CN103374240A

CN103374240A - Coloring composition, color filter and display device

Info

Publication number: CN103374240A
Application number: CN2013101164019A
Authority: CN
Inventors: 柳孝典; 蓑轮贵树; 和田夏子
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2012-04-13
Filing date: 2013-04-03
Publication date: 2013-10-30
Also published as: KR20130116176A; TW201402710A; TWI568802B; KR102095248B1

Abstract

The present invention provides a coloring composition which comprises a specific fluorene polymer and has excellent storage stability. The coloring composition is characterized by comprising the following components: (A) a colorant, (B1) a polymer with structural units which are respectively represented by a formula (1), and (C) at least one solvent selected from alcohols and ketones. The proportions of the alcohols and the ketones are 3-50wt% of the total mass of the solvent. In the formula (1), rings Z1 and Z2 represent monocyclic or polycyclic hydrocarbon rings; Y represents a residue which is obtained through eliminating four carboxyls from an organic compound with four carboxyls; R1a and R1b respectively represent a hydrogen atom or an alkyl; R2a and R2b respectively represent an alkyl, an alkoxy, etc.; R3a and R3b respectively represent a hydrogen atom or a methyl; Ra represents a group with a (methyl)acryloxy; Rb represents a group with a hydrogen atom or (methyl)acryloxy; k1 and k2 respectively represent an integer selected from 0-4; m1 and m2 respectively represent an integer selected from 0-3; n1 and n2 respectively represent an integer selected from 0-10; and t and u respectively represent an integer selected from 0-3.

Description

Coloured composition, colour filter and display element

Technical field

The present invention relates to coloured composition, colour filter and display element, more specifically, relate to the color composition for color filter that can be used for forming to the useful pigmented layer of the colour filter that in infiltration type or reflection-type color liquid crystal display element, solid-state imager, organic EL display element, Electronic Paper etc., uses, possess with the colour filter of the pigmented layer of this coloured composition formation and the display element that possesses this colour filter.

Background technology

When using colored radiation-sensitive composition to make colour filter, known have a following methods: after coating pigment decentralized colored radiation-sensitive composition and drying on the substrate, pattern form on demand shines radioactive rays (hereinafter referred to as " exposure ") to dry coating, develop, obtain thus the method (for example can referring to patent documentation 1～2) of each color pixel.In addition, also known have a method of utilizing the optical polymerism composition be dispersed with carbon black to form black matrix (for example can referring to patent documentation 3).In addition, also known have a method (for example can referring to patent documentation 4) of using the pigment-dispersed resin combination to obtain each color pixel by ink-jetting style.

In recent years, in the technical field of colour filter, the trend that shortens pitch time (takt time) by reducing exposure becomes main flow, and this has with regard to strong request a kind ofly can carry out under low exposure that pattern is that form, highly sensitive coloured composition.In addition, because experience surpasses 200 ℃ heating (rear baking) operation in the manufacturing process of colour filter, therefore, the colour filter that is formed by coloured composition has also been required thermotolerance.

For this requirement, the someone proposes to use fluorenes polymer, and for example, patent documentation 5 reports use the photosensitive polymer combination that contains the fluorenes polymer with ad hoc structure, can form in high sensitivity and film.

The prior art document

Patent documentation:

Patent documentation 1: Japanese kokai publication hei 2-144502 communique

Patent documentation 2: Japanese kokai publication hei 3-53201 communique

Patent documentation 3: Japanese kokai publication hei 6-35188 communique

Patent documentation 4: TOHKEMY 2000-310706 communique

Patent documentation 5: No. 4733231 specification sheets of Japanese Patent

Summary of the invention

Yet the present inventor learns that by research if only just the specific fluorenes polymer of reporting in the patent documentation 5 is used for coloured composition, the storage stability of coloured composition is poor, is difficult to practical application.

Therefore, problem of the present invention is to provide a kind of coloured composition that contains specific fluorenes polymer and excellent storage stability.In addition, problem of the present invention also is to provide a kind of display element that possesses the colour filter of the pigmented layer that is made of above-mentioned coloured composition and possess this colour filter.

In view of the foregoing, the present inventor conducts in-depth research, and found that, can solve above-mentioned problem by adding specific solvent, and finish thus the present invention.

