CN102221779B

CN102221779B - Color composition for color filter, color filter and color liquid crystal display device

Info

Publication number: CN102221779B
Application number: CN201110091486.0A
Authority: CN
Inventors: 成濑秀则; 高见朋宏; 柳政完; 梶田彻
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2010-04-14
Filing date: 2011-04-07
Publication date: 2015-08-26
Anticipated expiration: 2031-04-07
Also published as: TW201300941A; JP5668539B2; TWI507817B; KR20110115082A; JP2011237769A; CN102221779A

Abstract

The invention provides color composition for color filter, color filter and color liquid crystal display device, the colorimetric properties of this color composition for color filter, developability and storage stability are good, it contains A and contains the colorant of pigment, B block multipolymer and C crosslinking chemical, described B block multipolymer has the repetitive 1 shown in formula 1, the repetitive 2 shown in formula 2 and has the repetitive 3 of acidic-group, and the A block had containing repetitive 1 and the B block containing repetitive 2 and repetitive 3.In formula 1, R ¹represent hydrogen atom or methyl, Z represents-N ⁺r ²r ³r ⁴y ^-,-NR ⁵r ⁶maybe can have substituent nitrogen heterocycle, X ¹represent divalent linking group.In formula 2, R ⁷represent the alkylidene of carbon number 2 ~ 4, R ⁸represent the alkyl of carbon number 1 ~ 6, R ⁹represent hydrogen atom or methyl, n represents the integer of 1 ~ 150.R ²~ R ⁴, R ⁵and R ⁶represent hydrogen atom independently of each other, maybe can have substituent alkyl, Y-represents counter anion.

Description

Color composition for color filter, color filter and color liquid crystal display device

Technical field

The present invention relates to color composition for color filter, color filter and color liquid crystal display device, in more detail, relate to for the formation of for the useful dyed layer of color filter used in the color liquid crystal display device, solid-state imager, organic EL display element, electronic paper etc. of transmission-type or reflection-type coloured composition, there is the color filter of the dyed layer using this coloured composition to be formed and there is the color liquid crystal display device of this color filter.

Background technology

When using colored radiation-sensitive composition to manufacture color filter, the colored radiation-sensitive composition of known coating pigment decentralized on substrate after drying, according to required pattern form, radioactive ray (hereinafter referred to as " exposure ") are irradiated to dry coating, and develop, thus obtain the method (patent documentation 1 ~ 2) of assorted pixel.In addition, the optical polymerism composition that also known utilization is dispersed with carbon black forms the method (patent documentation 3) of black matrix.And then also the colored resin composition of known use pigment-dispersing type obtains the method (patent documentation 4) of assorted pixel by ink-jetting style.

But in the field of the color filter for liquid crystal display cells, solid-state imager, along with the requirement of high brightness, high-contrast, the pigment of use has more and more micronized tendency.In order to realize so stable and good dispersiveness through micronized pigment, knownly effectively use spreading agent.Propose and use this spreading agent to improve the dispersiveness of pigment, not only improve contrast, dispersion stabilization but also improve the various methods (patent documentation 5 ~ 6) of developability etc.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 2-144502 publication

Patent documentation 2: Japanese Unexamined Patent Publication 3-53201 publication

Patent documentation 3: Japanese Unexamined Patent Publication 6-35188 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2000-310706 publication

Patent documentation 5: Japanese Unexamined Patent Publication 2003-26949 publication

Patent documentation 6: Japanese Unexamined Patent Publication 2009-25813 publication

Summary of the invention

But, even if utilize these methods described in patent documentation 5 ~ 6, also be difficult to realize the requirement of the high-contrast of color liquid crystal display device in recent years, high color purity and high brightness, and the various problems such as developability in the volume production of color filter can be solved hardly.Therefore, in the urgent need to developing the requirement of high-contrast, high color purity and high brightness and the color composition for color filter of developability excellence that can realize in recent years.

Therefore, problem of the present invention is to provide the good color composition for color filter of colorimetric properties excellence, developability and storage stability.And then problem of the present invention is to provide the dyed layer possessing and formed by above-mentioned coloured composition and the color filter formed and the color liquid crystal display device possessing this color filter.

In view of these actual conditions, the present inventor conducts in-depth research, and found that by using the segmented copolymer with specific repetitive, can solve above-mentioned problem, thus completing the present invention.

That is, the invention provides color composition for color filter, it is characterized in that, containing following composition (A), (B) and (C);

(A) colorant containing pigment;

(B) segmented copolymer, there is the repetitive (1) shown in following formula (1), the repetitive (2) shown in following formula (2) and there is the repetitive (3) of acidic-group, and the A block had containing repetitive (1) and the B block containing repetitive (2) and repetitive (3);

(C) crosslinking chemical.

[in formula (1), R ¹represent hydrogen atom or methyl, Z represents-N ⁺r ²r ³r ⁴y ^-(wherein, R ²~ R ⁴represent hydrogen atom independently of each other, maybe can have substituent alkyl, Y ^-represent counter anion) ,-NR ⁵r ⁶(wherein, R ⁵and R ⁶represent hydrogen atom independently of each other, maybe can have substituent alkyl), maybe can have substituent nitrogen heterocycle, X ¹represent the linking group of divalent.]

[in formula (2), R ⁷represent that carbon number is the alkylidene of 2 ~ 4 independently of each other, R ⁸represent that carbon number is the alkyl of 1 ~ 6, R ⁹represent hydrogen atom or methyl, n represents the integer of 1 ~ 150.]

In addition, the invention provides to have and use above-mentioned coloured composition and the color filter of dyed layer that formed and the color liquid crystal display device possessing this color filter.And then, the invention provides color filter colorant dispersion, it is characterized in that, comprising: the colorant containing above-mentioned (A) pigment, containing above-mentioned (B) segmented copolymer and (F) solvent.Here, so-called " dyed layer " referred to for each color pixel of color filter, black matrix, spacing body night (spacer) etc.

Use coloured composition of the present invention, the color filter of each color pixel with colorimetric properties excellence can be obtained.In addition, the developability of color composition for color filter of the present invention, storage stability are also excellent.

Therefore, color composition for color filter of the present invention can perform well in making the various color filters being representative with the look decomposition color filter of color liquid crystal display device color filter, solid-state imager, organic EL display element color filter, electronic paper color filter.

Embodiment

The present invention is described in detail below.

color composition for color filter

Below, the constituent of color composition for color filter of the present invention (hereinafter referred to as " coloured composition ") is described.

-(A) colorant-

Coloured composition of the present invention contains pigment as (A) colorant.As pigment, there is no particular limitation, organic pigment, inorganic pigment.In the present invention, pigment can be used alone or two or more is used in combination.Certainly, can also by organic pigment and inorganic pigment used in combination.

As above-mentioned organic pigment, such as pigment index (C.I. can be enumerated; The Society of Dyersand Colourists corporation issues) in be categorized as the compound of pigment.Particularly, the compound being endowed following pigment index (C.I.) name can be enumerated.

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

C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 68, C.I. pigment orange 70, C.I. pigment orange 71, C.I. pigment orange 72, C.I. pigment orange 73, C.I. pigment orange 74;

C.I. paratonere 1, C.I. paratonere 2, C.I. paratonere 5, C.I. paratonere 17, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 41, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. pigment red179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 209, C.I. pigment red 21 4, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 262, C.I. paratonere 264, C.I. paratonere 272,

C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38;

C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60, C.I. alizarol saphirol 80;

C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58;

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

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

In addition, as inorganic pigment, such as titanium dioxide, barium sulphate, calcium carbonate, the flowers of zinc, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine can be enumerated, Prussian blue, chrome oxide green, cobalt green, umber, titanium are black, synthesis is iron black, carbon black etc.

Also can by recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method or these combination, pigment be refined and use in the present invention.In addition, pigment can use its improving particle surface with resin as required.As the resin of the improving particle surface by pigment, the resin of vehicles resin or the commercially available various pigment dispersions recorded in such as Japanese Unexamined Patent Publication 2001-1088147 publication can be enumerated.As the resin-coated method of carbon blacksurface, the method recorded in such as Japanese Unexamined Patent Publication 9-71733 publication, Japanese Unexamined Patent Publication 9-95625 publication, Japanese Unexamined Patent Publication 9-124969 publication etc. can be adopted.In addition, primary particle miniaturization uses preferably by so-called salt mill method by organic pigment.Such as method disclosed in Japanese Unexamined Patent Publication 08-179111 publication can be adopted as salt mill method.

Further, by using dyestuff as colorant in color composition for color filter, the high brightness making cannot to reach with pigment separately, high-contrast change into as may.But if use dyestuff as colorant in coloured composition in the past, then alkali-developable significantly worsens (with reference to comparative example 4).On the other hand, in coloured composition of the present invention, by (B) segmented copolymer is used as pigment dispersing agent, even if thus pigment and dye combinations are used as colorant, also can obtain the good coloured composition of alkali-developable (with reference to embodiment 14).

As dyestuff, the compound being such as endowed following pigment index (C.I.) name can be enumerated.

C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. directly red 28, C.I. directly red 83, C.I. direct Huang 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. medium red 7, C.I. medium Huang 5, C.I. based dye such as azo such as Mordant Black 7 grade,

C.I. the anthraquinone based dye such as Vat blue 4 (バ Star ト Block Le 1), C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60;

C.I. the phthalocyanine based dye such as ciba blue 2b 5 (パ Star De Block Le 1);

C.I. the quinone imines based dye such as alkali blue 3, C.I. alkali blue 9;

C.I. the quinoline based dye such as solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64;

C.I. the nitro based dye such as Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42;

Based dye such as methine such as disperse yellow 201 grade.

When using dyestuff as colorant in the present invention, dyestuff can be used alone, or two or more is used in combination.

From the high and aspect of the black matrix of the pixel of excitation excellence or light-proofness excellence of formation brightness, (A) colorant containing proportional be 5 ~ 70 quality % in the solid constituent of coloured composition usually, be preferably 5 ~ 60 quality %.Here solid constituent refers to the composition beyond solvent composition described later.

