CN101082772A - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device Download PDF

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CN101082772A
CN101082772A CN 200710106446 CN200710106446A CN101082772A CN 101082772 A CN101082772 A CN 101082772A CN 200710106446 CN200710106446 CN 200710106446 CN 200710106446 A CN200710106446 A CN 200710106446A CN 101082772 A CN101082772 A CN 101082772A
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methyl
acid
unsaturated compound
oxetanes
pigment
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CN101082772B (en
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森下聪
依田杏介
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JSR Corp
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JSR Corp
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Abstract

A radiation sensitive composition comprising a colorant, an alkali-soluble resin, a polyfunctional monomer and a photopolymerization initiator. The alkali-soluble resin is a copolymer of (b1) at least one first unsaturated compound selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride and an unsaturated phenolic compound and at least one second unsaturated compound selected from the group consisting of (b2) an unsaturated compound having an oxetane skeleton and (b3) an unsaturated compound having a tetrahydrofuran skeleton. The radiation sensitive composition is used to form a colored layer.

Description

Be used to form radiation-ray sensitive composition, color filter and the color liquid crystal display device of dyed layer
Technical field
The present invention relates to be used to form radiation-ray sensitive composition, color filter and the color liquid crystal display device of dyed layer.More particularly, the present invention relates to be used to form the radiation-ray sensitive composition of dyed layer useful in the color filter that in infiltration type or Reflexible color LCD, colour pick-up tube element etc., uses, the color liquid crystal display device that possesses the color filter of the dyed layer that forms by this radiation-ray sensitive composition and possess this color filter.
Background technology
In the past, when using colored radiation-sensitive composition to make color filter, known have a following method: on the substrate or be pre-formed on the substrate of light shield layer of required pattern and be coated with colored radiation-sensitive composition, dry then, again to dry coating irradiation radioactive ray, form required pattern form (hereinafter referred to as " exposure "), obtain versicolor pixel (with reference to Japanese kokai publication hei 2-144502 communique, Japanese kokai publication hei 3-53201 communique) by development.
In recent years in the color filter technique field, performance demands to formed pixel and black matrix and colored radiation-sensitive composition is more strict, remove the sensitivity of colored radiation-sensitive composition, resolution, outside the pattern form etc., for pixel and black matrix also its solvent resistance of strong request to the solvent of wide scope, tack excellence with substrate, in addition, consider from color filter production management aspect, also it contains the excellent storage stability of the fluid composition form of solvent to employed colored radiation-sensitive composition strong request in forming color filter, but can not fully completely organize above-mentioned requirements in the colored radiation-sensitive composition in the past.
Summary of the invention
The object of the present invention is to provide a kind of novel radiation-ray sensitive composition that is used to form dyed layer, in the said composition, the storage stability of fluid composition form that contains solvent is good, can form solvent resistance to the solvent of wide scope, with the excellent pixel and the black matrixes such as tack of substrate.
Another object of the present invention is to provide color filter and color liquid crystal display device.
Other purpose of the present invention and advantage are as described below.
According to the present invention, above-mentioned purpose of the present invention and advantage first aspect realize by radiation-ray sensitive composition, it is characterized in that: this radiation-ray sensitive composition contains (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, above-mentioned radiation-ray sensitive composition is used to form dyed layer, wherein, (B) alkali soluble resin contains the multipolymer of the 1st unsaturated compound and the 2nd unsaturated compound, described the 1st unsaturated compound is selected from unsaturated carboxylic acid for (b1), unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds at least a, described the 2nd unsaturated compound are selected from unsaturated compound at least a that (b2) has the unsaturated compound of oxetanes skeleton and (b3) have the tetrahydrofuran skeleton.
Among the present invention, dyed layer is meant " pixel and/or black matrix ".
According to the present invention, above-mentioned purpose of the present invention and advantage second aspect realize that by color filter this color filter possesses the dyed layer that uses above-mentioned radiation-ray sensitive composition to form.
According to the present invention, the above-mentioned purpose of the present invention and the advantage third aspect realize that by color liquid crystal display device this color liquid crystal display device possesses color filter of the present invention.
The best mode that carries out an invention
Below the present invention is described in detail.
Radiation-ray sensitive composition
-(A) colorant-
Its tone of colorant of the present invention is not particularly limited, and can suitably select according to the purposes of gained color filter, and pigment, dyestuff or natural colouring matter all can.
Color filter requires high meticulous colour developing and thermotolerance, therefore as colorant of the present invention, and preferred colour rendering height and the high colorant of thermotolerance, the high colorant of preferred especially heat-resisting decomposability.Preferred organic pigment or the inorganic pigment of using especially preferably uses organic pigment and carbon black.
As above-mentioned organic pigment, for example have at Colour Index (C.I.; The compound of the pigment that is categorized as The Society of Dyersand Colourists company distribution) can be enumerated following Colour Index (C.I.) numbering specifically.
C.I. pigment yellow 1, C.I. pigment yellow 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 65, C.I. pigment yellow 71, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 116, C.I. pigment yellow 117, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 17 5, C.I. pigment yellow 180, C.I. pigment yellow 185;
C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73;
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38;
C.I. paratonere 1, C.I. paratonere 2, C.I. pigment red 3, C.I. pigment red 4, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. pigment Red 8, C.I. Pigment Red 9, C.I. paratonere 10, C.I. paratonere 11, C.I. paratonere 12, C.I. paratonere 14, C.I. paratonere 15, C.I. paratonere 16, C.I. paratonere 17, C.I. paratonere 18, C.I. paratonere 19, C.I. pigment red 21, C.I. paratonere 22, C.I. paratonere 23, C.I. pigment red 30, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 37, C.I. pigment red 38, C.I. pigment red 40, C.I. pigment red 41, C.I. pigment red 42, C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 4 9:1, C.I. pigment red 4 9:2, C.I. paratonere 50:1, C.I. paratonere 52:1, C.I. paratonere 53:1, C.I. paratonere 57, C.I. paratonere 57:1, C.I. paratonere 57:2, C.I. paratonere 58:2, C.I. paratonere 58:4, C.I. paratonere 60:1, C.I. paratonere 63:1, C.I. paratonere 63:2, C.I. paratonere 64:1, C.I. pigment red 81: 1, C.I. pigment Red 83, C.I. pigment Red 88, C.I. Pigment Red 9 0:1, C.I. Pigment Red 97;
C.I. paratonere 101, C.I. paratonere 102, C.I. paratonere 104, C.I. paratonere 105, C.I. paratonere 106, C.I. paratonere 108, C.I. pigment red 112, C.I. paratonere 113, C.I. paratonere 114, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 146, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 151, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 172, C.I. paratonere 174, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 188, C.I. paratonere 190, C.I. paratonere 193, C.I. paratonere 194, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 226, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 245, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 265;
C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60;
C.I. pigment Green 7, C.I. pigment green 36;
C.I. bistre 23, C.I. bistre 25;
C.I. pigment black 1, C.I. pigment black 7.
Above-mentioned organic pigment can use by the purifying such as method of for example sulfuric acid recrystallization method, solvent wash method or their combination.
In addition, above-mentioned inorganic pigment for example can be enumerated titanium dioxide, barium sulphate, lime carbonate, zinc white, lead sulfate, lead and yellow-collation, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, umber, black, the synthetic iron oxide black of titanium, carbon black etc.
Among the present invention, above-mentioned organic pigment and inorganic pigment can be distinguished separately and to use or 2 kinds or above mixing are used.For example organic pigment and inorganic pigment can also be used in combination.When forming pixel, preferably use one or more organic pigment, in addition, form when deceiving matrix, preferably use 2 kinds or above organic pigment and/or carbon black.
Among the present invention, above-mentioned each pigment can use its particle surface as required with polymer modification.Be used for polymkeric substance that particle surface to pigment carries out modification and for example can be polymkeric substance that record polymkeric substance such as Japanese kokai publication hei 8-259876 communique or commercially available various pigment dispersing use or oligomer etc.
Among the present invention, colorant can use with spreading agent as required.
Above-mentioned spreading agent for example has surfactants such as cationic, anionic species, nonionic class, both sexes, type siloxane, fluorine class.
As above-mentioned surfactant, for example have: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Polyethylene glycol di such as polyethylene glycol dilaurate, polyglycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyester; The tertiary amine modified polyurethane; Polyethyleneimines etc. are discussed the KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing) that the name of an article is represented face to face below also having in addition, Port リ Off ロ-(common prosperity chemistry (strain) manufacturing), エ Off ト Star プ (ト-ケ system プ ロ ダ Network Star (strain) is made), メ ガ Off ア Star Network (big Japanese イ Application キ chemical industry (strain) manufacturing), Off ロ ラ-De (Sumitomo ス リ-エ system (strain) is made), ア サ ヒ ガ-De, サ-Off ロ Application (above) by Asahi Glass (strain) manufacturing, BYK, Disperbyk (above) by PVC Star Network ケ ミ-ジ ヤ パ Application (strain) manufacturing, ソ Le ス パ-ス (セ ネ カ (strain) manufacturing) etc.
These surfactants can use separately or 2 kinds or above mixing are used.
With respect to 100 weight portion colorants, preferred 50 weight portions of the use amount of surfactant or following, more preferably 0-30 weight portion.
Among the present invention, radiation sensitive resin composition can be by suitable method preparation.For example, can be according to circumstances the adjuvant of (A)-(D) composition and solvent and/or back number be mixed together and prepares.When using pigment as colorant, preferably in solvent, in the presence of spreading agent, use for example ball mill, roller mill etc., according to circumstances with the part of (B) composition, this pigment is pulverized and mixed, disperse, make dispersible pigment dispersion, it with (B)-(D) composition and further add solvent or the adjuvant that appends as required, is mixed with.
Preparation is during dispersible pigment dispersion, and the use amount of spreading agent is with respect to 100 weight portion pigment optimizations, 100 weight portions or following, more preferably 0.5-100 weight portion, further preferred 1-70 weight portion, preferred especially 10-50 weight portion.The use amount of spreading agent surpasses 100 weight portions, and then development property etc. may be impaired.
The solvent that preparation is used during dispersible pigment dispersion for example can be the identical solvent of solvent that is exemplified in the fluid composition with radiation sensitive resin composition described later.
During the preparation dispersible pigment dispersion, with respect to 100 weight portion pigment, the preferred 500-1 of the use amount of solvent, 000 weight portion, more preferably 700-900 weight portion.
During the preparation dispersible pigment dispersion, if use ball mill to be prepared, beaded glass about for example can using diameter as 0.5-10mm or titania pearl etc. disperse to implement Yi Bian will contain preferred the mixing with coolings such as chilled waters of the pigment mixed liquor of pigment, solvent and spreading agent on one side.
At this moment, the filling rate of pearl is preferably the 50-80% of grinding machine capacity, and the injection rate IR of pigment mixed liquor is preferably about the 20-50% of grinding machine capacity.Preferred 2-50 of processing time hour, more preferably 2-25 hour.
When using roller mill to prepare, for example can use triple-roller mill or two roller mills etc., preferred on one side the pigment mixed liquor processing with coolings such as chilled waters on one side implemented.
At this moment, the preferred 10 μ m or following of roller spacing, shearing force is preferably 10 8Dyn/ is about second.Preferred 2-50 of processing time hour, more preferably 2-25 hour.
-(B) alkali soluble resin-
Alkali soluble resin of the present invention contains the multipolymer of the 1st unsaturated compound (below can be described as " acid unsaturated compound ") and the 2nd unsaturated compound, wherein, described the 1st unsaturated compound is selected from least a of unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds for (b1), and the 2nd unsaturated compound is selected from (b2) and has at least a of the unsaturated compound of oxetanes skeleton and the unsaturated compound that (b3) has the tetrahydrofuran skeleton; This alkali soluble resin is that colorant (A) is played the bonding agent effect, and has the composition for the solubility of the alkaline-based developer that uses in the development treatment step when forming dyed layer.
More particularly, alkali soluble resin (B) has: (B1) acid unsaturated compound and the multipolymer with unsaturated compound (hereinafter referred to as " oxetanes unsaturated compound ") of oxetanes skeleton; (B2) acid unsaturated compound and multipolymer with unsaturated compound (hereinafter referred to as " tetrahydrofuran unsaturated compound ") of tetrahydrofuran skeleton; And (B3) multipolymer of acid unsaturated compound and oxetanes unsaturated compound and tetrahydrofuran unsaturated compound.
Multipolymer (B1), (B2) and (B3) in, for example as follows in the acid unsaturated compound as unsaturated carboxylic acid or its acid anhydrides:
Unsaturated monocarboxylic acids such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid;
Unsaturated dicarboxylic acid or its acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Ternary or above unsaturated polybasic carboxylic acid or its acid anhydrides;
List [(methyl) acryloxyalkyl] ester of 2 yuan of mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] esters etc. or above polybasic carboxylic acid;
ω-two ends such as carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.
In these unsaturated carboxylic acids or its acid anhydrides, mono succinate (2-acryloxy ethyl) ester and phthalic acid list (2-acryloxy ethyl) ester are sold with the trade name of ラ イ ト エ ス テ Le HOA-MS and ラ イ ト エ ス テ Le HOA-MPE (above is common prosperity society chemistry (strain) preparation) respectively.
In addition, for example have as unsaturated phenolic compounds in the acid unsaturated compound: adjacent vinylphenol, a vinylphenol, to vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, neighbour-isopropenyl phenol ,-isopropenyl phenol, right-unsaturated phenol such as isopropenyl phenol;
2-vinyl-1-naphthols, 3-vinyl-1-naphthols, 1-vinyl-beta naphthal, 3-vinyl-beta naphthal, 2-isopropenyl-1-naphthols, 3-isopropenyl-unsaturated naphthols such as 1-naphthols etc.
Among the present invention, preferred (methyl) acrylic acid of acid unsaturated compound, to vinylphenol etc., preferred especially (methyl) acrylic acid.
(B1), in (B3) multipolymer, oxetanes unsaturated compound preference is as shown in the formula compound (hereinafter referred to as " oxetanes unsaturated compound (2) ") shown in compound shown in (1) (hereinafter referred to as " oxetanes unsaturated compound (1) "), the following formula (2) etc.
