CN102286218A

CN102286218A - Pigment resin composition, resin composition for ink jet mode color filter, color filter and liquid crystal display device

Info

Publication number: CN102286218A
Application number: CN2011101885583A
Authority: CN
Inventors: 田中真悟; 服部达哉; 成濑真吾; 长塚富雄
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2006-09-04
Filing date: 2006-09-04
Publication date: 2011-12-21

Abstract

The invention relates to a pigment resin composition, a resin composition for an ink jet mode color filter, a color filter and a liquid crystal display device. The resin composition for the ink jet mode color filter is characterized by comprising pigment, multifunctional monomers and binding agent resin. The invention also relates to the color filter for pixel patterns formed in an ink jet mode and the liquid crystal display device with the color filter.

Description

Pigmental resin composition, ink-jet color filter resin combination, colour filter and liquid crystal indicator

The present patent application is patent application 200610129045.4, and the applying date is denomination of invention on September 4th, 2006 dividing an application for the application for a patent for invention of " pigmental resin composition, ink-jet color filter with resin combination, colour filter and liquid crystal indicator ".

Technical field

The present invention relates to be used for make by ink-jetting style the colour filter of uses such as color liquid crystal display arrangement or colour pick-up tube element the pigmental resin composition, use this pigmental resin composition ink-jet color filter with resin combination, colour filter and liquid crystal indicator with the pattern of pixels that forms by ink-jetting style with resin combination by this colour filter.

Background technology

Make color liquid crystal display arrangement (LCD) wait in during the colour filter of use, usually on the substrate or be pre-formed the tunicle that forms colored radiation-sensitive composition on the substrate of light shield layer of expected pattern, by having the photic mask irradiation radioactive rays (hereinafter referred to as " exposure ") of required pattern form, develop then, after unexposed portion is removed in dissolving, use process furnace or hot-plate to carry out the back baking, form pattern of pixels of all kinds thus, this method is known (opening flat 2-144502 communique and the spy opens flat 3-53201 communique with reference to the spy).But, in these methods, have the formation complex procedures of pattern of pixels, and the also high problem of cost.

On the other hand, Te Kaiping 4-261503 communique, spy open flat 7-318723 communique, the spy opens in the 2000-310706 communique, proposed to make to have manufacturing method of color filter operation, ink-jetting style that forms the pigmented layer of colour filter with ink gun, and the ink-jet color filter resin combination.

But, because popularizing of high definition television etc. in recent years has this requirement of high depth of shade to color liquid crystal display device and becomes very high.In addition, require to improve productivity, in the manufacturing method of color filter of ink-jetting style, require to shorten the time of ejection printing ink for this reason in order to reduce cost.In order to satisfy these requirements, need to begin the high pigment levelsization and the higher-solid concentrationization of printing ink gradually.Correspondingly, during the pigment high density, have following problems, that is, because the content of pigment in the printing ink increases, so the high boiling solvent that contains in the printing ink destroys colo(u)rant dispersion system and the foreign matters such as throw out that produce increase, and it is bad that the printing ink ejection takes place.During the solids component high density, have following problems, that is, because the amount of the high boiling solvent that contains reduces in the printing ink, so printing ink becomes easily dry, and dry thing is attached to around the nozzle and that ejection takes place is bad during the printing ink ejection.When requiring pigment high densityization and solids component high density simultaneously, the problem that foreign matter increases, also is easy to dry this two aspect takes place simultaneously.

Summary of the invention

The object of the invention be to provide dispersion stabilization good, be difficult to drying and the also excellent ink-jet color filter resin combination of printing ink ejection property.

Other problems of the present invention are to provide the colour filter that is formed by above-mentioned composition of the present invention.

Other problems of the present invention also are to provide the liquid crystal indicator that possesses colour filter of the present invention.

By following explanation other purposes of the present invention as can be known and advantage etc.

According to the present invention, above-mentioned first purpose of the present invention and advantage are reached with resin combination by a kind of ink-jet color filter, it is characterized in that: contain solvent that (A) pigment, (B) dispersion agent, (C) intramolecularly has two acetic ester structures, (D) multi-functional monomer and (E) adhesive resin.

According to the present invention, above-mentioned second purpose of the present invention and advantage are reached by a kind of colour filter, it is characterized in that, have to use above-mentioned ink-jet color filter resin combination, by the pattern of pixels of ink-jetting style formation.

According to the present invention, above-mentioned the 3rd purpose of the present invention and advantage are reached by a kind of liquid crystal indicator that possesses above-mentioned colour filter.

Description of drawings

Fig. 1 wants portion's longitudinal diagram for what colour filter of the present invention manufacturing process was described; (a) the formation operation in expression next door, (b) the formation operation of expression pattern of pixels, (c) expression drying process; (d) the formation operation of expression protective layer, (e) the formation operation of expression common electrode.

Fig. 2 be for illustrate have the liquid crystal indicator that utilizes the colour filter that color filter manufacturing method of the present invention makes want portion's longitudinal diagram.

Fig. 3 is the orthographic plan that utilizes 1 example of the colour filter that color filter manufacturing method of the present invention makes.

Fig. 4 is the exemplary plot of the summary of the colour filter manufacturing installation that uses in the color filter manufacturing method of the present invention.

Fig. 5 is the fragmentary cross-sectional view of wanting portion of the ink gun that uses in the illustration color filter manufacturing method of the present invention.

Fig. 6 is the configuration of each nozzle on the ink gun that uses in the illustration color filter manufacturing method of the present invention and the orthographic plan that forms filter element in the septate substrate.

Embodiment

Below, the present invention is described in detail.

As mentioned above, ink-jet color filter of the present invention contains (A)～(E) composition with resin combination, according to circumstances further contains the poly-initiator of (F) light.The composition exhibiting that does not contain (F) composition is passed through heating and solidified thermoset, contains the composition exhibiting radiation-curable of (F) composition.

The invention provides and comprise (A), (B) and (C) pigment dispensing composition of composition, this pigment dispensing composition is applicable to the manufacturing of above-mentioned ink-jet color filter with resin combination.

Below, unless otherwise noted, employed ink-jet color filter with resin combination comprise above-mentioned heat-curable composition and radiation-curing composition the two.

The ink-jet color filter resin combination

(A) pigment

Pigment among the present invention is not particularly limited, and can be in pigment dyestuff, the mineral dye any.Wherein, because colour filter requires high purity and high radioparent color development and thermotolerance, therefore preferred especially pigment dyestuff.

As above-mentioned pigment dyestuff, for example, can be set forth in color index (C.I.; The distribution of dyers and colorist association) is classified as the compound of pigment (Pigment) in, can enumerates the compound that indicating color index as described below (C.I.) numbering particularly.

C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. Pigment Yellow 73 20, C.I. Pigment Yellow 73 24, C.I. Pigment Yellow 73 31, C.I. Pigment Yellow 73 55, C.I. pigment yellow 83, C.I. Pigment Yellow 73 93, C.I. Pigment Yellow 73 109, C.I. Pigment Yellow 73 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 153, C.I. pigment yellow 154, C.I. Pigment Yellow 73 155, C.I. Pigment Yellow 73 166, C.I. Pigment Yellow 73 168, C.I. Pigment Yellow 73 180, C.I. Pigment Yellow 73 211, C.I. Pigment Yellow 73 213, C.I. Pigment Yellow 73 214, C.I. Pigment Yellow 73 219;

C.I. pigment orange 36, C.I. pigment orange 43, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 71; C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 123, C.I. pigment red 149, C.I. Pigment red 168, C.I. Pigment red 176, C.I. Pigment red 177, C.I. Pigment red 180, C.I. Pigment red 185, C.I. Pigment Red 207, C.I. Pigment red 208, C.I. Pigment red 209, C.I. pigment red 21 5, C.I. Pigment red 224, C.I. Pigment red 242, C.I. Pigment red 243, C.I. Pigment red 254; C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29; C.I. pigment Blue 15, C.I. pigment blue 60, 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 green 136, C.I. Pigment green 210;

C.I. bistre 23, C.I. bistre 25, bromination Phthalocyanine Zinc (big Japanese ink Co., Ltd. system).

These pigment dyestuffs can use separately or mix 2 kinds with on use.

In the present invention, pigment dyestuff also can be made with extra care by for example recrystallization method, reprecipitation method, solvent wash method, subliming method, vaccum heating method or their combination etc. and use.

In addition, as above-mentioned mineral dye, for example, can enumerate titanium oxide, barium sulfate, lime carbonate, zinc white, lead sulfate, lead and yellow-collation, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, dark purple, chromoxide green, cobalt green, umber, black, the synthetic iron oxide black of titanium, carbon black etc.

These mineral dyes may be used singly or as a mixture of two or more.

In addition, in the present invention, according to circumstances, also can be with above-mentioned pigment also with the dyestuff more than a kind, natural pigment.

In the present invention, pigment can utilize polymkeric substance that its particle surface is carried out modification as required and use.As the polymkeric substance that the particle surface of pigment is carried out modification, for example, can enumerate the spy and open the polymkeric substance of record such as flat 8-259876 communique or commercially available various colo(u)rant dispersion with polymkeric substance or oligopolymer etc.

(B) dispersion agent

Dispersion agent among the present invention can use, suitable dispersion agents such as cationic, anionic species, nonionic class, both sexes class for example preferably contain polyethyleneimine: amine dispersion agent or have the dispersion agent of the compound (hereinafter referred to as " ammonia ester class dispersion agent ") of ammonia ester bond.