-(B) segmented copolymer-

(B) segmented copolymer in the present invention has repetitive (1), repetitive (2) and repetitive (3), and possess there is repetitive (1) A block, with there is the B block of repetitive (2) and repetitive (3), play the function of the spreading agent of (A) colorant.

Repetitive (1) is represented by above-mentioned formula (1).

In above-mentioned formula (1), as R ¹, in hydrogen atom and methyl, preferable methyl.

In addition, Z represents-N ⁺r ²r ³r ⁴y ^-,-NR ⁵r ⁶, maybe can have substituent nitrogen heterocycle, R ²~ R ⁶represent hydrogen atom independently of each other, maybe can have substituent alkyl, so-called " alkyl " is the concept comprising aliphatic alkyl, ester ring type alkyl and aromatic hydrocarbyl in the present invention, it can be any form in straight-chain, branch-like and ring-type, can be stable hydrocarbon in addition, also can be unsaturated hydrocarbon, in molecule, unsaturated link can be had with the arbitrary portion of end.

As above-mentioned aliphatic alkyl, preferred carbon number be 1 ~ 20 aliphatic alkyl of (being preferably 1 ~ 12), more specifically can enumerate alkyl that carbon number is 1 ~ 20 (being preferably 1 ~ 12), alkynyl that alkenyl that carbon number is 2 ~ 20 (being preferably 2 ~ 12), carbon number are 2 ~ 20 (being preferably 2 ~ 12).In addition, be the ester ring type alkyl of 3 ~ 20 (being preferably 3 ~ 12) as the preferred carbon number of above-mentioned ester ring type hydrocarbon, more specifically can enumerate the naphthenic base that carbon number is 3 ~ 20 (being preferably 3 ~ 12).And then, as above-mentioned aromatic hydrocarbyl, preferred carbon number be 6 ~ 20 aromatic hydrocarbyl of (being preferably 6 ~ 10), more specifically can enumerate aryl that carbon number is 6 ~ 20 (being preferably 6 ~ 10), aralkyl that carbon number is 7 ~ 16 (being preferably 7 ~ 12).Here, in the present invention, so-called " aryl " refers to monocycle ~ 3 ring type aromatic hydrocarbyl.

Wherein, as R ²~ R ⁶in alkyl, preferred carbon number be 1 ~ 12 alkyl of (being preferably 1 ~ 6), carbon number are the aralkyl of 7 ~ 16 (being preferably 7 ~ 12), particularly preferably methyl, ethyl, propyl group, butyl, benzyl.

In addition, in the present invention, so-called " nitrogen heterocycle " refers to that the inscape as ring at least has the heterocyclic radical of 1 nitrogen-atoms, preferred heteromonocyclic group or the annelated heterocycles base condensed by these 2.These heterocyclic radicals both can be unsaturated rings also can be saturated rings, can have the heteroatoms (such as oxygen atom, sulphur atom) beyond nitrogen-atoms in ring.

As unsaturated heterocycle, can enumerate such as pyridine ring, imidazole ring, thiazole ring, azoles ring, triazole ring, imidazoline ring, tetrahydropyrimidine ring etc.In addition, as saturated rings, such as, can enumerate morpholine ring, piperidine ring, piperazine ring etc.In addition, as the substituting group in nitrogen heterocycle, alkyl, halogen atom, carboxyl, ester group, ether, hydroxyl, amino, amide group, mercapto, thioether group etc. that such as carbon number is 1 ~ 6 can be enumerated.

As above-mentioned heteromonocyclic group, preferably 5 ~ 7 rings, particularly, can enumerate the group with following formula (1-1) or the basic framework shown in (1-2), these heteromonocyclic groups can have substituting group further.

In formula (1-1), R represents hydrogen atom, maybe can have substituent alkyl, " * " represent binding site ( close hand), as the alkyl in R, can enumerate and above-mentioned R ²identical alkyl.

In formula (1-2), " * " represents binding site.

In addition, as above-mentioned annelated heterocycles base, specifically can enumerate the group with the basic framework shown in following formula (1-3) ~ (1-5), these heteromonocyclic groups can have substituting group.

In formula (1-3) ~ (1-5), " * " represents binding site.

As the linking group (X of divalent in above-mentioned formula (1) ¹), such as methylene can be enumerated, alkylidene, arlydene ,-CONH-R that carbon number is 2 ~ 10 (being preferably 2 ~ 6) ¹¹-Ji ,-COO-R ¹²-Ji etc.Here, R ¹¹and R ¹²independently of each other for singly-bound, methylene, carbon number to be the alkylidene of 2 ~ 10 (being preferably 2 ~ 6) or carbon number be 2 ~ 10 ether (alkylidene oxyalkylene (ア Le キレ Application オキシア Le キレ Application base)).Wherein, as X ¹preferably-COO-R ¹²-Ji, as R ¹²preferred carbon number is the alkylidene of 2 ~ 6.

In above-mentioned formula (1), as Y ^-, can Cl be enumerated ^-, Br ^-, I ^-deng halide ion, ClO ₄ ^-, BF ₄ ^-, CH ₃cOO ^-, PF ₆ ^-deng the counter anion of acid.

Repetitive (2) is by shown in above-mentioned formula (2).

In above-mentioned formula (2), R ⁷represent that carbon number is the alkylidene of 2 ~ 4, but can be made up of alkylidene of more than two kinds, preferred ethylidene and/or propylidene.

R ⁸represent that carbon number is the alkyl of 1 ~ 6, but preferable methyl, ethyl, propyl group, butyl.

As R ⁹, in hydrogen atom and methyl, preferable methyl.

N represents the integer of 1 ~ 150, but preferably 1 ~ 20 integer, the more preferably integer of 1 ~ 10, the particularly preferably integer of 1 ~ 5.

Repetitive (3) has acidic-group, and as this acidic-group, there is no particular limitation, can enumerate such as phenolic hydroxyl group, carboxyl, sulfo group ,-SO ₂nH ₂,-C (CF ₃) ₂-OH etc.In the present invention, from the aspect of the alkali-developable of dispersed and gained coloured composition, as acidic-group, preferred phenolic hydroxyl group, carboxyl, particularly preferably carboxyl.

As repetitive (3), such as, can enumerate the repetitive shown in following formula (3).

In formula (3), R ¹⁰represent hydrogen atom or methyl, A represents acidic-group, X ²represent the linking group of singly-bound or divalent.

In above-mentioned formula (3), as R ¹⁰, in hydrogen atom and methyl, preferable methyl.

As the linking group (X of divalent ²), such as methylene can be enumerated, alkylidene that carbon number is 2 ~ 10 (being preferably 2 ~ 6), arlydene ,-CONH-R ¹¹-Ji ,-COO-R ¹²-Ji ,-OCOR ¹³-Ji ,-R ¹⁴-OCO-R ¹⁵-,-COO-(C _mh _2mcOO) l-C _mh _2m-Ji ,-COO-R ¹⁶-OCO-R ¹⁷-etc.Here, R ¹¹~ R ¹⁵represent that singly-bound, methylene, carbon number be 2 ~ 10 alkylidene of (being preferably 2 ~ 6) or carbon number are the ether (alkylidene oxyalkylene) of 2 ~ 10 independently of each other, m represents the integer of 1 ~ 10, and l represents the integer of 1 ~ 4, R ¹⁶represent that methylene or carbon number are alkylidene, the R of 2 ~ 10 (being preferably 2 ~ 6) ¹⁷represent that singly-bound, methylene, carbon number are alkylidene, cyclohexane-1,2-bis-base or the phenylene (such as 1,2-phenylene, Isosorbide-5-Nitrae-phenylene) of 2 ~ 10 (being preferably 2 ~ 6).

Wherein, as X ², preferred singly-bound, phenylene ,-COO-R ¹²-Ji ,-COO-(C _mh _2mcOO) l-C _mh _2m-Ji or-COO-R ¹⁶-OCO-R ¹⁷-.

(B) segmented copolymer can have repetitive other than the above (hereinafter referred to as " repetitive (4) ").As the example of such repetitive (4), can enumerate from the styrenic monomers such as styrene, α-methyl styrene, (methyl) acrylamide, vinyl acetate base ester, the repetitive of the monomers such as vinyl cyanide; The repetitive that following formula (4) represents.Wherein, from the view point of dispersiveness, as repetitive (4), preferably there is the repetitive that following formula (4) represents.Here, so-called " (methyl) acrylate " refers to " acrylate or methacrylate " in the present invention.

In formula (4), R ¹⁸represent that hydrogen atom maybe can have substituent alkyl, R ¹⁹represent hydrogen atom or methyl.

In above-mentioned formula (4), as R ¹⁹, in hydrogen atom and methyl, preferable methyl.

As R ¹⁸in alkyl, can enumerate and above-mentioned R ²identical group, and can have and above-mentioned R ²identical substituting group.Wherein, as R ¹⁸the aryl that the alkyl that preferred carbon number is 1 ~ 12 (being preferably 1 ~ 10), carbon number are 6 ~ 14, carbon number are the aralkyl of 7 ~ 16, particularly preferably methyl, ethyl, propyl group, butyl, 2-ethylhexyl, phenyl, benzyl, phenylethyl.

(B) molecular weight of segmented copolymer is with gel permeation chromatography (GPC, stripping solvent: DMF) weight-average molecular weight (hereinafter also referred to " Mw ") that converts of the polymethylmethacrylate that measures, be preferably 1,000 ~ 30,000, be particularly preferably 5,000 ~ 15,000.In addition, (B) ratio (Mw/Mn) of number-average molecular weight (hereinafter also referred to " Mn ") that converts with the polymethylmethacrylate measured with GPC (stripping solvent: DMF) of the Mw of segmented copolymer preferably 1.0 ~ 1.8, be more preferably 1.0 ~ 1.7, more preferably 1.0 ~ 1.6, be particularly preferably 1.0 ~ 1.3.By such state of (B) segmented copolymer, coloured composition that is dispersed and alkali-developable excellence can be obtained.