Figure A20071010644600091
[in the formula (1), R represents the alkyl of hydrogen atom or carbon atom 1-4, R 1The alkyl of expression hydrogen atom or carbon number 1-4, R 2, R 3, R 4And R 5Separate, expression hydrogen atom, fluorine atom, the alkyl of carbon number 1-4, the fluoroalkyl of carbon number 1-4 or the aryl of carbon number 6-20, n represents the integer of 0-6].
Figure A20071010644600092
[in the formula (2), R, R 1, R 2, R 3, R 4, R 5With n respectively with following formula (1) in R, R 1, R 2, R 3, R 4, R 5With the n identical meanings].
In formula (1) and the formula (2), R, R 1, R 2, R 3, R 4And R 5The alkyl of carbon number 1-4 methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group etc. are for example arranged.
R 2, R 3, R 4And R 5The fluoroalkyl of carbon number 1-4 methyl fluoride, difluoromethyl, trifluoromethyl, 1-fluoro ethyl, 2-fluoro ethyl, 1 are for example arranged, 1-two fluoro ethyls, 2,2,2-trifluoroethyl, pentafluoroethyl group, seven fluorine n-pro-pyls, seven fluorine isopropyls, nine fluorine normal-butyls, nine fluorine isobutyls, nine fluorine sec-butyls, the nine fluorine tert-butyl groups etc.
R 2, R 3, R 4And R 5The aryl of carbon number 6-20 phenyl, o-tolyl, a tolyl, p-methylphenyl etc. are for example arranged.
Oxetanes unsaturated compound (1) for example has:
The 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-methyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-3-methyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-ethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-pentafluoroethyl group oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2,2-difluoro oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2,2,4-trifluoro oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2,2,4,4-tetrafluoro oxetanes;
3-[2-(methyl) acryloyl group oxygen base ethyl] oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2-methyl oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-3-methyl oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2-ethyl oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-3-ethyl oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2-trifluoromethyl oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2-pentafluoroethyl group oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2-phenyl oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2; 2-difluoro oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2; 2; 4-trifluoro oxetanes; 3-[2-(methyl) acryloyl group oxygen base ethyl]-2; 2; 4,4-tetrafluoro oxetanes etc. (methyl) acrylate etc.
Oxetanes unsaturated compound (2) for example has:
The 2-[(methyl) acryloyl group oxygen ylmethyl] oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-2-methyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3-methyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-4-methyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-2-ethyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3-ethyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-4-ethyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-2-trifluoromethyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3-trifluoromethyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-4-trifluoromethyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-2-pentafluoroethyl group oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3-pentafluoroethyl group oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-4-pentafluoroethyl group oxetanes;
The 2-[(methyl) acryloyl group oxygen ylmethyl]-2-phenyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3-phenyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-4-phenyl oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-2,3-difluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-2,4-difluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3,3-difluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3,4-difluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-4,4-difluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3,3,4-trifluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3,4,4-trifluoro oxetanes, the 2-[(methyl) acryloyl group oxygen ylmethyl]-3,3,4,4-tetrafluoro oxetanes;
2-[2-(methyl) acryloyl group oxygen base ethyl] oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-2-methyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-3-methyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-4-methyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-2-ethyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-3-ethyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-4-ethyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-2-trifluoromethyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-3-trifluoromethyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-4-trifluoromethyl oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-2-pentafluoroethyl group oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-3-pentafluoroethyl group oxetanes, 2-[2-(methyl) acryloyl group oxygen base ethyl]-4-pentafluoroethyl group oxetanes;
2-[2-(methyl) acryloyl group oxygen base ethyl]-2-phenyl oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-3-phenyl oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-4-phenyl oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-2; 3-difluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-2; 4-difluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-3; 3-difluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-3; 4-difluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-4; 4-difluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-3; 3; 4-trifluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-3; 4; 4-trifluoro oxetanes; 2-[2-(methyl) acryloyl group oxygen base ethyl]-3; 3; 4,4-tetrafluoro oxetanes etc. (methyl) acrylate etc.
In these oxetanes unsaturated compounds (1) and the oxetanes unsaturated compound (2); preferred 3-[(methyl) acryloyl group oxygen ylmethyl] oxetanes; the 3-[(methyl) acryloyl group oxygen ylmethyl]-3-ethyl oxetanes; the 3-[(methyl) acryloyl group oxygen ylmethyl]-2-trifluoromethyl oxetanes; the 3-[(methyl) acryloyl group oxygen ylmethyl]-2-phenyl oxetanes; the 2-[(methyl) acryloyl group oxygen ylmethyl] oxetanes; the 2-[(methyl) acryloyl group oxygen ylmethyl]-4-trifluoromethyl oxetanes etc.; angle wide from the development surplus of gained radiation-ray sensitive composition and that the chemical reagent resistance gained dyed layer is high is considered, preferred especially 3-(methacryl oxygen ylmethyl) oxetanes; 3-(methacryl oxygen ylmethyl)-3-ethyl oxetanes; 3-(methacryl oxygen ylmethyl)-2-trifluoromethyl oxetanes; 3-(methacryl oxygen ylmethyl)-2-phenyl oxetanes; 2-(methacryl oxygen ylmethyl) oxetanes; 2-(methacryl oxygen ylmethyl)-4-trifluoromethyl oxetanes etc.
Among the present invention, outside oxetanes unsaturated compound deoxygenation heterocycle butane unsaturated compound (1) and the oxetanes unsaturated compound (2), for example can also use (3-oxetanes ylmethoxy)-to vinyl benzene, [2-(3-oxetanyl) ethoxy]-to vinyl benzene, (2-oxetanes ylmethoxy)-to vinyl benzene, [2-(2-oxetanyl) ethoxy]-to (oxetanyl alkyl) ether of vinylphenols such as vinyl benzene;
(oxetanyl alkyl) vinyl ethers such as (3-oxetanes ylmethyl) vinyl ether, [2-(3-oxetanyl) ethyl] vinyl ether, (2-oxetanes ylmethyl) vinyl ether, [2-(2-oxetanyl) ethyl] vinyl ether etc.
Above-mentioned oxetanes unsaturated compound can be separately or two kinds or above mixing is used.
(B2), in (B3) multipolymer, the tetrahydrofuran unsaturated compound for example has:
(methyl) acrylic acid tetrahydrofuran-2-base ester, (methyl) acrylic acid tetrahydrofuran-(methyl) acrylic acid tetrahydrofuran esters such as 3-base ester;
(methyl) acrylic acid esters that contain tetrahydrofurfuryl such as (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid 3-tetrahydro furfuryl ester, (methyl) acrylic acid 2-(tetrahydrofurfuryl oxygen base) ethyl ester, (methyl) acrylic acid 2-(3-tetrahydrofurfuryl oxygen base) ethyl ester;
The ester that contains tetrahydrofurfuryl of 2-(methyl) acryloxy propionic such as 2-(methyl) acryloxy propionic tetrahydro furfuryl ester, 2-(methyl) acryloxy propionic 3-tetrahydro furfuryl ester, 2-(methyl) acryloxy propionic 2-(tetrahydrofurfuryl oxygen base) ethyl ester, 2-(methyl) acryloxy propionic 2-(3-tetrahydrofurfuryl oxygen base) ethyl ester;
(tetrahydrofuran-2-yl) oxygen base-to vinyl benzene, (tetrahydrofurfuryl) oxygen base-to vinyl benzene, 2-(tetrahydrofurfuryl oxygen base) ethoxy-to vinyl benzene derivants such as vinyl benzenes;
Vinyl ether such as (tetrahydrofuran-2-yl) vinyl ether, (tetrahydrofurfuryl) vinyl ether, [2-(tetrahydrofurfuryl oxygen base) ethyl] vinyl ether etc.
Among the present invention, preferred (methyl) the acrylic acid ester that contains tetrahydrofurfuryl of tetrahydrofuran unsaturated compound, preferred especially (methyl) acrylic acid tetrahydro furfuryl ester, succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester.
Above-mentioned tetrahydrofuran unsaturated compound can be separately or two kinds or above mixing is used.
(B1), (B2) and (B3) multipolymer can according to circumstances further contain unsaturated compound (hereinafter referred to as " other unsaturated compound ") beyond acid unsaturated compound, oxetanes unsaturated compounds and the tetrahydrofuran unsaturated compounds as constituent.
Other unsaturated compound for example has:
Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to aromatic ethenyl compounds such as vinyl benzyl glycidyl ethers;
Indenes classes such as indenes, 1-methyl indenes;
Unsaturated acyl imines such as maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, clothing health acid imide, citraconimide;
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, (methyl) allyl acrylate, (methyl) acrylic acid benzyl ester, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid methoxyl diglycol ester, (methyl) acrylic acid methoxyl triethyleneglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid bicyclopentadiene ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, esters of unsaturated carboxylic acids such as glycerine list (methyl) acrylate;
Unsaturated carboxylic acid aminoalkyl esters such as (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid 2-, (methyl) acrylic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) acrylic acid 3-, (methyl) acrylic acid 3-dimethylamino propyl ester;
Unsaturated carboxylic acid ethylene oxidic ester classes such as (methyl) acrylic acid glycidyl esters;
Acrylonitrile compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene dinitrile;
Unsaturated amides such as (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Aliphatic conjugated diene such as 1,3-butadiene, isoprene, chlorbutadiene;
Has the macromonomer of list (methyl) acryloyl group etc. on the polymer molecule chain ends such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane.
Above-mentioned other unsaturated monomer can use separately or 2 kinds or above mixing are used.
Among the present invention, (B1) multipolymer is preferably and contains (b1) with at least a acid unsaturated compound of (methyl) acrylic acid as necessary composition; (b2) be selected from 3-(methacryl oxygen ylmethyl) oxetanes; 3-(methacryl oxygen ylmethyl)-3-ethyl oxetanes; 3-(methacryl oxygen ylmethyl)-2-trifluoromethyl oxetanes; 3-(methacryl oxygen ylmethyl)-2-phenyl oxetanes; at least a oxetanes unsaturated compound of 2-(methacryl oxygen ylmethyl) oxetanes and 2-(methacryl oxygen ylmethyl)-4-trifluoromethyl oxetanes; and (b4) that according to circumstances contain is selected from styrene; N-phenylmaleimide; (methyl) methyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) acrylic acid allyl ester; (methyl) acrylic acid benzyl ester; single (methyl) acrylic acid glyceride; the multipolymer of at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (hereinafter referred to as " multipolymer (BI) ").
More particularly, multipolymer (BI) for example has:
Multipolymer (BI-1): this multipolymer (BI-1) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl] the oxetanes unsaturated compound of oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BI-2): this multipolymer (BI-2) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 3-ethyl oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BI-3): this multipolymer (BI-3) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 2-trifluoromethyl oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BI-4): this multipolymer (BI-4) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 2-phenyl oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BI-5): this multipolymer (BI-5) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b2) contain the 2-[(methyl) acryloyl group oxygen ylmethyl] the oxetanes unsaturated compound of oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BI-6): this multipolymer (BI-6) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound; (b2) contain the 2-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 4-trifluoromethyl oxetanes; (b4) that according to circumstances contain is selected from styrene; N-phenylmaleimide; (methyl) methyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) allyl acrylate; (methyl) benzyl acrylate; single (methyl) acrylic acid glyceride; at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer etc.
In these multipolymers (BI), special preferred copolymer (BI-1), multipolymer (BI-2) etc.
(BI) in the multipolymer, the preferred 1-40 weight of the copolymerization ratio % of acid unsaturated compound, preferred especially 5-30 weight %; The preferred 1-60 weight of the copolymerization ratio % of oxetanes unsaturated compound, preferred especially 10-45 weight %; The preferred 0-70 weight of the copolymerization ratio % of other unsaturated compound, more preferably 1-70 weight %, especially preferably 1-50 weight %.
Among the present invention, copolymerization ratio by making each unsaturated compound in (BI) multipolymer is in above-mentioned scope, can obtain under high pigment levels sensitivity, solvent resistance, with the tack of substrate etc. and as dispersible pigment dispersion and solvent-laden fluid composition, the radiation-ray sensitive composition of excellent storage stability.
In addition, (B2) multipolymer is preferably and contains (b1) and contain (methyl) acrylic acid at least a acid unsaturated compound, (b3) be selected from least a tetrahydrofuran unsaturated compound of (methyl) acrylic acid tetrahydro furfuryl ester and succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester, and (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid allyl ester, (methyl) acrylic acid benzyl ester, single (methyl) acrylic acid glyceride, the multipolymer of at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (hereinafter referred to as " multipolymer (BII) ").
More particularly, multipolymer (BII) is for example preferred:
Contain (b1) and contain (methyl) acrylic acid at least a acid unsaturated compound, (b3) at least a tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, the multipolymer of at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (hereinafter referred to as " multipolymer (BII-1) ");
Contain (b1) and contain (methyl) acrylic acid at least a acid unsaturated compound, (b3) contain at least a tetrahydrofuran unsaturated compound of succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, the multipolymer of at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (hereinafter referred to as " multipolymer (BII-2) ") etc.
(B2) in the multipolymer, the preferred 1-40 weight of the copolymerization ratio % of acid unsaturated compound, preferred especially 5-30 weight %; The preferred 1-70 weight of the copolymerization ratio % of tetrahydrofuran unsaturated compound, preferred especially 5-50 weight %; The preferred 0-80 weight of the copolymerization ratio % of other unsaturated compound, more preferably 1-80 weight %, especially preferably 1-50 weight %.
Among the present invention, copolymerization ratio by making each unsaturated compound in (B2) multipolymer in above-mentioned scope, can obtain under high pigment levels sensitivity, solvent resistance, with the tack of substrate etc. and as dispersible pigment dispersion, contain the radiation-ray sensitive composition of excellent storage stability of the fluid composition of solvent.
Multipolymer (B3) is preferably and contains (b1) and comprise (methyl) acrylic acid at least a acid unsaturated compound; (b3) be selected from least a tetrahydrofuran unsaturated compound of (methyl) acrylic acid tetrahydro furfuryl ester and succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester; (b2) be selected from 3-(methacryl oxygen ylmethyl) oxetanes; 3-(methacryl oxygen ylmethyl)-3-ethyl oxetanes; 3-(methacryl oxygen ylmethyl)-2-trifluoromethyl oxetanes; 3-(methacryl oxygen ylmethyl)-2-phenyl oxetanes; at least a oxetanes unsaturated compound of 2-(methacryl oxygen ylmethyl) oxetanes and 2-(methacryl oxygen ylmethyl)-4-trifluoromethyl oxetanes; according to circumstances further contain (b4) and be selected from styrene; N-phenylmaleimide; (methyl) methyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) acrylic acid allyl ester; (methyl) acrylic acid benzyl ester; single (methyl) acrylic acid glyceride; the multipolymer of at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer (hereinafter referred to as " multipolymer (BIII) ").
