CN101158812A

CN101158812A - Radiation sensitive resin composition and color filter

Info

Publication number: CN101158812A
Application number: CNA2007101613154A
Authority: CN
Inventors: 河本达庆; 丰岛司; 荒井雅史; 松本龙; 长塚富雄; 槙平勇
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2006-09-29
Filing date: 2007-09-28
Publication date: 2008-04-09
Also published as: TW200830043A; JP2008089732A; KR20080029882A; SG141402A1

Abstract

The invention provides a radiation sensitive resin composition comprising (A) a pigment, (B) an alkali-soluble resin, (C) a poly-functional monomer and (D) a radiation sensitive radical generator, wherein the component (B) has resin with terminal shown by the following formula (i) or (ii), and the component (D) has compound of the following formula (1) and/or formula (2). In formula (i) or (ii), Z1 and Z2 denote hydrogen atom, chlorine atom, alkyl, alkoxy and so on. In formula (1) and/or formula (2), R3 denotes (cyclic) alkyl or phenyl, R4 and R5 denote hydrogen atom, (cyclic) alkyl and so on, R6 denotes univalent heterocyclic radical, R7 denotes hydrogen atom, (cyclic) alkyl and so on, n=1-5, m=0-5, (n + m)<=5, p=0-6. The invention can form a color filter without 'image retention' and this radiation sensitive resin composition has a high product yield and high sensitivity and high solubility in a solvent after it becomes dry.

Description

Radiation sensitive resin composition and color filter

Technical field

The present invention relates to radiation sensitive resin composition that can be used for preparing the color filter that in transmission-type or reflection-type color liquid crystal device, colour pick-up tube element etc., uses and preparation method thereof, the color liquid crystal display arrangement that also relates to the color filter that forms by this radiation sensitive resin composition and have this color filter.

Background technology

The method that known use colored radiation-sensitive resin combination forms color filter has: on the substrate or be pre-formed on the substrate of light shield layer of required pattern and form filming of colored radiation-sensitive resin combination, via photomask irradiation radioactive ray (hereinafter referred to as " exposure ") with required pattern form, develop by alkaline developer, unexposed portion is removed in dissolving, use cleaning oven or hot plate to carry out the back baking then, obtain the method (with reference to TOHKEMY 2000-329929 communique) of versicolor pixel.

In recent years, the substrate size that is used to form color filter maximizes day by day, therefore, to change the liquid teat that makes the coating radiation sensitive resin composition into by the mode of the spinner that uses central drippage type be the mode of more small-bore gap nozzle (slit nozzle) to the coating process of radiation sensitive resin composition.In the mode of the latter's gap nozzle, the diameter of liquid teat little (narrow), therefore after coating finishes, the most residual radiation sensitive resin composition that has of the periphery of nozzle tip portion, will drop onto on the color filter by the dry foreign matter when next time being coated with after its drying, the quality of color filter is significantly reduced, therefore, will advance in coating usually and exercise the jet cleaning of nozzle tip portion ejection cleaning solvent.But, can't prevent effectively also that even so the color filter quality that dry foreign matter causes from reducing, and becomes the main cause that yield rate reduces.

At the problems referred to above, people need the washing performance height of cleaning solvent badly in recent years, the dissolubility still high color filter radiation sensitive resin composition of promptly dry back in cleaning solvent.

In recent years, people require its life-span longer for the liquid crystal indicator with color filter, and the requirement to the anti-image retention function of color filter also strengthens day by day thereupon.

" image retention (

I つ I) " being that liquid crystal indicator shows bad a kind of, is that the image that should not show originally shows on picture, the phenomenon of black or white " mist " shape overlapping demonstration on the image that script will show.Above-mentioned phenomenon is that the potential difference (PD) that applies in order to make liquid crystal molecular orientation can't keep the regular hour owing to charged impurity in the liquid crystal spreads in liquid crystal.When above-mentioned impurity not only comes from liquid crystal molecule and prepares, recognize again recently, also can stripping from the color filter that forms.As disclosed in the TOHKEMY 2000-329929 communique, for preventing " image retention ", known raising pigment purity is effectively, but impurity also may come from the composition beyond the pigment in the radiation sensitive resin composition, therefore, improving pigment purity merely may not be enough.

In recent years, people need develop the requirement of the high finished product rate in the time of can satisfying the color filter manufacturing strongly, and do not produce the color filter radiation sensitive resin composition that is further improved of " image retention ".

Summary of the invention

The object of the present invention is to provide and to form the color filter that " image retention " can not take place, the radiation sensitive resin composition that the dissolubility of highly sensitive, dry back in cleaning solvent is also high simultaneously etc. with high finished product rate.

Other purpose of the present invention is to provide the preparation method of above-mentioned radiation-ray sensitive composition.

Another purpose of the present invention is to provide color filter that contains radiation sensitive resin composition of the present invention and the color liquid crystal display device with this color filter.

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 realize by the radiation sensitive resin composition of first scheme, it is characterized in that: radiation sensitive resin composition contains (A) colorant, (B) alkali soluble resins, (C) polyfunctional monomer and (D) radiation-sensitive free radical generating agent, (B) alkali soluble resins at least one end of containing its polymer chain have following formula (i) or formula (ii) shown in the resin of group, (D) the radiation-sensitive free radical generating agent contains the compound shown in compound shown in the following formula (1) and/or the following formula (2):

[formula (i) and formula (ii) in, Z ¹And Z ²Monovalence aryl, carbon atom and the heteroatomic total atomicity of representing alkyl, the carbon number 6～20 of hydrogen atom, chlorine atom, carboxyl, cyano group, carbon number 1～20 independently of each other be 3～20 monovalence heterocyclic radical ,-OR ¹,-SR ¹,-OC (=O) R ¹,-N (R ¹) (R ²) ,-C (=O) OR ¹,-C (=O) N (R ¹) (R ²) ,-P (=O) (OR ¹) ₂,-P (=O) (R ¹) ₂Or have a univalent perssad of polymer chain, R ¹And R ²The alkyl of representing carbon number 1～18 independently of each other, the monovalence aryl of the thiazolinyl of carbon number 2～18, carbon number 6～18 or carbon atom and heteroatomic total atomicity are 3～18 monovalence heterocyclic radical, and the monovalence aryl of the alkyl of above-mentioned carbon number 1～20, carbon number 6～20, carbon atom and heteroatomic total atomicity are 3～20 monovalence heterocyclic radical, R ¹And R ²Can be substituted respectively];

[in formula (1) and the formula (2), each R ³The alkyl of representing carbon number 1～20 independently of each other, the naphthenic base of carbon number 3～8 or phenyl, each R ⁴With each R ⁵Represent independently of each other alkyl, the carbon number 3～8 of hydrogen atom, carbon number 1～20 naphthenic base, can substituted phenyl or the monovalence alicyclic group (except the above-mentioned naphthenic base) of carbon number 7～20, each R ⁶Represent the monovalence oxygen-containing heterocycle of carbon number 4～20, the monovalence nitrogen heterocycle of carbon number 4～20 or the monovalence sulfur heterocyclic ring base of carbon number 4～20 independently of each other, each R ⁷Represent the alkyl of hydrogen atom, carbon number 1～12, the naphthenic base of carbon number 3～8, the alkoxy of carbon number 1～12 or the cycloalkyloxy of carbon number 3～8 independently of each other, each n is 1～5 integer independently of each other, each m is 0～5 integer independently of each other, (n+m)≤5, p is 0～6 integer].

According to the present invention, above-mentioned purpose of the present invention and advantage realize by the preparation method of the above-mentioned radiation sensitive resin composition of second aspect, it is characterized in that: in solvent, in the presence of spreading agent, to pulverize as the pigment of (A) colorant, and mix, disperse, dispersible pigment dispersion and (B) alkali soluble resins of gained, (C) polyfunctional monomer and (D) radiation-sensitive free radical generating agent are mixed.

According to the present invention, above-mentioned purpose of the present invention and advantage realize that by the above-mentioned radiation sensitive resin composition of the third aspect said composition is used for color filter (hereinafter referred to as " color filter radiosensitivity resin combination ").

According to the present invention, above-mentioned purpose of the present invention and advantage realize that by the color filter of fourth aspect this color filter is formed with the radiosensitivity resin combination by color filter.

According to the present invention, above-mentioned purpose of the present invention and advantage realize that by the color liquid crystal display arrangement of the 5th aspect this device has above-mentioned color filter.

Embodiment

Below, the present invention is described in detail.

Radiation sensitive resin composition

-(A) colorant-

Colorant of the present invention is not particularly limited, but because color filter requires the colour developing (or barrier) and the thermotolerance of high-purity, high transmitance, so preferred pigments, preferred especially organic pigment or carbon black.

As above-mentioned organic pigment, can enumerate the compound that in pigment index (Color Index), is categorized as pigment (Pigment), specifically can enumerate the compound of following pigment index (C.I.) numbering.

C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 211;

C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, 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 61, C.I. pigment orange 64, C.I. pigment orange 68, C.I. pigment orange 70, C.I. pigment orange 71, C.I. pigment orange 72, C.I. pigment orange 73, C.I. pigment orange 74;

C.I. paratonere 1, C.I. paratonere 2, C.I. paratonere 5, C.I. paratonere 17, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 41, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, 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 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 209, C.I. pigment red 21 4, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 262, C.I. paratonere 264, C.I. paratonere 272;

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. 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. alizarol saphirol 80;

C.I. pigment Green 7, C.I. pigment green 36;

C.I. pigment brown 23, C.I. pigment brown 25;

C.I. pigment black 1, C.I. pigment black 7.

In these organic pigments, preferred C.I. pigment yellow 83, C.I. pigment yellow 13 9, C.I. pigment yellow 13 8, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. paratonere 177, C.I. paratonere 254, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment Violet 23, C.I. pigment blue 60 and C.I. alizarol saphirol 80.

Above-mentioned organic pigment can use separately or be use mixing two or more, and organic pigment and carbon black can also be mixed use.

