CN103376659B - Photosensitive polymer combination - Google Patents
Photosensitive polymer combination Download PDFInfo
- Publication number
- CN103376659B CN103376659B CN201310142849.8A CN201310142849A CN103376659B CN 103376659 B CN103376659 B CN 103376659B CN 201310142849 A CN201310142849 A CN 201310142849A CN 103376659 B CN103376659 B CN 103376659B
- Authority
- CN
- China
- Prior art keywords
- methyl
- solvent
- coated film
- photosensitive polymer
- acid
- 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.)
- Active
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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
Abstract
A kind of photosensitive polymer combination; containing (A) binder resin, (B) polymerizable compound, (C) polymerization initiator and cause auxiliary agent and (D) solvent; wherein; (A) weight average molecular weight of binder resin is 8; 000 or more, 100; 000 or less; (C) polymerization initiator and initiation auxiliary agent at least contain oxime compound, acylphosphine oxide compound and thioxanthones based compound, and solubility parameter of (D) solvent containing 70 mass of mass %~99 % in total solvent is 8.0~9.1 (cal/cm3)1/2Solvent, solubility parameter containing 1 mass of mass %~30 % in total solvent is 9.2~11.0 (cal/cm3)1/2Solvent.
Description
Technical field
The present invention relates to photosensitive polymer combinations.
Background technique
It recites a kind of photosensitive polymer combination in JP2010-140042-A, contains resin, optical polymerism chemical combination
Object, colorant, N- benzoyloxy -1- (4- Phenylsulfanylphenyl) -1- octanone -2- imines [trade name: IRGACURE (registrar
Mark) OXE-01], use propylene glycol monoethyl ether acetate as solvent.
For previous photosensitive polymer combination, there is the hardness of the pattern as made from the composition and viscosity not
Certain abundant situation.
The inventors of the present invention to solve the above-mentioned problems and study as a result, having found that the composition containing certain solvent can
To prepare the pattern with the hardness for being able to satisfy requirement and viscosity.
Summary of the invention
That is, the present invention provides following [1]~[11].
[1] a kind of photosensitive polymer combination causes containing (A) binder resin, (B) polymerizable compound, (C) polymerization
Agent and cause auxiliary agent and (D) solvent, wherein the weight average molecular weight of (A) binder resin 8,000 or more 100,000 hereinafter,
(C) polymerization initiator and initiation auxiliary agent at least contain oxime compound, acylphosphine oxide compound and thioxanthones based compound,
For (D) solvent, the solubility parameter containing 70 mass of mass %~99 % in total solvent is 8.0~9.1 (cal/
cm3)1/2Solvent, solubility parameter containing 1 mass of mass %~30 % in total solvent is 9.2~11.0 (cal/cm3)1/2
Solvent.
[2] photosensitive polymer combination according to [1], wherein the acid value of the solid state component of (A) binder resin
It is 80 or more 200 or less.
[3] photosensitive polymer combination according to [1] or [2], wherein (A) binder resin and (B) polymerism
It is 50/50 or more when the ratio of compound is counted on the basis of quality and indicated with (A) binder resin/(B) polymerizable compound
80/20 or less.
[4] photosensitive polymer combination according to any one of [1]~[3] also contains (E) colorant.
[5] photosensitive polymer combination according to any one of [1]~[4] also contains (F) levelling agent,
The amount of levelling agent 0.3 mass % or less more than 0.001 mass %.
[6] a kind of patterned coated film, the photosensitive polymer combination shape as described in any one of [1]~[5]
At.
[7] a kind of manufacturing method of patterned coated film, including by photonasty described in any one of [1]~[5]
Resin combination is coated on supporting mass, removing solvent, the process for forming coated film,
And be exposed after the masking coated film, the work of the unexposed portion of the coated film is removed with developer solution
Sequence.
[8] a kind of manufacturing method of patterned coated film only includes by sense described in any one of [1]~[5]
Photosensitive resin composition is coated on supporting mass, removing solvent, the process for forming coated film,
And be exposed after the masking coated film, the work of the unexposed portion of the coated film is removed with developer solution
Sequence.
[9] a kind of manufacturing method of patterned coated film, including by photonasty described in any one of [1]~[5]
Resin combination is coated on supporting mass, remove solvent, formed coated film process,
It is exposed after sheltering the coated film, the process that the unexposed portion of the coated film is removed with developer solution,
And preservation developer solution removes the coated film after unexposed portion at 23 DEG C or more 200 DEG C of temperature below
Process.
[10] a kind of colour filter includes patterned coated film described in [6].
[11] a kind of colour filter, comprising being patterned made from the manufacturing method according to any one of [7]~[9]
Coated film.
According to the present invention, it is possible to provide the photoresist of the pattern with the hardness and viscosity that are able to satisfy requirement can be prepared
Composition.
Specific embodiment
Photosensitive polymer combination of the invention contains (A) binder resin, (B) polymerizable compound, (C) polymerization initiation
Agent and initiation auxiliary agent and (D) solvent.
Photosensitive polymer combination of the invention contains (A) binder resin.(A) binder resin contains binder resin
(A1) (hereinafter, having the case where referred to as " resin (A1) "), the binder resin (A1) are to make to have from unsaturated carboxylic
The addition polymers (a) (hereinafter, having the case where referred to as " (a) ") of the structural unit of acid and the unsaturated compound with epoxy ethyl
(b) (hereinafter, having the case where referred to as " (b) ") reacts.
And, it is specified that the resin (bonding in the dispersible pigment dispersion of following (E) colorants is not included in (A) binder resin
Agent resin).
It as (a), can enumerate such as: make unsaturated carboxylic acid (a1) (hereinafter, having the case where referred to as " (a1) ") and there is energy
The monomer (a2) (hereinafter, having the case where referred to as " (a2) ") for (a1) and (b) carrying out the unsaturated bond of sudden reaction is added
Addition polymers obtained by poly-.
As (a1), acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, vinyl can be specifically enumerated
Benzoic acid, to the unsaturated monocarboxylic acids class such as vinyl benzoic acid；
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acid, 4- vinyl neighbour benzene two
Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-
The unsaturated dicarboxylics class such as cyclohexene dioctyl phthalate；
Bicyclic [2.2.1] hept-2-ene" of methyl -5- norbornene -2,3- dicarboxylic acids, 5- carboxyl, 5,6- dicarboxyl are bicyclic
[2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] the hept- 2- of 5- carboxyl -5- ethyl
Alkene, 5- carboxyl -6- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- carboxyl -6- ethyl etc. contain carboxyl
Bicyclic unsaturated compound class；
Mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid list [2- (methyl) acryloxy second
Base] 2 yuan or more of the polybasic carboxylic acid such as ester single [(methyl) acryloxyalkyl] esters of unsaturation；
Unsaturated esters of acrylic acid etc. as alpha-hydroxymethyl acrylic acid containing hydroxyl and carboxyl in same molecule.
Among them, it is preferable to use acrylic acid, methacrylic acid in terms of the copolyreaction and from the aspect of alkali-solubility
Deng.
Herein, in the present specification, " (methyl) acrylic acid " is indicated from the group being made of acrylic acid and methacrylic acid
That selects is at least one kind of.The labels such as " (methyl) acryloyl group " and " (methyl) acrylate " the also meaning having the same.
It as (a2), can enumerate such as: (methyl) methyl acrylate, (methyl) ethyl acrylate, the positive fourth of (methyl) acrylic acid
(methyl) alkyl-acrylates such as ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate；
(methyl) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyl, (methyl) acrylic acid tricyclic [5.2.1.02 , 6] decyl- 8- base ester (in the art, as popular name, the referred to as bicyclic pentyl ester of (methyl) acrylic acid.), (methyl) acrylic acid
(methyl) acrylic acid cyclic alkyl esters such as bicyclic amoxy ethyl ester, (methyl) isobornyl acrylate；
(methyl) acrylic acid aryl or aralkyl esters such as (methyl) phenyl acrylate, (methyl) benzyl acrylate；
The dicarboxylic diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate；
The hydroxyalkyls esters such as (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- hydroxypropyl acrylate；
Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycle [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- ethyl,
Bicyclic [2.2.1] hept-2-ene" of 5- hydroxyl, bicyclic [2.2.1] hept-2-ene" of 5- methylol, 5- (2 '-ethoxy) are bicyclic [2.2.1]
Bicyclic [2.2.1] hept-2-ene" of hept-2-ene", 5- methoxyl group, bicyclic [2.2.1] hept-2-ene" of 5- ethyoxyl, 5,6- dihydroxy are bicyclic
Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5,6- dihydroxymethyl, bicyclic [2.2.1] hept- of 5,6- bis- (2 '-ethoxy)
Bicyclic [2.2.1] hept-2-ene" of 2- alkene, 5,6- dimethoxy, bicyclic [2.2.1] hept-2-ene" of 5,6- diethoxy, 5- hydroxyl -5-
Bicyclic [2.2.1] hept-2-ene" of methyl bicycle [2.2.1] hept-2-ene", 5- hydroxyl -5- ethyl, 5- methylol -5- methyl bicycle
Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- tert-butoxycarbonyl, bicyclic [2.2.1] hept- of 5- cyclohexyloxy carbonyl
Bicyclic [2.2.1] hept-2-ene" of 2- alkene, 5- phenyloxycarbonyl, bicyclic [2.2.1] hept-2-ene" of 5,6- bis- (tert-butoxycarbonyl), 5,
The bicyclic unsaturated compound classes such as bicyclic [2.2.1] hept-2-ene" of 6- bis- (cyclohexyloxy carbonyl)；
N-phenylmaleimide, N- N-cyclohexylmaleimide, N- benzyl maleimide, N- succinimido-
3- maleimidobenzoyl ester, N- succinimide ester -4- malimidobutanoate, the Malaysia N- succinimide -6- acyl
The dicarbapentaborane such as imines capronate, N- succinimide -3- maleimidopropionic acid ester, N- (9- acridinyl) maleimide acyl is sub-
Amine derivative class；
Styrene, α-methylstyrene, m-methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second
Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3-
Butadiene, isoprene, 2,3- dimethyl -1,3-butadiene etc..
As (a2), particularly preferably has and select from the group being made of tricyclodecane skeleton and tricyclo decene skeleton
The compound (a2-1) (having the case where referred to as " (a2-1) " below) of at least one kind of skeleton and ethylene unsaturated bond.(a2) it is
(a2-1) when, the film thickness that can inhibit the pattern caused by developing is reduced.