More particularly, multipolymer (BIII) for example has:
Multipolymer (BIII-1): this multipolymer (BIII-1) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b3) the tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester, (b2) contain the oxetanes unsaturated compound of 3-((methyl) acryloyl group oxygen ylmethyl) oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BIII-2): this multipolymer (BIII-2) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b3) the tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 3-ethyl oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BIII-3): this multipolymer (BIII-3) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b3) the tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 2-trifluoromethyl oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BIII-4): this multipolymer (BIII-4) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b3) the tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester, (b2) contain the 3-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 2-phenyl oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BIII-5): this multipolymer (BIII-5) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound, (b3) the tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester, (b2) contain the 2-[(methyl) acryloyl group oxygen ylmethyl] the oxetanes unsaturated compound of oxetanes, (b4) that according to circumstances contain is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, single (methyl) acrylic acid glyceride, at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer;
Multipolymer (BIII-6): this multipolymer (BIII-6) contains (b1) and contains (methyl) acrylic acid acid unsaturated compound; (b3) the tetrahydrofuran unsaturated compound that contains (methyl) acrylic acid tetrahydro furfuryl ester; (b2) contain the 2-[(methyl) acryloyl group oxygen ylmethyl]-the oxetanes unsaturated compound of 4-trifluoromethyl oxetanes; (b4) that according to circumstances contain is selected from styrene; N-phenylmaleimide; (methyl) methyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) allyl acrylate; (methyl) benzyl acrylate; single (methyl) acrylic acid glyceride; at least a other unsaturated compound of polystyrene macromolecular monomer and polymethylmethacrylate macromonomer etc.
In these multipolymers (BIII), special preferred copolymer (BIII-1), multipolymer (BIII-2) etc.
In the multipolymer (BIII), the preferred 1-40 weight of the copolymerization ratio % of acid unsaturated compound, preferred especially 5-30 weight %; The preferred 1-70 weight of the copolymerization ratio % of tetrahydrofuran unsaturated compound, preferred especially 1-40 weight %; The preferred 1-60 weight of the copolymerization ratio % of oxetanes unsaturated compound, preferred especially 1-40 weight %; The preferred 0-70 weight of the copolymerization ratio % of other unsaturated compound, more preferably 1-60 weight %.
Among the present invention, the copolymerization ratio by making each unsaturated compound in the multipolymer (BIII) in above-mentioned scope, can obtain sensitivity, with the radiation-ray sensitive composition that is used to form dyed layer of excellences such as the tack of substrate, solvent resistance.
Among the present invention, the alkali soluble resin that can also make other with (B1), (B2) and (B3) multipolymer use.
Above-mentioned other alkali soluble resin is not particularly limited so long as to (A) colorant performance bonding agent effect and when forming dyed layer, the alkaline developer that uses in the development treatment step is had solubility get final product.The for example preferred alkali soluble resin (hereinafter referred to as " other carboxylic alkali soluble resin ") that uses with carboxyl.
Other carboxylic alkali soluble resin for example has: (B1), (B2) and (B3) exemplify in the multipolymer contain at least a of carboxyl unsaturated compound with (B1), at least a multipolymer of (B2) and other unsaturated compound of (B3) exemplifying in the multipolymer etc.
More specifically, preferably other alkali soluble resin that contains carboxyl for example has (i) to contain (methyl) acrylic acid carboxyl unsaturated compound and at least a multipolymer that (ii) is selected from styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) acrylic acid benzyl ester, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and polymethylmethacrylate macromonomer etc. of containing.
Among the present invention, multipolymer (B1), (B2) and (B3) and other alkali soluble resin by gel permeation chromatography (GPC, eluting solvent: the weight-average molecular weight through polystyrene conversion of Ce Dinging (hereinafter referred to as " Mw ") preferred separately 3 tetrahydrofuran), 000-300,000, more preferably 5,000-100,000.
(B1), (B2) and (B3) multipolymer and other alkali soluble resin by gel permeation chromatography (GPC, eluting solvent: the number-average molecular weight through polystyrene conversion of Ce Dinging (hereinafter referred to as " Mn ") preferred separately 3 tetrahydrofuran), 000-60,000, more preferably 5,000-25,000.
Among the present invention, by (B1) multipolymer and (B2) the copolymer in combination use that will have above-mentioned specific Mw and Mn, perhaps use (B3) multipolymer, perhaps, can obtain the good radiation-ray sensitive composition of development property by have other alkali soluble resin of above-mentioned specific Mw and Mn further combined with use.Can form pixel and black matrix thus with clear pattern edge, when developing simultaneously in that be difficult to produce residue, scum, film on the substrate of unexposed portion and on the light shield layer residual etc.
The Mw of multipolymer and the ratio (Mw/Mn) of Mn are preferred separately 1～5 with respect to (B1), (B2) with (B3) for other alkali soluble resin, and further preferred 1～4.
In the present invention, (B1), (B2) and (B3) multipolymer and other alkali soluble resin can be distinguished and use separately or 2 kinds or above mixing are used.
Among the present invention, with respect to 100 weight portions (A) colorant, preferred 10～1,000 weight portion of total consumption of alkali soluble resin, more preferably 20～500 weight portions.Total consumption of alkali soluble resin is lower than 10 weight portions, have then that alkali-developable for example reduces, on the substrate of unexposed portion or may produce scum on the light shield layer, film is residual, and if surpass 1,000 weight portion, then because colorant concentration reduces relatively, film is difficult to reach aim colour density sometimes.
(B1) multipolymer in the alkali soluble resin and (B2) the total usage ratio or (B3) the preferred 5-100 weight of the usage ratio % of multipolymer of multipolymer, more preferably 10-100 weight %, preferred especially 30-100 weight %.This total usage ratio is lower than 5 weight %, then may damage Expected Results of the present invention.
(B1) multipolymer is with respect to (B1) multipolymer and (B2) the preferred 1-90 weight of the usage ratio % of the total of multipolymer, preferred especially 5-80 weight %.(B1) usage ratio of multipolymer is lower than 1 weight %, and then solvent resistance reduces, and surpasses 90 weight %, and then storage stability reduces.
-(C) multi-functional monomer-
Multi-functional monomer of the present invention comprises the monomer with 2 or above polymerism unsaturated link.
Multi-functional monomer for example has:
Two (methyl) acrylate of alkylene glycol such as ethylene glycol, propylene glycol;
Two (methyl) acrylate of ployalkylene glycol such as polyglycol, polypropylene glycol;
Many (methyl) acrylate of 3 yuan of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritols etc. or above polyvalent alcohol and their dicarboxylic acid modifier;
Oligomeric (methyl) acrylate of polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, spirane resin etc.;
Two (methyl) acrylate of the both-end hydroxylation polymkeric substance such as polycaprolactone of the poly--1,3-butadiene of both-end hydroxyl, the polyisoprene of both-end hydroxyl, both-end hydroxyl,
Tricresyl phosphate [2-(methyl) acryloxy ethyl] ester etc.
In these multi-functional monomers, many (methyl) esters of acrylic acid of preferred 3 yuan or above polyvalent alcohol, their dicarboxylic acid modifier, specifically, preferred trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, compound shown in the following formula (3);
Figure A20071010644600221
Compound shown in the following formula (4) etc.,
Figure A20071010644600222
Wherein good and be difficult to produce considerations such as scum, film be residual, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate on the substrate of unexposed portion and on the light shield layer for the flatness on dyed layer intensity height, dyed layer surface.
These multi-functional monomers can use separately or 2 kinds or above mixing are used.
With respect to 100 weight portion alkali soluble resins, preferred 5～500 weight portions of the consumption of multi-functional monomer of the present invention, more preferably 20～300 weight portions.Multi-functional monomer consumption is lower than the words of 5 weight portions, the intensity of dyed layer, surface smoothing have the tendency of reduction, if and surpass 500 weight portions, for example have that alkali-developable reduces, perhaps producing residual etc. the tendency of scum, film on the substrate of unexposed portion or on the light shield layer easily.
Can also be used in combination simple function monomer with multi-functional monomer among the present invention with 1 polymerism unsaturated link.
Above-mentioned simple function monomer for example have with (B) alkali soluble resin in acid unsaturated compound, maleimide that N-replaces or other unsaturated compound in the same compound of the compound that exemplifies or N-(methyl) acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-'epsilon '-hexanolactam, also have commercially available commodity M-5600 (trade name, East Asia synthetic (strain) preparation) etc. in addition.
These simple function monomers can use separately or 2 kinds or above mixing are used.
With respect to the total of multi-functional monomer and simple function monomer, the usage ratio of simple function monomer is preferably 90 weight % or following, more preferably 50 weight % or following.If the usage ratio of simple function monomer surpasses 90 weight %, then the intensity of the dyed layer of gained, surface smoothing may be not enough.
With respect to 100 weight portion alkali soluble resins, the total consumption of multi-functional monomer of the present invention and simple function monomer is preferably the 5-500 weight portion, more preferably the 20-300 weight portion.This total consumption is lower than 5 weight portions, and then the intensity of dyed layer or surface smoothing have and reduce tendency, and surpass 500 weight portions, and then for example alkali-developable reduces, or generations such as scum, film be residual are easily arranged on the substrate of unexposed portion or on the light shield layer.
-(D) Photoepolymerizationinitiater initiater-
Photoepolymerizationinitiater initiater of the present invention is the compound that produces spike by the exposure of rays such as visible light, ultraviolet ray, far ultraviolet, electron ray, X ray, and wherein said spike can cause above-mentioned (C) multi-functional monomer and the polymerization of the simple function monomer of use according to circumstances.
Above-mentioned Photoepolymerizationinitiater initiater for example has acetophenone compound, united imidazole, triaizine compounds, benzoin compound, benzophenone cpd, α-dione compounds, multinuclear naphtoquinone compounds, xanthone compound, diazo-compounds, O-acyl group oxime compound,  salt compound, imido sulfonate compound etc.These compounds are the compositions that produce living radical or live acid or living radical and live acid by exposure.
Among the present invention, Photoepolymerizationinitiater initiater can separately or with two kinds or above mixing use, Photoepolymerizationinitiater initiater of the present invention be preferably selected from least a of acetophenone compound, united imidazole, triaizine compounds and O-acyl group oxime compound.
Among the present invention, with respect to the multi-functional monomer of 100 weight portions (C) or the multi-functional monomer of 100 weight portions (C) and simple function monomer (if you are using, as follows) total, the preferred 0.01-120 weight portion of the conventional amount used of Photoepolymerizationinitiater initiater, more preferably 1-100 weight portion.The consumption of Photoepolymerizationinitiater initiater is lower than 0.01 weight portion, and then deficiency is solidified in exposure, is difficult to obtain the color filter of dyed layer pattern alignment arrangements according to the rules, and the dyed layer that then forms above 120 weight portions comes off from substrate when developing easily.
Among the present invention in the preferred Photoepolymerizationinitiater initiater, the object lesson of acetophenone compound has: 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenyl second-1-ketone, 1,2-acetyl caproyl etc.
In these acetophenone compounds, preferred especially 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone, 1,2-acetyl caproyl etc.
Above-mentioned acetophenone compound can be separately or two kinds or above mixing is used.
Among the present invention, when using acetophenone compound as Photoepolymerizationinitiater initiater, its consumption with respect to the multi-functional monomer of 100 weight portions (C) or the multi-functional monomer of 100 weight portions (C) and simple function monomer (if you are using, as follows) the preferred 0.01-80 weight portion of total, more preferably 1-60 weight portion, further preferred 1-30 weight portion.The consumption of acetophenone compound is lower than 0.01 weight portion and then exposes and solidify not enoughly, is difficult to obtain the dyed layer pattern color filter of arranged in order according to the rules, surpasses the dyed layer that 80 weight portions then form and comes off from substrate easily when developing.
As the concrete example of above-mentioned united imidazole, can enumerate as 22 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In these united imidazoles, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., preferred especially 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
These united imidazoles are to the dissolubility excellence of solvent, can not produce not impurity such as dissolved matter, sediment, and sensitivity height, the exposure by little energy can fully be cured reaction, curing reaction can not take place in unexposed portion simultaneously, therefore filming after the exposure can be divided into the cured portion that is insoluble to developer solution clearly and developer solution is had the uncured portion of highly dissoluble, can form thus do not have lateral erosion, the dyed layer pattern high meticulous color filter of alignment arrangements according to the rules.
Above-mentioned united imidazole can be separately or two kinds or above mixing is used.
Among the present invention, when using united imidazole as Photoepolymerizationinitiater initiater, total with respect to the multi-functional monomer of 100 weight portions (C) or multi-functional monomer of 100 weight portions (C) and simple function monomer, the preferred 0.01-40 weight portion of its consumption, more preferably 1-30 weight portion, further preferred 1-20 weight portion.At this moment, the consumption of united imidazole be lower than 0.01 weight portion then expose solidify not enough, be difficult to obtain the dyed layer pattern color filter of series arrangement configuration according to the rules, surpass the dyed layer that forms when 40 weight portions then develop and come off or cause the film on dyed layer surface coarse easily from substrate easily.
Among the present invention, when using united imidazole, consider, preferably with following hydrogen donor and usefulness from the angle that can further improve sensitivity as Photoepolymerizationinitiater initiater.
At this so-called " hydrogen donor " is the compound that hydrogen atom can be provided the free radical that produces from united imidazole through exposure.
As hydrogen donor of the present invention, be preferably with undefined mercaptan compound, amines etc.
Above-mentioned mercaptan compound comprises that with phenyl ring or heterocycle be parent nucleus, has 1 or above, preferred 1～3, the compound of further preferred 1～2 sulfydryl that directly combines with this parent nucleus (below, be called " mercaptan hydrogen donor ").
Above-mentioned amines comprises with phenyl ring or heterocycle having 1 or above, preferred 1～3 as parent nucleus, more preferably the compound of 1～2 amino that directly combines with this parent nucleus (below, be called " amine hydrogen donor ").
