CN101256356B - Radiation sensitive composition, color filter, and liquid crystal display device - Google Patents

Radiation sensitive composition, color filter, and liquid crystal display device Download PDF

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CN101256356B
CN101256356B CN2007103059401A CN200710305940A CN101256356B CN 101256356 B CN101256356 B CN 101256356B CN 2007103059401 A CN2007103059401 A CN 2007103059401A CN 200710305940 A CN200710305940 A CN 200710305940A CN 101256356 B CN101256356 B CN 101256356B
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蓑轮贵树
饭岛孝浩
成濑秀则
林俊仁
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JSR Corp
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to a radiation sensitive composition, a color filter and a liquid crystal display element. The radiation sensitive composition comprises (A) a colorant, (B) an alkaline-soluble resin, (C) a multi-functional monomer and (D) a photopolymerization initiator, characterized in that the radiation sensitive composition is used for forming a coloring layer, and (B) the alkaline-soluble resin has a structure represented by the formula (B-1): where R1, R2 and R3 independently represent a hydrogen atom or a alkyl having 1 to 10 carbon atoms, X is a univalent group having acryloyl and methacryloyl or vinyl or 1-methyl vinyl, Y is a bivalent organic group, and h is an integral of 1 to 5.

Description

Radiation-ray sensitive composition, colored filter and liquid crystal display cells
Technical field
The present invention relates to be used to form radiation-ray sensitive composition, colored filter and the black matrix and the color liquid crystal display device of the dyed layer that uses in color liquid crystal display arrangement and the kinescope element etc.In more detail; Relate to excellent dyed layer and dyed layers that development property is excellent such as easily to make all performances such as the rerum natura of filming and form and use radiation-ray sensitive composition, have the colored filter of the dyed layer that forms by said composition and black matrix that constitutes by the dyed layer that said composition forms and the color liquid crystal display device that possesses this colored filter or black matrix.
Background technology
In the past; When using radiation-ray sensitive composition to form colored filter or black matrix; On the substrate of the light shield layer that perhaps is pre-formed required pattern on the substrate, be coated with radiation-ray sensitive composition; Remove and desolvate, the exposure of filming that obtains, development are required pattern, obtain dyed layer as pel array of all kinds or black matrix.There is following problem in the dyed layer that so forms: when developing; Be easy to generate residue or scum on unexposed the substrate or on the light shield layer; The dyed layer that forms in the exposure portion is insufficient to the adaptation of substrate or light shield layer, and then the poor properties of filming of the dyed layer that after development, is dried by the fire by the back.
Japanese kokai publication hei 7-110577 communique discloses and has contained addition polymerization property monomer that (1) Photoepolymerizationinitiater initiater, (2) have an ethylenic unsaturated double-bond and (3) and make the optical polymerism composition of the alkali soluble resin that styrene or its nuclear substitutive derivative obtain with the aralkylamine compound reaction amino with having uncle of the multipolymer of maleic anhydride have alkali dissolution property, can form the colored filter of excellences such as anti-development fluidity, alkali resistance, substrate adaptation.But,, therefore must further improve pigment concentration in the composition owing to seeking to form the radiation-ray sensitive composition of the black matrix of high colored filter of excitation and high light-proofness in recent years.As a result, during the development of composition, residue becomes and is easy to residually more, and then produces the problem of substrate and the adaptation deficiency of dyed layer, and people hope and can address this problem.
In recent years in the technical field of colored filter; Forming the employed substrate size of colored filter maximizes; And reduce exposure and shorten pitch time and become main flow, pixel of seeking to form under the low exposure and black matrix have the excellent pattern shape, with the adaptation of substrate etc.But; For known in the past colored radiation-sensitive composition; If exposure reduces, then damaged or undercut takes place in pattern, perhaps owing to be easy to take place pattern from peeling off of substrate etc. with the adaptation deficiency of substrate; Therefore, be difficult to when shortening pitch time, obtain the pixel and the black matrix of good pattern form.
Still do not know not take place this problem in the past and can form the radiation-ray sensitive composition of the high black matrix" of the high colored filter of excitation and light-proofness.
Summary of the invention
The present invention is in order to address the above problem; The radiation-ray sensitive composition that provides the dyed layer that shows excellent development property to form usefulness more particularly, provides a kind of novel dyed layer to form and uses radiation-ray sensitive composition; Said composition can not produce pattern edge yet under low exposure damaged and undercut; And can residual not dissolved matter when developing or can not produce scum silica frost at pattern edge, can form fine pattern, can form the high black matrix of high colored filter of excitation and light-proofness.
Other purposes of the present invention are to provide black matrix that colored filter with the dyed layer that is formed by above-mentioned radiation-ray sensitive composition and the dyed layer that is formed by this radiation-ray sensitive composition constitute and the color liquid crystal display device that possesses this colored filter or black matrix.
But other purpose and advantage by following explanation knowledge capital invention.
According to the present invention; Above-mentioned purpose of the present invention and advantage, the first, realize through a kind of radiation-ray sensitive composition; It contains (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer, (D) Photoepolymerizationinitiater initiater; (B) alkali soluble resin has the structure of following formula (B-1) expression, and above-mentioned radiation-ray sensitive composition is used to form dyed layer
(in the formula (B-1), each R 1, R 2And R 3The alkyl of representing hydrogen atom or carbon number 1～10 independently of one another, X are any monovalent organic radical group or vinyl or the 1-methyl ethylene with acryloyl group or methacryl, and Y is the organic group of divalence, and h is 1～5 integer.)
Above-mentioned purpose of the present invention and advantage; Second; The black matrix that colored filter through having the dyed layer that is formed by above-mentioned radiation-ray sensitive composition or the dyed layer that is formed by this radiation-ray sensitive composition constitute realizes, the 3rd realizes through the color liquid crystal display device that possesses above-mentioned colored filter or black matrix.
Among the present invention, " radioactive ray " comprise visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc., the layer that " dyed layer " expression is made up of the pel array that constitutes colored filter or as itself layer of black matrix.
Among the present invention, " colored filter " at least by substrate be formed at its lip-deep each color pixel array (dyed layer) and constitute, also can further have black matrix, nesa coating, thin film transistor (TFT), diaphragm, sept etc.
Embodiment
Below, the present invention is elaborated.
Radiation-ray sensitive composition of the present invention contains (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater.
(A) colorant
The tone of (A) colorant that contains in the radiation-ray sensitive composition of the present invention does not have special qualification, can suitably select according to the purposes of target dyed layer, can be that toner also can be an inorganic colourant.
Toner can be enumerated out for example organic pigment, natural colouring matter etc.Inorganic colourant can be enumerated out inorganic pigment, extender pigment etc.
As above-mentioned organic pigment, for example at color index (C.I.; The distribution of The society of Dyers andColourists company) is classified as the compound of pigment (Pigment) in, specifically can enumerates as being labeled as the compound of following color index (C.I.) numbering.
C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 180;
C.I. pigment orange 36, C.I. pigment orange 43, C.I. pigment orange 51;
C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 123, C.I. pigment red 149, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 180, C.I. pigment red 21 5, C.I. paratonere 242, C.I. paratonere 254;
C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29;
C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6;
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58;
C.I. pigment brown 23, C.I. pigment brown 25;
C.I. pigment black 1, C.I. pigment black 7.
As above-mentioned inorganic pigment, can enumerate like lead sulfate, yellow lead (yellow plumbous), zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, amber (amber), black, the synthetic iron oxide black of titanium, carbon black etc.
As above-mentioned extender pigment, can enumerate like titanium dioxide, barium sulphate, zinc white, lime carbonate etc.
Above-mentioned carbon black; Can enumerate like furnace black, thermal black, acetylene black etc.; Specifically can enumerate out furnace blacks such as SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, MAF, FEF, FEF-HS, SRF, SRF-LM, SRF-LS, GPF, ECF, N-339, N-351 respectively; Thermal black such as FT, MT.
As their commercially available article, can enumerate out respectively, for example ダ イ ア Block ラ Star Network A (Mitsubishi Chemical's (strain) production), シ one ス ト 9 SAF such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network SA (Mitsubishi Chemical's (strain) production), シ one ス ト 9H SAF-HS such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network I (Mitsubishi Chemical's (strain) production), シ one ス ト 6 ISAF such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network LI (Mitsubishi Chemical's (strain) production), シ one ス ト 60 ISAF-LS such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network 234 (Mitsubishi Chemical's (strain) production), シ one ス ト 7HM ISAF-HS such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network H (Mitsubishi Chemical's (strain) production), シ one ス ト 3 HAF such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network LH (Mitsubishi Chemical's (strain) production), シ one ス ト 300 HAF-LS such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network SH (Mitsubishi Chemical's (strain) production), シ one ス ト KH HAF-HS such as (productions of East Sea カ one ボ Application (strain));
ダ イ ア Block ラ Star Network 550M (Mitsubishi Chemical's (strain) production), シ one ス ト 116 MAF such as (productions of East Sea カ one ボ Application (strain));
The ダ イ ア Block ラ Star Network E (Mitsubishi Chemical's (strain) production) that Mitsubishi Chemical Ind produces, シ one ス ト SO, シ one ス ト F, シ one ス ト FM FEF such as (above are the production of カ one ボ Application (strain) in the East Sea);
ダ イ ア Block ラ Star Network N760M (Mitsubishi Chemical's (strain) production), HTC#SL SRF-LM such as (Nippon Steel's chemistry (strain) are produced);
ダ イ ア Block ラ Star Network G (Mitsubishi Chemical's (strain) production), シ one ス ト V GPF such as (productions of East Sea カ one ボ Application (strain)).
These colorants can use with its particle surface of polymer modification as required.For the polymer overmold method of carbon blacksurface, for example the spy open flat 9-71733 communique, spy open flat 9-95625 communique, spy open have in the flat 9-124969 communique etc. disclosed.
Said colorant can use separately also and can use mixing more than 2 kinds.