Herein, " tricyclodecane skeleton " in this specification and " tricyclo decene skeleton " are referred respectively to flowering structure (its point
Not there is bonding position at an arbitrary position).
As (a2-1), can specifically enumerate the bicyclic pentyl ester of (methyl) acrylic acid, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate,
The bicyclic amoxy ethyl ester of (methyl) acrylic acid, the bicyclic amylene oxygroup ethyl ester of (methyl) acrylic acid.They can individually or 2 kinds
Combination of the above uses.
As (b), can enumerate as: have the monomer of structure made of chain type alkene epoxidation and ethylene unsaturated bond
(b-1) (having the case where referred to as " (b-1) " below), have structure made of cycloolefin epoxidation and ethylene unsaturated bond
Monomer (b-2) (having the case where referred to as " (b-2) " below).As (b), from the viewpoint of reactivity preferably (b-1).
As (b-1), it is sweet can specifically to enumerate (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl
Grease, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl ether,
Between vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether, Alpha-Methyl-neighbour's vinylbenzyl glycidyl ether,
Alpha-Methyl-vinylbenzyl glycidyl ether, Alpha-Methyl-are to vinylbenzyl glycidyl ether, 2,3-, bis- (glycidol ether
Oxygroup methyl) styrene, 2,4- bis- (glycidyl ether oxygen ylmethyl) styrene, 2,5- bis- (glycidyl ether oxygen ylmethyl) benzene
Ethylene, 2,6- bis- (glycidyl ether oxygen ylmethyl) styrene, 2,3,4- tri- (glycidyl ether oxygen ylmethyl) styrene, 2,3,
5- tri- (glycidyl ether oxygen ylmethyl) styrene, 2,3,6- tri- (glycidyl ether oxygen ylmethyl) styrene, 3,4,5- tri- (contractings
Water glycerin ether oxygroup methyl) styrene, 2, institute in 4,6- tri- (glycidyl ether oxygen ylmethyl) styrene, JPH07-248625-A
The compound etc. stated.
As (b-2), can enumerate vinylcyclohexene monoxide, 1,2- epoxy -4- vinyl cyclohexane (for example,
Celloxide(セロキサイド)2000；Daicel chemical industry (strain) system), 3,4- epoxycyclohexyl-methyl acrylate
(for example, Cyclomer (サ イ Network ロ マ mono-) A400；Daicel chemical industry (strain) system), 3,4- epoxycyclohexyl-methyl methyl
Acrylate is (for example, Cyclomer M100；Daicel chemical industry (strain) system), compound, formula (II) represented by formula (I)
Represented compound etc..
[in formula (I) and formula (II), R1And R2The alkyl of hydrogen atom or carbon atom number 1~4, the alkane are indicated independently of each other
The hydrogen atom for including in base can be optionally substituted by a hydroxyl group.
X1And X2Singly-bound ,-R are indicated independently of each other3-、*-R3-O-、*-R3-S-、*-R3-NH-。
R3Indicate the alkylidene of carbon atom number 1~6.
* the bonding end with O is indicated.]
Binder resin (A1) can be manufactured by the process of such as two-stage.At this point it is possible to see, for example document " high score
In the experimental method of sub synthesis " (the big grand row of saliva sale room (strain) chemistry issued the 1st edition the 1st printing on March 1st, 1972 with people)
Method described in the method and Japanese Patent Laid-Open 2001-89533 bulletin etc. manufactures binder resin (A1).
In the manufacture of binder resin (A1), firstly, the addition polymers (a) of (a1) and (a2) are made as the first stage.
Can concrete example show and put into (a1) of specified amount and (a2), polymerization initiator and solvent etc. in reaction vessel, by with nitrogen
Gas displacement oxygen, in the atmosphere of deoxidation, stirring, heating, the method kept the temperature.Polymerization initiator and solvent used herein etc. do not have
There is special limitation, the arbitrary substance being typically used in the art can be used.It as polymerization initiator, can enumerate such as: even
Nitrogen compound (2,2 '-azodiisobutyronitriles, 2,2 '-azos two (2,4- methyl pentane nitrile) etc.) or organic peroxide (peroxide
Change benzoyl etc.), as solvent, as long as dissolving the solvent of each monomer, it can be used and be used as coloring phototonus resin combination
The solvent etc. that the solvent of object is mentioned later.
In addition, addition polymers obtained can be carried out with the state of the solution after reacting using can also be to be concentrated or dilute
The state for the solution crossed carry out using, also can be used by the methods of reprecipitation extract out solid (powder).
Relative to the total mole number for the entire infrastructure unit for constituting addition polymers, it is preferably derived from the structure list of (a1) and (a2)
The ratio of member is in following range.
From the structural unit of (a1)；5~50 moles of % (more preferably 10~45 moles of %)
From the structural unit of (a2)；50~95 moles of % (more preferably 55~90 moles of %)
Then, as second stage, keep a part of the carboxylic acid from (a1) in addition polymers obtained and (b) anti-
It answers.Because reactive high, unreacted (b) is not easy to remain, and pretending as (b) is preferably (b-1).
Specifically, and then above-mentioned, the nitrogen of the atmosphere in flask is replaced into air, in flask investment relative to
(a1) (b) of 5~80 moles of % of molal quantity, relative to (a1), (b) and (a2) total amount be 0.001~5 mass % it is anti-
Answering catalyst (such as three (dimethylamino methyl) phenol etc.) and the total amount relative to (a1), (b) and (a2) is 0.001~5
Resin can be made in general, reacting it 1~10 hour at 60~130 DEG C in the polymerization inhibitor (such as hydroquinone etc.) of quality %
(A1).Moreover, identically as polymerizing condition, it is contemplated that the appropriate adjustments side of feeding intake such as manufacturing equipment and the calorific value caused by polymerizeing
Method and reaction temperature.
In addition, at this point, molal quantity relative to (a1), the preferably molal quantity of (b) are 10~75 moles of %, more preferably 15
~70 moles of %.Molal quantity by making (b) within this range, has the balance of storage stability, solvent resistance and heat resistance to become
Obtain good tendency.
As the concrete example of binder resin (A1), (methyl) acrylic acid of sening as an envoy to/(methyl) acrylic acid bicyclic penta can be enumerated
Resin made of the copolymer of ester is reacted with (methyl) glycidyl acrylate makes (methyl) acrylic acid/(methyl) acrylic acid
Resin made of the copolymer of benzyl ester is reacted with (methyl) glycidyl acrylate makes (methyl) acrylic acid/(methyl) propylene
Resin made of the copolymer of sour cyclohexyl is reacted with (methyl) glycidyl acrylate makes (methyl) acrylic/styrene
Copolymer reacted with (methyl) glycidyl acrylate made of resin, make (methyl) acrylic acid/(methyl) acrylic acid first
Resin made of the copolymer of ester is reacted with (methyl) glycidyl acrylate makes (methyl) acrylic acid/N- cyclohexyl Malaysia
Resin made of imido copolymer is reacted with (methyl) glycidyl acrylate keeps crotonic acid/(methyl) acrylic acid double
Resin made of the copolymer of ring pentyl ester is reacted with (methyl) glycidyl acrylate；
It is set made of reacting crotonic acid/(methyl) benzyl acrylate copolymer with (methyl) glycidyl acrylate
Rouge, react crotonic acid/(methyl) cyclohexyl acrylate copolymer with (methyl) glycidyl acrylate made of resin,
Resin made of reacting crotonic acid/styrene copolymer with (methyl) glycidyl acrylate makes crotonic acid/crotonic acid
Resin made of the copolymer of methyl esters is reacted with (methyl) glycidyl acrylate makes crotonic acid/N- cyclohexyl maleimide
Resin made of the copolymer of amine is reacted with (methyl) glycidyl acrylate；
React maleic acid/(methyl) acrylic acid bicyclic pentyl ester copolymer with (methyl) glycidyl acrylate
Resin, react maleic acid/(methyl) benzyl acrylate copolymer with (methyl) glycidyl acrylate made of set
Rouge, react maleic acid/(methyl) cyclohexyl acrylate copolymer with (methyl) glycidyl acrylate made of resin,
Resin made of reacting maleic acid/styrene copolymer with (methyl) glycidyl acrylate makes maleic acid/maleic acid
Resin made of the copolymer of methyl esters is reacted with (methyl) glycidyl acrylate makes maleic acid/N- cyclohexyl maleimide
Resin made of the copolymer of amine is reacted with (methyl) glycidyl acrylate；
(methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid bicyclic pentyl ester copolymer and (methyl) acrylic acid is set to contract
Resin made of the reaction of water glyceride makes (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate copolymer and (first
Base) glycidyl acrylate reaction made of resin, make (methyl) acrylic acid/maleic anhydride/(methyl) cyclohexyl acrylate
Copolymer reacted with (methyl) glycidyl acrylate made of resin, make (methyl) acrylic acid/maleic anhydride/styrene
Copolymer reacted with (methyl) glycidyl acrylate made of resin, make (methyl) acrylic acid/maleic anhydride/(methyl)
Resin made of the copolymer of methyl acrylate is reacted with (methyl) glycidyl acrylate makes (methyl) acrylic acid/Malaysia
Resin made of acid anhydrides/N- N-cyclohexylmaleimide copolymer is reacted with (methyl) glycidyl acrylate；
Make (methyl) acrylic acid/(methyl) acrylic acid bicyclic pentyl ester copolymer and 3,4- epoxycyclohexyl-methyl methyl-prop
Resin made of the reaction of olefin(e) acid ester makes (methyl) acrylic acid/(methyl) benzyl acrylate copolymer and 3,4- epoxycyclohexyl
Resin made of methylmethacylate reaction makes (methyl) acrylic acid/(methyl) cyclohexyl acrylate copolymer and 3,
Resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate, the copolymer and 3 for making (methyl) acrylic/styrene,
Resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate makes (methyl) acrylic acid/(methyl) methyl acrylate
Copolymer and 3, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make (methyl) acrylic acid/N- cyclohexyl
The copolymer of maleimide and 3, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate；
Make crotonic acid/(methyl) acrylic acid bicyclic pentyl ester copolymer and 3,4- epoxycyclohexyl-methyl methacrylate
Resin made of reaction makes crotonic acid/(methyl) benzyl acrylate copolymer and 3,4- epoxycyclohexyl-methyl metering system
Resin made of acid esters reaction makes crotonic acid/(methyl) cyclohexyl acrylate copolymer and 3,4- epoxycyclohexyl-methyl first
Resin made of base acrylate reactions makes crotonic acid/styrene copolymer and 3,4- epoxycyclohexyl-methyl metering system
Resin made of acid esters reaction makes crotonic acid/ethyl crotonate copolymer and 3,4- epoxycyclohexyl-methyl methacrylic acid
Resin made of ester reaction makes crotonic acid/N- N-cyclohexylmaleimide copolymer and 3,4- epoxycyclohexyl-methyl methyl
Resin made of acrylate reactions；
Make maleic acid/(methyl) acrylic acid bicyclic pentyl ester copolymer and 3,4- epoxycyclohexyl-methyl methacrylate
Resin made of reaction makes maleic acid/(methyl) benzyl acrylate copolymer and 3,4- epoxycyclohexyl-methyl metering system
Resin made of acid esters reaction makes maleic acid/(methyl) cyclohexyl acrylate copolymer and 3,4- epoxycyclohexyl-methyl first
Resin made of base acrylate reactions makes maleic acid/styrene copolymer and 3,4- epoxycyclohexyl-methyl metering system
Resin made of acid esters reaction makes maleic acid/methyl maleate copolymer and 3,4- epoxycyclohexyl-methyl methacrylic acid
Resin made of ester reaction makes maleic acid/N- N-cyclohexylmaleimide copolymer and 3,4- epoxycyclohexyl-methyl methyl
Resin made of acrylate reactions；
Make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid bicyclic pentyl ester copolymer and 3,4- epoxycyclohexyl
Resin made of methylmethacylate reaction makes the copolymerization of (methyl) acrylic acid/maleic anhydride/(methyl) benzyl acrylate
Object and 3, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make (methyl) acrylic acid/maleic anhydride/(first
Base) cyclohexyl acrylate copolymer and 3,4- epoxycyclohexyl-methyl methacrylate reaction made of resin, make (first
Base) acrylic acid/maleic anhydride/styrene copolymer and 3, it is set made of the reaction of 4- epoxycyclohexyl-methyl methacrylate
Rouge makes (methyl) acrylic acid/maleic anhydride/(methyl) methyl acrylate copolymer and 3,4- epoxycyclohexyl-methyl methyl-prop
Resin made of the reaction of olefin(e) acid ester, the copolymer and 3,4- for making (methyl) acrylic acid/maleic anhydride/N- N-cyclohexylmaleimide
Resin made of the reaction of epoxycyclohexyl-methyl methacrylate etc..