Object lesson as this polyethyleneimine: amine dispersion agent can list, for example commodity S24000, S56000 by name (Japanese Le one プリゾ one Le (strain) system).

Above-mentioned ammonia ester bond is generally used formula R-NH-COO-R ', and (wherein R and R ' are aliphatics, alicyclic or aromatic 1 valency or polyvalent organic group, this polyvalent organic group further has group or other group bondings of ammonia ester bond with other) expression, can be present in lipophilicity group and/or hydrophilic radical in the ammonia ester class dispersion agent, the main chain and/or the straight chain that also can be present in ammonia ester class dispersion agent also can be present in more than one in the ammonia ester class dispersion agent.When having 2 above ammonia ester bonds in the ammonia ester class dispersion agent, each ammonia ester bond can be the same or different.

As this ammonia ester class dispersion agent, can list, for example polyester and/or two ends with hydroxyl of vulcabond and/or triisocyanate and an end have the reaction product of the polyester of hydroxyl.

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

Above-mentioned triisocyanate can list, benzene-1,2 for example, 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 aromatic series triisocyanates such as dimethylbenzene triisocyanates such as 6-triisocyanate etc.

These vulcabond and triisocyanate can use separately separately or mix 2 kinds with on use.

Have the polyester of hydroxyl and can list at an above-mentioned end at the polyester that two ends have a hydroxyl, for example terminal or two ends have hydroxyl polycaprolactone, have the poly-valerolactone of hydroxyl at terminal or two ends, the poly-propiolactone etc. that has hydroxyl at terminal or two ends has hydroxyl at terminal or two ends polylactone; The polybutylene terephthalate etc. that have the polyethylene terephthalate of hydroxyl at terminal or two ends, has a hydroxyl at terminal or two ends has the polycondensation kind polyester of hydroxyl etc. at terminal or two ends.

These an end have hydroxyl polyester or the polyester that two ends have a hydroxyl can use separately separately or mix 2 kinds with on use.

Ammonia ester class dispersion agent preferred fragrance (cyclo) aliphatic diisocyanates among the present invention with have the polylactone of hydroxyl and/or have the reaction product of the polylactone of hydroxyl at an end at two ends, preferred especially tolylene diisocyanate with have the polycaprolactone of hydroxyl and/or have the reaction product of the polycaprolactone of hydroxyl at two ends at an end.

The object lesson of this ammonia ester class dispersion agent can list, for example commodity Disperbyk161, Disperbyk170 (PVC Star Network ケミ one (BYK) corporate system) by name, EFKA (エ Off カ one ケミカ Le ズ PVC one Block イ (EFKA) corporate system), デイスパロ Application series product such as (nanmu originally change into (strain) system).

The weight-average molecular weight (Mw) of the ammonia ester class dispersion agent among the present invention is preferred 5,000～50,000, and more preferably 7,000～20,000.

Above-mentioned ammonia ester class dispersion agent can use separately or mix 2 kinds with on use.

(methyl) acrylic dispersants of being made up of (being total to) polymkeric substance of (methyl) acrylic monomer is also preferably as dispersion agent.

The object lesson of this (methyl) acrylic dispersants can list, and for example commodity are called Disperbyk2000, Disperbyk2001 (PVC Star Network ケミ one (BYK) corporate system) etc.

Above-mentioned (methyl) acrylic dispersants can use separately or mix 2 kinds with on use.

The usage quantity of the dispersion agent during the pigment preparation dispersion liquid is preferably below 100 weight parts with respect to pigment 100 weight parts, 0.5～100 weight part more preferably, and more preferably 1～70 weight part is preferably 10～50 weight parts especially.

Employed solvent can list and the same solvent of the illustrated solvent of the liquid composition of aftermentioned resin combination during the pigment preparation dispersion liquid.

The usage quantity of the solvent during the pigment preparation dispersion liquid is preferably 500～1,000 weight part, more preferably 700～900 weight parts with respect to pigment 100 weight parts.

During the pigment preparation dispersion liquid, can use microballon mill, roller mill, dissolving machine and rod mill to prepare, when using the microballon mill, can use diameter for example is glass microballon about 0.5～10mm and titanium dioxide microballon etc., the preferred pigment mixed solution of forming by pigment, solvent and dispersion liquid with coolings such as water coolants on one side, blending dispersion can be prepared thus on one side.

At this moment, the filling ratio of microballon is preferably 50～80% of mill capacity, and the injection rate of pigment mixed solution is preferably about 20～50% of mill capacity.Treatment time is preferably 2～50 hours, more preferably 2～25 hours.

When using the roller mill preparation, can use for example 3 rollers mill or 2 roller mills etc., preferred on one side with cooling pigment mixed solutions such as water coolants, Yi Bian handle, can prepare thus.

At this moment, below the preferred 10 μ m, the preferred 108dyn/ of shearing force is about second at interval for roller.Treatment time is preferably 2～50 hours, more preferably 2～25 hours.

(C) intramolecularly has the solvent of 2 acetic ester structures

Intramolecularly of the present invention has the solvent of 2 acetic ester structures, can list for example propylene-glycol diacetate, 1,3 butylene glycol diacetate esters.Wherein, consider that the 1,3 butylene glycol diacetate esters has dispersion stabilization, drying property, therefore preferred especially.

In the present invention, also can and use other solvents.

This other solvents can list, for example,

Alcohol such as methyl alcohol, ethanol, benzylalcohol;

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene Glycol list positive propyl ether, the Diethylene Glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, dipropylene glycol list ether, dipropylene glycol list positive propyl ether, the dipropylene glycol mono-n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkane glycol monoalkyl ethers such as tripropylene glycol list ether;

(gathering) alkane glycol monoalkyl ether acetic ester such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol propyl ether acetic ester, ethylene glycol mono-n-butyl ether acetic ester, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, Diethylene Glycol list positive propyl ether acetic ester, Diethylene Glycol mono-n-butyl ether acetic ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, acetate 3-methoxyl group butyl ester;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran (THF);

Ketone such as methylethylketone, pimelinketone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methyl pentane-2-ketone), 4-hydroxy-4-methyl hexane-2-one;

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

Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, Isoamyl Acetate FCC, acetate 3-methyl-3-methoxyl group butyl ester, n-butyl propionate, propionic acid 3-methyl-3-methoxyl group butyl ester, ethyl butyrate, the butyric acid n-propyl, isopropyl butyrate, the positive butyl ester of butyric acid, hydroxyl ethyl acetate, ethoxy ethyl acetate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, the pyruvic acid n-propyl, methyl acetoacetate, methyl aceto acetate, 2-hydroxy-2-methyl ethyl propionate, 2-hydroxy-3-methyl methyl-butyrate, esters such as 2-ketobutyric acid ethyl ester;

Aromatic hydrocarbon such as toluene, dimethylbenzene;

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

In these solvents, consider solvability, pigment-dispersing, coating etc., preferred benzylalcohol, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, the triethylene glycol dme, tetraethyleneglycol dimethyl ether, Polyethylene glycol dimethyl ether, the dipropylene glycol monomethyl ether acetic ester, hexalin acetate, pimelinketone, 2-heptanone, the 3-heptanone, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, Isoamyl Acetate FCC, acetate 3-methoxyl group butyl ester, n-butyl propionate, ethyl butyrate, isopropyl butyrate, the positive butyl ester of butyric acid, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, propionic acid 3-methyl-3-methoxyl group butyl ester, Pyruvic Acid Ethyl ester etc.

Above-mentioned solvent can use separately or mix 2 kinds with on use.

With above-mentioned solvent, can also and with high boiling solvents such as benzyl ether, two hexyl ethers, acetonyl-acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, jasmal, ethyl benzoate, oxalic acid diethyl ester, ethyl maleate, gamma-butyrolactone, ethylene carbonate, propylene carbonate, ethyleneglycol monophenylether acetic ester.

The usage ratio of other solvents has the total amount of solvent He other solvents of 2 acetic ester structures with respect to (C) intramolecularly, is preferably 0～60 weight %, more preferably 0～40 weight %.If the usage ratio of other solvents surpasses 60 weight %, then, the trend of the dry thing of easy generation is arranged because printing ink becomes easily dry, perhaps, the sedimentary trend of easy generation is arranged because colo(u)rant dispersion system becomes easily destroyed.

The usage quantity of solvent considers that the printing ink of the resin combination that obtains sprays property, storage stability etc., preferred 5～35 weight % of total concn that remove each composition that desolvates of said composition, further preferred 15～30 weight %.

(D) multi-functional monomer

Multi-functional monomer of the present invention is the monomer with the polymerizability unsaturated link(age) more than 2.

As multi-functional monomer, for example, can enumerate two (methyl) acrylate of alkane glycol such as ethylene glycol, propylene glycol;

Two (methyl) acrylate of poly-alkane glycol such as polyoxyethylene glycol, polypropylene glycol;

Poly-(methyl) acrylate or its dicarboxylic acid modifier of the polyvalent alcohols more than 3 yuan such as glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol;

Oligomeric (methyl) acrylate such as polyester, Resins, epoxy, ammonia ester resin, Synolac, silicone resin, spirane resin;

Two terminal hydroxyls are poly--two (methyl) acrylate of two terminal hydroxyl fluidized polymers such as 1,3-butadiene, two terminal hydroxyl polyisoamylenes, two terminal hydroxyl polycaprolactones, tricresyl phosphate [2-(methyl) acryloxy ethyl] ester etc.

