CN103676479A - Radiation-sensitive linear composition, method of forming cured film for display element, cured film for display element and display element - Google Patents

Radiation-sensitive linear composition, method of forming cured film for display element, cured film for display element and display element Download PDF

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CN103676479A
CN103676479A CN201310381387.5A CN201310381387A CN103676479A CN 103676479 A CN103676479 A CN 103676479A CN 201310381387 A CN201310381387 A CN 201310381387A CN 103676479 A CN103676479 A CN 103676479A
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radiation
sensitive linear
linear composition
display element
methyl
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中川刚志
西川耕二
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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
    • G03F7/028—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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • 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
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    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image

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  • Spectroscopy & Molecular Physics (AREA)
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  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention aims to provide a radiation-sensitive linear composition capable of forming a cured film of excellent resolution, sensitivity, highly-developing tolerance, heat resistance, solvent resistance and the like. The radiation-sensitive linear composition comprises [A] a polymerizable compound with an olefinic unsaturated bond, and [B] a radiation-sensitive linear composition of a photo-polymerization initiator represented by the formula (1). In the formula (1), R1 represents a morpholino, piperidino, dimethylamino or diethylamino group; R2 and R3 independently represent a C1-6 alkyl group; R4 and R5 independently represent a hydroxyl, hydroxymethyl or C1-6 alkyl group; n is an integer of 0-6; X represents an oxygen atom or sulfur atom. Preferably, the radiation-sensitive linear composition further comprises [C] alkali-soluble resin. Furthermore, the radiation-sensitive linear composition preferably comprises [D] colorant.

Description

Radiation-sensitive linear composition, display element formation method, display element cured film and the display element of cured film
Technical field
The present invention relates to a kind of radiation-sensitive linear composition, the display element formation method of cured film, cured film and display element for display element.
Background technology
Generally speaking, in the display devices such as film transistor type liquid crystal display cells, in order to insulate between the wiring of stratiform being configured to, thereby be provided with the cured film as interlayer dielectric.For example, film transistor type liquid crystal display cells is manufactured via following operation: in above-mentioned cured film, form ELD, further form liquid crystal orientation film thereon.In such manufacturing process, above-mentioned cured film is exposed to high temperature in the formation operation of ELD, or be exposed to the stripper that forms middle used resist layer at the pattern of electrode, thereby cured film need to have high development tolerance, thermotolerance and solvent resistance.
In recent years; consider the fine patterns of liquid crystal display cells and the efficient activity of throughput rate following the high-precision refinement of demonstration and come; for the radiation-sensitive linear composition that is used to form the cured film such as sept, diaphragm and colored pattern of interlayer dielectric as described above, used for liquid crystal display element, require to have high resolving power and light sensitivity.To this, proposed to use the technology (with reference to TOHKEMY 2005-227525 communique) of the radiation-sensitive linear composition that comprises oxime ester class Photoepolymerizationinitiater initiater.
But, even if used such technology, can not say and fully meet light sensitivity etc.In addition, for radiation-sensitive linear composition, also require to have storage stability, and for formed cured film, on the basis of above-mentioned high development tolerance, thermotolerance and solvent resistance, also require to have excellent compression performance.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-227525 communique
Summary of the invention
The problem that invention will solve
The present invention is based on above such situation and complete.Its object is to provide a kind of radiation-sensitive linear composition, and it is excellent and have a cured film of high development tolerance, thermotolerance, solvent resistance etc. that this radiation-sensitive linear composition can form resolution and light sensitivity.
For the scheme of dealing with problems
The invention completing in order to address the above problem is a kind of radiation-sensitive linear composition, and it contains the Photoepolymerizationinitiater initiater (being also called below " [B] Photoepolymerizationinitiater initiater ") that polymerizable compound (being also called below " [A] polymerizable compound ") that [A] have ethylenic unsaturated bond and [B] are represented by following formula (1).
[Chemical formula 1]
Figure BDA0000373218530000021
In formula (1), R 1morpholino base, piperidino, dimethylamino or diethylamino.R 2and R 3be the alkyl of carbon number 1～6 independently of one another.R 4and R 5be the alkyl of hydroxyl, methylol or carbon number 1～6 independently of one another.N is 0～6 integer.X is oxygen atom or sulphur atom.
Again, other invention completing in order to address the above problem comprises the display element that formed by this radiation-sensitive linear composition by cured film and possesses the display element of cured film for this display element.
Further, another invention completing in order to address the above problem is a kind of formation method of cured film for display element, and it has following operation:
(1) use this radiation-sensitive linear composition, on substrate, form the operation of filming,
(2) operation to above-mentioned at least a portion useful to irradiation of rays of filming,
(3) by above-mentioned, irradiated the operation that filming of ray developed, and
(4) by the above-mentioned operation of filming and heating of having developed.
The effect of invention
The present invention can provide a kind of radiation-sensitive linear composition, and it is excellent and have a cured film of high development tolerance, thermotolerance, solvent resistance etc. that it can form resolution and light sensitivity.Therefore, display element of the present invention can contribute to the high-precision refinement of the display devices such as liquid crystal display cells and the efficient activity of throughput rate etc. with formation method, the display element of cured film with cured film and display element.
Embodiment
< radiation-sensitive linear composition >
Radiation-sensitive linear composition of the present invention contains [A] polymerizable compound and [B] Photoepolymerizationinitiater initiater.About this radiation-sensitive linear composition, also can contain [C] alkali soluble resin and [D] colorant as preferred component again.Further, in this radiation-sensitive linear composition, only otherwise damage effect of the present invention, also can contain other the optional member such as Photoepolymerizationinitiater initiater except [B] Photoepolymerizationinitiater initiater (being also called below " [B '] Photoepolymerizationinitiater initiater ").According to this radiation-sensitive linear composition, can form the cured film with high development tolerance, thermotolerance, solvent resistance etc., thereby this radiation-sensitive linear composition can be preferred for forming for example display element cured film.Below each composition is described in detail.
< [A] polymerizable compound >
[A] polymerizable compound is the polymerizable compound with ethylenic unsaturated bond.Should can be used alone or be used in combination of two or more by [A] polymerizable compound.
As [A] polymerizable compound, for example, list: ω-carboxyl polycaprolactone list (methyl) acrylate, ethylene glycol (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, TEG two (methyl) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, two phenoxetol fluorenes two (methyl) acrylate, dihydroxymethyl tristane two (methyl) acrylate, methacrylic acid 2-hydroxyl-3-(methyl) acryloxy propyl ester, (methyl) acrylic acid 2-(2 '-ethyleneoxy ethoxy) ethyl ester, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, three (2-(methyl) acryloxy ethyl) phosphate, oxirane modification dipentaerythritol acrylate, succinic acid modification pentaerythritol triacrylates etc., in addition also list: by making to have straight-chain alkyl-sub-and ester ring type structure and having the compounds of two above isocyanate group, polyurethane (methyl) acrylate compounds that reacts with the compound that there is more than one hydroxyl and there are 3～5 (methyl) acryloxies in molecule and obtain etc.
As [A] polymerizable compound, be preferably potpourri, three (the 2-acryloxy ethyl) isocyanuric acid ester of potpourri, succinic acid modification pentaerythritol triacrylate, tetramethylol methane tetraacrylate and pentaerythritol triacrylate and the potpourri of two (2-acryloxy ethyl) isocyanuric acid esters, the more preferably potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate of dipentaerythritol five acrylate and dipentaerythritol acrylate.By [A] polymerizable compound being made as to above-claimed cpd (potpourri that comprises compound), thereby can take into account the light sensitivity of this radiation-sensitive linear composition and the thermotolerance of formed display element use cured film etc. with high level.
Commercially available product as [A] polymerizable compound, for example, list:
Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050, Aronix TO-756, Aronix TO-1450, Aronix TO-1382 (more than, the synthetic system in East Asia)
KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, KAYARAD MAX-3510 (more than, Japanese chemical drug system),
Biscoat295, Biscoat300, Biscoat360, Biscoat GPT, Biscoat3PA, Biscoat400, Biscoat802 (more than, Osaka organic chemistry industry system),
As the New Frontier R-1150 (Dai-ichi Kogyo Seiyaku Co., Ltd. system) of urethane acrylate compounds,
KAYARAD DPHA-40H, UX-5000 (more than, Japanese chemical drug system),
UN-9000H (Negami Chemical Industrial Co., Ltd system),
Aronix M-5300, Aronix M-5600, Aronix M-5700, M-210, Aronix M-220, Aronix M-240, Aronix M-270, Aronix M-6200, Aronix M-305, Aronix M-309, Aronix M-310, Aronix M-315 (more than, the synthetic system in East Asia)
KAYARAD HDDA, KAYARAD HX-220, KAYARAD HX-620, KAYARAD R-526, KAYARAD R-167, KAYARAD R-604, KAYARAD R-684, KAYARAD R-551, KAYARAD R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (more than, Japan's chemical drug system)
Art Resin UN-9000PEP, Art Resin UN-9200A, Art Resin UN-7600, Art Resin UN-333, Art Resin UN-1003, Art Resin UN-1255, Art Resin UN-6060PTM, Art Resin UN-6060P (more than, Negami Chemical Industrial Co., Ltd system)
SH-500B Biscoat260, Biscoat312, Biscoat335HP (more than, Osaka organic chemistry industry system) etc.
As the content of [A] polymerizable compound in this radiation-sensitive linear composition, with respect to the gross mass of this radiation-sensitive linear composition, be preferably 5 quality %～90 quality %, more preferably 10 quality %～70 quality %.
In addition, the content as [A] polymerizable compound in the situation that using [C] described later alkali soluble resin, with respect to [C] alkali soluble resin 100 mass parts, is preferably 10 mass parts～700 mass parts, more preferably 20 mass parts～600 mass parts.By the content of [A] polymerizable compound is made as to above-mentioned scope, even if the display element being formed by this radiation-sensitive linear composition also can have sufficient thermotolerance, solvent resistance by cured film when the low exposure.
< [B] Photoepolymerizationinitiater initiater >
[B] Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater being represented by above-mentioned formula (1).By making this radiation-sensitive linear composition contain [B] Photoepolymerizationinitiater initiater, can make this radiation-sensitive linear composition improve compression performance, resistance to developability, thermotolerance and the solvent resistance of cured film for formed display element.Be explained, [B] Photoepolymerizationinitiater initiater can be used alone or be used in combination of two or more.
In above-mentioned formula (1), R 1morpholino base, piperidino, dimethylamino or diethylamino.R 2and R 3be the alkyl of carbon number 1～6 independently of one another.R 4and R 5be the alkyl of hydroxyl, methylol or carbon number 1～6 independently of one another.N is 0～6 integer.X is oxygen atom or sulphur atom.