When radiation-ray sensitive composition of the present invention is used to form colored filter; Require colored filter to have high meticulous color development and thermotolerance, therefore, as (A) colorant; Preferred color emissivity height and the high colorant of thermotolerance; The high colorant of preferred especially heat-resisting decomposability has preferred toner, especially preferably uses organic pigment.
On the other hand, when radiation-ray sensitive composition of the present invention is used to form black matrix, require black matrix to have the light-proofness of height, therefore,, preferably use organic pigment or carbon black as (A) colorant.
Colorant of the present invention can use spreading agent, dispersing aid as required together.
As above-mentioned spreading agent, can use various surfactants like kation, negative ion, nonionic and both sexes, or suitable spreading agent such as polymeric dispersant, wherein preferred polymers spreading agent.Specifically can enumerate out alkylammonium salt or phosphate ester salt, the kation sex comb type graft polymer etc. of acrylic copolymer, modified acroleic acid analog copolymer, polyurethane, polyester, high-molecular copolymer.At this; Kation sex comb type graft polymer is meant that on trunk polymkeric substance 1 molecule with a plurality of basic groups (cationic functional group) grafting combines the polymkeric substance of the structure of the branched polymers more than 2 molecules; For example, can enumerate out by the trunk polymer moieties is that polyethyleneimine, branched polymers partly are polymkeric substance of constituting of the ring-opening polymerization polymer of 6-caprolactone etc.Preferred modified acroleic acid analog copolymer, polyurethane, kation sex comb type graft polymer in these spreading agents.
This spreading agent can obtain through commercial sources; For example can enumerate out Disperbyk-2000, Disperbyk-2001 modified acroleic acid analog copolymers such as (above are that PVC Star Network ケ ミ one (BYK) company produces) respectively; Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 polyurethane such as (above are that PVC Star Network ケ ミ one (BYK) company produces), ソ Le ス パ one ス 24000 kation sex comb type graft polymer such as (above are the production of Japanese Le one Block リ ゾ one Le (strain)) etc.
These spreading agents can use separately also and can use mixing more than 2 kinds.
The use amount of spreading agent with respect to (A) colorant 100 weight portions, is preferably below 50 weight portions, more preferably below 30 weight portions.
Said dispersing aid can be enumerated out, and for example blue pigment derivant, yellow uitramarine derivant etc. specifically can be enumerated out for example copper phthalocyanine derivative thing etc.
(B) alkali soluble resin
(B) alkali soluble resin that contains in the radiation-ray sensitive composition of the present invention has the structure of above-mentioned formula (B-1) expression.
In the above-mentioned formula (B-1), R 1And R 2Be preferably hydrogen atom.R 3Be preferably hydrogen atom or methyl, more preferably hydrogen atom.H is preferably 1.
In the above-mentioned formula (B-1), X is preferably the univalent perssad of following formula (X-1) expression.
Figure S2007103059401D00061
(in the formula (X-1), R is hydrogen atom or methyl, and i is 2～5 integer, and j is 0～10 integer.)
In the above-mentioned formula (X-1), i is preferably 2 or 5, and j is preferably 0～4 integer.
In the above-mentioned formula (X-1), Y is preferably alkylidene or the alkenylene of methylene, carbon number 2～6, and (these alkylidenes and alkenylene also can be cut off by oxygen atom halfway.), (this arlydene also can have carboxyl or anhydride group for the arlydene of cyclohexane two bases, cyclohexene two bases or carbon number 6～12.), more preferably methylene, ethylidene, 1,3-propylidene, 1,2-ethenylidene, 1; 2-allylidene, 1,3-allylidene, 2,3-allylidene, cyclohexane-1,2-two bases, 4-cyclohexene-1; 2-two bases, 1,2-phenylene, biphenyl-2,2 '-two bases or formula-CH 2-O-CH 2The divalent group of-expression.
Except the structure of above-mentioned formula (B-1) expression, (B) alkali soluble resin that radiation-ray sensitive composition of the present invention contains also preferably has at least a structure in the structure of the structure that is selected from following formula (B-2) expression and following formula (B-3) expression.
Figure S2007103059401D00071
In the formula (B-2), R 4Be the aryl of carbon number 6～10 or the alicyclic group of carbon number 3～10.
Figure S2007103059401D00072
In the formula (B-3), R 5～R 10Be hydrogen atom, halogen atom, hydroxyl, methylol or carboxyl independently of one another.
R in the above-mentioned formula (B-2) 4The aryl of carbon number 6～10 can enumerate out for example phenyl, o-hydroxy-phenyl, a hydroxy phenyl, p-hydroxybenzene, o-tolyl, a tolyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, naphthyl etc.; The alicyclic group of carbon number 3～10 can be enumerated out, for example cyclohexyl etc.R in the above-mentioned formula (B-2) 4Preferred phenyl.
R in the above-mentioned formula (B-3) 5～R 10Halogen atom, can enumerate out chlorine atom, bromine atoms or iodine atom, preferred chlorine atom.
In the above-mentioned formula (B-3), R 5～R 10Preferred all is hydrogen atom, perhaps R 7Be chlorine atom, hydroxyl or methylol and R 5And R 6And R 8～R 10All be hydrogen atom, more preferably R 5～R 10Preferred all is hydrogen atom, perhaps R 7Be hydroxyl and R 5And R 6And R 8～R 10It all is hydrogen atom.
In (B) alkali soluble resin that contains in the radiation-ray sensitive composition of the present invention, the structure of above-mentioned formula (B-1) expression is preferably 5～80 weight %, more preferably 10～60 weight % with respect to the total amount of (B) alkali soluble resin.The ratio of the structure through making formula (B-1) expression in (B) alkali soluble resin is in this scope, and the development property that contains its radiation-ray sensitive composition improves, and the inhibition of the generation of the residue during development becomes more effective, thereby preferred.
(B) alkali soluble resin that contains in the radiation-ray sensitive composition of the present invention; The structure that preferably has above-mentioned formula (B-2) expression in the scope of total amount below 50 weight % with respect to (B) alkali soluble resin more preferably has the structure of above-mentioned formula (B-2) expression in the scope of 5～45 weight %.(B) alkali soluble resin preferably has the structure of above-mentioned formula (B-3) expression in the scope of total amount below 60 weight % with respect to (B) alkali soluble resin, more preferably in the scope of 5～40 weight %, have the structure of above-mentioned formula (B-3) expression.(B) alkali soluble resin; Also can have the structure of above-mentioned formula (B-2) expression and (B-3) expression structure the two; At this moment, the proportional summation that contains of the two is preferably below the 80 weight % with respect to the total amount of (B) alkali soluble resin, more preferably 10～70 weight %.At this moment, containing separately of the structure of the structure of above-mentioned formula (B-2) expression or above-mentioned formula (B-3) expression is proportional, preferably in the scope of above-mentioned value separately.
The structure through making formula (B-2) expression in (B) alkali soluble resin and the structure of above-mentioned formula (B-3) expression contain the proportional above-mentioned scope that is in, the advantage that the dyed layer that can obtain to form further improves the adaptation of substrate, thereby preferred.
The polystyrene conversion weight-average molecular weight Mw that (B) alkali soluble resin that contains in the radiation-ray sensitive composition of the present invention is measured through gel permeation chromatography (GPC) is preferably 2000～100000, and more preferably 3000～50000.Weight-average molecular weight through making (B) alkali soluble resin is in this scope, can obtain the advantage that the dissolubility of alkali soluble resin in solvent or developer solution further improves.For (B) alkali soluble resin, polystyrene conversion weight-average molecular weight Mw that measures through GPC and the ratio Mw/Mn of number-average molecular weight Mn are preferably 1.0～4.0, and more preferably 1.0～3.0.Mw/Mn through making (B) alkali soluble resin is in above-mentioned scope, and the resolution of the radiation-ray sensitive composition that can obtain to obtain and the dyed layer of formation are to the further advantage that improves of the adaptation of substrate.
This (B) alkali soluble resin can be through for example having following formula (B-1 ')
(formula (B-1 ') in, R 1, R 2, R 3With h respectively with above-mentioned formula (B-1) in synonym.)
The resin (below be called " styrene epoxy resin ") of the structure of expression; Preferably have the structure of above-mentioned formula (B-1 ') expression and be selected from the resin of at least a structure in the structure of structure and (B-3) expression of above-mentioned formula (B-2) expression, the compound of the following formula of addition (a1) expression (below be called " unsaturated monocarboxylic acid (a1).)，
X-COOH(a1)
(in the formula (a1), synonym in X and the above-mentioned formula (B-1).)
Then, the compound of the following formula of addition (a2) expression (below be called " multi-anhydride (a2) ".) make.
Figure S2007103059401D00091
(in the formula (a2), synonym in Y and the above-mentioned formula (B-1).)
Above-mentioned styrene epoxy resin be preferably for example following formula (b1) expression compound (below be called " compound (b1) ".) the multipolymer of polymkeric substance or compound (b1) and other free-radical polymerised compounds.
Figure S2007103059401D00092
(in the formula (b-1), R 1, R 2, R 3With h respectively with above-mentioned formula (B-1) in synonym.)
As the object lesson of compound (b-1), for example can enumerate out adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether, Alpha-Methyl between vinyl benzyl glycidol ether, the adjacent vinyl benzyl glycidol ether of Alpha-Methyl, Alpha-Methyl to vinyl benzyl glycidol ether, 2,3-2-glycidyl oxygen ylmethyl styrene, 2; 4-2-glycidyl oxygen ylmethyl styrene, 2,5-2-glycidyl oxygen ylmethyl styrene, 2,6-2-glycidyl oxygen ylmethyl styrene, 2; 3,4-three-glycidyl oxygen ylmethyl styrene, 2,3; 5-three-glycidyl oxygen ylmethyl styrene, 2,3,6-three-glycidyl oxygen ylmethyl styrene, 3; 4; 5-three-glycidyl oxygen ylmethyl styrene, 2,4,6-three-glycidyl oxygen ylmethyl styrene etc.Wherein, preferred adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to the vinyl benzyl glycidol ether.These compounds also can make up 2 kinds with on use.