Further, as binder resin (A1), more preferably make addition polymers reacted with (b) prepared by resin, wherein
The addition polymers are that (a1), (a2-1) and (a2) in addition to (a2-1) is made to be copolymerized and be made.Pass through binder resin (A1)
For above-mentioned composition, the adaptation and excellent solvent resistance of the pattern and substrate that have the tendency that.
When addition polymers (a) are made of (a1), (a2-1) and (a2) other than (a2-1), it is preferably derived from (a2-
1) ratio of the structural unit of (a2) and other than (a2-1) is 10: 90~60: 40, more preferably 10: 90~40: 60, into one
Step preferably 10: 90~30: 70.
It is obtained as (b) is reacted with the addition polymers of (a2) copolymerization for making (a1) and (a2-1) and other than (a2-1)
Resin, can specifically enumerate (methyl) acrylic acid of the sening as an envoy to/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymerization
Resin made of object is reacted with (methyl) glycidyl acrylate, make (methyl) acrylic acid/bicyclic pentyl ester of (methyl) acrylic acid/
Resin made of the copolymer of (methyl) cyclohexyl acrylate is reacted with (methyl) glycidyl acrylate makes (methyl) propylene
Resin made of the copolymer of the bicyclic pentyl ester/styrene of acid/(methyl) acrylic acid is reacted with (methyl) glycidyl acrylate,
(methyl) acrylic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) methyl acrylate copolymer and (methyl) acrylic acid is set to contract
Resin made of the reaction of water glyceride makes (methyl) acrylic acid/bicyclic pentyl ester of (methyl) acrylic acid/N- N-cyclohexylmaleimide
Copolymer reacted with (methyl) glycidyl acrylate made of resin；
Make the crotonic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer and (methyl) acrylic acid
Resin made of ethylene oxidic ester reaction is total to the crotonic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) cyclohexyl acrylate
Resin made of polymers is reacted with (methyl) glycidyl acrylate makes the crotonic acid/bicyclic pentyl ester of (methyl) acrylic acid/benzene second
Resin made of the copolymer of alkene is reacted with (methyl) glycidyl acrylate makes crotonic acid/(methyl) acrylic acid bicyclic penta
Resin made of ester/ethyl crotonate copolymer is reacted with (methyl) glycidyl acrylate makes crotonic acid/(methyl) third
The bicyclic pentyl ester of olefin(e) acid/N- N-cyclohexylmaleimide copolymer is set made of reacting with (methyl) glycidyl acrylate
Rouge；
Make the maleic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer and (methyl) acrylic acid
Resin made of ethylene oxidic ester reaction is total to the maleic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) cyclohexyl acrylate
Resin made of polymers is reacted with (methyl) glycidyl acrylate makes the maleic acid/bicyclic pentyl ester of (methyl) acrylic acid/benzene second
Resin made of the copolymer of alkene is reacted with (methyl) glycidyl acrylate makes maleic acid/(methyl) acrylic acid bicyclic penta
Resin made of ester/methyl maleate copolymer is reacted with (methyl) glycidyl acrylate makes maleic acid/(methyl) third
The bicyclic pentyl ester of olefin(e) acid/N- N-cyclohexylmaleimide copolymer is set made of reacting with (methyl) glycidyl acrylate
Rouge；
Make (methyl) acrylic acid/maleic anhydride/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer
Resin made of reacting with (methyl) glycidyl acrylate keeps (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid double
Resin made of ring pentyl ester/(methyl) cyclohexyl acrylate copolymer is reacted with (methyl) glycidyl acrylate makes (first
Base) acrylic acid/maleic anhydride/(methyl) acrylic acid bicyclic pentyl ester/styrene copolymer and (methyl) glycidyl
Resin made of ester reaction makes (methyl) acrylic acid/maleic anhydride/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) acrylic acid first
Resin made of the copolymer of ester is reacted with (methyl) glycidyl acrylate makes (methyl) acrylic acid/maleic anhydride/(first
Base) the bicyclic pentyl ester of acrylic acid/N- N-cyclohexylmaleimide copolymer reacts with (methyl) glycidyl acrylate
Resin；
Make (methyl) acrylic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer and 3,4- ring
Oxygen cyclohexyl methyl methacrylate reaction made of resin, make (methyl) acrylic acid/bicyclic pentyl ester of (methyl) acrylic acid/
The copolymer and 3 of (methyl) cyclohexyl acrylate, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make
(methyl) acrylic acid/(methyl) acrylic acid bicyclic pentyl ester/styrene copolymer and 3,4- epoxycyclohexyl-methyl metering system
Resin made of acid esters reaction makes (methyl) acrylic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) methyl acrylate copolymerization
Object and 3, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make (methyl) acrylic acid/(methyl) acrylic acid
Bicyclic pentyl ester/N- N-cyclohexylmaleimide copolymer and 3, made of the reaction of 4- epoxycyclohexyl-methyl methacrylate
Resin；
Make the crotonic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer and 3,4- epoxy hexamethylene
Resin made of methyl methacrylate reaction makes the crotonic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) acrylic acid ring
The copolymer of own ester and 3, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make crotonic acid/(methyl) third
The copolymer and 3 of the bicyclic pentyl ester/styrene of olefin(e) acid, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make
Crotonic acid/(methyl) acrylic acid bicyclic pentyl ester/ethyl crotonate copolymer and 3,4- epoxycyclohexyl-methyl methacrylic acid
Resin made of ester reaction makes the crotonic acid/bicyclic pentyl ester of (methyl) acrylic acid/N- N-cyclohexylmaleimide copolymer and 3,
Resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate；
Make the maleic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer and 3,4- epoxy hexamethylene
Resin made of methyl methacrylate reaction makes the maleic acid/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) acrylic acid ring
The copolymer of own ester and 3, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make maleic acid/(methyl) third
The copolymer and 3 of the bicyclic pentyl ester/styrene of olefin(e) acid, resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate make
Maleic acid/(methyl) acrylic acid bicyclic pentyl ester/methyl maleate copolymer and 3,4- epoxycyclohexyl-methyl methacrylic acid
Resin made of ester reaction makes the maleic acid/bicyclic pentyl ester of (methyl) acrylic acid/N- N-cyclohexylmaleimide copolymer and 3,
Resin made of the reaction of 4- epoxycyclohexyl-methyl methacrylate；
Make (methyl) acrylic acid/maleic anhydride/bicyclic pentyl ester of (methyl) acrylic acid/(methyl) benzyl acrylate copolymer
Resin made of reacting with 3,4- epoxycyclohexyl-methyl methacrylate makes (methyl) acrylic acid/maleic anhydride/(methyl)
The bicyclic pentyl ester of acrylic acid/(methyl) cyclohexyl acrylate copolymer and 3, the reaction of 4- epoxycyclohexyl-methyl methacrylate
Made of resin, make (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid bicyclic pentyl ester/styrene copolymer and 3,4-
Resin made of the reaction of epoxycyclohexyl-methyl methacrylate makes (methyl) acrylic acid/maleic anhydride/(methyl) acrylic acid
Bicyclic pentyl ester/(methyl) methyl acrylate copolymer and 3 is set made of the reaction of 4- epoxycyclohexyl-methyl methacrylate
Rouge, make (methyl) acrylic acid/maleic anhydride/bicyclic pentyl ester of (methyl) acrylic acid/N- N-cyclohexylmaleimide copolymer with
Resin made of the reaction of 3,4- epoxycyclohexyl-methyl methacrylates etc..
These binder resins (A1) can be used singly or two or more kinds in combination.
The weight average molecular weight (Mw) of the polystyrene conversion of binder resin (A1) is 8,000~100,000, preferably
10,000~50,000.If the weight average molecular weight of resin (B1) is within the above range, there are coating and viscosity to become good and incline
To, furthermore development when be not susceptible to film thickness reduce, further, development when there is the removability of non-pixel portion is good to incline
To.