As above-mentioned by R 2and R 3the alkyl of the carbon number 1～6 representing, such as listing methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group etc.Among them, as above-mentioned R 2and R 3, be preferably methyl.
As above-mentioned by R 4and R 5the alkyl of the carbon number 1～6 representing, for example list with as above-mentioned by R 2and R 3the alkyl of the carbon number 1～6 representing and the same group of the group that exemplifies etc.
As said n, be preferably 0～3, more preferably 0 or 1, more preferably 1.
As [B] Photoepolymerizationinitiater initiater, the Photoepolymerizationinitiater initiater preferably being represented by following formula (1-1).By making [B] Photoepolymerizationinitiater initiater, be following specific compound, can make this radiation-sensitive linear composition further improve compression performance, resistance to developability, thermotolerance and the solvent resistance of cured film for formed display element.
[Chemical formula 2]
In above-mentioned formula (1-1), R 4and R 5define identical with above-mentioned formula (1).
About [B] Photoepolymerizationinitiater initiater, as the Photoepolymerizationinitiater initiater being represented by above-mentioned formula (1-1), such as listing by the compound of following formula (b1)～(b7) represent etc.
[chemical formula 3]
Figure BDA0000373218530000081
Among them, as [B] Photoepolymerizationinitiater initiater, be preferably the compound being represented by above-mentioned formula (b1)～(b5), the compound more preferably being represented by (b1), (b2).(b2) compound shown in is because OH base is present in two molecules, thereby can improve developability, can improve the resolution of obtained pattern, therefore further preferred.
As the content of [B] Photoepolymerizationinitiater initiater, with respect to [A] polymerizable compound 100 mass parts, be preferably 0.1 mass parts～70 mass parts, more preferably 0.1 mass parts～40 mass parts.By making the content of [B] Photoepolymerizationinitiater initiater, be above-mentioned scope, can effectively improve the compression performance of cured film, the resistance to developability etc. for display element that by this radiation-sensitive linear composition, are formed.
In addition, the content as [B] Photoepolymerizationinitiater initiater in the situation that using [C] alkali soluble resin, with respect to [C] alkali soluble resin 100 mass parts, is preferably 0.1 mass parts～70 mass parts, more preferably 0.1 mass parts～40 mass parts.By the content of [B] Photoepolymerizationinitiater initiater is made as to above-mentioned scope, can further improve the light sensitivity of this radiation-sensitive linear composition and the transmissivity of cured film for the display element that obtains.
< [B '] Photoepolymerizationinitiater initiater >
[B '] Photoepolymerizationinitiater initiater is the Photoepolymerizationinitiater initiater beyond [B] Photoepolymerizationinitiater initiater.Should can be used alone or be used in combination of two or more by [B '] Photoepolymerizationinitiater initiater.
As [B '] Photoepolymerizationinitiater initiater, such as listing thioxanthones compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class, O-acyl group oxime compound, salt compounds, benzoin compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, diazonium compounds, imide sulfonates compounds etc.Among them, as [B '] Photoepolymerizationinitiater initiater, preferably comprise at least one that select the group forming from thioxanthones compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class and O-acyl group oxime compound.
As above-mentioned thioxanthones compounds, for example list thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2,4-bis-clopenthixal ketones, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones etc.
As above-mentioned acetophenone compounds, such as listing 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino phenyl) fourth-1-ketone etc.
As above-mentioned bisglyoxaline compounds, for example, list 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.In addition, use in the situation of bisglyoxaline compounds as Photoepolymerizationinitiater initiater, consider can improve light sensitivity viewpoint and preferably and use hydrogen donor.Hydrogen donor refers to can supply with to the free radical being produced by bisglyoxaline compounds by exposure the compound of hydrogen atom.As hydrogen donor, such as listing the thio-alcohol hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-amine hydrogen donors such as bis-(diethylamino) benzophenone.In the present invention, hydrogen donor can be used alone or is used in combination of two or more, but considers and can further improve the viewpoint of light sensitivity and preferably more than one thio-alcohol hydrogen donor and more than one amine hydrogen donor are combined and used.
As above-mentioned compound in triazine class, for example list 2, 4, 6-tri-(trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(4-lignocaine-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(3, 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazine of 6-etc.
As above-mentioned O-acyl group oxime compound; for example list 1; 2-octane diketone, 1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-DOX base) methoxybenzoyl base }-9H-carbazole-3-yl]-1-(O-acetyl oxime) etc.
Content as [B '] Photoepolymerizationinitiater initiater, with respect to [A] polymerizable compound 100 mass parts, is preferably 0 mass parts～70 mass parts, more preferably 0 mass parts～50 mass parts, more preferably 0.1 mass parts～40 mass parts.By the content of [B '] Photoepolymerizationinitiater initiater being made as to above-mentioned scope, can effectively improving the compression performance of cured film, the resistance to developability etc. for display element that formed by this radiation-sensitive linear composition.
Again, content as [the B '] Photoepolymerizationinitiater initiater in the situation that using [C] alkali soluble resin, with respect to [C] alkali soluble resin 100 mass parts, is preferably 0 mass parts～70 mass parts, more preferably 0.1 mass parts～50 mass parts, more preferably 0.1 mass parts～40 mass parts.The content of [B '] Photoepolymerizationinitiater initiater is above-mentioned scope by making, and can carry out fully based on the solidifying of exposure, and can improve the stickability of formed cured film and substrate.
< [C] alkali soluble resin >
[C] alkali soluble resin is not particularly limited, for example, for being dissolved in the resin of the 0.40 quality % potassium hydroxide aqueous solution of 23 ℃.By making this radiation-sensitive linear composition contain [C] alkali soluble resin, can optimize the dissolubility in aqueous alkali.Be somebody's turn to do [C] as long as alkali soluble resin is dissolved in developer solution to be just not particularly limited, but be preferably multipolymer.Again, [C] alkali soluble resin preferably has by the structural unit of following formula (2) expression (following, to be also called " structural unit (C1) "), is derived from the structural unit (being also called below " structural unit (C2) ") containing the unsaturated compound of epoxy radicals.Further, [C] alkali soluble resin also can have structural unit described later (C3).In addition, [C] alkali soluble resin, in not damaging the scope of effect of the present invention, also can have other structural unit in addition of said structure unit (C1)～(C3).Again, [C] alkali soluble resin also can have two or more above-mentioned each structural units.
As above-mentioned multipolymer, be preferably there is structural unit (C1) and structural unit (C3) multipolymer, there is the multipolymer of structural unit (C2) and structural unit (C3).
The in the situation that [C] alkali soluble resin existing polymerization initiator in solvent, can make the compound that produces each structural unit synthesize by free radical polymerization.Below, each structural unit is described in detail.
[structural unit (C1)]
Structural unit (C1) is represented by following formula (2).By making [C] alkali soluble resin there is structural unit (C1), can improve the curability of obtained display element use cured film etc.
[chemical formula 4]
Figure BDA0000373218530000121
In above-mentioned formula (2), R 6and R 7be hydrogen atom or methyl independently of one another.R 8it is the divalent group being represented by following formula (2-i) or following formula (2-ii).M is 1～6 integer.
[chemical formula 5]
Figure BDA0000373218530000122
In above-mentioned formula (2-i), R 9hydrogen atom or methyl.In above-mentioned formula (2-i) and formula (2-ii), * represents the position of being combined with oxygen atom.
Structural unit (C1), by the carboxyl epoxy radicals contained with (methyl) acyclic compound that contains epoxy radicals in structural unit described later (C3) reacted, obtains thereby form ester bond.When listing object lesson and describing in detail, such as in the situation that glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester etc. are reacted with the polymkeric substance with structural unit (C3) containing (methyl) acyclic compound of epoxy radicals, the R in above-mentioned formula (2) 8it is the group being represented by above-mentioned formula (2-i).On the other hand, make methacrylic acid 3, in the situation that 4-epoxycyclohexyl methyl esters etc. react with the polymkeric substance with structural unit (C3) containing (methyl) acyclic compound of epoxy radicals, the R in above-mentioned formula (2) 8it is the group being represented by above-mentioned formula (2-ii).
Proportional as containing of structural unit (C1), the entire infrastructure unit with respect to forming [C] alkali soluble resin, is preferably 5 % by mole～60 % by mole, more preferably 10 % by mole～50 % by mole.By by structural unit (C1) containing proportional, be made as above-mentioned scope, can form the display element cured film with excellent curability etc.
[structural unit (C2)]
Structural unit (C2) is the structural unit being derived from containing the unsaturated compound of epoxy radicals.By making [C] alkali soluble resin there is structural unit (C2), thereby can further improve obtained display element by the curability of cured film etc.
As above-mentioned epoxy radicals, list epoxy ethyl (1,2-epoxy radicals structure) and oxa-cyclobutyl (1,3-epoxy radicals structure).
As the unsaturated compound that contains above-mentioned epoxy ethyl, for example list glycidyl acrylate, glycidyl methacrylate, α-ethylacrylate ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid 3, 4-epoxy butyl ester, methacrylic acid 3, 4-epoxy butyl ester, acrylic acid 6, 7-epoxy heptyl ester, methacrylic acid 6, 7-epoxy heptyl ester, α-ethylacrylate 6, 7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, between vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylate etc.
About containing the unsaturated compound of above-mentioned oxa-cyclobutyl, for example,
As acrylate, list 3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-Ethyloxetane, 3-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-pentafluoroethyl group oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2-difluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4-trifluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2,2,4,4-tetrafluoro oxetanes, 3-(2-acryloxy ethyl) oxetanes, 3-(2-acryloxy ethyl)-2-Ethyloxetane, 3-(2-acryloxy ethyl)-3-Ethyloxetane, 3-(2-acryloxy ethyl)-2-trifluoromethyl oxetanes, 3-(2-acryloxy ethyl)-2-pentafluoroethyl group oxetanes, 3-(2-acryloxy ethyl)-2-phenyl oxetanes, 3-(2-acryloxy ethyl)-2,2-difluoro oxetanes, 3-(2-acryloxy ethyl)-2,2,4-trifluoro oxetanes, 3-(2-acryloxy ethyl)-2,2,4,4-tetrafluoro oxetanes etc.,
As methacrylate, list 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-pentafluoroethyl group oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(methacryloxy methyl)-2,2-difluoro oxetanes, 3-(methacryloxy methyl)-2,2,4-trifluoro oxetanes, 3-(methacryloxy methyl)-2,2,4,4-tetrafluoro oxetanes, 3-(2-methacryloxyethyl) oxetanes, 3-(2-methacryloxyethyl)-2-Ethyloxetane, 3-(2-methacryloxyethyl)-3-Ethyloxetane, 3-(2-methacryloxyethyl)-2-trifluoromethyl oxetanes, 3-(2-methacryloxyethyl)-2-pentafluoroethyl group oxetanes, 3-(2-methacryloxyethyl)-2-phenyl oxetanes, 3-(2-methacryloxyethyl)-2,2-difluoro oxetanes, 3-(2-methacryloxyethyl)-2,2,4-trifluoro oxetanes, 3-(2-methacryloxyethyl)-2,2,4,4-tetrafluoro oxetanes etc.