(B) as long as segmented copolymer has repetitive (1) as A block, has repetitive (2) and repetitive (3) as B block, then there is no particular limitation, can be A-B segmented copolymer, also can be A-B-A segmented copolymer.

(B) copolymerization ratio (mass ratio) of the A block/B block in segmented copolymer is preferably 1/99 ~ 90/10, and more preferably 10/90 ~ 70/30, particularly preferably 15/85 ~ 60/30.

In A block, repetitive of more than two kinds (1) can be contained in 1 A block, now, various repetitive can be contained with the either type in random copolymerization, block copolymerization in this A block.

In addition, B block such as has repetitive (2) and repetitive (3), or there is repetitive (2), repetitive (3) and repetitive (4), in the present invention, from the view point of dispersiveness, as B block, preferably there is repetitive (2), repetitive (3) and repetitive (4).

The repetitive being formed B block can be contained with the either type in random copolymerization, block copolymerization.In addition, each repetitive respectively containing two or more in 1 B block, now, can contain each repetitive in this B block with the either type in random copolymerization, block copolymerization.

In (B) segmented copolymer, the copolymerization ratios of repetitive (1), is preferably 5 ~ 70 quality %, is more preferably 10 ~ 60 quality %, more preferably 15 ~ 40 quality % in whole repetitive.The copolymerization ratios of repetitive (2), in whole repetitive, is preferably 1 ~ 50 quality %, is more preferably 2 ~ 40 quality.The copolymerization ratios of repetitive (3), is preferably 0.5 ~ 20 quality %, is more preferably 0.5 ~ 15 quality %, more preferably 1 ~ 11 quality % in whole repetitive.The copolymerization ratios of repetitive (4), in whole repetitive, is preferably 10 ~ 80 quality %, is more preferably 20 ~ 70 quality %.By each repetitive is carried out copolymerization with such ratio, coloured composition that is dispersed and alkali-developable excellence can be obtained.

(B) segmented copolymer like this can by such as carrying out living polymerization to manufacture by the monomer giving above-mentioned each repetitive.As living polymerization, Japanese Unexamined Patent Publication 9-62002 publication can be adopted; Japanese Unexamined Patent Publication 2002-31713 publication; P.Lutz, P.Masson et al, Polym.Bull.12,79 (1984); B.C.Anderson, G.D.Andrews et al, Macromolecules, 14,1601 (1981); K.Hatada, K.Ute, et al, Polym.J.17,977 (1985); K.Hatada, K.Ute, et al, Polym.J.18,1037 (1986); The right hand is great one, tagayasu Den one, Process Technology of Polymer, 36,366 (1987); This light of East Village quick Yan, swamp man, macromolecule collection of thesis, 46,189 (1989); M.Kuroki, T.Aida, J.Am.Chem.Soc, 109,4737 (1987); Phase Tian Zhuosan, aboveground auspicious flat, Synthetic Organic Chemistry, 43,300 (1985); D.Y.Sogoh, W.R.Hertler et al, Macromolecules, 20,1473 (1987); J.Polym.Sci.Part A Polym.Chem., 47,3773-3794 (2009); The known method that J.Polym.Sci.Part A Polym.Chem., 47,3544-3557 (2009) etc. record.

As the monomer giving repetitive (1), and the Z in formula (1) is-N ⁺r ²r ³r ⁴y ^-or-NR ⁵r ⁶monomer, such as can enumerate (methyl) Acryloyl amino hydroxypropyltrimonium chloride, (methyl) acryloyl group oxy-ethyl-trimethyl salmiac, (methyl) acryloyl group oxygen ethyl triethyl ammonium chloride, (methyl) acryloyl group oxygen ethyl (4-benzoylbenzyl) ditallowdimethyl ammonium bromide, (methyl) acryloyl group oxygen Ethylbenzyl alkyl dimethyl ammonium chloride, (methyl) acryloyl group oxygen Ethylbenzyl diethylammonium chloride, (methyl) dimethylaminoethyl acrylate ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate propyl diester, (methyl) acrylic acid diethyl amino propyl ester etc.Further, Z is-N ⁺r ²r ³r ⁴y ^-repetitive (1) can also be obtained by such as following methods: be-NR by Z ⁵r ⁶monomer (such as, (methyl) dimethylaminoethyl acrylate ester) be polymerized after, make the halogenated hydrocarbon compounds such as benzyl chloride and this polymer reaction, thus partly that amino is quaternized.

In addition, as the monomer giving repetitive (1), and the Z in formula (1) is the monomer of nitrogen heterocycle, compound group α (monomer 1 ~ 18), the compound etc. shown in following formula (5) of such as following formula can be enumerated.Further, give the monomer of repetitive (1), to can be used alone or two or more is used in combination.

Compound group α

In addition, as the monomer giving repetitive (2), (methyl) acrylic acid 2-methoxy acrylate, methoxyl diglycol (methyl) acrylate, methoxy triethylene (methyl) acrylate, MPEG (methyl) acrylate, methoxyl dipropylene glycol (methyl) acrylate etc. can be enumerated such as.These can be used alone or two or more is used in combination.

As the monomer giving repetitive (3), such as (methyl) acrylic acid can be enumerated, maleic acid, maleic anhydride, (methyl) acrylic acid carboxymethyl ester, (methyl) acrylic acid 2-carboxy ethyl ester, mono succinate [2-(methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, 2-acryloyloxyethyl sulphonic acid, 2-methacryloxyethyl sulfonic acid, 2-acryloyloxyethyl sulphonic acid sodium, 2-acryloyloxyethyl sulphonic acid lithium, 2-acryloyloxyethyl sulphonic acid ammonium, 2-acryloyloxyethyl sulphonic acid imidazoles 2-acryloyloxyethyl sulphonic acid pyridine 2-methacryloxyethyl sodium sulfonate, 2-methacryloxyethyl Sulfonic Lithium, 2-methacryloxyethyl ammonium sulphonate, 2-methacryloxyethyl sulfonic acid imidazoles 2-methacryloxyethyl sulfonic acid pyridine styrene sulfonic acid, Sodium styrene sulfonate, styrene sulfonic acid lithium, styrene sulfonic acid ammonium, styrene sulfonic acid imidazoles styrene sulfonic acid pyridine deng.These can be used alone or two or more is used in combination.

In addition, as the monomer giving repetitive (4), such as (methyl) methyl acrylate can be enumerated, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid bicyclopentane base ester (ジシ Network ロペ Application タニ Le (メタ) ア Network リレ mono-ト), (methyl) isobornyl acrylate, (methyl) benzyl acrylate, (methyl) phenylethyl acrylate etc.These can be used alone or two or more is used in combination.

(B) segmented copolymer can be used alone or two or more is used in combination.Relative to pigment 100 mass parts, the content of (B) segmented copolymer is generally 1 ~ 100 mass parts, is preferably 5 ~ 70 mass parts, more preferably 10 ~ 50 mass parts.If (B) content of segmented copolymer is too much, developability may be damaged.

In the present invention, in order to improve dispersiveness, known spreading agent can also be contained further.As known spreading agent, such as, can enumerate polyurethane series spreading agent, polyethyleneimine system spreading agent, polyoxyethylene alkyl ether system spreading agent, polyoxyethylene alkyl phenyl ether system spreading agent, polyethylene glycol di system spreading agent, sorbitan fatty acid ester system spreading agent, fatty acid modified Polyester spreading agent, dispersant containing acrylic, pigment derivative etc.

As the object lesson of such spreading agent, commodity can be enumerated and be called EFKA (manufacture of EFKAChemicals b.v. (EFKA) company), Disperbyk (BYK Chemie (BYK) Inc.), Disparlon (nanmu originally changes into (strain) makes), Solsperse (Lubrizol Inc.), KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), Polyflow (common prosperity society chemistry (strain) system), EFTOP (TohkemProducts Inc.), Megaface (large Japanese ink chemical industry (strain) system), Fluorad (Sumitomo 3M (strain) system), Asahi Guard, Surflon (being made by Asahi Glass (strain) above) etc.In addition, as the object lesson of pigment derivative, the sulfonic acid etc. of copper phthalocyanine, diketopyrrolopyrrolecocrystals, Kui phthalein ketone can be enumerated.

-(C) crosslinking chemical-

In the present invention, so-called (C) crosslinking chemical refers to the compound of the polymerizable groups with more than 2.As polymerizable groups, such as ethene unsaturated group, epoxy ethyl, oxetanylmethoxy, N-alkoxy methyl amino etc. can be enumerated.In the present invention, as (C) crosslinking chemical, the compound of the compound preferably with (methyl) acryloyl group of more than 2 or the N-alkoxy methyl amino with more than 2.

As the above-mentioned object lesson with the compound of (methyl) acryloyl group of more than 2, can enumerate and aliphatic polyhydroxy compound and (methyl) acrylic acid be reacted and multifunctional (methyl) acrylate of obtaining, multifunctional (methyl) acrylate of caprolactone modification, multifunctional (methyl) acrylate of alkylene oxide modification, make to have multifunctional polyurethane (methyl) acrylate that (methyl) acrylate of hydroxyl and polyfunctional isocyanate react and obtain, make to have (methyl) acrylate of hydroxyl and anhydride reaction and multifunctional (methyl) acrylate etc. with carboxyl obtained

Here, as above-mentioned aliphatic polyhydroxy compound, such as can enumerate the aliphatic polyhydroxy compound of ethylene glycol, propylene glycol, polyglycol, polypropylene glycol and so on 2 yuan, the aliphatic polyhydroxy compound of more than 3 yuan of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol and so on.As above-mentioned (methyl) acrylate with hydroxyl, (methyl) acrylic acid 2-hydroxyethyl ester, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine dimethacrylate etc. can be enumerated such as.As above-mentioned polyfunctional isocyanate, such as, can enumerate toluene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc.As acid anhydrides, the acid anhydride of the dibasic acid of such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride and so on can be enumerated, the tetra-atomic acid dianhydride of pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and so on.