That is, the invention provides a kind of coloured composition, it is characterized in that, contain following composition (A), (B1) and (C):

(A) tinting material,

(B1) have the structural unit of following formula (1) expression polymkeric substance (below be also referred to as " (B1) particular polymers ") and

(C) contain at least a solvent that is selected from alcohols and the ketone,

Aforementioned alcohols and ketone contain proportional 3～50 quality % of solvent total amount that are.

(changing 1)

(in the formula (1),

Ring Z ¹And ring Z ²Represent independently of each other monocyclic or condensed ring formula hydrocarbon ring.

Y represents to remove 4 residues behind the carboxyl from the organic compound with 4 carboxyls.

R ^1aAnd R ^1bRepresent independently of each other hydrogen atom or alkyl.

R ^2aAnd R ^2bRepresent independently of each other alkyl, alkoxyl group, acyl group, carbalkoxy, halogen atom, nitro or cyano group.

R ^3aAnd R ^3bRepresent independently of each other hydrogen atom or methyl.

R ^aExpression has the group of (methyl) acryloxy.

R ^bExpression has the group of hydrogen atom or (methyl) acryloxy.

K1 and k2 represent 0～4 integer independently of each other.

M1 and m2 represent 0～3 integer independently of each other.

N1 and n2 represent 0～10 integer independently of each other.

T and u represent 0～3 integer independently of each other.〕

In addition, the invention provides a kind of coloured composition, it is characterized in that, contain following composition (A), (B2) and (C):

(A) tinting material,

(B2) pass through at least compound in following formula (2) expression with quadribasic acid dianhydride (tetrabasic acid dianhydride) reaction polymkeric substance on adduction have the operation of (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical and the polymkeric substance that obtains (below be also referred to as " (B2) particular polymers ") reaches

(C) contain at least a solvent that is selected from alcohols and the ketone,

(changing 2)

(in the formula (2),

R ^1aAnd R ^1bRepresent independently of each other hydrogen atom or alkyl.

R ^3aAnd R ^3bRepresent independently of each other hydrogen atom or methyl.

K1 and k2 represent 0～4 integer independently of each other.

M1 and m2 represent 0～3 integer independently of each other.

N1 and n2 represent 0～10 integer independently of each other.

P1 and p2 represent 1～4 integer independently of each other.〕

In addition, the present invention also provides a kind of indicating meter that possesses the colour filter of the pigmented layer that uses this coloured composition formation and possess this colour filter.Here, " pigmented layer " refers to each color pixel that uses in the colour filter, black matrix, black separator etc.

The storage stability of coloured composition of the present invention is good.In addition, this coloured composition is highly sensitive and can form the pigmented layer that demonstrates high heat resistance.In addition, use coloured composition of the present invention can also form the also pigmented layer of excellence of solvent resistance.

Therefore, coloured composition of the present invention can be very well be used for take color liquid crystal display device with the dichroic filter of colour filter, solid-state imager, organic EL with the making as the various colour filters of representative of colour filter, Electronic Paper colour filter.

Embodiment

Below, the present invention is described in detail.

Below the coloured composition, the constituent of coloured composition of the present invention is described.

-(A) tinting material-

As (A) tinting material among the present invention, can use without particular restriction ground, can do suitable selection to color, material according to the purposes of colour filter etc.Particularly, as tinting material, can list pigment, dye well natural pigment, these coloring agent components both can use separately, also can be used in combination.Wherein, consider from the angle that obtains the high pixel of briliancy, contrast gradient and purity of color, as pigment, be preferably pigment dyestuff, and as dyestuff, be preferably organic dye.

As pigment dyestuff, for example can list at pigment index (C.I.; The distribution of The Society of Dyers and Colourists company) is categorized as the compound of pigment in, namely is presented the compound of following pigment index (C.I.) numbering.

C.I. red pigments such as Pigment red 166, C.I. Pigment red 177, C.I. Pigment red 224, C.I. Pigment red 242, C.I. Pigment red 254, C.I. Pigment red 264;

C.I. veridians such as pigment Green 7, C.I. pigment green 36, C.I. Pigment green 58;

C.I. pigment Blue 15: 6, the blue pigments such as C.I. Pigment blue 80;

C.I. yellow ultramarines such as pigment yellow 83, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. pigment yellow 17 9, C.I. Pigment Yellow 73 180, C.I. Pigment Yellow 73 185, C.I. Pigment Yellow 73 211, C.I. Pigment Yellow 73 215;

C.I. pigment orange 38 orange pigmentss such as grade;

C.I. the violet pigment such as pigment Violet 23;

C.I. the black pigment such as Pigment black 1, C.I. Pigment black 7.