The acid value of preferred binder resin (A1) be 50~200mg-KOH/g, more preferably 60~190mg-KOH/g, into
One step is preferably 80~180mg-KOH/g.Acid value is measurement for potassium hydroxide needed for neutralizing 1g binder resin (A1)
It measures and is worth obtained by (mg), can be titrated by using potassium hydroxide aqueous solution to find out.
Although it is preferred that the binder resin (A) for including in photosensitive polymer combination of the invention only includes above-mentioned binder
Resin (A1), but as long as being the degree for not damaging effect of the invention, so that it may contain other resins.As such resin,
It can enumerate such as: epoxy resin, acrylic resin, urethane resin, polyester resin, polyimide resin, polyolefin resin, line style phenol
Urea formaldehyde, polyamines resin etc..
When binder resin (A) is containing resin other than binder resin (A1), relative to binder resin (A),
The content of preferred binder resin (A1) is 1~80 mass %, more preferably 1~50 mass %.
Photosensitive polymer combination of the invention contains (B) polymerizable compound.As long as (B) polymerizable compound is to utilize
(C) polymerization initiator does not just have by the compound that living radical, acid etc. that the effect of light or heat generates can cause polymerization
Especially limitation.As (B) polymerizable compound, the compound etc. with polymerism carbon-to-carbon unsaturated bond can be enumerated, is preferably made
With polyfunctional monomers more than monofunctional monomer, bifunctional monomer, 3 functions.
As the concrete example of monofunctional monomer, nonylphenol acrylate phenyl carbitol ester, acrylic acid 2- hydroxyl-can be enumerated
3- phenoxy-propyl, acrylic acid 2- ethylhexyl carbitol ester, acrylic acid 2- hydroxyl ethyl ester, n-vinyl pyrrolidone etc..
In addition, the concrete example as bifunctional monomer, can enumerate 1,6- hexylene glycol two (methyl) acrylate, ethylene glycol
Two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A it is double
(acryloyl-oxyethyl) ether, 3- methyl pentanediol two (methyl) acrylate etc..
As the concrete example of polyfunctional monomers more than 3 functions, trimethylolpropane tris (methyl) acrylic acid can be enumerated
Ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylic acid
Product, the dipentaerythritol of ester, dipentaerythritol six (methyl) acrylate, pentaerythrite three (methyl) acrylate and acid anhydrides
The product of five (methyl) acrylate and acid anhydrides, Osaka organic chemistry society V#1000, V#802, STAR-501, common prosperity society chemistry
The carbamates such as (strain) UA-306H, UA-306T processed, UA-306I, the first industrial pharmaceutical society New frontier R-1150
Acrylate etc..Wherein, it is preferable to use more than bifunctional monomer, 3 functions polyfunctional monomer.
In addition, can also add following polymerizable compounds.
(B) polymerizable compound can individually or two kinds or more and with use.
Relative to the solid state component of photosensitive polymer combination, preferably the content of (B) polymerizable compound is 1~50 matter
Measure %, more preferably 5~30 mass %.In addition, the ratio of (A) binder resin and (B) polymerizable compound is using quality as base
When standard is counted and is indicated with (A) binder resin/(B) polymerizable compound, preferably 50/50 or more and 80/20 or less.
If the ratio of (A) binder resin and (B) polymerizable compound is within the above range, because viscosity is suppressed, have
Be made there is no the non-uniform colour filter of color tendency so it is preferred that.
Photosensitive polymer combination of the invention contains (C) polymerization initiator and causes auxiliary agent.
As (C) polymerization initiator and cause auxiliary agent, living radical initiator, acid initiator, polymerization rush can be enumerated
Into agent, sensitizer etc..Living radical initiator generates living radical by the effect of light or heat.(C) polymerization initiator and
Cause auxiliary agent and contains oxime compound, acylphosphine oxide based compound and thioxanthones based compound.
As above-mentioned oxime compound, the compound with part-structure represented by formula (C-1) can be enumerated.Following formula
In, * indicates bonding position.
It as such oxime compound, can enumerate such as: N- benzoyloxy -1- (4- Phenylsulfanylphenyl) butane -1- ketone -
2- imines, N- benzoyloxy -1- (4- Phenylsulfanylphenyl) octane -1- ketone -2- imines, N- benzoyloxy -1- (4- thiophenyl
Phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl group -1- [9- ethyl -6- (2- methyl benzoyl) -9H- click
Azoles -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- { 2- methyl -4- (3,3- dimethyl -2,4- dioxanes
Amyl methoxyl group) benzoyl } -9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- (2- methyl
Benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1- imines, N- benzoyloxy -1- [9- ethyl -6- (2- methyl
Benzoyl) -9H- carbazole -3- base] compounds or the IRGACURE (registered trademark) such as -3- cyclopenta propane -1- ketone -2- imines
Commercially available products such as OXE01, OXE02 (more than, BASF AG's system), N-1919 (Chinese mugwort Dicon A/S's system) etc..Wherein preferably
IRGACURE (registered trademark) OXE01 (BASF AG's system).
As above-mentioned acylphosphine oxide compound, can enumerate 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides etc..Lucirin (registered trademark) TPO (BASF AG can be used
System), the commercially available products such as IRGACURE (registered trademark) 819 (BASF AG's system).
It as above-mentioned thioxanthones based compound, can enumerate such as: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- bis-
Ethyl thioxanthones, 2,4-, bis- clopenthixal ketone, the chloro- 4- propoxythioxanthone of 1- etc..It is wherein preferably 2,4- diethyl thioxanthone.
As long as in addition, not damaging the degree of effect of the invention, so that it may further and with usually used in this field
Polymerization initiator or polymerization trigger auxiliary agent can be enumerated such as: acetophenone as the polymerization initiator or polymerization trigger auxiliary agent
Based compound, bisglyoxaline based compound, triazine based compound, benzoin based compound, benzophenone based compound, anthracene system chemical combination
Object, amine compound, thiazoline based compound, alkoxy anthracene based compound, carboxylic acid based compound etc..
As above-mentioned acetophenone based compound, diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl -1- can be enumerated
Acetone, benzil dimethyl ketal, 2- hydroxyl-1- [4- (2- hydroxyl-oxethyl) phenyl]-2- methyl-1-acetone, 1- hydroxyl ring
Hexyl phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholinopropane-1- ketone, 2- benzyl-2- dimethylamino-1-
(4- morpholinyl phenyl) butane -1- ketone, 2- (2- methylbenzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (3- first
Base benzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (4- methylbenzyl) -2- dimethylamino -1- (4-
Quinoline phenyl)-butanone, 2- (2- Ethylbenzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (2- benzyl) -
2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (2- butyl benzyl) -2- dimethylamino -1- (4- morpholinyl phenyl) -
Butanone, 2- (2,3- dimethyl benzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (2,4- dimethyl benzyl) -
2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (2- chlorobenzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-fourth
Ketone, 2- (2- bromobenzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (3- chlorobenzyl) -2- dimethylamino -1-
(4- morpholinyl phenyl)-butanone, 2- (4- chlorobenzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (3- bromobenzyl) -
2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (4- bromobenzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-fourth
Ketone, 2- (2- methoxy-benzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (3- methoxy-benzyl) -2- diformazan
Base amino -1- (4- morpholinyl phenyl)-butanone, 2- (4- methoxy-benzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone,
2- (2- methyl -4- methoxy-benzyl) -2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (2- methyl -4- bromobenzyl) -
2- dimethylamino -1- (4- morpholinyl phenyl)-butanone, 2- (the bromo- 4- methoxy-benzyl of 2-) -2- dimethylamino -1- (4- morpholine
Phenyl)-butanone, the oligomer of 2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] propane -1- ketone etc..
As above-mentioned bisglyoxaline based compound, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyls connection miaow can be enumerated
Azoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines are (for example, referring to JPH06-75372-A, JPH06-
75373-A etc..), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ',
5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxalines,
2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines (for example, referring to JPS48-38403-B,
JPS62-174204-A etc..), 4,4 ' 5, the phenyl of 5 '-positions by alkoxy carbonyl group instead of imidazolium compounds (for example, referring to
JPH07-10913-A etc..) etc., 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines, 2 are preferably enumerated,
2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxalines.
As above-mentioned triazine based compound, bis- (the trichloromethyl) -6- (4- methoxyphenyl) -1,3,5- of 2,4- can be enumerated
Triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5-triazines, bis- (the trichloromethyl) -6- piperonyls-of 2,4-
Bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5-triazines of 1,3,5-triazines, 2,4-, 2,4- bis- (trichloromethyls) -
6- [2- (5- methylfuran -2- base) vinyl] -1,3,5-triazines, bis- (the trichloromethyl) -6- of 2,4- [2- (furans -2- base) second
Alkenyl] -1,3,5-triazines, bis- (the trichloromethyl) -6- of 2,4- [2- (4- diethylamino -2- aminomethyl phenyl) vinyl] -1,3,
Bis- (the trichloromethyl) -6- of 5- triazine, 2,4- [2- (3,4- Dimethoxyphenyl) vinyl] -1,3,5-triazines etc..
As above-mentioned benzoin based compound, can enumerate such as: benzoin, benzoin methylether, benzoin ethyl ether, benzoin are different
Propyl ether, benzoin isobutyl ether etc..
It as above-mentioned benzophenone based compound, can enumerate such as: benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- benzene
Base benzophenone, 4- benzoyl -4 '-methyldiphenyl thioether, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,
4,6- tri-methyl benzophenones etc..
As above-mentioned anthracene based compound, can enumerate such as: 9,10- dimethoxy anthracenes, 2-ethyl-9,10-dimethoxypyrene, 9,
10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene etc..
It as above-mentioned amine compound, can enumerate such as: triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethyl
Methyl anthranilate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid -2- diformazan
Base amino ethyl ester, 4- dimethylaminobenzoic acid -2- ethylhexyl, N, N- dimethyl-p-toluidine, 4,4 '-bis- (dimethylaminos)
Benzophenone (common name Michler's keton), 4,4 '-bis- (lignocaine) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone
Deng, wherein preferably 4,4 '-bis- (lignocaine) benzophenone.
As thiazoline based compound, compound represented by formula (III-1)~formula (III-3) etc. can be enumerated.
It as above-mentioned alkoxy anthracene based compound, can enumerate such as: 9,10- dimethoxy anthracenes, 2- ethyl -9,10- dimethoxy
Base anthracene, 9,10- diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene etc..