In these multi-functional monomers, poly-(methyl) acrylate or its dicarboxylic acid modifier of preferred polyvalent alcohol more than 3 yuan, preferred particularly trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, especially, because the intensity and the surface smoothing excellence of pixel, and be difficult to producing scum on the substrate at unexposed position and on the light shield layer, residual film etc., preferred Viscoat 295, pentaerythritol triacrylate and dipentaerythritol acrylate.

Above-mentioned multi-functional monomer may be used singly or as a mixture of two or more.

(A) pigment optimization of relative 100 weight parts of multi-functional monomeric usage quantity among the present invention is 5～1,000 weight part, more preferably 20～300 weight parts.When multi-functional monomeric usage quantity is lower than 5 weight parts, there be the intensity or the surface smoothing downward trend of pixel, on the other hand,,, the possibility of the aim colour concentration that is difficult to realize film is arranged because pigment concentration is low relatively if surpass 1,000 weight part.

(E) adhesive resin

Adhesive resin among the present invention can use suitable resin as long as (A) played the tackiness agent effect.

Preferred adhesive resin among the present invention is the polymkeric substance that contains carboxyl, especially preferably have the carboxyl more than 1 ethylenically unsaturated monomers (below, be called " containing the carboxyl unsaturated monomer ".) with other can copolymerization the multipolymer (below, be called " carboxy-containing copolymer (E1) ") of ethylenically unsaturated monomers (below, be called " other unsaturated monomers (e1) ").

As the above-mentioned carboxyl unsaturated monomer that contains, for example, can enumerate unsaturated monocarboxylic acids such as vinylformic acid, methacrylic acid, Ba Dousuan, α-Lv Bingxisuan, TRANSCINNAMIC ACID;

Unsaturated dicarboxylic acid or its acid anhydrides such as toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid;

Unsaturated polycarboxylic acid more than 3 yuan or its acid anhydrides;

List [(methyl) acryloyloxyalkyl] ester of polycarboxylic acid more than 2 yuan such as mono succinate (2-acrylyl oxy-ethyl) ester, mono succinate (2-methylacryoyloxyethyl) ester, phthalic acid list (2-acrylyl oxy-ethyl) ester, phthalic acid list (2-methylacryoyloxyethyl) ester;

ω-carboxyl polycaprolactone single-acrylate, ω-two ends such as carboxyl polycaprolactone monomethacrylates have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.

It should be noted that mono succinate (2-acrylyl oxy-ethyl) ester and phthalic acid list (2-acrylyl oxy-ethyl) ester are on sale on market with the trade(brand)name of M-5300 and M-5400 (East Asia synthetic (strain) produces) respectively.

These carboxylic ethylenically unsaturated monomers may be used singly or as a mixture of two or more.

In addition, as other unsaturated monomers (e1), for example, can enumerate vinylbenzene, alpha-methyl styrene, adjacent Vinyl toluene, a Vinyl toluene, to Vinyl toluene, to chloro-styrene, O-methoxy vinylbenzene, meta-methoxy vinylbenzene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to aromatic ethenyl compounds such as vinyl benzyl glycidyl ethers;

Indenes classes such as indenes, 1-methyl indenes;

Methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, the vinylformic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, the methacrylic tert-butyl acrylate, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, vinylformic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, vinylformic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, vinylformic acid 2-hydroxyl butyl ester, methacrylic acid 2-hydroxyl butyl ester, vinylformic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, vinylformic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, allyl acrylate, allyl methacrylate(AMA), benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, vinylformic acid 2-methoxyl group ethyl ester, methacrylic acid 2-methoxyl group ethyl ester, vinylformic acid 2-phenoxy ethyl, methacrylic acid 2-phenoxy ethyl, vinylformic acid methoxyl group binaryglycol ester, methacrylic acid methoxy base binaryglycol ester, vinylformic acid methoxyl group triglycol ester, methacrylic acid methoxy base triglycol ester, vinylformic acid MPEG ester, methacrylic acid methoxy base propylene glycol ester, vinylformic acid methoxyl group dipropylene glycol ester, methacrylic acid methoxy base dipropylene glycol ester, isobornyl acrylate, isobornyl methacrylate, vinylformic acid dicyclopentadienyl ester, methacrylic acid dicyclopentadienyl ester, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, methacrylic acid 2-hydroxyl-3-phenoxy group propyl ester, single vinylformic acid glyceryl ester, esters of unsaturated carboxylic acids such as monomethyl vinylformic acid glyceryl ester;

Unsaturated carboxylic acid aminoalkyl esters such as vinylformic acid 2-amino ethyl ester, methacrylic acid 2-amino ethyl ester, vinylformic acid 2-dimethylamino ethyl ester, methacrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of vinylformic acid 2-, the amino propyl ester of methacrylic acid 2-, vinylformic acid 2-dimethylamino propyl ester, methacrylic acid 2-dimethylamino propyl ester, the amino propyl ester of vinylformic acid 3-, the amino propyl ester of methacrylic acid 3-, vinylformic acid 3-dimethylamino propyl ester, methacrylic acid 3-dimethylamino propyl ester;

Unsaturated carboxylic acid such as glycidyl acrylate, glycidyl methacrylate glycidyl ester;

Vinyl carboxylates such as vinyl-acetic ester, propionate, vinyl butyrate, M-nitro benzoic acid vinyl acetate;

Unsaturated ethers such as vinyl methyl ether, EVE, glycidyl allyl ether, methylpropenyl glycidyl ether;

Acrylonitrile based compounds such as vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, acrylonitrile;

Unsaturated amides or unsaturated acyl imines such as acrylamide, Methacrylamide, α-propenyl chloride acid amides, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl Methacrylamide, maleimide;

Aliphatics conjugated diolefines such as 1,3-butadiene, isoprene, chloroprene;

Polystyrene, polymethyl acrylate, polymethylmethacrylate, the positive butyl ester of polyacrylic acid, Vinalac 5920, polysiloxane etc. have macromonomer of single acryl or monomethyl acryl etc. at the end of polymer molecular chain.

These other unsaturated monomers (e1) may be used singly or as a mixture of two or more.

Carboxy-containing copolymer (E1), preferred (1) vinylformic acid and/or methacrylic acid and (2) are selected from the multipolymer of at least a kind of formation of vinylbenzene, methyl acrylate, methyl methacrylate, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, polystyrene macromolecular monomer and polymethylmethacrylate macromonomer.

As the object lesson of preferred carboxy-containing copolymer (E1), can enumerate:

Vinylformic acid/benzyl acrylate multipolymer, vinylformic acid/styrene/acrylic methyl terpolymer, vinylformic acid/styrene/acrylic benzyl ester copolymer, vinylformic acid/methyl acrylate/polystyrene macromolecular monomer copolymer, vinylformic acid/methyl acrylate/polymethylmethacrylate macromonomer multipolymer, vinylformic acid/benzyl acrylate/polystyrene macromolecular monomer copolymer, vinylformic acid/benzyl acrylate/polymethylmethacrylate macromonomer multipolymer, vinylformic acid/vinylformic acid 2-hydroxy methacrylate/benzyl acrylate/polystyrene macromolecular monomer copolymer, vinylformic acid/vinylformic acid 2-hydroxy methacrylate/benzyl acrylate/polymethylmethacrylate macromonomer multipolymer;

Vinylformic acid/benzyl methacrylate multipolymer, vinylformic acid/styrene/methacrylic acid methyl terpolymer, vinylformic acid/styrene/methacrylic acid benzyl ester copolymer, vinylformic acid/methyl methacrylate/polystyrene macromolecular monomer copolymer, vinylformic acid/methyl methacrylate/polymethylmethacrylate macromonomer multipolymer, vinylformic acid/benzyl methacrylate/polystyrene macromolecular monomer copolymer, vinylformic acid/benzyl methacrylate/polymethylmethacrylate macromonomer multipolymer, vinylformic acid/2-hydroxyethyl methacrylate/benzyl methacrylate/polystyrene macromolecular monomer copolymer, vinylformic acid/2-hydroxyethyl methacrylate/benzyl methacrylate/polymethylmethacrylate macromonomer multipolymer;

Methacrylic acid/benzyl methacrylate multipolymer, methacrylic acid/styrene/acrylic methyl terpolymer, methacrylic acid/styrene/acrylic benzyl ester copolymer, methacrylic acid/methyl acrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/methyl acrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/benzyl acrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/benzyl acrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/vinylformic acid 2-hydroxy methacrylate/benzyl acrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/vinylformic acid 2-hydroxy methacrylate/benzyl acrylate/polymethylmethacrylate macromonomer multipolymer;

Methacrylic acid/benzyl methacrylate multipolymer, methacrylic acid/styrene/methacrylic acid methyl terpolymer, methacrylic acid/styrene/methacrylic acid benzyl ester copolymer, methacrylic acid/methyl methacrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/methyl methacrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/benzyl methacrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/benzyl methacrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/2-hydroxyethyl methacrylate/benzyl methacrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/2-hydroxyethyl methacrylate/benzyl methacrylate/Sipacril 2739OFs such as polymethylmethacrylate macromonomer multipolymer.

In these carboxy-containing copolymers (E1), special preferable methyl vinylformic acid/benzyl methacrylate multipolymer, methacrylic acid/styrene/methacrylic acid methyl terpolymer, methacrylic acid/styrene/methacrylic acid benzyl ester copolymer, methacrylic acid/methyl methacrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/methyl methacrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/benzyl methacrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/benzyl methacrylate/polymethylmethacrylate macromonomer multipolymer, methacrylic acid/2-hydroxyethyl methacrylate/benzyl methacrylate/polystyrene macromolecular monomer copolymer, methacrylic acid/2-hydroxyethyl methacrylate/benzyl methacrylate/polymethylmethacrylate macromonomer multipolymer.

