ether, isobutyl group benzoin ether, 2,2- diethoxy acetophenones, 2,2- dimethoxy -2- Phenyl acetophenone, camphorquinone, benzanthrone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino propane -1- ketone is (for example, Trade name；Gorgeous good solid (IRGACURE) 907, Japanese BASF (BASF Japan) limited company), 2- benzyl -2- diformazans Base amino -1- (4- morphlinophenyls)-butanone -1 (for example, trade name；Gorgeous good solid (IRGACURE) 369, Japanese BASF (BASF Japan) limited company), EDMAB, 4- dimethylaminobenzoic acid isopentyl ester, 4, 4 '-two (tert-butyl hydroperoxide carbonyl) benzophenone, 3,4,4 '-three (tert-butyl hydroperoxide carbonyl) benzophenone, 1,2- pungent two Ketone -1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes) (for example, trade name；Gorgeous good solid (IRGACURE) OXE-01, day This BASF (BASF Japan) limited company), ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyls) -9- carbazole -3- Base]-, 1- (O- acetyl group oximes) (for example, trade name；Gorgeous good solid (IRGACURE) OXE-02, Japanese BASF (BASF Japan) Limited company), OXE-03 (for example, trade names；Japanese BASF (BASF Japan) limited company), 1,2- the third two Ketone -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- acetyl group oximes) (for example, trade name；Ai Dike sub-librarys Shandong Hereby (ADEKA ARKLS) NCI-930, Ai Dike (ADEKA) limited company), Ai Dike sub-librarys Shandong hereby (ADEKA ARKLS) NCI-831 (trade names；Ai Dike (ADEKA) limited company), Ai Dike Otto horses (ADEKA OPTOMER) N-1919 (trade name；Ai Dike (ADEKA) limited company), 2,4,6- trimethylbenzoyldiphenyl oxides, 2- (4 '- Methoxyl-styrene) -4,6- couple of (trichloromethyl)-s-triazine, 2- (3 ', 4 '-dimethoxy-styryl) -4,6- double (three Chloromethyl)-s-triazine, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- double (trichloromethyl)-s-triazine, 2- (2 '-methoxies Base styryl) -4,6- couple of (trichloromethyl)-s-triazine, 2- (4 '-amyl phenyl ether vinyl) -4,6- double (trichloromethyls)-equal Triazine, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- bis- (trichloromethyl)-s-triazine, 1,3- double (trichloromethyl) - 5- (2 '-chlorphenyl)-s-triazine, 1,3- double (trichloromethyl) -5- (4 '-methoxyphenyl)-s-triazine, 2- are (to dimethylamino Base styryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2- dredge base benzothiazole, 3,3 '-carbonyl Double (7- diethyl amino coumarins), 2- (Chloro-O-Phenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2- chlorine Phenyl) -4,4 ', 5,5 '-four (4- carboethoxyphenyls) -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4- Dichlorobenzene base) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2,2 '-bis- (2,4- dibromo phenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 2, 2 '-bis- (2,4,6- trichlorophenyls) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxaline, 3- (2- methyl -2- dimethylamino propionyl Base) carbazole, double (2- methyl -2- morpholino the propionos) -9- dodecyl carbazoles of 3,6-, 1- hydroxycyclohexylphenylketones and Double (η5- 2,4- cyclopentadiene -1- bases)-bis- (2,6- bis- fluoro- 3- (1H- pyrroles's -1- bases)-phenyl) titaniums etc..
Photoepolymerizationinitiater initiater can be used alone, and can also mix two or more and use.Expose oneself light when film sensitivity and From the viewpoint of the transparency of cured film, in Photoepolymerizationinitiater initiater, preferably alpha-amido benzene alkyl ketone system, acylphosphine oxide System, oxime ester system Photoepolymerizationinitiater initiater.In addition, in this manual, following thin film is referred to as into " film ", the thin film is by base The thin film preparation of the photosensitive composite formed using spin coating, printing and additive method on plate is dried (prebake conditions) and is obtained. The film after operation, by formal calcining (toasting afterwards) cured film is become through follow-up exposure-development-clean-be dried etc.. In this manual, " film " will be referred to as to the thin film in dry operation from the preparation heating, for example, by statement The film in which kind of stage of film formation process is represented for " film during exposure ", " film after development ".
From from the viewpoint of the transparency of the sensitivity of film and cured film, in Photoepolymerizationinitiater initiater, more preferably, 1,2- Octadione- 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes) or 1,2- propanedione -1- [4- [4- (2- hydroxyl-oxethyls) Thiophenyl] phenyl] -2- (O- acetyl group oximes) is more than 20 weight % relative to the gross weight of Photoepolymerizationinitiater initiater.And, such as Fruit is more than 50 weight %, then and then more preferably.Photoepolymerizationinitiater initiater also can only include 1,2- octadione- 1- [4- (thiophenyl) Phenyl] -2- (O- benzoyl oximes) or 1,2- propanedione -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- second Acyl group oxime).
1-4. molecular weight regulators
In order to suppress the molecular weight because of polymerization to uprise and show excellent analyticity, the photosensitive composite of the present invention Used in molecular weight regulator.Molecular weight regulator can be enumerated：Thio-alcohol, xanthan acids, quinones and 2,4- diphenyl -4- first Base -1- amylenes etc..
The concrete example of molecular weight regulator can be enumerated：HNQ, benzoquinone, 1,4-naphthoquinone, Isosorbide-5-Nitrae-dihydroxy naphthlene Quinone, 2,5- di-t-butyl hydroquinone, hydroquinone, methylnaphthohydroquinone, tertiary butylated hydroquinone, first quinone (methoquinone), 1,4-benzoquinone, methyl- 1,4-benzoquinone, tert-butyl-p-benzo-quinone, anthraquinone, n-hexyl mercaptan, n octylmercaptan, n-dodecyl mercaptan, tertiary dodecyl sulfur Alcohol, thioglycolic acid, dimethyl yellow ortho acid thioether, diisopropyl xanthic acid disulfide, 2,4- diphenyl -4-methyl-1-pentene Deng.
Molecular weight regulator can be used alone, and also can be combined using two or more.In molecular weight regulator, if naphthalene Quinone system molecular weight regulator, then from show from the aspect of excellent analyticity and it is preferred that.And, from after can suppress to parse From the aspect of cured film and ruffle near substrate it is also preferred that.So-called ruffle represents that near substrate non-analysis unit is projected To analysis unit.
In molecular weight regulator, if the HNQ with phenolic hydroxyl group, then the viewpoint of self-analytic data Consider and more preferably.And, from the viewpoint of self-analytic data, preferably, adjusted more than molecular weight with the content of Photoepolymerizationinitiater initiater 5.0 times of whole dose of content, the mode less than 30 times contain molecular weight regulator, more preferably, containing with Photoepolymerizationinitiater initiater Amount contains molecular weight regulator more than 5.1 times of content of molecular weight regulator, less than 20 times of mode.And then more preferably, Contain molecular weight in the way of the content of Photoepolymerizationinitiater initiater is more than 5.2 times of content of molecular weight regulator, less than 10 times to adjust Whole dose.
1-5. epoxide
Epoxide used in the present invention includes two～ten epoxy radicals, and weight average in each molecule Molecular weight is less than 3,000.By adding epoxide in the photosensitive composite of the present invention, the heat-resisting of cured film can be improved Property.If epoxide is 20 weight portion～150 weight portions relative to polyesteramide 100 weight portions of acid, flatness becomes It is good and preferred.
The preference of epoxide can be enumerated：3,4- 7-oxa-bicyclo[4.1.0 carboxylic acids -3 ', 4 '-epoxycyclohexanecarboxylate (example Such as, trade name；Sai Luo West Germany (Celloxide) 2021P, Daicel (Daicel) limited company), 1- methyl -4- (2- first Base oxiranyl) -7- oxabicyclos [4.1.0] heptane (for example, trade name；Sai Luo West Germany (Celloxide) 3000, contest Fine jade (Daicel) limited company), 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- (2,3- epoxies third Epoxide) phenyl] ethyl] phenyl] propane and 1,3- it is double [4- [1- [4- (2,3- glycidoxy) phenyl] -1- [4- [1- [4- (2, 3- glycidoxies) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propanol mixture, 2- [4- (2,3- epoxies Propoxyl group) phenyl] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] ethyls] phenyl] propane (for example, trade name； Tyke not (TECHMORE) VG3101L, general woods Tyke (Printec) limited company), 1,1,1- tri- (4- hydroxy phenyls) second Alkane triglycidyl ether (for example, trade name；JER 1032H60, limited company of Mitsubishi Chemical), double (the oxa- rings third of 1,3- Ylmethyl) -5- (2- acrylic) -1,3,5-triazines -2, double (the hydroxymethyl)-n-butyl alcohols of 4,6 (1H, 3H, 5H)-triketones, 2,2- 1,2- epoxy radicals -4- (2- oxiranyls) hexamethylene addition product (for example, trade name；EHPE-3150, Daicel (Daicel) limited company) etc..
1-6. epoxy curing agent