As carboxylic acid compound, thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, methyl can be enumerated
Ethylthiophenyl acetic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorophenylsulfanyl
Acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthalene ethyl thioglycollic acid, N- naphthalene glycine, naphthoxy second
Acid etc..
In addition, as polymerization initiator, it can also illustrated commercially available trade name " EAB-F " (hodogaya chemical industry
(strain) system) etc..
In addition, as the polymerization initiator with the group that can cause chain tra nsfer, can be used among (C) polymerization initiator
The polymerization initiator that recite in JP2002-544205-A.
Polymerization initiator with the group that can cause above-mentioned chain tra nsfer also acts as the constituent of above-mentioned copolymer
(A3).Then, copolymer obtained also acts as (A) binder resin.
Cause auxiliary agent as (C), can enumerate such as: amine compound described above, thiazoline based compound, alkoxy anthracene
Based compound, carboxylic acid based compound, commercially available trade name " EAB-F " etc..
With regard to (C) polymerization initiator and for causing the content of auxiliary agent, relative to the solid state component of photosensitive polymer combination,
Oxime compound, acylphosphine oxide compound, thioxanthones based compound are respectively preferably 1~20 mass %.In addition, relative to
(A) total amount of binder resin and (B) polymerizable compound preferably (C) polymerization initiator and is drawn on the basis of quality percentage
The content for sending out auxiliary agent is 0.1~40 mass %, more preferably 1~30 mass %.
If the total amount of (C) polymerization initiator and initiation auxiliary agent is within the above range, photosensitive polymer combination becomes high
Sensitivity, because there is the table of the intensity of the pixel portion of the colour filter formed using above-mentioned photosensitive polymer combination and above-mentioned pixel
The flatness in face become it is good must be inclined to so it is preferred that.
It is preferred that photosensitive polymer combination of the invention also contains (E) colorant.As such (E) colorant, can arrange
Pigment and dyestuff are enumerated, but in terms of heat resistance, light resistance, preferably comprises pigment.
As pigment, organic pigment and inorganic pigment can be enumerated, can be enumerated in Colour Index (The Society of
Dyers and Colourists is published) in be sorted in compound in pigment.
As organic pigment, can specifically enumerate such as: C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,
53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、166、173、
194, the yellow uitramarines such as 214；
C.I. the orange pigments such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73；
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,
216, the red pigments such as 224,242,254,255,264,265；
C.I. the blue pigments such as pigment blue 15,15: 3,15: 4,15: 6,60；C.I. pigment violet 1,19,23,29,32,36,
38 equal violet pigments；
C.I. the viridine greens such as pigment Green 7,36,58；
C.I. the browns such as pigment brown 23,25；
C.I. black pigments such as pigment black 1,7 etc..
Wherein, more preferable C.I. pigment yellow 13 8,139,150；C.I. paratonere 177,242,254；C.I. pigment purple
23；C.I. pigment blue 15: 3,15: 6 and C.I. pigment Green 7,36,58.These pigment can individually or two or more is used in mixed way.
As needed, rosin processing can be implemented to above-mentioned pigment, use the face for introducing acidic-group or basic group
Expect the surface treatment of the progress such as derivative or pigment dispersing agent, at the grafting carried out to surface of pigments by high-molecular compound etc.
Reason passes through the micronized processing of the progress such as sulfuric acid particles method or washing for the progress such as the organic solvent by removing impurity or water
Wash processing, handled by the removing of the progress such as ion-exchange of ionic impurity etc..Furthermore it is preferred that the uniform particle sizes of pigment.
By then carrying out decentralized processing containing pigment dispersing agent, the pigment dispersion of the evenly dispersed state in the solution of pigment can be made
Liquid.
As above-mentioned pigment dispersing agent, commercially available surfactant can be used, can enumerate such as: silicone-based, fluorine system, ester system,
Surfactants such as cationic system, anionic system, nonionic system, both sexes, Polyester, polyamines system, acrylic acid series etc..As above-mentioned
Surfactant, in addition to polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, sorbitan
Other than fatty acid ester, fatty acid modified polyesters, tertiary-amine modified polyurethanes, polyethyleneimine amine etc., commodity can be enumerated
Entitled KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Flowlen (mono- レ Application of Off ロ) (common prosperity society chemistry (strain) system), Solsperse are (prompt
Li Kang (strain) system), Efka (EFKA) (BASF AG's system), Ajisper (ア ジ ス パ mono-) (registered trademark) (aginomoto essence
(strain) system is learned in refinement), Disperbyk (Bi Ke chemistry society system) etc..They can individually or two or more is applied in combination.
When using pigment dispersing agent, relative to pigment, preferably its dosage is 100 mass % hereinafter, more preferably 5~50 matter
Measure %.If the dosage of pigment dispersing agent is within the above range, has the tendency that the dispersible pigment dispersion of obtained homogeneously dispersed state.
Relative to the solid state component of photosensitive polymer combination, preferably the content of (E) colorant is 5~60 mass %, more
Preferably 5~45 mass %.If the content of (E) colorant is within the above range, desired spectrum and color density can get.
It is 8.0~9.1 (cal/cm that (D) solvent of photosensitive polymer combination of the invention, which contains solubility parameter,3)1/2
Solvent and solubility parameter be 9.2~11.0 (cal/cm3)1/2Solvent.
It is 8.0~9.1 (cal/cm as solubility parameter3)1/2Solvent, ethylene glycol list isobutyl ether, two can be enumerated
Ethylene glycol single 2-ethyl hexyl ether, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol list positive propyl ether, 3 the third two
Alcohol mono-n-butyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, three second two
Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol methyl ether acetate, dipropyl two
Alcohol methyl ether acetate, ethyl -3- ethoxy-c acid esters, n-propyl acetate, n propyl propionate, n-butyl propionate, propionic acid positive penta
Ester, methyl iso-butyl ketone (MIBK), hexamethylene, toluene, ethyl acetate, butyl acetate, tetrahydrofuran, carbon tetrachloride, 2-HEPTANONE etc..Wherein
The preferred propylene glycol methyl ether acetate from the viewpoint of dissolubility.
It is 9.2~11.0 (cal/cm as solubility parameter3)1/2Solvent, ethylene glycol ether, second two can be enumerated
Alcohol list isopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monohexylether, ethyleneglycol monophenylether, ethylene glycol monobenzyl ether, ethylene glycol monoene third
Ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monohexyl ether, diethylene glycol single 2-ethyl hexyl ether, diethyl two
Alcohol list benzyl oxide, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, triethylene glycol mono-n-butyl ether, poly glycol monomethyl ether, propylene glycol
Monomethyl ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, propylene glycol monophenyl ether, dipropylene glycol list first
Ether, Tripropylene glycol monomethyl Ether, ethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol diacetate, methyl -3- methoxy propyl acid esters, cream
Sour methyl esters, butyl lactate, cyclohexanone, diacetone alcohol, 1- propyl alcohol, n-butyl alcohol, methyl ethyl ketone, dioxane, methylene chloride, chloroform,
Dimethyl sulfoxide, acetone, dimethyl carbonate, 1,1,2,2- tetrachloroethanes etc..Wherein preferably the third two from the viewpoint of dissolubility
Alcohol monomethyl ether.
For the content of solvent, relative to whole solvents in photosensitive polymer combination, preferably solubility parameter is
8.0~9.1 (cal/cm3)1/2Solvent be the 70 mass % of mass %~99, solubility parameter be 9.2~11.0 (cal/cm3)1/2
Solvent be 1 mass of mass %~30 %, more preferable solubility parameter be 8.0~9.1 (cal/cm3)1/2Solvent be 70 matter
The mass % of %~97 is measured, solubility parameter is 9.2~11.0 (cal/cm3)1/2Solvent be 3 mass of mass %~30 %.If molten
Within the above range, then having flatness when dissolubility, coating to become good must be inclined to the quality % ratio of agent.
And solubility parameter is found out by following formula.
Solubility parameter=(△ E/V)1/2
△ E: cohesive energy (enthalpy of vaporization), V: molal volume
For (D) solvent, be used for (A) binder resin synthesis when and when preparing photosensitive polymer combination, can contain
The solubility parameter for having 70 mass of mass %~99 % is 8.0~9.1 (cal/cm3)1/2Solvent and 1 matter of mass %~30
The solubility parameter for measuring % is 9.2~11.0 (cal/cm3)1/2Solvent.
Relative to photosensitive polymer combination, preferably the content of (D) solvent be 60~95 mass %, more preferably 70~90
Quality %.In other words, preferably the solid state component of photosensitive polymer combination is 5~40 mass %, more preferably 10~30 matter
Measure %.If the content of (D) solvent is within the above range, there is flatness when coating to become good tendency.
Photosensitive polymer combination of the invention can contain (F) surfactant.As surfactant, can enumerate
Such as: silicone-based surfactant, fluorine system surfactant, the silicone-based surfactant with fluorine atom.By containing table
Face activating agent, having flatness when coating to become good must be inclined to.
As silicone-based surfactant, the surfactant with siloxanes key can be enumerated.It can specifically enumerate
TORAY SILICONE DC3PA、TORAY SILICONE SH7PA、TORAY SILICONE DC11PA、TORAY
SILICONE SH21PA、TORAY SILICONE SH28PA、TORAY SILICONE SH29PA、TORAY SILICONE
SH30PA, polyether modified silicone oil SH8400 (trade name: east beautiful DOW CORNING (strain) system), KP321, KP322, KP323,
KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300,
TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (stepping contract commercial firm, figure new high-tech material Japan system) etc..
As fluorine system surfactant, the surfactant with fluorocarbon chain can be enumerated.It can specifically enumerate
Fluorinert (one ト of Off ロ リ Na) (registered trademark) FC430, Fluorinert FC431 (Sumitomo 3M (strain) system), Megafac
(メ ガ Off ア Star Network) (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac
F177, Megafac F183, Megafac R30 (big Japanese ink chemical (strain) system), Eftop (エ Off ト Star プ) (registrar
Mark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials electronics is melted into (strain) system), Surflon
(mono- Off ロ Application of サ) (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass
(strain) system), E5844 (Daikin Industries (strain) system) etc..
As the silicone-based surfactant with fluorine atom, can enumerate living with the surface of siloxanes key and fluorocarbon chain
Property agent.Can specifically enumerate Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477,
Megafac F443 (big Japanese ink chemical (strain) system) etc..Preferably enumerate Megafac (registered trademark) F475.