Among them, from improving reactivity and display element, by the viewpoint of the solvent resistance of cured film, consider, be preferably glycidyl methacrylate, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 6, 7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, between vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, methacrylic acid 3, 4-epoxy cyclohexyl, glycidyl methacrylate more preferably, methacrylic acid 2-methyl ethylene oxidic ester, methacrylic acid 6, 7-epoxy heptyl ester, glycidyl methacrylate more preferably.
Proportional as containing of structural unit (C2), the entire infrastructure unit with respect to forming [C] alkali soluble resin, is preferably 5 % by mole～60 % by mole, more preferably 10 % by mole～50 % by mole.By by structural unit (C2) containing proportional, be made as above-mentioned scope, can form the display element cured film with excellent curability etc.
[structural unit (C3)]
Structural unit (C3) is from being derived from the structural unit of unsaturated carboxylic acid and being derived from least one structural unit of selecting the group that the structural unit of unsaturated carboxylic acid anhydrides forms.As the compound that produces structural unit (C3), such as list the acid anhydrides of unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated dicarboxylic, the list of polybasic carboxylic acid [(methyl) acryloxyalkyl] ester, two ends have the polymkeric substance of carboxyl and hydroxyl list (methyl) acrylate, there is carboxyl unsaturated polycyclic compound with and acid anhydrides etc.
As above-mentioned unsaturated monocarboxylic, such as listing acrylic acid, methacrylic acid, crotonic acid etc.As above-mentioned unsaturated dicarboxylic, such as listing maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.As the acid anhydrides of above-mentioned unsaturated dicarboxylic, the acid anhydrides of illustrative compound etc. such as listing as above-mentioned dicarboxylic acid.As list [(methyl) acryloxyalkyl] ester of above-mentioned polybasic carboxylic acid, such as listing mono succinate [2-(methyl) acryloxy ethyl ester], phthalic acid list [2-(methyl) acryloxy ethyl ester] etc.As above-mentioned list (methyl) acrylate at two ends with the polymkeric substance of carboxyl and hydroxyl, for example, list ω-carboxyl polycaprolactone list (methyl) acrylate etc.As the above-mentioned unsaturated polycyclic compound with carboxyl with and acid anhydrides, for example list 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides etc.
Among them, be preferably the acid anhydrides of monocarboxylic acid, dicarboxylic acid, from copolyreaction, the dissolubility aqueous alkali and the easiness of obtaining, consider, more preferably (methyl) acrylic acid, maleic anhydride.
Proportional as containing of structural unit (C3), the entire infrastructure unit with respect to forming [C] alkali soluble resin, is preferably 5 % by mole～30 % by mole, more preferably 10 % by mole～25 % by mole.By by structural unit (C3) containing proportional, be made as above-mentioned scope, thereby optimize the dissolubility of [C] alkali soluble resin in aqueous alkali, and can obtain the radiation-sensitive linear composition of light sensitivity excellence.
[other structural unit]
As long as [C] alkali soluble resin does not damage effect of the present invention, containing structural unit (C1)～(C3) in addition, also can add the compound of other structural unit, such as listing, there is (methyl) acrylate, (methyl) acrylic acid chain-like alkyl ester, (methyl) acrylic acid cyclic alkyl ester, (methyl) acrylic acid aryl ester, unsaturated aromatics, the conjugated diolefine of hydroxyl, the unsaturated compound with tetrahydrofuran skeleton etc., maleimide etc.
As above-mentioned (methyl) acrylate with hydroxyl, such as listing acrylic acid 2-hydroxyl ethyl ester, acrylic acid 3-hydroxy propyl ester, acrylic acid 4-hydroxyl butyl ester, acrylic acid 5-hydroxyl pentyl ester, the own ester of acrylic acid 6-hydroxyl, HEMA, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, methacrylic acid 5-hydroxyl pentyl ester, the own ester of methacrylic acid 6-hydroxyl etc.
As above-mentioned (methyl) acrylic acid chain-like alkyl ester, for example list methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate, methacrylic acid-2-Octyl Nitrite, isodecyl methacrylate, the positive lauryl of methacrylic acid, methacrylic acid tridecyl ester, the positive stearyl of methacrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-EHA, isodecyl acrylate, the positive lauryl of acrylic acid, tridecyl acrylate, the positive stearyl of acrylic acid etc.
As above-mentioned (methyl) acrylic acid cyclic alkyl ester, for example, list cyclohexyl methacrylate, methacrylic acid 2-methyl cyclohexyl, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl ester, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, three ring [5.2.1.0 2,6] decane-8-base acrylate, three ring [5.2.1.0 2,6] decane-8-base oxygen base ethyl propylene acid esters, isobornyl acrylate etc.
As above-mentioned (methyl) acrylic acid aryl ester, such as listing phenyl methacrylate, benzyl methacrylate, phenyl acrylate, benzyl acrylate etc.
As above-mentioned unsaturated aromatics, such as listing styrene, α-methyl styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to methoxy styrene etc.
As above-mentioned conjugated diolefine, for example, list 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
As the above-mentioned unsaturated compound that contains tetrahydrofuran skeleton, such as listing (methyl) acrylic acid tetrahydro furfuryl ester, 2-methacryloxy-propionic acid tetrahydro furfuryl ester, 3-(methyl) acryloxy tetrahydrofuran-2-ketone etc.
As above-mentioned maleimide, such as listing N-phenylmaleimide, N-N-cyclohexylmaleimide, N-tolyl maleimide, N-naphthyl maleimide, NEM, N-hexyl maleimide, N-benzyl maleimide etc.
As the solvent using in the polyreaction for the synthesis of [C] alkali soluble resin, such as listing ethanol, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diethylene glycol monoalky lether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene-glycol monoalky lether propionic ester, ketone, ester etc.
As the polymerization initiator using in the polyreaction for the synthesis of [C] alkali soluble resin, generally can be used as radical polymerization initiator and known polymerization initiator.As radical polymerization initiator, for example list 2,2 '-azoisobutyronitrile, 2,2 '-azo is two-(2,4-methyl pentane nitrile), 2, and 2 '-azo is two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles).
In the polyreaction for the manufacture of [C] alkali soluble resin, in order to adjust molecular weight, can use molecular weight adjusting agent.As molecular weight adjusting agent, such as listing the halogenated hydrocarbons such as chloroform, carbon tetrabromide, the thio-alcohols such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tertiary lauryl mercaptan, mercaptoacetic acid, the xanthan acids such as dimethyl yellow ortho acid thioether, diisopropyl xanthogenic acid disulfide, terpinolene, α-methylstyrenedimer etc.
The polystyrene conversion weight-average molecular weight (Mw) obtaining based on gel permeation chromatography (GPC) as [C] alkali soluble resin, is preferably 1,000～30,000, and more preferably 5,000～20,000.By the Mw of [C] alkali soluble resin is made as to above-mentioned scope, can improve light sensitivity and the developability of this radiation-sensitive linear composition.
< [D] colorant >
[D] colorant is that formed display element is carried out to painted composition by cured film.By making this radiation-sensitive linear composition contain [D] colorant, thereby can form such as the display element cured film with colored pattern etc. as color filter.
As [D] colorant, if there is coloring, be not particularly limited, can suitably select color and material according to the purposes of color filter.As [D] colorant, for example can use any in pigment, dyestuff and natural colouring matter, but due to have relatively high expectations for color filter excitation, brightness, contrast etc., thereby preferred pigments, dyestuff.Should can be used alone or be used in combination of two or more by [D] colorant.
As above-mentioned pigment, can be any in organic pigment, inorganic pigment, as organic pigment, for example, list at color index (C.I.; The distribution of The Society of Dyers and Colourists company) in, be categorized as the compound of pigment.Specifically list the compound of following band colored index (C.I.) name.
List:
C.I. pigment Yellow 12, pigment yellow 13, pigment Yellow 14, pigment yellow 17, pigment yellow 20, pigment yellow 24, pigment yellow 31, pigment yellow 55, pigment yellow 83, pigment yellow 93, pigment yellow 109, pigment yellow 110, pigment yellow 13 8, pigment yellow 13 9, pigment yellow 150, pigment yellow 153, pigment yellow 154, pigment yellow 155, pigment yellow 166, pigment yellow 168, pigment yellow 180, pigment yellow 211
C.I. pigment orange 5, pigment orange 13, pigment orange 14, pigment orange 24, pigment orange 34, pigment orange 36, pigment orange 38, pigment orange 40, pigment orange 43, pigment orange 46, pigment orange 49, pigment orange 61, pigment orange 64, pigment orange 68, pigment orange 70, pigment orange 71, pigment orange 72, pigment orange 73, pigment orange 74
C.I. paratonere 1, paratonere 2, paratonere 5, paratonere 17, pigment red 31, pigment red 32, pigment red 41, pigment red 122, pigment red 123, paratonere 144, pigment red 149, paratonere 166, paratonere 168, paratonere 170, paratonere 171, paratonere 175, paratonere 176, paratonere 177, paratonere 178, pigment red179, paratonere 180, paratonere 185, paratonere 187, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209, pigment red 21 4, paratonere 220, paratonere 221, paratonere 224, paratonere 242, paratonere 243, paratonere 254, paratonere 255, paratonere 262, paratonere 264, paratonere 272,
C.I. pigment violet 1, pigment violet 19, pigment Violet 23, pigment violet 29, pigment violet 32, pigment violet 36, pigment violet 38,
C.I. pigment blue 15, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 60, alizarol saphirol 80,
C.I. pigment Green 7, pigment green 36, naphthol green 58,
C.I. pigment brown 23, pigment brown 25,
C.I. pigment black 1, pigment black 7 etc.
In addition, as above-mentioned inorganic pigment, such as listing titanium dioxide, barium sulphate, calcium carbonate, zinc paste, lead sulfate, lead and yellow-collation, zinc yellow, iron oxide red (di-iron trioxide (III)), cadmium red, ultramarine, barba hispanica, chrome oxide green, cobalt green, umber, black, the synthetic iron oxide black of titanium, carbon black etc.