As above-mentioned other free-radical polymerised compounds, can enumerate out the compound (below be called " compound (b2) ") of following formula (b2) expression, the compound of following formula (b3) expression (below be called " compound (b3) ") and compound (b1), (b2) and (b3) in addition free-radical polymerised compound (below be called " compound (b4) ").
Figure S2007103059401D00101
(in the formula (b2), R 4With synonym in the above-mentioned formula (B-2).)
Figure S2007103059401D00102
(in the formula (b3), R 5～R 10Respectively with the middle synonym of above-mentioned formula (B-3).)
Above-claimed cpd (b2) is the compound that on (B) alkali soluble resin, imports the structure of above-mentioned formula (B-2) expression.As the object lesson of compound (b2), for example can enumerate out between N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, N-aminomethyl phenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide, N-cyclohexyl maleimide etc. between hydroxy phenyl maleimide, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, N-.Wherein, preferred N-phenylmaleimide.
Above-claimed cpd (b3) is the compound that on (B) alkali soluble resin, imports the structure of above-mentioned formula (B-3) expression.As the object lesson of compound (b3), for example can enumerate out acenaphthylene, 5-chlorine acenaphthylene, 5-hydroxymethyl acenaphthylene, 5-hydroxyl acenaphthylene etc.Wherein preferred acenaphthylene and 5-hydroxyl acenaphthylene.
As compound (b4), for example can enumerate out styrene, AMS, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, indenes, to aromatic ethenyl compounds such as vinyl benzyl methyl ethers;
Methyl acrylate; Methyl methacrylate; Ethyl acrylate; Jia Jibingxisuanyizhi; The acrylic acid n-propyl; N propyl methacrylate; Isopropyl acrylate; Isopropyl methacrylate; N-butyl acrylate; N-BMA; Isobutyl acrylate; Isobutyl methacrylate; Sec-butyl acrylate; The secondary butyl ester of methacrylic acid; Tert-butyl acrylate; The metering system tert-butyl acrylate; Acrylic acid 2-hydroxyl ethyl ester; Methacrylic acid 2-hydroxyl ethyl ester; Acrylic acid 2-hydroxypropyl acrylate; Methacrylic acid 2-hydroxypropyl acrylate; Acrylic acid 3-hydroxypropyl acrylate; Methacrylic acid 3-hydroxypropyl acrylate; Acrylic acid 2-hydroxy butyl ester; Methacrylic acid 2-hydroxy butyl ester; Acrylic acid 3-hydroxy butyl ester; Methacrylic acid 3-hydroxy butyl ester; Acrylic acid 4-hydroxy butyl ester; Methacrylic acid 4-hydroxy butyl ester; Allyl acrylate; Allyl methacrylate; Benzyl acrylate; Benzyl methacrylate; Phenyl acrylate; Phenyl methacrylate; Methoxyl triethylene glycol acrylic ester; Methoxyl triethylene glycol methacrylate; Single acrylic acid glyceride; Esters of unsaturated carboxylic acids such as monomethyl acrylic acid glyceride;
Unsaturated carboxylic acid aminoalkyl esters such as acrylic acid 2-amino ethyl ester, methacrylic acid 2-amino ethyl ester, the amino propyl ester of acrylic acid 2-, the amino propyl ester of methacrylic acid 2-, the amino propyl ester of acrylic acid 3-, the amino propyl ester of methacrylic acid 3-;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether, methyl propenoic acid glycidyl ether;
Vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, 1, vinyl cyanide based compounds such as 1-two acrylonitriles;
Unsaturated amides such as acrylic amide, Methacrylamide, α-chloropropene acid amides, N-hydroxyethyl acrylic amide, N-hydroxyethyl Methacrylamide;
Aliphatics conjugated diolefines such as 1,3-butadiene, isoprene, chlorbutadiene;
Polystyrene, PMA, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, polysiloxane etc. have the macromonomer of single acryloyl group or monomethyl acryloyl group etc. at the polymer molecule chain end.
These compounds (b4) can be separately or mix 2 kinds with on use.
When styrene epoxy resin is the multipolymer of compound (b1) and other free-radical polymerised compounds; Consider the synthetic complexity of (B) alkali soluble resin; The copolymerization ratio of compound (b1) and other free-radical polymerised compounds, can according to the structure of the structure of the structure of above-mentioned formula (B-1) expression in (B) alkali soluble resin, above-mentioned formula (B-2) expression and above-mentioned formula (B-3) expression separately the expectation value of proportion come suitably to set.
For example, the copolymerization ratio of compound (b1) is preferably 5～80 weight %, more preferably 10～60 weight %.If the copolymerization ratio of compound (b1) surpasses 80 weight %, be prone to take place gelation during the addition reaction of the unsaturated monocarboxylic acid of stating after then (a1), make difficulty sometimes.On the other hand; The copolymerization ratio of compound (b1) is less than 5 weight %; The alkali-soluble of the resin that then obtains as the result of the addition reaction of styrene epoxy resin and unsaturated monocarboxylic acid (a1) and multi-anhydride (a2) is not enough; When use contains its radiation-ray sensitive composition formation dyed layer, have in the anxiety that produces residue or scum on unexposed the substrate or on the light shield layer.
The copolymerization ratio of compound (b2) is preferably below the 50 weight %, more preferably 5～45 weight %.The copolymerization ratio of compound (b3) is preferably below the 60 weight %, more preferably 5～40 weight %.Can coupling compound (b2) during copolymerization and (b3), the copolymerization ratio of this moment is preferably below the 80 weight % as compound (b2) and total amount (b3), more preferably below 5～70 weight %.The copolymerization ratio of coupling compound (b2) and each compound (b3) time is preferably in the scope of above-mentioned value separately.
Styrene epoxy resin is preferably especially
(1) compound (b1),
(2) compound (b2) and (b3) at least a and
(3) compound (b4)
Multipolymer; Copolymerization ratio as each compound at this moment; Preferred compound (b1) is 10～60 weight %, compound (b2) and (b3) at least a (coupling compound (b2) and be its total amount (b3) time) be 5～60 weight %, and compound (b4) is below the 50 weight %.
The ratio Mw/Mn of the weight-average molecular weight Mw of styrene epoxy resin and weight-average molecular weight and number-average molecular weight can suitably set according to the Mw and the Mw/Mn of (B) alkali soluble resin of expectation.
Above-mentioned styrene epoxy resin can be made the polymerization of mixtures of for example above-claimed cpd or compound in the presence of suitable radical polymerization initiator through in appropriate solvent.When making styrene epoxy resin operable solvent for example can use with after state the identical solvent of solvent that uses in the radiation-ray sensitive composition of the present invention.Radical polymerization initiator for example can be enumerated out, and 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile) etc.
Above-mentioned unsaturated carboxylic acid (a1) can suitably be selected according to the X kind of above-mentioned formula (B-1) desired.Preferred unsaturated carboxylic acid (a1) for example can be enumerated out acrylic acid, methacrylic acid, ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates, succinic acid (2-acryloxy ethyl) ester, succinic acid (2-methacryloxyethyl) ester etc.In above-mentioned ω-carboxyl polycaprolactone single-acrylate and ω-carboxyl polycaprolactone monomethacrylates, the number of repeat unit of polycaprolactone is preferably 1～10, and more preferably 2～4., therefore preferred especially in the above-mentioned unsaturated carboxylic acid (a1) because acrylic or methacrylic acid is imbued with reactivity.They can separately or mix 2 kinds with on use.
The addition reaction of unsaturated monocarboxylic acid (a1) on above-mentioned styrene epoxy resin can be carried out according to known method.For example can preferably in the presence of solvent or esterification catalyst, under 50～150 ℃ temperature, carry out addition reaction 6～24 hours.As the solvent that uses here; For example can enumerate out propylene glycol methyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2 hydroxy propanoic acid ethyl ester, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl butyl propionic ester, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.
Esterification catalyst for example can use tertiary amines such as triethylamine, trimethylamine, benzyl methylamine, benzyl diethylamine; Tertiary amine salt such as tetramethyl ammonium chloride, etamon chloride, benzyltriethylammoinium chloride, DTAC, tetrabutylammonium chloride etc.Can use polymerization inhibitors such as p methoxy phenol, methylnaphthohydroquinone as required.The epoxy radicals that the use amount of esterification catalyst has with respect to styrene epoxy resin is preferably below 0.5 equivalent, more preferably 0.01～0.1 equivalent.Polymerization inhibitor with respect to the reaction solution total amount preferably below 5000ppm, more preferably use in the scope of 500～3000ppm.
The use amount of unsaturated monocarboxylic acid (a1) is preferably the scope of 0.7～1.3 equivalent with respect to epoxy radicals 1 equivalent of styrene epoxy resin, further is preferably the scope of 0.9～1.2 equivalent.
Above-mentioned multi-anhydride (a2) can suitably be selected according to the kind of Y desired in the above-mentioned formula (B-1).Preferred multi-anhydride (a2) for example can be enumerated out; Malonic anhydride, maleic anhydride, methyl maleic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, anhydride diethylene glycol, phthalic anhydride, cyclohexane-1; 2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, biphenyl acid anhydrides etc.Wherein, because succinic anhydride, glutaric anhydride, phthalic acid or 4-cyclohexene-1, the 2-dicarboxylic acid anhydride is imbued with reactivity, and is therefore preferred especially.
Multi-anhydride (a2) can carry out under the same condition of the addition reaction on the styrene epoxy resin with above-mentioned unsaturated monocarboxylic acid (a1) to the addition reaction on the styrene epoxy resin.Also can at unsaturated monocarboxylic acid (a1) after the addition reaction on the styrene epoxy resin, in reaction mixture, append multi-anhydride (a2), proceed addition reaction.
The use amount of multi-anhydride (a2) is preferably the scope of 0.2～1.0 equivalent with respect to epoxy radicals 1 equivalent of styrene epoxy resin, further the scope of preferred 0.4～0.9 equivalent.