In addition, these hydrogen donors can have sulfydryl and amino simultaneously.
Below, these hydrogen donors are carried out more specific description.
The mercaptan hydrogen donor can have 1 or above phenyl ring or heterocycle separately, can also have phenyl ring and heterocycle concurrently.The time also can form condensed ring when having 2 or above these rings.
In addition, when the mercaptan hydrogen donor had 2 or above sulfydryl, as long as residual at least 1 free sulfhydryl groups, remaining 1 or above sulfydryl can be replaced by alkyl, aralkyl or aryl.And, perhaps have the structural unit of 2 sulphur atoms with the form combination of disulfide as long as residual at least 1 free sulfhydryl groups can have the structural unit of 2 sulphur atoms by divalent organic group combinations such as alkylene bases.
And the position of mercaptan hydrogen donor beyond sulfydryl can be by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl, itrile groups.
As the concrete example of this mercaptan hydrogen donor, can enumerate as 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
In these mercaptan hydrogen donors, preferred 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol are preferably 2-mercaptobenzothiazole especially.
The amine hydrogen donor can have 1 or above phenyl ring or heterocycle separately, can also have phenyl ring and heterocycle concurrently.The time also can form condensed ring when having 2 or above these rings.
In addition, 1 of amine hydrogen donor or above amino can be replaced by alkyl or substituted alkyl, and amino part in addition also can be by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl, itrile groups.
Concrete example as this amine hydrogen donor, can enumerate as 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylaminobenzoic acid, 4-dimethylamino benzonitrile etc.
In these amine hydrogen donors, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, preferred especially 4,4 '-two (diethylamino) benzophenone.
In addition, under the situation that adopts united imidazole Photoepolymerizationinitiater initiater in addition, the amine hydrogen donor also has the effect of sensitizer.
Among the present invention, hydrogen donor can use separately also and can use mixing more than 2 kinds, from the dyed layer that forms when developing, be not easy from substrate come off, the intensity of dyed layer and sensitive aspect consider, preferably a kind or above mercaptan hydrogen donor and a kind or above amine hydrogen donor are used in combination.
Concrete example as the preferred compositions of mercaptan hydrogen donor and amine hydrogen donor, 2-mercaptobenzothiazole/4 are arranged, 4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-sulfydryl benzoxazol/4,4 '-two (dimethylamino) benzophenone, 2-sulfydryl benzoxazol/4,4 '-two (diethylamino) benzophenone etc., further preferred combination has 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-sulfydryl benzoxazol/4,4 '-two (diethylamino) benzophenone, particularly preferred combination has 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone.
In the combination of mercaptan hydrogen donor and amine hydrogen donor, preferred 1: 1～1: 4 of the weight ratio of mercaptan hydrogen donor and amine hydrogen donor is more preferably 1: 1～1: 3.
Among the present invention, when hydrogen donor is used in combination with united imidazole, total with respect to the multi-functional monomer of 100 weight portions (C) or multi-functional monomer of 100 weight portions (C) and simple function monomer, the preferred 0.01-40 weight portion of its consumption, further preferred 1-30 weight portion, preferred especially 1-20 weight portion.The consumption of hydrogen donor is lower than the then improved effect reduction of sensitivity of 0.01 weight portion, and the dyed layer that then forms above 40 weight portions comes off from substrate when developing easily.
Concrete example as above-mentioned triaizine compounds, can enumerate as 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4,6-two (trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(furans-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-ethoxybenzene vinyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-n-butoxy phenyl)-4,6-two (trichloromethyl)-s-triazine etc. has the triaizine compounds of halogenated methyl.
In these triaizine compounds, preferred especially 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine.
Above-mentioned triaizine compounds can be separately or two kinds or above mixing is used.
Among the present invention, when using triaizine compounds as Photoepolymerizationinitiater initiater, its consumption is with respect to the total of the multi-functional monomer of 100 weight portions (C) or multi-functional monomer of 100 weight portions (C) and simple function monomer, preferred 0.01-40 weight portion, further preferred 1-30 weight portion, preferred especially 1-20 weight portion.Then exposing when the consumption of triaizine compounds is lower than 0.01 weight portion, it is not enough to solidify, and is difficult to obtain the dyed layer pattern color filter of sequence configuration according to the rules, and the dyed layer that then forms above 40 weight portions comes off from substrate when developing easily.
The object lesson of above-mentioned O-acyl group oxime compound has: 1-[4-(thiophenyl) phenyl]-heptan-1; 2-diketone 2-(O-benzoyl oxime); 1-[4-(thiophenyl) phenyl]-Xin-1; 2-diketone 2-(O-benzoyl oxime); 1-[4-(benzoyl) phenyl]-Xin-1,2-diketone 2-(O-benzoyl oxime); 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime); 1-[9-ethyl-6-(3-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime); 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime) etc.
In these O-acyl group oxime compounds, preferred especially 1-[4-(thiophenyl) phenyl]-heptan-1,2-diketone 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime) etc.
Above-mentioned O-acyl group oxime compound can be separately or two kinds or above mixing is used.
Among the present invention; when using O-acyl group oxime compound as Photoepolymerizationinitiater initiater; total with respect to the multi-functional monomer of 100 weight portions (C) or multi-functional monomer of 100 weight portions (C) and simple function monomer; the preferred 0.01-40 weight portion of its consumption; further preferred 1-30 weight portion, preferred especially 1-20 weight portion.At this moment, the consumption of O-acyl group oxime compound is lower than 0.01 weight portion and then exposes and solidify not enoughly, is difficult to obtain the dyed layer pattern color filter of sequence configuration according to the rules, surpasses the dyed layer that 40 weight portions then form and comes off from substrate easily when developing.
Above-mentioned  salt compound for example has diaryl iodine  salt, triarylsulfonium salt, diaryl microcosmic salt etc.
The object lesson of above-mentioned diaryl iodine  salt has: tetrafluoro boric acid diphenyl iodine , hexafluoro phosphonic acids diphenyl iodine , hexafluoroarsenate diphenyl iodine , trifluoromethanesulfonic acid diphenyl iodine , trifluoroacetic acid diphenyl iodine , p-toluenesulfonic acid diphenyl iodine , tetrafluoro boric acid 4-methoxyphenyl phenyl-iodide , hexafluoro phosphonic acids 4-methoxyphenyl phenyl-iodide , hexafluoroarsenate 4-methoxyphenyl phenyl-iodide , trifluoromethanesulfonic acid 4-methoxyphenyl phenyl-iodide , trifluoroacetic acid 4-methoxyphenyl phenyl-iodide , p-toluenesulfonic acid 4-methoxyphenyl phenyl-iodide , two (4-tert-butyl-phenyl) the iodine  of tetrafluoro boric acid, two (4-tert-butyl-phenyl) the iodine  of hexafluoroarsenate, two (4-tert-butyl-phenyl) the iodine  of trifluoromethanesulfonic acid, two (4-tert-butyl-phenyl) the iodine  of trifluoroacetic acid, two (4-tert-butyl-phenyl) iodine  of p-toluenesulfonic acid etc.
The object lesson of above-mentioned triarylsulfonium salt has: the tetrafluoro boric acid triphenylsulfonium, hexafluoro phosphonic acids triphenylsulfonium, the hexafluoroarsenate triphenylsulfonium, the trifluoromethanesulfonic acid triphenylsulfonium, the trifluoroacetic acid triphenylsulfonium, the p-toluenesulfonic acid triphenylsulfonium, tetrafluoro boric acid 4-methoxyphenyl diphenyl sulfonium, hexafluoro phosphonic acids 4-methoxyphenyl diphenyl sulfonium, hexafluoroarsenate 4-methoxyphenyl diphenyl sulfonium, trifluoromethanesulfonic acid 4-methoxyphenyl diphenyl sulfonium, trifluoroacetic acid 4-methoxyphenyl diphenyl sulfonium, p-toluenesulfonic acid 4-methoxyphenyl diphenyl sulfonium, tetrafluoro boric acid 4-phenyl sulfur phenenyl diphenyl sulfonium, hexafluoro phosphonic acids 4-phenyl sulfur phenenyl diphenyl sulfonium, hexafluoroarsenate 4-phenyl sulfur phenenyl diphenyl sulfonium, trifluoromethanesulfonic acid 4-phenyl sulfur phenenyl diphenyl sulfonium, trifluoroacetic acid 4-phenyl sulfur phenenyl diphenyl sulfonium, p-toluenesulfonic acid 4-phenyl sulfur phenenyl diphenyl sulfonium etc.
The object lesson of above-mentioned diaryl  salt has: hexafluoro phosphonic acids (1-6-η-cumene) (η-cyclopentadienyl group) iron etc.
In the above-mentioned  salt compound, preferred especially hexafluoro phosphonic acids diphenyl iodine , trifluoromethanesulfonic acid triphenylsulfonium etc.
Above-mentioned  salt compound can be separately or two kinds or above mixing is used.
Among the present invention, when using the  salt compound as Photoepolymerizationinitiater initiater, total with respect to the multi-functional monomer of 100 weight portions (C) and multi-functional monomer of 100 weight portions (C) and simple function monomer, the preferred 0.01-40 weight portion of its consumption, further preferred 1-30 weight portion, preferred especially 1-20 weight portion.The consumption of  salt compound is lower than 0.01 weight portion and then exposes and solidify not enoughly, is difficult to obtain the dyed layer pattern color filter of sequence configuration according to the rules, surpasses the dyed layer that 40 weight portions then form and comes off from substrate easily when developing.
-adjuvant-
The radiation-ray sensitive composition that is used to form dyed layer of the present invention can contain various adjuvants as required.
Above-mentioned adjuvant for example has organic acid or organic amino compounds (except the above-mentioned hydrogen donor), hardening agent, auxiliary curing agent etc.
Above-mentioned organic acid and organic amino compounds are to show further to improve radiation-ray sensitive composition composition of the residual effect of dissolved matter etc. not to the dissolubility of alkaline developer and after further suppressing to develop.
Have the aliphatic carboxylic acid of or above carboxyl in the preferred molecule of above-mentioned organic acid or contain the carboxylic acid of phenyl.
Above-mentioned aliphatic carboxylic acid for example has:
Formic acid, acetate, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, diethacetic acid, enanthic acid, monocarboxylic acid such as sad;
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brazilic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane cyclohexanedimethanodibasic, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid etc.
The above-mentioned phenyl carboxylic acid that contains for example has the direct compound that combines with phenyl of carboxyl, the carboxylic acid that carboxyl combines with phenyl via carbochain etc.
Containing the phenyl carboxylic acid for example has:
Benzoic acid, methyl benzoic acid, cumic acid, 2, one dollar aromatic carboxylic acids such as 3-mesitylenic acid, the acid of  woods;
Aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA);
Trimellitic acid, trimesic acid, partially ternary such as benzene tetracarboxylic acid, Pyromellitic Acid or above aromatic polycarboxylic acid or
Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, the acid of シ Application Na ミ リ デ Application, coumaric acid, the acid of Umbrella shape etc.
In these organic acids, from alkali dissolution, to the dissolubility of solvent described later, prevent on the substrate of unexposed portion or light shield layer forms scum or the residual equal angles of film is considered, aliphatic carboxylic acid preferred aliphatic series dicarboxylic acid, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.In addition, contain the preferred aromatic dicarboxylic acid of phenyl carboxylic acid, preferred especially phthalic acid.
Above-mentioned organic acid can be separately or two kinds or above mixing is used.
All with respect to the radiation-ray sensitive composition solid content, the preferred 15 weight % or following of organic acid consumption, more preferably 10 weight % or following.The organic acid use amount surpasses 15 weight %, and the tack of then formed dyed layer and substrate has the tendency of reduction.
Have the aliphatic amine of or above amino in the preferred molecule of above-mentioned organic amino compounds or contain phenyl amine.
Above-mentioned aliphatic amine for example has:
One (ring) alkyl amines such as n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, dodecyl amine, cyclohexylamine, 2-methyl cyclohexylamine, 3-methyl cyclohexylamine, 4-methyl cyclohexylamine, 2-ethyl cyclohexylamine, 3-ethyl cyclohexylamine, 4-ethyl cyclohexylamine;
Two (ring) alkyl amines such as Methylethyl amine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine, two tert-butylamines, two n-amylamines, two n-hexylamines, methyl cyclohexylamine, ethyl cyclohexylamine, dicyclohexyl amine;
Three (ring) alkyl amines such as dimethyl amine, methyl-diethyl-amine, triethylamine, dimethyl n propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, three n-hexylamines, dimethyl cyclohexyl amine, diethyl cyclohexylamine, methyl bicyclic hexylamine, ethyl dicyclohexyl amine, tricyclohexyltin amine;
The 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, 4-amino-one (ring) alkanolamines such as 1-cyclohexanol;
Two (ring) alkanolamines such as diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, two n-hexyl alcohol amine, two (4-cyclohexanol) amine;
Three (ring) alkanolamines such as triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, three n-hexyl alcohol amine, three (4-cyclohexanol) amine;
3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol, 4-amino-1,3 butylene glycol, 4-amino-1,2-cyclohexane diol, 4-amino-1,3-cyclohexane diol, 3-dimethylamino-1,2-propylene glycol, 3-diethylamino-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylamino-1, amino (ring) alkane glycol such as ammediol;
1-Aminocyclopentane methyl alcohol, 4-Aminocyclopentane methyl alcohol, 1-aminocyclohexane methyl alcohol, 4-aminocyclohexane methyl alcohol, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol etc. contain amino cycloalkanes methyl alcohol;
Amino carboxylic acids such as Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 1-amino-cyclopropane formic acid, 1-aminocyclohexane formic acid, 4-aminocyclohexane formic acid etc.
The above-mentioned phenyl amine that contains for example has: the compound that the amino compound that directly combines with phenyl, amino combine with phenyl via carbochain etc.
Containing phenyl amine for example has:
Aniline, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-pro-pyl aniline, 4-isopropyl aniline, 4-n-butyl aniline, 4-tert-butyl group aniline, 1-naphthylamine, 2-naphthylamine, N, accelerine, N, N-diethylaniline, 4-methyl-N, aromatic amines such as accelerine;
Aminobenzyl alcohol such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylamino benzyl alcohol, 4-diethylamino benzyl alcohol;
Amino phenol such as 2-amino-phenol, 3-amino-phenol, 4-amino-phenol, 4-dimethylamino phenol, 4-diethylamino phenol etc.