In the present invention, also can pass through recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or their combination, pigment is refined and used.Also can as required, with resin, the particle surface of pigment be carried out to modification and use again.As by the resin of the particle surface modification of pigment, such as listing resin that the figuration resin recorded in TOHKEMY 2001-108817 communique or commercially available various Pigments use etc.As the resin-coated method of carbon blacksurface, such as adopting the method for recording in Japanese kokai publication hei 9-71733 communique, Japanese kokai publication hei 9-95625 communique, Japanese kokai publication hei 9-124969 communique etc.Again, thus organic pigment preferably carries out primary particle by so-called pulverizing miniaturization to be used.As the method for pulverizing, such as listing in Japanese kokai publication hei 08-179111 communique disclosed method etc.
As above-mentioned dyestuff, as long as dissolve in organic solvent, just can use known dyestuff, such as listing oil-soluble dyes, acid dyes or derivatives thereof, direct dyes, mordant dye etc.Specifically list the dyestuff of following such band colored index (C.I.) name.
List:
C.I. solvent yellow 4, solvent yellow 14, solvent yellow 15, solvent yellow 23, solvent yellow 24, solvent yellow 38, solvent yellow 62, solvent yellow 63, solvent yellow 68, solvent yellow 82, solvent yellow 88, solvent yellow 94, solvent yellow 98, solvent yellow 99, solvent yellow 16 2, solvent yellow 179
C.I. solvent red 45, solvent red 49, solvent red 125, solvent red 130,
C.I. solvent orange 2, solvent orange 7, solvent orange 11, solvent orange 15, solvent orange 26, solvent orange 56,
C.I. solvent blue 35, solvent blue 37, solvent blue 59, solvent blue 67,
C.I. Indian yellow 1, quinoline yellow, Indian yellow 7, Indian yellow 9, acid yellow 11, Indian yellow 17, acid yellow 23, Indian yellow 25, Indian yellow 29, quinoline yellow 4, quinoline yellow 6, quinoline yellow 8, Indian yellow 40, Indian yellow 42, Indian yellow 54, Indian yellow 65, Indian yellow 72, Indian yellow 73, Indian yellow 76
C.I. eosin scarlet, acid red 92, acid red 97, azogeramine 14, azogeramine 38, acid red 151,
C.I. acid orange 51, acid orange 63,
C.I. acid blue 80, acid blue 83, acid blue 90,
C.I. acid green 9, acid green 16, ACID GREEN 25, acid green 27 etc.
By using dyestuff as [D] colorant, can realize high brightness, high-contrast that independent pigment cannot be reached.But, while using dyestuff as [D] colorant in existing radiation-sensitive linear composition, have the situation that the thermotolerance, solvent resistance etc. of alkali-developable, pixel significantly worsen.On the other hand, according to this radiation-sensitive linear composition, even in the situation that having used dyestuff as [D] colorant, also can obtain the radiation-sensitive linear composition that alkali-developable is good.
Content as [D] colorant, from forming the viewpoint of the black matrix of brightness is high and excitation is excellent pixel or light-proofness excellence, consider, with respect to the total solid matter of radiation-sensitive linear composition, be preferably 5 quality %～70 quality %, more preferably 5 quality %～60 quality %.
Other optional member > of <
In this radiation-sensitive linear composition, on the basis of [A] polymerizable compound, [B] Photoepolymerizationinitiater initiater, [C] alkali soluble resin and [D] colorant, in the scope of not damaging effect of the present invention, also can contain other the optional member such as [E] bonding auxiliary agent, [F] surfactant, [G] epoxy compound, antioxidant, preserving stabilizer.These other optional members, can be used separately respectively or be used in combination of two or more.Below each composition is described in detail.
[[E] bonding auxiliary agent]
[E] bonding auxiliary agent is the composition that improves the cementability of the cured film obtain and substrate.As [E] bonding auxiliary agent; be preferably there is carboxyl, the functional silanes coupling agent of methacryl, vinyl, isocyanate group, epoxy ethyl isoreactivity functional group; for example list trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane etc.
As the content of [E] bonding auxiliary agent, with respect to [A] polymerizable compound 100 mass parts, be preferably below 20 mass parts, more preferably below 15 mass parts, more preferably below 10 mass parts.When the content of [E] bonding auxiliary agent surpasses 20 mass parts, be tending towards that development easily occurs residual.
[[F] surfactant]
[F] surfactant is the composition that improves the coating of this radiation-sensitive linear composition.As [F] surfactant, such as listing fluorine class surfactant, siloxane type surfactants etc.
As above-mentioned fluorine class surfactant, at least any position preferably endways, in main chain and side chain has the compound of fluoroalkyl, fluorine alkylidene.Commercially available product as fluorine class surfactant, for example list Ftergent FT-100, Ftergent FT-110, Ftergent FT-140A, Ftergent FT-150, Ftergent FT-250, Ftergent FT-251, Ftergent FT-300, Ftergent FT-310, Ftergent FT-400S, Ftergent FTX-218, Ftergent FTX-251 (more than, NEOS system) etc.
Commercially available product as above-mentioned siloxane type surfactants, for example list Toray silicone DC3PA, Toray silicone DC7PA, Toray silicone SH11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH-190, Toray silicone SH-193, Toray silicone SZ-6032, Toray silicone SF-8428, Toray silicone DC-57, Toray silicone DC-190 (more than, Dow Corning Toray Co., Ltd. make) etc.
As the content of [F] surfactant, with respect to [A] polymerizable compound 100 mass parts, be preferably below 1.0 mass parts, more preferably below 0.7 mass parts.When the content of [F] surfactant surpasses 1.0 mass parts, easily in obtained filming, occur inhomogeneous.
[[G] epoxy compound]
[G] epoxy compound is the curing composition that promotes this radiation-sensitive linear composition.By making this radiation-sensitive linear composition contain [G] epoxy compound, can improve the compression performance of obtained cured film.As [G] epoxy compound, for example, list and in a part, have more than two 3, the compound of 4-epoxycyclohexyl etc.
As above-mentioned, in a part, have more than two 3, the compound of 4-epoxycyclohexyl, for example list 3, 4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3, 4-epoxycyclohexyl-5, 5-spiral shell-3, 4-epoxy radicals) a cyclohexyl-dioxan, two (3, 4-epoxycyclohexyl methyl) adipate, two (3, 4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, 3, 4-epoxy radicals-6-methylcyclohexyl-3 ', 4 '-epoxy radicals-6 '-methylcyclohexanecarboxylic acid ester, di-2-ethylhexylphosphine oxide (3, 4-7-oxa-bicyclo[4.1.0), dicyclopentadiene diepoxide, two (3 of ethylene glycol, 4-epoxycyclohexyl methyl) ether, ethylene two (3, 4-epoxycyclohexane carboxylate), interior ester modified 3, 4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate etc.
[G] epoxy compound about other, for example, list:
As the bisphenol-A diglycidyl ether of the diglycidyl ether of bisphenol compound, Bisphenol F diglycidyl ether, bisphenol-S diglycidyl base ether, hydrogenation bisphenol-A diglycidyl ether, hydrogenation Bisphenol F diglycidyl ether, hydrogenation bisphenol-A D diglycidyl ether, brominated bisphenol-A diglycidyl ether, bromo Bisphenol F diglycidyl ether, bromo bisphenol-S diglycidyl base ether etc.
As 1 of the poly epihydric alcohol base ether of polyvalent alcohol, 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerine triglycidyl group ether, trimethylolpropane tris glycidyl ether, polyglycol diglycidyl ether, polypropylene glycol diglycidyl ether etc.
By one or more alkylene oxide being added to the poly epihydric alcohol base ether of the polyether glycol that aliphatic polyols such as being formed in ethylene glycol, propylene glycol, glycerine obtains,
Phenol novolak type epoxy resin,
Cresols phenolic resin varnish type epoxy resin,
Many phenol-type epoxy resins,
Cyclic aliphatic epoxy resin,
The 2-glycidyl ester of aliphatic long-chain dibasic acid,
The ethylene oxidic ester of higher fatty acid,
Epoxidised soybean oil, epoxidation linseed wet goods.
Commercially available product as [G] epoxy compound, for example, list:
As Epikote604, the Epikote1001 of bisphenol A type epoxy resin, Epikote1002, Epikote1003, Epikote1004, Epikote1007, Epikote1009, Epikote1010, Epikote828 (more than, Japan Epoxy Resins Co., Ltd. make) etc.
As Epikote807 (Japan Epoxy Resins Co., Ltd. system) of bisphenol f type epoxy resin etc.,
As Epikote152, the Epikote154 of phenol novolak type epoxy resin, Epikote157S65 (more than, Japan Epoxy Resins Co., Ltd. system), EPPN201, EPPN202 (more than, Japanese chemical drug system) etc.,
As EOCN102, the EOCN103S of cresols phenolic resin varnish type epoxy resin, EOCN104S, 1020,1025,1027 (more than, Japanese chemical drug system), Epikote180S75 (Japan Epoxy Resins Co., Ltd. system) etc.,
As Epikote1032H60, Epikote XY-4000 of many phenol-type epoxy resins (more than, Japan Epoxy Resins Co., Ltd. system) etc.,
As CY-175, the CY-177 of cyclic aliphatic epoxy resin, CY-179, Araldite CY-182, Araldite CY-192,184 (more than, Ciba Specialty Chemicals Inc. system), ERL-4234,4299,4221,4206 (more than, U.C.C system), Shodyne509 (clear and electrician's system), EPICLON200, EPICLON400 (more than, large Japanese ink system), Epikote871, Epikote872 (more than, Japan Epoxy Resins Co., Ltd. system), ED-5661, ED-5662 (more than, Celanese Coating system) etc.
Epolight100MF (Kyoeisha Chemical Co., Ltd.'s system), Epioru TMP (Japanese grease system) etc. as aliphatic poly glycidyl ether.
Among them, preferred bisphenol A type epoxy resin, phenol novolak type epoxy resin.
As the content of [G] epoxy compound, with respect to [A] polymerizable compound 100 mass parts, be preferably below 50 mass parts, more preferably below 30 mass parts.When the content of [G] epoxy compound surpasses 50 mass parts, the storage stability of this radiation-sensitive linear composition trends towards reducing.
(antioxidant)
Antioxidant is compound from having hindered phenol structure, the compound with the structure of hindered amine, have the compound of phosphite ester structure and have at least one compound of selecting the group that the compound of sulfide based structural forms.By making this radiation-sensitive linear composition contain antioxidant, can improve the thermotolerance of obtained display element use cured film etc.Can infer that this is because the free radical that this antioxidant produced the moment such as when when exposure, the heating catches, or decomposes by the superoxide that oxidation is generated, thereby can suppress the molecule parallel off of contained resinous principle.In addition, because antioxidant is the compound with said structure, even thereby this radiation-sensitive linear composition contain this antioxidant, also maintain the ISO for ray, and the display element obtaining is also few with the reduction of the transmissivity of cured film etc.