In the photosensitive composite of the present invention, in order that flatness, chemical-resistant are improved and use epoxy curing agent. Epoxy curing agent there are anhydride system sclerosing agent, amine system sclerosing agent, phenol system sclerosing agent, imidazoles system sclerosing agent, catalyst type hardening Thermonasty acid producing agent such as agent and sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salts etc., avoids coloring and the cured film of cured film certainly Thermostability from the viewpoint of, preferred anhydrides system sclerosing agent or imidazoles system sclerosing agent.
The concrete example of anhydride system sclerosing agent can be enumerated：Aliphatic dicarboxylic acid acid anhydride (for example, maleic anhydride, tetrahydrochysene O-phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydro trimellitic anhydride etc.), aromatic polycarboxylic acid Acid anhydride (for example, phthalic anhydride, trimellitic anhydride etc.).Cured film can be particularly preferably improved in these anhydride system sclerosing agents Thermostability and do not undermine deliquescent trimellitic anhydride and hexahydro trimellitic anhydride of the photosensitive composite to solvent.
The concrete example of imidazoles system sclerosing agent can be enumerated：2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenylimidazoles, 2- phenyl -4-methylimidazole, 2,3- dihydro -1H- pyrrolo-es [1,2-a] benzimidazoles, 1- cyano ethyl -2- undecyl imidazoles Trimellitate.Particularly preferably can improve the hardening of cured film and not undermine photosensitive composition in these imidazoles system sclerosing agents Deliquescent 2- undecyl imidazole of the thing to solvent.
The acid of 1-7. polyesteramides, the compound with polymerism double bond, Photoepolymerizationinitiater initiater, epoxide, epoxy are hard The ratio of agent and molecular weight regulator
In the photosensitive composite of the present invention, relative to polyesteramide 100 weight portions of acid, the change with polymerism double bond The ratio of compound is 20 weight portion～300 weight portions.If the ratio of the compound with polymerism double bond is the scope, resistance to The balance of residual film ratio is good after hot, flatness, chemical-resistant, development.If the compound with polymerism double bond is 100 The scope of weight portion～300 weight portion, then and then more preferably.
Relative to polyesteramide 100 weight portions of acid, the ratio of Photoepolymerizationinitiater initiater is 2 weight portion～60 weight portions.Expose oneself From the viewpoint of the sensitivity of the film of light time, preferably the ratio of Photoepolymerizationinitiater initiater is the scope.And, expose oneself light when From the viewpoint of the sensitivity of film and the transparency of cured film, in Photoepolymerizationinitiater initiater, if 1,2- octadione- 1- [4- (benzene Sulfenyl) phenyl] -2- (O- benzoyl oximes) or 1,2- propanedione -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- acetyl group oximes) is more than 20 weight %, then more preferably relative to the gross weight of Photoepolymerizationinitiater initiater.And, if 50 More than weight %, then and then more preferably.
In the photosensitive composite of the present invention, relative to polyesteramide 100 weight portions of acid, the ratio of epoxide is 20 weight portion～200 weight portions.If the ratio of epoxide be the scope, thermostability, flatness balance it is good.Such as Fruit epoxide is the scope of 20 weight portion～150 weight portions, then and then more preferably.
Epoxy curing agent is relative to the weight portion of epoxide 100, hardenable epoxy relative to the ratio of epoxide Agent is 0.1 weight portion～60 weight portion.For example, it is the addition in the case of anhydride system sclerosing agent with regard to epoxy curing agent, more Specifically, preferably with for epoxy radicals, the acid anhydride or carboxyl in epoxy curing agent become 0.1 times of equivalent～ The mode of 1.5 times of equivalents is added.Now, acid anhydride is calculated with divalent.If to become 0.15 times of equivalent～0.8 The mode of times equivalent adds acid anhydride or carboxyl, then chemical-resistant is further improved, therefore and then more preferably.
1-8. other compositions
In the photosensitive composite of the present invention, various additives can be added to improve coating homogeneity, cementability.Addition Agent mainly can be enumerated：Solvent, the levelling agent/surfactant of anion system, cation system, nonionic system, fluorine system or silicon systems, silicon The antioxidants such as the coupling agents such as alkane coupling agent, hindered phenol series, amine system of being obstructed, phosphorus system, chalcogenide compound.
1-8-1. solvent
In the photosensitive composite of the present invention, it is also possible to add solvent.Institute is any in the photosensitive composite of the present invention The solvent of addition preferably can dissolve polyesteramide acid, the compound with polymerism double bond, epoxide, epoxy curing agent etc. Solvent.The concrete example of the solvent is ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methoxyl group second Sour methyl ester, ethyl methoxyacetate, 2-Methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3- epoxide propanoic acid Methyl ester, 3- hydroxypropionates, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxies Base ethyl propionate, 2 hydroxy propanoic acid methyl ester, 2 hydroxy propanoic acid propyl ester, 2- methoxy methyl propionates, 2- methoxypropionates, 2- Methoxy propyl propyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- hydroxy-2-methyl methyl propionates, 2- hydroxyls Base -2 Methylpropionic acid ethyl ester, 2- methoxyl groups -2 Methylpropionic acid methyl ester, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, methyl pyruvate, Ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl ester, 2-Oxobutyric acid second Ester, 4- hydroxy-4-methyl-2-pentanones, BDO, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, Propylene Glycol list second Ether acetic acid ester, propylene glycol monopropyl ether acetass, ethylene glycol monomethyl ether acetate, Ketohexamethylene, Ketocyclopentane, diethylene glycol monomethyl ether, Diethylene glycol monomethyl ether acetass, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, diethyl Glycol monobutyl ether acetass, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether.Solvent can be with It is one kind of these solvents, or the two or more mixture of these solvents.
1-8-2. surfactant
In the photosensitive composite of the present invention, surfactant can also be added to improve coating homogeneity.Live on surface The concrete example of property agent can be enumerated：Pohle not Lip river (Polyfllow) No.45, Pohle not Lip river (Polyflow) KL-245, Pohle not Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) No.90, Pohle not Lip river (Polyflow) No.95 (is trade name；Altogether Chemistry limited company of flourish society), Di Sipabike (Disperbyk) 161, Di Sipabike (Disperbyk) 162, Di Si Pa Bike (Disperbyk) 163, Di Sipabike (Disperbyk) 164, Di Sipabike (Disperbyk) 166, Di Sipa Bi Ke (Disperbyk) 170, Di Sipabike (Disperbyk) 180, Di Sipabike (Disperbyk) 181, Di Sipabi Gram (Disperbyk) 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (are trade name；Japanese Bi Ke chemistry (BYK Chemie Japan) limited company), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (are trade name；The limited public affairs of SHIN-ETSU HANTOTAI's chemical industry share Department), Sha Fulong (Surflon) SC-101, Sha Fulong (Surflon) KH-40, Sha Fulong (Surflon) S611 (be commodity Name；AGC beautifies clearly (AGC Seimi Chemical) limited company), Fu Jite (Ftergent) 222F, Fu Jite (Ftergent) 208G, Fu Jite (Ftergent) 251, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 601AD, Fu Jite (Ftergent) 602A, Fu Jite (Ftergent) 650A, FTX-218 (are trade name；Ni Aosi (Neos) limited company), Ai Futuo (EFTOP) EF- 351st, Ai Futuo (EFTOP) EF-352, Ai Futuo (EFTOP) EF-601, Ai Futuo (EFTOP) EF-801, Ai Futuo (EFTOP) EF-802 (is trade name；Mitsubishi Materials (Mitsubishi Material) limited company), Mei Jiafa (Megafac) F-171, Mei Jiafa (Megafac) F-177, Mei Jiafa (Megafac) F-410, Mei Jiafa (Megafac) F-430, Mei Jiafa (Megafac) F-444, Mei Jiafa (Megafac) F-472SF, Mei Jiafa (Megafac) F-475, Mei Jiafa (Megafac) F- 477th, Mei Jiafa (Megafac) F-552, Mei Jiafa (Megafac) F-553, Mei Jiafa (Megafac) F-554, Mei Jiafa (Megafac) F-555, Mei Jiafa (Megafac) F-556, Mei Jiafa (Megafac) F-558, Mei Jiafa (Megafac) F- 559th, Mei Jiafa (Megafac) R-30, Mei Jiafa (Megafac) R-94, Mei Jiafa (Megafac) RS-75, Mei Jiafa (Megafac) RS-72-K, Mei Jiafa (Megafac) RS-76-NS, Mei Jiafa (Megafac) DS-21 (is trade name；Enlightening is liked Raw (DIC) limited company), Di Gaotun (TEGO Twin) 4000, Di Gaotun (TEGO Twin) 4100, Di Gaofuluo (TEGO Flow) 370, Di Gaoge Riders (TEGO Glide) 420, Di Gaoge Riders (TEGO Glide) 440, Di Gaoge Riders (TEGO Glide) 450, the high rad of enlightening (TEGO Rad) 2200N, the high rad of enlightening (TEGO Rad) 2250N (are trade name, day This win create Degussa (Evonik-Degussa Japan) limited company), fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, Fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl glycine betaine, fluoroalkyl sulfonate, (the fluoroalkyl polyoxy second of two glycerol four Alkene ether), fluoroalkyl leptodactyline, fluoroalkyl sulfamate, ethylene nonyl phenyl ether, polyoxyethylene octylphenyl Ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxy second Alkene cetyl ether, polyoxyethylene stearyl base ether, polyoxyethylene laurate, polyoxyethylene oleate, Myrj 45, Polyoxyethylene laural base amine, sorbitol anhydride laurate, sorbitol anhydride cetylate, sorbitan tristearate, sorbitol anhydride It is oleate, sorbitan carboxylic esterses, polyoxyethylene sorbitol acid anhydride laurate, polyoxyethylene sorbitol acid anhydride cetylate, poly- Oxygen ethylene sorbitan tristearate, polyoxyethylene sorbitol acid anhydride oleate, Polyethylene oxide naphthyl ether, alkylbenzenesulfonate and Alkyl diphenyl base ether disulfonate.Preferably use at least one in these compounds.