In these organic amino compounds, from to the dissolubility of solvent described later, prevent on the substrate of unexposed portion or angle that light shield layer produces scum or residual film etc. is considered, aliphatic amine preferred one (ring) alkanolamine, amino (ring) alkane glycol, preferred especially 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol etc.Contain the preferred aminophenols of phenyl amine, preferred especially 2-amino-phenol, 3-amino-phenol, 4-amino-phenol etc.
Above-mentioned organic amino compounds can be separately or two kinds or above mixing is used.
All with respect to the radiation-ray sensitive composition solid content, the preferred 15 weight % or following of the consumption of organic amino compounds, more preferably 10 weight % or following.The consumption of organic amino compounds surpasses 15 weight %, and the tack of then formed dyed layer and substrate has the tendency of reduction.
Above-mentioned hardening agent be with (B1), (B3) multipolymer in carboxyl and/or oxetanes ring or (B2) carboxyl reaction in the multipolymer, the composition that these multipolymers are solidified.
Above-mentioned hardening agent for example has epoxy compound, oxetane compound etc.
The preferred multi-functional epoxy compound of above-mentioned epoxy compound, its object lesson has aromatic species epoxy resin such as bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, A Hydrogenated Bisphenol A F epoxy resin, linear phenolic resin varnish type epoxy resin; Alicyclic based epoxy resin, hetero ring type epoxy resin, glycidyl esters resin, glycidyl amine resins, other epoxy resin of epoxidation wet goods; In addition the brominated derivative of above-mentioned epoxy resin also has the epoxide, (being total to) polymkeric substance that contains the unsaturated compound of glycidyl, triglycidyl group isocyanuric acid ester etc. of (being total to) polymkeric substance of epoxide, the isoprene of (being total to) polymkeric substance of butadiene.
Above-mentioned epoxy compound preferably contains the unsaturated compound of epoxy radicals, its object lesson has (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid 6,7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether etc.
The preferred multifunctional oxetane compound of above-mentioned oxetane compound, its object lesson has: carbonic acid dioxygen heterocycle butane group ester, hexane diacid dioxygen heterocycle butane group ester, terephthalic acid (TPA) dioxygen heterocycle butane group ester, P-xylene dioctyl phthalate dioxygen heterocycle butane group ester, 1, low molecular compounds such as 4-cyclohexane cyclohexanedimethanodibasic dioxygen heterocycle butane group ester, or the oxetanes etherate of phenol molded lines novolac resin, have (being total to) polymkeric substance macromolecular compounds such as (except multipolymer (B1), (B3)) of the unsaturated compound of oxetanes skeleton.
Oxetane compound preferably has the compound of oxetanes ring structure and unsaturated double-bond, and its object lesson has above-mentioned oxetanes unsaturated compound.
These hardening agent can be separately or two kinds or above mixing are used.
Solid content with respect to radiation-ray sensitive composition is all, the preferred 30 weight % or following of the consumption of hardening agent, more preferably 20 weight % or following.The consumption of hardening agent surpasses 30 weight %, and then the storage stability of gained radiation-ray sensitive composition reduces.
Above-mentioned auxiliary curing agent is the composition by the curing reaction that makes epoxy radicals that above-mentioned hardening agent has and/or this hardening agent of oxetanes ring open loop the promotion.
Described auxiliary curing agent for example has polybasic carboxylic acid, polybasic acid anhydride, amino-compound, thermic acid-producing agent etc.
The object lesson of above-mentioned polybasic carboxylic acid have with above-mentioned organic acid in have the identical example of compound of two or more carboxyls, the object lesson of above-mentioned amino-compound has the example identical with above-mentioned organic amino compounds.
The object lesson of above-mentioned polybasic acid anhydride has: phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, 3,3 ', 4, aromatic polycarboxylic acid acid anhydrides such as 4 '-benzophenone tetracarboxylic acid dianhydride; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, 1,2,3, aliphatic multi-anhydrides such as 4-ethylene-dimalonic acid dianhydride; Hexahydrophthalic anhydride, 3,4-dimethyl tetrahydro phthalic anhydride, 1,2,4-cyclopentane front three acid anhydrides, 1,2,4-cyclohexane front three acid anhydrides, cyclopentane tetracarboxylic acid dianhydride, 1,2,4, alicyclic polybasic acid anhydrides such as 5-cyclohexane tetracarboxylic acid dianhydride, Ha イ ミ ッ Network acid anhydrides, Na ジ Application acid anhydrides; Two trimellitic anhydride glycol esters, three (trimellitic anhydride) glyceride etc. contain the ester group carboxylic acid anhydrides, in addition also have with the epoxy curing agent of ア デ カ Ha one De Na one EH-700 (rising sun electrochemical industry (strain) preparation), リ カ シ Star De HH (new Japanese physics and chemistry (strain) preparation), the sale of MH-700 trade names such as (new Japanese physics and chemistry (strain) preparations) etc.
Above-mentioned thermic acid-producing agent for example has sulfonium salt (in above-mentioned (D) Photoepolymerizationinitiater initiater cited triarylsulfonium salt except), benzothiazole  salt, ammonium salt,  salt, sulfonate compound, sulfimine compound, diazomethane compound etc., wherein preferred sulfonium salt, benzothiazole  salt, sulfonate compound, sulfimine compound, diazomethane compound etc.
The object lesson of above-mentioned sulfonium salt has:
Hexafluoro-antimonic acid 4-acetylphenyl dimethyl sulfonium, hexafluoroarsenate 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid dimethyl-4-(benzyloxycarbonyloxy base) phenyl sulfonium, hexafluoro-antimonic acid dimethyl-4-(benzoyl oxygen base) phenyl sulfonium, hexafluoroarsenate dimethyl-4-(benzoyl oxygen base) phenyl sulfonium, hexafluoro-antimonic acid dimethyl-alkyl sulfonium salts such as 3-chloro-4-acetoxyl group phenyl sulfonium;
Hexafluoro-antimonic acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl methyl sulfonium, hexafluoro-antimonic acid benzyl-4-methoxybenzene ylmethyl sulfonium, hexafluoro-antimonic acid benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium, hexafluoroarsenate benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid 4-methoxy-benzyl-benzyl sulfonium salts such as 4-hydroxy phenyl methyl sulfonium;
Hexafluoro-antimonic acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluorophosphoric acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl dibenzyl sulfonium, hexafluoro-antimonic acid dibenzyl-4-methoxyphenyl sulfonium, hexafluoroarsenate dibenzyl-3-chloro-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium, hexafluorophosphoric acid benzyl-4-methoxy-benzyl-dibenzyl sulfonium salts such as 4-hydroxy phenyl sulfonium;
Hexafluoro-antimonic acid p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid to nitrobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid o-chlorobenzyl-substituted benzyl sulfonium salts such as 3-chloro-4-hydroxy phenyl methyl sulfonium etc.
The object lesson of above-mentioned benzothiazole  salt has: hexafluoro-antimonic acid 3-benzyl benzothiazole , hexafluorophosphoric acid 3-benzyl benzothiazole , tetrafluoro boric acid 3-benzyl benzothiazole , hexafluoro-antimonic acid 3-(to methoxy-benzyl) benzothiazole , hexafluoro-antimonic acid 3-benzyl-benzyl benzothiazole  salt such as 2-methyl mercapto benzo thiazole , hexafluoro-antimonic acid 3-benzyl-5-chloro benzothiazole  etc.
The object lesson of above-mentioned sulfonate compound has: benzoin p-toluenesulfonic esters, alpha-hydroxymethyl benzoin p-toluenesulfonic esters, the positive hot sulphonic acid ester of alpha-hydroxymethyl benzoin, pyrogallol three (triflate), burnt Chinese parasol tree phenol three (the positive fourth sulphonic acid ester of nine fluorine), burnt Chinese parasol tree phenol three (methanesulfonates), nitrobenzyl-9,10-diethoxy anthracene-2-sulphonic acid ester etc.
The object lesson of above-mentioned sulfimine compound has: N-(trifluoro-methanesulfonyl oxy) succinimide, N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-(10-camphor sulfonyloxy) succinimide, N-(10-camphor sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-[(5-methyl-5-carboxyl methane dicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide etc.
The object lesson of above-mentioned diazomethane compound has: two (cyclohexane sulfonyl) diazomethane, two (tert-butyl group sulfonyl) diazomethane, two (1,4-dioxo spiro [4.5]-decane-7-sulfonyl) diazomethane etc.
In these thermic acid-producing agents, preferred especially hexafluoroarsenate 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl methyl sulfonium, hexafluoro-antimonic acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl sulfonium, hexafluoro-antimonic acid 3-benzyl benzothiazole , N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide etc.
Above-mentioned auxiliary curing agent can be separately or two kinds or above mixing is used.
Solid content with respect to radiation-ray sensitive composition is all, the preferred 15 weight % or following of the consumption of auxiliary curing agent, more preferably 10 weight % or following.The consumption of auxiliary curing agent surpasses 15 weight %, and then the storage stability of gained radiation-ray sensitive composition reduces, or the dyed layer that forms comes off from substrate when developing easily.
And above-mentioned adjuvant in addition for example has:
The dispersing aid of blue pigment derivants such as copper phthalocyanine derivative thing or yellow uitramarine derivant etc.;
Filling agent such as glass, aluminium oxide;
Polyvinyl alcohol (PVA), polyglycol one alkyl ether, poly-macromolecular compounds such as (fluoroalkyl acrylate);
Surfactants such as nonionic system, kation system, negative ion system;
Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, adhesion promoters such as 3-sulfydryl propyl trimethoxy silicane;
2, antioxidants such as 2 '-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol;
Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorinated benzotriazole, alkoxy benzophenone;
Anticoalescents such as sodium polyacrylate;
1,1 '-azo two (cyclohexane-1-nitrile), 2-phenylazo-4-methoxyl-2, thermal free radical initiators such as 4-methyl pentane nitrile etc.
Solvent
Radiation-ray sensitive composition of the present invention as necessary composition, contains above-mentioned additive component with above-mentioned (A)-(D) composition as required, cooperates solvent usually, makes fluid composition.
Above-mentioned solvent be so long as can disperse or dissolve (A)-(D) composition and the additive component that constitutes radiation-ray sensitive composition, and not with these compositions reactions, the volatility with appropriateness get final product, can suitably select use.
Above-mentioned solvent for example has:
The glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary n-propyl ether, the diglycol monotertiary n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, the tripropylene glycol monomethyl ether, (many) alkylene glycols monoalky lethers such as tripropylene glycol list ethylether;
(many) alkylene glycols monoalky lether acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters;
Other ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetate 3-methyl-3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other esters such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, dimethylbenzene;
N, acid amides such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or lactams etc.
In these solvents, from dissolubility, pigment-dispersing, the coating equal angles is considered, preferred propylene glycol monomethyl ether, the ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, propionic acid 3-methyl-3-methoxyl butyl ester, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.
Above-mentioned solvent can use separately or 2 kinds or above mixing are used.
Can also be used in combination high boiling solvents such as benzylisoeugenol, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, acetate benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, glycol monomethyl phenyl ether acetic acid esters with above-mentioned solvent.
These high boiling solvents can use separately or 2 kinds or above mixing are used.
The use amount of solvent is not particularly limited, consider from viewpoints such as the coating of the radiation-ray sensitive composition that obtains, stability, preferably make the total concentration of each composition outside the solvent of removing said composition reach 5～50 weight %, especially preferably reach the amount of 10～40 weight %.
Color filter
Color filter of the present invention possesses the dyed layer that uses radiation-ray sensitive composition of the present invention to form.
Below describe for the method for the dyed layer that forms color filter of the present invention.
At first, as required, on the surface of substrate, form light shield layer, in order to distinguish the part that forms pixel, coating for example is dispersed with the fluid composition of the radiation-ray sensitive composition of red pigment on this substrate, carries out preliminary drying then, evaporation removes and desolvates, and formation is filmed.
Then, via mask to this exposure of filming after, use alkaline developer to develop, the unexposed portion of filming is removed in dissolving, forms the pel array of red pattern of pixels sequence configuration according to the rules then by the back baking.
Use the fluid composition of each radiation-ray sensitive composition that is dispersed with green or blue pigment then, with above-mentioned coating, preliminary drying, exposure, development and the back baking of similarly carrying out each fluid composition, on same substrate, form green pixel array and blue pixel array successively, obtain the color filter of pixel array configuration on substrate of redness, green and blue three-primary colours.Among the present invention, the order that forms each color pixel is not limited to above-mentioned.
In addition, black matrix for example can use the fluid composition of the radiation-ray sensitive composition that is dispersed with black pigment, similarly forms with the formation of above-mentioned pixel.
The substrate that uses during as formation pixel and/or black matrix for example has glass, silicon, polycarbonate, polyester, aromatic poly amide, polyamidoimide, polyimide etc.
And, can also implement suitable pre-treatment to these substrates according to expectation, for example utilize the chemical reagent processing, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc. etc.
When coating the fluid composition of radiation-ray sensitive composition on the substrate, for example can adopt spraying process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, rod to be coated with suitable coating processes such as method, gunite.Preferred especially spin-coating method, slit die rubbing method.The thickness of coating calculates according to dried thickness, preferred 0.1-10 μ m, more preferably 0.2-8.0 μ m, especially preferably 0.2-6.0 μ m.
The radioactive ray that use during as formation pixel and/or black matrix can be enumerated visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc.Optimal wavelength is at the radioactive ray of 190～450nm scope.
The exposure of radioactive ray is preferably 10～10,000J/m 2
As above-mentioned alkaline developer, for example preferred sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene etc.
In above-mentioned alkaline-based developer, can also add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in right amount.Alkali is preferably washed after developing.
As developing method, can adopt spray development method, spray development method, immersion development method, stirring (liquid is contained り) development method etc.Development conditions was preferably carried out 5～300 seconds at normal temperatures.
The color filter of the present invention that obtains like this is for example extremely useful for transmission-type or reflection-type color liquid crystal display element, colour pick-up tube element, color sensor etc.
Color liquid crystal display device
Color liquid crystal display device of the present invention possesses color filter of the present invention.