Radiation-ray sensitive composition of the present invention preferably contains above-mentioned (B) alkali soluble resin 10～200 weight portions with respect to (A) colorant 100 weight portions, more preferably contains 20～150 weight portions.This value is less than 10 weight portions, and then the hardness owing to the not enough dyed layer that forms of sensitivity is not enough sometimes, and surpasses 200 weight portions, and the excitation of the chromatic color filter that then obtains sometimes or the light-proofness of black matrix are not enough.
(C) multi-functional monomer
(C) multi-functional monomer in the radiation-ray sensitive composition among the present invention for example can be enumerated out the diacrylate or the dimethylacrylate of alkane glycol such as monoethylene glycol, propylene glycol;
Polyglycol, polypropylene glycol etc. gather the diacrylate or the dimethylacrylate of alkane glycol;
The polyacrylate or the polymethacrylate of the polyvalent alcohol that ternarys such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol are above;
The polyacrylate or the polymethacrylate of the dicarboxylic acid modifier of the polyvalent alcohol that above-mentioned ternary is above;
Low-polyacrylate or oligomeric methacrylates such as polyester, epoxy resin, ammonia ester resin, alkyd resin, organic siliconresin, spirane resin;
The diacrylate or the dimethylacrylate of two ends hydroxylation polymkeric substance such as the hydroxylated polybutadiene in two ends, the hydroxylated polyisoprene in two ends, the hydroxylated polycaprolactone in two ends;
Tricresyl phosphate (acryloxy ethyl) ester, tricresyl phosphate (methacryloxyethyl) ester etc.Wherein, " polyacrylate or the polymethacrylate of the dicarboxylic acid modifier of the polyvalent alcohol that ternary is above " is meant the polyacrylate or the polymethacrylate of the monoester compound that 1 dicarboxylic acid of addition forms on the polybasic carboxylic acid more than the ternary.
In these multi-functional monomers; Be preferably the polyacrylate or the polymethacrylate of the dicarboxylic acid modifier of the above polyvalent alcohol of polyacrylate or polymethacrylate and the ternary of the above polyvalent alcohol of ternary, be specially trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, succinic acid modification pentaerythritol triacrylate, succinic acid modification pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylic ester, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylic ester etc.Wherein, succinic acid modification pentaerythritol triacrylate and succinic acid modification pentaerythritol acrylate trimethyl are the compound that following structural formula is represented.
Figure S2007103059401D00151
(in the above-mentioned formula, R is hydrogen atom or methyl.)
In these multi-functional monomers; Because the dyed layer intensity that obtains is high; The flatness on dyed layer surface is good; And be difficult to form that zone beyond the part produces scum, film is residual, thereby preferred trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol acrylate at the pattern of dyed layer.
Above-mentioned multi-functional monomer can use separately also and can use mixing more than 2 kinds.
The usage ratio of (C) the multi-functional monomer in the radiation-ray sensitive composition of the present invention with respect to (B) alkali soluble resin 100 weight portions, is preferably 5～500 weight portions, more preferably 20～300 weight portions.If (C) use amount of multi-functional monomer is less than 5 weight portions; Then the surface smoothing property of the intensity of dyed layer, dyed layer is not enough sometimes; On the other hand; If above 500 weight portions, then for example not enough to alkali-developable sometimes, the zone generation scum, the film that perhaps are easy to beyond the pattern of dyed layer forms partly are residual.
In the radiation-ray sensitive composition of the present invention, the part that can use simple function property monomer to replace above-mentioned multi-functional monomer is used.
Object lesson as this simple function property monomer; Can enumerate ω-carboxyl polycaprolactone single-acrylate, ω-carboxyl polycaprolactone monomethacrylates, methoxyl triethylene glycol acrylic ester, methoxyl triethylene glycol methacrylate, methoxyl DPG acrylic ester, methoxyl DPG methacrylate, 2-hydroxyl-3-phenoxy propyl acrylic ester, 2-hydroxyl-3-phenoxy propyl methacrylate, succinic acid (2-acryloxy ethyl) ester, succinic acid (2-methacryloxyethyl) ester etc.; Can enumerate out M-5300 (trade name, East Asia synthetic (strain) produces) etc. as commercially available article.
These simple function property monomers can use separately also and can use mixing more than 2 kinds.
The use amount of simple function property monomer with respect to the total amount of multi-functional monomer and simple function property monomer, is preferably below the 90 weight %, more preferably below the 50 weight %.
(D) Photoepolymerizationinitiater initiater
The Photoepolymerizationinitiater initiater that contains in the radiation-ray sensitive composition of the present invention is the irradiation through visible light, ultraviolet ray, far ultraviolet, electron ray, X ray isoradial, and generation can cause above-mentioned (C) multi-functional monomer and the composition of the free radical of the polymerization of the simple function property monomer that according to circumstances uses.Photoepolymerizationinitiater initiater can preferably use oxime compound; United imidazole; The benzoin compound; Acetophenone compound; Benzophenone cpd; α-dione compounds; Polynucleation quinone compound; The xanthone compound; Phosphine compound; Triaizine compounds; Diazo-compounds;
Figure 2007103059401_0
salt; Imino group sulfonate compound etc.
As above-mentioned oxime compound, for example can enumerate out carbazole compound, other oxime compound.
As carbazole compound, for example can enumerate out the compound of following formula (D-1) expression,
In the formula (D-1), R 11The alkyl of expression carbon number 1～20, the naphthenic base or the phenyl of carbon number 3～8, R 12And R 13Represent independently of one another alkyl, the carbon number 3～8 of hydrogen atom, carbon number 1～20 naphthenic base, can substituted phenyl or the 1 valency alicyclic group (wherein not comprising above-mentioned naphthenic base) of carbon number 7～20,
R 14Alkyl, the naphthenic base of carbon number 3～8, the alkoxy of carbon number 1～12 or the cycloalkyloxy of carbon number 3～8 of expression carbon number 1～12, R 14Exist when a plurality of, can be same to each other or different to each other,
R 151 valency oxygen-containing heterocycle, 1 valency nitrogen heterocycle of carbon number 4～20 or the 1 valency sulfur heterocyclic ring base of carbon number 4～20 of expression carbon number 4～20, R 15Exist when a plurality of, can be same to each other or different to each other,
P is 0～6 integer, and q is 0 or 1, and n is 0～5 integer, and m is 0～5 integer, (n+m)≤5.
In the formula (D-1), R 11Carbon number be that 1～20 alkyl for example has methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc.R 11Carbon number be that 3～8 naphthenic base for example has cyclopentyl, cyclohexyl etc.In the formula (D-1), R 11For example be preferably methyl, ethyl.
In the formula (D-1), R 12And R 13Carbon number be that 1～20 alkyl for example has methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc.R 12And R 13Carbon number be that 3～8 naphthenic base for example has cyclopentyl, cyclohexyl etc.R 12And R 13The substituting group of phenyl carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl are for example arranged is 1～6 alkyl; Carbon number such as cyclopentyl, cyclohexyl is 3～6 naphthenic base; Carbon numbers such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy are 1～6 alkoxy; Cyclopentyloxy, cyclohexyloxy or the like carbon number is 3～6 cycloalkyloxy; Phenyl; Halogen atoms such as fluorine atom, chlorine atom etc.R 12And R 13Preferred 0～4 of the replacement radix of phenyl, more preferably 0 or 1.
R 12And R 13Carbon number be that 7～20 1 valency alicyclic group (does not wherein comprise above-mentioned naphthenic base.) group, the group with dicyclo alkane skeleton, the group with three naphthenic hydrocarbon skeletons, the group with spirane skeleton, the group with terpene skeleton with 1-alkyl-cycloalk hydrocarbon skeleton for example arranged, have the group of diamantane skeleton etc.In the formula (D-1), R 12And R 13Be preferably hydrogen atom, methyl or ethyl.
In the formula (D-1), R 14Carbon number be that 1～12 alkyl for example has methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc.R 14Carbon number be that 3～8 naphthenic base for example has cyclopentyl, cyclohexyl etc.R 14The alkoxy of carbon number 1～12 methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, just own oxygen base, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy, n-undecane oxygen base, n-dodecane oxygen base etc. are for example arranged.R 14Carbon number be that 3～8 cycloalkyloxy for example has cyclopentyloxy, cyclohexyloxy etc.In the formula (D-1), R 14Preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, methoxy or ethoxy.
In the formula (D-1), R 15Carbon number be that 4～20 1 valency oxygen-containing heterocycle, carbon number are that 4～20 1 valency nitrogen heterocycle or carbon number are 4～20 1 valency sulfur heterocyclic ring base, for example have tetrahydro-thienyl (チ オ ラ ニ Le), azepine base (azepinyl), dihydro azepine base, dioxolanyl, triazinyl, thioxane base, thiazolyl,
Figure 2007103059401_1
Diazine, two Indanyl, two sulphur naphthyls, furyl, thienyl, pyrrole radicals,
Figure 2007103059401_3
Azoles base, different
Figure 2007103059401_4
The azoles base; Thiazolyl; Isothiazolyl; Pyrazolyl; Furan a word used for translation base (furazanyl); Pyranose; Pyridine radicals; Pyridazinyl; Pyrimidine radicals; Pyrazinyl; Pyrrolinyl; Morpholinyl; Piperazinyl; Quininuclidinyl; Indyl; Isoindolyl; Benzofuranyl; Benzothienyl; The indolizine base; The chromene base; Quinolyl; Isoquinolyl; Purine radicals; Quinazolyl; The cinnolines base; Phthalazinyl; Pteridyl; Carbazyl; Acridinyl; Phenanthridinyl; The thioxanthene base; Phenazinyl; Phenothiazinyl; Benzo oxathiin base (phenoxathiinyl); Fen
Figure 2007103059401_5
Piperazine base, thianthrene group (thianthrenyl), tetrahydrofuran base, THP trtrahydropyranyl etc.
In the formula (D-1), R 15Preferred dioxolanyl, tetrahydrofuran base or THP trtrahydropyranyl etc.
In the formula (D-1), p is preferably 0,1 or 2, is preferably 1 especially.