In these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Sha Fulong (Surflon) S611, Fu Jite (Ftergent) 710FL, Fu Jite (Ftergent) 710FM, Fu Jite (Ftergent) 710FS, Fu Jite (Ftergent) 601AD, Fu Jite (Ftergent) 650A, Mei Jiafa (Megafac) F- 477th, Mei Jiafa (Megafac) F-556, Mei Jiafa (Megafac) F-559, Mei Jiafa (Megafac) RS-72-k, Mei Jiafa (Megafac) DS-21, Di Gaotun (TEGO Twin) 4000, fluoroalkyl benzene sulfonate, fl muoroalkyl's salt, fluoroalkyl polyoxy second At least one in alkene ether, fluoroalkyl sulfonate, fluoroalkyl leptodactyline and fluoroalkyl sulfamate, then photonasty group The coating homogeneity of compound is uprised, therefore preferably.
The content of the surfactant in the photosensitive composite of the present invention is preferably with respect to photosensitive composite total amount For 0.01 weight %～10 weight %.
1-8-3. coupling agent
From from the viewpoint of making formed cured film further improve with the adhesion of substrate, the photonasty group of the present invention Compound can also further contain coupling agent.
This kind of coupling agent can for example use the coupling agent of silane system, aluminum system or titanate esters system.Specifically can enumerate：3- Glycidoxypropyl dimethylethoxysilane, 3- glycidoxypropyl diethoxy silanes, 3- shrink sweet Oily epoxide propyl trimethoxy silicane (for example, trade name；Sa Laaisi (Sila-Ace) S510, prompt grace intelligence (JNC) share are limited Company), 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane (for example, trade name；Sa Laaisi (Sila-Ace) S530, Prompt grace intelligence (JNC) limited company), 3-mercaptopropyi trimethoxy silane (for example, trade name；Sa Laaisi (Sila- Ace) S810, prompt grace intelligence (JNC) limited company), the copolymer (example of 3- glycidoxypropyltrimewasxysilanes Such as, trade name；Examine special Olso (CoatOSil) MP200, step figure new high-tech material (Momentive Performance Materials) limited company) etc. silane series coupling agent, the aluminium system coupling agent such as acetyl alkoxyl aluminum-diisopropoxide and four different The titanate esters system coupling agents such as double (dioctyl phosphito ester) titanate esters of propyl group.
In these coupling agents, 3- glycidoxypropyltrimewasxysilanes are because the effect for lifting adhesion is big It is preferred that.
The content of coupling agent is more than 0.01 weight %, below 10 weight % relative to photosensitive composite total amount, can The adhesion of the formed cured film of raising and substrate, therefore it is preferred that.
1-8-4. antioxidant
Pick up by oneself high transparent, prevent from the viewpoint of cured film exposure xanthochromia in the event of high temperatures, the sense of the present invention Photosensitiveness compositionss can also further contain antioxidant.
Hindered phenol series, amine system of being obstructed, phosphorus system, chalcogenide compound etc. can also be added in the photosensitive composite of the present invention to resist Oxidant.Wherein, from from the viewpoint of weatherability, preferred hindered phenol series.Concrete example can be enumerated：Easy fine jade Jia Nuosi (kganox) 1010th, Yi Lu Jia Nuosi (Irganox) FF, Yi Lu Jia Nuosi (Irganox) 1035, Yi Lu Jia Nuosi (Irganox) 1035FF, Easily fine jade Jia Nuosi (Irganox) 1076, Yi Lu Jia Nuosi (Irganox) 1076FD, Yi Lu Jia Nuosi (Irganox) 1076DWJ, Easy fine jade Jia Nuosi (Irganox) 1098, Yi Lu Jia Nuosi (Irganox) 1135, Yi Lu Jia Nuosi (kganox) 1330, Yi Lujia Northey (Irganox) 1726, the good promise of Yi Lu Jia Nuosi (Irganox) 1425WL, Yi Lu Jia Nuosi (Irganox) 1520L, Yi Lu This (Irganox) 245, Yi Lu Jia Nuosi (Irganox) 245FF, Yi Lu Jia Nuosi (Irganox) 245DWJ, Yi Lu Jia Nuosi (Irganox) 259, Yi Lu Jia Nuosi (Irganox) 3114, Yi Lu Jia Nuosi (kganox) 565, Yi Lu Jia Nuosi (Irganox) 565DD, Yi Lu Jia Nuosi (Irganox) 295 (is trade name；Japanese BASF (BASF Japan) share has Limit company), Ai Di Coase tower ripple (ADK STAB) AO-20, Ai Di Coase tower ripple (ADK STAB) AO-30, Ai Di Coase tower ripples (ADK STAB) AO-50, Ai Di Coase tower ripple (ADK STAB) AO-60, Ai Di Coase tower ripple (ADKSTAB) AO-70, Ai Dike Si Tabo (ADK STAB) AO-80 (is trade name；Ai Dike (ADEKA) limited company).Wherein more preferably easy fine jade is good Northey (Irganox) 1010, Ai Di Coase tower ripple (ADK STAB) AO-60.
Relative to photosensitive composite total amount, add the antioxidant of 0.1 weight portion～10 weight portion and use.
1-8-5. other additives
The photosensitive composite of the present invention can also further containing following polymer, (hereinafter sometimes referred to " free radical be common Poly polymer "), the polymer be make free-radical polymerised compound (a1) represented by following formula (6), with alkoxyl silicone The free-radical polymerised compound (a2) of alkyl and with epoxy radicals, carboxyl, hydroxy phenyl at least one radical polymerization Property compound (a3) carries out free-radical polymerized forming.
(R8For hydrogen or methyl, R9～R12For the alkyl of carbon number 1～5, R13For the alkyl of carbon number 1～10, m be 1～10 it is whole Number, n is 1～150 integer)
1-8-5-1. free-radical polymerised compounds (a1)
Free-radical polymerised compound (a1) represented by formula (6) plays a role as surfactant, therefore passes through (a1) is used in raw material, and makes free-radical polymerized polymer play a role as surfactant, even if not adding in addition Surfactant, is improved also can flatness, the adhesion to basal substrate, coating.By adding radical polymerization Property compound (a1), free-radical polymerized polymer becomes easily to be come to the surface on film surface.
In the present invention, in the free-radical polymerised compound (a1) represented by formula (6), preferably R8 be hydrogen or methyl, R9～R12For methyl, R13For integer that the alkyl of carbon number 1～10, m are 1～5, the compound of the integer that n is 1～150.More preferably For R8For methyl, R9～R12For methyl, R13For the compound that butyl, m are the integer that 3, n is 1～150, and and then more preferably n For the compound of 30～70 integer, particularly preferably n is the compound of 50～70 integer.Free radical represented by formula (6) The weight average molecular weight of polymerizable compound (a1) is preferably 500～8000.
Free-radical polymerised compound (a1) can be manufactured by known method.And, it is possible to use commercially available product.Example Such as, FM-0711, FM-0721, FM-0725 can be enumerated and (is trade name；Prompt grace intelligence (JNC) limited company) etc..
1-8-5-2. has the free-radical polymerised compound (a2) of alkoxysilane group
In the present invention, by the free-radical polymerised compound (a2) with alkoxysilane group be used as to obtain it is described from By the raw material of base copolymerized polymer.Preferred free-radical polymerised compound (a2) is selected from 3- (methyl) acryloxy third Base trimethoxy silane, 3- (methyl) acryloxypropyl triethoxysilane, 3- (methyl) acryloxypropyl Dimethoxysilane, 3- (methyl) acryloxypropyl diethoxy silane, vinyltrimethoxy silane, vinyl One or more of triethoxysilane, the group that styryl trimethoxy silane is constituted.These are free-radical polymerised In compound, 3- (methyl) acryloxypropyl trimethoxy silane, 3- (methyl) acryloxypropyl triethoxysilicane The flatness of alkane is good and preferred.It is improved by using (a2), the transparency, chemical-resistant etc..And, by silane idol Connection effect, is improved with the adhesion of base material.
1-8-5-3. has at least one free-radical polymerised compound (a3) of epoxy radicals, carboxyl, hydroxy phenyl
In the present invention, by with epoxy radicals, carboxyl, hydroxy phenyl at least one free-radical polymerised compound (a3) As the raw material to obtain the free-radical polymerized polymer.Preferred free-radical polymerised compound (a3) is to be selected from (methyl) glycidyl acrylate, 4- hydroxybutyls (methyl) acrylate glycidyl ether, (methyl) acrylic acid, 4- hydroxyls One or more of group that phenyl vinyl ketone is constituted.(a3) as polymer cross-linking agent and function, contribute to The raising of thermostability, chemical-resistant etc..
The manufacture method of the free-radical polymerized polymer of 1-8-5-4.
