CN1612042A - Colouring photosensitive resin composition - Google Patents

Colouring photosensitive resin composition Download PDF

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Publication number
CN1612042A
CN1612042A CNA200410086521XA CN200410086521A CN1612042A CN 1612042 A CN1612042 A CN 1612042A CN A200410086521X A CNA200410086521X A CN A200410086521XA CN 200410086521 A CN200410086521 A CN 200410086521A CN 1612042 A CN1612042 A CN 1612042A
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Prior art keywords
compound
photosensitive composition
methyl
acrylate
acid
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CNA200410086521XA
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CN100568096C (en
Inventor
武部和男
田中聪
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
    • 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
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • 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
    • 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
    • G03F7/0295—Photolytic halogen compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

A colored photosensitive resin composition contains a binder resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), the coloring material (D) and a solvent (E). The binder resin (A) is an unsaturated group-containing resin obtained by copolymerizing the following (A1)-(A3) and further reacting the resulting copolymer with (A4), and the photopolymerization initiator (C) is at least one compound selected from a group consisting of a triazine compound, an acetophenone compound, a biimidazole compound and an oxime compound: (A1) a compound having an unsaturated bond and at least one skeleton selected from a group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton within a molecule, (A2) a compound having an unsaturated bond and copolymerizable with (A1) and (A3), (A3) unsaturated carboxylic acid, (A4) a compound having an unsaturated bond and an epoxy group within a molecule.

Description

Photosensitive composition
Technical field
The present invention relates to a kind of photosensitive composition.
Background technology
Usually utilize the rotary coating machine on the substrate that forms black matrix pattern, after coating contains the photosensitive composition that is equivalent to red, green and blue pigment of all kinds equably, carry out heat drying (following often be called preceding oven dry), make its film exposure, video picture, as required, be heating and curing again (below, oven dry after often being called) operation, each look all carries out aforesaid operations repeatedly, is manufactured on the colored filter that uses in colour liquid crystal display device or the imaging apparatus etc. by forming pixel of all kinds.For such photosensitive composition, good from photostability, look with low uncertainty, use the acrylic resin that has carboxyl at side chain.For example disclose, behind additional unsaturated carboxylic acid on the polymkeric substance that constitutes by monomer with epoxy radicals and unsaturated double-bond, the photosensitive polymer combination (spy opens flat 8-297366 communique) of the acrylic resin that contains additional polybase formula acid anhydrides and constitute, but when using said composition to form pixel, exist in the such problem of video picture residue takes place on the substrate, or the so inadequately problem of the pencil hardness of the pixel that obtains.
This shows that above-mentioned existing photosensitive composition still has many defectives, and demands urgently further being improved.In order to solve the problem that photosensitive composition exists, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and common product does not have appropriate structure to address the above problem, and this obviously is the problem that the anxious desire of relevant dealer solves.
Because the defective that above-mentioned existing photosensitive composition exists, the inventor is based on being engaged in this type of product design manufacturing abundant for many years practical experience and professional knowledge, actively studied innovation, in the hope of founding a kind of novel photosensitive composition, can improve general existing photosensitive composition, make it have more practicality.Through constantly research, design, and after studying sample and improvement repeatedly, create the present invention who has practical value finally.
Summary of the invention
The objective of the invention is to, overcome the defective that existing photosensitive composition exists, and provide a kind of new photosensitive composition, technical matters to be solved is, when forming pixel, on substrate the generation of video picture residue less, can form the good pixel of pencil hardness, thereby be suitable for practicality more.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of photosensitive composition according to the present invention's proposition, it contains adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C), the photosensitive composition of coloured material (D) and solvent E, adhesive resin (A) is in the multipolymer that obtains in following (A1)～(A 3) generation copolymerization, the resin that contains unsaturated group that makes (A4) reaction again and obtain, and Photoepolymerizationinitiater initiater (C) is from three azines, acetophenone compound, at least a compound of selecting in the group that united imidazole and oxime compound are formed; (A1): in a part, have at least a skeleton from the group that tricyclodecane skeleton and bicyclopentadiene skeleton are formed, selected and the compound of unsaturated link, (A2): the compound that contains (A1) and unsaturated link that (A3) can copolymerization, (A3): unsaturated carboxylic acid, (A4): the compound that in a part, has unsaturated link and epoxy radicals.
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid photosensitive composition, wherein, by the ratio that imports the constituent of (A1)～(A3) separately, the total molal quantity of this constituent relatively, by a mole percent, be following scope: by the component unit that imports (A1): 2～30 moles of %; Component unit by importing (A2): 2～95 moles of %; Component unit by importing (A3): 2～70 moles of %; And, 5～80 moles of % (A4) are reacted and obtain containing the resin of unsaturated group relatively by the constituent that imports (A3).
Aforesaid photosensitive composition wherein contains photopolymerization and causes auxiliary agent (C-1).
Aforesaid photosensitive composition uses described photosensitive composition to form pattern.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.According to the colored filter that the present invention proposes, it contains the pattern that uses described photosensitive composition to form.
The object of the invention to solve the technical problems also adopts following technical scheme to realize.According to the LCD that the present invention proposes, it possesses above-mentioned colored filter.
The present invention compared with prior art has tangible advantage and beneficial effect.By above technical scheme as can be known, in order to reach aforementioned goal of the invention, the inventor etc., must find the above-mentioned few photosensitive composition of problem of picture, and having found that of research contained the adhesive resin of certain unsaturated group and the photosensitive composition of Photoepolymerizationinitiater initiater with keen determination, when forming pixel, on substrate the generation of video picture residue less, can form the good pixel of pencil hardness, thereby finished the present invention.
That is, the present invention provides the photosensitive composition of following [1]～[6].
[1] photosensitive composition, it is the photosensitive composition that contains adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C), coloured material (D) and solvent (E), adhesive resin (A) is in the polymkeric substance that obtains in following (A1)～(A3) generation copolymerization, the resin that contains unsaturated group that makes (A4) reaction again and obtain, and Photoepolymerizationinitiater initiater (C) is at least a compound of selecting from the group that three azines, acetophenone compound, united imidazole and oxime compound are formed.
(A1): in a part, have at least a skeleton from the group that tricyclodecane skeleton and bicyclopentadiene skeleton are formed, selected and the compound of unsaturated link.
(A2): the compound that contains (A1) and unsaturated link that (A3) can copolymerization.
(A3): unsaturated carboxylic acid.
(A4): the compound that in a part, has unsaturated link and epoxy radicals.
[2] photosensitive composition of record in [1], by the ratio that imports the constituent of (A1)～(A3) respectively, the total molal quantity of relative this constituent, by the mole percent, it is following scope, and contain relatively by the constituent that imports (A3), 5～80 moles of % (A4) are reacted and obtain contain the unsaturated group resin.
Component unit by importing (A1): 2～30 moles of %
Component unit by importing (A2): 2～95 moles of %
Component unit by importing (A3): 2～70 moles of %
[3] photosensitive composition of record in [1] or [2] also contains Photoepolymerizationinitiater initiater (C-1).
[4] pattern of the photosensitive composition formation of putting down in writing in each of use [1]～[3].
[5] colored filter pressed of figure that comprises [4] record.
[6] LCD that possesses the colored filter of [5] record.
Below, explain the present invention.
Photosensitive composition of the present invention is the photosensitive composition that contains adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C), coloured material (D) and solvent (E).