In addition, as multifunctional (methyl) acrylate of above-mentioned caprolactone modification, the compound that [0015] ~ [0018] section can enumerating such as Japanese Unexamined Patent Publication 11-44955 publication is recorded.As multifunctional (methyl) acrylate of above-mentioned alkylene oxide modification, oxirane and/or epoxy pronane modification two (methyl) acrylate of bisphenol-A can be enumerated, the oxirane of cyamelide and/or epoxy pronane modification three (methyl) acrylate, the oxirane of trimethylolpropane and/or epoxy pronane modification three (methyl) acrylate, the oxirane of pentaerythrite and/or epoxy pronane modification three (methyl) acrylate, the oxirane of pentaerythrite and/or epoxy pronane modification four (methyl) acrylate, the oxirane of dipentaerythritol and/or epoxy pronane modification five (methyl) acrylate, the oxirane of dipentaerythritol and/or epoxy pronane modification six (methyl) acrylate etc.

In addition, as the above-mentioned compound with the N-alkoxy methyl amino of more than 2, the compound etc. such as with melamine structure, benzene guanamine structure, urea structure can be enumerated.Should illustrate, so-called melamine structure, benzene guanamine structure refer to that the triazine ring with more than 1 or phenyl replace the chemical constitution of triazine ring as basic framework, are the concepts also comprising melamine, benzene guanamine or these condensation product.As the object lesson of compound of N-alkoxy methyl amino with more than 2, N can be enumerated, N, N, N, N, N-six (alkoxy methyl) melamine, N, N, N, N-tetra-(alkoxy methyl) benzene guanamine, N, N, N, N-tetra-(alkoxy methyl) glycoluril etc.

In these polyfunctional monomers, preferably make the aliphatic polyhydroxy compound of more than 3 yuan and (methyl) acrylic acid react and obtain multifunctional (methyl) acrylate, multifunctional (methyl) acrylate of caprolactone modification, multifunctional polyurethane (methyl) acrylate, there is multifunctional (methyl) acrylate, the N of carboxyl, N, N, N, N, N-six (alkoxy methyl) melamine, N, N, N, N-tetra-(alkoxy methyl) benzene guanamine.From the high intensity of the colored layer, the surface of the colored layer excellent in smoothness, and the light-shielding layer on the substrate unexposed portions and difficult to produce soil (earth dirt made me cry), film residues and other aspects of starting, when the more than 3 yuan aliphatic a polyhydroxy compound with (meth) acrylic acid obtained by reacting a polyfunctional (meth) acrylates, particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , the polyfunctional (meth) acrylate having a carboxyl group, and particularly preferable to pentaerythritol triacrylate succinic anhydride is reacted with the compound obtained, so dipentaerythritol pentaacrylate succinic anhydride is reacted with the compound obtained.

In the present invention, (C) crosslinking chemical can be used alone or two or more is used in combination.

Relative to (A) colorant 100 mass parts, content preferably 10 ~ 1,000 mass parts, particularly preferably 20 ~ 500 mass parts of (C) crosslinking chemical in the present invention.Now, if the content of multi-functional monomer is very few, then sufficient curability may be can not get.On the other hand, if the content of multi-functional monomer is too much, then when giving alkali-developable to coloured composition of the present invention, have alkali-developable reduce and easily produce dirt on the substrate in unexposed portion or on light shield layer, film remains etc. tendency.

-(D) resin glue-

Coloured composition of the present invention can contain (D) resin glue.Thus, the alkali-developable of coloured composition can be made, the cohesive of substrate is improved.As such resin glue, there is no particular limitation, but preferably have the resin of the acidic functionality such as carboxyl, phenolic hydroxyl group.Wherein, preferably there is the polymkeric substance (hereinafter referred to as " polymkeric substance containing carboxyl ") of carboxyl, the ethylene unsaturated monomer (hereinafter referred to as " unsaturated monomer (d1) ") of the carboxyl such as with more than 1 and the multipolymer of other polymerisable ethylene unsaturated monomer (hereinafter referred to as " unsaturated monomer (d2) ") can be enumerated.

As above-mentioned unsaturated monomer (d1), can enumerate such as (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate [2-(methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc.

These unsaturated monomers (d1) can be used alone or two or more is used in combination.

In addition, as above-mentioned unsaturated monomer (d2), can enumerate such as:

The N-substituted maleimide amine of N-phenylmaleimide, N-N-cyclohexylmaleimide and so on; Styrene, α-methyl styrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, aromatic ethenyl compound to vinylbenzyl glycidyl ether, acenaphthylene and so on;

(methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyglycol (n=2 ~ 10) methyl ether (methyl) acrylate, polypropylene glycol (n=2 ~ 10) methyl ether (methyl) acrylate, single (methyl) acrylate of polyglycol (n=2 ~ 10), single (methyl) acrylate of polypropylene glycol (n=2 ~ 10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, three ring [5.2.1.0 ^2,6] decane-8-base (methyl) acrylate, dicyclopentenyl (methyl) acrylate, glycerine list (methyl) acrylate, (methyl) acrylic acid 4-hydroxylphenyl ester, ethylene-oxide-modified (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate, 3-[(methyl) acryloyloxymethyl] oxetanes, 3-[(methyl) acryloyloxymethyl]-3-Ethyloxetane and so on to cumenyl phenol (methyl) acrylate,

Cyclohexyl vinyl ether, isobornyl vinyl ether, three ring [5.2.1.0 ^2,6] decane-8-base vinyl ether, pentacyclopentadecandimethanol base vinyl ether, 3-(ethene yloxymethyl)-3-Ethyloxetane and so on vinyl ether;

The end of the polymer molecular chain of polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane and so on has the macromonomer etc. of list (methyl) acryloyl group.

These unsaturated monomers (d2) can be used alone or two or more is used in combination.

In the multipolymer of unsaturated monomer (d1) with unsaturated monomer (d2), the copolymerization ratios of the unsaturated monomer (d1) in this multipolymer is preferably 5 ~ 50 quality %, more preferably 10 ~ 40 quality %.By making unsaturated monomer (d1) copolymerization in such scope, the coloured composition of alkali-developable and excellent storage stability can be obtained.

As the object lesson of unsaturated monomer (d1) with the multipolymer of unsaturated monomer (d2), such as multipolymer disclosed in Japanese Unexamined Patent Publication 7-140654 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-31308 publication, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 11-258415 publication, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2004-101728 etc. can be enumerated.

In addition; in the present invention, can as open in Japanese Unexamined Patent Publication 5-19467 publication, Japanese Unexamined Patent Publication 6-230212 publication, Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 09-325494 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 2008-181095 publication etc., side chain be such as used to have the polymkeric substance containing carboxyl of the polymerism unsaturated links such as (methyl) acryloyl group as resin glue.

The polystyrene conversion weight-average molecular weight that in the present invention, the employing GPC (stripping solvent: tetrahydrofuran) of resin glue measures, is generally 1,000-100,000, is preferably 3,000-50,000.If weight-average molecular weight is too small, the reductions such as the residual film ratio of the tunicle likely obtained, or pattern form, thermotolerance etc. are impaired, and electrical characteristics worsen, on the other hand, if excessive, likely exploring degree reduces, or pattern form is impaired, and easily produce dry foreign matter when adopting gap nozzle mode to be coated with.

In addition, in the present invention, the weight-average molecular weight of resin glue is preferably 1.0 ~ 5.0 with the ratio (weight-average molecular weight/number-average molecular weight) of the polystyrene conversion number-average molecular weight adopting GPC (stripping solvent: tetrahydrofuran) to measure, and is more preferably 1.0 ~ 3.0.

Resin glue in the present invention can adopt known method manufacture, also such as method disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, International Publication No. 07/029871 pamphlet etc. be can adopt, its structure, weight-average molecular weight, weight-average molecular weight/number-average molecular weight controlled.

In the present invention, resin glue can be used alone or two or more is used in combination.

In the present invention, relative to (A) colorant 100 mass parts, the content of resin glue is generally 10 ~ 1,000 mass parts, is preferably 20 ~ 500 mass parts.If the content of resin glue is very few, such as, likely alkali-developable reduces, or the storage stability of the coloured composition obtained reduces, on the other hand, if too much, relatively colorant concentration reduces, so realize likely becoming difficulty as the aim colour concentration of film.

-(E) Photoepolymerizationinitiater initiater-

(E) Photoepolymerizationinitiater initiater can be contained in coloured composition of the present invention.Thereby, it is possible to give radiation-sensitive to coloured composition.(E) Photoepolymerizationinitiater initiater used in the present invention is the compound that can be produced the spike that can cause the polymerization of above-mentioned (C) crosslinking chemical by the exposure of the radioactive ray such as luminous ray, ultraviolet, far ultraviolet, electron beam, X ray.

As such Photoepolymerizationinitiater initiater, can enumerate such as thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, O-acyl group oxime compound, salt based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, many rings quinone based compound, diazonium based compound, acid imide sulphonic acid ester based compound etc.

In the present invention, Photoepolymerizationinitiater initiater can be used alone or two or more is used in combination.As Photoepolymerizationinitiater initiater, be preferably selected from least a kind in thioxanthones based compound, acetophenone based compound, bisglyoxaline based compound, triazine based compound, O-acyl group oxime compound.

In the present invention in preferred Photoepolymerizationinitiater initiater, as the concrete example of thioxanthones based compound, thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2 can be enumerated, 4-bis-clopenthixal ketone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.

In addition, as the concrete example of above-mentioned acetophenone based compound, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morphlinophenyl) butane-1-ketone etc. can be enumerated.