Free-radical polymerized polymer is by making free-radical polymerised compound (a1) represented by formula (6), with alcoxyl The free-radical polymerised compound (a2) of base silane base and with epoxy radicals, carboxyl, hydroxy phenyl at least one free radical Polymerizable compound (a3) is carried out free-radical polymerized and obtained.There is no particular restriction for the manufacture method of free-radical polymerized polymer, The free-radical polymerised compound class can be heated in the presence of radical initiators and be manufactured free-radical polymerized poly- Compound.Radical initiator can be using organic peroxide, azo-compound etc..Free-radical polymerized reaction temperature has no especially Limit, usually 50 DEG C～150 DEG C of scope.Response time is also not particularly limited, the scope of usually 1 hour～48 hours. And, under the arbitrary pressure of pressurization, decompression or atmospheric pressure, can carry out the reaction.
Solvent used in described free radicals copolymerization reaction is preferably the solvent for dissolving generated polymer.Should The concrete example of solvent is ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methoxy menthyl acetate, first Ethoxyacetic acid ethyl ester, 2-Methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3- epoxide methyl propionates, 3- hydroxyls Base ethyl propionate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxy-propionic acid second Ester, 2 hydroxy propanoic acid methyl ester, 2 hydroxy propanoic acid propyl ester, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls Propyl propionate, 2- ethoxypropanoates, 2- ethoxyl ethyl propionates, 2- hydroxy-2-methyl methyl propionates, 2- hydroxy-2-methyls Ethyl propionate, 2- methoxyl groups -2 Methylpropionic acid methyl ester, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, methyl pyruvate, acetone acid second Ester, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl ester, 2-Oxobutyric acid ethyl ester, 4- hydroxyls- 4-methyl-2 pentanone, BDO, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetass, ethylene glycol monomethyl ether acetate, Ketohexamethylene, Ketocyclopentane, diethylene glycol monomethyl ether, diethylene glycol list Methyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetic acid esters, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetass, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether.Solvent can be these solvents One kind, or these solvents two or more mixture.
With regard to the free-radical polymerized polymer used in the present invention, the solvent used in polymerization can be made directly to remain And the free-radical polymerized polymer solution in view of operability etc. is made, or the solvent can also be removed and make and consider The free-radical polymerized polymer of the solid shape of carrying property etc..
If free-radical polymerized polymer by the gel permeation chromatography (gel with polystyrene as standard Permeation chromatography, GPC) analysis and the weight average molecular weight obtained for 1,000～50,000 model Enclose, then film property is good and preferred.Further, if weight average molecular weight for 2,500～20,000 scope, then cured film Flatness is well and more preferably.Further, if weight average molecular weight is 2,500～15,000 scope, then cured film is flat Smooth property, chemical-resistant are good and particularly preferred.
Relative to photosensitive composite total amount, add other additives of 0.1 weight portion～20 weight portion and use.
The preservation of 1-9. photosensitive composites
If the photosensitive composite of the present invention is preserved in the range of -30 DEG C～25 DEG C, stablize during the Jing of compositionss Property become it is good and preferred.If storage temperature is -20 DEG C～10 DEG C, have no precipitate and more preferably.
2. the cured film by obtained by photosensitive composite
The photosensitive composite of the present invention can be obtained in the following way：By polyesteramide acid, with polymerism pair The compound of key, epoxide, epoxy curing agent and molecular weight regulator are mixed, and according to target property, are further regarded Need and selectivity addition solvent, coupling agent, surfactant and other additives, these compounds are equably mixed into molten Solution.
If will as mentioned above and the photosensitive composite for preparing (and in the case of solvent-free solid state, is dissolved in After in solvent) it is coated on matrix surface, solvent is removed for example, by heating etc., then can form film.In matrix table Face coating photosensitive composite can use spin-coating method, rolling method, infusion process, flexographic printing process, nebulization and slot coated method Etc. existing known method.Secondly, the film is heated using heating plate (hot plate) or baking oven (oven) etc. (pre- Baking).Heating condition is different because of the species and allotment ratio of each composition, generally at 70 DEG C～150 DEG C, if using baking oven It it is 1 minute～5 minutes if using heating plate for 5 minutes～15 minutes.
Thereafter, be situated between every desired pattern form mask to film irradiation ultraviolet radiation.Suitably ultraviolet irradiation amount 5mJ/cm is calculated as with i rays2～1000mJ/cm2.The photosensitive composite of Jing ultraviolet irradiation is by with polymerism double bond Being polymerized as three-dimensional cross-linked body for compound, is carried out insoluble in alkaline-based developer.
Secondly, film be impregnated in into alkaline development by spraying development, spray development, covering liquid development, immersion development etc. In liquid, by unwanted removing is partly dissolved.The concrete example of alkaline-based developer is the nothings such as sodium carbonate, sodium hydroxide, potassium hydroxide The aqueous solution of machine bases, and the aqueous solution of the organic bases such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide.And, also may be used Add methanol, ethanol and surfactant of appropriate amount etc. in the alkaline-based developer and use.
Finally, in order that film is fully hardened, cured film can be obtained by heat treated, the heat treated be At 180 DEG C～250 DEG C, preferably 200 DEG C～250 DEG C, if baking oven is then carried out 30 minutes～90 minutes, if heating plate is then Carry out 5 minutes～30 minutes.
As mentioned above and the cured film of gained in heating, and then 1) the partially dehydrated cyclisation of polyamic acid of polyesteramide acid And imide bond is formed, and 2) carboxylic acid and the polymer reaction containing epoxy radicals of polyesteramide acid and molecular weight, therefore It is very tough, and the transparency, thermostability, chemical-resistant, flatness, adhesion, light resistance and resistant sputtering are excellent.Therefore, The cured film of the present invention is then effective used as the protecting film of colored filter, it is possible to use the colored filter is manufacturing liquid Crystal display element or solid-state imager.And, in addition to the protecting film of colored filter, if the cured film of the present invention As the transparent insulating film being formed between TFT and transparency electrode or the transparent insulation that is formed between transparency electrode and alignment films Film is then effective.Further, even if protecting film of the cured film of the present invention as LED illuminator is also effective.
[embodiment]
Secondly, the present invention is illustrated by synthesis example, reference example, embodiment and comparative example, but the present invention is simultaneously Any restriction of these embodiments is not received.First, as shown below synthesis includes tetracarboxylic dianhydride, diamidogen, multi-hydroxy compound Deng product polyesteramide acid solution (synthesis example 1, synthesis example 2, synthesis example 3, synthesis example 4, synthesis example 5, synthesis example 6 And synthesis example 7).
The synthesis of [synthesis example 1] polyesteramide acid solution (A1)
In the four-hole boiling flask with blender, being loaded with following weight has carried out the 3- methoxypropionic acid first of dehydration and purification Ester (being slightly designated as below " MMP "), 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride (being slightly designated as below " ODPA "), Isosorbide-5-Nitrae-fourth two Alcohol, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 130 DEG C.
Thereafter, reactant liquor is cooled to into 25 DEG C, with following weight input 3,3 '-diamino diphenyl sulfone (is slightly designated as below " DDS "), MMP, carry out at 20 DEG C～30 DEG C 2 hours stirring after, carry out at 115 DEG C 1 hour stir.
DDS 29.33g
MMP 183.04g
[Z/Y=3.0, (Y+Z)/X=0.8]
Solution is cooled to into room temperature, 30 weight % solution (A1) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (A1) is 4,200.
The synthesis of [synthesis example 2] polyesteramide acid solution (A2)
In the four-hole boiling flask with blender, sequentially loaded with following weight carried out the MMP of dehydration and purification, ODPA, 2,2- double (4- hydroxy-cyclohexyls) propane, benzylalcohols, flow down in drying nitrogen, carry out 3 hours stirring at 130 DEG C.
Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, MMP is put into following weight, at 20 DEG C～30 DEG C 2 hours are carried out After stirring, carry out 2 hours stirring at 130 DEG C.
DDS 24.50g
MMP 174.07g
[Z/Y=3.0, (Y+Z)/X=0.8]
Solution is cooled to into room temperature, 30 weight % solution (A2) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (A2) is 4,000.