In the formula (D-1), n is preferably 0,1 or 2, is preferably 1 especially, and m is preferably 0 or 1.
In the compound of above-mentioned formula (D-1) expression, preferred q be 0 compound (below be called " carbazole compound (1) ") or q be 1 and m be 1 compound (below be called " carbazole compound (2) ").
The object lesson of carbazole compound (1) can be enumerated out: 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1; 2-nonane-2-oxime-O-benzoic ether, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1; 2-nonane-2-oxime-O-acetic acid esters, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1; 2-pentane-2-oxime-O-acetic acid esters, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketoxime-O-acetic acid esters, 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether, 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters, 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9.H;-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2; 2-dimethyl-1, the 3-dioxolanyl) benzoyl]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) etc.
The object lesson of above-mentioned carbazole compound (2) can be enumerated out: ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) etc.
Wherein, 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters and the ethyl ketone-1-in the carbazole compound (2) [9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) or ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2 in the preferred carbazole compound (1); 2-dimethyl-1; The 3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); Ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2 in the preferred especially carbazole compound (2); 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime).
Above-mentioned other oxime compound for example can be enumerated out; 1; 2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), 1,2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), 1,2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-acetyl oxime), 1; 2-octadione-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oxime), 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-(4-toluyl oxime)) etc.Wherein, preferred especially 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime).
Above-mentioned united imidazole for example can be enumerated out, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyls)-4; 4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1; 2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2; 4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 '; 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1; 2 '-bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In the radiation-ray sensitive composition of the present invention, when using united imidazole, consider, preferably itself and hydrogen donor combination are used from the angle that can further improve sensitivity as (D) Photoepolymerizationinitiater initiater.At this, so-called " hydrogen donor " is the compound that hydrogen atom can be provided the free radical that produces from united imidazole through exposure.As this hydrogen donor, preferred mercaptan compound, amines etc.
Above-mentioned mercaptan compound for have more than 1, preferred 1～3, more preferably 1～2 compound with the sulfydryl of phenyl ring or heterocycle Direct Bonding.Object lesson as this mercaptan compound; Can enumerate 2-mercaptobenzothiazole, 2-sulfydryl benzo
Figure 2007103059401_6
azoles, 2-mercaptobenzimidazole, 2; 5-dimercapto-1; 3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
Above-mentioned amines for have more than 1, preferred 1～3, more preferably 1～2 compound with the amino of phenyl ring or heterocycle Direct Bonding.Object lesson as this amines; For example have 4; 4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid, 4-dimethylamino cyanobenzene etc.
Among the present invention; When using bisglyoxaline as (D) Photoepolymerizationinitiater initiater in the radiation-ray sensitive composition; Be difficult to when developing come off, consider aspect the intensity of dyed layer is high that preferably the two uses as hydrogen donor with mercaptan compound and amines from substrate from the dyed layer highly sensitive, that form of radiation-ray sensitive composition.
Above-mentioned benzoin compound for example has: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, 2-benzoyl methyl benzoate etc.
Above-mentioned acetophenone compound for example has: 2; 2-dimethoxy-acetophenone, 2; 2-diethoxy acetophenone, 2; 2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl-(4-methyl mercapto phenyl)-2-morpholino-1-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 1-hydroxycyclohexylphenylketone, 2; 2-dimethoxy-1,2-diphenylethane-1-ketone etc.
Above-mentioned benzophenone cpd for example has: 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone etc.
Above-mentioned α-dione compounds for example has: diacetyl, dibenzoyl, methyl benzoylformate etc.
Above-mentioned polynucleation quinone compound for example has: anthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1,4-naphthoquinones etc.
Above-mentioned xanthone compound for example has: xanthone, thioxanthones, 2-clopenthixal ketone etc.
Above-mentioned phosphine compound for example has: two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.
Above-mentioned triaizine compounds for example has: 2; 4,6-three (trichloromethyl) s-triazine, 2-methyl-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4; Two (trichloromethyl) s-triazine of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4; Two (trichloromethyl) s-triazine of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4; Two (trichloromethyl) s-triazine of 6-, 2-(4-methoxyphenyl)-4; Two (trichloromethyl) s-triazine of 6-, 2-(4-ethoxybenzene vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (trichloromethyl) s-triazine of 6-etc. have the compound of halogenated methyl etc.
These Photoepolymerizationinitiater initiaters can use separately or use mixing more than 2 kinds.
Among the present invention; With respect to (C) multi-functional monomer with total amount 100 weight portions of the simple function property monomer that according to circumstances uses; (D) use amount of Photoepolymerizationinitiater initiater is preferably 0.01～500 weight portion, and more preferably 1～300 weight portion is preferably 10～200 weight portions especially.If (D) use amount of Photoepolymerizationinitiater initiater is lower than 0.01 weight portion; Then because the curing that exposure causes becomes not enough; Be difficult to obtain the pattern matrix of dyed layer pattern alignment arrangements according to the rules; And if surpass 500 weight portions, the dyed layer that then forms comes off from substrate when developing easily, on unexposed the substrate or light shield layer to be easy to generate scum, film residual etc.
(D) Photoepolymerizationinitiater initiater that contains in the radiation-ray sensitive composition of the present invention preferably contains oxime compound, more preferably contains the compound of above-mentioned formula (D-1) expression.When (D) Photoepolymerizationinitiater initiater contains oxime compound with other Photoepolymerizationinitiater initiaters; As with the preferred united imidazole of other Photoepolymerizationinitiater initiaters of oxime compound coupling, acetophenone compound, triaizine compounds, benzoin compound, benzophenone cpd, α-dione compounds, polynucleation quinone compound, xanthone compound, diazo-compounds,
Figure 2007103059401_7
salt, imino group sulfonate compound etc., preferred especially acetophenone compound.
The usage ratio of the oxime compound among the present invention is more than the 20 weight % with respect to (D) Photoepolymerizationinitiater initiater total amount preferably, more preferably more than the 50 weight %.
Other adjuvants
Radiation-ray sensitive composition of the present invention contains above-mentioned (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, can also contain various other adjuvants as required.
As this other adjuvant, can enumerate like filling agent, surfactant, driving fit promoter, anti-oxidant, ultraviolet light absorber, anti flocculant, development property correctives etc.
Above-mentioned filling agent can be enumerated out, glass, aluminium oxide etc.;
Above-mentioned surfactant can be enumerated out, nonionic class surfactant, cationic surfactant, anionic species surfactant etc.;
Above-mentioned driving fit promoter can be enumerated out; Vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-ethoxy cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-sulfydryl propyl trimethoxy silicane etc.;
Above-mentioned anti-oxidant can be enumerated out, and 2,2-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol etc.;
Above-mentioned ultraviolet light absorber can be enumerated out, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.;
Above-mentioned anti flocculant can be enumerated out sodium polyacrylate etc.
Above-mentioned development property correctives since can further improve by radiation-ray sensitive composition of the present invention forms film in alkaline developer dissolubility and further suppress development after not dissolved matter residual, thereby can add.Said development property correctives can be enumerated out organic acid etc.This organic acid preferred molecular weight is aliphatic carboxylic acid below 1000 or the carboxylic acid with phenyl ring.
As the object lesson of above-mentioned aliphatic carboxylic acid, the formic acid of can giving an example out, acetate, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethacetic acid, enanthic acid, sad etc. monocarboxylic acid;
The dicarboxylic acid of oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brassylic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid etc.;
The tricarboxylic acids of tricarballylic acid, propylene three acid, camphoronic acid etc. etc.
As the above-mentioned carboxylic acid that contains phenyl, the carboxyl Direct Bonding of can giving an example out is bonded in carboxylic acid on the phenyl etc. at aromatic carboxylic acid on the phenyl and carboxyl through carbochain.As their object lesson, the aromatic series monocarboxylic acid of the benzoic acid of can giving an example out, toluic acid, cumfrey, half
Figure 2007103059401_8
acid,
Figure 2007103059401_9
woods acid etc.;
The aromatic dicarboxylic acid of m-phthalic acid, phthalic acid, terephthalic acid (TPA) etc.;
The aromatic multi-carboxy acid more than 3 yuan of trimellitic acid, trimesic acid, the inclined to one side tetracid of benzene, pyromellitic acid etc., and phenylacetic acid, hydratropic acid, hydrocinnamic acid, tussol, phenyl succinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, umbellic acid etc.
In these organic acids; From alkali dissolution property, for the dissolubility of following solvents, prevent to form zone beyond the part of dyed layer and produce viewpoints such as scum silica frost or residual film and see aromatic dicarboxylic acid and aromatic dicarboxylic acids such as preferred fat maleic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, phthalic acid.
Above-mentioned organic acid can use separately or use mixing more than 2 kinds.
The use amount of development property correctives among the present invention with respect to overall radiation sensitive compositions, is preferably below the 10 weight %, more preferably 0.001～10 weight %, further preferred 0.01～1 weight %.When the use amount of development property correctives surpassed 10 weight %, formed sometimes dyed layer reduced for the adaptation of substrate.
Solvent
Radiation-ray sensitive composition of the present invention is neccessary composition with above-mentioned (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer with (D) Photoepolymerizationinitiater initiater; Can contain above-mentioned other adjuvants as required; Preferred modulation is dissolved in appropriate solvent with each composition beyond (A) colorant, and with the homodisperse liquid composition of (A) colorant.
As above-mentioned solvent; So long as can disperse or dissolve (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater or other adjuvants and not with the suitable evaporative that has of these compositions reactions, can suitably select to use.