An embodiment of color liquid crystal display device of the present invention is to use radiation-ray sensitive composition of the present invention, as mentioned above, on the thin film transistor base plate array, form pixel and/or black matrix, thereby can prepare color liquid crystal display device with excellent especially characteristic.
Radiation-ray sensitive composition of the present invention contains above-mentioned (A)-(D) composition as must composition, below specifically provides particularly preferred composition, as following (a)-(j).
(a) (B1) multipolymer contains multipolymer (BI), and (B2) multipolymer contains the radiation-ray sensitive composition that is used to form dyed layer of multipolymer (BII).
(b) radiation-ray sensitive composition that is used to form dyed layer of above-mentioned (a), wherein, multipolymer (BI) contains and is selected from least a of multipolymer (BI-1)-(BI-6), and multipolymer (BII) contains and is selected from least a of multipolymer (BII-1) and multipolymer (BII-2).
(c) above-mentioned (a) or the radiation-ray sensitive composition that is used to form dyed layer (b), wherein, (C) multi-functional monomer comprises and is selected from least a of trimethylolpropane triacrylate, pentaerythritol triacrylate and six acrylic acid dipentaerythritol ester.
(d) above-mentioned (a) and (b) or the radiation-ray sensitive composition that is used to form dyed layer (c), wherein, Photoepolymerizationinitiater initiater comprises and is selected from least a of acetophenone compounds, bisglyoxaline compounds, compound in triazine class and O-acyl group oxime compound.
(e) above-mentioned (a) and (b), (c) or the radiation-ray sensitive composition that is used to form dyed layer (d), wherein, (A) colorant contains organic pigment or carbon black.
(f) be used to form the radiation-ray sensitive composition of dyed layer, wherein, (B) alkali soluble resin contains multipolymer (BII).
(g) radiation-ray sensitive composition that is used to form dyed layer of above-mentioned (f), wherein, multipolymer (BII) contains and is selected from least a of multipolymer (BII-1)-(BII-2).
(h) above-mentioned (f) or the radiation-ray sensitive composition that is used to form dyed layer (g), wherein, (C) multi-functional monomer contains and is selected from least a of trimethylolpropane triacrylate, pentaerythritol triacrylate and six acrylic acid dipentaerythritol ester.
(i) above-mentioned (f), (g) or the radiation-ray sensitive composition that is used to form dyed layer (h), wherein, Photoepolymerizationinitiater initiater comprises and is selected from least a of acetophenone compounds, bisglyoxaline compounds and compound in triazine class.
(j) above-mentioned (f), (g), (h) or the radiation-ray sensitive composition that is used to form dyed layer (i), wherein, (A) colorant contains organic pigment or carbon black.
In addition, the preferred color filter of the present invention is:
(k) possess pixel and/or the black matrix that forms by above-mentioned (a) and (b), (c), (d) or the radiation-ray sensitive composition that is used to form dyed layer (e).
(l) possess pixel and/or the black matrix that forms by above-mentioned (f), (g), (h), (i) or the radiation-ray sensitive composition that is used to form dyed layer (j).
In addition, the preferred color liquid crystal element of the present invention:
(m) possess above-mentioned (k) or color filter (l).
The color liquid crystal display device that the present invention is more preferably:
(n) on the thin film transistor base plate array, possess above-mentioned (k) or color filter (l).
As mentioned above, radiation-ray sensitive composition of the present invention can keep good sensitivity, resolution, pattern form etc., particularly the storage stability of fluid composition is good, and can form solvent to wide scope have solvent resistance, with the excellent pattern of pixels and the black matrix pattern such as tack of substrate.
Therefore, can the utmost point to be suitable for the color liquid crystal display device color filter in the electronics industry be the manufacturing of the various color filters of representative to radiation-ray sensitive composition of the present invention.
Embodiment
Below provide embodiment, further specify the present invention.The present invention is not subjected to the qualification of following embodiment.Wherein, part and % are weight basis.
Synthesizing of alkali-soluble multipolymer
Synthesis example 1
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 25 parts of 3-(methacryloxy methyl)-3-ethyl oxetanes, 60 parts of methacrylic acid benzyl esters and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-1) ".
Synthesis example 2
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 25 parts of 3-(methacryloxy methyl)-3-ethyl oxetanes, 20 parts of N-phenylmaleimides, 10 parts of styrene, 30 parts of methacrylic acid benzyl esters and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-2) ".
Synthesis example 3
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 25 parts of 3-(methacryloxy methyl) oxetanes, 60 parts of methacrylic acid benzyl esters and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-3) ".
Synthesis example 4
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 25 parts of methacrylic acid tetrahydro furfuryl esters, 60 parts of methacrylic acid benzyl esters and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-4) ".
Synthesis example 5
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 25 parts of methacrylic acid tetrahydro furfuryl esters, 20 parts of N-phenylmaleimides, 10 parts of styrene, 30 parts of methacrylic acid benzyl esters and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-5) ".
Synthesis example 6
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 60 parts of methacrylic acid benzyl esters, 25 parts of methacrylic acid n-butyl and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-6) ".
Synthesis example 7
In the flask that possesses condenser pipe, stirrer, add 3 part 2,2 '-azoisobutyronitrile, 200 parts of propylene glycol methyl ether acetates, then add 15 parts of methacrylic acids, 15 parts of methacrylic acid tetrahydro furfuryl esters, 15 parts of 3-(methacryloxy methyl)-3-ethyl oxetanes, 55 parts of methacrylic acid benzyl esters and 3 parts of α-Jia Jibenyixierjuwus as molecular weight regulator, replace with nitrogen, light and slow then stirring, the temperature of reaction solution is warming up to 80 ℃, this temperature is kept carrying out polymerization in 5 hours, obtain resin solution.With this resin as " alkali soluble resin (B-7) ".
Synthesis example 8-14 and comparison synthesis example 1-6
The unsaturated compound that constitutes alkali soluble resin is changed to kind shown in the table 1 and amount, in addition same with synthesis example 7, obtain each solution of alkali soluble resin (B-8)-(B-20).
Table 1
Synthesis example
7 8 9 10 11 12 13 14
Alkali soluble resin B-7 B-8 B-9 B-10 B-11 B-12 B-13 B-14
Acid unsaturated compound methacrylic acid 15 15 15 15 15 15 15 15
Tetrahydrofuran unsaturated compounds methacrylic acid tetrahydro furfuryl ester 15 20 23 15 20 23 27 27
Oxetanes unsaturated compounds 3-(methacryloxy methyl)-3-ethyl oxetanes 3-(methacryloxy methyl) oxetanes 15 - 10 - 7 - - 15 - 10 - 7 3 - - 3
Other unsaturated compound methacrylic acid benzyl ester N-phenylmaleimide styrene 55 - - 55 - - 55 - - 55 - - 55 - - 55 - - 25 20 10 25 20 10
Table 1 (continuing)
Compare synthesis example
1 2 3 4 5 6
Alkali soluble resin B-15 B-16 B-17 B-18 B-19 B-20
Acid unsaturated compound methacrylic acid 15 15 15 15 15 15
Tetrahydrofuran unsaturated compounds methacrylic acid tetrahydro furfuryl ester - - 30 - - -
Oxetanes unsaturated compounds 3-(methacryloxy methyl)-3-ethyl oxetanes 3-(methacryloxy methyl) oxetanes 30 - - 30 - 3 - 3 - -
Other unsaturated compound methacrylic acid benzyl ester N-phenylmaleimide styrene 55 - - 55 - - 55 - - 52 20 10 52 20 10 85 - -
The preparation of dispersible pigment dispersion
Preparation example 1
20 parts of C.I. paratonere 254/C.I. paratonere 177=80/20 (weight ratio) potpourris as (A) colorant, 5 parts of BYK-2001 as spreading agent (being converted into solid content), 75 parts of propylene glycol monomethyl ether as solvent are handled preparation dispersible pigment dispersion (R) with ball mill.
Preparation example 2
20 parts of C.I. pigment green 36s as (A) colorant/C.I. pigment yellow 150=50/50 (weight ratio) potpourri, 5 parts are handled preparation dispersible pigment dispersion (G) with ball mill as ソ Le ス パ one ス 24000 (being converted into solid content) of spreading agent, 75 parts of propylene glycol monomethyl ether as solvent.
Embodiment 1
With 100 parts of dispersible pigment dispersions (R), the solution that 10 parts (being converted into solid content) obtains as the synthesis example 1 of alkali soluble resin (B-1), the solution that 5 parts (being converted into solid content) obtains as the synthesis example 4 of alkali soluble resin (B-4), the trimethylolpropane triacrylate of the multi-functional monomer of 15 parts of conducts (C), the 2-methyl isophthalic acid of 5 parts of conducts (D) Photoepolymerizationinitiater initiater-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone and 3 parts of diethyl thioxanthones, and mix as the propylene glycol monomethyl ether of solvent, the preparation solid concentration is 25% fluid composition (R-1) (with reference to table 2).
For fluid composition (R-1), form pattern according to following order, estimate.Evaluation result is as shown in table 10.
The formation of pattern
Be coated with fluid composition (R-1) with spin coater at glass baseplate surface, under 90 ℃, carry out 4 minutes preliminary drying then, form filming of thickness 1.3 μ m.Then 3 these substrates are cooled to room temperature, with high-pressure sodium lamp via mask with 2,000J/m 2Exposure filming on each substrate exposed, then with 23 ℃ 0.04% potassium hydroxide aqueous solution with 1kgf/cm 2Development pressure (nozzle diameter 1mm) be sprayed onto on the filming on each substrate, spray development, then 220 ℃ of back bakings of carrying out 30 minutes, form the dot pattern of 200 * 200 μ m.
Solvent resistance is estimated
With 32,000J/m 2Exposure under the substrate that exposes be immersed in 25 ℃ N-Methyl pyrrolidone (being designated as " NMP " among the table 10-13) respectively, in 18%HCl aqueous solution (table 10-13 in be designated as " HCl ") or the 5%KOH aqueous solution (being designated as " KOH " among the table 10-13) 30 minutes, soak the dot pattern of front and back with sem observation, estimate, pattern is formed well, Film Thickness Ratio before and after soaking (thickness before soak the thickness after the immersion * 100/) is 95% or above is evaluated as zero, be lower than 95% or some damaged △ that is evaluated as of pattern with the Film Thickness Ratio before and after soaking, with soak the back pattern fully from being evaluated as of coming off of substrate *.
Tack is estimated
With spin coater fluid composition (R-1) is coated on the glass baseplate surface, under 90 ℃, carries out 4 minutes preliminary drying then, form filming of thickness 1.3 μ m, then this substrate is cooled to room temperature after, with high-pressure sodium lamp with 2,000J/m 2Exposure this filmed expose, then with 23 ℃ 0.04% potassium hydroxide aqueous solution with 1kgf/cm 2Development pressure (nozzle diameter 1mm) be sprayed onto film on, spray development, then 220 ℃ of back bakings of carrying out 30 minutes.Then, according to JIS K5400 standard, the cross of will filming draw lattice become 100 grid-like, carry out tack test, do not take place to be evaluated as zero when grid is peeled off, be evaluated as △ when having 1-10 to peel off in the grid, grid have when peeling off more than 10 be evaluated as *.
The storage stability evaluation of fluid composition
Fluid composition (R-1) is packed in the vial, in 40 ℃ constant temperature and humidity cabinet, preserve a week, measure the viscosity before and after preserving, calculate viscosity rate of change (viscosity before preserve the viscosity after the preservation * 100/).The solution viscosity of the solution viscosity of the viscosity of employed here dispersible pigment dispersion (R), alkali soluble resin (B-1) and alkali soluble resin (B-4) with above-mentioned same condition under preserve and also not see variation.
Embodiment 2-22
Among the embodiment 1, the kind of constituent and amount according to table 2 or table 3 change, are in addition prepared fluid composition (R-2)-(R-22) similarly to Example 1.
Then, use fluid composition (R-2)-(R-22) to replace fluid composition (R-1) respectively, in addition estimate similarly to Example 1.The solution viscosity of the alkali soluble resin (B-3) that uses among the solution viscosity of the alkali soluble resin (B-2) that uses among the solution viscosity of the alkali soluble resin that uses among the embodiment 8-10 (B-5), the embodiment 11-16 and the embodiment 17-22 with the same condition of the storage stability evaluation of above-mentioned fluid composition under preserve and also not see variation.Evaluation result is as shown in table 10.
Embodiment 23
With 100 parts of dispersible pigment dispersions (G), the solution that 10 parts (being converted into solid content) obtains as the synthesis example 1 of alkali soluble resin (B-1), the solution that 5 parts (being converted into solid content) obtains as the synthesis example 4 of alkali soluble resin (B-4), six acrylic acid dipentaerythritol ester of the multi-functional monomer of 12 parts of conducts (C), 2-benzyl-2-dimethylamino-the 1-of 5 parts of conducts (D) Photoepolymerizationinitiater initiater (4-morpholino phenyl)-Ding-1-ketone and 3 part 4,4 '-two (diethylamino) benzophenone, and mix as the propylene glycol monomethyl ether of solvent, the preparation solid concentration is 25% fluid composition (G-1) (with reference to table 4).
Then, use fluid composition (G-1) to replace fluid composition (R-1), in addition form pattern similarly to Example 1, estimate.The viscosity of dispersible pigment dispersion used herein (G) with the same condition of the storage stability evaluation of above-mentioned fluid composition under preserve and also not see variation.Evaluation result is as shown in table 11.
Embodiment 24-44
Among the embodiment 23, the kind of constituent and amount according to table 4 or table 5 change, are in addition prepared fluid composition (G-2)-(G-22) similarly to Example 23.
Then, use fluid composition (G-2)-(G-22) to replace fluid composition (R-1) respectively, in addition estimate similarly to Example 1.Evaluation result is as shown in table 11.
Comparative example 1-19
The kind and the amount of constituent among the embodiment 1 are changed according to table 6 or table 7, in addition prepare fluid composition (R-23)-(R-41) similarly to Example 1.
Then, use fluid composition (R-23)-(R-41) to replace fluid composition (R-1) respectively, in addition estimate similarly to Example 1.Evaluation result is as shown in table 12.
Comparative example 20-38
The kind and the amount of constituent among the embodiment 23 are changed according to table 8 or table 9, in addition prepare fluid composition (G-23)-(G-41) similarly to Example 23.