The copolymerization ratio that contains the carboxyl unsaturated monomer in the carboxy-containing copolymer (E1) is preferably 5～50 weight %, more preferably 10～40 weight %.

In the present invention, carboxy-containing copolymer (E1) can separately or mix use more than 2 kinds.

Other preferred adhesive resins (E) among the present invention but the ethylenically unsaturated monomers of the maleimide that replaces for the N position and other copolymerization (hereinafter referred to as " and other unsaturated monomers (e2)) multipolymer (hereinafter referred to as " maleimide copolymer (E2) of N position replacement).

N bit substituent in the maleimide that the N position replaces can list, the for example aralkyl of the aryl of (ring) alkyl of carbonatoms 1～20, carbonatoms 6～30, carbonatoms 7～30 and the substitutive derivative of their group etc., in these N bit substituents, the aryl and the substitutive derivative thereof of preferred carbonatoms 6～20.

The object lesson of the maleimide that the N position replaces can list N position (ring) alkyl substituted maleimide amine and substitutive derivatives thereof such as N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-sec.-propyl maleimide, N-normal-butyl maleimide, N-tertiary butyl maleimide, N-n-pentyl maleimide, N-n-hexyl maleimide, N-cyclohexyl maleimide, N-4-methylcyclohexyl maleimide, N-4-chlorine cyclohexyl maleimide;

N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, hydroxy phenyl maleimide between N-, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, aminomethyl phenyl maleimide between N-, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-adjacency pair p-methoxy-phenyl maleimide, N position aryl substituted maleimide amine and substitutive derivatives thereof such as N-p-chlorophenylmaleimide;

N-benzyl maleimide, N-styroyl maleimide, the adjacent hydroxybenzyl maleimide of N-, hydroxybenzyl maleimide between N-, N-is to the hydroxybenzyl maleimide, the adjacent methyl-benzyl maleimide of N-, methyl-benzyl maleimide between N-, N-is to the methyl-benzyl maleimide, N-O-methoxy benzyl maleimide, N-meta-methoxy benzyl maleimide, N-is to the methoxy-benzyl maleimide, N position aralkyl substituted maleimide amine such as N-p-chlorobenzyl maleimide and substitutive derivative thereof etc.

In these N position substituted maleimide amine, 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 preferred N-cyclohexyl maleimide, N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, N-.

Above-mentioned N position substituted maleimide amine can use separately or mix more than 2 kinds and use.

Other unsaturated monomers (e2) are as long as can just be not particularly limited with the maleimide amine copolymer that the N position replaces, and preferably contain above-mentionedly more than a kind to contain the carboxyl unsaturated monomer and the monomer mixture of above-mentioned other unsaturated monomers (e1) more than a kind.

The multipolymer of the preferred N-phenylmaleimide of N position substituted maleimide amine copolymer thing (E2), further preferred N-phenylmaleimide and the multipolymer that contains carboxyl unsaturated monomer and other unsaturated monomers (e1), preferred especially (1) N-phenylmaleimide, with (2) vinylformic acid and/or methacrylic acid, with (3) vinylbenzene, be selected from methyl acrylate with (4), methyl methacrylate, vinylformic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate(AMA), benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, glyceral methacrylate, mono acrylic ester, ω-carboxyl-polycaprolactone single-acrylate, at least a kind multipolymer in polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer.

The object lesson of preferred N position substituted maleimide amine copolymer thing (E2) can list, N-phenylmaleimide/methacrylic acid/styrene/acrylic allyl ester multipolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid allyl ester multipolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid benzyl ester copolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid phenyl ester multipolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid benzyl ester/polystyrene macromolecular monomer copolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid benzyl ester/polymethylmethacrylate macromonomer multipolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid phenyl ester/polystyrene macromolecular monomer copolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid phenyl ester/polymethylmethacrylate macromonomer multipolymer

N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid 2-hydroxy methacrylate/benzyl methacrylate/polystyrene macromolecular monomer copolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid 2-hydroxy methacrylate/benzyl methacrylate/polymethylmethacrylate macromonomer multipolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid 2-hydroxy methacrylate/phenyl methacrylate/polystyrene macromolecular monomer copolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid 2-hydroxy methacrylate/phenyl methacrylate/polymethylmethacrylate macromonomer multipolymer, N-phenylmaleimide/methacrylic acid/styrene/methacrylic acid glyceryl ester/ω-carboxyl-polycaprolactone single-acrylate multipolymer etc.

The copolymerization ratio of the N position substituted maleimide amine in the N position substituted maleimide amine copolymer thing (E2) is preferably 5～50 weight %, more preferably 10～40 weight %.

N position substituted maleimide amine copolymer thing is a N position substituted maleimide amine when containing the multipolymer of carboxyl unsaturated monomer and other unsaturated monomers (e1), the copolymerization ratio that contains the carboxyl unsaturated monomer is preferably 5～50 weight %, 10～40 weight % more preferably, the copolymerization ratio of other unsaturated monomer (e1) is preferably 10～90 weight %, more preferably 20～80 weight %.

In the present invention, N position substituted maleimide amine copolymer thing (E2) can use separately or mix more than 2 kinds and use.

By gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran (THF)) weight-average molecular weight that is converted into polystyrene of each resinous principle of the adhesive resin among the formation the present invention of Ce Dinging (below, abbreviate " weight-average molecular weight " as.) be preferably 3,000～300,000, more preferably 5,000～100,000.

Relative 100 weight parts of the usage ratio of the adhesive resin among the present invention (A) pigment optimization is 0～1,000 weight part, more preferably 20～500 weight parts.If the usage ratio of adhesive resin surpasses 1,000 weight part, then pigment concentration reduces relatively, therefore, as film, inaccessible sometimes aim colour concentration probably.

(F) the poly-initiator of light

In (radiation-curable) of the present invention resin combination, can cooperate (F) light to gather initiator.The poly-initiator of light among the present invention can cause (D) multi-functional monomer and the compound of the spike of the simple function monomer polymerization that according to circumstances uses for the exposure by visible light, ultraviolet ray, far ultraviolet rays yue, electron rays, X ray isoradial produces.

As the poly-initiator of this light, can enumerate, for example O-acyl oxime compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class, bitter almond oil camphor compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear benzoquinone compound, xanthone compounds, diazonium compounds etc.

In the present invention, the poly-initiator of light can use separately or mix more than 2 kinds and use, but the poly-initiator of the light among the present invention is preferably selected from least a in acetophenone compounds, bisglyoxaline compounds and the compound in triazine class.

In the poly-initiator of light among the present invention, as the object lesson of O-acyl oxime compounds, the O-acyl oxime type polymerization starter of preferred 9.H.-carbazoles.For example; can list 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-benzoic ether; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-nonane-1; 2-nonane-2-oxime-O-acetic ester; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-pentane-1; 2-pentane-2-oxime-O-acetic ester; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketoxime-O-acetic ester; 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-ketoxime-O-acetic ester; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-ethyl-6-(1; 3, the 5-trimethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether; 1-[9-butyl-6-(2-ethylamino benzonitrile acyl group)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether etc.

In these O-acyl oxime compounds, preferred especially 1-[9-ethyl-6-(2-methyl benzoyl)-9.H.-carbazole-3-yl]-ethane-1-ketoxime-O-acetic ester.

Above-mentioned O-acyl oxime compound can use separately or mix more than 2 kinds and use.

In the poly-initiator of preferred light among the present invention, object lesson as acetophenone compounds, can enumerate 2-hydroxy-2-methyl-1-phenyl-acetone-1,2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1,1-hydroxy-cyclohexyl benzophenone, 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone-1 etc.

In these acetophenone compounds, preferred especially 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1 etc.

Above-mentioned acetophenone compounds can use separately or mix more than 2 kinds and use.

As the object lesson of above-mentioned bisglyoxaline compounds, can list 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

In these bisglyoxaline compounds, further preferred 2,2 '-two (2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline and 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., preferred especially 2,2 '-two (2,4 dichloro benzene bases)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.

Above-mentioned bisglyoxaline compounds can use separately or mix more than 2 kinds and use.

Hydrogen donor

In the present invention, when using the bisglyoxaline compounds to gather initiator as light, owing to also can further improve sensitivity with following hydrogen donor, therefore preferred.

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 such hydrogen donor, be preferably as follows sulfur alcohol compound, aminated compounds of definition etc.

Above-mentioned sulfur alcohol compound is by being parent nucleus with phenyl ring or heterocycle, have more than 1, preferred 1～3, further preferred 1～2 compound with the sulfydryl of this parent nucleus Direct Bonding is (hereinafter referred to as " thio-alcohol hydrogen donor ".) constitute.

In addition, above-mentioned aminated compounds is by being parent nucleus with phenyl ring or heterocycle, have more than 1, preferred 1～3, further preferred 1～2 compound with the amino of this parent nucleus Direct Bonding is (hereinafter referred to as " amine hydrogen donor ".) constitute.

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

Below, hydrogen donor is illustrated in greater detail.

The thio-alcohol hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, in addition, can also have phenyl ring and heterocycle simultaneously.These whens ring when having more than 2 can form condensed ring, also can not form condensed ring.