Among the present invention, when the colorant of radiation-ray sensitive composition is pigment, be preferably as follows preparation: in solvent, in the presence of spreading agent, for example use ball mill, roller mill etc. this pigment is pulverized and to be mixed, disperse, make dispersible pigment dispersion, this dispersible pigment dispersion is mixed with (B) described later composition, (C) composition and solvent, other adjuvant described later of (D) composition and further interpolation as required.

Used spreading agent for example can use suitable spreading agents such as kation system, negative ion system, nonionic system or amphoteric dispersant when preparing above-mentioned dispersible pigment dispersion.Wherein, the compound (hereinafter referred to as " carbamates spreading agent ") that preferably has urethane bond.

Above-mentioned urethane bond is usually by formula R-NH-COO-R '] (R and R ' they are aliphatic, alicyclic or aromatic monovalence or multivalence organic group, this multivalence organic group further combines with group or other group that other has urethane bond) expression, can be present in the lipophilicity group and/or hydrophilic radical in the carbamates spreading agent, also may reside in the main chain and/or side chain of carbamates spreading agent, can have the urethane bond more than 1 in the carbamates spreading agent.When having the alkane key of urine more than 2 in the carbamates spreading agent, each urethane bond can be identical or different.

Above-mentioned carbamates spreading agent for example has: diisocyanate and/or triisocyanate and have the polyester of hydroxyl and/or have the reaction product of the polyester of hydroxyl at two ends at an end.

Above-mentioned diisocyanate for example has: benzene-1,3-diisocyanate, benzene-1, phenylene diisocyanates such as 4-diisocyanate; Toluene-2,4-diisocyanate, 4-diisocyanate, Toluene-2,4-diisocyanate, 5-diisocyanate, Toluene-2,4-diisocyanate, 6-diisocyanate, Toluene-3,4-dithiol, toluene diisocyanates such as 5-diisocyanate; 1,2-dimethylbenzene-3,5-diisocyanate, 1,2-dimethylbenzene-3,6-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, 1,3-dimethylbenzene-2,5-diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1,4-dimethylbenzene-2, other aromatic diisocyanates such as Xylene Diisocyanate such as 6-diisocyanate etc.

Above-mentioned triisocyanate for example has benzene-1,2,4-triisocyanate, benzene-1,2,5-triisocyanate, benzene-1,3, benzene triisocyanates such as 5-triisocyanate; Toluene-2,4-diisocyanate, 3,5-triisocyanate, Toluene-2,4-diisocyanate, 3,6-triisocyanate, Toluene-2,4-diisocyanate, 4,5-triisocyanate, Toluene-2,4-diisocyanate, 4, toluene triisocyanates such as 6-triisocyanate; 1,2-dimethylbenzene-3,4,5-triisocyanate, 1,2-dimethylbenzene-3,4,6-triisocyanate, 1,3-dimethylbenzene-2,4,5-triisocyanate, 1,3-dimethylbenzene-2,4,6-triisocyanate, 1,3-dimethylbenzene-4,5,6-triisocyanate, 1,4-dimethylbenzene-2,3,5-triisocyanate, 1,4-dimethylbenzene-2,3, other three aromatic isocyanates such as dimethylbenzene triisocyanates such as 6-triisocyanate etc.

These diisocyanate and triisocyanate can use separately respectively or be use mixing two or more.

An above-mentioned end has the polyester of hydroxyl and polyester that two ends have hydroxyl for example has: end or two ends have the polycaprolactone of hydroxyl, end or two ends and have the poly-valerolactone of hydroxyl, end or two ends and have end such as poly-propiolactone of hydroxyl or the polylactone that two ends have hydroxyl; End or two ends have that the polyethylene terephthalate of hydroxyl, end or two ends have end such as polybutylene terephthalate of hydroxyl or polycondensation that two ends have hydroxyl is a polyester etc.

These end has the polyester of hydroxyl and polyester that two ends have hydroxyl can use separately respectively or be use mixing two or more.

Polylactone and/or two ends that the preferred aromatic diisocyanates of carbamates spreading agent of the present invention and end have hydroxyl have the reaction product of the polylactone of hydroxyl, and polycaprolactone and/or two ends that preferred especially toluene diisocyanate and end have hydroxyl have the reaction product of the polycaprolactone of hydroxyl.

The object lesson of above-mentioned carbamates spreading agent has: the spreading agent of trade name Disperbyk 161, Disperbyk 170 (above by the production of PVC Star Network ケミ one (BYK) company) or EFKA (production of エ Off カ one ケミカ Le ズ PVC one Block イ (EFKA) company), デイスパロ Application series such as (nanmu originally change into (strain) company and produces).

The weight-average molecular weight of carbamates spreading agent of the present invention (Mw) is preferred 5,000～50,000, and more preferably 7,000～20,000.

Above-mentioned carbamates spreading agent can use separately or be use mixing two or more.

As spreading agent, in addition also preferably contain (methyl) acrylic acid series spreading agent of (being total to) polymkeric substance of (methyl) acrylic monomer.

The object lesson of above-mentioned (methyl) acrylic acid series spreading agent has: trade name Disperbyk2000, Disperbyk2001 (above by the production of PVC Star Network ケミ one (BYK) company) etc.

Above-mentioned (methyl) acrylic acid series spreading agent can use separately or be use mixing two or more.

During the dispersible pigment dispersion of preparation pigment or carbon black etc., with respect to 100 weight portion pigment, below preferred 100 weight portions of the consumption of spreading agent, more preferably 0.5～100 weight portion, further preferred 1～70 weight portion, preferred especially 10～50 weight portions.When the consumption of spreading agent surpasses 100 weight portions, can be detrimental to development etc.

In addition, the solvent that uses during dispersible pigment dispersion as preparation for example can be identical with the solvent enumerated in the fluid composition of radiation sensitive resin composition described later.

During the preparation dispersible pigment dispersion, with respect to 100 weight portion pigment, preferred 500～1,000 weight portion of the consumption of solvent, more preferably 700～900 weight portions.

During the preparation dispersible pigment dispersion, when using ball mill to be prepared, for example can use beaded glass about diameter 0.5～10mm or titanium dioxide pearl etc., will contain that the pigment mixed liquor of pigment, solvent and spreading agent is preferred to be mixed, disperse with coolings such as chilled waters on one side on one side.

At this moment, the filling rate of pearl is preferably 50～80% of grinding machine capacity.The injection rate IR of pigment mixed liquor is preferably about 20～50% of grinding machine capacity.Preferred 2～50 hours of processing time, more preferably 2～25 hours.

When using roller mill to prepare, for example can use triple-roller mill or two roller mills etc., Yi Bian the preferred one side of pigment mixed liquor is handled with coolings such as chilled waters.

At this moment, roller is preferably below the 10 μ m at interval, and shearing force is preferably 10 ⁸Dyn/ is about second.Preferred 2～50 hours of processing time, more preferably 2～25 hours.

-(B) alkali soluble resins-

Alkali soluble resins among the present invention contain at least one end at its polymer chain have following formula (i) or formula (ii) shown in the resin (hereinafter referred to as " resin (B) ") of group.

Formula (i) and formula (ii) in, Z ¹And Z ²Carbon number be that 1～20 alkyl for example has methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, n-octadecane base, n-eicosane base etc.

Z ¹And Z ²Carbon number be that 6～20 monovalence aryl for example has phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 9-anthryl, benzyl, phenethyl etc.

Z ¹And Z ²Carbon atom and heteroatomic total atomicity be that 3～20 monovalence heterocyclic radical for example has epoxy ethyl, the azacyclo-propyl group, the 2-furyl, the 3-furyl, the 2-tetrahydrofuran base, the 3-tetrahydrofuran base, the 1-pyrrole radicals, the 2-pyrrole radicals, the 3-pyrrole radicals, the 1-pyrrolidinyl, the 2-pyrrolidinyl, the 3-pyrrolidinyl, the 1-pyrazolyl, the 2-THP trtrahydropyranyl, the 3-THP trtrahydropyranyl, the 4-THP trtrahydropyranyl, the 2-thienyl, the 3-thienyl, the 4-thienyl, the 2-pyridine radicals, the 3-pyridine radicals, the 4-pyridine radicals, the 2-piperidyl, the 3-piperidyl, the 4-piperidyl, the 2-morpholinyl, morpholinyl etc.

Z ¹And Z ²In ,-OR ¹,-SR ¹,-C (=O) OR ¹,-N (R ¹) (R ²) ,-OC (=O) R ¹,-C (=O) N (R ¹) (R ²) ,-P (=O) (OR ¹) ₂Or-P (=O) (R ¹) ₂In R ¹And R ²Carbon number be that 1～18 alkyl, carbon number are that to add up to atomicity be that 3～18 monovalence heterocyclic radical for example has Z for 6～18 monovalence aryl or carbon atom and heteroatoms ¹And Z ²In the monovalence aryl of alkyl, carbon number 6～20 of cited carbon number 1～20 and carbon atom and heteroatoms to add up to atomicity be that carbon number in 3～20 the monovalence heterocyclic radical is the group below 18.

This R ¹And R ²Carbon number be that the thiazolinyl of 2-18 for example has vinyl, 1-propenyl, 2-propenyl, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl etc.

The monovalence aryl of the alkyl of above-mentioned carbon number 1～20, carbon number 6～20, carbon atom and heteroatomic total atomicity are 3～20 monovalence heterocyclic radical and R ¹And R ²Can be substituted, this substituting group for example can be from the chlorine atom; Carboxyl; Cyano group; At R ¹And R ²In monovalence aryl, carbon atom and the heteroatomic total atomicity of alkyl, carbon number 6～18 of the carbon number 1～18 enumerated be 3～18 the monovalence heterocyclic radical or the thiazolinyl of carbon number 2～18; With Z ¹And Z ²In enumerate-OR ¹,-SR ¹,-C (=O) OR ¹,-N (R ¹) (R ²) ,-OC (=O) R ¹,-C (=O) N (R ¹) (R ²) ,-P (=O) (OR ¹) ₂Or-P (=O) (R ¹) ₂Select in the same group, can in substituted each group, exist more than 1 or these substituting groups more than a kind.In substituted each group, the total atomicity when preferably adding up to carbon number and heterocyclic radical is no more than 20.

Z ¹And Z ²The univalent perssad with polymer chain for example have: by alpha-olefins such as ethene, propylene; Aromatic series such as styrene, α-Jia Jibenyixi olefinic compounds; Vinyl halides such as fluorothene, vinyl chloride, vinylidene chloride; Unsaturated alcohol such as vinyl alcohol, allyl alcohol; The ester of unsaturated alcohol such as vinyl acetate, allyl acetate; (methyl) acrylic acid, to unsaturated carboxylic acids such as vinyl benzoic acids; (methyl) acrylate such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate; (methyl) acrylamide, N, (methyl) acrylamides such as N-dimethyl (methyl) acrylamide; Unsaturated nitriles such as (methyl) vinyl cyanide, vinylidene dinitrile; In addition the univalent perssad with addition polymerization based polymer chain of more than one formation of unsaturated compounds such as butadiene, isoprene equiconjugate diene can also enumerate the univalent perssad of addition polymerization based polymer chains such as having polyethers, polyester, polyamide, polyimide or polycondensation based polymer chain etc.

Z in the formula (i) ¹With the Z of formula in (ii) ²Alkyl, carbon atom and the heteroatomic total atomicity of preferred respectively carbon number 1～20 be 3～20 monovalence heterocyclic radical ,-OR ¹,-N (R ¹) (R ²) etc., special preferable methyl, ethyl, 1-pyrrole radicals, 1-pyrazolyl, methoxyl, ethoxy, dimethylamino, diethylamino etc.

Above-mentioned resin (B) is so long as to the effect of (A) colorant performance bonding agent, and when making color filter, has solubility in the developer solution that uses, the preferred bases developer solution and get final product in development step, is not particularly limited.It for example can be the resin of addition polymerization system (pay and increase the weight of syzygy), addition polymerization system (heavily pay to add and be), polycondensation system etc., for example, it can be resin that has acidic functionality (for example carboxyl, acid anhydride, phenolic hydroxyl etc.) and/or alcohol hydroxyl group (below, these acidic functionalities and alcohol hydroxyl group are generically and collectively referred to as " alkali solubility functional group ") etc.

Among the present invention, preferred resin (B) for example has: the resin for preparing, has alkali solubility functional group through the polymerization of polymerizable unsaturated compound, more particularly, for example have: disulfide (hereinafter referred to as " disulfide (3) ") carries out the resin (hereinafter referred to as " resin (B1) ") that polymerization prepares, has alkali solubility functional group as molecular weight regulator with polymerizable unsaturated compound shown in the use following formula (3).

[in the formula (3), Z ¹And Z ²Respectively with formula (i) in Z ¹With the Z of formula in (ii) ²Implication is identical].

Among the present invention, preferred resin (B1) for example has: but have the multipolymer (hereinafter referred to as " alkali-soluble copolymer ") of the unsaturated compound of the polymerizable unsaturated compound of alkali solubility functional group and other copolymerization.

Particularly preferred alkali-soluble copolymer for example has: (b1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (below, they are generically and collectively referred to as " unsaturated compound (b1) ") with (b2) be selected from the aromatic series olefinic compounds; indenes; the maleimide that the N-position replaces; an end of polymer molecular chain has the macromonomer of (methyl) acryloyl group; esters of unsaturated carboxylic acids; the unsaturated carboxylic acid aminoalkyl ester; the unsaturated carboxylic acid ethylene oxidic ester; vinyl esters of carboxylic acids; unsaturated ethers; unsaturated amides; but the multipolymer (hereinafter referred to as " alkali-soluble copolymer (I) ") of the unsaturated compound of at least a copolymerization in the aliphatics conjugated diolefine (hereinafter referred to as " unsaturated compound (b2) ").

Unsaturated compound (b1) for example has:

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;

Unsaturated polybasic carboxylic acid more than 3 yuan or its acid anhydrides;

List [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;

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 compounds (b1), preferred especially (methyl) acrylic acid, mono succinate [2-(methyl) acryloxy ethyl] ester, ω-carboxyl polycaprolactone list (methyl) acrylate etc.

Above-mentioned unsaturated compound (b1) can use separately or be use mixing two or more.

Unsaturated compound (b2) for example has:

Styrene, α-Jia Jibenyixi, o-hydroxy ethene, between hydroxy styrenes, para hydroxybenzene ethene, adjacent hydroxyl-α-Jia Jibenyixi, between hydroxyl-α-Jia Jibenyixi, to hydroxyl-α-Jia Jibenyixi, p styrene sulfonic acid, adjacent vinyltoluene, between vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, between the vinyl benzyl methyl ether, to the vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, between the vinyl benzyl glycidyl ether, to aromatic series olefinic compounds such as vinyl benzyl glycidyl ethers; Indenes such as indenes, 1-methyl indenes;

N-(replacement) aryl maleimides such as aminomethyl phenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide between hydroxy phenyl maleimide, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, N-between N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, N-, or N-position substituted maleimide amine such as N-cyclohexyl maleimide;

An end of polymer molecular chains such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane has the macromonomer (being designated hereinafter simply as " macromonomer ") of (methyl) acryloxy;

(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, allyl methacrylate, (methyl) benzyl acrylate, (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 three ring [5.2.1.0 ^2,6] esters of unsaturated carboxylic acids such as decane-8-base ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) acrylic acid glyceride;

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 esters such as (methyl) glycidyl acrylate;

Vinyl esters of carboxylic acids such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;

Other unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;

Above-mentioned vinyl cyanide 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;

Aliphatic conjugated diene such as 1,3-butadiene, isoprene, chlorbutadiene, isoprene sulfonic acid etc.

In these unsaturated compounds (b2), optimization styrene, macromonomer, N-position substituted maleimide amine, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, list (methyl) acrylic acid glyceride etc., in the macromonomer, preferred especially polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, in the maleimide that the N-position replaces, preferred especially N-phenylmaleimide, N-cyclohexyl maleimide etc.

Above-mentioned unsaturated compound (b2) can use separately or be use mixing two or more.

Among the present invention, as preferred alkali-soluble copolymer (I), more specifically have: contain and be selected from (methyl) acrylic acid, at least a unsaturated compound (b1) of mono succinate [2-(methyl) propylene acyloxy ethyl] ester and ω-carboxyl polycaprolactone list (methyl) acrylate, with be selected from the polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl maleimide, (methyl) acrylic acid 2-hydroxy methacrylate, at least a unsaturated compound (b2) of (methyl) benzyl acrylate and single (methyl) acrylic acid glyceride according to circumstances can further contain and is selected from styrene, (methyl) methyl acrylate, the multipolymer (hereinafter referred to as " carboxy-containing copolymer (I-1) ") of the monomer mixture of at least a unsaturated compound (b2) of (methyl) allyl acrylate and (methyl) phenyl acrylate.

As the preferred multipolymer (I-1) that contains carboxyl, more specifically have: containing with (methyl) acrylic acid is necessary composition, the unsaturated compound (b1) that according to circumstances further contains mono succinate [2-(methyl) acryloxy ethyl] ester, with be selected from the polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl maleimide, (methyl) acrylic acid 2-hydroxy methacrylate, at least a kind of unsaturated compound (b2) of (methyl) benzyl acrylate and single (methyl) acrylic acid glyceride according to circumstances can further contain and is selected from styrene, (methyl) methyl acrylate, the multipolymer (hereinafter referred to as " carboxy-containing copolymer (I-2) ") of the monomer mixture of at least a unsaturated compound (b2) of (methyl) allyl acrylate and (methyl) phenyl acrylate.

The object lesson of carboxy-containing copolymer (I-2) has:

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate multipolymer,

(methyl) acrylic acid/polystyrene macromolecular monomer/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/poly-(methyl) methyl acrylate macromonomer/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride multipolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) phenyl acrylate multipolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/styrol copolymer,

(methyl) acrylic acid/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/polystyrene macromolecular monomer/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/poly-(methyl) methyl acrylate macromonomer/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/N-phenylmaleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/N-phenylmaleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/N-cyclohexyl maleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/N-cyclohexyl maleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride multipolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer etc.

The object lesson of carboxy-containing copolymer (I-1) has:

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/(methyl) acrylic acid 2-hydroxy methacrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/polystyrene macromolecular monomer/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/poly-(methyl) methyl acrylate macromonomer/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) phenyl acrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/(methyl) acrylic acid 2-hydroxy methacrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/polystyrene macromolecular monomer/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/poly-(methyl) methyl acrylate macromonomer/(methyl) acrylic acid 2-hydroxy methacrylate/(methyl) benzyl acrylate multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-phenylmaleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-phenylmaleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-cyclohexyl maleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/N-cyclohexyl maleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/mono succinate [2-(methyl) acryloxy ethyl] ester/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride multipolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/mono succinate [2-(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/mono succinate [2～(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/(methyl) allyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/mono succinate [2～(methyl) acryloxy ethyl] ester/N-cyclohexyl maleimide/(methyl) benzyl acrylate/styrol copolymer,

(methyl) acrylic acid/ω-carboxyl polycaprolactone list (methyl) acrylate/mono succinate [2～(methyl) acryloxy ethyl] ester/N-phenylmaleimide/(methyl) benzyl acrylate/list (methyl) acrylic acid glyceride/styrol copolymer etc.

The polymerization ratio of polymerizable unsaturated compound that has alkali solubility functional group in the resin (B1) is with respect to preferred 1～100 weight % of whole unsaturated compounds, further preferred 5～30 weight %, preferred especially 10～30 weight %.Be lower than 1 weight % if having the polymerization ratio of the polymerizable unsaturated compound of alkali solubility functional group, then the dissolubility of gained resin in alkaline developer has the tendency of reduction.

In the alkali-soluble copolymer, the copolymerization ratio of polymerizable unsaturated compound with alkali solubility functional group is with respect to preferred 1～40 weight % of whole unsaturated compounds, further preferred 5～30 weight %, preferred especially 10～30 weight %.Copolymerization ratio with polymerizable unsaturated compound of alkali solubility functional group for example really is lower than 1 weight %, then the dissolubility of gained alkali-soluble copolymer in alkaline developer has the tendency of reduction, and above 40 weight %, then the dissolubility of gained alkali-soluble copolymer in alkaline developer is too high, and pattern form etc. may be impaired.

Below, the polymerization for preparing resin (B1) is described.

Above-mentioned polymerization for example can followingly be implemented: in solvent, in the presence of radical polymerization initiator and disulfide (3), the polymerizable unsaturated compound that will constitute resin (B1) carries out polymerization.Thus, at terminal following formula (i) or the formula group shown in (ii) that imports of at least one of the polymer chain that generates.

The polymerization of the polymerizable unsaturated compound that carries out in the presence of disulfide (3) can also be adopted the active free radical polymerization form that has living radical at the growth end of polymer chain sometimes.

When the form of active free radical polymerization is adopted in above-mentioned polymerization; when use has the compound of functional group that possibility makes carboxyl isoreactivity free radical inactivation as polymerizable unsaturated compound; in order to make the terminal non-inactivation of growth; can be as required; for example the functional group in this unsaturated compound is protected the back polymerization by esterification etc.; carry out deprotection then, can obtain resin (B1) thus.

Above-mentioned radical polymerization initiator can suitably be selected according to the kind of employed polymerizable unsaturated compound, can use known radical polymerization initiator usually.For example have 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, 1, organic peroxides such as 1 '-two (tert-butyl peroxide) cyclohexane, tert-butyl peroxide neopentyl ester; Hydrogen peroxide; Contain the redox series initiators of these superoxide and reductive agent etc.

In these radical polymerization initiators, cause the angle of side reaction product to be considered from being difficult to produce oxygen etc., preferred especially 2,2 '-azoisobutyronitrile, 2,2 '-azo two azo-compounds such as (2, the 4-methyl pentane nitrile).

Above-mentioned radical polymerization initiator can use separately or be use mixing two or more.

Secondly, in the formula (3) of expression disulfide (3), Z ¹And Z ²The alkyl of the carbon number 1～20 that does not replace or replace for example can be and following formula (i) in Z ¹With the (ii) middle Z of formula ²The alkyl of the carbon number 1～20 that does not replace or replace in cited identical group, Z ¹And Z ²The carbon number that does not replace or replace be 6～20 monovalence aryl for example can be and following formula (i) in Z ¹With the (ii) middle Z of formula ²The monovalence aryl of the carbon number 6～20 that does not replace or replace in cited identical group.Z ¹And Z ²Not replacement or alternate c atoms and heteroatomic total atomicity be 3～20 monovalence heterocyclic radical for example can be and following formula (i) in Z ¹With the (ii) middle Z of formula ²The monovalence heterocyclic radical of the carbon atom that does not replace or replace and heteroatomic total atomicity 3-20 in cited identical group.Z ¹And Z ²-OR ¹,-SR ¹,-C (=O) OR ¹,-N (R ¹) (R ²) ,-OC (=O) R ¹,-C (=O) N (R ¹) (R ²) ,-P (=O) (OR ¹) ₂Or-P (=O) (R ¹) ₂For example can be and Z in following formula (i) ¹With the (ii) middle Z of formula ²The middle corresponding respectively same group of group that does not replace or replace.Z ¹And Z ²The univalent perssad with polymer chain for example can be Z with following formula (i) ¹With formula Z (ii) ²In have the same group of group cited in the univalent perssad of polymer chain.

In the formula (3), Z ¹And Z ²Respectively except the alkyl of carbon number 1～20, from consider the carbon atom and the Z of the thiocarbonyl group (C=S) in the special preferred formula (1) with the reactive aspect of polymerizable unsaturated compound ¹And Z ²In nitrogen-atoms or the group that forms of heteroatoms covalent bond such as oxygen atom, more particularly, preferred carbon atom and heteroatomic total atomicity be 3～20 monovalence heterocyclic radical ,-OR ¹,-N (R ¹) (R ²) etc., wherein special preferable methyl, ethyl, 1-pyrrole radicals, 1-pyrazolyl, methoxyl, ethoxy, dimethylamino, diethylamino etc.

Among the present invention, disulfide (3) can use separately or be use mixing two or more.

During above-mentioned polymerization, can and use more than one and disulfide (3) of other molecular weight regulator, for example α-Jia Jibenyixierjuwu, uncle's lauryl mercaptan etc.

The solvent that uses in the above-mentioned polymerization is not particularly limited, for example has: propylene-glycol monoalky lethers such as propylene glycol monomethyl ether, propylene glycol list ethylether;

(many) alkylene glycol monoalkyl ethers 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, dipropylene glycol monomethyl ether acetate, dipropylene glycol list ethylether acetic acid esters;

(many) alkylidene diol bisethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol Anaesthetie Ether;

Other ether such as tetrahydrofuran;

Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone;

Keto-alcohols such as diacetone alcohol (that is 4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one;

Lactic acid alkyl ester such as methyl lactate, ethyl lactate;

2-hydroxy-2-methyl ethyl propionate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic 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 hydrocarbons such as toluene, dimethylbenzene;

N-Methyl pyrrolidone, N, acid amides such as dinethylformamide, N,N-dimethylacetamide etc.

In these solvents, living radical non-inactivation during from active free radical polymerization, the dissolubility of each composition when making radiation sensitive resin composition, pigment-dispersing, aspects such as coating are considered, preferred propylene glycol monomethyl ether, the ethylene glycol monomethyl ether acetate, the diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, the dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, the dipropylene glycol dimethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl butyl propionic 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 be use mixing two or more.

In the above-mentioned polymerization, with respect to the whole unsaturated compounds of 100 weight portions, the preferred 0.1-50 weight portion of the consumption of radical polymerization initiator, more preferably 0.1-20 weight portion.

With respect to the whole unsaturated compounds of 100 weight portions, preferred 0.1～50 weight portion of the consumption of disulfide (1), more preferably 0.2～16 weight portion, preferred especially 0.4～8 weight portion.Disulfide (1) if consumption be lower than 0.1 weight portion, then the restriction effect of molecular weight and molecular weight distribution has and reduces tendency, and surpasses 50 weight portions, then may preferentially generate low molecular weight compositions.

With respect to the whole molecular weight regulators of 100 weight portions, below preferred 60 weight portions of the consumption of other molecular weight regulator, more preferably below 40 weight portions.The consumption of other molecular weight regulator surpasses 60 weight portions, and the effect that then the present invention expected may be impaired.

With respect to the whole unsaturated compounds of 100 weight portions, preferred 50～1,000 weight portion of the consumption of solvent, more preferably 100～500 weight portions.

Preferred 0～150 ℃ of polymerization temperature, more preferably 50～120 ℃, preferred 10 minutes～20 hours of polymerization time, more preferably 30 minutes～6 hours.

The Mw of resin (B) (Mw is the polystyrene conversion weight-average molecular weight of measuring by gel permeation chromatography (GPC)) is preferably 1,000～45,000, further preferred 3,000～20,000, preferred especially 4,000～10,000.

The Mw/Mn of resin (B) (Mn is the polystyrene conversion number-average molecular weight of measuring by gel permeation chromatography (GPC)) preferred 1～2.0, further preferred 1～1.4.

Have above-mentioned Mw, preferably further have the resin (B) of above-mentioned specific Mw/Mn by use, can obtain the radiation sensitive resin composition of development property excellence, can form pixel thus with clear pattern edge, simultaneously, during development, be difficult to take place residue, dirty version, residual film etc. on the substrate of unexposed portion He on the light shield layer, and the cleaning height of organic solvent, therefore, when making color filter, can not produce dry impurity, high finished product rate can be realized, and color filter " image retention " can be further effectively prevented.

Above-mentioned resin (B) can use separately or be use mixing two or more.

Among the present invention, can and use other alkali soluble resins and resin (B) more than a kind.

Among the present invention, with respect to 100 weight portions (A) colorant, preferred 10～1,000 weight portion of the consumption of resin (B), more preferably 20～500 weight portions.Resin (B) if consumption be lower than 10 weight portions, then for example alkali-developable reduces, or dirty version or residual film are taking place on the substrate of unexposed portion or on the light shield layer, and surpass 1,000 weight portion, then pigment concentration reduces relatively, is difficult to realize the aim colour concentration of film.

With respect to whole alkali soluble resinss, below the preferred 50 weight % of the usage ratio of other alkali soluble resins, more preferably below the 20 weight %.The usage ratio of other alkali soluble resins is if surpass 50 weight %, and the effect that then the present invention expected may be impaired.

-(C) polyfunctional monomer-

Polyfunctional monomer of the present invention is the monomer with 2 above polymerism unsaturated links.

Polyfunctional monomer for example has:

Two (methyl) acrylate of aklylene glycol such as ethylene glycol, propylene glycol;

Polyglycol more than the diglycol, two (methyl) acrylate of the poly alkylene glycol such as polypropylene glycol more than the dipropylene glycol;

Poly-(methyl) acrylate or their the dicarboxylic acid modifier of the polyvalent alcohols more than 3 yuan such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol; Oligomeric (methyl) acrylate of polyester, epoxy resin, carbamate resins, alkyd resin, organic siliconresin, spirane resin etc.;

Two ends have two (methyl) acrylate or three [2-(methyl) acryloxy ethyl] phosphate etc. that poly--1,3-butadiene of hydroxyl, polyisoprene that two ends have hydroxyl, two ends such as polycaprolactone that two ends have hydroxyl have the polymkeric substance of hydroxyl.

In these polyfunctional monomers, poly-(methyl) acrylate or their the dicarboxylic acid modifier of preferred polyvalent alcohol more than 3 yuan, specifically, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc., trimethylolpropane triacrylate particularly, the pixel intensity height of pentaerythritol triacrylate and dipentaerythritol acrylate, the flatness excellence on pixel surface, and be difficult to take place dirty version on the substrate of unexposed portion and on the light shield layer, residual film etc., therefore preferred.

Above-mentioned polyfunctional monomer can use separately or be use mixing two or more.

With respect to 100 weight portions (B) alkali soluble resins, the consumption of the polyfunctional monomer among the present invention is preferably 5～500 weight portions, more preferably 20～300 weight portions.At this moment, the polyfunctional monomer consumption is lower than 5 weight portions, and the intensity of pixel or surface smoothing have and reduce tendency, and if surpass 500 weight portions, then for example there is alkali-developable to reduce, perhaps easily on the substrate of unexposed portion or produce the tendency of dirty version, residual film etc. on the light shield layer.

Among the present invention, can be with polyfunctional monomer and monofunctional monomer with a polymerism unsaturated link and usefulness.

As above-mentioned monofunctional monomer, in above-mentioned alkali-soluble copolymer (I), the cited unsaturated monomer (b1) and unsaturated monomer (b2), can also be N-vinyl succinimide for example, the N-vinyl pyrrolidone, N-vinyl phthalimide, N-vinyl piperidones, N-vinyl-epsilon-caprolactams, the N-vinyl pyrrole, the N-ethenyl pyrrolidone, the N-vinyl imidazole, N-vinyl imidazole alkane, N-vinyl indoles, N-vinyl indoline, N-vinyl benzo imidazoles, the N-vinylcarbazole, N-vinyl piperidines, N-vinyl piperazine, N-vinyl morpholine, N-vinyl nitrogen-containing heterocycle compounds such as N-vinyl fen  piperazine; N-(methyl) acryloyl morpholine or as M-5300, the M-5400 of commercial goods, M-5600 (above is that East Asia synthetic (strain) produces) etc.

These monofunctional monomers can use separately or be use mixing two or more.

With respect to the total amount of polyfunctional monomer and monofunctional monomer, the usage ratio of monofunctional monomer is preferably below the 90 weight %, more preferably below the 50 weight %.If the usage ratio of monofunctional monomer surpasses 90 weight %, then the intensity of gained pixel or surface smoothing may reduce.

-(D) the radiation-sensitive free radical generating agent-

Radiation-sensitive free radical generating agent of the present invention (hereinafter referred to as " (D) free radical generating agent ") contains the compound (hereinafter referred to as " oxime type free radical generating agent (2) ") shown in compound shown in the following formula (1) (hereinafter referred to as " oxime type free radical generating agent (1) ") and/or the following formula (2), be the exposure by visible light, ultraviolet ray, far ultraviolet, electron ray, X ray isoradial, generation can cause above-mentioned (C) polyfunctional monomer and the free radical of the polymerization of the monofunctional monomer that according to circumstances uses.

In formula (1) and the formula (2), R ³The alkyl of carbon number 1～20 for example be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc.

R ³Carbon number be that 3～8 naphthenic base for example has cyclopentyl, cyclohexyl etc.

In formula (1) and (2), R ³For example preferable methyl, ethyl etc.

In formula (1) and the formula (2), R ⁴And R ⁵The alkyl of carbon number 1～20 methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc. are for example arranged.

R ⁴And R ⁵The naphthenic base of carbon number 3～8 cyclopentyl, cyclohexyl etc. are for example arranged.

R ⁴And R ⁵The substituting group of phenyl the alkyl of carbon numbers 1～6 such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl is for example arranged; The naphthenic base of carbon number such as cyclopentyl, cyclohexyl 3～6; The alkoxy of carbon numbers 1～6 such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy; The cycloalkyloxy of carbon number such as cyclopentyloxy, cyclohexyloxy 3～6; Phenyl; Halogen atoms such as fluorine atom, chlorine atom etc.

R ⁴And R ⁵The monovalence alicyclic group (except the above-mentioned naphthenic base) of carbon number 7～20 for example have: have 1-alkyl-cycloalk skeleton group, have dicyclo alkane skeleton group, have three cycloalkanes skeletons group, have the spirane skeleton group, have the terpenes skeleton group, have the group of diamantane skeleton etc.

In formula (1) and the formula (2), R ⁴And R ⁵Preferred hydrogen atom, methyl, ethyl etc.

In formula (1) and the formula (2), R ⁶The monovalence oxygen-containing heterocycle of carbon number 4～20, the monovalence sulfur heterocyclic ring base of the monovalence nitrogen heterocycle of carbon number 4～20 or carbon number 4～20 for example has tetrahydro-thienyl, the azacyclo-heptyl, dihydro azacyclo-heptyl, dioxolanyl, triazinyl, oxygen thia cyclohexyl, thiazolyl, the  diazine, two oxa-indanyls, thianaphthenyl (dithianaphthalenyl), furyl, thiophenyl, pyrrole radicals,  azoles base, different  azoles base, thiazolyl, isothiazolyl, pyrazolyl, the furazan base, pyranose, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, pyrrolinyl, morpholinyl, piperazinyl, quininuclidinyl, indyl, isoindolyl, benzofuranyl, the benzo thiophenyl, the indolizine base, the chromene base, quinolyl, isoquinolyl, purine radicals, quinazolyl, the cinnolines base, 2, the 3-phthalazinyl, pteridyl, carbazyl, acridinyl, phenanthridinyl, the thioxanthene base, phenazinyl, phenothiazinyl, fen thiophene  base, fen  piperazine base, thianthrene group, tetrahydrofuran base, THP trtrahydropyranyl etc.

In formula (1) and the formula (2), R ⁶Preferred tetrahydrofuran base, THP trtrahydropyranyl etc.

In formula (1) and the formula (2), R ⁷The alkyl of carbon number 1～12 methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl etc. are for example arranged.

R ⁷The naphthenic base of carbon number 3～8 cyclopentyl, cyclohexyl etc. are for example arranged.

R ⁷The alkoxy of carbon number 1～12 methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, n-pentyloxy, just own oxygen base, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy, n-undecane oxygen base, n-dodecane oxygen base etc. are for example arranged.

R ⁷The cycloalkyloxy of carbon number 3～8 cyclopentyloxy, cyclohexyloxy etc. are for example arranged.

In formula (1) and the formula (2), R ⁷Preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, methoxyl, ethoxy etc.

In formula (1) and the formula (2), n is preferred 1, and m is preferred 0,1 or 2, and is preferred especially 1, and p preferred 0,1 or 2, preferred especially 1.

The object lesson of oxime type free radical generating agent (1) has:

Ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime);

Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime);

Ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime);

Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1,3-two oxa-s penta cyclic group) benzoyl]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) etc.

These oxime type free radical generating agents (1) can use separately or be use mixing two or more.

The object lesson of oxime type free radical generating agent (2) has:

Ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime);

Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime);

Ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-2-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-3-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime);

Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl oxygen base benzoyl)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-benzoyl acetyl oxime); ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1,3-two oxa-s penta cyclic group) the methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) etc.

These oxime type free radical generating agents (2) can use separately or be use mixing two or more.

(D) of the present invention free radical generating agent preferably contains oxime type free radical generating agent (2) at least; especially preferably contain and be selected from ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl oxime); and ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2; 2-dimethyl-1,3-two oxa-s penta cyclic group) methoxybenzoyl base]-9.H.-carbazole-3-yl]-at least a among the 1-(O-acetyl oxime).

Among the present invention, (D) free radical generating agent can be with other radiation-sensitive free radical generating agent (being designated hereinafter simply as " other free radical generating agent ") and oxime type free radical generating agent (1) and oxime type free radical generating agent (2) and usefulness.

Other free radical generating agent can be oxime type free radical generating agent (1) and oxime type free radical generating agent (2) oxime type free radical generating agent (being designated hereinafter simply as " other oxime type free radical generating agent ") in addition.

The object lesson of other oxime type free radical generating agent has: 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), 1,2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime), 1,2-diacetyl-1-[4-(thiophenyl) phenyl]-2-(O-acetyl oxime), 1,2-octadione-1-[4-(methyl mercapto) phenyl]-2-(O-benzoyl oxime), 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-(4-toluyl oxime)) etc.

Wherein, preferred especially 1,2-octadione-1-[4-(thiophenyl) phenyl]-2-(O-benzoyl oxime).

Other free radical generating agent beyond other oxime type free radical generating agent for example has: have the bisglyoxaline compounds, benzoin compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, phosphine compound, compound in triazine class of the main skeleton shown at least a following formula (4-1), following formula (4-2) or the following formula (4-3) etc.

As above-mentioned bisglyoxaline compounds, 2,2 '-two (2-chlorphenyl)-4,4 ' for example arranged, 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.

-hydrogen donor-

Among the present invention, and with the bisglyoxaline compounds when (D) free radical generating agent, consider from can further improving the susceptibility aspect, preferably be used in combination with following hydrogen donor.

Here so-called " hydrogen donor " is meant the compound that hydrogen atom can be provided to the free radical that is produced by the bisglyoxaline compounds by exposure.

As above-mentioned hydrogen donor, the sulfur alcohol compound of preferred following definitions, the aminated compounds of following definitions.

Above-mentioned sulfur alcohol compound comprise with phenyl ring or heterocycle as parent nucleus, have more than 1, preferred 1～3, further preferred 1～2 compound (hereinafter referred to as " thio-alcohol hydrogen donor ") that is bonded directly to the sulfydryl on this parent nucleus.

Above-mentioned aminated compounds comprise with phenyl ring or heterocycle as parent nucleus, have more than 1, preferred 1～3, further preferred 1～2 compound (hereinafter referred to as " amine hydrogen donor ") that is bonded directly to the amino on this parent nucleus.

In addition, these hydrogen donors can have sulfydryl and amino simultaneously.

Below be described more specifically hydrogen donor.

The thio-alcohol hydrogen donor can have 1 above phenyl ring or heterocycle respectively, can also have phenyl ring and heterocycle the two.Have when these encircle more than 2, can form condensed ring.

When the thio-alcohol hydrogen donor had 2 above sulfydryls, as long as residual have at least 1 free sulfydryl, remaining 1 above sulfydryl can be by alkyl, aralkyl or aryl replacement.And then, as long as residual have at least 1 free sulfhydryl groups, can have structural unit by 2 sulphur atoms of divalent organic group bondings such as alkylidene or 2 sulphur atoms structural unit with the form bonding of disulfide bond.

And the thio-alcohol hydrogen donor can be in sulfydryl position in addition by carboxyl, replacement or unsubstituted alkoxy carbonyl, replacement or replacements such as unsubstituted phenoxy carbonyl, cyano group.

As the object lesson of such thio-alcohol hydrogen donor, can enumerate 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.

In these thio-alcohol hydrogen donors, preferred 2-mercaptobenzothiazole, 2-sulfydryl benzoxazol, preferred especially 2-mercaptobenzothiazole.

The amine hydrogen donor can have 1 above phenyl ring or heterocycle respectively, can also have phenyl ring and heterocycle the two.Have when these encircle more than 2, can form condensed ring.

And in the amine hydrogen donor, the amino more than 1 can be replaced by alkyl or substituted alkyl, and the position beyond amino also can be by carboxyl, replacement or unsubstituted alkoxy carbonyl, replacement or replacements such as unsubstituted phenoxy carbonyl, cyano group.

Object lesson as such amine hydrogen donor, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl 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.When not having the bisglyoxaline compounds, 4,4 '-two (dimethylamino) benzophenone or 4,4 '-two (diethylamino) benzophenone can be distinguished and brings into play the optical free radical action of evocating separately.

In the present invention, hydrogen donor can use separately, or is use mixing two or more.When the thio-alcohol hydrogen donor more than a kind and the amine hydrogen donor more than a kind were used in combination, formed dyed layer was difficult to come off from substrate when developing, and dyed layer intensity and susceptibility are also high, therefore preferred.

The object lesson of preferred thio-alcohol hydrogen donor and the combination of amine hydrogen donor has: 2-mercaptobenzothiazole/4,4 '-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 thio-alcohol hydrogen donor and amine hydrogen donor, the weight ratio of thio-alcohol hydrogen donor and amine hydrogen donor is preferably 1: 1～and 1: 4, more preferably 1: 1～1: 3.

Above-mentioned benzoin compounds for example has: benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, 2-benzoyl methyl benzoate etc.

Above-mentioned acetophenone compounds for example has: 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 2-methyl-(4-methyl mercapto phenyl)-2-morpholino base-1-propane-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino base phenyl) butane-1-ketone, the 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone etc.

Above-mentioned benzophenone compound for example has: 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone etc.

Above-mentioned α-cyclohexadione compounds for example has: diacetyl, dibenzoyl, toluyl carbamate etc.

Above-mentioned multinuclear quinones for example has: anthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1,4-naphthoquinones etc.

Above-mentioned xanthone compounds for example has: xanthone, thioxanthones, 2-clopenthixal ketone etc.

Above-mentioned phosphine compound for example has: two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc.

Above-mentioned compound in triazine class for example has: 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, compound shown in the following formula (5);

Compound shown in the following formula (6)

Deng compound with halogenated methyl etc.

Above-mentioned other free radical generating agent can use separately or be use mixing two or more.

Among the present invention, the usage ratio of other free radical generating agent is preferably below the 50 weight % of (D) free radical generating agent total amount, further preferred 1～30 weight %.If the usage ratio of other free radical generating agent surpasses 50 weight %, then the desired effect of the present invention may be impaired.

In the present invention, with respect to (C) polyfunctional monomer with total amount 100 weight portions of the monofunctional monomer that according to circumstances uses, (D) consumption of free radical generating agent is preferably 0.01～200 weight portion, and more preferably 1～120 weight portion is preferably 1～100 weight portion especially.If (D) consumption of free radical generating agent is lower than 0.01 weight portion, then exposure is solidified not enough, be difficult to obtain the pattern matrix of pattern of pixels or black matrix pattern alignment arrangements according to the rules, if and surpass 200 weight portions, then formed dyed layer comes off from substrate when developing easily, on the substrate of unexposed portion or dirty version, residual film etc. take place on the light shield layer easily.

Among the present invention, can also use crosslinked, the sensitizer of more than one sensitizers, curing accelerator or high-molecular optical with (D) free radical generating agent as required.

-other adjuvant-

Radiation sensitive resin composition of the present invention be with above-mentioned (A)～(D) composition as must composition, can further contain other adjuvant as required.

Above-mentioned other adjuvant for example has: filling agents such as glass, aluminium oxide; Macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl acrylate) class; Nonionic system, kation system, negative ion are surfactants such as surfactant; 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, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, applying promoter such as 3-sulfydryl propyl trimethoxy silicane; 2, ultraviolet light absorbers such as antioxidant such as 2-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; Anti-coagulants such as sodium polyacrylate etc.

The preparation of fluid composition

Radiation sensitive resin composition of the present invention can cooperate solvent usually, makes fluid composition.

As long as above-mentioned solvent can disperse or dissolve (A)～(D) composition or other additive component that constitutes radiation-ray sensitive composition, and do not react with these compositions, the volatility with appropriateness gets final product, and can suitably select to use.

Above-mentioned solvent for example has:

Propylene-glycol monoalky lethers such as propylene glycol monomethyl ether, propylene glycol list ethylether;

(many) aklylene glycols dialkyl ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol Anaesthetie Ether;

Other ether such as tetrahydrofuran;

Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone;

Lactic acid alkyl ester such as methyl lactate, ethyl lactate;

Aromatic hydrocarbons such as toluene, dimethylbenzene;

In these solvents, from dissolubility, pigment-dispersing, aspects such as coating are considered, preferred propylene glycol monomethyl ether, the ethylene glycol monomethyl ether acetate, the diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, the dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, the dipropylene glycol dimethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-methyl-3-methoxyl butyl propionic 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 be use mixing two or more.

Can also be with above-mentioned solvent and with high boiling solvents such as benzylisoeugenol, two n-hexyl ethers, 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.

These high boiling solvents can use separately or be use mixing two or more.

The consumption of solvent is not particularly limited, and considers from aspects such as the coating of the fluid composition that obtains, stability, preferably makes each composition total concentration of the solvent of removing said composition reach 5～50 weight %, especially preferably reaches the amount of 10～40 weight %.

The formation method of color filter

Below, the method for using radiation sensitive resin composition of the present invention to form color filter of the present invention is described.

The method that forms color filter comprises the step of following (1)～(4) at least.

(1) on substrate, forms the step of filming of color filter of the present invention with radiation sensitive resin composition;

(2) this at least a portion of filming is carried out step of exposing;

(3) this after will exposing filmed and carried out step of developing;

(4) after developing this filmed heat-treat the step of (hereinafter referred to as " back baking ").

Below these steps in sequence are described.

-(1) step-

At first, as required, on the surface of substrate, form light shield layer, to divide the part that will form pixel, coating for example contains the fluid composition of the color filter of red pigment with radiation-ray sensitive composition on this substrate, carries out preliminary drying then, make solvent evaporation, formation is filmed.

The substrate that uses in this step for example has glass, silicon, polycarbonate, polyester, aromatic poly amide, polyamidoimide, polyimide, polyethersulfone, in addition also has the ring-opening polymerization polymer of cyclic olefin or its hydride etc.

And, as required, can also implement to utilize suitable pre-service such as chemical reagent processing that silane coupling agent etc. carries out, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation to these substrates.

When coating fluid composition on the substrate, can adopt suitable coating processes such as rotary coating (spin coating), curtain coating coating, roller coat, gap nozzle coating.Even radiation sensitive resin composition of the present invention is after drying, the dissolubility in cleaning solvent is also high, is particularly suitable for the gap nozzle coating.

About 70～110 ℃, 2～4 minutes of the condition optimizations of preliminary drying.

Coating thickness calculates according to the thickness that removes after desolvating, preferred 0.1～10 μ m, more preferably 0.2～8.0 μ m, preferred especially 0.2～6.0 μ m.

-(2) step-

Then, formed at least a portion of filming is exposed.When a part of filming is exposed, preferably expose via photomask with suitable pattern.

The radioactive ray that use in this step can use for example 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 ²About.

-(3) step-

Filming after preferably using alkaline developer to exposure then developed, and the unexposed portion of filming is removed in dissolving, forms pattern.

As above-mentioned alkaline developer, preference such as 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 developer, can also add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in right amount.In addition, preferably after alkaline development, wash.

As developing method, can adopt spray development method, spray development method, immersion development method, paddle (liquid is contained り) development method etc.

Development conditions is preferably carried out about 5～300 seconds at normal temperatures.

-(4) step-

Then, carry out back baking, can obtain the substrate that pattern of pixels alignment arrangements according to the rules that the solidfied material by radiation sensitive resin composition forms obtains by filming after developing.

About 180～230 ℃, 20～40 minutes of the condition optimizations of back baking.

Preferred 0.5～5.0 μ m of the thickness of the pixel of above-mentioned formation, more preferably 1.5～3.0 μ m.

Further use the color filter that contains green or blue pigment each fluid composition of radiation-ray sensitive composition, carry out the step of above-mentioned (1)～(4) repeatedly, on same substrate, form green pixel pattern and blue pixel pattern thus, thereby can on substrate, form the dyed layer of red, green and blue trichromatic pattern of pixels alignment arrangements according to the rules.The formation of the pattern of pixels of all kinds among the present invention is not limited to said sequence in proper order.

-color filter-

Color filter of the present invention is formed with radiation sensitive resin composition by color filter of the present invention.

Color filter of the present invention 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 arrangement

Color liquid crystal display device of the present invention has color filter of the present invention.

Color liquid crystal display arrangement of the present invention can adopt appropriate configuration.For example can form color filter on the substrate different with substrate with the driving of having disposed thin film transistor (TFT) (TFT), driving accompanies liquid crystal layer with substrate and the substrate centre that has formed color filter and forms interposed structure.Further, can be dispose the substrate that is formed with color filter on the surface of driving with substrate of thin film transistor (TFT) (TFT), with the substrate that is formed with ITO (indium oxide of doped tin) electrode in the middle of accompany liquid crystal layer and form interposed structure.Back one structure has and can further improve aperture opening ratio, thereby can obtain to become clear, the advantage of high-precision liquid crystal display cells.

As mentioned above, radiation sensitive resin composition of the present invention can form the color filter that does not produce " image retention " with high yield rate, simultaneously highly sensitive, even under low exposure, on pattern of pixels edge crumbling or lateral erosion can not take place yet, in addition, even after the drying, dissolubility in cleaning solvent is also high, is suitable for the gap nozzle coating.

Embodiment

Below, enumerate embodiment and further specifically describe the present invention.But the present invention is not subjected to the qualification of following embodiment.

The Mw of the resin that following each synthesis example obtains and Mn measure by the gel permeation chromatography (GPC) of following specification.

Device: GPC-101 (clear and electrician's (strain) produces).

Post: with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 and usefulness.

Moving phase: the tetrahydrofuran that contains 0.5 weight % phosphoric acid.

Synthesis example 1

In the flask that has condenser pipe and stirring machine, add 10 weight portions 2,2 '-azoisobutyronitrile and 400 weight portion dipropylene glycol dimethyl ethers, then add 20 weight portion methacrylic acids, 31.2 weight portion N-phenylmaleimides, 30 weight portion benzyl methacrylates, 18.8 parts by weight of styrene and 10 weight portion α-Jia Jibenyixierjuwus (molecular weight regulator), carry out the nitrogen displacement, slowly stir on one side then, reaction solution is warming up to 80 ℃ on one side, keeps this temperature to carry out polymerization in 3 hours.Reaction solution is warming up to 100 ℃ then, further adds 2 weight portions 2,2 '-azoisobutyronitrile continued polymerization 1 hour again, obtained resin solution (solid component concentration=20.1 weight %).The Mw=5 of this resin, 000, Mw/Mn=3.6.With this resin as " resin (β-1) ".

Synthesis example 2

In the flask that has condenser pipe and stirring machine, add 2.5 weight portions 2,2 '-azoisobutyronitrile and 200 weight portion dipropylene glycol dimethyl ethers, then add 20 weight portion methacrylic acids, 31.2 weight portion N-phenylmaleimides, 30 weight portion benzyl methacrylates, 18.8 parts by weight of styrene and 3 weight portion α-Jia Jibenyixierjuwus (molecular weight regulator), carry out the nitrogen displacement, slowly stir on one side then, reaction solution is warming up to 80 ℃ on one side, keeps this temperature to carry out polymerization in 3 hours.Reaction solution is warming up to 100 ℃ then, further adds 0.5 weight portion 2,2 '-azoisobutyronitrile continued polymerization 1 hour again, obtained resin solution (solid component concentration=33.2 weight %).The Mw=14 of this resin, 000, Mw/Mn=2.1.With this resin as " resin (β-2) ".

Synthesis example 3

In the flask that has condenser pipe and stirring machine, add 3 weight portions 2,2 '-azoisobutyronitrile, 4 weight portion tetraethylthiuram disulfides (molecular weight regulator) and 200 weight portion dipropylene glycol dimethyl ethers, then add 20 weight portion methacrylic acids, 31.2 weight portion N-phenylmaleimides, 30 weight portion benzyl methacrylates and 18.8 parts by weight of styrene, carry out the nitrogen displacement, slowly stir on one side then, reaction solution is warming up to 80 ℃ on one side, keeps this temperature to carry out polymerization in 3 hours.Reaction solution is warming up to 100 ℃ then, further adds 2 weight portions 2,2 '-azoisobutyronitrile continued polymerization 1 hour again, obtained resin solution (solid component concentration=33.0 weight %).The Mw=5 of this resin, 000, Mw/Mn=1.7.With this resin as " resin (B-1) ".

Soak Test

Comparative example 1

To contain 40 weight portions as the C.I. paratonere 254 of (A) pigment and C.I. pigment yellow 13 9 according to the potpourri of 50/50 (weight ratio), 10 weight portions as the disperbyk2001 of spreading agent and 100 weight portions as the mixed liquor of the 3-ethoxyl ethyl propionate of solvent by ダイヤモ Application De Off アイ Application ミ Le (trade name, the ball mill (bead diameter 1.0mm) that Mitsubishi's マテリア Le (strain) is made) mixes dispersion 12 hours, the preparation dispersible pigment dispersion.

Then; with this dispersible pigment dispersion of 100 weight portions, 70 weight portions as the resin (β-1) of alkali soluble resins, 80 weight portions as the six acrylic acid dipentaerythritol ester of (C) polyfunctional monomer, 5 weight portions ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2 as (D) free radical generating agent; 2-dimethyl-1; 3-two oxa-s penta cyclic group) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime) and 1; 000 weight portion mixes as the propylene glycol methyl ether acetate of solvent, preparation fluid composition (r-1).

Then, use the spin coating instrument that this fluid composition (r-1) is coated on the surface and be formed with the SiO that prevents the sodion stripping ₂On the soda-lime glass substrate that the diameter of film is 4 inches, in 23 ℃ toilet, placed 12 hours then, drying, formation is filmed.

Then, this substrate was soaked 2 minutes the dissolving fully of filming in the 100cc propylene glycol methyl ether acetate.

Comparative example 2

Use 70 parts by weight resin (β-2) to replace resin (β-1), in addition be equipped with fluid composition (r-2) with legal system, on the soda-lime glass substrate, form and film with comparative example 1.

Then, this substrate was soaked 2 minutes in the 100cc propylene glycol methyl ether acetate, the dissolving fully of filming not can be observed a lot of foreign matters in the liquid.

Embodiment 1

Use 70 parts by weight resin (B-1) to replace resin (β-1), in addition be equipped with fluid composition (R-1) with legal system, on the soda-lime glass substrate, form and film with comparative example 1.

The evaluation of coating

Comparative example 3

The color filter that uses the gap nozzle mode is coated on the surface with the fluid composition (r-1) of preparation in the comparative example 1 and is formed with the SiO that prevents the sodion stripping with apparatus for coating TR63210S-CL (trade name, Tokyo are answered chemical industry (strain) manufacturing) ₂On the soda-lime glass substrate of film, placed at normal temperatures then 1 hour, drying, formation is filmed.

Then, with gap nozzle propylene glycol methyl ether acetate purge, once more by TR63210S-CL coating liquid composition (r-1) on new soda-lime glass substrate, form once more film on do not produce foreign matter.

Comparative example 4

Use the fluid composition (r-2) of preparation in the comparative example 2 to replace fluid composition (r-1), in addition similarly coating is estimated with comparative example 3, filming of forming once more upward produces foreign matter, can not form suitable filming.

Embodiment 2

Use the fluid composition (R-1) of preparation among the embodiment 1 to replace fluid composition (r-1), remove through similarly coating is estimated with comparative example 3, do not produce foreign matter on the filming of formation once more.

The evaluation of voltage retention

Comparative example 5

Be coated on the soda-lime glass substrate with the fluid composition (r-1) of spin coating instrument with preparation in the comparative example 1, this soda-lime glass substrate is formed with the SiO that prevents the sodion stripping from the teeth outwards ₂Film, and according to the rules the shape evaporation ITO (indium-tin oxide alloy) electrode.Preliminary drying 10 minutes in 90 ℃ toilet then, forming thickness is filming of 2.0 μ m.

Use high-pressure sodium lamp then, not via photomask with 5,000J/m ²Exposure the irradiation of filming is contained the radioactive ray of 365nm, 405nm and each wavelength of 436nm.Then this substrate was soaked 1 minute in 23 ℃ the developer solution that contains 0.04 weight % potassium hydroxide aqueous solution, develop, then with ultrapure water washing and air-dry, further baking after carrying out 30 minutes under 250 ℃, make curing of coating, on substrate, form red pixel.The thickness of this pixel is 1.60 μ m.

Then, with formed the substrate of this pixel and an evaporation substrate of ITO electrode of regulation shape fit with the sealant that has mixed the 0.8mm beaded glass, inject liquid crystal MLC6608 (trade name, メ Le Network are made) then, the preparation liquid crystal cell.

Then, liquid crystal cell is put into 60 ℃ thermostat layer, measure the voltage retention that the VHR-1A of system type (trade name, Dongyang テ Network ニカ (strain) make) is measured liquid crystal cell by the liquid crystal voltage conservation rate.This moment apply the rectangular wave that voltage is 5.5V, the mensuration frequency is 60Hz.Here, voltage retention is meant the value of (voltage that applies when beginning to apply liquid crystal cell potential difference (PD)/0 behind 16.7 milliseconds of the voltages millisecond).Voltage retention is 45% as a result.

If the voltage retention of liquid crystal cell is below 90%, then liquid crystal cell can't will apply the time that voltage keeps 16.7 milliseconds of prescribed levels, and liquid crystal aligning can't be fully carried out in expression.Therefore, " image retention " takes place in liquid crystal indicator with color filter that use fluid composition (r-1) forms easily.

Comparative example 6

Use the fluid composition (r-2) of preparation in the comparative example 2 to replace fluid composition (r-1), in addition similarly prepare liquid crystal cell with comparative example 5, measure voltage retention, the result is 92%.Therefore, that the possibility of " image retention " takes place is low for the liquid crystal indicator with color filter that use fluid composition (r-2) forms.

Embodiment 3

Use the fluid composition (R-1) of preparation among the embodiment 1 to replace fluid composition (r-1), in addition similarly prepare liquid crystal cell with comparative example 5, measure voltage retention, the result is 92%.Therefore, that the possibility of " image retention " takes place is low for the liquid crystal indicator with color filter that use fluid composition (R-1) forms.

The evaluation of sensitivity

Comparative example 7

(D) free radical generating agent of the fluid composition (r-1) of preparation in the comparative example 1 is changed to 50 weight portion 2-methyl-(4-methyl mercapto phenyl)-2-morpholino base-1-propane-1-ketone, in addition similarly prepare fluid composition (r-3) with comparative example 1.

Then, with the spin coating instrument fluid composition (r-3) is coated on the surface and is formed with the SiO that prevents the sodion stripping ₂On the soda-lime glass substrate of film, preliminary drying 2 minutes on 90 ℃ hot plate then, forming thickness is filming of 1.7 μ m.

Then, substrate is cooled to room temperature, uses high-pressure sodium lamp, via photomask (slit width 30 μ m), the ultraviolet ray that the irradiation of filming is comprised 365nm, 405nm and each wavelength of 436nm exposes, and the exposure of this moment is 400J/m ²Then substrate was soaked 1 minute in 23 ℃ 0.04 weight % potassium hydroxide aqueous solution, develop, then with ultrapure water washing and air-dry.Baking after carrying out 30 minutes under 220 ℃ the cleaning oven then forms red striated pattern of pixels and arranges the picture element matrix that forms on substrate.At this moment, by the picture element matrix on the observation by light microscope substrate, the edge of visible pixels pattern has damaged.In addition, observe the cross section of pattern of pixels, visible lateral erosion by scanning electron microscope (SEM).

Comparative example 8

(D) free radical generating agent of the fluid composition (r-2) of preparation in the comparative example 2 is changed to 50 weight portion 2-methyl-(4-methyl mercapto phenyl)-2-morpholino base-1-propane-1-ketone, in addition similarly prepare fluid composition (r-4) with comparative example 2.

Then, use fluid composition (r-4) to replace fluid composition (r-3), in addition similarly on substrate, form red striated pattern of pixels and arrange the picture element matrix that forms with comparative example 7.At this moment, with the picture element matrix on the observation by light microscope substrate, the edge of visible pixels pattern has damaged.In addition, observe the cross section of pattern of pixels, visible lateral erosion by scanning electron microscope (SEM).

Embodiment 4

Use the fluid composition (R-1) of preparation among the embodiment 1 to replace fluid composition (r-3), in addition similarly on substrate, form red striated pattern of pixels and arrange the picture element matrix that forms with comparative example 7.At this moment, with the picture element matrix on the observation by light microscope substrate, the edge of pattern of pixels is not seen damaged.In addition, observe the cross section of pattern of pixels, do not see lateral erosion by scanning electron microscope (SEM).

With the main composition composition of above evaluation result with each radiation sensitive resin composition, summary sheet is shown in table 1 and the table 2.Here, the radiation sensitive resin composition that uses red pigment is estimated, used the radiation-ray sensitive composition of the pigment of blueness, green, yellow or black also to obtain same result.

In table 1 and the table 2, each free radical generating agent is as described below.

D-1: ethyl ketone-1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-two oxa-s penta cyclic group) methoxybenzoyl base]-9.H.-carbazole-3-yl]-1-(O-acetyl oxime)

δ-1:2-methyl-(4-methyl mercapto phenyl)-2-morpholino base-1-propane-1-ketone

Table 1

	Resin	Free radical generating agent	Soak test	Coating	Voltage retention
	Resin	Free radical generating agent	Soak test	Coating	Voltage retention	Comparative example 1/3/5	β-1	D-1	○	○	×(45％)
Comparative example 2/4/6	β-2	D-1	* (generation foreign matter)	* (generation foreign matter)	○(92％)	Comparative example 1/3/5	β-1	D-1	○	○	×(45％)
Comparative example 2/4/6	β-2	D-1	* (generation foreign matter)	* (generation foreign matter)	○(92％)	Embodiment 1/2/3	B-1	D-1	○	○	○(92％)

Table 2

	Resin	Free radical generating agent	Sensitivity
	Resin	Free radical generating agent	Sensitivity	Comparative example 7	β-1	δ-1	×
Comparative example 8	β-2	δ-1	×	Comparative example 7	β-1	δ-1	×
Comparative example 8	β-2	δ-1	×	Embodiment 4	B-1	D-1	○

In table 1 and the table 2, in the evaluation of soak test, coating evaluation, voltage retention and the evaluation of sensitivity, zero expression is good, and * expression is bad.

Claims

1. radiation sensitive resin composition, it contains (A) colorant, (B) alkali soluble resins, (C) polyfunctional monomer and (D) radiation-sensitive free radical generating agent, wherein (B) alkali soluble resins at least one end of comprising polymer chain have following formula (i) or formula (ii) shown in the resin of group, (D) the radiation-sensitive free radical generating agent comprises the compound shown in compound shown in the following formula (1) and/or the following formula (2):

Formula (i) and formula (ii) in, Z ¹And Z ²Monovalence aryl, carbon atom and the heteroatomic total atomicity of representing alkyl, the carbon number 6～20 of hydrogen atom, chlorine atom, carboxyl, cyano group, carbon number 1～20 independently of each other be 3～20 monovalence heterocyclic radical ,-OR ¹,-SR ¹,-OC (=O) R ¹,-N (R ¹) (R ²) ,-C (=O) OR ¹,-C (=O) N (R ¹) (R ²) ,-P (=O) (OR ¹) ₂,-P (=O) (R ¹) ₂Or have a univalent perssad of polymer chain, R ¹And R ²The alkyl of representing carbon number 1～18 independently of each other, the monovalence aryl of the thiazolinyl of carbon number 2～18, carbon number 6～18 or carbon atom and heteroatomic total atomicity are 3～18 monovalence heterocyclic radical, and the monovalence aryl of the alkyl of above-mentioned carbon number 1～20, carbon number 6～20, carbon atom and heteroatomic total atomicity are 3～20 monovalence heterocyclic radical, R ¹And R ²Can be substituted respectively;

In formula (1) and the formula (2), each R ³The alkyl of representing carbon number 1～20 independently of each other, the naphthenic base of carbon number 3～8 or phenyl, each R ⁴With each R ⁵Represent independently of each other alkyl, the carbon number 3～8 of hydrogen atom, carbon number 1～20 naphthenic base, can substituted phenyl or the monovalence alicyclic group (except the above-mentioned naphthenic base) of carbon number 7～20, each R ⁶Represent the monovalence oxygen-containing heterocycle of carbon number 4～20, the monovalence nitrogen heterocycle of carbon number 4～20 or the monovalence sulfur heterocyclic ring base of carbon number 4～20 independently of each other, each R ⁷Represent the alkyl of hydrogen atom, carbon number 1～12, the naphthenic base of carbon number 3～8, the alkoxy of carbon number 1～12 or the cycloalkyloxy of carbon number 3～8 independently of each other, each n is 1～5 integer independently of each other, each m is 0～5 integer independently of each other, (n+m)≤5, p is 0～6 integer.

2. the described radiation sensitive resin composition of claim 1, wherein, Z ¹And Z ²Be respectively carbon atom and heteroatomic total atomicity be 3～20 monovalence heterocyclic radical ,-OR ¹Or-N (R ¹) (R ²) (R wherein ¹And R ²With the Z in the formula (i) ¹With the Z of formula in (ii) ²In each R ¹And R ²Implication is identical).

3. claim 1 or 2 described radiation sensitive resin compositions, wherein, (B) alkali soluble resins is to use the disulfide shown in the following formula (3) as molecular weight regulator, the resin that the polymerizable unsaturated compound polymerization is prepared:

In the formula (3), Z ¹And Z ²Respectively with formula (i) in Z ¹With the Z of formula in (ii) ²Implication is identical.

4. the described radiation sensitive resin composition of claim 3, wherein, during preparation (B) alkali soluble resins, the polymerization of polymerizable unsaturated compound is an active free radical polymerization.

5. any described radiation sensitive resin composition in the claim 1～4; wherein, (B) alkali soluble resins is to contain (b1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides and (b2) be selected from the aromatic series olefinic compounds; indenes; the maleimide that the N-position replaces; the macromonomer that has (methyl) acryloyl group at an end of polymer molecular chain; esters of unsaturated carboxylic acids; the unsaturated carboxylic acid aminoalkyl ester; the unsaturated carboxylic acid ethylene oxidic ester; vinyl esters of carboxylic acids; unsaturated ethers; unsaturated amides; but the multipolymer of the monomer mixture of the unsaturated compound of at least a copolymerization in the aliphatics conjugated diolefine.

6. any described radiation sensitive resin composition in the claim 1～5, wherein, (B) Mw of alkali soluble resins (Mw is the polystyrene conversion weight-average molecular weight of measuring by gel permeation chromatography (GPC)) is 1,000～45,000.

7. any described radiation sensitive resin composition in the claim 1～6, wherein, (B) Mw/Mn of alkali soluble resins (Mn is the polystyrene conversion number-average molecular weight of measuring by gel permeation chromatography (GPC)) is 1～2.0.

8. the preparation method of any described radiation sensitive resin composition in the claim 1～7, it is characterized in that: in solvent, in the presence of spreading agent, to pulverize and mix, disperse as the pigment of (A) colorant, dispersible pigment dispersion and (B) alkali soluble resins of gained, (C) polyfunctional monomer and (D) radiation-sensitive free radical generating agent will be mixed.

9. any described radiation sensitive resin composition in the claim 1～7, said composition is used for color filter.

10. color filter, this color filter is formed by the described radiation sensitive resin composition of claim 9.

11. color liquid crystal display arrangement, this color liquid crystal display arrangement have the described color filter of claim 10.