Photosensitive composition of the present invention, the preferential selection used as the pigment dispersing resist.The preferential adhesive resin A that selects), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C) and coloured material (D), at random other adjuvants (F) dissolve or are dispersed in the solvent (E) in addition.
Adhesive resin (A) usually, has the reactivity and the alkali dissolution that are caused by the effect of light or heat, works as coloured material.
The adhesive resin that uses in photosensitive composition of the present invention (A) is to make following (A1)～(A3) copolymerization and in the multipolymer that obtains, makes (A4) reaction again and the resin that contains unsaturated group that obtains.
(A1): be in a part, to have at least a skeleton from the group that tricyclodecane skeleton and bicyclopentadiene skeleton are formed, selected and the compound of unsaturated link.
(A2): the compound that contains (A1) and unsaturated link that (A3) can copolymerization.
(A3): unsaturated carboxylic acid.
(A4): the compound that in a part, has unsaturated link and epoxy radicals.
As in a part, having from the compound (A1) of tricyclodecane skeleton (tricyclodecane skeleton) and/or bicyclopentadiene skeleton (dicyclopentadiene skeleton) concrete enumerating (methyl) acrylic acid two cyclopentane base esters (dicyclopentanyl (meth) acrylate), (methyl) acrylic acid dicyclopentenyl ester (dicyclopentenyl (meth) acrylate), (methyl) acrylic acid two cyclopentane base hydroxyl ethyl esters (dicyclopentanyloxyethyl (meth) acrylate), (methyl) acrylic acid dicyclopentenyl hydroxyl ethyl ester (dicyclopentenyloxyethyl (meth) acrylate) etc.These can use separately separately, also can make up more than or equal to 2 kinds of uses.Here, so-called (methyl) acrylate ((meth) acrylate) means propionic ester (acrylate) and/or methacrylate (methacrylate).
As the compound (A2) with above-mentioned (A1) and unsaturated link that (A3) can copolymerization, the nothing of concrete enumerating (methyl) methyl acrylate (methyl (meth) acrylate), (methyl) ethyl acrylate (ethyl (meth) acrylate), (methyl) butyl acrylate (buthyl (meth) acrylate), (methyl) acrylic acid 2-hydroxyl ethyl ester (hydroxyethyl (meth) acrylate), (methyl) acrylic-amino ethyl ester unsaturated carboxylic acids such as (aminoethyl (meth) acrylate) replaces or the substituted alkyl ester;
Contain (methyl) acrylic acid ring pentyl ester (cyclopentyl (meth) acrylate), (methyl) cyclohexyl acrylate (cyclohexyl (meth) acrylate), (methyl) acrylic acid methyl cyclohexane ester (methyl cyclohexyl (meth) acrylate), (methyl) acrylic acid ring heptyl ester cycloheptyl (meth) acrylate), (methyl) acrylic acid ring monooctyl ester (cyclooctyl (meth) acrylate), (methyl) acrylic acid ester in the Meng (menthyl (meth) acrylate), (methyl) acrylic acid cyclopentene ester (cyclopentenyl (meth) acrylate), (methyl) acrylic acid cyclohexene ester (cyclohexenyl (meth) acrylate), (methyl) acrylic acid cycloheptene ester (cycloheptenyl (meth) acrylate), (methyl) acrylic acid cyclooctene ester (cyclooctenyl (meth) acrylate), (methyl) acrylic acid diene in Meng ester (menthadienyl (meth) acrylate), (methyl) isobornyl acrylate (isobornyl (meth) acrylate), (methyl) acrylic acid pinane ester (pinanyl (meth) acrylate), (methyl) acrylic acid adamantyl ester (adamantyl (meth) acrylate), (methyl) acrylic acid norborny ester (norbornyl (meth) acrylate), the substituent unsaturated carboxylic ester compound of ester ring type of (methyl) acrylic acid firpene ester (pinenyl (meth) acrylate) etc.;
One saturated carboxylic acid ester compounds of the glycols of oligomeric (methyl) acrylic acid ethylene glycol one Arrcostab (oligo ethyleneglycolmonoalkyl (meth) acrylate) etc.; The substituent unsaturated carboxylic ester compound that contains the aromatic rings of (methyl) acrylic acid benzyl ester is arranged (benzyl (meth) acrylate), (methyl) acrylic acid phenoxy group ester (phenoxy (meth) acrylate) etc.;
Styrene (styrene), α-Jia Jibenyixi (methyl styrene), vinyl-dimethyl benzene aromatic vinyl based compounds such as (vinyl toluene);
Vinyl acetate (vinyl acetate), propionate vinyl carboxylates such as (vinyl propionate);
(methyl) vinyl cyanide ((meth) acrylonitrile), α-Lv Bingxijing acrylonitrile compounds such as (chloroacrylonitrile);
N-cyclohexyl maleimide (cyclohexyl maleimide), N-phenylmaleimide maleimide compounds such as (phenyl maleimide) etc.
These can use separately separately, also can make up more than or equal to 2 kinds of uses.
As unsaturated carboxylic acid (A3), the concrete acrylic acid enumerated (acrylic acid), methacrylic acid (methacrylic acid) etc.Acrylic acid, methacrylic acid etc. can use separately separately, also can make up more than or equal to 2 kinds of uses.
In addition, except these acrylic or methacrylic acid, also can use a kind of other acid at least.As other acid, the concrete crotonic acid enumerated (crotonic acid), itaconic acid (itaconic acid), maleic acid (maleic acid), fumaric acid unsaturated carboxylic acids such as (fumaric acid) etc.In with a part, can also use the hydroxyl that contains α-(methoxyl) acrylic acid (α-(hydroxymethyl) acrylic acid) etc. and the monomer of carboxyl simultaneously.
(A1)～(A3) copolymerization of in making the present invention, using and in the multipolymer that obtains, by the ratio that imports the constituent of (A1)～(A3) respectively, constitute the total molal quantity of the constituent of above-mentioned multipolymer relatively,, preferentially be chosen in following scope by the mole percent.
Component unit by importing (A1): 2～30 moles of %
Component unit by importing (A2): 2～95 moles of %
Component unit by importing (A3): 2～70 moles of %
In addition, the ratio of above-mentioned constituent more preferably is chosen in following scope.
Component unit by importing (A1): 5～30 moles of %
Component unit by importing (A2): 5～80 moles of %
Component unit by importing (A3): 5～65 moles of %
If above-mentioned component ratio is in above-mentioned scope, then video picture, flexible and stable on heating balance are good, thereby are gratifying.
For example use as following method, make (A1)～(A3) carry out copolymerization and just can make above-mentioned multipolymer.
In the flask that possesses stirring machine, thermometer, backflow cooling tube, drip funnel and nitrogen ingress pipe, the total amount of (A1)～(A3) is pressed quality criteria relatively, imports 0.5～20 times solvent (E), and atmosphere in the flask is become nitrogen from air displacement.After this, after making solvent (E) be warming up to 40～140 ℃, with 0.1～8 hour from the funnel that drips, the ormal weight of (A1)～(A3) relatively drips in above-mentioned flask, the i.e. total amount of (A1)～(A3), press quality criteria, add 0～20 times solvent (E), and azobis isobutyronitrile (azobisisobutyronitrile) or benzoyl peroxide polymerization initiators such as (benzoyl peroxide), the total molal quantity of (A1)～(A3) adds the solution (stirring and dissolving under room temperature or heating) of 0.1～10 times of mole % relatively, stirs 1～10 hour at 40～140 ℃ again.