In addition, when the thio-alcohol hydrogen donor has 2 above sulfydryls, as long as residual at least 1 free sulfhydryl groups, just can be replaced more than 1 in the then residual sulfydryl by alkyl, aralkyl or aryl, in addition, as long as residual at least 1 free sulfhydryl groups, then can have by 2 sulphur atoms of divalent organic group bondings such as alkylidene group structural unit or with the structural unit of 2 sulphur atoms of form bonding of disulphide.

In addition, the position of thio-alcohol hydrogen donor beyond sulfydryl can also be by replacements such as the carbobenzoxy of the carbalkoxy of carboxyl, carbalkoxy, replacement, carbobenzoxy, replacement, itrile groups.

As the object lesson of such thio-alcohol hydrogen donor, can enumerate 2-mercaptobenzothiazole, 2-sulfydryl benzo

Azoles, 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 benzo

Azoles, preferred especially 2-mercaptobenzothiazole.

The amine hydrogen donor can have phenyl ring or the heterocycle more than 1 respectively, in addition, also can have phenyl ring and heterocycle simultaneously.These whens ring when having more than 2 can form condensed ring, also can not form condensed ring.

In addition, can be replaced by alkyl or substituted alkyl more than 1 in the amino of amine hydrogen donor,, other positions beyond amino can also be by replacements such as the carbobenzoxy of the carbalkoxy of carboxyl, carbalkoxy, replacement, carbobenzoxy, replacement, itrile groups.

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-dimethylamino M-nitro benzoic acid, 4-dimethylamino cyanobenzene etc.

In these amine hydrogen donors, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone etc., preferred especially 4,4 '-two (diethylamino) benzophenone.

Even it should be noted that poly-the initiation under the situation about counting of light beyond the bisglyoxaline compounds, the amine hydrogen donor also has the effect of sensitizer.

In the present invention, hydrogen donor may be used singly or as a mixture of two or more, but be used in combination thio-alcohol hydrogen donor more than a kind and the amine hydrogen donor more than a kind, because the pixel that forms is difficult to come off from substrate when developing, and the intensity of pixel and sensitivity are all high, thereby be preferred.

As the object lesson of the preferably combination of thio-alcohol hydrogen donor and amine hydrogen donor, can enumerate 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-sulfydryl benzo Azoles/4,4 '-two (dimethylamino) benzophenone, 2-sulfydryl benzo

Azoles/4,4 '-two (diethylamino) benzophenone etc., preferred combination is 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-sulfydryl benzo Azoles/4,4 '-two (diethylamino) benzophenone etc., particularly preferred combination is 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone.

The thio-alcohol hydrogen donor in the combination of thio-alcohol hydrogen donor and amine hydrogen donor and the weight ratio of amine hydrogen donor be preferably 1: 1～and 1: 4, more preferably 1: 1～1: 3.

In addition, object lesson as above-mentioned compound in triazine class, can list 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(5-methyl furan-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-p-methoxy-phenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-phenetole vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazine etc. of 6-have the compound in triazine class of monochloromethyl.

In these compound in triazine class, preferred especially 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazine of 6-.

Above-mentioned compound in triazine class may be used singly or as a mixture of two or more.

Additive component

In case of necessity, the colour filter among the present invention can also contain various additive components with radiation-ray sensitive composition.

As above-mentioned additive, for example can list, blue pigments derivative such as copper phthalocyanine derivative thing or yellow ultramarine derivative etc. disperse auxiliary agent;

Weighting agent such as glass, alumina;

Polyvinyl alcohol, polyalkylene glycol monoalkyl ether, poly-macromolecular compounds such as (fluoroalkyl acrylate);

Tensio-active agents such as anionic species, cationic, nonionic class;

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, 3-glycidyl ether propyl trimethoxy silicane, 3-glycidyl ether 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, driving fit promotor such as 3-sulfydryl propyl trimethoxy silicane;

2, antioxidants such as 2 '-sulphur two (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol;

UV light absorber such as 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone class;

Anticoalescents such as sodium polyacrylate;

1,1 '-azo two (hexanaphthene-1-formonitrile HCN), 2-phenylazos-4-methoxyl group-2, hot radicals such as 4-methyl pentane nitrile produce agent;

Ink-jet discharge performance stablizers such as methyl alcohol, ethanol, Virahol, propyl carbinol, glycerine;

Following commodity are called エ Off ト Star プ EF301, エ Off ト Star プ EF303, エ Off ト Star プ EF352 (above change into (strain) make) by new autumn fields, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F178K, F470 (R08), F474, F475, R30, F482, F483 (above) by big Japanese ink chemical industry (strain) manufacturing, Off ロラ one De FC430, Off ロラ one De FC431 (above) by the manufacturing of Sumitomo スリ one エ system (strain), アサヒガ one De AG710, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (above) by Asahi Glass (strain) manufacturing, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), Port リ Off ロ one No.75, Port リ Off ロ one No.95 (above) by common prosperity society chemistry (strain) manufacturing, DC-57 (East レダウコ one ニ Application グシリコ one Application (strain) is made) etc. tensio-active agent etc.

Ink-jet color filter among the present invention can contain thermic acidogenic agent, acid crosslinking agent with resin combination.

Above-mentioned thermic acidogenic agent can list sulfonium salt, benzothiazole for by the acidic composition of heating

Salt, ammonium salt, Salt etc. Salt, preferred especially sulfonium salt and benzothiazole

Salt.

The compound (hereinafter referred to as " sulfonium salt (1) ") of the preferred following formula of above-mentioned sulfonium salt (1) expression.

[in the formula (1), R ¹, R ²And R ³Separate, the 1 valency alkyl of expression carbonatoms 1～5 or the aryl or derivatives thereof of its substitutive derivative or carbonatoms 6～10, and R ¹, R ²And R ³At least one be aryl or its substitutive derivative of carbonatoms 6～10, Y ^-The negatively charged ion of representing 1 valency.

As the object lesson of sulfonium salt (1), can list dialkyl group sulfonium salts such as 4-acetyl phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetyl phenyl dimethyl sulfonium hexafluoro arsenate, 4-benzyloxycarbonyloxy base phenyl dimethyl sulfonium hexafluoro antimonate, 4-benzoyloxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-benzoyloxy phenyl dimethyl sulfonium hexafluoro arsenate, 3-chloro-4-acetyl oxygen phenyl dimethyl sulfonium hexafluoro antimonate;

Monobenzyl sulfonium salts such as 4-hydroxy phenyl benzyl methyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl benzyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, 4-p-methoxy-phenyl benzyl methyl sulfonium hexafluoro antimonate, 2-methyl-4-hydroxy phenyl benzyl methyl sulfonium hexafluoro antimonate, 3-chloro-4-hydroxy phenyl benzyl methyl sulfonium hexafluoro arsenate;

4-hydroxy phenyl dibenzyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl dibenzyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, 4-p-methoxy-phenyl dibenzyl sulfonium hexafluoro antimonate, 3-chloro-4-hydroxy phenyl dibenzyl sulfonium hexafluoro arsenate, 3-methyl-4-hydroxyl-dibenzyl sulfonium salts such as 5-tert-butyl-phenyl dibenzyl sulfonium hexafluoro antimonate;

4-hydroxy phenyl 4-methoxybenzyl ylmethyl sulfonium hexafluorophosphate, 4-hydroxy phenyl 4-benzyl chloride ylmethyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl 4-nitrobenzyl methyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl 4-benzyl chloride ylmethyl sulfonium hexafluorophosphate, 3-methyl-4-hydroxy phenyl 4-nitrobenzyl methyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl-3, substituted benzyl sulfonium salts such as 5-dichloro benzyl methyl sulfonium hexafluoro antimonate, 3-chloro-4-hydroxy phenyl 2-dichloro benzyl methyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl benzyl 4-methoxy-benzyl sulfonium hexafluorophosphate etc.

As above-mentioned benzothiazole

The object lesson of salt can list 3-benzyl benzothiazole

Hexafluoro antimonate, 3-benzyl benzothiazole

Hexafluorophosphate, 3-benzyl benzothiazole

A tetrafluoro borate, 3-(4-methoxy-benzyl) benzothiazole

Hexafluoro antimonate, 3-benzyl-2-methyl-thio-benzothiazole

Hexafluoro antimonate, 3-benzyl-5-chloro benzothiazole

Benzyl benzothiazoles such as hexafluoro antimonate

Salt.

Above-mentioned sulfonium salt (1) and benzothiazole

Preferred 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, 4-hydroxy phenyl benzyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, 4-hydroxy phenyl dibenzyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, 3-benzyl benzothiazole among the salt

Hexafluoro antimonate etc.In the commercially available product of these compounds, サ Application エイ De SI-L85, サ Application エイ De SI-L110, サ Application エイ De SI-L145, サ Application エイ De SI-L150, サ Application エイ De SI-L160 (above by the manufacturing of three new chemical industry (strain)) etc. are arranged.

Above-mentioned thermic acidogenic agent can use separately or mix more than 2 kinds and use.

Above-mentioned acid crosslinking agent is preferably to have 2 above following formula-CH in a part ₂OR ⁴(in the formula, R ⁴Be alkyl, preferred carbonatoms is 1～6, more preferably 1～4 alkyl.) expression 1 valency organic group (hereinafter referred to as " methylol (ether) base ".), the further preferred compound that by the compound of this 1 valency organic group and nitrogen atom bonding, promptly has N-methylol and/or a N-alkoxy methyl is formed.When acid crosslinking agent has 2 above methylols (ether) in a part, each methylol (ether) can be identical separately also can be different separately.

Acid crosslinking agent is at (B) when adhesive resin has carboxyl, and the methylol in the acid crosslinking agent (ether) with the carboxyl reaction in (B) adhesive resin, forms the composition of crosslinked configuration in the presence of the acid that is produced by the thermic acidogenic agent.