Relative to photosensitive polymer combination, preferred surfactant be 0.001 mass % or more, 0.3 mass % hereinafter,
More preferably 0.002 mass % or more, 0.2 mass % are hereinafter, particularly preferably 0.01 mass % or more, 0.1 mass % or less.
By the surfactant containing this range, the flatness of film can be made good.
As needed, photosensitive polymer combination of the invention can contain filler, other high-molecular compounds, attachment
The various additives such as power promotor, antioxidant, ultraviolet absorbing agent, light stabilizer, chain-transferring agent.
Photosensitive polymer combination of the invention as needed can depositing in (E) colorant, (D) solvent and other compositions
Under, prepared by mixing (A) binder resin, (B) polymerizable compound and (C) polymerization initiator and initiation auxiliary agent.
In addition, when pigment of the mixing as (E) colorant, such as preferably modulation in the following order.
Firstly, in advance mixing pigment with (D) solvent, make pigment dispersion until the average grain diameter of pigment using ball mill etc.
Fade to 0.2 μm of degree below.At this point, as needed, can with hybrid pigment dispersing agent, (A) binder resin a part or
All.Remaining (A) binder resin, (B) polymerizable compound or (C) polymerization can be added in obtained dispersible pigment dispersion
Sense can be made in initiator etc., other compositions used as needed, the solvent further added as needed to defined concentration
Photosensitive resin composition.
As photosensitive polymer combination of the invention to the coating method of substrate, can enumerate such as: extrusion coating methods, directly
Gravure coating process, reversed gravure coating process, CAP rubbing method, mold coating method etc..In addition, dip coaterd, roll-type also can be used to apply
Cloth machine, rod coater, spin coater, slit and spin coater, slit coater (also have referred to as mould coating machine, curtain
The case where machine, sol evenning machine (Spinless coater)), the apparatus for coating such as inkjet printing are coated.It is wherein, it is preferable to use narrow
Seam coating machine, spin coater, roll coater etc. are coated.
As the drying means for the film being coated on substrate, can enumerate such as: heat drying, aeration-drying, subtracts natural drying
Press dry it is the methods of dry, can by a variety of methods combine carry out.
As drying temperature, preferably 10~120 DEG C, more preferably 25~100 DEG C.In addition, as heating time, preferably
It is 10 seconds~60 minutes, more preferably 30 seconds~30 minutes.
It is preferred that being dried under reduced pressure within the temperature range of under the pressure of 50~150Pa, 20~25 DEG C.
The film thickness of coated film after drying is not particularly limited, can be according to the appropriate adjustments such as material, the purposes used, example
Such as, 0.1~20 μm, preferably 1~6 μm.
Across the photomask for being used to form target pattern, the coated film after drying is exposed.At this time on the photomask
Pattern form be not particularly limited, can be used and meet the pattern forms of intended applications.
As the light source for exposure, the preferably light source of the light of the wavelength of 250~450nm of sending.For example, truncation can be used
Light less than 350nm is truncated, using intercepting the bandpass filter of these wave-length coverages selectively in the filter of this wave-length coverage
Intercept the light of 436nm nearby, near 408nm, near 365nm.As light source, mercury lamp, light emitting diode, gold can be specifically enumerated
Belong to halide lamp, halogen lamp etc..
Because whole to plane of exposure can equably irradiate parallel rays, be aligned mask in correct position with substrate, thus it is excellent
Choosing uses the devices such as mask aligning machine, stepper.
After exposure, by making the prescribed portion of the coated film contacted with developer solution, for example, making unexposed portion dissolution, showing
Pattern can be obtained in shadow.As developer solution, although organic solvent can also be used, because developer solution is not easy to make the exposure of coated film
The reason of being partly dissolved or be swollen, the pattern of good shape can be obtained, it is preferable to use alkali compounds aqueous solution.
Developing method can be any one of sheathed immersion method, infusion process, spray-on process etc..It further can be in development
Substrate is tilted into any angle.
It is preferred that being washed after development.
As above-mentioned alkali compounds, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, phosphorus can be enumerated
Sour hydrogen diammonium, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium metasilicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus,
The inorganic alkaline compounds such as Boratex, potassium borate, ammonia；Tetramethylammonium hydroxide, 2- hydroxyethyl trimethylammonium hydroxide, a first
The organic basics chemical combination such as amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, Mono Isopropylamine, diisopropylamine, ethanol amine
Object.Wherein, preferably potassium hydroxide, sodium bicarbonate and tetramethylammonium hydroxide.
It is preferred that these concentration of inorganic and organic basic compound in aqueous solution are 0.01~10 mass %, more preferably
0.03~5 mass %.
The aqueous solution of above-mentioned alkali compounds can contain surfactant.
As surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyxyethylated aryl can be enumerated
Ether, other polyoxyethylene derivs, ethylene oxide/propylene oxide block copolymer, sorbitan aliphatic ester, polyoxyethylene mountain
Pears glycan aliphatic ester, polyoxyethylene sorbitol aliphatic ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxy second
The nonionic surfactants such as allylic alkylation amine；
Laruyl alcohol sodium sulfovinate, oleyl sulfate sodium, NaLS, Texapon Special, dodecyl benzene sulfonic acid
The anionic surfactants such as sodium, dodecyl sodium naphthalene sulfonate；
Cationic systems surfactant such as octadecylamine hydrochloride, lauryl trimethyl ammonium chloride etc..
It is preferred that the concentration of the surfactant in the aqueous solution of alkali compounds is 0.01~10 mass %, more preferably
0.05~8 mass %, particularly preferably 0.1~5 mass %.
In the present invention, the process for heating up and then being kept after development can also be omitted.Furthermore if can add it is necessary to if
The process for adding heating and then being kept.
As the temperature for the process for heating up and then being kept in the present invention, usually 23 DEG C or more, 200 DEG C hereinafter,
Preferably 25 DEG C or more, 180 DEG C hereinafter, more preferably 25 DEG C or more, 160 DEG C hereinafter, further preferably 25 DEG C or more, 120
DEG C or less.As the time heated up and then kept, usually 1~300 minute, preferably 1~180 minute, more preferably 1
~60 minutes.
If the process that can be omitted heating and then be kept, the working hour of process is reduced, and can reduce manufacturing cost.In addition,
If the process that can be omitted heating and then be kept, may be used film substrate, can manufacture flexible display.
It is good that color density, brightness, contrast, sensitivity, resolution ratio, heat resistance etc. can be made in photosensitive composite of the invention
Good pattern and the colour filter comprising the pattern.Furthermore, it is possible to having these colour filters or pattern as its constituting portion
In the display device of a part of part, for example, being related to well known liquid crystal display device, organic el device, solid state image sensing
It is used in the form of well known in the machine of the rendered images such as device, Electronic Paper.
Embodiment
<synthesis of binder resin solution A 1>
Propylene glycol list first is taken in the flask for having agitating device, dropping funel, condenser, thermometer, gas introduction tube
67 parts by weight of ether acetic acid ester, 33 parts by weight of propylene glycol monomethyl ether, stir when being replaced as nitrogen, are warming up to 120 DEG C.Then, exist
It is made of 11 parts by weight of methacrylic acid tricyclodecyl, 31 parts by weight of benzyl methacrylate, 23 parts by weight of methacrylic acid
Perbutyl O (the peroxidating 2 ethyl hexanoic acid tert-butyl ester, day are added relative to 100 parts by weight of monomer mixture in monomer mixture
This grease (strain) system) 1 parts by weight.It is instilled in flask from dropping funel with 2 hours, further, it is small that 2 is stirred at 120 DEG C
When be made copolymer.Then, it will be replaced into air in flask, it is sweet that Glycidyl methacrylate is put into the solution of above-mentioned copolymer
0.08 parts by weight of 10 parts by weight of grease, 0.46 parts by weight of triphenylphosphine and methylnaphthohydroquinone, the sustained response at 120 DEG C is until solid-state
Reaction was completed when ingredient acid value becomes 150KOHmg/g, and 75 parts by weight of propylene glycol methyl ether acetate, propylene glycol monomethyl ether 5 are added
Thus binder resin (Mw:30000) solution A 1 of the alkali-developable of non-volatile content 30% is made in parts by weight.
<synthesis of binder resin solution A 2>
Propylene glycol list first is taken in the flask for having agitating device, dropping funel, condenser, thermometer, gas introduction tube
67 parts by weight of ether acetic acid ester, 33 parts by weight of propylene glycol monomethyl ether, stir when being replaced into nitrogen, are warming up to 120 DEG C.Then, exist
It is made of 10 parts by weight of methacrylic acid tricyclodecyl, 34 parts by weight of benzyl methacrylate, 20 parts by weight of methacrylic acid
Perbutyl O (the peroxidating 2 ethyl hexanoic acid tert-butyl ester, day are added relative to 100 parts by weight of monomer mixture in monomer mixture
This grease (strain) system) 1 parts by weight.It is instilled in flask from dropping funel with 2 hours, further, it is small that 2 is stirred at 120 DEG C
When be made copolymer.Then, it will be replaced into air in flask, it is sweet that Glycidyl methacrylate is put into the solution of above-mentioned copolymer
0.08 parts by weight of 10 parts by weight of grease, 0.44 parts by weight of triphenylphosphine and methylnaphthohydroquinone, the sustained response at 120 DEG C is until solid-state
Reaction was completed when ingredient acid value becomes 130KOHmg/g, and 74 weight of propylene glycol methyl ether acetate, 5 weight of propylene glycol monomethyl ether is added
Part is measured, binder resin (Mw:30000) solution A 2 of the alkali-developable of non-volatile content 30% is thus made.
<Resin A described in the synthesis of binder resin solution A 3>JP2010-140042-A
Propylene glycol is added in the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe
Methyl ether acetate 182g, by atmosphere in flask from air displacement be nitrogen after, after being warming up to 100 DEG C, by methacrylic acid
Monomethacrylates (the day of benzyl ester 70.5g (0.40 mole), methacrylic acid 43.0g (0.5 mole), tricyclodecane skeleton
Vertical chemical conversion (strain) FA-513M processed) it adds in the mixture that constitutes of 22.0g (0.10 mole) and propylene glycol methyl ether acetate 136g
Azodiisobutyronitrile 3.6g, is made solution, instills the solution in flask from dropping funel with 2 hours, further at 100 DEG C
It persistently stirs 5 hours down.Then, atmosphere in flask is replaced into air from nitrogen, Glycidyl methacrylate is put into flask
Glyceride 35.5g [0.25 mole, (50 moles of % of the carboxyl relative to the methacrylic acid for this reaction)], three (diformazans
Base amino) methylphenol 0.9g and quinhydrones 0.145g, it persistently carries out reacting for 6 hours at 110 DEG C, solid state component acid value, which is made, is
The binder resin solution A 3 (Mw:13000) of 79mgKOH/g.