The synthesis of [synthesis example 3] polyesteramide acid solution (A3)
In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out the Propylene Glycol list first of dehydration and purification Ether acetic acid ester (being slightly designated as below " PGMEA "), 1,2,3,4- butane tetracarboxylic acid dianhydrides (being slightly designated as below " BT-100 "), 2,2- are double (4- hydroxy-cyclohexyls) propane, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 130 DEG C.
Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, MMP is put into following weight, at 20 DEG C～30 DEG C 2 hours are carried out After stirring, carry out 2 hours stirring at 130 DEG C.
DDS 30.80g
MMP 185.78g
[Z/Y=3.0, (Y+Z)/X=0.8]
Solution is cooled to into room temperature, 30 weight % solution (A3) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (A3) is 3,800.
The synthesis of [synthesis example 4] polyesteramide acid solution (A4)
In the four-hole boiling flask with blender, sequentially loaded with following weight carried out the MMP of dehydration and purification, ODPA, 2,2- double (4- hydroxy-cyclohexyls) propane, flow down in drying nitrogen, carry out 3 hours stirring at 130 DEG C.
MMP 483.84g
ODPA 187.78g
2,2- double (4- hydroxy-cyclohexyls) propane 72.75g
Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, MMP is put into following weight, at 20 DEG C～30 DEG C 2 hours are carried out After stirring, carry out 2 hours stirring at 130 DEG C.
DDS 9.47g
MMP 146.16g
[Z/Y=7.9, (Y+Z)/X=0.6]
Solution is cooled to into room temperature, 30 weight % solution (A4) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (A4) is 3,500.
The synthesis of [synthesis example 5] polyesteramide acid solution (B1)
In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out PGMEA, BT- of dehydration and purification 100th, SMA1000P (trade names；Styrene-maleic anhydride copolymer, river crude oil limited company), BDO, benzyl Alcohol, flows down in drying nitrogen, carries out 3 hours stirring at 125 DEG C.
Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, PGMEA is put into following weight, carry out 2 at 20 DEG C～30 DEG C little When stirring after, carry out at 125 DEG C 2 hours stir.
DDS 10.80g
PGMEA 148.63g
[Z/Y=2.7, (Y+Z)/X=0.9]
Solution is cooled to into room temperature, 30 weight % solution (B1) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (B1) is 10,000.
The synthesis of [synthesis example 6] polyesteramide acid solution (B2)
In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out PGMEA, BT- of dehydration and purification 100th, SMA1000P, BDO, benzylalcohol, flow down in drying nitrogen, carry out 3 hours stirring at 125 DEG C.
Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, PGMEA is put into following weight, carry out 2 at 20 DEG C～30 DEG C little When stirring after, carry out at 125 DEG C 2 hours stir.
DDS 3.53g
PGMEA 135.13g
[Z/Y=8.0, (Y+Z)/X=0.8]
Solution is cooled to into room temperature, 30 weight % solution (B2) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (B2) is 9,000.
The synthesis of [synthesis example 7] polyesteramide acid solution (B3)
In the four-hole boiling flask with blender, sequentially being loaded with following weight has carried out PGMEA, the diethyl of dehydration and purification Glycol methyl ethyl ether (being slightly designated as below " EDM "), ODPA, SMA1000P, BDO, benzylalcohol, flow down in drying nitrogen, Carry out 3 hours stirring at 120 DEG C.
Thereafter, reactant liquor is cooled to into 25 DEG C, DDS, MMP is put into following weight, at 20 DEG C～30 DEG C 2 hours are carried out After stirring, carry out 2 hours stirring at 120 DEG C.
DDS 12.72g
EDM 29.68g
[Z/Y=2.0, (Y+Z)/X=1.0]
Solution is cooled to into room temperature, 30 weight % solution (B3) of the polyesteramide acid of pale yellow transparent are obtained.To solution A part be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, gained is poly- The weight average molecular weight of compound (B3) is 21,000.
Secondly, following copolymer is synthesized as shown below as free-radical polymerized polymer, the copolymer is by making Free-radical polymerised compound (a1) represented by formula (6), the free-radical polymerised compound (a2) with alkoxysilane group, And with epoxy radicals, carboxyl, hydroxy phenyl at least one free-radical polymerised compound (a3) carry out it is free-radical polymerized and Obtain (synthesis example 8).
The synthesis of [synthesis example 8] free-radical polymerized polymer (D) solution
In the four-hole boiling flask with agitator, the carrying out that polymer solvent is loaded as with following weight dehydration and purification EDM, as free-radical polymerised compound (a1) FM-0721 (in formula (6), R8～R12For methyl, R13For butyl, m=3, N=66, weight average molecular weight：5,000, prompt grace intelligence (JNC) limited company), as with alkoxysilane group from By the 3- methacryloxypropyl trimethoxy silanes of base polymerizable compound (a2), as with epoxy radicals, carboxyl, hydroxyl The glycidyl methacrylate of at least one free-radical polymerised compound (a3) of base phenyl, and then with following weight The 2 of polymerization initiator are loaded as, double (2 Methylpropionic acid) dimethyl ester (V-601 of 2 '-azo；Trade name；With Wako Pure Chemical Industries stock Part company limited), flow down in drying nitrogen, carry out 2 hours stirring at 90 DEG C.
Solution is cooled to into room temperature, 33.3 weight % solution of the base copolymerized polymer (D) that gains freedom.One to solution Divide and be sampled, using gpc analysis (polystyrene standard) gravimetry mean molecule quantity.As a result, the free radical of gained is total to The weight average molecular weight of poly polymer (D) is 7,800.
[embodiment 1]
Nitrogen displacement is carried out to the detachable flask of the 1000ml with agitator, in the flask 131.74g is loaded Synthesis example 1 in gained polyesteramide acid solution (A1), the M- as the compound with polymerism double bond of 39.52g 520th, the 2- hydroxyls-Isosorbide-5-Nitrae-naphthalene as molecular weight regulator of NCI-930,1.10g as Photoepolymerizationinitiater initiater of 6.59g Quinone, the trimellitic anhydride as epoxy curing agent of VG3101L, 6.59g as epoxide of 52.69g (are omited below Be designated as " TMA "), as additive 2.47g 3- glycidoxypropyltrimewasxysilanes (for example, trade name；Sa La Ai Si (Sila-Ace) S510, prompt grace intelligence (JNC) limited company) and 1.48g Ai Di Coase tower ripple (ADK STAB) AO- 60 (trade names；Ai Dike (ADEKA) limited company), as solvent 187.71g carrying out dehydration and purification MMP and The EDM of 69.98g, carries out at room temperature 3hr stirrings so as to equably dissolve.Secondly, the Mei Jiafa of 0.13g is put into (Megafac) F-556 (trade names；Di Aisheng (DIC) limited company), carry out at room temperature 1 hour stirring, using membrane filtration Device (0.2 μm) is filtered and is prepared photosensitive composite.
10 seconds are lasted with 900rpm the photosensitive composite is spun on glass substrate, it is enterprising in 100 DEG C of heating plate 80 seconds prebake conditions of row.Secondly, in atmosphere, using proximity printing machine TME-150PRC (trade names；Open up Pu Kang (Topcon) stock Part company limited), and be exposed.Light exposure is using accumulative quantometer UIT-102 (trade names；Oxtail (USHIO) share has Limit company), optical receiver UVD-365PD (trade names；Oxtail (USHIO) limited company) it is measured and is set to 30mJ/ cm2.Using sodium carbonate. the buffer of sodium bicarbonate at 27 DEG C to exposure after film carry out 40 seconds covering liquid development after, profit After cleaning being carried out to film 20 seconds with pure water, using 100 DEG C of heating plates drying in 2 minutes is carried out.And then in an oven with 230 DEG C Toast after carrying out 30 minutes, obtain the glass substrate with cured film that thickness is 1.5 μm.
With regard to cured film obtained as described above, for residual film ratio after development, thermostability, the transparency, analyticity and flat Smooth property and evaluate characteristic.
[evaluation methodology of residual film ratio after development]
Device (trade name is determined using jump surface roughness fine shape；P-16, KLA-Tencor (KLA TENCOR) stock Part company limited) thickness after the front thickness of development and development is determined, and calculate residual film ratio (thickness × 100/ after development after developing Thickness before development).The situation that residual film ratio after development is more than 80% is evaluated as into zero, the residual film ratio after development is not enough 80% situation is evaluated as ×.
[evaluation methodology of thermostability]
The glass substrate with cured film of gained is carried out after the reheating of 1 hour at 250 DEG C, before determining heating Thickness after thickness and heating, using following calculating formulas residual film ratio is calculated.The measure of thickness uses P-16.It is residual after by heating Film rate is that more than 95% situation is evaluated as zero, situation of the residual film ratio after heating less than 95% is evaluated as ×.