In addition, as the concrete example of above-mentioned bisglyoxaline based compound, can 2 be enumerated, 2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

Further, when using bisglyoxaline based compound as Photoepolymerizationinitiater initiater, can improve in sensitivity, preferably and use hydrogen donor." hydrogen donor " mentioned here, meaning can to the compound by exposing the free radical supply hydrogen atom produced by bisglyoxaline based compound.As hydrogen donor, such as 2-mercaptobenzothiazole, 2-sulfydryl benzo can be enumerated the mercaptan system hydrogen donors such as azoles, the amine system hydrogen donors such as 4,4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone.In the present invention, hydrogen donor can be used alone or two or more is used in combination, from improving sensitivity aspect further, is preferably combinationally used by the amine system hydrogen donor of the mercaptan system hydrogen donor of more than a kind and more than a kind.

In addition, as the concrete example of above-mentioned triazine based compound, can 2 be enumerated, 4, 6-tri-(trichloromethyl) s-triazine, 2-methyl-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(5-methylfuran-2-base) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(furans-2-base) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(3, 4-Dimethoxyphenyl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-ethoxystyrene base)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-n-butoxyphenyl)-4, two (trichloromethyl) s-triazine etc. of 6-has the triazine based compound of halogenated methyl.

In addition, as the concrete example of O-acyl group oxime compound, can 1 be enumerated, 2-acetyl caproyl, 1-[4-(thiophenyl) phenyl]-, 2-(O-benzoyl oximes), ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-acetyl group oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-base]-, 1-(O-acetyl group oxime), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl base }-9H-carbazole-3-base]-, 1-(O-acetyl group oxime) etc.

In the present invention, when using the Photoepolymerizationinitiater initiater beyond the bisglyoxaline based compounds such as acetophenone based compound, also can be used together sensitizer.As such sensitizer; such as 4 can be enumerated; 4 '-bis-(dimethylamino) benzophenone, 4; 4 '-bis-(diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, EDMAB, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2,5-two (4-diethylamino benzal) cyclohexanone, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin, 4-(diethylamino) chalcone etc.

In the present invention, relative to (C) crosslinking chemical 100 mass parts, content preferably 0.01 ~ 120 mass parts of Photoepolymerizationinitiater initiater, particularly preferably 1 ~ 100 mass parts.In this case, if the content of Photoepolymerizationinitiater initiater is very few, what exposure produced is solidified with and may becomes insufficient, on the other hand, if too much, there is the dyed layer that formed when developing easily from the tendency that substrate comes off.

-(F) solvent-

Coloured composition of the present invention, usually can modulate according to following methods, namely, in (F) solvent, by the colorant containing (A) pigment and (B) segmented copolymer and other the spreading agent that adds as required, (D) part for resin glue together, use such as ball mill, roller mills etc. are pulverized and are mixed, disperse and make dispersible pigment dispersion, then, (C) crosslinking chemical is added in this dispersible pigment dispersion, (D) resin glue added as required, (E) Photoepolymerizationinitiater initiater, (F) solvent etc. added further, and mix.As (F) solvent, form composition (A) ~ (C), other composition of coloured composition as long as disperse or dissolve, and do not react with these compositions, there is the volatility of appropriateness, can suitably choice for use.But, from aspect that is dispersed and stability, when modulating above-mentioned dispersible pigment dispersion, the preferred solvent (hereinafter also referred to " solvent (f1) ") also using (f1) to have hydroxyl and (f2) do not have the solvent (hereinafter also referred to " solvent (f2) ") of hydroxyl.

In such solvent, as solvent (f1), such as glycol monoethyl ether can be enumerated, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary positive propyl ether, diglycol monotertiary n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol list ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol methyl ether, dipropylene monoethylether, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) alkylene glycol monoalkyl ethers such as tripropylene glycol list ether,

The lactic acid alkyl ester such as methyl lactate, ethyl lactate class;

(ring) alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutyl alcohol, the tert-butyl alcohol, octanol, 2-Ethylhexyl Alcohol, cyclohexanol;

The ketols etc. such as diacetone alcohol.

In these solvents (f1), preferably (gathering) alkylene glycol monoalkyl ethers, particularly preferably propylene glycol monomethyl ether, dihydroxypropane single-ether.Solvent (f1) can be used alone or two or more is used in combination.

In addition, as solvent (f2), (gathering) alkylene glycol monoalkyl ether acetate classes such as such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetic acid esters, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters can be enumerated;

Other ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethyl carbitol, tetrahydrofuran;

The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone;

The diacetate esters classes such as propylene glycol diacetate, oxalic acid 1,3-BDO ester, oxalic acid 1,6-hexanediol ester;

The alkoxyl carboxylate classes such as 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxybutyl propionic ester;

Other ester classes such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester;

Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;

Acid amides or the lactams etc. such as DMF, DMA, 1-METHYLPYRROLIDONE.

In these solvents (f2), preferably (gather) alkylene glycol monoalkyl ether acetate class, ethers, ketone, diacetate esters class, alkoxyl carboxylate class, particularly preferably ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetic acid esters, dipropylene glycol methyl ether acetic acid esters, diethylene glycol dimethyl ether, diglycol methyl ethyl ether, cyclohexanone, oxalic acid 1, 3-butanediol ester, oxalic acid 1, 6-hexanediol ester, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate.Solvent (f2) can be used alone or two or more is used in combination.

In the present invention, the solvent (f1) of colorant dispersion is preferably 0.5/99.5 ~ 40/60 with solvent (f2) containing mass ratio (f1/f2), is more preferably 1/99 ~ 30/70, and particularly preferably 5/95 ~ 25/75.

The content of solvent is not particularly limited, and no matter is dispersible pigment dispersion or coloured composition, and the total concentration preferably not comprising each composition of the solvent of this dispersible pigment dispersion or coloured composition is the amount of 5 ~ 50 quality %, is particularly preferably the amount of 10 ~ 40 quality %.By being in this state, color dispersion liquid dispersiveness can be obtained, having good stability, and coating, the coloured composition that has good stability.

-adjuvant-

Coloured composition of the present invention also can contain various adjuvant as required.

As adjuvant, the such as filling agent such as glass, aluminium oxide can be enumerated, the macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl) class, the surfactants such as fluorine system surfactant, silicon system surfactant, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, the closely sealed promoter such as 3-mercaptopropyi trimethoxy silane, the antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-DI-tert-butylphenol compounds, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl) ultraviolet light absorber such as-5-chlorobenzotriazole, alkoxy benzophenone class, the anti-polycoagulant such as sodium polyacrylate, malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, the residue improver such as 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-PD, 2-amino-1,3-propanediol, amino-1, the 2-butylene glycol of 4-, the developability improvers etc. such as mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester, ω-carboxy-polycaprolactone list (methyl) acrylate.

color filter and manufacture method thereof

Color filter of the present invention has the dyed layer using coloured composition of the present invention to be formed.

As the method manufacturing color filter, first can enumerate following method.First, light shield layer (black matrix) is formed on a surface of a substrate as required with the partial-partition by forming pixel.Secondly, after coating is dispersed with the liquid composition of the radiation-ray sensitive composition of such as red colorant on the substrate, carries out prebake conditions and solvent is evaporated, form film.Secondly, after this film being exposed by photomask, use alkaline developer to develop, the unexposed portion of film is dissolved removing.Then, by carrying out rear baking, form the pel array of the red pattern of pixels that is arranged specified.

Secondly, use each colored radiation-sensitive composition of green or cyan, carry out the coating of each colored radiation-sensitive composition, prebake conditions, exposure, development and rear baking as described above, form green pel array and the pel array of cyan on the same substrate successively.Thus, the color filter of the trichromatic pel array being configured with redness, green and cyan on substrate is obtained.But in the present invention, the order forming assorted pixel is not limited to said sequence.

In addition, black matrix by utilizing photoetching process to make employing sputtering, the metallic film such as chromium of evaporation film-forming becomes desired pattern and formed, but also can use the colored radiation-sensitive composition of the colorant being dispersed with black, be formed in the same manner as in time forming above-mentioned pixel.

As the substrate used when forming color filter, such as glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc. can be enumerated.

In addition, to these substrates, the pre-treatment adopting the agent treated, Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. of silane coupling agent etc. suitable also can be implemented as required.

When colored radiation-sensitive composition is coated on substrate, the rubbing method that spray-on process, rolling method, method of spin coating (spin-coating method), slot coating processes, scraping article rubbing method etc. are suitable can be adopted, particularly preferably adopt spin-coating method, slot coating processes.

Drying under reduced pressure and heat drying combine by prebake conditions usually to carry out.Drying under reduced pressure usually proceeds to and reaches 50 ~ 200Pa.In addition, drying about 1 ~ 10 minute at the condition of heat drying is generally 70 ~ 110 DEG C.

For coating thickness, as dried thickness, be generally 0.6 ~ 8.0 μm, be preferably 1.2 ~ 5.0 μm.

As the light source of the radioactive ray used when forming pixel and/or black matrix, the lamp source such as such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp can be enumerated, argon laser, YAG laser, XeCl excimer laser, N_2 laser etc., but optimal wavelength is at the radioactive ray of the scope of 190 ~ 450nm.

The exposure of radioactive ray general preferably 10 ~ 10,000J/m ².

In addition, as above-mentioned alkaline developer, preference is as the aqueous solution of sodium carbonate, NaOH, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1,5-diazabicyclo-[4.3.0]-5-nonene etc.

In above-mentioned alkaline developer, also can add appropriate water-miscible organic solvent such as such as methyl alcohol, ethanol etc., surfactant etc.Further, after alkali development, usually wash.

As development treatment method, spray development method, spray development method, immersion development method can be adopted, soak and put formula (covering liquid) development method etc.Development conditions preferably carries out 5 ~ 300 seconds at normal temperature.

About 10 ~ 60 minutes are carried out at the condition of rear baking is generally 180 ~ 280 DEG C.

The film thickness of the pixel of such formation is generally 0.5 ~ 5.0 μm, is preferably 1.0 ~ 3.0 μm.