As the above-mentioned compound with hindered phenol structure, for example, list pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], thio-diethylene glycol two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], propionic acid octadecyl-3-(3,5-di-tert-butyl-hydroxy phenyl) ester, three (3,5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, N, N '-hexane-1, the two [3-(3,5-di-tert-butyl-hydroxy phenyl propionamide) of 6-bis-bases, 3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl groups-a, a ', a "-(mesitylene-2,4,6-, tri-bases) three paracresol, two (octylsulfo the methyl)-orthoresols of 4,6-, two (dodecyl the sulphomethyl)-orthoresols of 4,6-, two (oxo ethylidene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters] of ethylene, hexa-methylene two [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], 1,3,5-tri-[(the 4-tert-butyl group-3-hydroxyl-2,6-xylyl) methyl]-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone, 2,6-di-t-butyl-4-(two (the pungent sulfenyl)-1,3,5-triazines-2-base amine of 4,6-) phenol, 2,5-di-tert-butyl hydroquinone etc.Among them, as the compound with hindered phenol structure, preferred pentaerythrite four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] 2,5-di-tert-butyl hydroquinone, three (3,5-di-tert-butyl-4-hydroxyl benzyl) chlorinated isocyanurates, 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene.
As the above-mentioned commercially available product with the compound of hindered phenol structure, for example, list ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330 (more than, ADEKA system), sumilizerGM, sumilizerGS, sumilizerMDP-S, sumilizerBBM-S, sumilizerWX-R, sumilizerGA-80 (more than, Sumitomo Chemical system), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1330, IRGANOX1726, IRGANOX1425WL, IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3114, IRGANOX565, IRGAMOD295 (more than, Ciba Japan system), Yoshinox BHT, Yoshinox BB, Yoshinox2246G, Yoshinox425, Yoshinox250, Yoshinox930, Yoshinox SS, Yoshinox TT, Yoshinox917, Yoshinox314 (more than, API Corporation system) etc.
As the above-mentioned compound with the structure of hindered amine, for example list: decanedioic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester, succinic acid two (2, 2, 6, 6-tetramethyl-4-piperidyl) ester, decanedioic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester, two (N-octyloxy-2 of decanedioic acid, 2, 6, 6-tetramethyl-4-piperidyl) ester, two (N-benzyl oxygen base-2 of decanedioic acid, 2, 6, 6-tetramethyl-4-piperidyl) ester, two (N-cyclohexyloxy-2 of decanedioic acid, 2, 6, 6-tetramethyl-4-piperidyl) ester, 2-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-2-butylmalonic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester, 2, 2-two (3, 5-di-tert-butyl-4-hydroxyl benzyl) two (1-acryloyl group-2 of-2-butylmalonic acid, 2, 6, 6-tetramethyl-4-piperidyl) ester, decanedioic acid two (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) ester, methacrylic acid 2, 2, 6, 6-tetramethyl-4-piperidyl ester, 4-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionyloxy] (3-(3 for-1-[2-, 5-di-tert-butyl-hydroxy phenyl) propionyloxy) ethyl]-2, 2, 6, 6-tetramethyl piperidine, 2-methyl-2-(2, 2, 6, 6-tetramethyl-4-piperidyl) amino-N-(2, 2, 6, 6-tetramethyl-4-piperidyl) propionamide, 1, 2, 3, 4-BTCA four (2, 2, 6, 6-tetramethyl-4-piperidyl) ester, 1, 2, 3, 4-BTCA four (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) compound such as ester,
N, N ', N ", N ' "-tetra--[4, 6-pair-[butyl-(N-methyl-2, 2, 6, 6-tetramethyl piperidine-4-yl) amino]-triazine-2-yl]-4, 7-diaza decane-1, 10-diamines and dibutylamine and 1, 3, 5-triazine N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl)-1, 6-hexamethylene diamine and N-(2, 2, 6, 6-tetramethyl-4-piperidyl) condensed polymer of butylamine, dibutylamine and 1, 3, 5-triazine and N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl) condensed polymer of butylamine, poly-[{ (1, 1, 3, 3-tetramethyl butyl) amino-1, 3, 5-triazine-2, 4-bis-bases } { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino group } hexa-methylene { (2, 2, 6, 6-tetramethyl-4-piperidyl) imino group }] with 1, 6-hexane diamines-N, N '-bis-(2, 2, 6, 6-tetramethyl-4-piperidyl) and morpholine-2, 4, 6-tri-chloro-1, 3, the condensed polymer of 5-triazine, poly-[(6-morpholino-guanamine, 4-bis-bases) [(2, 2, 6, 6-tetramethyl-4-piperidyl) imino group]-hexa-methylene [(2, 2, 6, 6-tetramethyl-4-piperidyl) imino group]] etc. the HMW HA LS that a plurality of piperidine ring bondings obtained by triazine skeleton of Jie, dimethyl succinate and 4-hydroxyl-2, 2, 6, the polymkeric substance of 6-tetramethyl-1-piperidines ethanol, 1, 2, 3, 4-BTCA and 1, 2, 2, 6, 6-pentamethyl-4-piperidine alcohols and 3, two (2-hydroxyl-1 of 9-, 1-dimethyl ethyl)-2, 4, 8, 10-tetra-oxaspiros [5, 5] polymkeric substance such as compound that Jie of undecanoic mixed ester compound etc. is obtained piperidine ring bonding by ester bond etc.Among them, as the compound with the structure of hindered amine, two (2,2,6, the 6-tetramethyl-4-piperidyl) esters of preferred decanedioic acid.
As the above-mentioned commercially available product with the compound of the structure of hindered amine, for example list ADK STAB LA-52, ADK STAB LA57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63P, ADK STAB LA-68LD, ADK STAB LA-77, ADK STAB LA-82, ADK STAB LA-87 (more than, ADEKA system), sumilizer9A (Sumitomo Chemical system), CHIMASSORB119FL, CHIMASSORB2020FDL, CHIMASSORB944FDL, TINUVIN622LD, TINUVIN144, TINUVIN765, TINUVIN770DF (Ciba Japan system) etc.
As the above-mentioned compound with phosphite ester structure, for example, list three (nonyl phenyl) phosphite ester, three (to tertiary octyl phenyl) phosphite ester, three [2,4,6-tri-(α-phenylethyl)] phosphite ester, three (to 2-butenyl group phenyl) phosphite ester, two (to nonyl phenyl) cyclohexyl phosphite ester, three (2,4-di-tert-butyl-phenyl) phosphite ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, 2,2 '-di-2-ethylhexylphosphine oxide (4,6-di-t-butyl-1-phenyl oxygen base) (2-ethylhexyl oxygen base) phosphorus, distearyl pentaerythrityl diphosphite, 4,4 '-isopropylidene-biphenol alkyl phosphite ester, four (tridecyl)-4,4 '-butylidene-bis-(3 methy 6 tert butyl phenol) diphosphites, four (2,4-di-tert-butyl-phenyls)-4,4 '-biphenylene phosphite ester, 2,6-di-t-butyl-4-methyl phenyl phenyl pentaerythritol diphosphites, 2, the 6-tert-butyl group-4-methyl phenyl phenyl pentaerythritol diphosphites, 2,6-di-t-butyl-4-ethylphenyl stearyl pentaerythritol diphosphites, two (2, the 6-tert-butyl group-4-aminomethyl phenyl) pentaerythritol diphosphites, 2,6-, bis-tertiary pentyls-4-methyl phenyl phenyl pentaerythritol diphosphites etc.Among them, as the compound with phosphite ester structure, preferably 2,2 '-di-2-ethylhexylphosphine oxide (4,6-di-t-butyl-1-phenyl oxygen base) (2-ethylhexyl oxygen base) phosphorus, distearyl pentaerythrityl diphosphite.
As the above-mentioned commercially available product with the compound of phosphite ester structure, for example list ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB260, ADK STAB522A, ADK STAB1178, ADK STAB1500, ADK STAB C, ADK STAB135A, ADK STAB3010, ADK STAB TPP (more than, ADEKA system), IRGAFOS168 (Ciba Japan system) etc.
As the above-mentioned compound with sulfide based structural, such as listing thiodipropionate dilauryl, thio-2 acid two (tridecyl) ester, thio-2 acid myristyl ester, thio-2 acid distearyl ester, pentaerythrite four (3-lauryl thiopropionate), pentaerythrite four (3-octadecyl thiopropionate), pentaerythrite four (3-myristyl thiopropionate), pentaerythrite four (3-stearyl thiopropionate) etc.Among them, as the compound with sulfide based structural, preferred pentaerythrite four (3-lauryl thiopropionate).
As the above-mentioned commercially available product with the compound of sulfide based structural, for example list ADK STAB AO-412S, ADK STAB AO-503 (more than, ADEKA system), sumilizerTPL-R, sumilizerTPM, sumilizerTPS, sumilizerTP-D, sumilizerMB (more than, Sumitomo Chemical system), IRGANOXPS800FD, IRGANOXPS802FD (Ciba Japan system), DLTP, DSTP, DMTP, DTTP (more than, API Corporation system) etc.
As the content of above-mentioned antioxidant, with respect to [A] polymerizable compound 100 mass parts, be preferably 0.01 mass parts～10 mass parts, more preferably 0.1 mass parts～5 mass parts.By making the content of antioxidant, be above-mentioned scope, can effectively improve the thermotolerance of the display element use cured film being formed by this radiation-sensitive linear composition etc.
(preserving stabilizer)
As preserving stabilizer, such as listing sulphur, quinones, hydroquinones, polyoxy compound, amine, nitro nitroso compound etc., more specifically list 4-metoxyphenol, N-nitroso--N-Phenylhydroxylamine aluminium etc.
As the content of preserving stabilizer, with respect to [A] polymerizable compound 100 mass parts, be preferably below 3.0 mass parts, more preferably below 1.0 mass parts.When the content of preserving stabilizer surpasses 3.0 mass parts, the light sensitivity that has this radiation-sensitive linear composition reduces and the deteriorated situation of pattern form.
The preparation method > of < radiation-sensitive linear composition
About this radiation-sensitive linear composition, can be prepared by [A] polymerizable compound and [B] Photoepolymerizationinitiater initiater and [C] alkali soluble resin as required, [D] colorant and the mixing of other optional member by the ratio with regulation.This radiation-sensitive linear composition is preferably prepared by being dissolved in or being scattered in suitable solvent.
As the solvent for the preparation of this radiation-sensitive linear composition, can use: [A] polymerizable compound, [B] Photoepolymerizationinitiater initiater, [C] alkali soluble resin, [D] colorant and other optional member are dissolved equably or disperseed, and the solvent not reacting with each composition.Be explained, above-mentioned solvent can be used alone or is used in combination of two or more.