Then, use fluid composition (G-23)-(G-41) to replace fluid composition (R-1) respectively, in addition estimate similarly to Example 1.Evaluation result is as shown in table 13.
Among the table 2-9, shown in the theing contents are as follows of multi-functional monomer, Photoepolymerizationinitiater initiater and adjuvant.
Multi-functional monomer
C-1: trimethylolpropane triacrylate
C-2: six acrylic acid dipentaerythritol ester
Photoepolymerizationinitiater initiater
D-1:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone
D-2:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl] ethyl ketone 1-(O-acetyl oxime)
D-3:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) fourth-1-ketone
D-4:2, the 4-diethyl thioxanthone
D-5:4,4 '-two (diethylamino) benzophenone
Adjuvant
E-1: the linear phenolic resin varnish type epoxy resin of bisphenol-A (trade name 157S65, ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) preparation)
E-2: trimellitic anhydride
E-3:N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide
Table 2
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 1 R-1 R(100) B-1(10) B-4(5) C-1(15) D-1(5) D-4(3) -
Embodiment 2 R-2 R(100) B-1(10) B-4(5) C-1(15) D-2(5) D-4(3) -
Embodiment 3 R-3 R(100) B-1(10) B-4(5) C-1(15) D-1(5) D-4(3) E-1(4)
Embodiment 4 R-4 R(100) B-1(10) B-4(5) C-1(15) D-1(5) D-4(3) E-2(2)
Embodiment 5 R-5 R(100) B-1(10) B-4(5) C-1(15) D-1(5) D-4(3) E-3(2)
Embodiment 6 R-6 R(100) B-1(5) B-4(10) C-1(15) D-1(5) D-4(3) -
Embodiment 7 R-7 R(100) B-1(2) B-4(13) C-1(15) D-1(5) D-4(3) -
Embodiment 8 R-8 R(100) B-1(10) B-5(5) C-1(15) D-1(5) D-4(3) -
Embodiment 9 R-9 R(100) B-1(5) B-5(10) C-1(15) D-1(5) D-4(3) -
Embodiment 10 R-10 R(100) B-1(2) B-5(13) C-1(15) D-1(5) D-4(3) -
Table 3
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 11 R-11 R(100) B-2(10) B-4(5) C-1(15) D-1(5) D-4(3) -
Embodiment 12 R-12 R(100) B-2(5) B-4(10) C-1(15) D-1(5) D-4(3) -
Embodiment 13 R-13 R(100) B-2(2) B-4(13) C-1(15) D-1(5) D-4(3) -
Embodiment 14 R-14 R(100) B-2(10) B-5(5) C-1(15) D-1(5) D-4(3) -
Embodiment 15 R-15 R(100) B-2(5) B-5(10) C-1(15) D-1(5) D-4(3) -
Embodiment 16 R-16 R(100) B-2(2) B-5(13) C-1(15) D-1(5) D-4(3) -
Embodiment 17 R-17 R(100) B-3(10) B-4(5) C-1(15) D-1(5) D-4(3) -
Embodiment 18 R-18 R(100) B-3(5) B-4(10) C-1(15) D-1(5) D-4(3) -
Embodiment 19 R-19 R(100) B-3(2) B-4(13) C-1(15) D-1(5) D-4(3) -
Embodiment 20 R-20 R(100) B-3(10) B-5(5) C-1(15) D-1(5) D-4(3) -
Embodiment 21 R-21 R(100) B-3(5) B-5(10) C-1(15) D-1(5) D-4(3) -
Embodiment 22 R-22 R(100) B-3(2) B-5(13) C-1(15) D-1(5) D-4(3) -
Table 4
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 23 G-1 G(100) B-1(10) B-4(5) C-2(12) D-3(5) D-5(3) -
Embodiment 24 G-2 G(100) B-1(10) B-4(5) C-2(12) D-2(5) D-5(3) -
Embodiment 25 G-3 G(100) B-1(10) B-4(5) C-2(12) D-3(5) D-5(3) E-1(4)
Embodiment 26 G-4 G(100) B-1(10) B-4(5) C-2(12) D-3(5) D-5(3) E-2(2)
Embodiment 27 G-5 G(100) B-1(10) B-4(5) C-2(12) D-3(5) D-5(3) E-3(2)
Embodiment 28 G-6 G(100) B-1(5) B-4(10) C-2(12) D-3(5) D-5(3) -
Embodiment 29 G-7 G(100) B-1(2) B-4(13) C-2(12) D-3(5) D-5(3) -
Embodiment 30 G-8 G(100) B-1(10) B-5(5) C-2(12) D-3(5) D-5(3) -
Embodiment 31 G-9 G(100) B-1(5) B-5(10) C-2(12) D-3(5) D-5(3) -
Embodiment 32 G-10 G(100) B-1(2) B-5(13) C-2(12) D-3(5) D-5(3) -
Table 5
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 33 G-11 G(100) B-2(10) B-4(5) C-2(12) D-3(5) D-5(3) -
Embodiment 34 G-12 G(100) B-2(5) B-4(10) C-2(12) D-2(5) D-5(3) -
Embodiment 35 G-13 G(100) B-2(2) B-4(13) C-2(12) D-3(5) D-5(3) -
Embodiment 36 G-14 G(100) B-2(10) B-5(5) C-2(12) D-3(5) D-5(3) -
Embodiment 37 G-15 G(100) B-2(5) B-5(10) C-2(12) D-3(5) D-5(3) -
Embodiment 38 G-16 G(100) B-2(2) B-5(13) C-2(12) D-3(5) D-5(3) -
Embodiment 39 G-17 G(100) B-3(10) B-4(5) C-2(12) D-3(5) D-5(3) -
Embodiment 40 G-18 G(100) B-3(5) B-4(10) C-2(12) D-3(5) D-5(3) -
Embodiment 41 G-19 G(100) B-3(2) B-4(13) C-2(12) D-3(5) D-5(3) -
Embodiment 42 G-20 G(100) B-3(10) B-5(5) C-2(12) D-3(5) D-5(3) -
Embodiment 43 G-21 G(100) B-3(5) B-5(10) C-2(12) D-3(5) D-5(3) -
Embodiment 44 G-22 G(100) B-3(2) B-5(13) C-2(12) D-3(5) D-5(3) -
Table 6
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 1 R-23 R(100) B-1(10) B-6(5) C-1(15) D-1(5) D-4(3) -
Comparative example 2 R-24 R(100) B-1(10) B-6(5) C-1(15) D-2(5) D-4(3) -
Comparative example 3 R-25 R(100) B-1(10) B-6(5) C-1(15) D-1(5) D-4(3) E-1(4)
Comparative example 4 R-26 R(100) B-1(10) B-6(5) C-1(15) D-1(5) D-4(3) E-2(2)
Comparative example 5 R-27 R(100) B-1(10) B-6(5) C-1(15) D-1(5) D-4(3) E-3(2)
Comparative example 6 R-28 R(100) B-1(5) B-6(10) C-1(15) D-1(5) D-4(3) -
Comparative example 7 R-29 R(100) B-1(2) B-6(13) C-1(15) D-1(5) D-4(3) -
Comparative example 8 R-30 R(100) B-2(10) B-6(5) C-1(15) D-1(5) D-4(3) -
Comparative example 9 R-31 R(100) B-2(5) B-6(10) C-1(15) D-1(5) D-4(3) -
Comparative example 10 R-32 R(100) B-2(2) B-6(13) C-1(15) D-1(5) D-4(3) -
Comparative example 11 R-33 R(100) B-3(10) B-6(5) C-1(15) D-1(5) D-4(3) -
Comparative example 12 R-34 R(100) B-3(5) B-6(10) C-1(15) D-1(5) D-4(3) -
Comparative example 13 R-35 R(100) B-3(2) B-6(13) C-1(15) D-1(5) D-4(3) -
Table 7
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 14 R-36 R(100) B-1(15) C-1(15) D-1(5) D-4(3) -
Comparative example 15 R-37 R(100) B-2(15) C-1(15) D-1(5) D-4(3) -
Comparative example 16 R-38 R(100) B-3(15) C-1(15) D-1(5) D-4(3) -
Comparative example 17 R-39 R(100) B-4(5) C-1(15) D-1(5) D-4(3) -
Comparative example 18 R-40 R(100) B-5(15) C-1(15) D-1(5) D-4(3) -
Comparative example 19 R-41 R(100) B-6(15) C-1(15) D-1(5) D-4(3) -
Table 8
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 20 G-23 G(100) B-1(10) B-6(5) C-2(12) D-3(5) D-5(3) -
Comparative example 21 G-24 G(100) B-1(10) B-6(5) C-2(12) D-2(5) D-5(3) -
Comparative example 22 G-25 G(100) B-1(10) B-6(5) C-2(12) D-3(5) D-5(3) E-1(4)
Comparative example 23 G-26 G(100) B-1(10) B-6(5) C-2(12) D-3(5) D-5(3) E-2(2)
Comparative example 24 G-27 G(100) B-1(10) B-6(5) C-2(12) D-3(5) D-5(3) E-3(2)
Comparative example 25 G-28 G(100) B-1(5) B-6(10) C-2(12) D-3(5) D-5(3) -
Comparative example 26 G-29 G(100) B-1(2) B-6(13) C-2(12) D-3(5) D-5(3) -
Comparative example 27 G-30 G(100) B-2(10) B-6(5) C-2(12) D-3(5) D-5(3) -
Comparative example 28 G-31 G(100) B-2(5) B-6(10) C-2(12) D-3(5) D-5(3) -
Comparative example 29 G-32 G(100) B-2(2) B-6(13) C-2(12) D-3(5) D-5(3) -
Comparative example 30 G-33 G(100) B-3(10) B-6(5) C-2(12) D-3(5) D-5(3) -
Comparative example 31 G-34 G(100) B-3(5) B-6(10) C-2(12) D-3(5) D-5(3) -
Comparative example 32 G-35 G(100) B-3(2) B-6(13) C-2(12) D-3(5) D-5(3) -
Table 9
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 33 G-36 G(100) B-1(15) C-2(12) D-3(5) D-5(3) -
Comparative example 34 G-37 G(100) B-2(15) C-2(12) D-3(5) D-5(3) -
Comparative example 35 G-38 G(100) B-3(15) C-2(12) D-3(5) D-5(3) -
Comparative example 36 G-39 G(100) B-4(15) C-2 (12) D-3(5) D-5(3) -
Comparative example 37 G-40 G(100) B-5(15) C-2(12) D-3(5) D-5(3) -
Comparative example 38 G-41 G(100) B-6(15) C-2(12) D-3(5) D-5(3) -
Table 10
Solvent resistance Tack The storage stability of fluid composition
NMP HCl KOH
Embodiment 1 ○ ○ ○ ○ 100
Embodiment 2 ○ ○ ○ ○ 100
Embodiment 3 ○ ○ ○ ○ 100
Embodiment 4 ○ ○ ○ ○ 100
Embodiment 5 ○ ○ ○ ○ 100
Embodiment 6 ○ ○ ○ ○ 100
Embodiment 7 ○ ○ ○ ○ 100
Embodiment 8 ○ ○ ○ ○ 100
Embodiment 9 ○ ○ ○ ○ 100
Embodiment 10 ○ ○ ○ ○ 100
Embodiment 11 ○ ○ ○ ○ 100
Embodiment 12 ○ ○ ○ ○ 100
Embodiment 13 ○ ○ ○ ○ 100
Embodiment 14 ○ ○ ○ ○ 100
Embodiment 15 ○ ○ ○ ○ 100
Embodiment 16 ○ ○ ○ ○ 100
Embodiment 17 ○ ○ ○ ○ 100
Embodiment 18 ○ ○ ○ ○ 100
Embodiment 19 ○ ○ ○ ○ 100
Embodiment 20 ○ ○ ○ ○ 100
Embodiment 21 ○ ○ ○ ○ 100
Embodiment 22 ○ ○ ○ ○ 100
Table 11
Solvent resistance Tack The storage stability of fluid composition
NMP HCl KOH
Embodiment 23 ○ ○ ○ ○ 100
Embodiment 24 ○ ○ ○ ○ 100
Embodiment 25 ○ ○ ○ ○ 100
Embodiment 26 ○ ○ ○ ○ 100
Embodiment 27 ○ ○ ○ ○ 100
Embodiment 28 ○ ○ ○ ○ 100
Embodiment 29 ○ ○ ○ ○ 100
Embodiment 30 ○ ○ ○ ○ 100
Embodiment 31 ○ ○ ○ ○ 100
Embodiment 32 ○ ○ ○ ○ 100
Embodiment 33 ○ ○ ○ ○ 100
Embodiment 34 ○ ○ ○ ○ 100
Embodiment 35 ○ ○ ○ ○ 100
Embodiment 36 ○ ○ ○ ○ 100
Embodiment 37 ○ ○ ○ ○ 100
Embodiment 38 ○ ○ ○ ○ 100
Embodiment 39 ○ ○ ○ ○ 100
Embodiment 40 ○ ○ ○ ○ 100
Embodiment 41 ○ ○ ○ ○ 100
Embodiment 42 ○ ○ ○ ○ 100
Embodiment 43 ○ ○ ○ ○ 100
Embodiment 44 ○ ○ ○ ○ 100
Table 12
Solvent resistance Tack The storage stability of fluid composition
NMP HCl KOH
Comparative example 1 × × △ × 100
Comparative example 2 × × △ × 100
Comparative example 3 △ △ △ × 100
Comparative example 4 △ △ △ × 100
Comparative example 5 △ △ △ × 100
Comparative example 6 × △ × × 100
Comparative example 7 × × × × 100
Comparative example 8 △ △ △ × 100
Comparative example 9 △ △ △ × 100
Comparative example 10 △ × × × 100
Comparative example 11 × △ △ × 100
Comparative example 12 × △ × × 100
Comparative example 13 × × × × 100
Comparative example 14 ○ ○ ○ ○ 304
Comparative example 15 ○ ○ ○ ○ 300
Comparative example 16 ○ ○ ○ ○ 405
Comparative example 17 × × × × 100
Comparative example 18 × × × × 100
Comparative example 19 × × × × 100
Table 13
Solvent resistance Tack The storage stability of fluid composition
NMP HCI KOH
Comparative example 20 × × × × 100
Comparative example 21 × × × × 100
Comparative example 22 △ △ △ × 100
Comparative example 23 △ × △ × 100
Comparative example 24 × △ △ × 100
Comparative example 25 × × × × 100
Comparative example 26 × × × × 100
Comparative example 27 △ △ △ × 100
Comparative example 28 △ × △ × 100
Comparative example 29 △ × × × 100
Comparative example 30 × × × × 100
Comparative example 31 × × × × 100
Comparative example 32 × × × × 100
Comparative example 33 ○ ○ ○ ○ 405
Comparative example 34 ○ ○ ○ ○ 387
Comparative example 35 ○ ○ ○ ○ 504
Comparative example 36 × × × × 100
Comparative example 37 × × × × 100
Comparative example 38 × × × × 100
Embodiment 45
With 100 parts of dispersible pigment dispersions (R), the resin solution that 15 parts (being converted into solid content) obtains as the synthesis example 7 of alkali soluble resin (B-7), six acrylic acid dipentaerythritol ester of the multi-functional monomer of 10 parts of conducts (C) and 5 parts of trimethylolpropane triacrylates, the 2-methyl isophthalic acid of 5 parts of conducts (D) Photoepolymerizationinitiater initiater-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone and 3 part 4,4 '-two (diethylamino) benzophenone, and mix as the propylene glycol monomethyl ether of solvent, the preparation solid concentration is 25% fluid composition (R-42) (with reference to table 14).