Moreover, in above-mentioned process, a part or the full dose of the polymerization initiator of can in flask, packing into, a part or the full dose of also can in flask, pack into (A1)～(A3).In addition, in order to control molecular weight or molecular weight distribution, move agent as chain and can use α-Jia Jibenyixierjuwu or sulfhydryl compound.The use amount of α-Jia Jibenyixierjuwu or sulfhydryl compound, the total amount of (A1)～(A3) is pressed quality criteria relatively, is 0.005～5%.Moreover above-mentioned polymerizing condition is considered manufacturing equipment or the thermal value that produced by polymerization etc., can adjust charging method or temperature of reaction aptly.
In the multipolymer that obtains making (A1)～(A3) copolymerization, make (A4) reaction just can access the adhesive resin (A) that uses among the present invention again.By in above-mentioned multipolymer additional (A4), can in adhesive resin, give light/Thermocurable.
As the compound that in a part, has unsaturated link and epoxy radicals (A4), concrete (methyl) glycidyl acrylate (glycidyl (meth) acrylate), (methyl) acrylic acid 3 enumerated, 4-epoxy cyclohexyl (3,4-epoxycyclohexyl (meth) acrylate), (methyl) acrylic acid 3,4-epoxycyclohexyl methyl esters (3,4-epoxycyclohexylmethyl (meth) acrylate), (methyl) acrylic acid diglycidyl methyl esters (methyl glycidyl (meth) acrylate) etc.Wherein, especially preferentially use (methyl) glycidyl acrylate (glycidyl (meth) acrylate).These can use separately separately, also can make up more than or equal to 2 kinds of uses.
(A4), making (A1)～(A3) polymerization relatively and carboxyl (from the A3 composition) in the resin that obtains, promptly by importing (A3) individual component unit, is 5～80 moles of %, preferably 10～80 moles of %.
(A4) if ratio of components just obtains sufficient photo-curable in above-mentioned scope, makes light sensitivity and pencil hardness and deposits, and reliability is good, thereby is gratifying.
For example make above-mentioned multipolymer and (A4) react, just can make adhesive resin (A) by using as following method.
Make the interior atmosphere of flask become air from nitrogen replacement, relatively by importing above-mentioned multipolymer, (A3) component unit, by the mole percent, in flask, put into 5～80 moles of % (A4), catalysts as carboxyl and epoxy radicals, the total amount of (A1)～(A4) relatively, press quality criteria, for example put into three dimethylamino cresols (tris (dimethyl-aminomethyl) phenol) of 0.01～5%, as polymerization inhibitor, the total amount of relative (A1)～(A4), press quality criteria, put into 0.001～5% quinhydrones (hydroquinone),, just can make above-mentioned multipolymer and (A4) react by 60～130 ℃ of reactions 10 hours.Moreover and polymerizing condition is similarly considered manufacturing equipment or the thermal value that produced by polymerization etc., can adjust charging method or temperature of reaction aptly.
Adhesive resin (A) by the weight-average molecular weight of its polystyrene conversion, more fortunately in 3,000～100,000 the scope, is preferably in 5,000～50,000 the scope.Adhesive resin (A) if weight-average molecular weight 3,000～100, in 000 the scope, when video picture, just be difficult for the film attenuate takes place, and when video picture, be in the good tendency of the property removed of non-pixel portion, be gratifying therefore.
The molecular weight distribution of adhesive resin (A) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] better is 1.5～6.0, preferably 1.8～4.0.Molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is if 1.5～6.0, and then video picture is good, is gratifying therefore.
The content of adhesive resin (A), full shape branch, normally 5～90 quality %, the preferably scope of 10～70 quality % admittedly in the photosensitive composition relatively.The content of adhesive resin (A), press quality criteria, if 5～90 quality %, dissolubility to imaging liquid then is sufficient, on the substrate of non-pixel portion, just be difficult for taking place the video picture residue, and also be difficult to take place the film attenuate of the pixel portion of exposure portion when video picture, the property removed of non-pixel portion is in good tendency, is gratifying therefore.
The optical polymerism compound (B) of Shi Yonging is to carry out polymerization and the compound that obtains under the effect of light and Photoepolymerizationinitiater initiater described later in the present invention, can enumerate monofunctional monomer, bifunctional monomer, other polyfunctional monomer etc.
As the object lesson of monofunctional monomer, can enumerate acrylic acid nonyl phenyl carbitol ester (nonylphenylcarbitol acrylate), acrylic acid 2-hydroxyl-3-phenoxy group propyl ester (2-hydroxy-3-phenoxypropyl acrylate), acrylic acid 2-second hexyl carbitol ester (2-ethylhexylcarbitol acrylate), acrylic acid 2-hydroxyl ethyl ester (2-hydroxyethyl acrylate), N-vinyl pyrrolidone (N-vinylpyrrolidone) etc.
Object lesson as bifunctional monomer, can enumerate two (methyl) acrylic acid (1, the 6-hexanediol) ester (1,6-hexanediol di (meth) acrylate), two (methyl) acrylic acid glycol ester (ethylene glycol di (meth) acrylate), two (methyl) acrylic acid DOPCP (neo-pentyl glycol di (meth) acrylate), two (methyl) acrylic acid triethyleneglycol ester (triethylene glycol di (meth) acrylate), two (acryloxy ethyl) ethers (bis (acryloyloxyethyl) ether of BisphenolA) of bisphenol-A, two (methyl) acrylic acid (3-methyl pentanediol) ester (3-methylpentanediol di (meth) acrylate) etc.
As other the object lesson of polyfunctional monomer, can enumerate trimethylolpropane tris (methyl) acrylate (trimethylolpropane tri (meth) acrylate), pentaerythrite three (methyl) acrylate (pentaerythritol tri (meth) acrylate), pentaerythrite four (methyl) acrylate (pentaerythritol tetra (meth) acrylate), dipentaerythritol five (methyl) acrylate (dipentaerythritol penta (meth) acrylate), dipentaerythritol six (methyl) acrylate (dipentaerythritol hexa (meth) acrylate) etc.
Among these, especially preferentially use bifunctional monomer, polyfunctional monomer.
Optical polymerism compound (B), total 100 parts by weight of adhesive resin (A) and optical polymerism compound (B) usually with 1～60 parts by weight, preferably use with the scope of 5～50 parts by weight relatively.Optical polymerism compound (B) by above-mentioned benchmark, if the scope of 1～60 parts by weight just has the intensity of pixel portions or the tendency that flatness becomes good, is gratifying therefore.
The Photoepolymerizationinitiater initiater of Shi Yonging (C) is at least a compound of selecting from the group that three azine based compounds, acetophenone based compound, bisglyoxaline based compound and oxime compound are formed in the present invention.
The photosensitive composition that contains above-mentioned Photoepolymerizationinitiater initiater (C) is an ISO, and the film that uses said composition to form, and it is good that the intensity of its pixel portions or surface smoothing become.
Have again, at Photoepolymerizationinitiater initiater (C) if in use photopolymerization to cause auxiliary agent (C-1) simultaneously, contain these photosensitive composition, then become more ISO, improve using said composition and throughput rate when forming colored filter, therefore is preferential the selection.