In addition, as the second method manufacturing color filter, ink-jetting style also disclosed in known Japanese Unexamined Patent Publication 7-318723 publication, Japanese Unexamined Patent Publication 2000-310706 publication etc., is adopted to obtain the method for assorted pixel.In the method, first, the next door having shade function concurrently is formed on a surface of a substrate.Then, after in the next door by ink discharge device the fluid composition of the coloured composition being dispersed with such as red colorant being ejected into formation, carry out prebake conditions and solvent is evaporated.Then, after this film is exposed as required, be cured by rear baking, form red pattern of pixels.

Then, use each coloured composition of green or cyan, form green pattern of pixels and the pattern of pixels of cyan as described above on the same substrate successively.Thus, the color filter of the trichromatic pattern of pixels being simultaneously configured with redness, green and cyan on substrate is obtained.But in the present invention, the order forming assorted pixel is not limited to said sequence.

Further, above-mentioned next door not only has shade function, also play the function of the coloured composition not colour mixture making the colors be ejected in subregion, therefore, thick compared to the black matrix film thickness used in above-mentioned first method.Therefore, next door uses black radiation-ray sensitive composition to be formed usually.

The substrate used when forming color filter, the light source of radioactive ray, and prebake conditions, the method for rear baking, condition are identical with the first above-mentioned method.Like this, the film thickness of pixel formed by ink-jetting style and the thickness of black matrix are same degree.

In the pattern of pixels obtained like this, after forming diaphragm as required, sputtering is utilized to form nesa coating.After forming nesa coating, can also distance piece be formed further and form color filter.Distance piece can use radiation-ray sensitive composition to be formed usually, but also can make the distance piece (spacing body night) with light-proofness.Now, use and be dispersed with the colored radiation-sensitive composition of black colorant, coloured composition of the present invention also can perform well in the formation of this of spacing body night.

The color filter brightness of the present invention obtained like this and excitation high, therefore exceedingly useful to color liquid crystal display device, colour pick-up tube element, color sensor, organic EL display element, electronic paper etc.

color liquid crystal display device

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

Color liquid crystal display device of the present invention can take suitable structure.Such as can adopt: on the substrate different from the driving substrate being configured with thin film transistor (TFT) (TFT), form color filter, driving substrate and the substrate being formed with color filter via the relative structure of liquid crystal layer, and then also can adopt: on the surface of driving substrate being configured with thin film transistor (TFT) (TFT), be formed with the substrate of color filter, with the substrate being formed with ITO (being doped with the indium oxide of tin) electrode via the relative structure of liquid crystal layer.The structure of the latter has can significantly improve aperture opening ratio, it is bright to obtain and the advantage of the liquid crystal display cells of fine.

Color liquid crystal display device of the present invention, except cold cathode fluorescent tube (CCFL:ColdCathode Fluorescent Lamp), can also possess the backlight unit using White LED as light source.As White LED, the red LED such as using and there is independently spectrum can be enumerated, green LED and cyan LED and obtain the White LED of white light, display predetermined colors in combination LED, green LED and cyan LED obtain the White LED of white light by colour mixture, combination cyan LED, red LED and green-emitting phosphor obtain the White LED of white light by colour mixture, combination cyan LED, red-emitting phosphors and green-emitting phosphor obtain the White LED of white light by colour mixture, the White LED of white light is obtained by the colour mixture of cyan LED and YAG system fluorophor, combination cyan LED, orange phosphor and green-emitting phosphor obtain the White LED of white light by colour mixture, combination ultraviolet LED, red-emitting phosphors, green-emitting phosphor and hanced cyan fluorescent body obtain the White LED etc. of white light by colour mixture.

Color liquid crystal display device of the present invention can be suitable for TN (Twisted Nematic, twisted-nematic) type, STN (Super Twisted Nematic, supertwist to row) type, IPS (In-PlanesSwitching, in face switch) type, VA (Vertical Alignment, vertical orientated) type, OCB (Optically Compensated Birefringence, optical compensation curved arrangement) type etc. be applicable to liquid crystal type.

Embodiment

Below enumerate embodiment, embodiments of the present invention are illustrated further.But the present invention is not limited to following embodiment.

The synthesis > of < (B) segmented copolymer

Synthesis example 1

In the flask possessing stirrer, by the methacrylic acid (hereinafter referred to as " MA ") of 1.4g, methoxy poly (ethylene glycol) monomethacrylates (the PME-200 of 5.6g, Japan Oil Co's system) (hereinafter referred to as " PME-200 "), the n-BMA (hereinafter referred to as " nBMA ") of 5.0g, the methacrylic acid 2-ethylhexyl (hereinafter referred to as " EHMA ") of 5.0g, the benzyl methacrylate (hereinafter referred to as " BzMA ") of 1.7g, the methyl methacrylate (hereinafter referred to as " MMA ") of 7.8g, 2 of 303mg, pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of 2 '-azoisobutyronitrile (hereinafter referred to as " AIBN ") and 781mg is dissolved in the toluene of 30mL, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 60 DEG C, this temperature is kept 24 hours, thus carry out active free radical polymerization.

Then, the dimethylamine ethyl ester (hereinafter referred to as " DAMA ") of AIBN and the 1.4g of 73mg is dissolved in the toluene of 20mL, carry out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 60 DEG C, carry out the active free radical polymerization of 24 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the block copolymer solution of B block of the repetitive from MA, PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-1) ".

Synthesis example 2

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 579mg of nBMA, 224mg of PME-200,12.9g of MA, 8.4g of 1.4g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 57 DEG C, this temperature is kept 34 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 5.3g of 277mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 57 DEG C, carry out the active free radical polymerization of 34 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200 and nBMA.Using the segmented copolymer that obtains as " segmented copolymer (B-2) ".

Synthesis example 3

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 357mg of MMA, 139mg of nBMA, 3.4g of PME-200,2.8g of MA, 4.2g of 1.4g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 60 DEG C, this temperature is kept 24 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 16.2g of 277mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 60 DEG C, carry out the active free radical polymerization of 24 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-3) ".

Synthesis example 4

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 261mg of BzMA, 101mg of nBMA, 2.8g of PME-200,2.8g of MA, 2.8g of 1.4g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 60 DEG C, this temperature is kept 24 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 18.2g of 946mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 60 DEG C, carry out the active free radical polymerization of 24 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA and BzMA.Using the segmented copolymer that obtains as " segmented copolymer (B-4) ".

Synthesis example 5

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 513mg of nBMA, 199mg of PME-200,10.9g of MA, 10.6g of 0.5g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 57 DEG C, this temperature is kept 34 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 5.9g of 306mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 57 DEG C, carry out the active free radical polymerization of 34 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200 and nBMA.Using the segmented copolymer that obtains as " segmented copolymer (B-5) ".

Synthesis example 6

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 768mg of MMA, 312mg of BzMA, 7.6g of EHMA, 1.4g of nBMA, 3.6g of PME-200,3.6g of MA, 2.8g of 3.1g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 57 DEG C, this temperature is kept 34 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 5.9g of 336mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 57 DEG C, carry out the active free radical polymerization of 34 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-6) ".

Synthesis example 7

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 696mg of nBMA, 270mg of PME-200,11.8g of MA, 4.8g of 5.6g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 60 DEG C, this temperature is kept 24 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 5.9g of 306mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 60 DEG C, carry out the active free radical polymerization of 24 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200 and nBMA.Using the segmented copolymer that obtains as " segmented copolymer (B-7) ".

Synthesis example 8

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 856mg of MMA, 332mg of BzMA, 2.8g of EHMA, 1.4g of nBMA, 1.4g of PME-200,2.8g of MA, 2.8g of 11.2g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 60 DEG C, this temperature is kept 24 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 5.6g of 291mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 60 DEG C, carry out the active free radical polymerization of 24 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-8) ".

Synthesis example 9

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 621mg of MMA, 337mg of BzMA, 7.2g of EHMA, 1.6g of nBMA, 3.5g of PME-200,3.5g of MA, 1.9g of 1.4g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 62 DEG C, this temperature is kept 20 hours, thus carry out active free radical polymerization.

Then, the DAMA of AIBN and the 8.8g of 640mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 62 DEG C, carry out the active free radical polymerization of 20 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-9) ".

Synthesis example 10

In the flask possessing stirrer, be dissolved in the toluene of 30mL by pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters of AIBN and 507mg of MMA, 197mg of BzMA, 1.5g of EHMA, 1.5g of nBMA, 2.8g of PME-200,5.6g of MA, 7.3g of 1.4g, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 57 DEG C, this temperature is kept 34 hours, thus carry out active free radical polymerization.

Then, the monomer-1 of AIBN and the 7.8g of 312mg is dissolved in the toluene of 20mL, carries out the nitrogen displacement of 30 minutes, obtained solution is added in above-mentioned reaction solution, at 57 DEG C, carry out the active free radical polymerization of 34 hours.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of monomer-1 A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-10) ".

Synthesis example 11

In flask, add the lithium chloride (3.63 quality % concentration THF solution) of the tetrahydrofuran (hereinafter referred to as " THF ") of 594.35g, 10.98g, be cooled to-60 DEG C.Then, the n-BuLi (15.36 quality % concentration hexane solution) of 7.89g is added, slaking 10 minutes.

Then, through methacrylic acid 1-ethoxy ethyl ester (hereinafter referred to as " EEMA "), the nBMA of 61.33g, the mixed liquor with the PME-200 of 26.19g of 30 minutes instillation 4.04g, after instillation, reaction 30 minutes is continued.Then use vapor-phase chromatography (hereinafter referred to as " GC ") GPC (mobile phase THF, DMF) to measure, thus determine the disappearance of monomer.

Then, the DAMA of instillation 39.71g, continues reaction 30 minutes after instillation.Then use GCGPC (mobile phase DMF) to measure, thus after confirming the disappearance of monomer, the methyl alcohol adding 3.21g stop reaction.