As above-mentioned solvent; Can enumerate out (gathering) alkane glycol monoalkyl ethers such as glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, DPG list ether, DPG list positive propyl ether, DPG mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol list ether;
(gathering) alkane glycol monoalkyl ether acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate;
Acetate (3-methoxyl butyl) ester;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl esters such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester;
2-hydroxy-2-methyl methyl propionate; 2-hydroxy-2-methyl ethyl propionate; 3-methoxypropionic acid methyl esters; 3-methoxy propyl acetoacetic ester; 3-ethoxy-propionic acid methyl esters; The 3-ethoxyl ethyl propionate; Ethoxy ethyl acetate; Hydroxyl ethyl acetate; 2-hydroxy-3-methyl ethyl butyrate; Acetate (3-methyl-3-methoxyl butyl) ester; Propionic acid (3-methyl-3-methoxyl butyl) ester; Ethyl acetate; N-propyl acetate; Isopropyl acetate; N-butyl acetate; Isobutyl acetate; N-amyl acetate; Isoamyl acetate; N-butyl propionate; Ethyl butyrate; The butyric acid n-propyl; Isopropyl isobutyrate; The positive butyl ester of butyric acid; Methyl pyruvate; Ethyl pyruvate; The pyruvic acid n-propyl; Methyl acetoacetate; Ethyl acetoacetate; Other esters such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, xylene;
N-Methyl pyrrolidone, N, acid amides such as dinethylformamide, DMAC N,N etc.
These solvents can use separately or mix 2 kinds with on use.
With above-mentioned solvent, can also and with high boiling solvents such as benzyl ether, two hexyl ethers, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethyleneglycol monophenylether acetic acid esters.
These high boiling solvents can use separately or mix 2 kinds with on use.
In the above-mentioned solvent; Consider dissolubility, pigment-dispersing, coating etc., preferred ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate (3-methoxyl butyl) ester, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2 hydroxy propanoic acid ethyl ester, propionic acid (3-methyl-3-methoxyl butyl) ester, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.The preferred gamma-butyrolacton of high boiling solvent etc.
The use amount of the solvent in the radiation-ray sensitive composition of the present invention as the total amount of the solvent that also contains high boiling solvent, with respect to (B) alkali soluble resin 100 weight portions, is preferably 100～10000 weight portions, more preferably 500～5000 weight portions.When the solvent in the radiation-ray sensitive composition of the present invention contains high boiling solvent,, be preferably below the 20 weight % with respect to the total amount of solvent, more preferably below the 10 weight % as the use amount of high boiling solvent.
The formation method of dyed layer
Then, the method for using radiation-ray sensitive composition of the present invention to form dyed layer is described.At first, describe, then describe for the situation of dyed layer for black matrix for the serve as reasons situation of the layer that the pel array that constitutes colored filter constitutes of dyed layer.
[dyed layer that constitutes by pel array form method]
At first; Form light shield layer (black matrix) to divide the part of the lip-deep pixel that forms substrate, after being coated with the liquid composition of the radiation-ray sensitive composition that for example is dispersed with red pigment on this substrate, carry out heat treated (preliminary drying); Evaporation removes and desolvates, and formation is filmed.Then, behind this a part of zone of filming of radioactive ray exposures, use alkaline developer to develop, non-exposure portion is removed in dissolving, and then forms the pel array that red pixel is arranged with the pattern arrangement of stipulating through heat treated (back roasting).
Afterwards; Use is dispersed with the liquid composition of each radiation-ray sensitive composition of green or blue pigment; With likewise above-mentioned, carry out coating, preliminary drying, exposure and the development of each liquid composition, on same substrate, form green pel array and blue pixels array successively; Thus, can obtain on substrate, to dispose the colored filter of redness, green and blue trichromatic pel array (dyed layer).But in the present invention, the formation of each color pixel array does not have special qualification in proper order.
The substrate that uses during as the formation dyed layer can be enumerated out glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.Can implement suitable pre-treatments such as chemical treatments, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation in advance to these substrates with silane coupling agent etc. as required.
Method for coating radiation-ray sensitive composition on substrate does not have special qualification, can enumerate out the method (below, be called " gap nozzle rubbing method ") of the use gap nozzle of slit and method of spin coating, slit die rubbing method etc.
Coating condition in the gap nozzle rubbing method is because of different there are differences such as size of slit with method of spin coating, slit die rubbing method, coated substrates; For example; When through the slit die rubbing method the 5th generation glass substrate (when 1100mm * 1250mm) went up coating, the discharge-amount of the radiation-ray sensitive composition that spues from gap nozzle was preferably for 500～2000 microlitre/seconds, more preferably 800～1500 microlitre/seconds; Coating speed is preferably 500～1500mm/ second in addition, more preferably 700～1200mm/ second.
The solid formation branch concentration of the radiation-ray sensitive composition that uses in the gap nozzle rubbing method (general assembly (TW) of the composition beyond the solvent in the composition accounts for the ratio of the general assembly (TW) of composition) is preferably 10～20 weight %, more preferably 13～18 weight %.
When adopting the gap nozzle rubbing method; " vacuum(-)baking " that preliminary drying preferably under reduced pressure carries out, the condition of this vacuum(-)baking do, vacuum tightness is preferably 10～150Pa, more preferably about 25～75Pa; Temperature is preferably 60～120 ℃; More preferably about 70～110 ℃, the time of curing is preferably 1～5 minute, more preferably about 2～4 minutes.
Formed thickness of filming, the film thickness gauge by removing after desolvating is preferably 0.1～10 μ m, and more preferably 0.2～8.0 μ m is preferably 0.2～6.0 μ m especially.
Then, with at least a portion of the filming exposure that forms.The exposure of a part of filming for example can be situated between and undertaken by the photomask irradiation radioactive ray with suitable pattern.
The radioactive ray that use during as exposure can use like visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc., are preferably the radioactive ray of wavelength in 190～450nm scope.
The exposure of radioactive ray is preferably 10～10000J/m 2About.
Then, use developing liquid developing, the unexposed portion dissolving of filming is removed.
As above-mentioned developer solution; Preference is as by sodium carbonate, NaOH, potassium hydroxide, tetramethylphosphonihydroxide hydroxide amine, choline, 1; 8-diazabicyclo-[5.4.0]-7-undecylene, 1, the alkaline developer that 5-diazabicyclo-WS such as [4.3.0]-5-nonene constitute.
In above-mentioned alkaline developer, can add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in right amount.In addition,, preferably washes in alkali after developing.
As developing method, can adopt shower development method, spraying development method, immersion development method, (liquid the contain り) development method etc. of striking.
Development conditions is preferably at normal temperatures carried out about 5～300 seconds.
Then, can on substrate, form dyed layer through the back baking.
The condition of back baking is preferably under 180～230 ℃, carries out about 20～40 minutes.
Can use each dyed layer that is dispersed with redness, green perhaps blue pigment to form and use composition; The above-mentioned all operations of repetitive operation can obtain on same substrate, to form red pel array, the pel array of green and the colored filter of blue pixels array (dyed layer) in any order.
Formation method as the dyed layer of deceiving matrix
In above-mentioned " dyed layer that constitutes by pel array form method "; Use the radiation-ray sensitive composition of the potpourri that is dispersed with black pigment or red pigment, yellow uitramarine and blue pigment as composition; Carry out above-mentioned operation successively, can obtain to dispose the substrate of the pattern of black matrix thus with predetermined arrangement.
Have the colored filter of the dyed layer that forms thus or the black matrix that constitutes by dyed layer, extremely useful for for example color liquid crystal display arrangement, colorful visualization tube elements, color sensor etc.
Liquid crystal display cells
The black matrix that liquid crystal display cells of the present invention possesses colored filter or is made up of dyed layer; Said colored filter has the dyed layer that is formed by radiation-ray sensitive composition of the present invention, and said dyed layer is formed by radiation-ray sensitive composition of the present invention.
Color liquid crystal element of the present invention can adopt suitable structure.For example, can adopt following structure, promptly with the driving of disposing thin film transistor (TFT) (TFT) substrate different with substrate on form colored filter, drive with substrate mutually opposed by liquid crystal layer with substrate Jie who is formed with colored filter.Perhaps also can be employed in the substrate that is formed with the substrate of colored filter on the surface of driving with substrate that disposes thin film transistor (TFT) (TFT) and is formed with the electrode that is made up of ITO (being doped with the indium oxide of tin), opposed structure is situated between by liquid crystal layer.The latter's structure can improve aperture opening ratio greatly, have can obtain to become clear, the advantage of high meticulous color liquid crystal display device.
Other embodiments of above-mentioned liquid crystal display cells it will be apparent to those skilled in the art that.
Liquid crystal display cells of the present invention has excellent excitation.
Embodiment
Below, enumerate embodiment and illustrate in greater detail the present invention, but the invention is not restricted to following embodiment.
Among the following embodiment; Use polystyrene conversion weight-average molecular weight (Mw) to use the GPC post of east beautiful (strain) production (series connection G2000HXL2 root, G3000HXL1 root and G4000HXL1 root); At eluting solvent is that tetrahydrofuran, flow are that 0.1 ml/min, column temperature are under 40 ℃ the condition, through being that the gel permeation chromatography (GPC) of standard is measured with the monodisperse polystyrene.
The synthetic example of styrene epoxy resin
Synthetic example 1
In the flask that has condenser pipe and stirrer; Dissolving is to vinyl benzyl glycidol ether 40.0g, N-phenylmaleimide 27.0g, styrene 17.0g and benzyl methacrylate 16.0g in propylene glycol methyl ether acetate 300g; And then drop into 2; 2 '-azobis isobutyronitrile 4.0g and α-Jia Jibenyixierjuwu 6.0g, nitrogen purging (nitrogen purge) is 15 minutes afterwards.Behind the nitrogen purging, on one side stirred autoclave 80 ℃ of down heating on one side, reacted 5 hours, obtain containing the solution of the styrene epoxy resin [A-1] of 25 weight % thus.The polystyrene conversion weight-average molecular weight (Mw) of this styrene epoxy resin [A-1] is 6000.
Synthetic example 2～8
The kind of monomer and use amount and 2; The use amount of 2 '-azobis isobutyronitrile and α-Jia Jibenyixierjuwu is as shown in table 1; In addition likewise implement with synthetic example 1, obtain containing the solution of styrene epoxy resin [A-2]～[A-8] of 25 weight % respectively.What should explain is that the use amount of each composition is weight (g) in the table 1.