As above-mentioned solvent, from the dissolubility of each composition, consider with the viewpoint such as the reactivity of each composition, coating, for example, list:
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) the alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether,
Acetic acid (gathering) the alkylene glycol monoalkyl ethers classes such as acetic acid glycol monoethyl ether, ethylene glycol monoethyl ether acetate, acetic acid ethylene glycol list n-propyl ether, acetic acid ethylene glycol list n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol list n-propyl ether, acetic acid diethylene glycol list n-butyl ether, acetic acid propylene glycol monomethyl ether, acetic acid dihydroxypropane single-ether, acetic acid 3-methoxyl butyl ester, acetic acid 3-methyl-3-methoxyl butyl ester
Other the ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran,
The ketones such as MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one,
Propylene-glycol diacetate, 1,3-BDO diacetate esters, 1, the diacetate esters classes such as 6-hexanediol diacetate esters,
The lactic acid such as methyl lactate, ethyl lactate alkane ester class,
Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, acetic acid 3-methoxyl butyl ester, acetic acid 3-methyl-3-methoxyl butyl ester, n-butyl propionate, acetic acid 3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl butyrate, other the ester class such as 2-Oxobutyric acid ethyl ester,
Toluene, dimethylbenzene etc. are aromatic hydrocarbon based,
The amide-types such as 1-METHYLPYRROLIDONE, DMF, DMA etc.
Among these solvents, be preferably propylene glycol monomethyl ether, dihydroxypropane single-ether, acetic acid glycol monoethyl ether, acetic acid propylene glycol monomethyl ether, acetic acid dihydroxypropane single-ether, acetic acid 3-methoxyl butyl ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-HEPTANONE, 3-heptanone, 1, 3-butylene glycol diacetate esters, 1, 6-hexanediol diacetate esters, ethyl lactate, 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, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate, acetic acid propylene glycol monomethyl ether more preferably.
Further, in order to improve the inner evenness of thickness, can with above-mentioned solvent together and use high boiling solvent.As high boiling solvent, such as listing benzylisoeugenol, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol list phenyl ether acetic acid esters etc.Above-mentioned high boiling solvent can be used alone or is used in combination of two or more.
Content as above-mentioned solvent, from viewpoints such as the coating of obtained radiation-sensitive linear composition, stability, consider, be preferably make radiation-sensitive linear composition removal the total concentration of each composition of solvent become the amount of 5 quality %～60 quality %, more preferably become the amount of 10 quality %～50 quality %.In the mode of solution state, prepare in the situation of this radiation-sensitive linear composition, solid concentration (in composition solution shared the composition except solvent) can be set as concentration (for example 5 quality %～50 quality %) arbitrarily according to value of application target, desirable thickness etc.Although further preferred solid concentration, because the formation method of filming on substrate is different, sees below about this content.The radiation-sensitive linear composition of the solution state of preparing by such operation can by after using the millipore filter etc. of 0.5 μ m left and right, aperture to filter for use.
The formation method > of cured film for < display element
Display element of the present invention has following operation by the formation method of cured film:
(1) use this radiation-sensitive linear composition, on substrate, form the operation (being also called below " operation (1) ") of filming,
(2) to the operation of above-mentioned at least a portion useful to irradiation of rays of filming (being also called below " operation (2) "),
(3) by above-mentioned, irradiated the operation (being also called below " operation (3) ") that filming of ray developed, and
(4) by the above-mentioned operation (being also called below " operation (4) ") of filming and heating of having developed.
Formation method according to this display element by cured film, owing to using this radiation-sensitive linear composition to form display element cured film, thereby can form resolution and light sensitivity excellence and there is the display element cured film of high development tolerance, thermotolerance, solvent resistance etc.Below, each operation is described in detail.
[operation (1)]
In this operation, for example at the one side of transparency carrier, form nesa coating, on this nesa coating, use this radiation-sensitive linear composition and form and film.As above-mentioned transparency carrier, such as listing the glass substrates such as soda-lime glass, alkali-free glass, the resin substrate being formed by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide etc.
As the nesa coating that is formed at the one side of above-mentioned transparency carrier, for example, list by tin oxide (SnO 2) form NESA film (registered trademark of U.S. PPG company), by indium oxide-tin oxide (In 2o 3-SnO 2) the ITO film that forms etc.
By rubbing method, form in above-mentioned situation of filming, on above-mentioned nesa coating, be coated with after the solution of this radiation-sensitive linear composition, can, preferably by by coated face heating (prebake), thereby form, film.As the solid concentration of the radiation-sensitive linear composition solution for rubbing method, be preferably 5 quality %～70 quality %, more preferably 10 quality %～60 quality %, more preferably 15 quality %～50 quality %.As the coating process of this radiation-sensitive linear composition, for example, can adopt the suitable methods such as spray-on process, rolling method, method of spin coating (spin-coating method), slit rubbing method (slit die rubbing method), scraper rubbing method, ink-jet application method.Among them, preferred spin-coating method or slit rubbing method.
The condition of above-mentioned prebake because of the kind of each composition, compounding ratio etc. different, but prebake temperature is preferably 70 ℃～120 ℃, the prebake time is generally 1 minute～15 minutes.Thickness after the prebake of filming is preferably 0.5 μ m～10 μ m, more preferably 1.0 μ m～7.0 μ m.
[operation (2)]
In this operation, to formed at least a portion useful to irradiation of rays of filming.In the situation of only a part of filming being irradiated, for example, can irradiate by following method, the method is for to irradiate across the photomask with the pattern of regulation.
As the ray using in irradiating, such as listing visible ray, ultraviolet ray, far ultraviolet etc.Among them, be preferably the ray of the scope of wavelength in 250nm～550nm, more preferably comprise the ultraviolet ray of 365nm.
About radiation exposure (exposure), the value that the intensity at the wavelength 365nm place of the ray irradiating determines by illuminometer (OAI model356, Optical Associates Inc. system) is preferably 100J/m 2～5,000J/m 2, 200J/m more preferably 2～3,000J/m 2.
It is high that this radiation-sensitive linear composition and the composition known to existing are compared light sensitivity, even be 700J/m in above-mentioned radiation exposure 2below, even further at 600J/m 2below, also can obtain desirable thickness, good shape, the stickability of excellence and the display element cured film of high rigidity.
[operation (3)]
In this operation, by developing having irradiated filming of ray, remove unwanted part, thereby form the pattern of regulation.As the developer solution using in developing, such as listing the inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, the aqueous solution of the alkali compounds such as quaternary ammonium salt such as Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide.Also can, in the aqueous solution of above-mentioned alkali compounds, add water-miscible organic solvent, the surfactants such as appropriate methyl alcohol, ethanol.
As developing method, can be to revolve any that cover in immersion method, infusion process, shower method etc., development time is preferably 10 seconds at normal temperatures～about 180 seconds.After development treatment, for example, carry out flowing water washing after 30 seconds～90 seconds, thereby utilize pressurized air or compressed nitrogen to carry out the air-dry pattern of wishing that obtains.
[operation (4)]
In this operation, by the suitable heating arrangements such as hot plate, baking oven add thermal development film.Form thus display element cured film.As heating-up temperature, be 100 ℃～250 ℃ left and right.As the heat time, for example, on hot plate, be 5 minutes～30 minutes, in baking oven, be about 20 minutes～180 minutes.
< display element cured film >
Display element of the present invention is formed by this radiation-sensitive linear composition by cured film.Cured film such as interlayer dielectric as display element for this display element, sept, diaphragm, color filter are with colored pattern etc.Because this display element is formed by this radiation-sensitive linear composition by cured film, thereby this display element has high compression performance, resistance to developability, thermotolerance and solvent resistance by cured film.This display element is not particularly limited by the formation method of cured film, but can preferably use the formation method of cured film for this above-mentioned display element.
< display element >
Display element of the present invention possesses this display element cured film.This display element is such as consisting of liquid crystal cells described later, polaroid etc.Because this display element has this display element cured film, thereby this display element has high compression performance etc.
Manufacture method as this display element; first prepare the transparency carrier that a pair of (two) have nesa coating (electrode) on one side; on the nesa coating of a substrate therein by using this radiation-sensitive linear composition, and form according to the method described above sept or diaphragm or this both.Then, on the nesa coating of these substrates and sept or diaphragm, form the alignment films with liquid crystal aligning function.For these substrates, the face that is formed with a side of this alignment films is made as to inner side, liquid crystal aligning direction according to alignment films is separately that quadrature or antiparallel mode are carried out subtend configuration with certain gap (box is thick), the thick interior filling liquid crystal of box marking to the surface by substrate (alignment films) and spacer region, seals filler opening and forms liquid crystal cells.Then, at two outside surfaces of liquid crystal cells, by polaroid is fitted with the liquid crystal aligning direction mode consistent or quadrature of alignment films that is formed at the one side of this substrate according to its polarization direction, thereby obtain display element of the present invention.
As other method, in the mode identical with said method, operate, prepare to be formed with nesa coating; Interlayer dielectric, diaphragm or sept or this both; The a pair of transparency carrier of alignment films., along the end of a substrate, use divider coating ultraviolet hardening sealant, then use liquid crystal dispensing apparatus to drip the liquid crystal of fine droplet shape, under vacuum, carry out the laminating of two substrates thereafter.Then, thus use high-pressure mercury-vapor lamp to above-mentioned sealant portion irradiation ultraviolet radiation, two substrates to be sealed.Finally, by the two outside surface laminating polaroids at liquid crystal cells, thereby obtain display element of the present invention.
As the liquid crystal using in each above-mentioned method, such as listing nematic crystal, smectic crystal etc.In addition, the polaroid using in outside as liquid crystal cells, list with cellulose acetate diaphragm clamping and be called the light polarizing film of " H film " and the polaroid that obtains, this be called " H film " while light polarizing film by making polyvinyl alcohol (PVA) stretch orientation absorb iodine, obtain; The polaroid being formed by H film itself etc.
Embodiment
Below, based on embodiment, illustrate the present invention, but the present invention is not limited to these embodiment.The assay method of each physics value shown in following.
[weight-average molecular weight (Mw) and number-average molecular weight (Mn)]
According to following condition, determine Mw and Mn.
Device: GPC-101 (clear and electrician's system)
Chromatographic column: in conjunction with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804
Mobile phase: tetrahydrofuran
Chromatogram column temperature: 40 ℃
Flow velocity: 1.0mL/ minute
Sample solution concentration: 1.0 quality %
Sample injection rate IR: 100 μ L
Detecting device: differential refraction detector
Standard substance: monodisperse polystyrene
[ 1h-NMR analyzes]
1h-NMR analyzes by using nuclear magnetic resonance device (JNM-ECX400, NEC system), measuring frequency number: 300MHz, measures solvent: DMSO-d 8condition under carry out.