As three above-mentioned azine based compounds, for example can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3,5-three azines (2,4-bis (trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine), 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3,5-three azines (2,4-bis (trichloromethyl)-6-(4-methoxynaphtyl)-1,3,5-triazine), 2, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3,5-three azines (2,4-bis (trichloromethyl)-6-(piperonyl)-1,3,5-triazine), 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, and 5-three azines (2,4-bis (trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine), 2, two (trichloromethyl)-6-[2-(the 5-methylfuran base-2-yl) vinyl of 4-]-1,3,5-three azines (2,4-bis (trichloromethyl)-6-[2-(5-methylfuran-2-yl) ethenyl]-1,3,5-triazine), 2, two (trichloromethyl)-6-[2-(furyl-2-yl) vinyl of 4-]-1,3, and 5-three azines (2,4-bis (trichloromethyl)-6-[2-(furan-2-yl) ethenyl]-1,3,5-triazine), 2, two (trichloromethyl)-6-[2-(4-lignocaine-2-tolyl) vinyl of 4-]-1,3,5-three azines (2,4-bis (trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) ethenyl]-1,3,5-triazine), 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 4-Dimethoxyphenyl) vinyl]-1,3,5-three azines (2,4-bis (trichloromethyl)-6-[2-(3,4-dimethoxyphenyl) ethenyl]-1,3,5-triazine) etc.
In addition, as above-mentioned acetophenone based compound, for example can enumerate diethoxy acetophenone (diethoxy acetophenone), 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone (2-hydroxy-2-methyl-1-phenylpropane-1-on), benzyl dimethyl ketal (benzyl dimethyl ketal), 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone (2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methylpropane-1-on), 1-hydroxy-cyclohexyl benzophenone (1-hydroxycyclohexylphenylketone), 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-on), 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butane-1-on), 2-hydroxy-2-methyl-1-[4-(1-ethylene methacrylic) alkane phenyl] oligomer etc. of propane-1-ketone (2-hydroxy-2-methyl-1-[4-(1-methylvinyl) phenyl] propane-1-on).As the acetophenone based compound, can use the spy to open the acetophenone based compound of putting down in writing in the clear 63-264560 communique, as this acetophenone based compound, for example can enumerate compound with following formula (1) expression.
In the formula (1), R 1～R 4Respectively hydrogen atom, halogen atom, hydroxyl, the phenyl that can replace benzyl that can replace or the naphthyl that can replace independently with the alkyl of carbon number 1～12 with the alkyl of carbon number 1～12 with the alkyl of carbon number 1～12.
As the object lesson of the compound of representing with formula (1), can enumerate 2-methyl-2-amino (4-morpholino phenyl) ethane-1-ketone (2-methyl-2-amino (4-morpholinophenyl) ethane-1-on), 2-ethyl-2-amino (4-morpholino phenyl) ethane-1-ketone (2-ethyl-2-amino (4-morpholinophenyl) ethane-1-on), 2-propyl group-2-amino (4-morpholino phenyl) ethane-1-ketone (2-propyl-2-amino (4-morpholinophenyl) ethane-1-on), 2-butyl-2-amino (4-morpholino phenyl) ethane-1-ketone (2-butyl-2-amino (4-morpholinophenyl) ethane-1-on), 2-methyl-2-amino (4-morpholino phenyl) propane-1-ketone (2-methyl-2-amino (4-morpholinophenyl) propane-1-on), 2-methyl-2-amino (4-morpholino phenyl) butane-1-ketone (2-methyl-2-amino (4-morpholinophenyl) butane-1-on), 2-ethyl-2-amino (4-morpholino phenyl) propane-1-ketone (2-ethyl-2-amino (4-morpholinophenyl) propane-1-on), 2-ethyl-2-amino (4-morpholino phenyl) butane-1-ketone (2-ethyl-2-amino (4-morpholinophenyl) butane-1-on), 2-methyl-2-methylamino (4-morpholino phenyl) propane-1-ketone (2-methyl-2-methylamino (4-morpholinophenyl) propane-1-on), 2-methyl-2-dimethylamino (4-morpholino phenyl) propane-1-ketone (2-methyl-2-diamino (4-morpholinophenyl) propane-1-on), 2-methyl-2-lignocaine (4-morpholino phenyl) ethane-1-ketone (2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-on) etc.
As above-mentioned united imidazole, for example can enumerate 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole), 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline (2,2 '-bis (2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole) (for example open flat 6-75372 communique with reference to the spy, Te Kaiping 6-75373 communique etc.), 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (alkoxyphenyl radical) bisglyoxaline (2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraalkoxyphenylbiimidazole), 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline (2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetradialkoxyphenylbiimidazole), 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (three alkoxyphenyl radicals) bisglyoxaline (2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetratrialkoxyphenylbiimidazole) (for example with reference to special public clear 48-38403 communique, the spy opens clear 62-174204 communique etc.), 4,4 ', 5,5 '-imidazolium compounds (for example opening flat 7-10913 communique with reference to the spy) that replaced by the carboxylic alkoxy of phenyl of position etc.Among these, especially preferentially use 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl bisglyoxaline.
As above-mentioned oxime compound, for example can enumerate adjacent carbethoxyl group-α-oximido-1-phenyl-propane-1-ketone (o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-on) etc.
Figure A20041008652100121
In addition, if do not damage the degree of effect of the present invention, can also use normally used other Photoepolymerizationinitiater initiater etc. in this field simultaneously.As other Photoepolymerizationinitiater initiater, for example can enumerate benzoin based compound, benzophenone based compound, thioxanthones based compound, anthracene based compound etc.These can use separately separately, also can make up more than or equal to 2 kinds of uses.
As the benzoin based compound, for example can enumerate benzoin (benzoin), benzoin methylether (benzoin methyl ether), benzoin ethyl ether (benzoin ethyl ether), benzoin iso-propylether (benzoin isopropyl ether), benzoin isobutyl ether (benzoinisobutyl ether) etc.
As the benzophenone based compound, for example can enumerate benzophenone (benzophenone), methyl o-benzoylbenzoate (methyl o-benzoyl benzoate), 4-phenyl benzophenone (4-phenylbenzophenone), 4-benzoyl-4 '-methyldiphenyl sulphur (4-benzoyl-4 '-methyldiphenylsulfide), 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone (3,3 ', 4,4 '-tetra (tert-butylperoxycarbonyl)-benzophenone), 2,4, the 6-tri-methyl benzophenone (2,4,6-trimethylbenzophenone) etc.
As the thioxanthones based compound, for example can enumerate 2-isopropyl thioxanthone (2-isopropylthioxanthone), 4-isopropyl thioxanthone (4-isopropylthioxanthone), 2,4-diethyl thioxanthone (2,4-diethylthioxanthone), 2,4-two clopenthixal ketones (2,4-dichlorothioxanthone), 1-chloro-4-propoxyl group thioxanthones (1-chloro-4-propoxythioxanthone) etc.
As the anthracene based compound, for example can enumerate 9,10-dimethoxy anthracene (9,10-dimethoxyanthracene), 2-ethyl-9,10-dimethoxy anthracene (2-ethyl-9,10-dimethoxyanthracene), 9,10-diethoxy anthracene (9,10-diethoxyanthracene), 2-ethyl-9,10-diethoxy anthracene (2-ethyl-9,10-diethoxyanthracene) etc.