Residual film ratio=(thickness before thickness/heating after heating) × 100
[evaluation methodology of the transparency]
In the glass substrate with cured film of gained, using UV, visible light near infrared spectrometer (trade name；V- 670th, Japanese light splitting limited company) wavelength that determines only cured film is the absorbance under the light of 400nm.It is by absorbance More than 95% situation is evaluated as zero, the situation less than 95% is evaluated as ×.
[making of analyticity evaluation substrate]
Secondly, last 10 seconds with 900rpm and photosensitive composite is spun on glass substrate, in 100 DEG C of heating plate Carry out 80 seconds prebake conditions.Secondly, in atmosphere, Jie is exposed every a width of 20 μm of the mask with hole and line pattern using proximity Ray machine TME-150PRC is exposed for 100 μm with exposing clearance.Light exposure is using accumulative quantometer UIT-102, optical receiver UVD-365PD is measured and is set to 30mJ/cm2.Using sodium carbonate. the buffer of sodium bicarbonate at 27 DEG C to exposure after Film is carried out after the covering liquid development of 40 seconds, and unexposed portion is removed.After cleaning being carried out to the film after development 20 seconds using pure water, Drying in 2 minutes is carried out using 100 DEG C of heating plates.And then toast after being carried out 30 minutes with 230 DEG C in an oven, obtain and carry film Thickness is the glass substrate of 1.5 μm of pattern-like cured film.
With regard to cured film obtained as described above, characteristic is evaluated for analyticity.
[evaluation methodology 1 of analyticity]
The glass substrate with pattern-like cured film of gained is observed using 1,000 times of optical microscope, and Evaluate and 20 μm wide corresponding holes of mask size and the analyticity of line pattern.The situation that hole and line pattern Jing are parsed is evaluated as "○", by situation about not parsing "×" is evaluated as.
[evaluation methodology 2 of analyticity]
Using SEM to the glass substrate with pattern-like cured film of gained and 20 μm wide corresponding holes of mask size The section in portion is observed, determine the bottom equivalent to substrate surface as shown in Figure 1 point footpath AB and in vertical direction away from The bottom surface of substrate surface is the aperture CD at 0.5 μm of position, and according to the value of CD/AB come evaluate cured film near substrate Ruffle.The value of CD/AB is less, and ruffle is more inhibited.Good state will be set to less than 1.1 and be evaluated as "○", by 1.1 with On be evaluated as "×".
[making of flatness evaluation substrate]
Secondly, the resin black being spun on photosensitive composite using maximum about 0.8 μm of jump for 10 seconds is lasted with 900rpm On pigment self-dispersible color optical filter (being slightly the designated as CF below) substrate of colour moment battle array, 80 seconds preliminary dryings are carried out in 100 DEG C of heating plate It is roasting.Secondly, using proximity printing machine TME-150PRC (trade names；Open up Pu Kang (Topcon) limited company) exposed Light.Light exposure is using accumulative quantometer UIT-102 (trade names；Oxtail (USHIO) limited company), optical receiver UVD- 365PD (trade names；Oxtail (USHIO) limited company) it is measured and is set to 30mJ/cm2.Using sodium carbonate. bicarbonate The buffer of sodium at 27 DEG C to exposure after film carry out 40 seconds covering liquid development after, cleaning 20 is carried out to film using pure water After second, using 100 DEG C of heating plates drying in 2 minutes is carried out.And then toast after being carried out 30 minutes with 230 DEG C in an oven, obtain CF with the cured film that thickness is 1.5 μm.
With regard to cured film obtained as described above, characteristic is evaluated for flatness.
[evaluation methodology of flatness]
Device (trade name is determined using jump surface roughness fine shape；P-16, KLA-Tencor (KLA TENCOR) stock Part company limited) determine obtained by the colored filter substrate with cured film cured film surface jump.Will be comprising black The situation of (being slightly designated as maximum jump below) less than 0.16 μm maximum of the jump between R, G, B pixel of matrix is evaluated as zero, More than 0.16 μm of situation is evaluated as ×.
[2～embodiment of embodiment 10]
According to the method for embodiment 1, with ratio (unit described in table 1：G) each composition mixed dissolution is felt Photosensitiveness compositionss.In addition, with regard to the abbreviation of the additive in 1～table of table 4, M-520, M-402 are represented with polymerism double bond Compound Asia Luo Nisi (Aronix) M-520, Asia Luo Nisi (Aronix) M-402 (are trade name；East Asia synthesis share is limited Company), NCI-930 represents Photoepolymerizationinitiater initiater Ai Dike sub-librarys Shandong hereby (ADEKA ARKLS) NCI-930 (trade names；Ai Dike (ADEKA) limited company), VG3101L represents epoxide Tyke not (TECHMORE) VG3101L (trade names；Pu Lin Tyke (Printec) limited company), TMA represents epoxy curing agent trimellitic anhydride, and S510 represents coupling agent Sa Laai This (Sila-Ace) S510 (trade name；Prompt grace intelligence (JNC) limited company), AO-60 represents antioxidant Ai Di Coase towers Ripple (ADK STAB) AO-60 (trade names；Ai Dike (ADEKA) limited company), F-556 represents surfactant Mei Jiafa (Megafac) F-556 (trade names；Di Aisheng (DIC) limited company), MMP represents solvent 3- methoxy methyl propionates, PGMEA represents solvent propylene glycol methyl ether acetate, and EDM represents diethylene glycol methyl ethyl ether.
Table 1
Unit [g]
[11～embodiment of embodiment 19]
According to the method for embodiment 1, with the ratio (unit of table 2：G) each composition mixed dissolution is obtained into photosensitive composition Thing.
Table 2
Unit [g]
[1～comparative example of comparative example 9]
According to the method for embodiment 1, with the ratio (unit of table 3：G) each composition mixed dissolution is obtained into photosensitive composition Thing.
Table 3
Unit [g]
[10～comparative example of comparative example 18]
According to the method for embodiment 1, with the ratio (unit of table 4：G) each composition mixed dissolution is obtained into photosensitive composition Thing.
Table 4
Unit [g]
Hereinafter, the evaluation result of the cured film of 1～embodiment of embodiment 10 is collected respectively and is recorded in table 5, will be implemented The evaluation result of the cured film of 11～embodiment of example 19 collects be recorded in table 6 respectively, by the hardening of 1～comparative example of comparative example 9 The evaluation result of film collects be recorded in table 7 respectively, and the evaluation result of the cured film of 10～comparative example of comparative example 18 is converged respectively In being always recorded in table 8.
Table 5
Table 6
Table 7
Table 8
It can be seen from the result shown in 5～table of table 8：The thermostability of the cured film of 1～embodiment of embodiment 10, the transparency, Flatness is excellent, and then all aspects of residual film ratio and analyticity obtain balance after comprising development.11～embodiment of embodiment 19 cured film is poor unlike 1～embodiment of embodiment 10 in addition to the meansigma methodss of flatness are bigger.On the other hand, compare All of each assessment item of the cured film of 1～comparative example of example 18 is not "○".The cured film of comparative example 1 and comparative example 10 Analyticity is poor, and after development film all dissolves the cured film of comparative example 2 and comparative example 11.The hardening of comparative example 3 and comparative example 12 Residual film ratio is low after the development of film, also observes the ruffle of cured film.Comparative example 4, comparative example 6, comparative example 8, comparative example 13, compare Example 15, the analyticity of the cured film of comparative example 17 are excellent, but residual film ratio is poor after developing.And, comparative example 5, comparative example 7, compare Residual film ratio no problem after example 9, comparative example 14, comparative example 16, the development of the cured film of comparative example 18, but analyticity is poor.As above institute State, using the acid of following polyesteramide, and the ratio of [content of the content of Photoepolymerizationinitiater initiater/molecular weight regulator] is this In the case of in bright scope, all characteristics can be met, the polyesteramide acid is derived from containing tetracarboxylic dianhydride, diamidogen and many Product of first hydroxy compounds as the raw material of required composition.
[industrial applicability]
Thermostability of cured film, the transparency, flatness and analyticity by obtained by the photosensitive composite of the present invention etc. are made Characteristic for optical material is excellent, since then from the aspect of, can be used as colored filter, LED light-emitting component and light receiving element Deng various optical materials etc. protecting film and be formed between TFT and transparency electrode and between transparency electrode and alignment films Transparent insulating film.