The synthetic > of < [B] Photoepolymerizationinitiater initiater
[synthesis example 1] ((B-1's) is synthetic)
To being provided with in the 500ml four-hole boiling flask of thermometer, condenser pipe and stirrer, add 2-methyl isophthalic acid-[4-chlorphenyl]-2-morpholino-1-acetone 33.0g (0.1235mol), dimethyl formamide 165g, 2-ethyl hexane mercaptan 23.5g (0.1606mol), to carrying out nitrogen replacement in above-mentioned flask.Add wherein 48 quality % sodium hydrate aqueous solution 12.4g (0.1482mol).This mixed liquor is stirred 7 hours at 80 ℃ under nitrogen environment, react.After reaction finishes, make water 100g and toluene 100g and dissolve generated salt, make water layer carry out separated with oil reservoir.Further use the water washing oil reservoir of 100g, make water layer carry out separated with oil reservoir.Repeatedly carry out several water washing, then from oil reservoir, toluene and unreacted 2-ethyl hexane mercaptan are under reduced pressure distilled to removal, thereby obtain, take the filemot viscous liquid that 2-methyl isophthalic acid-[4-(2-ethyl hexyl sulfenyl) phenyl]-2-morpholino-1-acetone is principal ingredient.The output of this sulfide compound is 46.2g (yield: 99 quality % of theoretical yield).In addition, the chemical purity of sulfide compound is by being used high performance liquid chromatograph (HPLC) to measure, and result is 98% (HPLC area %).In addition, even if the compound obtaining is cooled to-25 ℃, can there is not crystallization yet, and be aqueous.Measure 1h-NMR analyzes, and result is as follows.
1H-NMR(DMSO-d 8，300MHz)；δ0.93(6H)，δ1.28(4H)，δ1.38(2H)，δ1.47(6H)，δ1.57(2H)，δ1.78(1H)，δ2.54(4H)，δ2.61-2.86(2H)，δ3.69(4H)，δ7.48(2H)，δ7.85(2H)。
[synthesis example 2] ((B-2's) is synthetic)
To being provided with in the 500ml four-hole boiling flask of thermometer, condenser pipe and stirrer, add 2-methyl isophthalic acid-[4-chlorphenyl]-2-morpholino-1-acetone 33.0g (0.1235mol), dimethyl formamide 165g, 3-sulfydryl-1,2-propylene glycol 17.4g (0.1606mol), to carrying out nitrogen replacement in above-mentioned flask.Add wherein 48 quality % sodium hydrate aqueous solution 12.4g (0.1482mol).Under nitrogen environment, at 80 ℃, stir this mixed liquor 7 hours, react.After reaction finishes, make water 100g and ethyl acetate 100g dissolve the salt generating, make water layer carry out separated with oil reservoir.Further use the water washing oil reservoir of 100g, make water layer carry out separated with oil reservoir.Repeatedly carry out after several water washing, from oil reservoir by toluene and unreacted 3-sulfydryl-1,2-propylene glycol under reduced pressure distills while removing, and obtains the filemot viscous liquid so that 2-methyl isophthalic acid-[4-(2,3-hydroxyl rosickyite base) phenyl]-2-morpholino-1-acetone is principal ingredient.By this liquid being carried out from ethyl acetate/heptane mixed solvent to crystallization, separation, thereby obtain white solid.The output of this sulfide compound is 21.0g (yield: theoretical yield 50%).In addition, use HPLC to measure the chemical purity of sulfide compound, result is 99% (HPLC area %).Measure 1h-NMR analyzes, and result is as follows.
1H-NMR(DMSO-d 8，300MHz)；δ1.46(6H)，δ2.55(4H)，δ2.75-3.06(2H)，δ3.55(1H)，δ3.56(1H)，δ3.64(4H)，δ3.66(1H)，δ3.56-3.82(2H)，δ7.48(2H)，δ7.83(2H)。
The synthetic > of < [C] alkali soluble resin
[synthesis example 3] ((C-1's) is synthetic)
To possessing in the flask that has condenser pipe and stirrer, add 2, 2 '-azoisobutyronitrile, 4 mass parts and diethylene glycol methyl ethyl ether 300 mass parts, then add methacrylic acid 23 mass parts that produce structural unit (C3), produce styrene 10 mass parts of other structural unit, benzyl methacrylate 32 mass parts and methyl methacrylate 35 mass parts, and as α-methylstyrenedimer 2.7 mass parts of molecular weight regulator, gently stir on one side the temperature of solution is elevated to 80 ℃ on one side, this temperature is kept 4 hours, then be increased to 100 ℃, by this temperature is kept 1 hour and polymerization, thereby obtain the solution (solid concentration=24.9 quality %) that contains multipolymer.The Mw of the multipolymer obtaining is 12,500.Then, by adding tetrabutyl ammonium bromide 1.1 mass parts in the solution to comprising multipolymer, as 4-metoxyphenol 0.05 mass parts of polymerization inhibitor, under air ambient, at 90 ℃, stir after 30 minutes, add glycidyl methacrylate 16 mass parts, under the state of 90 ℃, react 10 hours, thereby obtain multipolymer (C-1) (solid concentration=29.0 quality %).The Mw of multipolymer (C-1) is 14,200.Multipolymer (C-1) is dripped and in hexane, precipitates refiningly again, by the resin solid content to being settled out again, undertaken 1h-NMR analyzes, thereby calculates the reaction rate (production rate of structural unit (C1)) of glycidyl methacrylate.According near near the peak and the comparison of integration ratio that is derived near the proton of the aromatic rings 6.8ppm～7.4ppm of structural unit of benzyl methacrylate of multipolymer being derived from the methacryl of glycidyl methacrylate 6.1ppm and 5.6ppm, calculate the reaction rate of the carboxyl in glycidyl methacrylate and multipolymer.Its results verification, 96 % by mole of the glycidyl methacrylate that reaction obtains are reacted with the carboxyl in multipolymer.
[synthesis example 4] ((C-2's) is synthetic)
To possessing in the flask that has condenser pipe and stirrer, add 2,2 '-azo two-(2,4-methyl pentane nitrile) 5 mass parts and diethylene glycol methyl ethyl ether 220 mass parts, styrene 20 mass parts and the methacrylic acid three ring [5.2.1.0 of the structural unit that then add methacrylic acid 12 mass parts, glycidyl methacrylate 40 mass parts that produce structural unit (C2) that produce structural unit (C3), produces other 2,6] decane-8-base ester 28 mass parts, and carry out nitrogen displacement.Gently stir on one side the temperature of solution is elevated to 70 ℃ on one side.By this temperature is kept 5 hours and polymerization, obtain the solution (solid concentration=31.3 quality %) that contains multipolymer (C-2).The Mw=12 of multipolymer (C-2), 000.
Provide below [A] polymerizable compound for the preparation of radiation-sensitive linear composition, [B '] Photoepolymerizationinitiater initiater, [D] colorant, [E] bonding auxiliary agent, [F] surfactant and [G] epoxy compound.
[[A] polymerizable compound]
A-1: the potpourri of dipentaerythritol five acrylate and dipentaerythritol acrylate (KAYARAD DPHA, Japanese chemical drug system)
A-2: succinic acid modification pentaerythritol triacrylate (Aronix TO-756, the synthetic system in East Asia)
A-3: the potpourri of tetramethylol methane tetraacrylate and pentaerythritol triacrylate (NK ESTER A-TMM-3LM-N, Xin Zhong village chemistry system)
A-4: the potpourri of three (2-acryloxy ethyl) isocyanuric acid ester and two (2-acryloxy ethyl) isocyanuric acid esters (Aronix M-313, the synthetic system in East Asia)
[[B '] Photoepolymerizationinitiater initiater]
B '-1:2-methyl isophthalic acid-(4-methylbenzene sulfenyl)-2-morpholino third-1-ketone (IRGACURE907, Ciba Specialty Chemicals Inc. system)
B '-2: ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime)
B '-3:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone
B '-4: two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide
B '-5:2-(2-chlorphenyl)-1-[2-(2-chlorphenyl)-4,5-diphenyl-2H-imidazoles-2-yl]-4,5-diphenyl-1H-imidazoles
B '-6:4,4 '-bis-(diethylamino) benzophenone
B '-7:2,4-diethyl thioxanthone-9-ketone
[[D] colorant]
D-1:C.I. solvent red 45
D-2:C.I. solvent yellow 82
[[E] bonding auxiliary agent]
E-1: γ-glycidoxypropyltrime,hoxysilane
[[F] surfactant]
F-1:FTX-218 (NEOS system)
[[G] epoxy compound]
G-1: phenol novolak type epoxy resin (Epikote152, Japan Epoxy Resins Co., Ltd. system)
The preparation > of < radiation-sensitive linear composition
Each composition in each radiation-sensitive linear composition of embodiment and comparative example is shown in to table 1.In addition, "-" in table 1 represents not use suitable composition.The solid concentration of each radiation-sensitive linear composition is shown in to table 1 in the lump.
[embodiment 1]
Will be as (A-1) 100 mass parts of [A] polymerizable compound, (F-1) 0.5 mass parts mixing of (E-1) 5 mass parts of (B-1) 30 mass parts of conduct [B] Photoepolymerizationinitiater initiater, the bonding auxiliary agent of conduct [E] and conduct [F] surfactant, the mode that is 30 quality % according to solid concentration adds acetic acid propylene glycol monomethyl ether, then with the millipore filter of aperture 0.5 μ m, filter, thereby prepare radiation-sensitive linear composition.
[embodiment 2]
Using the multipolymer (C-2) of (B-1) 30 mass parts of (A-1) 100 mass parts as [A] polymerizable compound, conduct [B] Photoepolymerizationinitiater initiater, conduct [C] alkali soluble resin according to solid content convert 100 mass parts obtain, as (E-1) 5 mass parts of [E] bonding auxiliary agent and as (F-1) 0.5 mass parts mixing of [F] surfactant, the mode that is 30 quality % according to solid concentration adds acetic acid propylene glycol monomethyl ether, then with the millipore filter of aperture 0.5 μ m, filter, thereby prepare radiation-sensitive linear composition.
[embodiment 3～8 and comparative example 1～2]
Except using each composition of the kind shown in following table 1 and compounding amount, in the mode identical with embodiment 2, operate, thereby prepare each radiation-sensitive linear composition.
[embodiment 9]
Will be as (A-1) 55 mass parts of [A] polymerizable compound, (B-1) 15 mass parts as [B] Photoepolymerizationinitiater initiater, (B '-6) 10 mass parts and (B '-7) 5 mass parts as [B '] Photoepolymerizationinitiater initiater, 50 mass parts that convert and obtain according to solid content as the multipolymer (C-1) of [C] alkali soluble resin, as (D-1) 27 mass parts of [D] colorant and (D-2) 8 mass parts, and mix as (G-1) 15 mass parts of [G] epoxy compound, the mode that is 30 quality % according to solid concentration adds acetic acid propylene glycol monomethyl ether, thereby prepare radiation-sensitive linear composition.