Other, Photoepolymerizationinitiater initiater as other can enumerate 2,4,6-trimethylbenzene formyl oxidation diphenyl sulfide (2,4,6-trimethylbenzoyldiphenylphosphineoxide), 10-butyl-2-chloro-acridine ketone (10-butyl-2-chloroacridone), 2-EAQ (2-ethylanthraquinone), benzil (benzil), 9, the 10-phenanthrenequione (9,10-phenanthrenequinone), camphorquinone (camphorquinone), phenyl glyoxalic acid methylester (phenyl methyl glyoxylate), two luxuriant titanium (titanocene) compounds etc.
In addition, also can use Photoepolymerizationinitiater initiater,, for example can enumerate the spy and show this Photoepolymerizationinitiater initiater put down in writing in the 2002-544205 communique as this Photoepolymerizationinitiater initiater with the base that can cause that chain moves.
As Photoepolymerizationinitiater initiater, for example can enumerate compound with following formula (2)～(7) expression with the base that can cause that above-mentioned chain moves.
Figure A20041008652100141
Figure A20041008652100151
The constituent (A2) of the multipolymer that obtains as making above-mentioned (A1)～(A3) copolymerization also can use the Photoepolymerizationinitiater initiater with the base that can cause that above-mentioned chain moves.Use the multipolymer have the Photoepolymerizationinitiater initiater of the base that can cause that above-mentioned chain moves and to obtain as constituent (A2), can and adhesive resin (A) and using.
In addition, also can in Photoepolymerizationinitiater initiater (C), the combined light polymerization cause auxiliary agent (C-1) and use.
Cause auxiliary agent (C-1) as photopolymerization, preferentially use amines, carboxylic acid compound.
Object lesson as amines, can enumerate triethanolamine (triethanol amine), methyldiethanolamine (methyl diethanol amine), triisopropanolamine fatty amine compounds such as (triisopropanolamine), 4-dimethylaminobenzoic acid methyl esters (methyl 4-dimethylamino benzoate), 4-dimethyl ethyl aminobenzoate (ethyl 4-dimethylamino benzoate), 4-dimethylaminobenzoic acid isopentyl ester (isoamyl 4-dimethylamino benzoate), 4-dimethylaminobenzoic acid 2-b hexyl (2-ethylhexyl4-dimethylamino benzoate), benzoic acid 2-dimethylaminoethyl (2-dimethylaminoethyl benzoate), N, N-dimethyl-p-toluidine (N, N-dimethylp-toluidine), 4,4 '-two (dimethylamino) benzophenone (4,4 '-bis (dimethylamino) benzophenone) (common name Michler's keton), 4,4 '-aromatic amines compound such as two (lignocaine) benzophenone (4,4 '-bis (diethylamino) benzophenone).As amines, preferentially use aromatic amines compound.
As the object lesson of carboxylic acid compound, can enumerate thiophenyl acetate (phenylthioaceticacid), methylbenzene ethyl thioglycollic acid (methylphenylthioacetic acid), ethylbenzene ethyl thioglycollic acid (ethylphenylthioacetic acid), methylthio phenyl ethyl thioglycollic acid (methylethylphenylthioacetic acid), dimethyl benzene ethyl thioglycollic acid (dimethylphenylthioacetic acid), methoxybenzene ethyl thioglycollic acid (methoxyphenylthioacetic acid), dimethoxy benzene ethyl thioglycollic acid (dimethoxyphenylthioacetic acid), chlorobenzene ethyl thioglycollic acid (chlorophenylthioacetic acid), dichloro-benzenes ethyl thioglycollic acid (dichlorophenylthioacetic acid), N-phenylglycine (N-phenylglycine), naphthoxy acetic acid aromatic series heteroacid classes such as (phenoxyacetic acid).
The use amount of Photoepolymerizationinitiater initiater (C), total 100 mass fractions of relative adhesive resin (A) and optical polymerism compound (B), 0.1～40 mass fraction normally, 1～30 mass fraction preferably, photopolymerization causes the use amount of auxiliary agent (C-1), by above-mentioned benchmark, normally 0.1～50 mass fraction, preferably 1～40 mass fraction.
Photoepolymerizationinitiater initiater (C) if use amount in above-mentioned scope, photosensitive composition just becomes ISO, using the intensity of the pixel portions that said composition forms or in the lip-deep flatness of this pixel portions the tendency that becomes good is just arranged, is gratifying therefore.Have again, photopolymerization cause auxiliary agent (C-1) if use amount in above-mentioned scope, it is higher that the light sensitivity of photosensitive composition just becomes, and uses the throughput rate of the colored filter of said composition formation just to be in the tendency of raising, so be gratifying.
The coloring pigment that uses among the present invention (D), pigment normally, normally used organic pigment or inorganic pigment are preferential the selections in the pigment dispersing resist.
As inorganic pigment, can enumerate the metallic compound of metal oxide or metallic complex salt etc., the metal oxide of the concrete iron enumerated, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. or composite metal oxide etc.
As organic pigment and inorganic pigment, can enumerate the compound that in Colour Index (Colour Index) (The Societyof Dyers and Colourists publication), is categorized into pigment, more specifically can enumerate the pigment of the following color index (C.I.) of picture number, but be not limited to these.
C.I. pigment yellow 20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173 and 180;
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242,254,255 and 264;
C.I. pigment violet 14,19,23,29,32,33,36,37 and 38;
C.I. pigment blue 15, (15: 3,15: 4,15: 6 etc.), 21,28,60,64 and 76;
C.I. pigment Green 7,10,15,25,36 and 47;
C.I. pigment brown 28;
C.I. pigment black 1 and 7 etc.
These coloring pigments (D) can use separately, also can make up more than or equal to 2 kinds of uses.The content of coloring pigment (D) is benchmark with the full shape component admittedly in the photosensitive composition, normally 3～60 quality %, the preferably scope of 5～55 quality %.By above-mentioned benchmark, the content of coloring pigment (D) is if the scope of 5～60 quality %, even form film, the colour saturation of pixel also is enough, the property removed of non-pixel portions does not reduce yet when video picture, thereby the non-incident tendency of residue is arranged, and is gratifying therefore.
The solvent that uses among the present invention (E) can use the various organic solvents that use in the photosensitive composition field.
As its concrete example, can enumerate glycol monomethyl ether (ethylene glycol monomethylether), ethylene glycol monoethyl ether (ethylene glycol monoethyl ether), propyl cellosolve (ethylene glycol monopropyl ether), ethylene glycol monobutyl ether (EGMBE) ethylene glycol one alkyl ethers such as (ethyleneglycol monobutyl ether);
Diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), diethyl carbitol (diethylene glycol diethyl ether), diglycol dipropyl ether (diethyleneglycol dipropyl ether), diethylene glycol dibutyl ether diglycol dialkyl ethers such as (diethylene glycol dibutylether);
Methyl Cellosolve acetic acid esters (methyl cellosolve acetate), ethyl Cellosolve acetic acid esters alkyl Cellosolve acetate esters such as (ethyl cellosolve acetate);
Propylene glycol monomethyl ether acetic acid esters (propylene glycol monomethyl etheracetate), ethoxy propyl acetate (propylene glycol monoethyl etheracetate), propylene glycol one propyl ether acetic acid esters (propylene glycol monopropyl etheracetate), butylene glycol methyl ether acetate (methoxy butyl acetate), pentanediol methyl ether acetate alkylene glycol alkyl ether acetate esters such as (methoxy pentyl acetate);
Benzene (benzene), toluene (toluene), dimethylbenzene (xylene), rice arenes such as (mesitylene);
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine;
3-ethoxyl ethyl propionate (ethyl 3-ethoxy propionate), 3-methoxypropionic acid methyl esters ester classes such as (methyl 3-methoxy propionate);
(γ-butyrolactone) waits cyclic ester class etc. to gamma-butyrolacton.