For fluid composition (R-42), form pattern according to following order, estimate.Evaluation result is shown in table 18.
The formation of pattern
On glass baseplate surface, be coated with fluid composition (R-42) with spin coater, under 90 ℃, carry out 4 minutes preliminary drying then, form filming of thickness 1.3 μ m.Then 3 these substrates are cooled to room temperature, with high-pressure sodium lamp via mask with 2,000J/m 2Exposure filming on each substrate exposed, then with 23 ℃ 0.04 weight % potassium hydroxide aqueous solution with 1kgf/cm 2Development pressure (nozzle diameter 1mm) be sprayed onto on the filming on each substrate, spray development, then 220 ℃ of back bakings of carrying out 30 minutes, form the dot pattern of 200 * 200 μ m.
Solvent resistance is estimated
With 32,000J/m 2Exposure under the substrate that exposes be immersed in 25 ℃ N-Methyl pyrrolidone (being designated as " NMP " in table 18 and the table 19) respectively, in 18%HCl aqueous solution (being designated as " HCl " in table 18 and the table 19) or the 5%KOH aqueous solution (being designated as " KOH " in table 18 and the table 19) 30 minutes, soak the dot pattern of front and back with sem observation, estimate, pattern is formed well, Film Thickness Ratio before and after soaking (thickness before soak the thickness after the immersion * 100/) is 95% or above is evaluated as zero, be lower than 95% or some damaged △ that is evaluated as of pattern with the Film Thickness Ratio before and after soaking, with soak the back pattern fully from being evaluated as of coming off of substrate *.
Tack is estimated
With spin coater fluid composition (R-42) is coated on the glass baseplate surface, under 90 ℃, carries out 4 minutes preliminary drying then, form filming of thickness 1.3 μ m, then this substrate is cooled to room temperature after, with high-pressure sodium lamp with 2,000J/m 2Exposure expose to filming, then with 23 ℃ 0.04% potassium hydroxide aqueous solution with 1kgf/cm 2Development pressure (nozzle diameter 1mm) be sprayed onto film on, spray development, then 220 ℃ of back bakings of carrying out 30 minutes.Then, according to JIS K5400 standard, the cross of will filming draw lattice become 100 grid-like, carry out tack test, do not take place to be evaluated as zero when grid is peeled off, be evaluated as △ when having 1-10 to peel off in the grid, grid have when peeling off more than 10 be evaluated as *.
The storage stability evaluation of fluid composition
Fluid composition (R-42) is packed in the vial, in 40 ℃ constant temperature and humidity cabinet, preserve a week, measure the viscosity before and after preserving, calculate viscosity rate of change (viscosity before preserve the viscosity after the preservation * 100/).The solution viscosity of the viscosity of employed here dispersible pigment dispersion (R), alkali soluble resin (B-7) with above-mentioned same condition under preserve and also not see variation.
Embodiment 46-56
Constituent among the embodiment 45 is pressed table 14 change, in addition similarly prepare fluid composition (R-43)-(R-53) with embodiment 45.
Then, use fluid composition (R-43)-(R-56) to replace fluid composition (R-42) respectively, in addition similarly estimate with embodiment 45.Each solution viscosity of the alkali soluble resin that uses among the embodiment 50-53 (B-8)-(B-14) with the same condition of the storage stability evaluation of above-mentioned fluid composition under preserve and also not see variation.Evaluation result is shown in table 18.
Embodiment 57
The resin solution that 100 parts of dispersible pigment dispersions (G), 15 parts (being converted into solid content) are obtained as the synthesis example 7 of alkali soluble resin (B-7), 5 parts mix as the six acrylic acid dipentaerythritol ester of (C) multi-functional monomer and 10 parts of pentaerythritol tetracrylates, 5 parts of 2-benzyl-2-dimethylamino-1-as (D) Photoepolymerizationinitiater initiater (4-morpholino phenyl)-Ding-1-ketone and 5 parts of diethyl thioxanthones and as the propylene glycol monomethyl ether of solvent, and the preparation solid concentration is 25% fluid composition (G-42).
Then, use fluid composition (G-42) to replace fluid composition (R-42), in addition similarly form pattern, estimate with embodiment 45.The viscosity of dispersible pigment dispersion used herein (G) with the same condition of the storage stability evaluation of above-mentioned fluid composition under preserve and also not see variation.Evaluation result is shown in table 18.
Embodiment 58-68
Constituent among the embodiment 57 according to table 15 change, is in addition similarly prepared fluid composition (G-43)-(G-53) with embodiment 57.
Then, use fluid composition (G-43)-(G-53) to replace fluid composition (R-42) respectively, in addition similarly estimate with embodiment 45.Evaluation result is shown in table 18.
Comparative example 39-48
Constituent among the embodiment 45 according to table 16 change, is in addition similarly prepared fluid composition (R-54)-(R-63) with embodiment 45.
Then, use fluid composition (R-54)-(R-63) to replace fluid composition (R-42) respectively, in addition similarly estimate with embodiment 45.Evaluation result is shown in table 19.
Comparative example 49-58
Constituent among the embodiment 57 according to table 17 change, is in addition similarly prepared fluid composition (G-54)-(G-63) with embodiment 57.
Then, use fluid composition (G-54)-(G-63) to replace fluid composition (R-42) respectively, in addition similarly estimate with embodiment 45.Evaluation result is shown in table 19.
Among the table 14-17, shown in the theing contents are as follows of multi-functional monomer, Photoepolymerizationinitiater initiater and adjuvant.
Multi-functional monomer
C-1: six acrylic acid dipentaerythritol ester
C-2: trimethylolpropane triacrylate
C-3: pentaerythritol tetracrylate
Photoepolymerizationinitiater initiater
D-1:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone
D-2:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone
D-3:4,4 '-two (diethylamino) benzophenone
D-5:2, the 4-diethyl thioxanthone
Adjuvant
E-1: the linear phenolic resin varnish type epoxy resin of bisphenol-A (trade name 157S65, ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) preparation)
E-2: trimellitic anhydride
E-3:N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide
Table 14
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 45 R-42 R(100) B-7(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 46 R-43 R(100) B-7(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 47 R-44 R(100) B-7(15) C-1(10) C-2(5) D-1(5) D-3(3) E-1(4)
Embodiment 48 R-45 R(100) B-7(15) C-1(10) C-2(5) D-1(5) D-3(3) E-2(2)
Embodiment 49 R-46 R(100) B-7(15) C-1(10) C-2(5) D-1(5) D-3(3) E-3(2)
Embodiment 50 R-47 R(100) B-8(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 51 R-48 R(100) B-9(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 52 R-49 R(100) B-10(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 53 R-50 R(100) B-11(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 54 R-51 R(100) B-12(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 55 R-52 R(100) B-13(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Embodiment 56 R-53 R(100) B-14(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Table 15
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 57 G-42 G(100) B-7(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 58 G-43 G(100) B-7(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 59 G-44 G(100) B-7(15) C-1(5) C-3(10) D-2(5) D-4(5) E-1(4)
Embodiment 60 G-45 G(100) B-7(15) C-1(5) C-3(10) D-2(5) D-4(5) E-2(2)
Embodiment 61 G-46 G(100) B-7(15) C-1(5) C-3(10) D-2(5) D-4(5) E-3(2)
Embodiment 62 G-47 G(100) B-8(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 63 G-48 G(100) B-9(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 64 G-49 G(100) B-10(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 65 G-50 G(100) B-11(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 66 G-51 G(100) B-12(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 67 G-52 G(100) B-13(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Embodiment 68 G-53 G(100) B-14(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Table 16
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 39 R-54 R(100) B-15(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Comparative example 40 R-55 R(100) B-15(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Comparative example 41 R-56 R(100) B-15(15) C-1(10) C-2(5) D-1(5) D-3(3) E-1(4)
Comparative example 42 R-57 R(100) B-15(15) C-1(10) C-2(5) D-1(5) D-3(3) E-2(2)
Comparative example 43 R-58 R(100) B-15(15) C-1(10) C-2(5) D-1(5) D-3(3) E-3(2)
Comparative example 44 R-59 R(100) B-16(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Comparative example 45 R-60 R(100) B-17(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Comparative example 46 R-61 R(100) B-18(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Comparative example 47 R-62 R(100) B-19(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Comparative example 48 R-63 R(100) B-20(15) C-1(10) C-2(5) D-1(5) D-3(3) -
Table 17
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resin (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 49 G-54 G(100) B-15(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Comparative example 50 G-55 G(100) B-15(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Comparative example 51 G-56 G(100) B-15(15) C-1(5) C-3(10) D-2(5) D-4(5) E-1(4)
Comparative example 52 G-57 G(100) B-15(15) C-1(5) C-3(10) D-2(5) D-4(5) E-2(2)
Comparative example 53 G-58 G(100) B-15(15) C-1(5) C-3(10) D-2(5) D-4(5) E-3(2)
Comparative example 54 G-59 G(100) B-16(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Comparative example 55 G-60 G(100) B-17(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Comparative example 56 G-61 G(100) B-18(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Comparative example 57 G-62 G(100) B-19(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Comparative example 58 G-63 G(100) B-20(15) C-1(5) C-3(10) D-2(5) D-4(5) -
Table 18
Solvent resistance Tack The storage stability of fluid composition
NMP HCI KOH
Embodiment 45 ○ ○ ○ ○ 100
Embodiment 46 ○ ○ ○ ○ 100
Embodiment 47 ○ ○ ○ ○ 100
Embodiment 48 ○ ○ ○ ○ 100
Embodiment 49 ○ ○ ○ ○ 100
Embodiment 50 ○ ○ ○ ○ 100
Embodiment 51 ○ ○ ○ ○ 100
Embodiment 52 ○ ○ ○ ○ 100
Embodiment 53 ○ ○ ○ ○ 100
Embodiment 54 ○ ○ ○ ○ 100
Embodiment 55 ○ ○ ○ ○ 100
Embodiment 56 ○ ○ ○ ○ 100
Embodiment 57 ○ ○ ○ ○ 100
Embodiment 58 ○ ○ ○ ○ 100
Embodiment 59 ○ ○ ○ ○ 100
Embodiment 60 ○ ○ ○ ○ 100
Embodiment 61 ○ ○ ○ ○ 100
Embodiment 62 ○ ○ ○ ○ 100
Embodiment 63 ○ ○ ○ ○ 100
Embodiment 64 ○ ○ ○ ○ 100
Embodiment 65 ○ ○ ○ ○ 100
Embodiment 66 ○ ○ ○ ○ 100
Embodiment 67 ○ ○ ○ ○ 100
Embodiment 68 ○ ○ ○ ○ 100
Table 19
Solvent resistance Tack The storage stability of fluid composition
NMP HCI KOH
Comparative example 39 ○ ○ ○ ○ 280
Comparative example 40 ○ ○ ○ ○ 304
Comparative example 41 ○ ○ ○ ○ 334
Comparative example 42 ○ ○ ○ ○ 456
Comparative example 43 ○ ○ ○ ○ 345
Comparative example 44 ○ ○ ○ ○ 298
Comparative example 45 × × × × 100
Comparative example 46 × △ × × 100
Comparative example 47 × △ × × 100
Comparative example 48 × × × × 100
Comparative example 49 ○ ○ ○ ○ 350
Comparative example 50 ○ ○ ○ ○ 460
Comparative example 51 ○ ○ ○ ○ 315
Comparative example 52 ○ ○ ○ ○ 316
Comparative example 53 ○ ○ ○ ○ 317
Comparative example 54 ○ ○ ○ ○ 406
Comparative example 55 × × × × 100
Comparative example 56 × △ × × 100
Comparative example 57 × × × × 100
Comparative example 58 × × × × 100

Claims (5)

1. radiation-ray sensitive composition, it contains (A) colorant, (B) alkali soluble resin, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, wherein (B) alkali soluble resin contains the multipolymer of the 1st unsaturated compound and the 2nd unsaturated compound, described the 1st unsaturated compound is selected from unsaturated carboxylic acid for (b1), unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds at least a, described the 2nd unsaturated compound is selected from (b2) and has at least a of the unsaturated compound of oxetanes skeleton and the unsaturated compound that (b3) has the tetrahydrofuran skeleton, and above-mentioned radiation-ray sensitive composition is used to form dyed layer.
2. the radiation-ray sensitive composition of claim 1, wherein, (B) alkali soluble resin is the multipolymer that has the unsaturated compound of oxetanes skeleton in the 1st unsaturated compound and the 2nd unsaturated compound, or has the multipolymer of the unsaturated compound of tetrahydrofuran skeleton in the 1st unsaturated compound and the 2nd unsaturated compound.
3. the radiation-ray sensitive composition of claim 1, wherein, (B) alkali soluble resin is the multipolymer that has the unsaturated compound of oxetanes skeleton in the 1st unsaturated compound and the 2nd unsaturated compound and have the unsaturated compound of tetrahydrofuran skeleton.
4. color filter, it possesses the dyed layer that forms with each the radiation-ray sensitive composition that is used to form dyed layer among the claim 1-3.
5. color liquid crystal display device, it possesses the color filter of claim 4.
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