[embodiment 10 and comparative example 3]
Except using each composition of the kind shown in following table 1 and compounding amount, in the mode identical with embodiment 9, operate, thereby prepare each radiation-sensitive linear composition.
Figure BDA0000373218530000431
< evaluates >
Use each prepared radiation-sensitive linear composition to implement following evaluation.Specifically, about embodiment 1, use radiation-sensitive linear composition and form display element cured film, the pencil hardness of cured film is evaluated.About embodiment 2～6 and comparative example 1, use each radiation-sensitive linear composition and form display element cured film, the resolution as sept, light sensitivity and compression performance are evaluated.About embodiment 7～8 and comparative example 2, the storage stability of each radiation-sensitive linear composition is evaluated.About embodiment 9～10 and comparative example 3, use each radiation-sensitive linear composition and form display element cured film, development tolerance, thermotolerance and solvent resistance as colored pattern are evaluated.Evaluation result is shown in to table 2.In addition, "-" in table 2 represents not carry out suitable evaluation.
About thering is the substrate of the diaphragm forming as described above, by " the 8.4.1 pencil of JISK-5400-1990 scratches test ", determine the pencil hardness (skin hardness) of diaphragm.This value is for 4H or while being greater than 4H, and the skin hardness of judgement cured film is good.
[resolution (μ m)]
On alkali-free glass substrate, utilize spinner by after each radiation-sensitive linear composition solution coat, by prebake on the hot plate at 100 ℃ 2 minutes, thereby form filming of thickness 4.0 μ m.In the situation of embodiment 1, do not use photomask, take exposure as 1000J/m 2thereby expose, obtain cured film, effects on surface hardness is evaluated.About embodiment 2～6 and comparative example 1, on obtained filming, the photomask of the incomplete pattern of a plurality of round shape of different sizes that utilization has the scope of diameter 8 μ m～20 μ m, is used high-pressure mercury-vapor lamp (predominant wavelength 365nm), according to making exposure at 200J/m 2～1,000J/m 2scope carry out the mode of variable and useful to irradiation of rays.Afterwards, by using the 0.40 quality % potassium hydroxide aqueous solution of 23 ℃ as developer solution, and to develop, press 1kgf/cm 2, nozzle diameter 1mm ejection and carry out shower development.Then, carry out pure water washing 1 minute.By further curing after carrying out 30 minutes at 230 ℃, thereby form filming of pattern-like in baking oven.The pattern dimension of formed minimum is made as to resolution (μ m), is 14 μ m following in the situation that in resolution, resolution can be evaluated as well.
[light sensitivity (J/m 2)]
Except using the photomask of the incomplete pattern of round shape with a plurality of diameter 15 μ m, the mode identical with the evaluation with above-mentioned resolution operates, thereby on substrate, forms the incomplete pattern of circle shape.Height before using laser microscope (VK-8500, KEYENCE system) to measure the development of the incomplete pattern of circle shape and after developing.Use this measured value, according to following formula, obtain residual film ratio (%).
Residual film ratio (%)=(height after developing/height before developing) * 100
By this residual film ratio, be that more than 90% minimum exposure is made as light sensitivity (J/m 2).Exposure is 800J/m 2in following situation, light sensitivity can be evaluated as well.
[compression performance]
The mode identical with the evaluation with above-mentioned light sensitivity operates, and the residual film ratio of take is justified the incomplete pattern of shape as more than 90% exposure forms on substrate.For this pattern, utilize micro-compression test (FISCHER SCOPE H100C, FISCHER INSTRUMENS system), use the plane of the square shape of 50 μ m to press son, with the load of 40mN, carry out compression test, measure displacement (μ m) with respect to the variation of load.The displacement of displacement during again, according to the load of 40mN during with the load of having removed 40mN calculated recovery rate (%).Recovery rate is more than 85% and the displacement during load of 40mN is in situation more than 0.15 μ m, can judge that compression performance is good.
[storage stability]
The keeping at-15 ℃ of each radiation-sensitive linear composition, after 1 week, is confirmed to have or not precipitate.Now, produce in the absence of precipitate, storage stability is evaluated as to " good (A) "; Produce in the situation of precipitate, be evaluated as " bad (B) ".
The formation > of < colored pattern
On surface, be formed with the SiO of the wash-out that prevents sodion 2on the soda-lime glass substrate of film, use rotary coating machine to be coated with each radiation-sensitive linear composition.Then, utilize the hot plate of 90 ℃ to carry out 2 minutes prebake, the thickness forming after prebake is filming of 2.5 μ m, thereby produces evaluation substrate.These are evaluated after substrate cool to room temperature, use high-pressure mercury-vapor lamp, be situated between by photomask, by the ray of each wavelength that comprises 365nm, 405nm and 436nm with 100J/m 2, 300J/m 2, 500J/m 2, 700J/m 2and 1,000J/m 2exposure above-mentioned filming exposed.Afterwards, for these, evaluate substrate, by developer solution (the 0.04 quality % potassium hydroxide aqueous solutions of 23 ℃) is pressed to 1kgf/cm to develop 2, nozzle diameter 1mm ejection and carry out shower development, thereby form the colored pattern of 200 μ m * 200 μ m.Further, after 180 ℃, cure 30 minutes, thereby form colored pattern.
[development tolerance]
Film Thickness Ratio before and after development in the formation of above-mentioned colored pattern is calculated by following formula.
Film Thickness Ratio=(thickness before the thickness/development after development) * 100 before and after developing
This value is made as to development tolerance, more than 95% situation is made as to " good (A) ", by the situation of less than 95% or in a part for colored pattern, confirm that the situation of breach is made as " generally bad (B) "), the situation that pattern is all peeled off from substrate is made as " bad (C) ".
[thermotolerance]
Divided by 1,000J/m 2exposure expose beyond, the mode identical with the formation with above-mentioned colored pattern operates, thereby forms colored pattern.Further at 180 ℃, append heating 30 minutes.Obtain the change color Δ Eab* that appends heating front and back.This value is made as to thermotolerance, the situation of Δ Eab* less than 3 is made as " good (A) ", by more than 3 and the situation of less than 5 be made as " generally good (B) ", more than 5 situations is made as to " bad (C) ".
[solvent resistance]
In the mode identical with above-mentioned stable on heating evaluation, operate, thereby form colored pattern.The substrate that forms this colored pattern is immersed in to the 1-METHYLPYRROLIDONE 30 minutes of 60 ℃.To after submergence, keep the 1-METHYLPYRROLIDONE after colored pattern and submergence not have painted situation to be made as " good (A) " completely, but will after submergence, keep a little the painted situation of 1-METHYLPYRROLIDONE after colored pattern submergence to be made as " generally good (B) ", by after submergence, can be observed from the colored pattern of strippable substrate and the 1-METHYLPYRROLIDONE submergence painted situation be made as " defective (C) ".
Table 2
Figure BDA0000373218530000471
Known according to the result of table 2, this radiation-sensitive linear composition has good resolution, light sensitivity and storage stability, and the display element being formed by this radiation-sensitive linear composition has good compression performance, development tolerance, thermotolerance and solvent resistance by cured film.
Utilizability in industry
The present invention can provide a kind of radiation-sensitive linear composition, and it is excellent and have a display element cured film of high compression performance, storage stability, development tolerance, thermotolerance, solvent resistance that it can form resolution and light sensitivity.Therefore, this radiation-sensitive linear composition is applicable to: color filter for display element, for array the look of interlayer dielectric, solid-state imager decompose with color filter, the organic EL color filter for flexible display such as color filter, Electronic Paper display element for, diaphragm for touch panel, in the formation of metal line and metal coupling, in the processing of substrate etc. the photo-fabrication of use with resist layer etc.

Claims (11)

1. a radiation-sensitive linear composition, it contains [A] and has the polymerizable compound of ethylenic unsaturated bond and the Photoepolymerizationinitiater initiater that [B] represented by following formula (1),
[Chemical formula 1]
Figure FDA0000373218520000011
In formula (1), R 1morpholino base, piperidino, dimethylamino or diethylamino, R 2and R 3be the alkyl of carbon number 1～6 independently of one another, R 4and R 5be the alkyl of hydroxyl, methylol or carbon number 1～6 independently of one another, the integer that n is 0～6, X is oxygen atom or sulphur atom.
2. radiation-sensitive linear composition according to claim 1, wherein, [B] Photoepolymerizationinitiater initiater represents by following formula (1-1),
[Chemical formula 2]
Figure FDA0000373218520000012
In formula (1-1), R 4and R 5identical with the definition of above-mentioned formula (1).
3. radiation-sensitive linear composition according to claim 1, it further contains [C] alkali soluble resin.
4. radiation-sensitive linear composition according to claim 3, wherein, [C] alkali soluble resin has the structural unit being represented by following formula (2),
[chemical formula 3]
Figure FDA0000373218520000021
In formula (2), R 6and R 7be hydrogen atom or methyl independently of one another, R 8the divalent group being represented by following formula (2-i) or following formula (2-ii), the integer that m is 1～6,
[chemical formula 4]
Figure FDA0000373218520000022
In formula (2-i), R 9hydrogen atom or methyl,
In formula (2-i) and formula (2-ii), * represents the position of being combined with oxygen atom.
5. radiation-sensitive linear composition according to claim 1, it further contains [D] colorant.
6. radiation-sensitive linear composition according to claim 3, wherein, [C] alkali soluble resin has the structural unit being derived from containing the unsaturated compound of epoxy radicals.
7. according to the radiation-sensitive linear composition described in any one in claim 1～6, it is used to form display element cured film.
8. a Photoepolymerizationinitiater initiater, it is the Photoepolymerizationinitiater initiater shown in the formula (1-1) of recording in claim 2.
9. the formation method of cured film for display element, it has following operation:
(1) right to use requires the radiation-sensitive linear composition described in 7, forms the operation of filming on substrate,
(2) operation to above-mentioned at least a portion useful to irradiation of rays of filming,
(3) by above-mentioned, irradiated the operation that filming of ray developed, and
(4) by the above-mentioned operation of filming and heating of having developed.
10. a display element cured film, it is formed by radiation-sensitive linear composition claimed in claim 7.
11. 1 kinds of display elements, it possesses display element cured film claimed in claim 9.
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CN110520796A (en) * 2017-06-20 2019-11-29 株式会社艾迪科 Polymerizable composition, polymerizable composition, black matrix" photosensitive composite and black column spacer photosensitive composite
CN109324479A (en) * 2017-08-01 2019-02-12 北京英力科技发展有限公司 A kind of photoetching compositions

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