In the above-mentioned solvent, consider from the aspect of coating, drying property, in above-mentioned solvent, can enumerate the organic solvent of 100 ℃～200 ℃ of boiling points preferably, better can enumerate ester classes such as alkylene glycol alkyl ether acetate esters, acetone class, 3-ethoxyl ethyl propionate or 3-methoxypropionic acid methyl esters, the best propylene glycol enumerated monomethyl ether acetic acid esters, ethoxy propyl acetate, cyclohexanone, triethoxy ethyl propionate, trimethoxy methyl propionate etc.
These solvents (E) can use separately separately, also can make up more than or equal to 2 kinds of uses.
The content of the solvent in the photosensitive composition of the present invention (E), the photosensitive composition that contains this solvent is relatively all measured, and presses quality percentage, normally 60～90 quality %, preferably 70～85 quality %.The content of solvent (E) is by above-mentioned benchmark, if 60～90 quality % are using roll coater (roller coater), rotary coating machine (spin coater), slit and rotary coating machine (slit ﹠amp; Spin coater), gap coating machine (slit coater) (also often being called crack coating machine (die coater)), when ink-jet apparatus for coating such as (ink jet) is coated with, then exist coating to be in good tendency, be gratifying therefore.
In photosensitive composition of the present invention, as required, also can contain filling agent, other the adjuvant (F) of macromolecular compound, pigment dispersing agent, adhesion promoter, antioxidant, ultraviolet light absorber, anti-condensation logging material etc.
As filling agent, example illustrates glass, silicon dioxide, aluminium oxide etc. particularly.
As other macromolecular compound, can enumerate curable resins such as epoxy resin (epoxy resin), maleimide (maleimide resin) resin particularly, the thermoplastic resin of polyvinyl alcohol (PVA) (polyvinylalcohol), polyacrylic acid (polyacrylic acid), polyglycol one alkyl ether (polyethylene glycol monoalkyl ether), polyacrylic acid fluoroalkyl ester (polyfluoroalkyl acrylate), polyester (polyester), polyurethane (polyurethane) etc. etc.
As pigment dispersing agent, can use commercially available surfactant, for example can enumerate surfactants such as silicon system, fluorine system, ester system, kation system, negative ion system, nonionic system, both sexes etc.These can use separately separately, also can make up more than or equal to 2 kinds of uses.As above-mentioned surfactant, for example except polyoxyethylene alkyl ether class (polyoxyethylene alkyl ethers), polyoxyethylene alkyl phenyl ether class (polyoxyethylene alkyl phenyl ethers), polyethylene glycol di class (polyoxyethylene glycol diethers), the sorbitan fatty acid esters class, fatty acid modified polyesters, the tertiary amine modified polyurethane, polyethyleneimine: amine etc., can enumerate with trade name KP (Shin-Etsu Chemial Co., Ltd's system), POLYFLOW (Kyoeisha Chemical Co., Ltd.'s system), EFTOP (ト-ケ system プ ロ ダ Network Star society system), MEGAFAC (big Japanese イ Application キ chemical industry Co., Ltd. system), Fluorad (Sumitomo ス リ-エ system Co., Ltd. system), AsahiGuard, Surflon (more than, Asahi Glass Co., Ltd's system), SOLSPERSE (ゼ ネ カ Co., Ltd. system), EFKA (EFKA CHEMICALS corporate system), PB821 (monosodium glutamate Co., Ltd. system) etc.
As adhesion promoter, can enumerate vinyltrimethoxy silane (vinyltrimethoxysilane) particularly, vinyltriethoxysilane (vinyl triethoxysilane), vinyl three (2-methoxy ethoxy) silane (vinyltris (methoxyethoxy) silane), N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane (N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane), N-(2-aminoethyl)-3-aminopropyl methyltrimethoxy silane (N-(2-aminoethyl)-3-aminopropyltrimethoxy silane), 3-aminopropyl triethoxysilane (3-aminopropyltriethoxy silane), the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-isobutylene acyl-oxygen base propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane etc.
As antioxidant, can enumerate 2,2 particularly '-thiobis (4-methyl-6-tert-butyl phenol), 2,6-di-t-butyl-4-cresols etc.
As ultraviolet light absorber, can enumerate 2-(the 3-tert-butyl group-2-hydroxy-5-methyl phenyl)-5-chlorobenzotriazole, alkoxy benzo benzophenone etc. particularly.
As anti-condensation logging material, can enumerate sodium polyacrylate etc. particularly.
Photosensitive composition of the present invention for example can use the following method preparation of picture.In advance coloured material (D) and solvent (E) are mixed, become until the mean grain size of coloured material and be less than or equal to 0.2 μ m degree, use bead grinding machine etc. to disperse.At this moment, as required, use pigment dispersing agent, and also often cooperate adhesive resin (A) part or all.Resulting dispersion liquid (below, often be called abrasive) in, for the concentration that becomes regulation is added remainder, optical polymerism compound (B) and the Photoepolymerizationinitiater initiater (C) of adhesive resin (A), employed other compositions, the solvent that appends as required again as required, and obtain the photosensitive composition of purpose.
The photo-curable resin composition that is prepared into so for example, is coated on as following on the ground, carries out photocuring and video picture, just can form black matrix" or colored pixels (rendered image).At first, at substrate (normally glass) or divide the layer that constitutes to go up the coating said composition by the solid shape of the photosensitive composition that forms earlier, by the volatile ingredient of prebake removal solvent etc., and obtain level and smooth filming.The thickness of filming of this moment is about 1～3 μ m degree.Obtain like this film on, by being used to form the mask irradiation ultraviolet radiation of black matrix" or pixel (image).At this moment, shine parallel rays equably on all, and for the aligning of the tram of carrying out mask and substrate, preferably use mask aligner or device such as portable exposure device one by one in exposure portion.After this make the contact aqueous alkali of filming that solidify to finish, dissolve non-exposure portion,, just obtain black matrix" or pixel (image) as purpose by video picture.After the video picture, as required, also can be 150～230 ℃ of back oven dry of implementing about 10～60 minutes (min).
The imaging liquid that uses in the video picture after pattern forms exposure normally contains the aqueous solution of alkali compounds and surfactant.
Alkali compounds can be any of inorganic or organic alkali compounds.
As the object lesson of inorganic alkaline compound, can enumerate NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium borate, potassium borate, ammoniacal liquor etc.
In addition, as the object lesson of organic basic compound, can enumerate tetramethylammonium hydroxide, hydroxide 2-hydroxyethyl trimethylammonium, monomethyl amine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, Mono Isopropylamine, diisopropylamine, monoethanolamine etc.These inorganic and organic basic compounds can use separately separately, also can make up more than or equal to 2 kinds of uses.
The preferred concentration of the alkali compounds in the alkali imaging liquid is the scope of 0.01～10 quality %, preferably 0.03～5 quality %.