The propylene glycol methyl ether acetate solution 200g of 50 quality % concentration of precursor copolymer before obtaining is heated to 160 DEG C of reactions 3 hours, thus carries out the deprotection of EEMA.Then, by adding propylene glycol methyl ether acetate, nonvolatile component is made to be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200 and nBMA.Using the segmented copolymer that obtains as " segmented copolymer (B-11) ".

Synthesis example 12

In flask, add the lithium chloride (3.63 quality % concentration THF solution) of THF, 11.20g of 578.66g, be cooled to-60 DEG C.Then, the n-BuLi (15.36 quality % concentration hexane solution) of 7.34g is added, slaking 10 minutes.

Then, add the MMA of 4.30g, continue reaction 5 minutes.Then, after being measured the disappearance confirming monomer by GC, GPC mensuration is carried out in part sampling, generates the polymkeric substance that molecular weight is 293 (2.92 aggressiveness).

Then, through the BzMA of MMA, 15.03g of nBMA, 36.48g of EHMA, 19.50g of EEMA, 19.80g of 30 minutes instillation 4.52g, the mixed liquor with the PME-200 of 11.99g, after instillation, reaction 30 minutes is continued.Then the disappearance determining monomer is measured by GCGPC (mobile phase THF, DMF).

Then, the DAMA of instillation 36.98g, continues reaction 30 minutes after instillation.Then, after confirming the disappearance of monomer by GCGPC (mobile phase DMF) mensuration, the methyl alcohol adding 3.21g stops reaction.

The propylene glycol methyl ether acetate solution 200g of 50 quality % concentration of precursor copolymer before obtaining is heated to 160 DEG C of reactions 3 hours, thus carries out the deprotection of EEMA.Then, by adding propylene glycol methyl ether acetate, nonvolatile component is made to be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from MA, PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (B-12) ".

Relatively synthesis example 1

In flask, add the lithium chloride (3.63 quality % concentration THF solution) of THF, 0.28g of 558.67g, be cooled to-60 DEG C.Then, the n-BuLi (15.36 quality % concentration hexane solution) of 7.60g is added, slaking 10 minutes.

Then, add the MMA of 4.38g, continue reaction 5 minutes.Then, after being measured the disappearance confirming monomer by GC, GPC mensuration is carried out in part sampling, generates the polymkeric substance that molecular weight is 346 (3.46 aggressiveness).

Then, through the BzMA of MMA, 8.01g of nBMA, 31.66g of EHMA, 16.95g of 30 minutes instillation 17.08g, the mixed liquor with the PME-200 of 9.48g, after instillation, reaction 30 minutes is continued.Then the disappearance determining monomer is measured by GCGPC (mobile phase THF, DMF).

Then, the DAMA of instillation 42.98g, continues reaction 30 minutes after instillation.Then, after confirming the disappearance of monomer by GCGPC (mobile phase DMF) mensuration, the methyl alcohol adding 2.40g stops reaction.Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain comprise have from the repetitive of DAMA A block and there is the segmented copolymer of B block of the repetitive from PME-200, nBMA, EHMA, BzMA and MMA.Using the segmented copolymer that obtains as " segmented copolymer (b-1) ".

Relatively synthesis example 2

In the flask possessing stirrer, be dissolved in toluene 50mL by the AIBN of DAMA, 451mg of nBMA, 5.3g of PME-200,12.9g of MA, 8.4g of 1.4g and pyrazoles-1-carbodithioic acid cyano group (dimethyl) methyl esters 579mg, the nitrogen carrying out 30 minutes froths.Then slowly stir, make the temperature of reaction solution rise to 57 DEG C, this temperature is kept 34 hours, thus carry out active free radical polymerization.

Then, by reduced pressure concentration, solvent propylene glycol methyl ether acetate is replaced, and make nonvolatile component be 40 quality %.Thus, obtain by the random copolymers of the repetitive had from MA, PME-200, nBMA and DAMA.Using the random copolymers that obtains as " multipolymer (b-2) ".

The mensuration > of <Mw and Mw/Mn

Mw and the Mn GPC of utilization as described below of (B) segmented copolymer obtained in above-mentioned each synthesis example is measured.In Table 1, measurement result is represented together with the copolymerization ratios (quality %) of each monomer in (B) segmented copolymer.

Device: GPC-104 (Showa Denko K. K's system).

Post: KD-G, KF-603, KF-602, KF-601 are combined.

Mobile phase: DMF

The mensuration > of < acid number

The acid number of (B) segmented copolymer obtained in above-mentioned each synthesis example is measured with following main points.Measurement result is shown in table 1.

By the block copolymer solution precision weighing of 0.5g to the unit of 1mg, and be divided in glass container.After being diluted to 50mL with propylene glycol methyl ether acetate, adding phenolphthalein, carry out titration with the alcohol repellency potassium hydroxide aqueous solution of 0.1N, and will the point of pink colour be coloured to as terminal.Carry out blank test equally.By (B) segmented copolymer and blank test the alcohol repellency potassium hydroxide solution infusion volume of 0.1N and calculate acid number (unit: mgKOH/g).Should illustrate, the acid number in the present invention represents that neutralization does not comprise the milligram number of the KOH required for the nonvolatile component 1g of the solvent of block copolymer solution.

The mensuration > of < amine value

The amine value of (B) segmented copolymer obtained in above-mentioned each synthesis example is measured with following main points.Measurement result is shown in table 1.

By the block copolymer solution precision weighing of 0.5g to the unit of 1mg, and be divided in glass container.Add acetic anhydride/acetic acid=9/1 (volume ratio) 20mL and make it dissolve, placing 3 hours in room temperature.Then, after adding acetic acid 30mL further, use potential difference (PD) determinator AT-510 (capital of a country electronics industry Co., Ltd. system), carry out titration with 0.1mol/L perchloric acid acetum.Carry out blank test equally.Amine value (unit: mgKOH/g) is calculated by the 0.1mol/L perchloric acid acetum infusion volume of (B) segmented copolymer and blank test.Should illustrate, the amine value in the present invention represents the milligram number of the KOH of the sour equivalent required for the nonvolatile component 1g not comprising the solvent of block copolymer solution with neutralization.

Table 1

The modulation > of < colorant dispersion

Modulation example 1

Be used as segmented copolymer (B-1) solution (nonvolatile component=40 quality %) of the C.I. naphthol green 58 (DIC Inc.) of 9 mass parts of colorant and C.I. pigment yellow 150,12.5 mass parts of 6 mass parts, the propylene glycol methyl ether acetate as solvent of 64.5 mass parts and the propylene glycol monomethyl ether of 8 mass parts, ball mill is adopted to process, modulation colorant dispersion (A-1).

Modulation example 2 ~ 14 modulates example 1 ~ 5 with comparing

In modulation example 1, except by except the kind of colorant, segmented copolymer (B) and solvent and quantitative change are more shown in table 1, carry out with modulating in the same manner as example 1, modulated colorant dispersion (A-2) ~ (A-19).

The evaluation > of < colorant dispersion

E type viscosity meter (Tokyo instrument system) is utilized to measure the viscosity of the colorant dispersion obtained.In addition, the colorant dispersion obtained is filled in front glass container, leave standstill 14 days with 23 DEG C under air-tight state after, utilizes E type viscosity meter (Tokyo instrument system) again to measure viscosity.Then, calculate the increment rate of the viscosity after the preserving for 14 days of the viscosity after relative to just modulation, situation increment rate being less than 5% be set to " A ", by more than 5% and the situation being less than 10% be set to " B ", the situation of more than 10% be set to " C " and evaluate.Evaluation result is shown in table 2.

Table 2

In table 2, " G58 " represents C.I. naphthol green 58, " Y150 " represents C.I. pigment yellow 150, " B15:6 " represents C.I. pigment blue 15: 6, " V23 " represents C.I. pigment Violet 23, and " Y179 " represents organic dyestuff C.I. solvent yellow 179, and " PGMEA " represents propylene glycol methyl ether acetate, " PGME " represents propylene glycol monomethyl ether, and " BYK6919 " represents commercially available dispersant B YK-LPN6919 (BYK Inc.).Should illustrate, BYK-LPN6919 is the multipolymer having repetitive (1) and repetitive (2) but do not possess the repetitive with acidic-group, acid number=0, amine value=120mgKOH/g (nonvolatile component conversion), nonvolatile component=60 quality %.

The synthesis > of < resin glue

Synthesis example 13

In the flask possessing cooling tube and stirrer, 44.0g is dissolved in propylene glycol methyl ether acetate 300g to the N-phenylmaleimide of vinylbenzyl glycidyl ether, 40.0g, the BzMA of 16.0g, the α-methylstyrenedimer of AIBN and 8.0g of further input 8.0g, the nitrogen then carried out 15 minutes purges.After nitrogen purges, while reaction solution is stirred the limit and nitrogen froths to be heated to the polymerization that 80 DEG C are carried out 5 hours.

Then, in this reaction solution, the p methoxy phenol of MA, 0.5g of 17.0g and the tetrabutyl ammonium bromide of 4.4g is added, 120 DEG C of reactions 9 hours.Further, add the succinic anhydride of 18.5g, after 6 hours, make fluid temperature remain on 85 DEG C 100 DEG C of reactions, and carry out 2 washings, carry out reduced pressure concentration, resulting in the solution containing 33 quality % resin glues (D-1).Weight-average molecular weight=7 of the polystyrene conversion measured by GPC (stripping solvent: tetrahydrofuran) of this resin glue (D-1), 800, the weight-average molecular weight of polystyrene conversion measured by GPC (stripping solvent: tetrahydrofuran) and ratio=2.8 of number-average molecular weight.