The polystyrene conversion weight-average molecular weight (Mw) of the styrene epoxy resin that obtains in each synthetic example is as shown in table 1.
Table 1
Synthetic example 1 Synthetic example 2 Synthetic example 3 Synthetic example 4 Synthetic example 5 Synthetic example 6 Synthetic example 7 Synthetic example 8
The resin name A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8
To the vinyl benzyl glycidol ether 40.0 4.0 50.0 44.0 40.0 44.0 40.0 34.0
N-phenylmaleimide 27.0 38.0 27.0 40.0 27.0 40.0 - 43.0
Acenaphthylene - - - - - 16.0 40.0 -
Styrene 17.0 28.0 17.0 - 17.0 - - 7.0
Benzyl methacrylate 16.0 30.0 6.0 16.0 6.0 - 20.0 16.0
Methacrylic acid (2-hydroxyethyl) ester - - - - 10.0 - - -
2,2 '-azobis isobutyronitrile 4.0 3.0 3.0 4.0 5.0 4.0 4.0 8.0
α-Jia Jibenyixierjuwu 6.0 5.0 4.0 6.0 6.0 4.0 6.0 8.0
Weight-average molecular weight (Mw) 6,000 12,000 15,000 6,000 5,000 8,000 6,000 5,500
Synthesizing of the alkali soluble resin of above-mentioned formula (1) expression
Synthetic example 9
The solution 200g, the methacrylic acid 10.0g as unsaturated monocarboxylic acid, p methoxy phenol 0.2g, TBAB 0.2g and the propylene glycol methyl ether acetate 300g that in flask, pack into and contain the styrene epoxy resin [A-1] that obtains in above-mentioned synthetic routine 1,120 ℃ were reacted 9 hours down.Thus, with respect to epoxy radicals 1 equivalent of styrene epoxy resin, reaction acrylic acid 1 equivalent.And then, add 4-cyclohexene-1 as multi-anhydride, 2-dicarboxylic acid anhydride 16.0g, 80 ℃ were reacted 6 hours down.For this reaction mixture, the liquid temperature is remained on 80 ℃ wash 2 times down, carry out concentrating under reduced pressure, obtain containing the solution of the alkali soluble resin [B-1] of 20 weight % thus.The polystyrene conversion weight-average molecular weight (Mw) of alkali soluble resin [B-1] is 7800.
Synthetic example 10～18
The kind and the use amount of the kind of the styrene epoxy resin solution that uses, the kind of unsaturated monocarboxylic acid and use amount and multi-anhydride are as shown in table 2; In addition likewise implement with synthetic example 9, obtain containing the solution of alkali soluble resin [B-2]～[B-10] of 20 weight % respectively.
The polystyrene conversion weight-average molecular weight (Mw) of the alkali soluble resin that obtains in each synthetic example is as shown in table 2.
Table 2
Synthetic example 9 Synthetic example 10 Synthetic example 11 Synthetic example 12 Synthetic example 13 Synthetic example 14 Synthetic example 15 Synthetic example 16 Synthetic example 17 Synthetic example 18
The alkali soluble resin name B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10
The kind of styrene epoxy resin A-1 A-1 A-2 A-3 A-1 A-4 A-5 A-6 A-7 A-8
Methacrylic acid (g) 10.0 - 1.0 12.5 10.0 11.0 10.0 11.0 - 8.5
Acrylic acid (g) - 8.4 - - - - - - 8.4 -
4-cyclohexene-1,2-dicarboxylic acid anhydride (g) 16.0 4.8 1.3 20.0 - - 16.0 12.8 - -
Succinic anhydride (g) - - - - - 11.6 - - - 6.9
Glutaric anhydride (g) - - - - 9.6 - - - 12.0 -
P methoxy phenol (g) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
TBAB (g) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Weight-average molecular weight (Mw) 7,800 7,100 14,000 17,000 7,700 8,000 7,000 10,000 8,000 7,200
The relatively more synthetic example of alkali soluble resin
Relatively more synthetic example 1
In the flask that has condenser pipe and stirrer; Dissolving styrene 30.0g, benzyl methacrylate 45.0g and methacrylic acid 15.0g in propylene glycol methyl ether acetate 200g; And then drop into 2; 2 '-azobis isobutyronitrile 4.0g and α-Jia Jibenyixierjuwu 6.0g, nitrogen purging is 15 minutes afterwards.Behind the nitrogen purging, on one side stirred autoclave 80 ℃ of heating down on one side, reacted 5 hours, obtain containing the solution of the alkali soluble resin [R-1] of 33 weight % thus.The polystyrene conversion weight-average molecular weight (Mw) of this alkali soluble resin [R-1] is 6000.
Relatively more synthetic example 2
In the flask that has condenser pipe and stirrer; Dissolving N-phenylmaleimide 30.0g, styrene 30.0g, benzyl methacrylate 35.0g and methacrylic acid 15.0g in propylene glycol methyl ether acetate 200g; And then drop into 2; 2 '-azobis isobutyronitrile 3.0g and α-Jia Jibenyixierjuwu 5.0g, nitrogen purging is 15 minutes afterwards.Behind the nitrogen purging, on one side stirred autoclave 80 ℃ of heating down on one side, reacted 5 hours, obtain containing the solution of the alkali soluble resin [R-2] of 33 weight % thus.The polystyrene conversion weight-average molecular weight (Mw) of this alkali soluble resin [R-2] is 12000.
The preparation of radiation-ray sensitive composition and evaluation
Embodiment 1
Will be as potpourri 15 weight portions of the C.I. paratonere 177 of the C.I. paratonere 254 of the 80 weight % of (A) colorant and 20 weight %, as the Disperbyk-2000 (trade name of 4 weight portions (being converted into solid constituent (weight beyond the solvent)) of spreading agent; PVC Star Network ケ ミ one (BYK) company produces) and as propylene glycol methyl ether acetate 81 weight portions of pigment dispersing medium; Handle with ball mill, process dispersible pigment dispersion.
Then; With dispersible pigment dispersion 100 weight portions, as the solution that contains alkali soluble resin [B-1] (resin concentration 20 weight %) 65 weight portions of (B) alkali soluble resin, as dipentaerythritol acrylate 13 weight portions of (C) multi-functional monomer, mix as 2-methyl-(4-methyl thio phenyl)-2-morpholino-1-propane-1-ketone 4.3 weight portions of (D) Photoepolymerizationinitiater initiater with as 3-ethoxyl ethyl propionate 63 weight portions of solvent, the preparation dyed layer forms uses composition.
Composition is used in formation for the gained dyed layer, estimates according to following rules.Evaluation result is shown in table 3.
The evaluation of radiation-ray sensitive composition
Use spinner that the dyed layer formation that obtains is coated on the surface with composition and be formed with the SiO that prevents the sodion stripping 2On the soda-lime glass substrate of film, preliminary drying 2 minutes on 90 ℃ hot plate forms filming of thickness 1.7 μ m thus afterwards.
After this is had the substrate cool to room temperature of filming, use high-pressure mercury-vapor lamp, be situated between by the photomask that has a plurality of slits that vary in size in wide 5～50 mu m ranges, the ultraviolet ray of each wavelength through containing 365nm, 405nm and 436nm is with 1000J/m 2The exposure exposure of filming.
Then, for the band substrate of filming after the exposure, uses the potassium hydroxide aqueous solution of 23 ℃ 0.04 weight %, the shower of carrying out 1 minute is developed, and is after washing with ultrapure water, air-dry.And then baking after in 220 ℃ clean stove, carrying out 30 minutes, on substrate, form the pel array that is arranged with red strip pattern of pixels.
Be formed with the substrate of pel array with observation by light microscope, that whether the edge of observing pattern of pixels has is damaged, the residual residue that pigment is arranged whether of the zone beyond the pattern of pixels on the substrate, with following 3 level evaluations.
Pattern of pixels edge damaged
Zero: the pattern of pixels of wide 30 μ m do not see damaged,
△: the pattern of pixels of wide 30 μ m have slightly damaged,
*: the pattern of pixels of wide 30 μ m is visible a plurality of damaged.
The pigment residue in the zone beyond the pattern of pixels
Zero: do not see residue,
△: have slightly residue,
*: visible numerous residues.
At this moment, pattern is not totally peeled off and the minimum value of the width of residual pattern of pixels is estimated as the minimum pattern width that can form (μ m).
The result sees table 3.
Embodiment 2, comparative example 1
(A) colorant, spreading agent and dispersing of pigments medium are as shown in table 3, in addition likewise operate with embodiment 1, prepare dispersible pigment dispersion respectively.
Use the dispersible pigment dispersion of above-mentioned preparation respectively; (B) use amount of the dipentaerythritol acrylate of alkali soluble resin, (D) Photoepolymerizationinitiater initiater and solvent types and amount and conduct (C) multi-functional monomer is seen shown in the table 3; In addition likewise operate with embodiment 1, prepare, estimate dyed layer formation respectively and use composition.The result sees table 3.
Table 3
Embodiment 1 Embodiment 2 Comparative example 1
Dispersible pigment dispersion (A) colorant kind Red pigment Viridine green Red pigment
The spreading agent kind BYK-2000 BYK-2001 BYK- 2000
Dispersing of pigments medium kind PGMEA 3MBA PGMEA
Radiation-ray sensitive composition (B) alkali soluble resin Kind B-1 B-4 R-1
Amount 65 70 40
(C) multi-functional monomer Amount 13 14 13
(D) Photoepolymerizationinitiater initiater Kind Initiator A Initiator B Initiator A
Amount 4.3 2.0 4.3
Solvent Kind 3EPE 3EPE 3MBA
Amount 63 59 88
Evaluation result Have or not residue ○ ○ ×
Have unskirted damaged △ ○ ×
The pattern magnitude that can form (μ m) 18 6 45
What should explain is that in the table 3, the abbreviation of each composition has following implication respectively.