This acid crosslinking agent can list, the N of following formula (2) expression for example, N, N ', N ', N ", N " alkoxy methyl trimeric cyanamide such as-six (alkoxy methyl) trimeric cyanamide,

[in the formula (2), R ⁵～R ¹⁰Be alkyl independently of one another, preferred carbonatoms 1～6, further preferred 1～4 alkyl.]

The N of following formula (3) expression, N, N ', alkoxy methyl glycolurils such as N '-four (alkoxy methyl) glycoluril

[in the formula (3), R ¹¹～R ¹⁴Be alkyl independently of one another, preferred carbonatoms 1～6, further preferred 1～4 alkyl.] etc.

Acid crosslinking agent beyond above-mentioned can use the compound that imports hydroxyl first (ether) base in urea-formaldehyde resins, thiocarbamide-formaldehyde resin, melamine formaldehyde resin, triamino triazine-formaldehyde resin, benzo triamino triazine-formaldehyde resin, glycoluril-formaldehyde resin, polyvinyl benzene sulfone derivatives etc.

These acid crosslinking agents can use separately or mix more than 2 kinds and use.

In the above-mentioned acid crosslinking agent, preferred alkoxy methyl melamine class and alkoxy methyl glycoluril class, preferred especially alkoxy methyl melamine class.In addition, owing to have good bridging property, thermotolerance and solvent resistance concurrently, can obtain the cured article of low-k, therefore with mass ratio (preferred 5/95～95/5, further preferred 10/90～90/10 the mixed of α/β) acid crosslinking agent of alkoxy methyl melamine class (α) and alkoxy methyl glycoluril (β) can especially preferably use.

The ink-jet color filter preparation method of resin combination

Ink-jet color filter of the present invention is not particularly limited with the preparation method of resin combination, preferably through having the operation of disperseing (A) pigment in the medium of solvent of 2 acetic ester structures containing (B) dispersion agent, (C) in advance, is prepared.

Below, will in above-mentioned medium, disperse the operation of (A) pigment to be called " pre-dispersed operation " in advance, will in above-mentioned medium, disperse (A) dispersing of pigments liquid to be called " pre-dispersed liquid " in advance.

For example use mixing devices such as dissolving machine, roller mill, microballon mill and rod mill to mix above-mentioned each composition, can implement pre-dispersed operation thus.

Preferred 50～the 400nm of median size of (A) pigment in the pre-dispersed liquid that makes thus, further preferred 50～150nm.

After the pre-dispersed operation, further add pre-dispersed liquid, (D) multi-functional monomer and (E) adhesive resin and the poly-initiator of (F) light as required, solvent, utilize well-established law that they are mixed together, can make ink-jet color filter composition of the present invention thus.

The formation method of colour filter

Below, describe with manufacturing method of color filter resin combination, that utilize ink-jetting style of the present invention (being designated hereinafter simply as " manufacturing method of color filter ") using above-mentioned ink-jet color filter.

As shown in Figure 2; colour filter 1 constitutes following parts lamination substantially; described parts are the protective layer 103 of substrate 101, next door 102, pattern of pixels of all kinds 20 (for example red), 21 (for example green) and 22 (for example blue) and covering pattern of pixels; these component parts are except next door 102; all have light transmission, next door 102 can be light transmission also can be opacifying property.

And then; liquid crystal indicator 6 is the exterior side configuration Polarizer 201 at substrate 101 substantially, and lamination common electrode 202, alignment films 203, liquid crystal layer 204, alignment films 205, pixel electrode 206, substrate 207 and Polarizer 208 form on protective layer 103.

As the material of substrate 101, have in the manufacturing process of colour filter thermotolerance to heating condition, as long as have the material of certain above physical strength, can adopt material with suitable light transmission.Its example can be enumerated glass, silicon, polycarboxylate, polyester, aromatic polyamide, polyamidoimide, polyimide, norbornylene class ring-opening polymerization polymer and hydride thereof etc.And, as required, suitable pre-treatments such as the medicine processing that can implement to carry out to the substrate that contains these materials, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum vapour deposition with silane coupling agent etc.

These materials can also be used in the substrate 207, as required, can also change material in two substrates.

Next door 102 is to be formed with resin combination by suitable next door to form, and the surface of substrate 101 is divided into reticulation with figure, and the zone that is divided in the next door 102 forms the transmission region that sees through light.But the division shape in next door 102 also can change as required.

The employed resin combination of the formation in next door 102, can use (i) to contain irradiations adhesive resin, multi-functional monomer, Photoepolymerizationinitiater initiater etc., by radioactive rays and solidified radioactivity sensitive resin composition, (ii) contain adhesive resin, by the irradiation of radioactive rays acidic compound, utilize acidic effect and irradiation cross-linked compound that can be crosslinked etc., that pass through radioactive rays and solidified radioactivity sensitive resin composition etc. by the irradiation of radioactive rays.These next doors form uses radioactivity sensitive resin compositions, mixed solvent and preparing when it uses normally as liquid composition, and this solvent can be that high boiling solvent also can be a low boiling point solvent.

As formation radioactivity sensitive resin composition in next door of the present invention, preferably open flat 11-281815 communique and contain following compound compositions putting down in writing as special, described compound is: (a) multipolymer of the ethylene unsaturated monomer that R 1216 and unsaturated carboxylic acid (acid anhydride) and other can copolymerization, (b) the acidic compound of irradiation by radioactive rays, (c) utilize acidic effect and cross-linked compound that can be crosslinked by the irradiation of radioactive rays, (d) fluorinated organic compound except that above-mentioned (a) composition and the solvent that (e) can dissolve above-mentioned (a)～(d) composition.

Pattern of pixels 20 is formed with resin combination by the colour filter that contains just like the tinting material of redness, pattern of pixels 21 is formed with resin combination by the colour filter that contains just like the tinting material of green, and pattern of pixels 22 is formed with resin combination by the colour filter that contains just like the tinting material of blueness.These pattern of pixels form by ink-jetting style described later.

The sum of the pattern of pixels that is divided in the next door 102 is that the number that former chromatic number (being red, green and blue three primary colors among the figure) multiply by the pattern of pixels of all kinds in the liquid crystal indicator is obtained.For example, during for the liquid crystal indicator of employed VGA mode in intelligent terminals such as PC, the number of pattern of pixels of all kinds is 640 row * 480 row, therefore forms by adding up to (640 * 480 * 3) individual pattern of pixels to constitute.The arrangement pitches of pattern of pixels for example is 100 μ m.Among the figure,, the reduced number of pattern of pixels is represented for easy to understand.

Material as protective layer 103; can be to be used for the common material that the colour filter protective layer forms; preferably use effect as can utilizing general exposure apparatus, baking oven, hot plate, by light or heat or by and with light and heat solidified material, can realize equipment cost reduction and save space thus.

Common electrode 202 can use the material with light transmission and electroconductibility, and for example ITO (indium tin oxide) is processed to form by well-established law.

Alignment films 203 and 205 for example, can be carried out activation treatment to the film that is formed by suitable liquid crystal aligning agent and forms, and has the effect of liquid crystal molecule in the certain orientation orientation that make.

Liquid crystal layer 204 is that the liquid crystal molecule by split pole constitutes, and can control by applying voltage that the differently-oriented directivity of liquid crystal molecule constitutes.

Pixel electrode 206 disposes corresponding to each pattern of pixels of colour filter 1, is connected with the output terminal of drive unit (with reference to Fig. 4).Pixel electrode 206 also contains the material with light transmission and electroconductibility, and this material can use and common electrode 202 identical materials, as required, also can change over the material different with common electrode 202.Above-mentioned drive unit can use TFT (thin film transistor), TFD (thin film diode) etc.

Be stained with Polarizer 201 and 208 in the outside of substrate 101 and 207.From the behind of liquid crystal indicator 6 irradiation backlight, these Polarizers only allow the light transmission of specific polarized condition.These two Polarizers are following configurations, and the polarization direction that promptly sees through their light afterwards only brings the polarisation rotation angle of light that deviation is arranged with liquid crystal molecule when liquid crystal layer 204 is not applied voltage.

Then, see figures.1.and.2, the manufacturing process of colour filter is described.

At this, only the manufacturing process to the colour filter in the liquid crystal indicator 61 describes.The manufacturing of other composed components of liquid crystal indicator 6 can be in known techniques for application.

Fig. 1 be for the manufacturing process that colour filter 1 is described want portion's longitudinal diagram, the A-A of presentation graphs 3 is to the pairing tangent plane of view.Fig. 3 is the orthographic plan of colour filter 1.

At first, make with radiation sensitive resin composition in the process of solution coat to the substrate 101 in that the next door is formed, carry out preliminary drying (PB) and make solvent evaporation, film thereby form.The PB condition of this moment is: for example, Heating temperature is about 50～150 ℃, and be about 30～600 seconds heat-up time.

Then, by photic mask to these irradiation radioactive rays of filming, carry out postexposure bake (PEB) afterwards, carry out development treatment with alkaline developer, with the radioactive rays of filming not the dissolving of irradiation portion remove, shown in Fig. 1 (a), the partition pattern that obtains the regulation shape of dividing by next door 102 according to the rules arrangement and dispose, and on the surface of substrate 101, be formed with substrate through a plurality of transmission regions 105 of light.The PEB condition of this moment is: for example, Heating temperature is 50～150 ℃, and be about 30～600 seconds heat-up time.The illuminate condition of radioactive rays is for example 1～500mJ/cm ²About.Development conditions is for for example about 10～300 seconds, and developing method can adopt the method for striking (liquid is contained the り method), pickling process, vibration pickling process etc.In addition, also can further carry out the back baking after development, its condition is: for example, Heating temperature is 150～280 ℃, and be about 3 minutes～2 hours heat-up time.