Synthesis example 14

In the flask possessing cooling tube and stirrer, the MA of the hydroxyethyl methacrylate of nBMA, 15.0g of BzMA, 20.0g of 30.0g, the styrene of 20.0g and 15.0g is dissolved in propylene glycol methyl ether acetate 200g, the α-methylstyrenedimer of AIBN and 5.0g of further input 3.0g, the nitrogen then carried out 15 minutes purges.After nitrogen purges, while reaction solution is stirred the limit and nitrogen froths to be heated to the polymerization that 80 DEG C are carried out 5 hours, obtain the solution of the resin glue (D-2) containing 33 quality %.Weight-average molecular weight=10 of the polystyrene conversion measured by GPC (stripping solvent: tetrahydrofuran) of this resin glue (D-2), 000, the weight-average molecular weight of polystyrene conversion measured by GPC (stripping solvent: tetrahydrofuran) and ratio=2.5 of number-average molecular weight.

Synthesis example 15

In the flask possessing cooling tube and stirrer, the hydroxyethyl methacrylate of the mono succinate 2-propionyloxy ethyl ester of the methacrylic acid of the 3-methyl-prop acyloxymethyl-3-Ethyloxetane of 25.0g, 18.0g, 9.0g, the N-phenylmaleimide of 10.0g, BzMA, 14.0g of 24.0g is dissolved in propylene glycol methyl ether acetate 300g, the α-methylstyrenedimer of AIBN and 6.0g of further input 6.0g, the nitrogen then carried out 15 minutes purges.After nitrogen purges, while reaction solution is stirred the limit and nitrogen froths to be heated to the polymerization that 80 DEG C are carried out 5 hours, obtain precursor copolymer solution.

The 2-methacryloxyethyl isocyanates of 13.4g, the 4-metoxyphenol as the 0.2g of polymerization inhibitor is added, 90 DEG C of reactions 2 hours in the precursor copolymer solution obtained of 200g.With regard to this reactant liquor, the ion exchange water of each 75g, washes 2 times, carries out reduced pressure concentration, resulting in the solution containing 33 quality % resin glues (D-3).Weight-average molecular weight=11 of the polystyrene conversion measured by GPC (stripping solvent: tetrahydrofuran) of this resin glue (D-3), 000, the weight-average molecular weight of polystyrene conversion measured by GPC (stripping solvent: tetrahydrofuran) and ratio=1.9 of number-average molecular weight.

The modulation of < coloured composition and evaluation >

The modulation of coloured composition

Embodiment 1

By the colorant dispersion (A-1) of 100 mass parts, the resin glue as resin glue (D-2) of 33.5 mass parts, the M-402 (dipentaerythritol acrylate is principal ingredient) of the Toagosei Co., Ltd as crosslinking chemical of 9.7 mass parts, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone (the trade name IRGACURE369 as Photoepolymerizationinitiater initiater of 4.3 mass parts, CibaSpecialtyChemicals Inc.), and 78.4 the 3-ethoxyl ethyl propionate as solvent of mass parts mix, the coloured composition that modulation is liquid.

The evaluation of checkout time

On the glass substrate, after utilizing spin-coating method to be coated with the fluid composition obtained, carry out the prebake conditions of 2 minutes with the heating plates of 100 DEG C, form the film that film thickness is 2.7 μm.Then, after this substrate is cooled to room temperature, to the film on substrate, utilize high-pressure sodium lamp to each film with the radioactive ray comprising each wavelength of 365nm, 405nm and 436nm via photomask with 1,000J/m ²exposure expose.Then, by spraying the 0.04 quality % potassium hydroxide aqueous solution of 23 DEG C to the film on substrate, carry out spray development.Now, the film of unexposed portion is measured until time (checkout time) of peeling off completely.Further, situation checkout time being less than 60 seconds is set to " A ", by more than 60 seconds and the situation being less than 120 seconds be set to " B ", the situation of more than 120 seconds is set to " C ", evaluates.This time is shorter, and developing powder is faster, has the advantage that can shorten production interval time that color filter manufactures.Evaluation result is shown in table 3.

The evaluation of colorimetric properties

On the glass substrate, after utilizing spin-coating method to be coated with the coloured composition obtained, carry out the prebake conditions of 2 minutes with the heating plates of 100 DEG C, form 3 films that film thickness is different.Then, after this substrate is cooled to room temperature, to the film on substrate, utilize high-pressure sodium lamp to each film with the radioactive ray comprising each wavelength of 365nm, 405nm and 436nm not via photomask with 1,000J/m ²exposure expose.Then, carry out the rear baking of 20 minutes at 220 DEG C, substrate forms cured film.To 3 cured film obtained, with color analyzer (large tomb electronics (strain) MCPD2000 processed), with illuminant-C, 2 degree of visuals field, measure the chromaticity coordinate value (x, y) in CIE color specification system and values (Y).According to measurement result, chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.590 and values (Y).Evaluation result is shown in table 3.Y value, x value when y value is 0.090 is obtained for blueness.

Embodiment 2 ~ 14 and comparative example 1 ~ 5

Except in embodiment 1 by the kind of colorant dispersion, resin glue, crosslinking chemical, Photoepolymerizationinitiater initiater and solvent and quantitative change more as shown in table 3 except, carry out similarly to Example 1, thus carried out modulation and the evaluation of coloured composition.Evaluation result is shown in table 3.Should illustrate, about the coloured composition (embodiment 6 and comparative example 3) of cyan, obtain coordinate figure x and the values (Y) of the look of chromaticity coordinate value y=0.090.Evaluation result is shown in table 3.

Table 3

Each composition is as follows in table 3.

C-1: the potpourri (trade name M402, Toagosei Co., Ltd's system) of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate

C-2: the potpourri (trade name TO-1382, Toagosei Co., Ltd's system) of the monoester compound of Dipentaerythritol Pentaacrylate and succinic acid, dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate

E-1: ethyl ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-, 1-(O-acetyl group oxime) (trade name IRGACURE OX02, CibaSpecialtyChemicals Inc.)

E-2:2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone (trade name IRGACURE369, CibaSpecialtyChemicals Inc.)

EEP:3-ethoxyl ethyl propionate

MBA:3-methoxybutyl acetic acid esters

Claims

1. a color composition for color filter, is characterized in that, containing following composition (A), (B) and (C):

(A) colorant containing pigment;

(B) segmented copolymer, this segmented copolymer has the repetitive (1) shown in following formula (1), the repetitive (2) shown in following formula (2) and has the repetitive (3) of acidic-group, and the A block had containing described repetitive (1) and the B block containing described repetitive (2) and described repetitive (3), in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 0.5 ~ 15 quality %;

(C) crosslinking chemical;

In formula (1), R ¹represent hydrogen atom or methyl,

Z represents-N ⁺r ²r ³r ⁴y ^-,-NR ⁵r ⁶, maybe can have substituent nitrogen heterocycle, wherein, R ²~ R ⁴represent hydrogen atom independently of each other, maybe can have substituent alkyl, Y ^-represent counter anion, R ⁵and R ⁶represent hydrogen atom independently of each other, maybe can have substituent alkyl,

X ¹represent the linking group of divalent;

In formula (2), R ⁷represent that carbon number is the alkylidene of 2 ~ 4 independently of each other,

R ⁸represent that carbon number is the alkyl of 1 ~ 6,

R ⁹represent hydrogen atom or methyl,

N represents the integer of 1 ~ 150.

2. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (1) in whole repetitive is 5 ~ 70 quality %.

3. color composition for color filter according to claim 1, wherein, the weight-average molecular weight Mw of described (B) segmented copolymer is 1.0 ~ 1.8 with the ratio Mw/Mn of number-average molecular weight Mn.

4. color composition for color filter according to claim 1, wherein, further containing (D) resin glue, should not comprise described (B) composition by (D) resin glue.

5. color composition for color filter according to claim 1, wherein, further containing (E) Photoepolymerizationinitiater initiater.

6. color composition for color filter according to claim 1, wherein, contains dyestuff further as colorant.

7. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 1 ~ 11 quality %.

8. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, described B block has the repetitive (4) that following formula (4) represents, the copolymerization ratios of described repetitive (4), be 10 ~ 80 quality % in whole repetitive

9. color composition for color filter according to claim 1, wherein, in described (B) segmented copolymer, the copolymerization ratio of described A block and B block and the copolymerization ratio of A block/B block are 10/90 ~ 70/30 by quality ratio.

10. a color filter, is characterized in that, possesses and uses coloured composition according to any one of claim 1 ~ 9 and the dyed layer that formed.

11. 1 kinds of color liquid crystal display devices, is characterized in that, possess color filter according to claim 10.

12. 1 kinds of pigment dispersing liquid for colour filter, is characterized in that, containing following composition (A), (B) and (F):

(A) colorant containing pigment;

(F) solvent;

In formula (1), R ¹represent hydrogen atom or methyl,

X ¹represent the linking group of divalent;

R ⁸represent that carbon number is the alkyl of 1 ~ 6,

R ⁹represent hydrogen atom or methyl,

N represents the integer of 1 ~ 150.

13. pigment dispersing liquid for colour filter according to claim 12, wherein, in described (B) segmented copolymer, the copolymerization ratios of the described repetitive (3) in whole repetitive is 1 ~ 11 quality %.

14. pigment dispersing liquid for colour filter according to claim 12, wherein, in described (B) segmented copolymer, described B block has the repetitive (4) that following formula (4) represents, the copolymerization ratios of described repetitive (4), be 10 ~ 80 quality % in whole repetitive

15. pigment dispersing liquid for colour filter according to claim 12, wherein, in described (B) segmented copolymer, the copolymerization ratio of described A block and B block and the copolymerization ratio of A block/B block are 10/90 ~ 70/30 by quality ratio.

16. pigment dispersing liquid for colour filter according to claim 12, wherein, described (F) solvent contains (f1) and has the solvent that the solvent of hydroxyl and (f2) do not have hydroxyl.

17. pigment dispersing liquid for colour filter according to claim 16, wherein, what described (f1) in described (F) solvent had that the solvent of hydroxyl and described (f2) do not have the solvent of hydroxyl is 0.5/99.5 ~ 40/60 containing mass ratio.