Surfactant in the alkali imaging liquid can use any of non-ionic surfactant, anionic surfactant or cationic surfactant.
As the object lesson of non-ionic surfactant, can enumerate polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyethylene oxide derivatives, ethylene oxide/propylene oxide segmented copolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene D-sorbite fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid esters, polyoxyethylene alkyl amine etc.
As the object lesson of anionic surfactant, can enumerate alkarylsulphonic acid salts such as alkylsurfuric acid salts such as higher alcohol sulfuric ester salt, NaLS or Texapon Special, neopelex or dodecyl sodium sulphosuccinate such as lauryl alcohol sodium sulfovinate or oleyl alcohol sodium sulfovinate etc.
As the object lesson of cationic surfactant, can enumerate amine salt such as stearyl amine hydrochloride or chlorination lauryl trimethylammonium or quaternary ammonium salt etc.
These surfactants can use separately separately, also can make up more than or equal to 2 kinds of uses.
Surfactant concentrations in the alkali imaging liquid, normally 0.01～10 quality % is more preferably 0.05～8 quality %, preferably 0.1～5 quality %.
Through as the coating of above coloring phototonus resin solution, drying, form exposure, be called the operation of video picture then to the pattern of the dry coating that obtains, just obtain being equivalent to the pixel or the black matrix" of the look of the coloured material in the photo-curable resin composition, again according to the chromatic number of colored filter needs, only carry out these operations repeatedly, just obtain colored filter.
Colored filter, normally on substrate, dispose the colored filter of the three primary colors pixel of black matrix" and red, green and blue, but use the photosensitive composition of the present invention that contains the coloured material that is equivalent to certain look, by carrying out above-mentioned operation, obtain the black matrix" or the pixel of this look, about other look, also use the photosensitive composition of the present invention that contains the coloured material that is equivalent to the look that requires, carry out same operation, just can on substrate, dispose black matrix" and three primary colors pixel.Certainly, the arbitrary look in black matrix" and the three primary colors, only two looks or three looks, it also is possible using photo-curable resin composition of the present invention.
Moreover, be the black matrix" of light shield layer, for example can use formation such as chromium layer.
The colored filter that uses photosensitive composition of the present invention to make, the film thickness difference in the face is little, for example is 1～3 μ m, film thickness difference is less than or equals 0.15 μ m, and then be less than or equal 0.05 μ m.Therefore, the colored filter that obtains like this, flatness is good, in addition this colored filter is assembled on the colour liquid crystal display device, just can be with the good LCD of high qualification rate quality bills of materials.
Can provide according to the present invention, when forming pixel, on substrate the generation of video picture residue less, can form the photosensitive composition of the good pixel of pencil hardness.
Photosensitive composition of the present invention, light sensitivity are also good, and when forming pixel, it is few that the video picture residue takes place on substrate.In addition, few at pixel portions generation rough surface, resulting pixel pencil hardness height, reliability is good, thereby high-quality colored filter can be provided.
Therefore, use as pigment dispersing resist (pigment dispersed reist),, just can reach the good and high-quality colored filter of throughput rate if make colored filter with photosensitive composition of the present invention.
In addition, photosensitive composition of the present invention also can be used as ultraviolet hardening China ink, photoresist (photoresist), painted optical confinement layer (photo spacer) use.Remove the photosensitive polymer combination of coloured material from photosensitive composition of the present invention, also can be in the middle use of becoming a useful person of the protrusion-shaped of dielectric film, optical confinement layer, finishing coat (over coat) (planarization film), liquid crystal aligning control usefulness.
Photosensitive composition of the present invention can be suitable for being formed on the colored pixels of using in colour liquid crystal display device or the imaging apparatus etc. (rendered image).
In sum, the photosensitive composition of special construction of the present invention, it has above-mentioned many advantages and practical value, and in like product, do not see have similar structural design to publish or use and really genus innovation, no matter it structurally or bigger improvement all arranged on the function, have large improvement technically, and produced handy and practical effect, and more existing photosensitive composition has the multinomial effect of enhancement, thereby be suitable for practicality more, and have the extensive value of industry, really be a novelty, progressive, practical new design.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of instructions, below with preferred embodiment of the present invention and conjunction with figs. describe in detail as after.
Embodiment
Below in conjunction with preferred embodiment, to its embodiment of photosensitive composition, feature and the effect thereof that foundation the present invention proposes, describe in detail as after.Illustrate in greater detail the present invention based on embodiment, but much less, the present invention is not subjected to the restriction of embodiment.Moreover in following embodiment, Comparative Examples, the % and the umber of expression content, use amount unless otherwise specified, are to be benchmark with the quality.
Synthesizing of＜Resin A 〉
Possessing stirring machine, thermometer, the backflow cooling tube, drip in the flask of funnel and nitrogen ingress pipe, import 182g propylene glycol monomethyl ether acetic acid esters, after atmosphere in the flask become nitrogen from air displacement, be warming up to 100 ℃, then from the funnel that drips, with 2 hours 70.5g (0.40mol) methacrylic acid alkene benzyl esters that in flask, drip, 43.0g (0.5mol) methacrylic acid, and the solution that adds the 3.6g azobis isobutyronitrile in the compound that constitutes by monomethyl acrylate of 22.0g (0.10mol) tricyclodecane skeleton (Hitachi changes into the system FA-513M of Co., Ltd.) and 136g propylene glycol monomethyl ether acetic acid esters, continue stirrings 5 hours at 100 ℃ again.Then, atmosphere in the flask is become air from nitrogen replacement, in flask, drop into 35.5g[0.25mol, (carboxyl of the methacrylic acid that uses in this reaction is 50mol% relatively)], three dimethylamino cresols of 0.9g and 0.145g quinhydrones, make reaction continue 6 hours at 110 ℃, obtaining solid shape branch acid value is the Resin A of 79mgKOH/g.The weight-average molecular weight that is converted into polystyrene of utilizing GPC (gel permeation chromatography) to measure is 13000, and molecular weight distribution (Mw/Mn) is 2.1.
Synthesizing of＜resin B 〉
Possessing stirring machine, thermometer, the backflow cooling tube, drip in the flask of funnel and nitrogen ingress pipe, import 333g propylene glycol monomethyl ether acetic acid esters, after atmosphere in the flask become nitrogen from air displacement, be warming up to 100 ℃, then from the funnel that drips, with 2 hours 70.5g (0.40mol) methacrylic acid alkene benzyl esters that in flask, drip, 71.1g (0.50mol) glycidyl methacrylate, and the solution that adds the 3.6g azobis isobutyronitrile in the compound that constitutes by monomethyl acrylate of 22.0g (0.10mol) tricyclodecane skeleton (Hitachi changes into the system FA-513M of Co., Ltd.) and 164g propylene glycol monomethyl ether acetic acid esters, continue stirrings 5 hours at 100 ℃ again.Then, atmosphere in the flask is become air from nitrogen replacement, in flask, drop into 43.0g[0.5mol, (glycidyl of the glycidyl methacrylate of using in this reaction is 100mol% relatively)], three dimethylamino cresols of 0.9g and 0.145g quinhydrones, make reaction continue 6 hours at 110 ℃, when solid shape branch acid value becomes 1mgKOH/g, finish reaction.Then add 60.9g (0.40mol) tetrahydrophthalic anhydride, 0.8g triethylamine, 120 ℃ of reactions 3.5 hours, obtaining solid shape branch acid value was the resin B of 80mgKOH/g.The weight-average molecular weight that is converted into polystyrene of utilizing GPC (gel permeation chromatography) to measure is 12000, and molecular weight distribution (Mw/Mn) is 2.1.