Claims (22)

1. a kind of photosensitive composite, it is comprising polyesteramide acid, the compound with polymerism double bond, photopolymerization initiation The compositionss of agent, epoxide, epoxy curing agent and molecular weight regulator；The photosensitive composite is characterised by：
Polyesteramide acid is derived from the ratio set up with the relation of following formula (1) and formula (2) comprising X mole of tetracarboxylic dianhydride, Y Mole diamidogen and Z mole of multi-hydroxy compound raw material product, with the structure list represented by following formula (3) Construction unit represented by unit and formula (4)；
Compound with polymerism double bond includes plural polymerism double bond in each molecule；
Epoxide includes two～ten epoxy radicals in each molecule, and weight average molecular weight is less than 3,000；
Relative to polyesteramide 100 weight portions of acid, the total amount of the compound with polymerism double bond is 20 weight portion～300 weight Part, the total amount of epoxide is 20 weight portion～200 weight portions, and the content of Photoepolymerizationinitiater initiater is more than molecular weight adjustment 5.0 times of the content of agent, less than 30 times；
0.2≤Z/Y≤8.0 (1)
0.2≤(Y+Z)/X≤5.0 (2)
In formula (3) and formula (4), R1Be from tetracarboxylic dianhydride remove two-CO-O-CO- residue, R2It is to remove from diamidogen Remove two-NH2Residue, R3It is the residue that two-OH are removed from multi-hydroxy compound.
2. photosensitive composite according to claim 1, it is characterised in that：Molecular weight regulator is selected from thio-alcohol, Huang One or more of ortho acid class, quinones, 2,4- diphenyl -4-methyl-1-pentene.
3. photosensitive composite according to claim 1, it is characterised in that：Molecular weight regulator is naphthoquinone class.
4. photosensitive composite according to claim 1, it is characterised in that：Molecular weight regulator is 2- hydroxyls-Isosorbide-5-Nitrae-naphthalene Quinone.
5. photosensitive composite according to claim 1, it is characterised in that：The material composition of polyesteramide acid is further wrapped Containing monohydroxy compound.
6. photosensitive composite according to claim 5, it is characterised in that：Monohydroxy compound is selected from isopropanol, alkene In propanol, benzylalcohol, hydroxyethyl methacrylate, dihydroxypropane single-ether and 3- ethyl -3- hydroxymethyl oxetanes one More than kind.
7. photosensitive composite according to any one of claim 1 to 5, it is characterised in that：The weight of polyesteramide acid Mean molecule quantity is 1,000～200,000.
8. photosensitive composite according to any one of claim 1 to 5, it is characterised in that：Tetracarboxylic dianhydride is to be selected from 3,3 ', 4,4 '-sulfobenzide. tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride, 2,2- [double (3,4- dicarboxyls Phenyl)] one kind in hexafluoropropane dianhydride, 1,2,3,4- butane tetracarboxylic acid dianhydrides and ethylene glycol double (dehydration trimellitate) More than.
9. photosensitive composite according to any one of claim 1 to 5, it is characterised in that：Diamidogen is selected from 3,3 '-two One or more of ADP base sulfone and double [4- (3- amino-benzene oxygens) phenyl] sulfones.
10. photosensitive composite according to any one of claim 1 to 5, it is characterised in that：Multi-hydroxy compound is Selected from ethylene glycol, Propylene Glycol, BDO, 1,5-PD, 1,6- hexanediol, 1,7- heptandiols, 1,8- ethohexadiols, 2,2- Double (4- hydroxy-cyclohexyls) propane, 4, the one kind in 4 '-dihydroxyl dicyclohexyl and fulminuric acid three (2- hydroxyethyls) ester More than.
11. photosensitive composites according to any one of claim 1 to 5, it is characterised in that：Relative to polymerism The gross weight of the compound of double bond, the compound with polymerism double bond contain it is more than 50 weight % selected from dipentaerythritol five Acrylate, dipentaerythritol acrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, different melamine One or more of the ethylene-oxide-modified triacrylate of acid and modified by polyacid (methyl) acrylate oligomers.
12. photosensitive composites according to any one of claim 1 to 5, it is characterised in that：Epoxide is to be selected from 3,4- 7-oxa-bicyclo[4.1.0 carboxylic acids -3 ', 4 '-epoxycyclohexanecarboxylate, 1- methyl -4- (2- methyl oxiranyls) -7- oxa-s are double Ring [4.1.0] heptane, 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] Ethyl] phenyl] double [4- [1- [4- (2,3- glycidoxy) phenyl] -1- [4- [1- [4- (2,3- the third oxygen of epoxy of propane and 1,3- Base) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propanol mixture, 2- [4- (2,3- glycidoxy) benzene Base] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] ethyls] phenyl] propane, 1,1,1- tri- (4- hydroxy phenyls) second Double (oxiranyl methyl) -5- (2- acrylic) -1,3,5-triazines -2 of alkane triglycidyl ether, 1,3-, 4,6 (1H, 3H, In 1,2- epoxy radicals -4- (2- oxiranyls) the hexamethylene addition product of double (the hydroxymethyl)-n-butyl alcohols of 5H)-triketone, 2,2- More than one.
13. photosensitive composites according to any one of claim 1 to 5, it is characterised in that：Photoepolymerizationinitiater initiater is choosing From one or more of alpha-amido benzene alkyl ketone system, acylphosphine oxide system, oxime ester system Photoepolymerizationinitiater initiater.
14. photosensitive composites according to any one of claim 1 to 5, it is characterised in that：Epoxy curing agent is to be selected from One or more of trimellitic anhydride, hexahydro trimellitic anhydride and 2- undecyl imidazoles.
15. photosensitive composites according to claim 5, it is characterised in that：Tetracarboxylic dianhydride be selected from 3,3 ', 4,4 '- One or more of diphenyl ether tetracarboxylic dianhydride and 1,2,3,4- butane tetracarboxylic acid dianhydrides；
Diamidogen is 3,3 '-diamino diphenyl sulfone；
Multi-hydroxy compound is BDO；
Monohydroxy compound is benzylalcohol；
Compound with polymerism double bond is selected from Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate and many One or more of first sour modified (methyl) acrylate oligomers；
Relative to the gross weight of Photoepolymerizationinitiater initiater, Photoepolymerizationinitiater initiater contain it is more than 50 weight % selected from 1,2- octadione- 1- [4- (thiophenyl) phenyl] -2- (O- benzoyl oximes), ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyls) -9- carbazoles - 3- yls] -, 1- (O- acetyl group oximes) and 1,2- propanedione -1- [4- [4- (2- hydroxyl-oxethyls) thiophenyl] phenyl] -2- (O- second One or more of acyl group oxime)；
Epoxide is selected from 2- [4- (2,3- glycidoxy) phenyl] -2- [4- [1,1- double [4- (2,3- the third oxygen of epoxy Base) phenyl] ethyl] phenyl] double [4- [1- [4- (2, the 3- glycidoxy) phenyl] -1- [4- [1- [4- (2,3- of propane and 1,3- Glycidoxy) phenyl] -1- Methylethyls] phenyl] ethyl] phenoxy group] -2- propanol mixture and 2- [4- (2,3- epoxies One or more of propoxyl group) phenyl] -2- [4- [1,1- double [4- (2,3- glycidoxy) phenyl] ethyls] phenyl] propane；
Epoxy curing agent is selected from one or more of trimellitic anhydride and 2- undecyl imidazoles；
Molecular weight regulator is HNQ, and is become more than molecular weight regulator with the content of Photoepolymerizationinitiater initiater 5.0 times of content, the mode less than 30 times contain molecular weight regulator；
Further contain selected from one or more of 3- methoxy methyl propionates and propylene glycol methyl ether acetate as solvent.
A kind of 16. cured films, it is characterised in that：It is the photosensitive composition by any one of according to claim 1 to 15 Thing and obtain.
A kind of 17. colored filters, it is characterised in that：It uses cured film according to claim 16 as protecting film.
A kind of 18. display elements, it is characterised in that：It uses colored filter according to claim 17.
A kind of 19. solid-state imagers, it is characterised in that：It uses colored filter according to claim 17.
A kind of 20. display elements, it is characterised in that：It is using cured film according to claim 16 as being formed in thin film Transparent insulating film between transistor AND gate transparency electrode.
A kind of 21. display elements, it is characterised in that：It is transparent as being formed in using cured film according to claim 16 Transparent insulating film between electrode and alignment films.
A kind of 22. LED illuminant hearts, it is characterised in that：It uses cured film according to claim 16 as guarantor Cuticula.
CN201610915919.2A 2015-10-21 2016-10-20 Photosensitive composition and application thereof Withdrawn CN106610565A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-207024 2015-10-21
JP2015207024 2015-10-21