Then, shown in Fig. 1 (b), ink-jet color filter is ejected into each transmission region 105 from ink gun 10 with resin combination, the top formation of resin combination stockpiles in each transmission region 105 than the state of the last terminal drum in next door 102, thus form resin combination stockpile layer 21,22 ...In addition, 20 examples go out the state of resin combination in the ejection way.The spouting velocity of the resin combination of this moment is 0.01～100m/ for example about second.

Then, shown in Fig. 1 (c), heat-treat and make solvent evaporation,, thereby form the pattern of pixels 20,21,22 of specific thickness thus with the resin combination drying to forming the resin combination respectively stockpile layer ...In addition, by such processing, the volume that respectively stockpiles layer reduces.

The thermal treatment of this moment is for example carried out with well heater, and the temperature (for example about 50 ℃) that integral body is heated to regulation is carried out.

Then, as required, after the irradiation radioactive rays,, under the temperature (for example about 150～280 ℃) of regulation, carry out the specified time heating of (about for example 3 minutes～2 hours) in order to make the resin combination complete drying crosslinked.The illuminate condition of the radioactive rays of this moment is for example 1～500mJ/cm ²About.

Form pattern of pixels 20,21,22 ... the time, by using for example red, green or blue resin combination successively, can be to substrate 101 with red, green, blue trichromatic pixel array configuration.

Then, shown in Fig. 1 (d),, use suitable resin, form protective layer 103 by the mode that covers formed each pattern of pixels in order to make protective layer and colour filter flattening surface.

And then, use material with light transmission and electroconductibility (for example ITO etc.), by the method for for example sputtering method, vapour deposition method etc., on protective layer 103, form common electrode 202.When on common electrode 202, forming pattern, make its pattern corresponding, common electrode 202 is carried out etching with other composed components of pixel electrode 206 grades.

Through each above operation, can make colour filter 1.

Then, as shown in Figure 2, at colour filter 1 with dispose between the substrate 207 of pixel electrode 206 of other purposes, further form alignment films 203, liquid crystal layer 204 and alignment films 205 successively, adhere to Polarizer 201 and 208 in two outside, make liquid crystal indicator 6 thus.

When being applied to substrate 101 on the radioactivity sensitive resin composition next door formation, can adopt rotary coating, stream to mould suitable coating method such as coating, roller coat cloth.For the thick thickness of PB, coating thickness is generally 0.1～10 μ m, is preferably 0.5～3.0 μ m.

As forming next door 102 and pattern of pixels 20,21,22 ... the time employed radioactive rays, can use visible rays, ultraviolet ray, far ultraviolet rays yue, X ray, electron beam etc., optimal wavelength is in the radioactive rays of 190～450nm scope.

Employed alkaline developer during as formation next door 102, preferably as yellow soda ash, sodium hydroxide, potassium hydroxide, silicon sodium, inclined to one side silicon sodium, ammoniacal liquor, ethylamine, n-propyl amine, diethylamine, di-n-propyl amine, triethylamine, methyl diethylamide, dimethylethanolamine, trolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 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 water-miscible organic solvents such as amount of methanol, ethanol or tensio-active agent etc.In addition, after the development that utilizes alkaline developer to carry out, wash usually.

This color filter structure is to be made of the control device 2 of control ink gun 10, motor 3 and 4, position transducer 5 etc.

Ink gun 10 sprays with resin combination the colour filter of being supplied with from its nozzle, there is no particular limitation for its mode, it can be known ink-jetting style, and in the present invention, owing to use the colour filter resin combination, therefore preferably this resin combination is not acted on the piezoelectric ink jet formula of heat, with harmless its material.

Being provided with N (N is for counting arbitrarily) in the ink gun 10 of piezoelectric ink jet formula is used for the piezoelectric element 40 of colour filter with the resin combination ejection.Piezoelectric element 40 constitutes in the mode that can control driving and non-driving separately.

Fig. 5 is the fragmentary cross-sectional view of wanting portion of illustration ink gun 10.

Ink gun 10 mainly is made of pressure chamber's substrate 11, oscillating plate 12 and nozzle plate 13, and oscillating plate 12 is located at the one side of pressure chamber's substrate 11, and nozzle plate 13 is located at the another side of pressure chamber's substrate 11.

By the etching silicon substrate, on pressure chamber's substrate 11, form pressure chamber 14, side plate 15, circulation groove 16, supplying opening 17 etc., in order in pressure chamber 14, to produce volume change, therefore will be arranged at the piezoelectric element 40 in the oscillating plate 12 and the position of each pressure chamber 14 and overlap by the distortion of oscillating plate 12.

Oscillating plate 12 is the elasticas that contain pottery etc., arranges and is provided with piezoelectric element 40, and the mode that deforms by the strain owing to piezoelectric element 40 constitutes.In addition, be provided with print cartridge mouth 18 in the oscillating plate 12, so that the colour filter that is stored in the not shown print cartridge can be supplied in pressure chamber's substrate 11 with resin combination, the colour filter that is fed in pressure chamber's substrate 11 circulates by the path of circulation groove 16 → each supplying opening 17 → each pressure chamber 14 with resin combination.Piezoelectric element 40 constitutes with the crystallization that electrode clips the piezoelectricity pottery.

Be provided with in the nozzle plate 13 and be used to spray the nozzle 19 of colour filter with resin combination.Each nozzle 19 is set as corresponding with each pressure chamber 16.

Ink gun 10 only is provided with the kind that colour filter is used resin combination, and in fact, for example redness is used, green is used and each ink gun 10 of blue usefulness in use.Yet, for easy to understand, only show an ink gun 10 at this.

For such ink gun 10, only be applied with the piezoelectric element 40 generation strains of voltage at driving circuit, oscillating plate 12 distortion, thus the pressure chamber corresponding with this piezoelectric element 14 exerted pressure, make from nozzle 19 ejection colour filter resin combinations.Do not produce strain owing to do not apply the piezoelectric element 40 of voltage, therefore can not spray this resin combination in the pressure chamber relative 14 with it.Therefore, constitute a working cell by one group of piezoelectric element 40, pressure chamber 14 and nozzle 19.

Fig. 6 is the orthographic plan of filter element in the substrate that is formed with next door 102 101 of the configuration of each nozzle 19 in the illustration ink gun 10 and the material that becomes colour filter 1.

N nozzle number is used as hn (n is the number from 1 to N), and as shown in the figure, the position Nn of each nozzle 19 (xn, yn) is specially appointed with relative coordinate x2 axle and y2 axle.

To be called filter element with the minimum pixel factor that the lattice in next door 102 is divided, for example, forming the wide of x1 axle (horizontal stroke) direction is 300 μ m, the length of y1 axle (indulging) direction is the window of the size about 100 μ m, for the substrate that has formed the next door, the position Wm of each filter element (xm, ym) (m is from 1 number to the maximum number of filter element), and specify with relative coordinate x1 axle and y1 axle.

The spacing of each nozzle 19 is set as the integral multiple of the axial spacing of x1.For example, in ink gun 10, arrange 60 nozzles 19, when in a filter element, making colour filter spray 3 with resin combination, make ink gun 10 work with driving frequency 14.4kHz, then in the colour filter of 10 type VGA modes of about 900,000 pixels, in 900,000 pixels * 3 droplet/(14400 times/second * 60)=about 3 seconds mode, can store resin combination.But, because in fact therefore the essential traveling time of considering ink gun 10 can be stored to resin combination in all filter elements with interior at 1 minute.

Such manufacturing method of color filter, its manufacturing process is easy, and cost is also low, industrial extremely useful.And, in the present invention, contain the ink-jet color filter resin combination of high boiling solvent by use, then as mentioned above, the formation of pattern of pixels operates in industrial very favourable.

By the colour filter that above-mentioned manufacturing method of color filter is made,, extremely useful in color liquid crystal display arrangement, colour pick-up tube element, color sensor etc. as addition colour mixture type and subtractive colour mixture type.

Colour filter

Being characterized as of colour filter of the present invention used ink-jet color filter resin combination of the present invention, has the pattern of pixels that forms by ink-jetting style.

Except the color liquid crystal display arrangement of transmission-type or reflection-type, colour filter of the present invention is also extremely useful in colour pick-up tube element, color sensor etc.

Liquid crystal indicator

Liquid crystal indicator of the present invention possesses colour filter of the present invention.

Liquid crystal indicator of the present invention can be made suitable structure.For example, colour filter is formed at is different from the driving of disposing thin film transistor (TFT) with on other substrates of substrate, drive and can form relative structure by liquid crystal layer with the substrate that is formed with colour filter with substrate, so the driving of disposing thin film transistor (TFT) with the surface of substrate on the substrate of formation colour filter also can form relative structure with the substrate that is formed with ITO (tin-doped indium oxide) electrode by liquid crystal layer.The latter's structure has can significantly improve aperture opening ratio, can obtain clear, high meticulous liquid crystal indicator.

As mentioned above, pigment dispensing composition of the present invention, ink-jet color filter good with the dispersion stabilization of resin combination, be difficult to drying and printing ink ejection property excellence.

Embodiment

Following mask goes out embodiment and further specifies embodiments of the present invention.But the present invention is not limited to following embodiment.