<synthesis of binder resin solution A 4>
Propylene glycol is added in the flask for having blender, thermometer, reflux condensing tube, dropping funel and nitrogen ingress pipe
591 parts of methyl ether acetate, by atmosphere in flask from air displacement be nitrogen after, after being warming up to 110 DEG C, by methacrylic acid
Monomethacrylates (Hitachi's chemical conversion of 17.6 parts of benzyl ester, 113.7 parts of glycidyl methacrylate and tricyclodecane skeleton
(strain) FA-513M processed) 22.0 parts and 153 parts of propylene glycol methyl ether acetate compositions monomer mixtures in add two isobutyl of azo
3.6 parts of nitrile, solution is made, the solution is instilled in flask from dropping funel with 2 hours, is further persistently stirred at 100 DEG C
It mixes 2 hours.Then, atmosphere in flask is replaced into air from nitrogen, 68.9 parts of methacrylic acid, three (two is put into flask
Methylamino) methylphenol 0.9g and quinhydrones 0.145, it persistently carries out reacting for 6 hours at 110 DEG C, until solid state component acid
Reaction was completed when value becomes 1mgKOH/g.
It is subsequently added into 53.3 parts of tetrabydrophthalic anhydride, 0.8 part of triethylamine, makes its reaction 3.5 hours
Obtain the binder resin solution A 4 (Mw:7900) of solid state component 37.9%, acid value 68.6mgKOH/g (solid state component conversion).
<synthesis of binder resin solution A 5>
It is passed through appropriate nitrogen in the flask for the 1L for having reflux condenser, dropping funel and blender, nitrogen gas is made
Atmosphere puts into 100 parts by weight of propylene glycol methyl ether acetate, is heated to 85 DEG C while stirring.Then, in the flask, by methyl
19 parts by weight of acrylic acid, 3,4- epoxy tricyclic [5.2.1.02.6] decyl acrylate (compound and formula represented by formula (I-1)
(II-1) compound represented by) 171 parts by weight are dissolved in 40 parts by weight of propylene glycol methyl ether acetate, obtained solution, with drop
Instilled the solution within the liquid pump used time about 5 hours.On the other hand, by 2,2 '-azo two (2,4- methyl pentane nitrile) of polymerization initiator
26 parts by weight are dissolved in 120 parts by weight of propylene glycol methyl ether acetate, obtained solution, small with the other dropping liquid pump used time about 5
When will the solution instill flask in.After polymerization initiator is added dropwise, keeps about 3 hours, cool down later at the same temperature
To room temperature, the binder resin solution A 5 of 43.5 weight % of solid state component, acid value 52mgKOH/g (solid state component conversion) is made
(Mw:8000).
Using GPC method, the weight average molecular weight of the binder resin solution as made from synthesis example is carried out under the following conditions
(Mw) measurement.
Device: K2479 ((strain) Shimadzu Seisakusho Ltd. system)
Column: Shimadzu Seisakusho Ltd. Shim-pack GPC-80M
Column temperature: 40 DEG C
Solvent: THF (tetrahydrofuran)
Flow velocity: 1.0mL/min
Detector: RI
Embodiment 1
[preparation of photosensitive polymer combination 1]
Mixing
Keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 1 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 92.7 matter in total solvent
Measure %, propylene glycol monomethyl ether is 7.3 mass %.In addition, converted by solid state component, binder resin (A1) and polymerism chemical combination
The ratio of object (B) is 70/30.
Embodiment 2
[preparation of photosensitive polymer combination 2]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 2 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 96.4 matter in total solvent
Measure %, propylene glycol monomethyl ether is 3.6 mass %.In addition, converted by solid state component, binder resin (A1) and polymerism chemical combination
The ratio of object (B) is 60/40.
Embodiment 3
[preparation of photosensitive polymer combination 3]
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
, photosensitive polymer combination 3 is made.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 93.7 matter in total solvent
Measure %, propylene glycol monomethyl ether is 6.3 mass %.In addition, converted by solid state component, binder resin (A1) and polymerism chemical combination
The ratio of object (B) is 70/30.
Embodiment 4
[preparation of photosensitive polymer combination 4]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 4 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 94.7 matter in total solvent
Measure %, propylene glycol monomethyl ether is 5.3 mass %.In addition, converted by solid state component, binder resin (A2) and polymerism chemical combination
The ratio of object (B) is 60/40.
Embodiment 5
[preparation of photosensitive polymer combination 5]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 5 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 93.2 matter in total solvent
Measure %, propylene glycol monomethyl ether is 6.8 mass %.In addition, converted by solid state component, binder resin (A1) and polymerism chemical combination
The ratio of object (B) is 75/25.
Embodiment 6
[preparation of photosensitive polymer combination 6]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 6 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 70.7 matter in total solvent
Measure %, propylene glycol monomethyl ether is 29.3 mass %.In addition, converted by solid state component, binder resin (A2) and polymerism
The ratio for closing object (B) is 70/30.
Embodiment 7
[preparation of photosensitive polymer combination 7]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 7 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 70.7 matter in total solvent
% is measured, propylene glycol monomethyl ether is 29.3 mass %.In addition, converted by solid state component, binder resin (A2) and polymerism
The ratio for closing object (B) is 70/30.
Comparative example 8
[preparation of photosensitive polymer combination 8]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By the dispersible pigment dispersion with
Photosensitive polymer combination 8 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 100 matter in total solvent
Measure %.In addition, being converted by solid state component, the ratio of binder resin (A3) and polymerizable compound (B) are 46/57.
Comparative example 9
[preparation of photosensitive polymer combination 9]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
Make dispersible pigment dispersion with
Photosensitive polymer combination 9 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 93.0 matter in total solvent
Measure %, propylene glycol monomethyl ether is 7.0 mass %.In addition, converted by solid state component, binder resin (A1) and polymerism chemical combination
The ratio of object (B) is 70/30.
Comparative example 10
[preparation of photosensitive polymer combination 10]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By dispersible pigment dispersion with
Photosensitive polymer combination 10 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 100 matter in total solvent
Measure %.In addition, being converted by solid state component, the ratio of binder resin (A1) and polymerizable compound (B) are 70/30.
Comparative example 11
[preparation of photosensitive polymer combination 11]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By dispersible pigment dispersion with
Photosensitive polymer combination 11 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 100 matter in total solvent
Measure %.In addition, being converted by solid state component, the ratio of binder resin (A1) and polymerizable compound (B) are 70/30.
Comparative example 12
[preparation of photosensitive polymer combination 12]
Mixing
, keep pigment fully dispersed into dispersible pigment dispersion using ball mill；
By dispersible pigment dispersion with
Photosensitive polymer combination 12 is made in mixing.
In the solvent of photosensitive polymer combination obtained, propylene glycol methyl ether acetate is 65.0 matter in total solvent
Measure %, propylene glycol monomethyl ether is 35.0 mass %.In addition, converted by solid state component, binder resin (A1) and polymerism
The ratio for closing object (B) is 70/30.
<production of patterned coating film>
PET film (beautiful Lumirror (the Le ミ ラ mono-) 75-T60 processed in east) production base is bonded on the glass plate of 2 inch squares
Plate.It is coated with by spin-coating method by photosensitive polymer combination obtained above, 80 on electric hot plate in the PET film side of substrate
Preliminary drying 2 minutes at DEG C.After placing cooling, exposure machine (TME-150RSK is used；Open up Pu Kang (strain) system), under air atmosphere, with
150mJ/cm2Light exposure (on the basis of 365nm) the entire real estate of the substrate for being coated with this solidification compound is carried out
Light irradiation.Moreover, use be formed with 10~100 μm line width and line pitch pattern photomask as photomask.It is irradiated in light
Afterwards, the photomask is shown in the water system containing nonionic surfactants 0.12% and potassium hydroxide 0.04% at 23 DEG C
It impregnates 50 seconds and develops in shadow liquid, by being washed with purified water, patterned coating film is made.Use elcometer
(DEKTAK3；Japanese vacuum technique (strain) system) film thickness of patterned coating film obtained is measured, result is 2 μm.
<evaluation resolution ratio>
Patterned coating film obtained is observed with laser microscope (Axio Imager MAT karr Zeiss society system), will be differentiated
Minimum dimension out is as resolution ratio.Resolution ratio is higher, can more be used for the manufacture of high-accuracy colour filter.
<evaluation development is uneven>
Patterned coating film obtained is observed with laser microscope (Axio Imager MAT karr Zeiss society system), will schemed
There is no water stain film to be evaluated as zero (not observing that development is uneven) in case, there will be water stain film to be evaluated as × (observe aobvious
Shadow is uneven).When observing the manufacture in the case where developing unevenness, for colour filter, uneven color is generated.
<evaluation solvent resistance>
Drip 1ml propylene glycol methyl ether acetate on the pattern formed on aforesaid substrate, after standing 30 seconds, uses rotation
Painting machine rotates it 10 seconds with revolution 1000rpm, gets rid of the propylene glycol methyl ether acetate on pattern.
The film thickness value measured before contacting with propylene glycol methyl ether acetate and after contact is substituted into following formula, calculates film thickness
Conservation rate.The more high then curability of film thickness conservation rate is the better, when manufacture for colour filter, can prevent colour mixture, develops uneven
To improve.
(film thickness conservation rate) (%)=(film thickness after contact)/(film thickness before contact)
<production of full version film (film of entire surface exposure)>
PET film (the beautiful Lumirror75-T60 processed in east) production substrate is bonded on the glass plate of 2 inch squares.In substrate
PET film side by spin-coating method coating by photosensitive polymer combination obtained above, it is pre- at 80 DEG C on electric hot plate
It dries 2 minutes.After placing cooling, exposure machine (TME-150RSK is used；Open up Pu Kang (strain) system), under air atmosphere, with 150mJ/
cm2Light exposure (on the basis of 365nm) light irradiation is carried out to the entire real estate of the substrate for being coated with this solidification compound.