In the mensuration of the weight-average molecular weight (Mw) of above-mentioned binder polymer and number-average molecular weight (Mn), use the GPC method, under following condition, carry out.
Device: HLC-8120GPC (eastern ソ-Co., Ltd.'s system)
Post: TSK-GELG4000HXL+TSK-GELG2000HXL (being connected in series)
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran
Flow velocity: 1.0ml/min
Injection rate IR: 50 μ l
Detecting device: RI
Measure test portion concentration: 0.6 quality % (solvent: tetrahydrofuran)
Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (eastern ソ-Co., Ltd.'s system)
With likening to of above-mentioned weight-average molecular weight that obtains and number-average molecular weight is molecular weight distribution (Mw/Mn).
Embodiment 1
In each composition of in following table 1, putting down in writing, be precolor material (D) pigment and be the total amount of the pigment dispersing agent of adjuvant (F), the potpourri of relative pigment dispersing agent and propylene glycol monomethyl ether acetic acid esters, becoming 20 quality % ground mixes, after using the bead grinding machine that pigment is disperseed fully, bead isolation contains the residual components of the surplus of propylene glycol monomethyl ether acetic acid esters in interpolation, mix, obtain photosensitive composition.
Table 1
Coloured material (D) C.I. pigment green 36 C.I. pigment yellow 150 5.51 umber 2.43 umbers
Adhesive resin (A) Resin (A) (being converted into solid shape branch) 6.59 umber
Optical polymerism compound (B) Six acrylic acid dipentaerythritol ester (KAYARAD DPHA, Japanese medicine Co., Ltd. system) 5.71 umber
Photoepolymerizationinitiater initiater (C) (Irgacure 369 for butanone for 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl), Ciba Specialty Chemical corporate system) 4,4 '-two (N, the N-lignocaine) benzophenone (BAB-F, hodogaya chemical Co., Ltd. system) 1.46 umber 0.49 umber
Solvent (E) Propylene glycol monomethyl ether acetic acid esters 76.00 umber
Adjuvant (F) Pigment dispersing agent (polyester system) epoxy resin (SUMI-EPOXY ESCN-195XL, Sumitomo Chemical Company Ltd's system) 1.20 umber 0.61 umber
With neutral lotion, water and alcohol successively with 2 inches square glass substrates (コ one ニ Application グ society system, #1737) clean after, carry out drying.Make with 100mJ/cm 2Exposure (365nm) exposure, the thickness after the thick oven dry when having omitted videograph process becomes 1.9 μ m ground and be coated with above-mentioned photosensitive composition on this glass substrate, then, in the purification baking oven, 100 ℃ carry out 3 minutes in advance=preceding oven dry.After the cooling, be coated with the substrate of this photosensitive composition and the interval of quartz glass system photomask (scope that has 1～100% makes transmissivity that the pattern of step-like variation and line/space pattern of 1 μ m to 50 μ m take place) and reached 100 μ m, use the extra-high-pressure mercury vapour lamp (trade name: USH-250D) of ウ シ オ Electric Co., Ltd system, under air atmosphere, with 100mJ/cm 2Exposure (265nm) carry out rayed.After this, above-mentioned filming in containing the water system imaging liquid that 0.12% nonionic is surfactant and 0.06% potassium hydroxide, 26 ℃ the dipping official hours carry out video picture, after the washing, 220 ℃ carry out 30 minutes after the oven dry.Do not see rough surface in the pixel portions that obtains.In addition, for pixel portions, the video picture residue does not take place on substrate.And, even video picture is only 15mJ/cm in order to form the necessary minimum necessary exposure of no shaggy pattern 2
Embodiment 2
In embodiment 1, except Irgacure-369 being altered to following oxime series initiators, carry out 1 identical operations with embodiment, evaluation result is shown in Table 2.
Figure A20041008652100241
Comparative Examples 1
In embodiment 1, except Resin A is altered to resin B, carry out 1 identical operations with embodiment.Evaluation result is shown in Table 2.
Table 2
Embodiment 1 Embodiment 2 Comparative Examples 1
Light sensitivity * 1 (mJ/cm 2) ????15 ????12 ????20
Video picture residue * 2 on the substrate ????○ ????○ ????×
Section configuration * 3 ????○ ????○ ????○
Pencil hardness * 4 ????6H ????6H
The explanation of note in the table
* 1: even the expression video picture is used to form the necessary minimum necessary exposure of no shaggy pattern.
* 2: zero, no video picture residue on the substrate, * the video picture residue arranged on substrate
* 3: the section configuration of observing the pixel end with SEM (scanning electron microscope).Zero: along coniform, *: anti-coniform
* 4: except not using photomask and embodiment 1 make in the same manner, make cured coating film.The mensuration of pencil hardness is according to JIS K5600-5-4.
As known from Table 2, containing the embodiment 1 of unsaturated group adhesive resin and 2 the photo-curable resin composition of containing of the present invention, is ISO, and the shape residue is also few, and the pencil hardness height of resulting pixel, obtains high-quality colored filter.And do not contain the photosensitive composition that contains the Comparative Examples 1 of unsaturated group adhesive resin of the present invention, the quality that makes colored filter of video picture residue reduces, the pencil hardness of resulting pixel reduces, and can not obtain high-quality colored filter.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.

Claims (6)

1, a kind of photosensitive composition, it is characterized in that: it contains the photosensitive composition of adhesive resin (A), optical polymerism compound (B), Photoepolymerizationinitiater initiater (C), coloured material (D) and solvent E, adhesive resin (A) is in the multipolymer that obtains in following (A1)～(A3) generation copolymerization, the resin that contains unsaturated group that makes (A4) reaction again and obtain, and Photoepolymerizationinitiater initiater (C) is at least a compound of selecting from the group that three azines, acetophenone compound, united imidazole and oxime compound are formed;
(A1): in a part, have at least a skeleton from the group that tricyclodecane skeleton and bicyclopentadiene skeleton are formed, selected and the compound of unsaturated link,
(A2): contain the compound of (A1) and unsaturated link that (A3) can copolymerization,
(A3): unsaturated carboxylic acid,
(A4): the compound that in a part, has unsaturated link and epoxy radicals.
2, photosensitive composition according to claim 1 is characterized in that wherein by the ratio that imports the constituent of (A1)～(A3) separately, and the total molal quantity of this constituent relatively by a mole percent, is following scope:
Component unit by importing (A1): 2～30 moles of %;
Component unit by importing (A2): 2～95 moles of %;
Component unit by importing (A3): 2～70 moles of %; And, 5～80 moles of % (A4) are reacted and obtain containing the resin of unsaturated group relatively by the constituent that imports (A3).
3, photosensitive composition according to claim 1 and 2 is characterized in that wherein containing photopolymerization and causes auxiliary agent (C-1).
4,, it is characterized in that using described photosensitive composition to form pattern according to the described photosensitive composition of arbitrary claim in the claim 1 to 3.
5, colored filter contains the described pattern of claim 4.
6, LCD, it possesses the described colored filter of claim 5.
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