Pre-dispersed liquid preparation example 1

Handle following material with ball mill, make pre-dispersed liquid (R1).Described material is: as mixture 15 weight parts of the C.I. Pigment red 254/C.I. Pigment red 177/C.I. Pigment red 139=50/35/15 (weight part) of (A) pigment, Disperbyk-2001 (solid component concentration 45.0 weight %) 8.7 weight parts (being scaled 4.0 weight parts) as (B) dispersion agent by solids component, benzyl methacrylate/vinylbenzene N-phenylmaleimide/glyceral methacrylate/methacrylic acid/ω-carboxyl polycaprolactone single-acrylate copolymer solution (copolymerization weight ratio=25/11.25/18.75/5/10/30 as (E) adhesive resin, Mw (by the weight-average molecular weight of polystyrene conversion)=10,000, Mn (by the weight-average molecular weight of polystyrene conversion)=6,000, polymer solvent is the propylene glycol monomethyl ethylhexoate, solid component concentration 33.0 weight %: hereinafter referred to as copolymer solution 1) oxalic acid 1 of 12.1 weight parts and conduct (C), 3-butanediol ester 30.0 weight parts, and as propylene glycol methyl ether acetate 18.2 weight parts of other solvents, 2-oxyethyl group propyl alcohol 16.0 weight parts.

Pre-dispersed liquid preparation example 2

Handle following material with ball mill, make pre-dispersed liquid (G1).Described material is: as mixture 15 weight parts of the C.I. pigment green 36/C.I. Pigment Yellow 73 150=50/50 (weight part) of (A) pigment, Disperbyk-2001 (solid component concentration 45.0 weight %) 8.7 weight parts (being scaled 4.0 weight parts) as (B) dispersion agent by solids component, 1: 12.1 weight part of copolymer solution and as the oxalic acid 1 of (C), 3-butanediol ester 46.0 weight parts, and as propylene glycol methyl ether acetate 18.2 weight parts of other solvents.

Pre-dispersed liquid preparation example 3

Handle following material with ball mill, make pre-dispersed liquid (G2).Described material is: as mixture 15 weight parts of the C.I. pigment green 36/C.I. Pigment Yellow 73 150=50/50 (weight part) of (A) pigment, S56000 (solid component concentration 100 weight %) 4.5 weight parts as (B) dispersion agent, 1: 12.1 weight part of copolymer solution and as the oxalic acid 1 of (C), 3-butanediol ester 46.0 weight parts, and as propylene glycol methyl ether acetate 22.4 weight parts of other solvents.

Pre-dispersed liquid preparation example 4

Handle following material with ball mill, make pre-dispersed liquid (B1).Described material is: as the C.I. pigment Blue 15 of (A) pigment: mixture 15 weight parts of 6/C.I. pigment Violet 23=90/10 (weight part), Disperbyk-2000 (solid component concentration 47.0 weight %) 8.5 weight parts (being scaled 4.0 weight parts) as (B) dispersion agent by solids component, 1: 12.1 weight part of copolymer solution and as the oxalic acid 1 of (C), 3-butanediol ester 30.0 weight parts, and as propylene glycol methyl ether acetate 18.4 weight parts, 2-oxyethyl group propyl alcohol 16.0 weight parts of other solvents.

Pre-dispersed liquid preparation example 5

Except replacing oxalic acid 1,3 butylene glycol ester 30.0 weight parts, make pre-dispersed liquid (r1) in the same manner with pre-dispersed liquid preparation example 1 with butyl carbitol acetic ester 30 weight parts.

Pre-dispersed liquid preparation example 6

Except replacing oxalic acid 1 with propylene glycol methyl ether acetate 48.2 weight parts, 2-oxyethyl group propyl alcohol 16.0 weight parts, outside 3-butanediol ester 30.0 weight parts, propylene glycol methyl ether acetate 18.2 weight parts, make pre-dispersed liquid (r2) in the same manner with pre-dispersed liquid preparation example 1.

Pre-dispersed liquid preparation example 7

Except replacing oxalic acid 1,3 butylene glycol ester 46.0 weight parts, make pre-dispersed liquid (g1) in the same manner with pre-dispersed liquid preparation example 3 with butyl carbitol acetic ester 46.0 weight parts.

Pre-dispersed liquid preparation example 8

Except replace oxalic acid 1,3 butylene glycol ester 46.0 weight parts, propylene glycol methyl ether acetate 18.2 weight parts with propylene glycol methyl ether acetate 64.2 weight parts, make pre-dispersed liquid (g2) in the same manner with pre-dispersed liquid preparation example 2.

Pre-dispersed liquid preparation example 9

Except replacing oxalic acid 1,3 butylene glycol ester 30.0 weight parts, make pre-dispersed liquid (b1) in the same manner with pre-dispersed liquid preparation example 3 with butyl carbitol acetic ester 30 weight parts.

Pre-dispersed liquid preparation example 10

Except replacing oxalic acid 1 with propylene glycol methyl ether acetate 48.4 weight parts, 2-oxyethyl group propyl alcohol 16.0 weight parts, outside 3-butanediol ester 30.0 weight parts, propylene glycol methyl ether acetate 18.4 weight parts, make pre-dispersed liquid (b2) in the same manner with pre-dispersed liquid preparation example 1.

Embodiment 1

Mix following material, make resin combination.Described material is: pre-dispersed liquid (R1) 426 weight parts, benzyl methacrylate/vinylbenzene/N-phenylmaleimide/glyceral methacrylate/methacrylic acid/ω-carboxyl polycaprolactone single-acrylate copolymer solution (copolymerization weight ratio=25/11.25/18.75/5/10/30 as (E), Mw=10,000, Mn=6,000, polymer solvent is an oxalic acid 1, the 3-butanediol ester, solid component concentration 33.2 weight %: hereinafter referred to as copolymer solution 2) 117 weight parts, as (D) multi-functional monomeric dipentaerythritol acrylate 56 weight parts, and the oxalic acid 1 of conduct (C), 3-butanediol ester 394 weight parts, as glycerine 4 weight parts of additive component, MEGAFAC F475 (big Japanese ink chemical industry (strain) is made) 0.4 weight part.

Then, carry out various evaluations by following main points.The results are shown in the table 2.

Initial viscosity is estimated

With the initial viscosity under 25 ℃ of the E type viscometer determinings.The initial viscosity of pre-dispersed liquid is below the 30mPas, considers that from the ejection stability aspect of ink discharge device the initial viscosity of resin combination is preferably below the 15mPas.

Ftheoloqical measurements

Use the visco-elasticity device to measure.At this moment, when being rate of straining 10s ^-1The time complex viscosity be made as 1 o'clock, then consider that from the ejection of ink discharge device stability aspect rate of straining is 500s ^-1The time the velocity of variation of complex viscosity value be preferably below 20%.

The evaluation of storage stability

Each pre-dispersed liquid and resin combination 50g are packed in the front glass container, after 40 ℃ left standstill for 1 week, use the initial viscosity under 25 ℃ of the E type viscometer determinings with air-tight state.At this moment, calculate and leave standstill the velocity of variation of back viscosity, consider that from dispersion stabilization and storage stability the advantageous variant rate is below 5% for initial viscosity.

Settleability is estimated

Each pre-dispersed liquid and resin combination 50g are packed in the front glass container, and after 23 ℃ left standstill 3 months, sedimentary in the visual assessment container a situation arises with air-tight state.Settled being designated as " zero " do not taken place, and settled be designated as " * " takes place.

The ink-jet ejection is estimated

Use the ink-jet blowoff, the visco-elasticity of the drop when spraying each resin combination, continuously ejection property and intermittently ejection property estimate.In visco-elasticity, ejection property and intermittently no problem being designated as " zero " in the evaluation of ejection property continuously, problematic be designated as " * " in any one is estimated.

Contrast gradient is estimated

Make each resin combination after forming thickness on the glass substrate and being the film of 2.0 μ m, (1) has photosensitive material after carrying out 10 minutes preliminary dryings under 80 ℃, with UV irradiation dose 200mJ/cm ²Expose, then 220 ℃ of down bakings 30 minutes, and (2) do not have photosensitive material after carrying out 10 minutes preliminary dryings under 80 ℃, 220 ℃ of bakings 30 minutes down, then, estimate contrast gradient with the contrast gradient determinator respectively.

Embodiment 2～13, comparative example 1～7

Except using each composition by the amount of each composition shown in the table 1, make resin combination in the same manner with embodiment, then estimate in the same manner with embodiment 1.Evaluation result is shown in table 1 and the table 2.

As mentioned above, pigment dispensing composition of the present invention and ink-jet color filter resin combination, because the dispersion stabilization excellence, to be difficult to drying and printing ink ejection property also excellent, in the printing ink that the colour filter when therefore can be used for making colour filter by ink-jetting style is used.

Claims

1. pigment dispensing composition, it is characterized in that: contain (A) pigment, (B) dispersion agent and (C) solvent of intramolecularly with two acetic ester structures, above-mentioned (B) dispersion agent contains and is selected from least a of polyethyleneimine: amine dispersion agent, ammonia ester class dispersion agent and (methyl) acrylic dispersants.

2. ink-jet color filter resin combination is characterized in that: contain the described pigment dispensing composition of claim 1, (D) multi-functional monomer and (E) adhesive resin.

3. colour filter is characterized in that, has the described ink-jet color filter resin combination of the claim 2 of use, by the pattern of pixels of ink-jetting style formation.

4. liquid crystal indicator, it possesses the described colour filter of claim 3.