Moreover, not using photomask, entire surface is exposed.With elcometer (DEKTAK3；Japanese vacuum technique (strain) system) it surveys
The film thickness of fixed solid paint film obtained, result are 2 μm.
<gridiron pattern cutting test>
For solid paint film obtained, belt stripping test (the gridiron pattern cutting examination based on JIS K5600-5-6 is carried out
Test), evaluate its adaptation with PET film.As the result is shown in table 1,2.
<pencil hardness>
To solid paint film obtained, it is based on using pencil scratch hardness instrument (Co., Ltd.'s An Tianjing mechanism is made made)
The measurement of the pencil hardness of JIS-K5400.Moreover, setting 1,000g for load.
<viscosity evaluation>
Using film-making machine (helping very much machine material Co. Ltd. system AP75) 5cm square PET film (the beautiful system in east
Lumirror75-T60 coating passes through photosensitive polymer combination obtained above, on electric hot plate, the preliminary drying 2 at 80 DEG C on)
Minute.After placing cooling, the PET film that uncoated 5cm square is bonded on the face for be coated with this solidification compound is (eastern beautiful
Lumirror75-T60 processed) after, remove the PET film (the beautiful Lumirror75-T60 processed in east) of uncoated 5cm square.It will coating
The PET film crossed does not generate unevenness, and the PET film of not formed transfer is evaluated as zero (sight in uncoated PET film
Examine less than viscosity), unevenness will be generated in coated PET film, and the PET of transfer is formed in uncoated PET film
Film is evaluated as × (observing viscosity).When observing viscosity, when manufacture for colour filter, uneven color is generated.
[table 1]
[table 2]
According to the present invention, the photoresist that can prepare the pattern with the hardness and viscosity that are able to satisfy requirement can be provided
Composition.
By using photosensitive polymer combination of the invention, it can must improve that development is uneven and the pattern of high resolution.
The pattern obtained through the invention is as in liquid crystal display device or organic EL display device, display device of electronic paper etc.
Display with colour filter and it is useful.
Claims (9)
1. a kind of photosensitive polymer combination, containing (A) binder resin, (B) polymerizable compound, (C) polymerization initiator and
Cause auxiliary agent and (D) solvent,
Wherein, the weight average molecular weight of (A) binder resin is 8000~100000, and (C) polymerization initiator and initiation auxiliary agent are at least
Containing oxime compound, acylphosphine oxide compound and thioxanthones based compound,
For (D) solvent, the solubility parameter containing 70 mass of mass %~99 % in total solvent is 8.0~9.1 (cal/
cm3)1/2Solvent, and the propylene glycol monomethyl ether containing 1 mass of mass %~30 % in total solvent.
2. photosensitive polymer combination according to claim 1, wherein the acid value of the solid state component of (A) binder resin
It is 80~200.
3. photosensitive polymer combination according to claim 1 or 2, wherein (A) binder resin and (B) polymerism
The ratio for closing object is 50/50 or more when being counted on the basis of quality and being indicated with (A) binder resin/(B) polymerizable compound
And 80/20 or less.
4. photosensitive polymer combination according to claim 1 or 2 also contains (E) colorant.
5. photosensitive polymer combination according to claim 1 or 2, also contains (F) levelling agent, the amount of levelling agent exists
0.001 mass of mass %~0.3 %.
6. a kind of manufacturing method of patterned coated film, including by photonasty tree described in any one in Claims 1 to 5
Oil/fat composition is coated on supporting mass, removing solvent, the process for forming coated film, and
It is exposed after sheltering the coated film, the process of the unexposed portion of the coated film is removed with developer solution.
7. a kind of manufacturing method of patterned coated film, only includes following process:
Photosensitive polymer combination described in any one in Claims 1 to 5 is coated on supporting mass, solvent is removed,
The process for forming coated film, and
It is exposed after sheltering the coated film, the process of the unexposed portion of the coated film is removed with developer solution.
8. a kind of manufacturing method of patterned coated film, including by photonasty tree described in any one in Claims 1 to 5
Oil/fat composition is coated on supporting mass, removing solvent, the process for forming coated film,
It is exposed after sheltering the coated film, the process that the unexposed portion of the coated film is removed with developer solution, and
The process of coated film after 23 DEG C~200 DEG C of at a temperature of holding developer solution removes unexposed portion.
9. a kind of manufacturing method of colour filter, includes
Photosensitive polymer combination described in any one in Claims 1 to 5 is coated on supporting mass, solvent is removed,
The process for forming coated film, and
The process of fabricating patterned coated film, the process include that will be exposed after coated film masking, removed with developer solution
The process of the unexposed portion of the coated film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012099593 | 2012-04-25 | ||
| JP2012-099593 | 2012-04-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103376659A CN103376659A (en) | 2013-10-30 |
| CN103376659B true CN103376659B (en) | 2019-05-17 |
Family
ID=49461983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310142849.8A Active CN103376659B (en) | 2012-04-25 | 2013-04-23 | Photosensitive polymer combination |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2013242551A (en) |
| KR (1) | KR20130120394A (en) |
| CN (1) | CN103376659B (en) |
| TW (1) | TWI588606B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170043084A (en) * | 2015-10-12 | 2017-04-20 | 동우 화인켐 주식회사 | A self-light emitting photosensitive resin composition, color filter and display device comprising the same |
| CN106569389B (en) * | 2015-10-12 | 2021-07-16 | 东友精细化工有限公司 | Self-luminous photosensitive resin composition, color filter and display device including the same |
| CN110462560B (en) * | 2017-03-28 | 2023-07-28 | 株式会社力森诺科 | Transfer photosensitive film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101183217A (en) * | 2006-11-15 | 2008-05-21 | 太阳油墨制造株式会社 | Photosensitive composition |
| CN102375337A (en) * | 2010-08-10 | 2012-03-14 | 住友化学株式会社 | Photosensitive resin composition |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI300795B (en) * | 2001-08-21 | 2008-09-11 | Mitsubishi Chem Corp | Curable resin composition for die coating and process for producing color filter |
| JP4505353B2 (en) * | 2005-03-01 | 2010-07-21 | 富士フイルム株式会社 | Dye-containing negative curable composition, color filter and method for producing the same |
| TW200710572A (en) * | 2005-05-31 | 2007-03-16 | Taiyo Ink Mfg Co Ltd | Photocuring/thermosetting resin composition, curing/setting product thereof and printed wiring board obtained using the same |
| JP4835210B2 (en) * | 2006-03-10 | 2011-12-14 | 東洋インキＳｃホールディングス株式会社 | Coloring composition for color filter, color filter, and method for producing color filter |
| JP4790460B2 (en) * | 2006-03-24 | 2011-10-12 | 富士フイルム株式会社 | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern forming method, and printed circuit board |
| JP2007310060A (en) * | 2006-05-17 | 2007-11-29 | Fujifilm Corp | Photosensitive resin composition and photosensitive film, permanent pattern forming method, and printed wiring board |
| JP2007333885A (en) * | 2006-06-13 | 2007-12-27 | Toyo Ink Mfg Co Ltd | Photosensitive colored composition and color filter formable from the same |
| KR100996046B1 (en) * | 2007-03-29 | 2010-11-22 | 도쿄 오카 고교 가부시키가이샤 | Colored photosensitive resin composition, black matrix, color filter, and liquid crystal display |
| JP4959411B2 (en) * | 2007-04-27 | 2012-06-20 | 富士フイルム株式会社 | Colored photopolymerizable composition, color filter using the same, and method for producing color filter |
| JP2010026362A (en) * | 2008-07-23 | 2010-02-04 | Toyo Ink Mfg Co Ltd | Photosensitive color composition for color filter of transflective liquid crystal display, method for manufacturing color filter using the composition, color filter manufactured by the method, and the transflective liquid crystal display device |
| JP5291405B2 (en) * | 2008-07-31 | 2013-09-18 | 東京応化工業株式会社 | Colored photosensitive resin composition, color filter, and liquid crystal display |
| JP5834379B2 (en) * | 2009-06-25 | 2015-12-24 | Jsr株式会社 | Coloring composition, color filter and color liquid crystal display element |
-
2013
- 2013-04-22 JP JP2013089090A patent/JP2013242551A/en active Pending
- 2013-04-22 KR KR1020130044088A patent/KR20130120394A/en not_active Application Discontinuation
- 2013-04-23 TW TW102114333A patent/TWI588606B/en active
- 2013-04-23 CN CN201310142849.8A patent/CN103376659B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101183217A (en) * | 2006-11-15 | 2008-05-21 | 太阳油墨制造株式会社 | Photosensitive composition |
| CN102375337A (en) * | 2010-08-10 | 2012-03-14 | 住友化学株式会社 | Photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103376659A (en) | 2013-10-30 |
| TWI588606B (en) | 2017-06-21 |
| KR20130120394A (en) | 2013-11-04 |
| JP2013242551A (en) | 2013-12-05 |
| TW201403233A (en) | 2014-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101625525B (en) | Light-sensitive resin composition | |
| CN102799067A (en) | Colouring solidification resin composition | |
| CN105652596A (en) | Colored photosensitive resin composition | |
| CN102375337A (en) | Photosensitive resin composition | |
| JP6303436B2 (en) | Photosensitive resin composition | |
| CN102736416A (en) | Dyeing photosensory resin composition | |
| CN102902160A (en) | Colored solidification resin composition | |
| CN102629076A (en) | Colored photosensitive resin composition | |
| CN103365080A (en) | Colored photopolymer composition | |
| CN102681346B (en) | Photosensitive composition | |
| CN102621809B (en) | Photosensitive composition | |
| CN102445844A (en) | Colored photosensitive resin composition | |
| CN102445851B (en) | Coloring photosensitive combination | |
| CN102681347A (en) | Colored photosensitive resin composition | |
| CN103365088A (en) | Colored curable resin composition | |
| CN103034056A (en) | Colored photosensitive resin composition | |
| CN103376659B (en) | Photosensitive polymer combination | |
| CN103676480A (en) | Photosensitive resin composition | |
| JP7374985B2 (en) | Cyan colored curable composition | |
| CN102914943A (en) | Colored curable resin composition | |
| CN103116247B (en) | Colored curable resin composition | |
| CN102486610A (en) | Coloring photosensitive resin composition | |
| CN102749807A (en) | Photosensitive resin composition | |
| CN102681343A (en) | Colored photosensitive resin composition | |
| CN102809897A (en) | Curable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |