CN102445847A

CN102445847A - Colored photosensitive resin composition, color filter and liquid crystal display

Info

Publication number: CN102445847A
Application number: CN2011103054476A
Authority: CN
Inventors: 权凤一; 姜台洙; 金在成
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2010-10-07
Filing date: 2011-09-30
Publication date: 2012-05-09
Also published as: KR20120035995A; JP2012083753A; TW201216001A

Abstract

The present invention provides a colored photosensitive resin composition, a color filter and a liquid crystal display. The colored photosensitive resin composition has excellent intermiscibility with dye and can be used for manufacturing the color filter with improved reliability. The colored photosensitive resin composition of the invention comprises alkali-soluble resin, colorant with pigment or dye, photopolymerizable compound, photopolymerization initiating agent and dissolvent, wherein, the alkali-soluble resin comprises a repetition unit which is represented by a formula and is derived from an acid anhydride (A1). In the formula, R1 and R2 represent hydrogen atom, aliphatic or aromatic hydrocarbon which comprises or does not comprise hetero atom and has 1-12 carbon atoms independently from each other.

Description

Photosensitive composition, color filter and liquid crystal indicator

Technical field

The present invention relates to a kind of photosensitive composition, color filter and liquid crystal indicator, thereby relate in particular to and excellent photosensitive composition, the color filter that uses said photosensitive composition and the liquid crystal indicator that possesses color filter that can produce the color filter that reliability improved of the intermiscibility of dyestuff.

Background technology

Color filter (color filter) is built in; Like complementary burning film semiconductor (compl ementary metal oxide semiconductor; CMOS) or charge coupled cell (charge coupled device; CCD) in the colour phhotograpy device of this imageing sensor, can be used in and obtain coloured image practically, in addition; Also be widely used among other imaging apparatus, plasma display device (PDP), liquid crystal indicator (LCD), Field Emission Display (FED) and the active display (LED) etc., and its range of application enlarges rapidly.Especially, the most proximad the purposes of LCD is more extensive, thus, aspect the tone that reproduces LCD, can think that color filter is one of most important parts.

This color filter contains the photosensitive composition of colorant with utilization and the method that forms desirable colored pattern is made.Particularly; Make through carrying out following a series of process repeatedly, that is, on substrate, form the coating of forming by photosensitive composition; And on formed coating, form pattern and make public and develop, heat again and make it thermmohardening.

Use pigment with as colorant all the time, still recently, the trial of the dyestuff of bright and excellent heat resistance occurred using.When only using dyestuff as colorant, owing to can all embody the characteristic of the excellence of dyestuff, thus be preferred, still relatively poor with the intermiscibility of other compositions of composition because dyestuff compares with pigment, so it uses and goes up existence and limit.Thereby, though attempted using the method for colorant that pigment and dyestuff all be used as the mixed type of colorant, up to the present, the problem that is occurred when also the solution use contains the colorant of dyestuff fully.

Contain the photosensitive composition of dyestuff and when making color filter when adopting, owing to can when forming dyed layer, produce foreign matter with the deficiency of the solubility of employed material as colorant.In addition, when making color filter,, thereby there is the problem of peeling off frequent generation of formed pattern when implementing developing procedure through alkaline developer because developing powder is slow and the deficiency of sensitivity.Therefore, need the exploitation photosensitive composition, said photosensitive composition is suitable for, and can eliminate when use contains the colorant of dyestuff or when dyestuff used as colorant separately in the photo-mask process of existing problem.

Summary of the invention

Invent problem to be solved

The present invention makes in order to address the above problem; The objective of the invention is to, thereby provide a kind of intermiscibility of and dyestuff excellent photosensitive composition, the color filter that uses said photosensitive composition and the liquid crystal indicator that possesses color filter that can produce the color filter that reliability improved.

Solve the method for problem

Be used to realize that photosensitive composition above-mentioned purpose, according to an aspect of the present invention does; Contain: the photosensitive composition of alkali soluble resin, the colorant that contains pigment or dyestuff, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent; Wherein, Alkali soluble resin has, by following formula 1 repetitive represented, that induce from acid anhydrides (A1).

[Chemical formula 1]

(formula 1)

In the formula, R ₁And R ₂Represent hydrogen atom independently of one another, comprise or do not comprise heteroatomic carbon number and be 1～12 aliphatics or aromatic hydrocarbon.

Alkali soluble resin can for; The multipolymer of acid anhydrides (A1) and compound (A2); Perhaps; Make the compound of said multipolymer and compound (A3) be combined into the functional group that can combine with acid anhydrides (A1), wherein, said compound (A2) have can with the unsaturated link of acid anhydrides (A1) copolymerization.

With respect to the total molal quantity of whole repetitives of alkali soluble resin, the ratio of the repetitive of inducing from acid anhydrides (A1) can be molar percentage 2～80%.

With respect to the total molal quantity of whole repetitives of alkali soluble resin, the ratio of the repetitive of inducing from the compound (A2) with the unsaturated link that can combine with acid anhydrides (A1) can be molar percentage 2～95%.

With respect to the molal quantity of the repetitive of (A1) in the alkali soluble resin, have the ratio of the repetitive that the compound (A3) of the functional group that can combine with acid anhydrides (A1) induces, can be molar percentage 2～95%.

Have can with the compound (A2) of the unsaturated link of acid anhydrides (A1) copolymerization can for; Be selected from unsaturated carboxylic acid, unsaturated carboxylic acid do not replace or substituted alkyl ester compound, have the substituent unsaturated carboxylic ester compound of ester ring type, glycols the saturated mono carbonate, have the substituent unsaturated carboxylic ester compound, aromatic ethenyl compound, the vinyl esters of carboxylic acids that comprise aromatic ring, at least a in vinyl cyanide based compound and the maleimide compound.

Have can with the compound (A2) of the unsaturated link of acid anhydrides (A1) copolymerization can for; Be selected from: methyl (methyl) acrylic ester, ethyl (methyl) acrylic ester, butyl (methyl) acrylic ester, aminoethyl (methyl) acrylic ester, cyclopentyl (methyl) acrylic ester, cyclohexyl (methyl) acrylic ester, methylcyclohexyl (methyl) acrylic ester, suberyl (methyl) acrylic ester, ring octyl group (methyl) acrylic ester, menthyl (methyl) acrylic ester, cyclopentenyl (methyl) acrylic ester, cyclohexenyl group (methyl) acrylic ester, cycloheptenyl (methyl) acrylic ester, cyclooctene base (methyl) acrylic ester, menthadiene base (methyl) acrylic ester, isobornyl (methyl) acrylic ester, pinane base (methyl) acrylic ester, adamantyl (methyl) acrylic ester, norborny (methyl) acrylic ester, firpene base (methyl) acrylic ester, glycidyl (methyl) acrylic ester, 3; 4-epoxycyclohexyl (methyl) acrylic ester, 3, at least a compound in 4-epoxycyclohexyl methyl (methyl) acrylic ester, methyl glycidyl (methyl) acrylic ester, polyalkylene glycol monoalkyl (methyl) acrylic ester, benzyl (methyl) acrylic ester, phenoxy group (methyl) acrylic ester, styrene, AMS, vinyltoluene, vinyl acetate, vinyl propionate, (methyl) vinyl cyanide, α-Lv Daibingxijing, N-cyclohexyl maleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and the fumaric acid.

Have the functional group that can combine with acid anhydrides (A1) compound (A3) can for, be selected from: at least a in hydroxyethyl (methyl) acrylic ester, 2-hydroxypropyl (methyl) acrylic ester, 2-hydroxyl-3-chloropropyl (methyl) acrylic ester, 4-hydroxyl butyl (methyl) acrylic ester, acyl group octyloxy-2-hydroxypropyl (methyl) acrylic ester (acyloctyloxy-2-hydroxypropyl (meth) acrylate), 2-hydroxyl-3-benzene oxygen propyl group acrylic ester and 3-(the propenyloxy group)-2-hydroxypropyl methyl acrylic ester.

The weight average molecular weight with polystyrene conversion of alkali soluble resin is preferably 3,000～100,000.

According to another side of the present invention, a kind of color filter that comprises dyed layer is provided, wherein, said dyed layer contains with good grounds photosensitive composition of the present invention.

According to another side of the present invention, a kind of liquid crystal indicator that possesses according to color filter of the present invention is provided.

The effect of invention

According to photosensitive composition of the present invention; Because the constituent of composition is with excellent as the intermiscibility of the pigment of colorant or dyestuff; Even thereby contain pigment simultaneously and the dyestuff developing powder is also very fast; And sensitivity and cohesive are excellent, therefore in developing procedure, peeling off of pattern can not taken place, and solvent resistance is excellent.

In addition, because photosensitive composition according to the present invention is excellent with respect to the drug resistance of employed solvent in the preparation section of color filter, and takes care of excellent in stability for a long time, thereby has the effect that reliability improves.

Description of drawings

Fig. 1 a is the figure of the making step of expression color filter involved in the present invention.

Fig. 1 b is the figure of the making step of continuation expression color filter involved in the present invention.

Fig. 1 c is the figure of the making step of continuation expression color filter involved in the present invention.

Fig. 2 a is the stereographic map of expression color filter involved in the present invention.

Fig. 2 b is for continuing the stereographic map of expression color filter involved in the present invention.

Symbol description

1: substrate;

2: formed colored pattern;

3: dyed layer;

3 ': colored pattern;

10: photomask;

11: glass plate;

12: light shield layer;

13: the transmittance section;

20: light.

Embodiment

Below, with reference to accompanying drawing embodiment of the present invention is described.But embodiment of the present invention can be deformed into multiple mode, and scope of the present invention is not limited to the embodiment of following explanation.Embodiment of the present invention is in order more completely to describe and to provide those skilled in the art.

Photosensitive composition according to the present invention comprises: alkali soluble resin (A), the colorant (B) that contains pigment or dyestuff, optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E).Below, each composition that is comprised in the photosensitive composition of the present invention is described in more detail.

Alkali soluble resin (A)

In photosensitive composition of the present invention; The alkali soluble resin (A) that adds as the bond resin; Generally have the effect reactivity and the alkali dissolution property that show, and play a role as the dispersion medium of colorant (B) according to light or heat.

Alkali soluble resin (A) has, from the repetitive of being induced by the acid anhydrides (A1) of following formula 1 expression.

[Chemical formula 1]

(formula 1)

Alkali soluble resin (A) does, have the compound of polymerization (also comprising copolymerization) formula 1 and the repetitive that obtains, unsaturated group contains resin.That is, the compound of formula 1 is perhaps to constitute alkali soluble resin (A) with other compound polymerizations separately.With the not restriction of condition of other compound of the compound co-polymerized of formula 1, and all comprise in the present invention.

Can do, the co-polymer of acid anhydrides (A1) and compound (A2) according to alkali soluble resin of the present invention (A), wherein, said compound (A2) have can with the unsaturated link of acid anhydrides (A1) copolymerization.In addition; According to alkali soluble resin of the present invention (A) also can be through making acid anhydrides (A1) and compound (A2) multipolymer with have can and the compound (A3) of the functional group that combines of acid anhydrides (A1) combine to obtain; Wherein, said compound (A2) have can with the unsaturated link of acid anhydrides (A1) copolymerization.

In one embodiment of the invention; Have can with the compound (A2) of the unsaturated link of acid anhydrides (A1) copolymerization can for, be selected from: unsaturated carboxylic acid, unsaturated carboxylic acid do not replace or substituted alkyl ester compound, unsaturated monocarboxylic ester compound thing, substituent unsaturated carboxylic ester compound, aromatic ethenyl compound, vinyl esters of carboxylic acids, vinyl cyanide based compound and maleimide compound with aromatic ring with the substituent unsaturated carboxylic ester compound of ester ring type, glycols at least a.

Have and to adopt with the compound (A2) of the unsaturated link of acid anhydrides (A1) copolymerization; Be selected from: methyl (methyl) acrylic ester, ethyl (methyl) acrylic ester, butyl (methyl) acrylic ester, aminoethyl (methyl) acrylic ester, cyclopentyl (methyl) acrylic ester, cyclohexyl (methyl) acrylic ester, methylcyclohexyl (methyl) acrylic ester, suberyl (methyl) acrylic ester, ring octyl group (methyl) acrylic ester, menthyl (methyl) acrylic ester, cyclopentenyl (methyl) acrylic ester, cyclohexenyl group (methyl) acrylic ester, cycloheptenyl (methyl) acrylic ester, cyclooctene base (methyl) acrylic ester, menthadiene base (methyl) acrylic ester, isobornyl (methyl) acrylic ester, pinane base (methyl) acrylic ester, adamantyl (methyl) acrylic ester, norborny (methyl) acrylic ester, firpene base (methyl) acrylic ester, glycidyl (methyl) acrylic ester, 3; 4-epoxycyclohexyl (methyl) acrylic ester, 3, at least a compound in 4-epoxycyclohexyl methyl (methyl) acrylic ester, methyl glycidyl (methyl) acrylic ester, polyalkylene glycol monoalkyl (methyl) acrylic ester, benzyl (methyl) acrylic ester, phenoxy group (methyl) acrylic ester, styrene, AMS, vinyltoluene, vinyl acetate, vinyl propionate, (methyl) vinyl cyanide, α-Lv Daibingxijing, N-cyclohexyl maleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and the fumaric acid.

In one embodiment of the invention; With (A1) and (A2) copolymerization and in the multipolymer (situation of carrying out copolymerization with the mode that also contains (A1) to (A2) monomer in addition also belongs to the present invention) that obtains; About respectively by the ratio of (A1) and the component unit of (A2) inducing; The molal quantity that amounts to respect to whole component units of alkali soluble resin; The ratio of the component unit of being induced by acid anhydrides (A1) can be 2～80 moles of %, and can be 2～95 moles of % by the ratio with the component unit that can induce with the compound (A2) of the unsaturated link of acid anhydrides (A1) copolymerization.

That is, when alkali soluble resin (A) is (A1) and multipolymer (A2), be preferably respectively, with in the scope of 2～80 moles of % and 2～95 moles of % and involved by (A1) and the component unit of (A2) inducing.In addition, when alkali soluble resin (A) is (A1) and multipolymer (A2), further be preferably, with in the scope of 5～70 moles of % and 5～80 moles of % and involved by (A1) and the component unit of (A2) inducing.When component unit is respectively in said scope,, therefore can obtain excellent multipolymer because development property, solubility and thermotolerance are balanced.

Compound (A3) with the functional group that can combine with acid anhydrides (A1) can be to alkali soluble resin (A) additional optical hardening or thermosetting.

Compound (A3) with the functional group that can combine with acid anhydrides (A1) can adopt, and is selected from least a in hydroxyethyl (methyl) acrylic ester, 2-hydroxypropyl (methyl) acrylic ester, 2-hydroxyl-3-chloropropyl (methyl) acrylic ester, 4-hydroxyl butyl (methyl) acrylic ester, acyl group octyloxy-2-hydroxypropyl (methyl) acrylic ester (acyloctyloxy-2-hydroxypropyl (meth) acrylate), 2-hydroxyl-3-benzene oxygen propyl group acrylic ester and 3-(the propenyloxy group)-2-hydroxypropyl methyl acrylic ester.Above-claimed cpd can use separately, perhaps two or more combinations used, but is not limited to these compounds.

The ratio of the component unit of inducing by compound (A3) with the functional group that can combine with acid anhydrides (A1), in alkali soluble resin, with respect to the formation of (A1) repeatedly the molal quantity of unit can be 2～95 moles of %.10～90 moles of % more preferably.When the ratio of components of (A3) is in this scope, owing to can access sufficient photo-curable, Thermocurable, thus have susceptibility and pencil hardness concurrently, and reliability is excellent, so be preferred.

In one embodiment of the invention, when alkali soluble resin (A) is (A1) and multipolymer (A2), can prepare as follows.

In the flask that possesses stirrer, thermometer, reflux condensing tube, tap funnel and gas introduction tube, with respect to (A1) and total amount (A2), import the solvent (E) of 0.5～20 times of amount, and atmosphere in the flask is become nitrogen from air displacement with weight standard.Thereafter; Solvent (E) is warming up to 40～140 ℃; Afterwards; To measure by weight the solvent (E) of 0～20 times of amount of standard and the polymerization initiator of azoisobutyronitrile (azobisisobutyronitrile) and t-butyl peroxy 2-ethylhexyl carbonic ester etc. to the total of (A2) with respect to (A1); Add with 0.1～10 mole of % with respect to (A1) and total molal quantity (A2), and the solution that is obtained (stirring and dissolving under room temperature or heating) is dripped in said flask with 0.1～8 hour through tap funnel, and under 40～140 ℃, stirred 1～10 hour again.

In addition; Can the part or all of amount of polymerization initiator be dropped in the flask; Also can be with in (A1) and a part (A2) or the whole amount input flask; In addition, in order to control molecular weight and molecular weight distribution, can AMS dimer or sulfhydryl compound be used as chain mobile agent.The use amount of AMS dimer or sulfhydryl compound, measuring by weight with respect to (A1) and total (A2), standard is 0.005～5%.

In one embodiment of the invention; (A) does when alkali soluble resin; Under the situation of the compound that has formed having combined on (A1) and the multipolymer (A2) to have the compound (A3) of the functional group that can combine, can prepare as follows with acid anhydrides (A1).

Atmosphere in the flask is become air from nitrogen replacement; With respect to the repetitive of inducing by (A1) and multipolymer (A2); 3～95 moles of % of mole fraction (A3) put into flask, as the reaction catalyst of acid anhydrides and alcohol, for example with the dimethylamino methyl methyl acrylate with respect to the total amount of (A1) to (A3) and put into flask with weight standard 0.01～5%; And forbid agent as polymerization; For example p-dihydroxy-benzene is put into flask with respect to the total amount of (A1) to (A3) with weight standard 0.001～5%, and 60～130 ℃ of reactions 1～10 hour down, thereby can make (A1) and multipolymer (A2) and (A3) react.Polymerizing condition is considered preparation equipment and the thermal value that produces owing to polymerization etc., also can be to regulate input method and temperature of reaction with above-mentioned different mode.

Alkali soluble resin (A) can be 3,000～100,000 with the weight average molecular weight of polystyrene conversion, is preferably 5,000～50,000.When the weight average molecular weight of alkali soluble resin (A) 3,000～100, in the time of in 000 scope, reduce owing to when developing, will be difficult to produce film, and the apparent recessiveness of non-pixel portion has the tendency that becomes good when developing, so be preferred.

The molecular weight distribution of alkali soluble resin (A) [weight average molecular weight (Mw)/number mean molecular weight (Mn)] is preferably 1.5～6.0, and more preferably 1.8～4.0.If the molecular weight distribution of alkali soluble resin (A) is 1.5～6.0, then show recessive excellent, so be preferred.

In photosensitive composition, the content of alkali soluble resin (A) is generally percentage by weight 5～90% with respect to all solids composition of photosensitive composition, is preferably in the scope of percentage by weight 10～70%.When the content of alkali soluble resin (A) is weight percentage 5～90% the time; Because it is abundant to the dissolubility of developer solution; Therefore on the substrate of non-pixel portion, be difficult to produce the development residue, and, reduce owing to when developing, be difficult to produce the film of the pixel portion of exposure portion; Therefore the development property of non-pixel portion has the tendency that becomes good, so be preferred.

Colorant (B)

Employed colorant (B) can comprise pigment or dyestuff in photosensitive composition of the present invention, perhaps can comprise pigment and dyestuff simultaneously.

Pigment can use normally used in the art organic pigment or inorganic pigment, and can use individually separately, perhaps two or more the combination is used.

Can implement following the processing to pigment as required; That is, plastic resin treatment, utilize the surface treatment of the pigment derivative imported acidic groups or basic group etc., the grafting to surface of pigments implemented through macromolecular compound etc. is handled, the micronize implemented through sulfuric acid micronize method etc. is handled, perhaps be used to remove passing through development treatment that organic solvent and water etc. implement, passing through the removal processing of the ionic impurity that ion exchange process etc. implements etc. of impurity.

Pigment can adopt the various pigment that are used to ink-jet ink etc.; Particularly; Can list water-soluble azo pigment, insoluble azo colour, phthalocyanine color, quinacridine ketone pigment, isoindolyl pigment, isoindoline pigment, perylene dye, pyrene ketone pigment, triazine dioxin pigment, anthraquinone pigment, DIANTHRAQUINONE (dianthraquinonyl) pigment, anthracene pyrimidine pigment, anthanthrone (anthanthrone) pigment, indanthrone (indanthrone) pigment, yellow anthrone pigment, pyrene anthrone (pyranthrone) pigment and diketo-pyrrolo pyrrole pigments etc.

In addition; As inorganic pigment, can use metallic compound, particularly like metal oxide or bimetallic salt complex; Can enumerate out the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black etc. or composite metal oxide etc.

Especially; As pigment; Specifically can use the compound of on pigment, classifying by color index (The society of Dyers and Colourists publication); More specifically, can use pigment, but might not be defined in these pigment like following color index (C.I.) number.

C.I. pigment yellow 20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173,180 and 185

C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242,254,255 and 264

C.I. pigment violet 14,19,23,29,32,33,36,37 and 38

C.I. pigment blue 15 (15:3,15:4,15:6 etc.), 21,28,60,64 and 76

C.I. pigment Green 7,10,15,25,36,47 and 58

C.I. pigment brown 28

C.I. pigment black 1 and 7 etc.

In the illustrative C.I. pigment of institute, the preferred use is selected from: C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment orange 38, C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. pigment Violet 23, C.I. pigment blue 15: 6, the pigment in C.I. pigment Green 7, C.I. pigment green 36 or the C.I. naphthol green 58.

The dispersible pigment dispersion that pigment optimization uses its particle diameter to disperse equably.An example of the method for disperseing equably as the particle diameter that is used to make pigment can enumerate making it contain pigment dispersing agent and carry out method of dispersion treatment etc.According to this method, can obtain pigment and be scattered in the dispersible pigment dispersion under the state in the solution equably.

Can enumerate out as pigment dispersing agent, for example, the surfactant of kation system, negative ion system, nonionic system, both sexes, polyester system and polyamines system etc. etc., and these materials can use separately, or two or more combinations are used.

Concrete example as surfactant; Have: polyoxyethylene alkyl ether class, polyxyethylated phenylate class, polyethylene glycol di class, Span class, fatty acid sex change polyesters, tertiary amine sex change polyurethanes and polyethyleneimine: amine etc.; In addition; Can enumerate out by trade name; KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), POLYFLOW (common prosperity society chemistry (strain) system), EFTOP (ト one ケ system プロダ Network Star corporate system), MEGAFAC (Japanese ink chemical industry (strain) system), Flourad (Sumitomo 3M (strain) system), Asahi guard, Surflon (Asahi Glass (strain) system), SOLSPERSE (Jie Likang (strain) system), EFKA (EFKA chemical company system) and PB821 (aginomoto (strain) system) etc.

Pigment dispersing agent uses smaller or equal to 1 weight portion with respect to pigment 1 weight portion usually, preferably uses 0.05～0.5 weight portion.When pigment dispersing agent uses with aforesaid content, can obtain pigment uniform grading, that disperse, so be preferred.

Dyestuff then has no particular limits as long as organic solvent is had dissolubility.Preferred use following dyestuff, that is, said dyestuff has the dissolubility to organic solvent, and can guarantee the reliability to the dissolubility of alkaline developer and thermotolerance, solvent resistance etc.

As dyestuff; Can use the acid dyes with acidic groups, the acid dyes that are selected from sulfonic acid or carboxylic acid etc. and the material in the salt that contains nitrogen compound, the sulfamido of acid dyes etc. and their derivant; In addition, can also use azo system, xanthene system, the acid dyes of phthalocyanine dye system and their derivant.

Preferred dyestuff can be enumerated out, the compound of in color index table (The Society of Dyers and Colourists publication), classifying with dyestuff, the known dyestuff of perhaps in dyeing notes (look dyes corporate system), being put down in writing.

About the concrete example of dyestuff, can enumerate out as the C.I. solvent dye,

C.I. the weld of solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162 etc.;

C.I. the orchil of solvent red 45,49,122,125,130 etc.;

C.I.

solvent orange

2,7,11,15,26,56 etc. orange;

C.I. the blue dyes of solvent blue 35,37,59,67 etc.; And,

C.I. the green colouring material of solvent green 1,3,4,5,7,28,29,32,33,34,35 etc.

In addition, can enumerate out as the C.I. acid dyes,

C.I. Indian yellow 1; 3; 7; 9; 11; 17; 23; 25; 29; 34; 36; 38; 40; 42; 54; 65; 72; 73; 76; 79; 98; 99; 111; 112; 113; 114; 116; 119; 123; 128; 134; 135; 138; 139; 140; 144; 150; 155; 157; 160; 161; 163; 168; 169; 172; 177; 178; 179; 184; 190; 193; 196; 197; 199; 202; 203; 204; 205; 207; 212; 214; 220; 221; 228; 230; 232; 235; 238; 240; 242; 243; The weld of 251 grades;

C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80; 87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,182,183,198,206,211,215; 216,217,227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,295,308,312,315,316,339,341,345,346,349,382,383,394,401,412,417,418,422,426 etc. orchil;

C.I. the orange of

acid orange

6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173 grades;

C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92; 96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340 etc. blue dyes;

C.I. acid violet 6B, 7,9,17,19 etc. cudbear; And

C.I. green colouring material of acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109 etc. etc.

In addition, can enumerate out as the C.I. direct dyes,

C.I. direct yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141 etc. weld;

C.I. direct red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250 etc. orchil;

C.I. the orange of direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107 etc.;

C.I. direct blue 38; 44; 57; 70; 77; 80; 81; 84; 85; 86; 90; 93; 94; 95; 97; 98; 99; 100; 101; 106; 107; 108; 109; 113; 114; 115; 117; 119; 137; 149; 150; 153; 155; 156; 158; 159; 160; 161; 162; 163; 164; 166; 167; 170; 171; 172; 173; 188; 189; 190; 192; 193; 194; 196; 198; 199; 200; 207; 209; 210; 212; 213; 214; 222; 228; 229; 237; 238; 242; 243; 244; 245; 247; 248; 250; 251; 252; 256; 257; 259; 260; 268; 274; 275; The blue dyes of 293 grades;

C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104 etc. cudbear; And

C.I. green colouring material of direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82 etc. etc.

As the C.I. mordant dye, can enumerate out,

C.I. the weld of mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65 etc.;

C.I. the orchil of

mordant rouge

1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95 etc.;

C.I. the orange of

mordant dyeing orange

3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47,48 etc.;

C.I. the blue dyes of mordant dyeing blue 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83,84 etc.;

C.I. the purple C.I.1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53 of mordant dyeing, 58 etc. cudbear; And

C.I. green colouring material of

viridon

1,3,4,5,10,15,19,26,29,33,34,35,41,43,53 etc. etc.

The content of the dyestuff in the colorant (B) is with respect to the solid constituent in the colorant (B); Preferably contain in the scope of percentage by weight 0.5～80% in weight fraction; More preferably contain percentage by weight 0.5～60%, especially preferably contain percentage by weight 1～50%.Owing to when the content of the dyestuff in the colorant (B) is in this scope, can prevent that forming the back at pattern causes problem that dyestuff is gushed out, the reliability reduction because of organic solvent, so be preferred.

The content of colorant (B) contains percentage by weight 5～70% with respect to the solid constituent in the photosensitive composition in weight fraction, preferably contains percentage by weight 10～50%.Since when colorant (B) contains percentage by weight 5～70% with standard, also can be abundant even form the colour saturation of film pixel, thus the development property of the non-pixel portions when developing can not reduce, so be difficult to produce residue, so be preferred.

In the present invention, the content of the total solid composition in the photosensitive composition is meant, the total content of the composition of the remnants from photosensitive composition behind the removal solvent.

Optical polymerism compound (C)

Optical polymerism compound (C) so long as can through after the photopolymerization stated and polymeric compounds; Then there is not special qualification; But be preferably multifunctional gathering property of the light compound that gathering property of simple function light compound, difunctionality light gathering property compound or trifunctional are above.

Concrete example as monofunctional monomer; Can enumerate out; Nonyl phenolic group carbitol acrylic ester (nonylphenyl carbitolacrylate); 2-hydroxyl-3-benzene oxygen propyl group acrylic ester, 2-ethylhexyl carbitol acrylic ester (2-ethylhexylcarbitolacrylate), 2-hydroxy ethyl methacrylate, N-vinyl pyrrolidone etc.; And, can enumerate out Aronix M-101 (East Asia Synesis Company system), KAYARAD TC-110S (Japanese chemical drug corporate system) and Viscoat158 (Osaka organic chemistry industrial group system) etc. as commercially available product.

Concrete example as 2 functional monomers; Can enumerate out; 1; Two (acryloyl group ethoxy) ethers of 6-hexanediol two (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, bisphenol-A and 3-methyl pentanediol two (methyl) acrylic ester etc., and commercially available product has: Aronix M-210, M-1100,1200 (East Asia Synesis Company system), KAYARAD HDDA (Japanese chemical drug corporate system); Viscoat 260 (Osaka organic chemistry industrial group system), AH-600, AT-600, UA-306H (chemical company of common prosperity society system) etc.

Concrete example as the above multifunctional optical polymerism compound of 3 officials ability; Can enumerate out; Trimethylolpropane tris (methyl) acrylic ester, ethoxylated trimethylolpropane three (methyl) acrylic ester, propoxylation trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol pentaerythrite penta (methyl) acrylic ester, own (methyl) acrylic ester of ethoxylation dipentaerythritol, own (methyl) acrylic ester of propoxylation dipentaerythritol and oneself (methyl) acrylic ester of dipentaerythritol etc.; Commercially available product has: Aronix M-309, TO-1382 (East Asia Synesis Company system), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Japanese chemical drug corporate system) etc.

In illustrative optical polymerism compound (C), (methyl) acrylic ester that trifunctional is above and the polymerism of carbamate (methyl) acrylic ester are more excellent, and can improve on the intensity this point especially preferred.In addition, illustrative optical polymerism compound (C) can use separately, perhaps two or more combinations used.

The content of optical polymerism compound (C) is with respect to the solid constituent in the photosensitive composition, preferably contains the scope of percentage by weight 5～45% in weight fraction, especially preferably contains the scope of percentage by weight 7～45%.When the optical polymerism compound (C) in the scope that contains percentage by weight 5～45%, because pixel portions intensity and flatness become well, so be preferred.

Photoepolymerizationinitiater initiater (C)

Photoepolymerizationinitiater initiater (D) so long as material that can polymerization light polymerizable compound (C) then have no particular limits.Especially; Photoepolymerizationinitiater initiater (D) considers that from viewpoints such as polymerization property, efficiency of initiation, absorbing wavelength, operability, prices preferred the use is selected from least a compound in acetophenone based compound, benzophenone based compound, triaizine compounds, bisglyoxaline based compound, oxime compound and the thioxanthones based compound.

Concrete example as the acetophenone based compound; Can enumerate out diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone and 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholino base phenyl) butane-1-ketone etc.

As the benzophenone based compound, can enumerate out, for example benzophenone, O-benzoyl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfide, 3; 3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone; 2,4,6-tri-methyl benzophenone etc.

As the concrete example of triaizine compounds, can enumerate out, 2, two (the trichloromethyl)-6-(4-methoxyphenyl)-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-piperonyls-1 of 4-; 3,5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl] of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-[2-(furans-2-yl) vinyl]-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl] of 4--1,3,5-triazines and 2; Two (the trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl] of 4--1,3,5-triazines etc.

As the concrete example of bisglyoxaline based compound, can enumerate out 2,2 '-two (2-Chloro-O-Phenyl)-4,4 ', 5; 5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2; 2 '-two (2-Chloro-O-Phenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-two (2-Chloro-O-Phenyl)-4,4 '; 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline, 2, two (2, the 6-dichlorophenyl)-4,4 ', 5 of 2-; 5 '-tetraphenyl-1,2 '-bisglyoxaline, or 4,4 ', 5, the phenyl of 5 positions are by the substituted imidazolium compounds of carboxyl alkoxy etc.Wherein, preferably use 2,2 '-two (2-Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2; 2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline and 2,2-two (2; The 6-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.

As the concrete example of oxime compound, can enumerate out O-ethoxy carboxyl-alpha-oxo-imido grpup-1-phenyl-propane-1-ketone etc., the OXE01 of BASP corporate system, OXE02 are arranged as commercially available product.

As the thioxanthones based compound, can enumerate out 2-isopropyl thioxanthone, 2 for example, 4-diethyl thioxanthone, 2,4-two clopenthixal ketones and 1-chloro-4-propoxyl group thioxanthones etc.

In addition, only otherwise influence effect of the present invention, then can also and with other Photoepolymerizationinitiater initiaters etc.As other Photoepolymerizationinitiater initiaters, can enumerate out, for example benzoin based compound and anthracene based compound etc., these compounds can use separately, also can two or more combinations be used.

As the benzoin based compound, can enumerate out, for example benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether and benzoin isobutyl ether etc.

As the alkoxy anthracene based compound, can enumerate out, for example 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-ethoxy anthracene and 2-ethyl-9,10-ethoxy anthracene etc.

In addition, can also enumerate out 2; 4; 6-trimethylbenzene formyl diphenyl phosphine oxide, 10-butyl-2-chloro-acridine ketone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, or luxuriant titanium (titanocene) compound etc. are with as Photoepolymerizationinitiater initiater.

Also can in Photoepolymerizationinitiater initiater (D), the combined light polymerization cause auxiliary agent and use.Because when in Photoepolymerizationinitiater initiater (D) and with photopolymerization, causing auxiliary agent, the photosensitive polymer combination that contains these compounds will further improve sensitivity, thereby improve productivity, so be preferred.

Causing auxiliary agent as photopolymerization can preferably use, and for example is selected from amines, carboxylic acid compound and contains at least a compound in the organic sulfur compound of mercapto.

As amine compound; Can enumerate out; Fatty amine compound, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, benzoic acid 2-dimethylamino ethyl ester, N like triethanolamine, methyldiethanolamine and triisopropanolamine etc.; N-dimethyl-p-toluidine, 4; The aromatic amines compound of 4 '-two (dimethylamino) benzophenone (common name, Michler's keton) and 4,4 '-two (lignocaine) benzophenone etc.As amine compound, preferably use aromatic amines compound.

Concrete example as carboxylic acid compound; Can enumerate out the heteroaromatic acetate class of phenyl thioacetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, Dimethoxyphenyl thioacetic acid, chlorphenyl thioacetic acid (Chlorophenylthio acetic acid), dichlorophenyl thioacetic acid (dichlorophenyl thioacetic acid), N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid (Naphtylthio acetic acid), N-naphthyl glycocoll and naphthoxy acetic acid (Naphtoxy acetic acid) etc.

As the concrete example of organosulfur compound, can enumerate out 2-mercaptobenzothiazole, 1 with mercapto; Two (the 3-sulfydryl butoxy) butane, 1,3 of 4-, 5-three (3-sulfydryl butoxyethyl group)-1; 3,5-triazine-2,4; 6 (1H, 3H, 5H)-triketone, trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-sulfydryl butyric ester), pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester) and tetraethylene glycol two (3-mercaptopropionic acid ester) etc.

About the use amount of Photoepolymerizationinitiater initiater (D), be standard with the solid constituent, and with respect to alkali soluble resin (A) and optical polymerism compound (C) total amount in weight fraction, operating weight number percent 0.1～40%, preferred operating weight number percent 1～30%.Because when Photoepolymerizationinitiater initiater (D) is in the scope of percentage by weight 0.1～40%; Thereby photosensitive composition is shortened the time shutter by high sensitivityization; Therefore throughput rate improves and can keep high resolving power, thus be preferred, and; Owing to the flatness on the surface of the intensity of the pixel portions of using said composition to form and this pixel portions is good, so be preferred.

In addition; When using photopolymerization to cause auxiliary agent; Cause the use amount of auxiliary agent about photopolymerization; With the solid constituent standard and with respect to the total amount of alkali soluble resin (A) and optical polymerism compound (C), in weight fraction operating weight number percent 0.1～50%, preferred operating weight number percent 1～40%.Because when photopolymerization causes auxiliary agent in the scope of percentage by weight 0.1～50% time, the sensitivity of photosensitive composition further improves, and use said composition and the productivity raising of the color filter that forms, so be preferred.

Solvent (E)

Solvent (E) is so long as the material of other compositions that can disperse or dissolve photosensitive composition effectively and comprised, and then its kind has no particular limits.Especially, be preferably ethers, aromatic hydrocarbon based, ketone, alcohols, ester class or amide-type etc.

Solvent (E) specifically can be enumerated out, the ethers of glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list propyl ether, propylene glycol single-butyl ether, DPG dimethyl ether, DPG Anaesthetie Ether, DPG dipropyl ether, DPG dibutyl ethers etc.; Benzene,toluene,xylene, mesitylene etc. aromatic hydrocarbon based; The ketone of MEK, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone etc.; The alcohols of ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, glycerine etc.; And 3-ethoxyl ethyl propionate; 3-methoxypropionic acid methyl esters; Methylcellosolve acetate; Ethyl cellosolve acetate; Ethyl acetate; Butyl acetate; Pentyl acetate; Methyl lactate; Ethyl lactate; Butyl lactate; 3-methoxyl butylacetic acid ester; 3-methyl-3-methoxyl-1-butylacetic acid ester; Methoxyl amyl group acetic acid esters; Ethylene glycol acetate; Ethylene acetate; Ethylene glycol monomethyl ether acetate; Ethylene glycol monoethyl ether acetate; The diglycol monotertiary acetic acid esters; Diethylene glycol diacetate; The diethylene glycol monobutyl ether acetic acid esters; The propylene glycol monoacetate; Propylene-glycol diacetate; Propylene glycol methyl ether acetate; Propylene glycol monoethyl ether acetate; Vinyl carbonate; Propylene carbonate; The ester class of gamma-butyrolacton etc. etc.

In illustrative solvent; If consider coating and drying property aspect, then preferably use propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, 3-ethoxyl ethyl propionate or 3-methoxypropionic acid methyl esters.

Illustrative solvent (E) can use separately, perhaps also can mix two kinds and use.

About the content of solvent (E), with respect to the total amount of the photosensitive composition that contains this solvent, contain percentage by weight 60～90% in weight fraction, preferably contain percentage by weight 70～85%.Because when the content of solvent is pressed above-mentioned standard and in the scope of percentage by weight 60～90% time; Utilize the apparatus for coating of winding film coating machine, rotary coating machine, rotation and knife type coater, knife type coater (or slit coater (Die Coater)) and ink jet type etc. and when being coated with; Coating is good, so be preferred.

Adjuvant

The material of adjuvant for can optionally adding as required can be enumerated out as adjuvant, for example other macromolecular compounds, hardening agent, surfactant, adhesion promotor, anti-oxidant, ultraviolet light absorber and anti-polycoagulant etc.

Concrete example as other macromolecular compounds; Can enumerate out; The curable resin of epoxy resin, maleimide resin etc., gathers the thermoplastic resin of fluoroalkyl acrylic ester, polyester, polyurethane etc. etc. at polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether.

Hardening agent is for the curing in deep and improves physical strength and use.As the concrete example of hardening agent, can enumerate out epoxy compound, polyfunctional isocyanate's compound, melamine compound, oxetane compound etc.

In hardening agent; Concrete example as epoxy compound; Can enumerate out, bisphenol-A is that epoxy resin, hydrogenated bisphenol A are that epoxy resin, Bisphenol F are that epoxy resin, A Hydrogenated Bisphenol A F are that epoxy resin, phenolic resin varnish type epoxy resin, other aromatic ring epoxy resins, alicyclic ring family epoxy resin, ethylene oxidic ester are that resin, glycidyl amine are aliphatics beyond brominated derivative, epoxy resin and the brominated derivative thereof of resin or these epoxy resin, alicyclic or aromatic epoxy compound, the epoxide of butadiene (being total to) polymkeric substance, epoxide, (methyl) glycidyl acrylate (being total to) polymkeric substance and the triglycidyl isocyanurate etc. of isoprene (being total to) polymkeric substance.

In hardening agent; Concrete example as oxetane compound; Can enumerate out carbonic acid dioxygen heterocycle butane, xylene dioxygen heterocycle butane, hexane diacid dioxygen heterocycle butane, terephthalic acid (TPA) dioxygen heterocycle butane and cyclohexane dicarboxylic acid dioxygen heterocycle butane etc.

Hardening agent can use with the curing auxiliary compounds of the oxetanes skeleton ring-opening polymerization of the epoxy radicals that can make epoxy compound, oxetane compound jointly.Solidifying auxiliary compounds for example has: polybasic carboxylic acid class, polybasic acid anhydride class and acid-producing agent etc.The polybasic acid anhydride class can be used as epoxy curing agent and commercially available product.Concrete example as epoxy curing agent; Can enumerate out the example (MH-700) (New Japan Chem Co., Ltd's system) of trade name (アデカ Ha De Na EH-700) (rising sun electrochemical industry (strain) system), trade name (リカシ Star ト HH) (New Japan Chem Co., Ltd's system) and name of product etc.As illustrative hardening agent, can use separately or mix two or more and use.

The film forming that surfactant can be used for further improving photosensitive polymer combination forms property, and its preferably to use fluorine be that surfactant or silicon are surfactant.

Silicon is that surfactant for example can list as commercially available product, the DC3PA of eastern レダウコ one ニ Application グシリコ Application society, DC7PA, SH11PA, SH21PA, SH8400 etc.In addition, can enumerate out: the TSF-4440 of シリコ Application society of Toshiba, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 etc.Fluorine is that surfactant for example can be enumerated out as commercially available article, the メガピス F-470 of big Japanese イ Application キ chemical industry society, F-471, F-475, F-482, F-489 etc.Illustrative surfactant can use separately, perhaps can make up two or more and uses.

Concrete example as adhesion promotor; Can enumerate out; Vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane, 3-isocyanates trimethoxy silane and 3-isocyanates triethoxysilane etc.Illustrative adhesion promotor can use separately, perhaps can make up two or more and uses.Adhesion promotor in weight fraction, contains percentage by weight 0.01～10% with respect to photosensitive composition usually, preferably contains percentage by weight 0.05～2%.

As the concrete example of anti-oxidant, can enumerate out, for example 2,2 '-thiobis (4-methyl-6-tert butyl phenol) and 2,6-two-tert-butyl group-4-sylvan etc.

As the concrete example of ultraviolet light absorber, can enumerate out, for example 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole and alkoxy benzophenone.

As the concrete example of anti-polycoagulant, can enumerate out, for example sodium polyacrylate etc.

Photosensitive composition of the present invention for example can prepare with following method.That is, colorant (B) is mixed with solvent (E) in advance, and utilize ball mill (bead mill) etc. and disperse, so that the mean grain size of coloured material is less than the degree that equals 0.2 μ m.At this moment, use pigment dispersing agent as required, in addition, mixed base soluble resin (A) is part or all of sometimes.In the dispersion liquid that is obtained; Further add remainder, photopolymerization compounds (C) and the Photoepolymerizationinitiater initiater (D) of alkali soluble resin (A), as required and the adjuvant that uses, the solvent (E) that appends as required; Making it to become the concentration of regulation, thereby obtain required photosensitive composition.

The another side according to the present invention provides a kind of color filter that has according to the dyed layer of photosensitive composition of the present invention that comprises.Color filter according to the present invention constitutes with the form that comprises dyed layer, and said dyed layer does, through the coating photosensitive composition on substrate top, and makes public and develops and form with the pattern of stipulating.Between each colored pattern, barrier layer can also be formed, and black matrix" can be added.In addition, can also form diaphragm on color filter top.

Fig. 1 a～1c is that expression is according to the figure of the making step of color filter of the present invention.When using photosensitive composition according to the present invention to make color filter, for example to photosensitive composition carry out pattern handle and form colored pattern 3 '.That is, make the color layers 3 that forms by photosensitive composition be formed on substrate 1 top and (Fig. 1 a), and the color layers 3 (Fig. 1 b) that rayed is formed thus with the pattern of regulation, make its development (Fig. 1 c) afterwards.Also on said substrate 1, there is established colored pattern 2 sometimes.Also can after development, implement heating process.

Whether substrate 1 limits, and it can be the substrate of color filter itself, also can be the residing position of color filter on display device etc.Substrate 1 can be plastic plate of glass plate, silicon wafer and PES (polyethersulfone) and PC (gathering carbonic acid) etc. etc.That is, substrate 1 can be silicon (Si), Si oxide (SiO _X), glass substrate or polymeric substrate.

Shown in Fig. 1 a; For the dyed layer 3 that is formed by photosensitive composition is formed on the substrate 1; For example; Will be through solvent diluted photosensitive composition after the rubbing method through spin coating after spin coating, the gap coating, gap coating, roller coat, atomizing coating, ink-jetting style etc. is coated on the substrate, makes the volatile ingredient volatilization like solvent etc.Thus, form the dyed layer of being made up of photosensitive composition 3, dyed layer 3 is made up of the solid constituent of photosensitive composition, and contains volatile ingredient hardly.

The thickness of dyed layer 3 determines that according to the coating condition of the concentration of the viscosity of composition, solid constituent, coating speed etc. when using photosensitive composition of the present invention, can obtain thickness is the dyed layer 3 of 0.5～5 μ m.

Next, shown in Fig. 1 b, the dyed layer of being made up of photosensitive composition 3 is made public.In order to make its exposure, for example, through photomask 10 and with the regulation pattern to dyed layer 3 irradiation light 20.As light, use ultraviolet g line (wavelength: 436nm), h line, i line (wavelength: 365nm) etc. usually.Light 20 sees through according to the pattern of photomask 10.Photomask 10 is provided at glass plate 11 surfaces and goes up the light shield layer 12 of shield lights through the pattern of regulation.Light 20 crested through light shield layer 12.Do not provide glass plate 11 parts of this light shield layer 12 to do, transmittance section 13 that can transmitted light 20.Through the pattern of this transmittance section 13, thereby dyed layer 3 is made public.The exposure of light 20 can suitably be selected according to employed photosensitive composition.By the part of light 20 irradiations, significantly do not reduce than the partial solubility of being shone, thereby the difference of both solubleness is maximized by light 20.

After described exposure operation, shown in Fig. 1 c and develop.In order to develop, the photosensitive composition layer after for example will making public impregnated in the developer solution.Use alkali compounds as developer solution, for example, the WS of sodium carbonate, NaOH, potassium hydroxide, sal tartari or tetramethyl ammonium hydroxide.

Through developing, thereby removed in dyed layer not by the light of irradiate light irradiation area not.With respect to this, constituted colored pattern 3 ' thereby be retained by the irradiate light zone of irradiate light.After development, general water cleans and makes its drying.In addition, also can after drying, implement heat treated.Through heat treated formed colored pattern 3 ' is cured, has improved physical strength thus.So, owing to can improve the physical strength of colored pattern 3 ' through heat treated, the therefore preferred coloring photosensitive combination that contains hardening agent that uses.Heating-up temperature is generally more than 180 ℃, is preferably 200～250 ℃.

As everyone knows; Color filter is generally; The member of configuration black matrix" and red, green and blue 3 former color pixels on substrate, still, comprise through use the coloured material that is equivalent to certain color, photosensitive composition of the present invention carries out aforesaid operations; Thereby the black matrix" or the pixel of this color have been obtained; And for other colors, also through use comprise the coloured material that is equivalent to color of object, photosensitive composition of the present invention carries out same operation, thereby can on substrate, dispose black matrix" and and 3 former color pixels.Certainly, in black matrix" and 3 primary colors, also can only be suitable for photosensitive composition of the present invention to any 1 look, 2 looks or 3 looks.

Fig. 2 a and Fig. 2 b are the stereographic map according to color filter of the present invention.In the present invention, colored pattern is meant that the for example implication of RGB colored pixels (2,3 ', 4 '), black matrix" 5 etc., and colored pixels is by painted hyaline layer, and black matrix" is the layer of shield light.These colored pixels and black matrix" are formed on usually on the substrate 1 and constitute color filter.Because colored pixels (2,3 ', 4 ') is transparent and by painted, therefore the light of transmission shows the color of each colored pixels via these colored pixels.Because black matrix" 5 is the layer of shield light, therefore appear as black.This colored pattern can exist with grid form (mosaic) and (Fig. 2 a), perhaps have (Fig. 2 b) with the form of row.

And,, a kind of liquid crystal indicator that possesses color filter of the present invention is provided according to another side of the present invention.Liquid crystal indicator except possessing color filter, be included in those skilled in the art in the technical field of the present invention known structure.That is, can be suitable for the liquid crystal indicator of color filter of the present invention, be included among the present invention.As an example; Can enumerate out; The comparative electrode substrate that will have thin film transistor (TFT) (TFT unit), pixel electrode and oriented layer is opposed with the interval of regulation, and injects liquid crystal material in the clearance therebetween portion, thereby with its transmissive liquid crystal display device as liquid crystal layer.In addition, the reflection-type liquid-crystal display device that the reflection horizon is set is also arranged between the substrate of color filter and dyed layer.

In addition, as another example, can enumerate out a kind of liquid crystal indicator, it comprises: and TFT (thin film transistor (TFT): substrate Thin Film Transistor), it overlaps on the transparency electrode of color filter; And backlight, it is fixed on the position of TFT substrate and color filter overlapping.The TFT substrate can possess: external frame, and it is made up of the anti-photopolymer resin (light-proof resin) that surrounds the color filter periphery surface; Liquid crystal layer, it is made up of the nematic crystal that is attached in the external frame; A plurality of pixel electrodes, it is provided to each zone of liquid crystal layer; Transparent glass substrate, it is formed with pixel electrode; And polarization plate, it is formed on the surface of exposing of transparent glass substrate.

Below; Preferred embodiment is provided in order to understand the present invention; But following examples only are used for the present invention is carried out illustration, and those skilled in the art should be clear and definite; In category of the present invention and technological thought scope, can carry out various deformation and modification, therefore this distortion and modification obviously also belong in the claim scope of the present invention.

In following embodiment and comparative example, do not having under the situation about specifying, " % " and " part " of expression content is weight standard, and addition is the ratio with respect to all coloring photosensitive polymer combination.

In order to prepare photosensitive composition, at first prepared dispersible pigment dispersion, and prepared alkali soluble resin through synthetic example 1～9.

The preparation of dispersible pigment dispersion

< dispersible pigment dispersion M1 >

With 16.2 weight portion C.I. pigment green 36s, 1.8 weight portion C.I. pigment yellows 150, as 4.2 weight portion アジスパ PB821 (aginomoto TECHNO Co., Ltd. system) of spreading agent, 50 weight portion 1-Methoxy-2-propyl acetates, 27.8 parts of cyclohexanone as solvent; Through ball mill dispersing and mixing 12 hours (M1), thereby prepared dispersible pigment dispersion M1.

Synthesizing of alkali soluble resin (A)

< synthetic example 1 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 176.4g (1.8 moles); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; Pass through tap funnel then with the 2 hours following solution of dropping in flask; Promptly; In the potpourri that contains bicyclopentadiene methacrylate 66.0g (0.3 mole), vinyltoluene 106.2g (0.9 mole) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g, and stirred again 2 hours 120 ℃ of following continuation, thus the precursor of acquisition polymkeric substance.Then; Atmosphere in the flask is become air from nitrogen replacement; And after in copolymer solution, adding 2-hydroxy ethyl methacrylate 139.2g (1.2 moles), dimethylaminoethyl methacrylate 1.5g and methyl hydroquinone 1.5g; Continuing reaction down at 120 ℃, is the resin of 180mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 6700, and molecular weight distribution (Mw/Mn) is 2.3.

< synthetic example 2 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 176.4g (1.8 moles); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; Pass through tap funnel then with the 2 hours following solution of dropping in flask; Promptly; In the potpourri that contains cyclohexyl methyl acrylic ester

50.4g (0.3 mole), cyclohexyl methyl acrylic ester

1g (0.9 mole) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g; And stirred again 2 hours, thereby obtain the precursor of polymkeric substance 120 ℃ of following continuation.Then; Atmosphere in the flask is become air from nitrogen replacement; And after in copolymer solution, adding 2-hydroxy ethyl methacrylate 139.2g (1.2 moles), dimethylaminoethyl methacrylate 1.5g and methyl hydroquinone 1.5g; Continuing reaction down at 120 ℃, is the resin of 173mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 8900, and molecular weight distribution (Mw/Mn) is 2.4.

< synthetic example 3 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 58.8g (0.6 mole); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; Pass through tap funnel then with the 2 hours following solution of dropping in flask; Promptly; In the potpourri that contains bicyclopentadiene methacrylate 264.0g (1.2 moles), vinyltoluene 141.6g (1.2 moles) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g, and stirred again 2 hours 120 ℃ of following continuation, thus the precursor of acquisition polymkeric substance.Then; Atmosphere in the flask is become air from nitrogen replacement; And after in copolymer solution, adding 2-hydroxy ethyl methacrylate 59.2g (0.5 mole), dimethylaminoethyl methacrylate 1.5g and methyl hydroquinone 1.5g; Continuing reaction down at 120 ℃, is the resin of 130mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 12,700, and molecular weight distribution (Mw/Mn) is 2.2.

< synthetic example 4 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 176.4g (1.8 moles); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; Pass through tap funnel then with the 2 hours following solution of dropping in flask; Promptly; In the potpourri that contains bicyclopentadiene methacrylate 132.0g (0.6 mole), vinyltoluene 70.8g (0.6 mole) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g, and stirred again 2 hours 120 ℃ of following continuation, thus the precursor of acquisition polymkeric substance.Then the atmosphere in the flask is become air from nitrogen replacement; And after in copolymer solution, adding 2-hydroxy ethyl methacrylate 156.0g (1.2 moles), dimethylaminoethyl methacrylate 1.5g and methyl hydroquinone 1.5g; Continuing reaction down at 120 ℃, is the resin of 167mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 10,300, and molecular weight distribution (Mw/Mn) is 2.4.

< synthetic example 5 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 176.4g (1.8 moles); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; In flask, drip following solution through tap funnel with 2 hours then, that is, in the potpourri that contains vinyltoluene 141.6g (1.2 moles) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g; And stirred again 2 hours, thereby obtain the precursor of polymkeric substance 120 ℃ of following continuation.Then; Atmosphere in the flask is become air from nitrogen replacement; And after in copolymer solution, adding 2-hydroxy ethyl methacrylate 156.0g (1.2 moles), dimethylaminoethyl methacrylate 1.5g and methyl hydroquinone 1.5g; Continuing reaction down at 120 ℃, is the resin of 187mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 11,400, and molecular weight distribution (Mw/Mn) is 2.3.

< synthetic example 6 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 176.4g (1.8 moles); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; In flask, drip following solution through tap funnel with 2 hours then, that is, in the potpourri that contains cyclohexyl acrylic ester 201.6g (1.2 moles) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g; And stirred again 2 hours, thereby obtain the precursor of polymkeric substance 120 ℃ of following continuation.Then; Atmosphere in the flask is become air from nitrogen replacement; And in copolymer solution, add; Behind 2-hydroxy ethyl methacrylate 156.0g (1.2 moles), dimethylaminoethyl methacrylate 1.5g and the methyl hydroquinone 1.5g, continuing reaction down at 120 ℃, is the resin of 170mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 11,000, and molecular weight distribution (Mw/Mn) is 2.4.

< synthetic example 7 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 426.1g and anhydrous maleic acid 176.4g (1.8 moles); And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 120 ℃; In flask, drip following solution through tap funnel with 2 hours then, that is, in the potpourri that contains vinyltoluene 70.8g (0.6 mole) and propylene glycol methyl ether acetate 136g, added the solution of tert-butyl hydroperoxide 2-ethylhexyl carbonic ester 24.4g; And stirred again 2 hours, thereby obtain the precursor of polymkeric substance 120 ℃ of following continuation.Then the atmosphere in the flask is become air from nitrogen replacement; And after in beaker, dropping into acrylic acid 43.2g (0.6 mole), 3-dimethylaminomethylphenol 0.9g and p-dihydroxy-benzene 0.145g; Continuing reaction down at 120 ℃, is the resin of 110mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 5,800, and molecular weight distribution (Mw/Mn) is 2.5.

< synthetic example 8 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 182g; And with the atmosphere in the flask after air displacement becomes nitrogen; Be warming up to 100 ℃; Pass through tap funnel then with the 2 hours following solution of dropping in flask; Promptly; (Hitachi changes into (strain) system to the monomethacrylates of benzyl methacrylate 70.5g (0.4 mole), methacrylic acid 43.0g (0.5 mole), tricyclodecane skeleton

; FA-513M) added the solution of azoisobutyronitrile 3.6g in the potpourri of 22.0g (0.10 mole) and propylene glycol methyl ether acetate 136g, and stirred again 5 hours 100 ℃ of following continuation.Next; Atmosphere in the flask is become air from nitrogen replacement; And after in beaker, dropping into glycidyl methacrylate 15 grams [0.1 mole (carboxyl with respect to the methacrylic acid that uses in this reflection is 20 moles of %)], 3-dimethylaminomethylphenol 0.9g and p-dihydroxy-benzene 0.145g; Continuing reaction 6 hours down at 110 ℃, is the resin of 102mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 30,000, and molecular weight distribution (Mw/Mn) is 2.1.

< synthetic example 9 >

In the flask that possesses stirrer, thermometer reflux condensing tube, tap funnel and nitrogen ingress pipe, import propylene glycol monomethyl ether capronate 182g; And with the atmosphere in the flask after air displacement becomes nitrogen atmosphere; Be warming up to 100 ℃; Pass through tap funnel then with the 2 hours following solution of dropping in flask; That is, (Hitachi changes into (strain) system, FA-513M) has added the solution of azoisobutyronitrile 3.6g in the potpourri of 22.0g (0.10 mole) and propylene glycol methyl ether acetate 136g to the monomethacrylates of benzyl methacrylate 105.7g (0.6 mole), methacrylic acid 25.3g (0.3 mole), tricyclodecane skeleton; And stir 5 hours again 100 ℃ of following continuation, be the resin of 120mgkOH/g thereby obtained the solid constituent acid value.Through GPC weight average molecular weight that measure, polystyrene conversion is 24,000, and molecular weight distribution (Mw/Mn) is 2.1.

In the mensuration of synthetic routine 1～9 weight average molecular weight (Mw) and number mean molecular weight (Mn), adopt the GPC method also under following condition, to measure.

Device: HLC-8120GPC (eastern ソ one (strain) system)

Post: TSK-GELG4000HXL+TSK-GELG2000HXL (being connected in series)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow velocity: 1.0ml/ minute

Injection rate IR: 50 μ m

Detecting device: RI

Test sample concentration: percentage by weight 0.6% (solvent=tetrahydrofuran)

Proofread and correct and use standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (eastern ソ one (strain) system)

The ratio of weight average molecular weight that is obtained (Mw) and number mean molecular weight (Mn) is made as molecular weight distribution (Mw/Mn).

The preparation of photosensitive composition

Utilize alkali soluble resin, and prepared the resin photosensitive polymer combination according to embodiment 1～8 and comparative example 1 and 2 according to synthetic example 1～9 preparation.Wherein,

embodiment

1 and 2 has used synthetic routine 1 resin.

< embodiment 1 >

17.6 parts of 8.86 parts of resins, 2.95 parts of KAYARAD DPHA (Japanese chemical drug system), 0.59 part of Irgacure OXE01 (BASF society system), 35.2 parts of ethyl lactates, 11.77 parts of propylene glycol methyl ether acetates, the photosensitive colored resin mixing propylene glycol monomethyl ethers of < dispersible pigment dispersion M1>22.52 parts, 0.51 part of VALIFAST Yellow 1101 (オリヱ Application ト chemical industry (post) system), < synthetic example 1>are mixed and prepared photosensitive composition.

< embodiment 2 >

17.6 parts of 8.86 parts of resins, 2.95 parts of KAYARAD DPHA (Japanese chemical drug system), 0.59 part of Irgacure OXE01 (BASF society system), 35.2 parts of ethyl lactates, 11.77 parts of propylene glycol methyl ether acetates, the photosensitive colored resin mixing propylene glycol monomethyl ethers of < dispersible pigment dispersion M1>23.03 parts, < synthetic example 1>are mixed and prepared photosensitive composition.

< embodiment 3 >

Except the resin that alkali soluble resin is made into < synthetic example 2 >, to have prepared photosensitive composition with embodiment 1 identical method.

< embodiment 4 >

Except the resin that alkali soluble resin is made into < synthetic example 3 >, to have prepared photosensitive composition with embodiment 1 identical method.

< embodiment 5 >

Except the resin that alkali soluble resin is made into < synthetic example 4 >, to have prepared photosensitive composition with embodiment 1 identical method.

< embodiment 6 >

Except the resin that alkali soluble resin is made into < synthetic example 5 >, to have prepared photosensitive composition with embodiment 1 identical method.

< embodiment 7 >

Except the resin that alkali soluble resin is made into < synthetic example 6 >, to have prepared photosensitive composition with embodiment 1 identical method.

< embodiment 8 >

Except the resin that alkali soluble resin is made into < synthetic example 7 >, to have prepared photosensitive composition with embodiment 1 identical method.

< comparative example 1 >

Except the resin that alkali soluble resin is made into < synthetic example 8 >, to have prepared photosensitive composition with embodiment 1 identical method.

< comparative example 2 >

Except the resin that alkali soluble resin is made into < synthetic example 9 >, to have prepared photosensitive composition with embodiment 1 identical method.

< Test Example >

Be utilized in the photosensitive composition of preparation in embodiment 1～8 and the comparative example 1 and 2 and made color filter.That is, the photosensitive composition that will in embodiment 1～8 and comparative example 1 and 2, prepare is positioned on the heating plate after being coated on the glass substrate through spin-coating method, under 100 ℃ temperature, keeps 3 minutes, thereby has formed film.Then; On film, place the test photomask; And with and the mode that be spaced apart 100 μ ms and the irradiation ultraviolet radiation of test between the photomask, wherein, said test photomask has: in transmissivity 1～100% scope with the pattern of stepped variation and line/space pattern of 1 μ m～50 μ m.

At this moment, ultraviolet light source has used the high-pressure mercury-vapor lamp of the whole 1KW that comprises g, h, i line, thereby with 100mJ/cm ²Exposure intensity shine, and do not use special optical filter.With illuminated ultraviolet thin film dipped in the KOH of pH10.5 WS developing solution two minutes and develop.Next, will be used by the glass plate that film covers after the distilled water cleaning, and carry out drying through blowing, and in 230 ℃ heating oven, heated 20 minutes, thereby produced color filter with nitrogen.The film thickness of the color filter of producing is 2.0 μ m.

Developing powder, sensitivity, cohesive and the Superficial Foreign Body that utilizes the color filter of the photosensitive composition of preparation in embodiment 1～8 and the comparative example 1 and 2 carried out measuring and estimating, and its result is as shown in table 1 below.

< developing powder >

The required time that non-exposure portion is dissolved in the developer solution fully when developing is measured.

< sensitivity >

After the development, to measuring in order to form the required lowest exposure amount of film that does not have pattern defect and peel off.

< cohesive >

When formed pattern being estimated, in the following manner by pattern defect and the degree peeled off and estimate through optical microscope.

Zero: do not have the defective of pattern or peel off

△: the defective of pattern or peel off and have 1～3

*: the defective of pattern or peel off exists more than 4

The color filter of making impregnated in the N-Methyl pyrrolidone solvent 30 minutes, carried out comparative evaluation and the look before and after estimating changed.At this moment, employed formula be change by the look in the three-dimensional colorimeter of L*, a*, b* definition through expression, following mathematical expression 1 calculates, the look changing value is more little, then can produce the color filter of high reliability more.

[mathematical expression 1]

ΔEab ^*＝[(ΔL ^*) ²+(Δa ^*) ²+(Δb ^*) ²] ^(1/2)

< affirmation of Superficial Foreign Body >

When formed pattern being estimated, confirmed the number of the foreign matter that 3 μ m on the pattern are above as follows through optical microscope.

Zero: less than 2

△: 2～10

*: more than 10

[table 1]

As shown in table 1; Have in use under the situation of embodiment 1～8 of alkali soluble resin of the repetitive represented by above-mentioned formula 1; Not only sensitivity, cohesive and solvent resistance are excellent; And excellent with the compatibility of the colorant that contains dyestuff, when therefore forming dyed layer, can confirm Superficial Foreign Body is shown excellent characteristic.

Especially; Embodiment 1 that pigment and dyestuff all comprise, and 3～8 situation under; Compare with the embodiment that only uses pigment 2, also all demonstrated excellent characteristic, thereby can know; Owing to better, therefore prepared photosensitive composition with excellent specific property as the intermiscibility of the pigment of colorant or dyestuff according to alkali soluble resin of the present invention.

But; Can find out; Under the situation of the comparative example 1 that uses following photosensitive composition and 2, sensitivity is low and pattern defect has taken place and peeled off phenomenon, thereby cohesive is relatively poor; Wherein, said photosensitive composition comprises as the alkali soluble resin compound shown in the formula 1, that do not use anhydrous maleic acid (by synthesizing the resin that example 8 and 9 is synthesized).In addition, therefore dissolubility resistent is relatively poor because the look changing value is big, and, produce the Superficial Foreign Body more than 10, thereby demonstrated bad characteristic on the whole.

Hence one can see that, when utilizing the photosensitive composition that contains following alkali soluble resin according to the present invention, can produce color filter very excellent on multiple rerum natura, and wherein, said alkali soluble resin has by the repetitive shown in the formula 1.

The present invention is not limited to above-mentioned embodiment and accompanying drawing; And should make an explanation according to appended claim; In addition; It will be understood by a person skilled in the art that in the scope that does not break away from the technological thought of the present invention that claim of the present invention puts down in writing, can variformly replace, be out of shape and change.

Claims

1. photosensitive composition, it contains: alkali soluble resin, the colorant that contains pigment or dyestuff, optical polymerism compound, Photoepolymerizationinitiater initiater and solvent, it is characterized in that,

Said alkali soluble resin has, by following formula 1 repetitive represented, that induce from acid anhydrides (A1),

[Chemical formula 1]

(formula 1)

2. photosensitive composition as claimed in claim 1 is characterized in that,

Said alkali soluble resin does, the multipolymer of said acid anhydrides (A1) and compound (A2), wherein, said compound (A2) have can with the unsaturated link of said acid anhydrides (A1) copolymerization.

3. photosensitive composition as claimed in claim 2 is characterized in that,

With respect to the total molal quantity of whole repetitives of said alkali soluble resin, the ratio of the repetitive of inducing from said acid anhydrides (A1) is molar percentage 2～80%.

4. photosensitive composition as claimed in claim 2 is characterized in that,

With respect to the total molal quantity of whole repetitives of said alkali soluble resin, be molar percentage 2～95% from ratio with the repetitive that can induce with the compound (A2) of the unsaturated link of said acid anhydrides (A1) copolymerization.

5. photosensitive composition as claimed in claim 2 is characterized in that,

Have to be to be selected from the compound (A2) of the unsaturated link of said acid anhydrides (A1) copolymerization: unsaturated carboxylic acid, unsaturated carboxylic acid do not replace or substituted alkyl ester compound, have the substituent unsaturated carboxylic ester compound of ester ring type, glycols the saturated mono carbonate, have at least a compound in substituent unsaturated carboxylic ester compound, aromatic ethenyl compound, vinyl esters of carboxylic acids, vinyl cyanide based compound and the maleimide compound that comprises aromatic ring.

6. photosensitive composition as claimed in claim 2 is characterized in that,

Have and with the compound (A2) of the unsaturated link of said acid anhydrides (A1) copolymerization to do; Be selected from: methyl (methyl) acrylic ester, ethyl (methyl) acrylic ester, butyl (methyl) acrylic ester, aminoethyl (methyl) acrylic ester, cyclopentyl (methyl) acrylic ester, cyclohexyl (methyl) acrylic ester, methylcyclohexyl (methyl) acrylic ester, suberyl (methyl) acrylic ester, ring octyl group (methyl) acrylic ester, menthyl (methyl) acrylic ester, cyclopentenyl (methyl) acrylic ester, cyclohexenyl group (methyl) acrylic ester, cycloheptenyl (methyl) acrylic ester, cyclooctene base (methyl) acrylic ester, menthadiene base (methyl) acrylic ester, isobornyl (methyl) acrylic ester, pinane base (methyl) acrylic ester, adamantyl (methyl) acrylic ester, norborny (methyl) acrylic ester, firpene base (methyl) acrylic ester, glycidyl (methyl) acrylic ester, 3; 4-epoxycyclohexyl (methyl) acrylic ester, 3,4-epoxycyclohexyl methyl (methyl) acrylic ester, methyl glycidyl (methyl) acrylic ester, polyalkylene glycol monoalkyl (methyl) acrylic ester, benzyl (methyl) acrylic ester, phenoxy group (methyl) acrylic ester, styrene, AMS, vinyltoluene, vinyl acetate, vinyl propionate,

At least a compound in (methyl) vinyl cyanide, α-Lv Daibingxijing, N-cyclohexyl maleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and the fumaric acid.

7. photosensitive composition as claimed in claim 2 is characterized in that,

Said alkali soluble resin does; Make the compound of compound (A3) with the functional group that can combine and the multipolymer be combined into of said acid anhydrides (A1) and compound (A2) with said acid anhydrides (A1); Wherein, said compound (A2) have can with the unsaturated link of said acid anhydrides (A1) copolymerization.

8. photosensitive composition as claimed in claim 7 is characterized in that,

Among said alkali soluble resin, with respect to the molal quantity of the repetitive of said acid anhydrides (A1), the ratio of the repetitive of inducing from the compound (A3) with the unsaturated link that can combine with said acid anhydrides (A1) is molar percentage 2～95%.

9. photosensitive composition as claimed in claim 7 is characterized in that,

Compound (A3) with the functional group that can combine with said acid anhydrides (A1) is to be selected from: at least a compound in hydroxyethyl (methyl) acrylic ester, 2-hydroxypropyl (methyl) acrylic ester, 2-hydroxyl-3-chloropropyl (methyl) acrylic ester, 4-hydroxyl butyl (methyl) acrylic ester, acyl group octyloxy-2-hydroxypropyl (methyl) acrylic ester, 2-hydroxyl-3-benzene oxygen propyl group acrylic ester and 3-(the propenyloxy group)-2-hydroxypropyl methyl acrylic ester.

10. photosensitive composition as claimed in claim 1 is characterized in that,

Said alkali soluble resin, be 3,000～100,000 with the weight average molecular weight of polystyrene conversion.

11. a color filter, it comprises dyed layer, and said dyed layer contains each described photosensitive composition in claim 1 to the claim 10.

12. a liquid crystal indicator, it possesses the described color filter of claim 11.