Publications (1)

Publication Number Publication Date
CN106610565A true CN106610565A (en) 2017-05-03

Family

ID=58615095

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610915919.2A Withdrawn CN106610565A (en) 2015-10-21 2016-10-20 Photosensitive composition and application thereof

Country Status (4)

Country Link
JP (1) JP2017078856A (en)
KR (1) KR20170046585A (en)
CN (1) CN106610565A (en)
TW (1) TW201714966A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110007563A (en) * 2017-12-12 2019-07-12 奇美实业股份有限公司 Negative photosensitive resin constituent, clearance body, protective film and liquid crystal display element
CN110373080A (en) * 2018-04-12 2019-10-25 捷恩智株式会社 Thermosetting composition, cured film and colored filter

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG11201806952SA (en) * 2016-03-30 2018-09-27 Toray Industries Negative-type photosensitive resin composition, cured film, display device that includes the cured film, and production method therefor
CN110419001B (en) * 2017-03-21 2023-07-07 东丽株式会社 Photosensitive resin composition, photosensitive resin composition film, insulating film, and electronic component
JP2019211719A (en) * 2018-06-08 2019-12-12 Jnc株式会社 Liquid crystal element with insulating film, light control window, and manufacturing method
US20210395533A1 (en) * 2018-10-31 2021-12-23 Sumitomo Chemical Company, Limited Curable composition, film, laminated body, and display apparatus
CN114644897B (en) * 2022-03-17 2023-12-01 宁波启合新材料科技有限公司 Ultrathin conductive adhesive film and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003516A (en) * 2000-06-26 2002-01-09 Kanegafuchi Chem Ind Co Ltd Composition and photosensitive composition as well as cover layer film using the same
CN101620377A (en) * 2008-07-03 2010-01-06 富士胶片株式会社 Curing combination for nanometer stamping, condensate and method for producing the same, and members for liquid crystal display device
CN103282828A (en) * 2010-12-28 2013-09-04 太阳油墨制造株式会社 Photocurable resin composition
CN103365084A (en) * 2012-03-30 2013-10-23 太阳油墨制造株式会社 Photocurable resin composition, dry film, cured product and printed wiring board
CN104017482A (en) * 2013-03-01 2014-09-03 捷恩智株式会社 Thermosetting composition, lamination body, substrate, film, display device, and window material
CN104098756A (en) * 2013-04-08 2014-10-15 捷恩智株式会社 Thermosetting Composition, Curing Film, And Electronic Part Possessing Curing Film
CN104619512A (en) * 2012-09-20 2015-05-13 富士胶片株式会社 Original planographic printing plate, and plate making method
CN104804638A (en) * 2014-01-28 2015-07-29 捷恩智株式会社 Thermosetting composition, cured film and color filter

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002003516A (en) * 2000-06-26 2002-01-09 Kanegafuchi Chem Ind Co Ltd Composition and photosensitive composition as well as cover layer film using the same
CN101620377A (en) * 2008-07-03 2010-01-06 富士胶片株式会社 Curing combination for nanometer stamping, condensate and method for producing the same, and members for liquid crystal display device
CN103282828A (en) * 2010-12-28 2013-09-04 太阳油墨制造株式会社 Photocurable resin composition
CN103365084A (en) * 2012-03-30 2013-10-23 太阳油墨制造株式会社 Photocurable resin composition, dry film, cured product and printed wiring board
CN104619512A (en) * 2012-09-20 2015-05-13 富士胶片株式会社 Original planographic printing plate, and plate making method
CN104017482A (en) * 2013-03-01 2014-09-03 捷恩智株式会社 Thermosetting composition, lamination body, substrate, film, display device, and window material
CN104098756A (en) * 2013-04-08 2014-10-15 捷恩智株式会社 Thermosetting Composition, Curing Film, And Electronic Part Possessing Curing Film
CN104804638A (en) * 2014-01-28 2015-07-29 捷恩智株式会社 Thermosetting composition, cured film and color filter

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110007563A (en) * 2017-12-12 2019-07-12 奇美实业股份有限公司 Negative photosensitive resin constituent, clearance body, protective film and liquid crystal display element
CN110007563B (en) * 2017-12-12 2024-04-02 奇美实业股份有限公司 Negative photosensitive resin composition, spacer, protective film, and liquid crystal display element
CN110373080A (en) * 2018-04-12 2019-10-25 捷恩智株式会社 Thermosetting composition, cured film and colored filter
CN110373080B (en) * 2018-04-12 2022-05-17 捷恩智株式会社 Thermosetting composition, cured film and color filter

Also Published As

Publication number Publication date
KR20170046585A (en) 2017-05-02
JP2017078856A (en) 2017-04-27
TW201714966A (en) 2017-05-01

Similar Documents

Publication Publication Date Title
CN106610565A (en) Photosensitive composition and application thereof
CN105086316B (en) Thermosetting composition, cured film, colored filter, liquid crystal display cells, solid-state imager and LED illuminant heart
CN105607419A (en) Photosensitive composition and use thereof
CN106950800A (en) Photosensitive composition
CN104098756B (en) Thermoset composition, cured film and the electronic component with this cured film
EP2698389B1 (en) Photosensitive alkali-soluble resin, method of preparing the same, and color photosensitive resist containing the same
CN107778485A (en) Polyesteramide acid and the photosensitive composite containing it
CN104880908A (en) Photosensitive resin composition
CN105954972A (en) A photosensitive composition, a cured membrane, a color filter, a display element, a solid shooting element, a touch screen and an LED illuminant body
CN107629678A (en) Thermosetting composition, cured film, colored filter, liquid crystal display cells and touch panel device
CN106959576A (en) Photosensitive composite and its application
JP6048106B2 (en) Thermosetting resin composition
CN108628094A (en) Photosensitive composite, cured film, colored filter and electronic device
TWI643835B (en) Photosensitive resin composition and the usage thereof
CN106554618A (en) Thermosetting compositionss and application thereof
CN106010219A (en) THERMOSETTING RESIN COMPOSITION, hardened film and uses thereof
CN107722685A (en) Thermosetting composition, cured film and colored filter
CN108628097A (en) Photosensitive composite, cured film, colored filter, display element, solid-state imager and LED illuminant heart
CN108342044A (en) Photosensitive composite and application thereof
CN109423192A (en) Thermosetting composition, cured film and colored filter
CN108693706A (en) Photosensitive composite and its application
CN107589632A (en) Photosensitive composite and cured film
TWI774872B (en) Thermosetting composition, cured film and color filter
TWI783001B (en) Thermosetting compositions, hardened film and color filter
CN108535958A (en) Photosensitive composite, cured film, colored filter, interlayer dielectric and application type polarizer

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20170503