(A) colorant:
Red pigment: the potpourri of the C.I. paratonere 177 of the C.I. paratonere 254 of 80 weight % and 20 weight %
Viridine green: the potpourri of the C.I. pigment yellow 150 of the C.I. pigment green 36 of 60 weight % and 40 weight %
Spreading agent:
BYK-2000:Disperbyk-2000 (trade name, PVC Star Network ケ ミ one (BYK) company produces)
BYK-2001:Disperbyk-2001 (trade name, PVC Star Network ケ ミ one (BYK) company produces)
The dispersing of pigments medium:
PGMEA: propylene glycol methyl ether acetate
3MBA: acetate (3-methoxyl butyl) ester
(D) Photoepolymerizationinitiater initiater:
Initiator A: 2-methyl-(4-methyl thio phenyl)-2-morpholino-1-propane-1-ketone
Initiator B: ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime)
Solvent:
The 3EPE:3-ethoxyl ethyl propionate
3MBA: acetate (3-methoxyl butyl) ester
The use amount of each composition in the table 3 is a weight portion.
Spreading agent in the preparation of dispersible pigment dispersion adds as solvent, and the use amount of the spreading agent in the table 3 is for being scaled the value of solid constituent (weight beyond the solvent).
(B) alkali soluble resin adds as the solution that contains each alkali soluble resin for preparing in the above-mentioned synthetic example, and the use amount of the alkali soluble resin in the table 3 is the amount as solution.
Embodiment 3
Will be as the carbon black of the 20 weight % of (A) colorant, as the Disperbyk-167 (trade name of 4 weight portions of spreading agent; PVC Star Network ケ ミ one (BYK) company produces) and as acetate (3-methoxyl butyl) ester 76 weight portions of pigment dispersing medium; Handle with ball mill, process the dispersible pigment dispersion of black.
Then; With dispersible pigment dispersion 100 weight portions, as solution (resin concentration 20 weight %) 52.5 weight portions of the alkali soluble resin that contains above-mentioned preparation [B-2] of (B) alkali soluble resin, as tetramethylol methane tetraacrylate 5.6 weight portions of (C) multi-functional monomer and dipentaerythritol acrylate 2.4 weight portions, as ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2 of (D) Photoepolymerizationinitiater initiater; 2-dimethyl-1; The 3-dioxolanyl) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) 3.7 weight portions and mix as propylene glycol methyl ether acetate 76 weight portions of solvent, the preparation dyed layer forms uses composition.
Composition is used in formation for the gained dyed layer, and the thickness of filming that makes formation is 1.0 μ m, in addition estimates according to the rules of embodiment 1.Evaluation result is shown in table 4.
Embodiment 4～10, comparative example 2
Embodiment 4～6,8,9 and 10 and comparative example 2 in, likewise prepare dispersible pigment dispersion respectively with embodiment 1.In embodiment 7, remove and use propylene glycol methyl ether acetate as after the dispersing of pigments medium, likewise prepare dispersible pigment dispersion with embodiment 3.
Use the dispersible pigment dispersion of above-mentioned preparation respectively; (B) alkali soluble resin and solvent types are as described in Table 4 with amount; Use (C) multi-functional monomer of table 4 record and (D) Photoepolymerizationinitiater initiater with the amount of table 4 record, in addition likewise prepare, estimate dyed layer formation respectively and use composition with embodiment 3.The result sees table 4.
Table 4
Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Comparative example 2
Radiation-ray sensitive composition (B) alkali soluble resin Kind B-2 B-5 B-6 B-7 B-8 B-9 B-3 B-10 R-2
Amount 52.5 52.5 46.5 52.5 52.5 52.5 52.5 61.7 32.0
(C) multi-functional monomer
The amount of dipentaerythritol acrylate 2.4 2.4 9.3 2.4 - 2.4 2.4 6.2 2.4
The amount of tetramethylol methane tetraacrylate 5.6 5.6 - 5.6 8.0 5.6 5.6 - 5.6
(D) Photoepolymerizationinitiater initiater
The amount of initiator A - - - 1.0 - - - - -
The amount of initiator B 3.7 3.7 3.7 2.7 3.7 3.7 3.7 3.7 3.7
Solvent Kind 3MBA 3MBA 3MBA 3EPE 3MBA 3MBA 3MBA 3MBA 3EPE
Amount 76 76 81 76 76 76 76 68.6 97
Evaluation result Have or not residue ○ ○ ○ ○ ○ ○ ○ ○ △
Have unskirted damaged ○ ○ ○ ○ ○ ○ △ ○ ×
The pattern magnitude that can form (μ m) 6 7 5 5 5 5 20 5 50
What should explain is, in the table 4, (D) abbreviation of Photoepolymerizationinitiater initiater and solvent respectively with table 3 in synonym.
The use amount of each composition is a weight portion in the table 4.
(B) alkali soluble resin adds as the solution that contains each alkali soluble resin for preparing in the above-mentioned synthetic example, and the use amount of the alkali soluble resin in the table 4 is the amount as solution.
As stated; Radiation-ray sensitive composition of the present invention; Damaged and the undercut that under low exposure, also can not produce pattern edge; Can form fine pattern, can residual not dissolved matter during development or can not produce scum silica frost at pattern edge, therefore applicable to forming the dyed layer that forms by the pixel that constitutes colored filter or as the dyed layer of deceiving matrix.

Claims (8)

1. radiation-ray sensitive composition; It contains (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater; It is characterized in that; (B) alkali soluble resin has the structure of following formula (B-1) expression, and above-mentioned radiation-ray sensitive composition is used to form dyed layer
Figure FSB00000662123000011
In the formula (B-1), R 1And R 2Be hydrogen atom, R 3Be hydrogen atom or methyl, X is the univalent perssad of following formula (X-1) expression,
Figure FSB00000662123000012
In the formula (X-1), R is hydrogen atom or methyl, and i is 2～5 integer, and j is 0～4 integer,
Y is methylene, ethylidene, 1,3-propylidene, 1,2-ethenylidene, 1,2-allylidene, 1,3-allylidene, 2,3-allylidene, cyclohexane-1,2-two bases, 4-cyclohexene-1,2-two bases, 1,2-phenylene, biphenyl-2,2 '-two bases or formula-CH 2-O-CH 2The divalent group of-expression, h is 1.
2. radiation-ray sensitive composition as claimed in claim 1, wherein, except the structure of above-mentioned formula (B-1) expression, (B) alkali soluble resin also has at least a structure in the structure of the structure that is selected from following formula (B-2) expression and following formula (B-3) expression,
Figure FSB00000662123000013
In the formula (B-2), R 4Be the aryl of carbon number 6～10 or the alicyclic group of carbon number 3～10,
Figure FSB00000662123000021
In the formula (B-3), R 5～R 10Be hydrogen atom, halogen atom, hydroxyl, methylol or carboxyl independently of one another.
3. according to claim 1 or claim 2 radiation-ray sensitive composition, wherein, (D) Photoepolymerizationinitiater initiater contains the compound of following formula (D-1) expression,
Figure FSB00000662123000022
In the formula (D-1), R 11The alkyl of expression carbon number 1～20, the naphthenic base or the phenyl of carbon number 3～8,
R 12And R 13Represent independently of one another alkyl, the carbon number 3～8 of hydrogen atom, carbon number 1～20 naphthenic base, can substituted phenyl or 1 valency alicyclic group of carbon number 7～20, but said alicyclic group does not comprise above-mentioned naphthenic base,
R 14Alkyl, the naphthenic base of carbon number 3～8, the alkoxy of carbon number 1～12 or the cycloalkyloxy of carbon number 3～8 of expression carbon number 1～12, R 14Exist when a plurality of, can be same to each other or different to each other,
R 151 valency oxygen-containing heterocycle, 1 valency nitrogen heterocycle of carbon number 4～20 or the 1 valency sulfur heterocyclic ring base of carbon number 4～20 of expression carbon number 4～20, R 15Exist when a plurality of, can be same to each other or different to each other,
P is 0～6 integer, and q is 0 or 1, and n is 0～5 integer, and m is 0～5 integer, (n+m)≤5.
4. the colored filter that has the dyed layer that forms by claim 1 or 2 described radiation-ray sensitive compositions.
5. the liquid crystal display cells that possesses the described colored filter of claim 4.
6. black matrix that is made up of dyed layer, wherein, said dyed layer is formed by claim 1 or 2 described radiation-ray sensitive compositions.
7. the liquid crystal display cells that possesses the described black matrix of claim 6.
8. have the manufacturing approach of alkali soluble resin of the structure of following formula (B-1) expression, it is characterized in that, on the polymkeric substance of structure with following formula (B-1 ') expression; The compound of the following formula of addition (a1) expression; Then, the compound of the following formula of addition (a2) expression
Figure FSB00000662123000031
In the formula (B-1), R 1And R 2Be hydrogen atom, R 3Be hydrogen atom or methyl, h is 1, and X is the univalent perssad of following formula (X-1) expression,
Figure FSB00000662123000032
In the formula (X-1), R is hydrogen atom or methyl, and i is 2～5 integer, and j is 0～4 integer,
Y is methylene, ethylidene, 1,3-propylidene, 1,2-ethenylidene, 1,2-allylidene, 1,3-allylidene, 2,3-allylidene, cyclohexane-1,2-two bases, 4-cyclohexene-1,2-two bases, 1,2-phenylene, biphenyl-2,2 '-two bases or formula-CH 2-O-CH 2The divalent group of-expression,
Formula (B-1 ') in, R 1, R 2, R 3With h respectively with above-mentioned formula (B-1) in synonym,
X-COOH (a1)
In the formula (a1), synonym in X and the above-mentioned formula (B-1),
Figure FSB00000662123000042
In the formula (a2), synonym in Y and the above-mentioned formula (B-1),
With respect to the epoxy radicals that polymkeric substance had 1 equivalent of the structure with above-mentioned formula (B-1 ') expression, the use amount of the compound of above-mentioned formula (a1) expression is 0.7～1.3 equivalent, and
With respect to the epoxy radicals that polymkeric substance had 1 equivalent of the structure with above-mentioned formula (B-1 ') expression, the use amount of the compound of above-mentioned formula (a2) expression is 0.2～1.0 equivalent.
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