In addition, as pigment, also can use pigment lake (lake pigment).In the present invention, " pigment lake " refer to precipitation agent make the dyestuff of solubility become insoluble pigment and material.The present inventor finds to possess the thermotolerance of the colour filter that uses the pigmented layer that contains the coloured composition in the past of pigment lake and form and the balanced differences of solvent resistance by research.Tinting material by will containing pigment lake with (B1) particular polymers or (B2) particular polymers use, can solve this problem.

In the present embodiment, as pigment lake, without particular restriction, such as listing xanthene class pigment lake, triarylmethane class pigment lake, azo pigment lake, phthalocyanines pigment lake etc.In the present embodiment, be preferably xanthene class pigment lake, triarylmethane class pigment lake, especially be preferably triarylmethane class pigment.

On the other hand, as the precipitation agent that is used to form the color lake, such as listing bariumchloride, calcium chloride, ammonium sulfate, aluminum chloride, Burow Solution, plumbic acetate, Weibull, catarrh promise (katanol), Ta Molu (tamol), isopoly-acid, heteropolyacid etc.As isopoly-acid, such as listing with many wolframic acids, with many vanadic acid, isopolymolybdic acid etc., as heteropolyacid, such as listing phospho-wolframic acid, phospho-molybdic acid, phosphotungstomolybdic acid, silicon tungsten molybdic acid, silicotungstic acid, silicomolybdic acid etc.Among these, be preferably take isopoly-acid, heteropolyacid as precipitation agent, by the pigment lake that the color lake forms, the especially preferred pigment lake that forms take heteropolyacid as precipitation agent, by the color lake.The pigment lake that forms take isopoly-acid, heteropolyacid as precipitation agent, by the color lake for example can be by the method manufacturing of putting down in writing in the TOHKEMY 2011-186043 communique.

In addition, as above-mentioned dyestuff, can list xanthene class dyestuff, triarylmethane class dyestuff, cyanine class dyestuff, anthraquinone dyes, azo dyes, phthalocyanines dye, quinone imides dyestuff, quinoline dyestuff, nitro class dyestuff, methine dyes etc., wherein, be preferably xanthene class dyestuff, triarylmethane class dyestuff, cyanine class dyestuff, anthraquinone dyes, azo dyes etc.More specifically, can list at TOHKEMY 2010-32999 communique, TOHKEMY 2010-254964 communique, TOHKEMY 2011-138094 communique, PCT and apply for the organic dye put down in writing in No. 10/123071 open communique, TOHKEMY 2011-116803 communique, TOHKEMY 2011-117995 communique, TOHKEMY 2011-133844 communique, the TOHKEMY 2011-174987 communique etc.

In the present invention, pigment and dyestuff both can have been distinguished separately use, also can two or more mixing use.

In the present invention, also can pass through the combination of recrystallization method, reprecipitation method, solvent wash method, subliming method, vaccum heating method or these methods with refining rear use of pigment.In addition, pigment can carry out using after the modification to its particle surface with resin as required.As the resin that the particle surface of pigment is carried out modification, for example can list the Vehicle resins (vehicle resin) in TOHKEMY 2001-108817 communique, put down in writing or commercially available various colo(u)rant dispersion resins.As the method in the carbon blacksurface coated with resins, such as the method that can adopt record in Japanese kokai publication hei 9-71733 communique, Japanese kokai publication hei 9-95625 communique, Japanese kokai publication hei 9-124969 communique etc.In addition, pigment dyestuff also can use after with the primary particle miniaturization by so-called salt mill method.Method as salt mill method for example can adopt disclosed method in Japanese kokai publication hei 08-179111 communique.

In addition, in the present invention, with pigment, can also add known dispersion agent and dispersing auxiliary.As known dispersion agent, such as listing polyurethanes dispersion agent, polyethyleneimine: amine dispersion agent, Voranol EP 2001 class dispersion agent, polyoxyethylene alkyl phenyl ether class dispersion agent, polyethylene glycol di class dispersion agent, sorbitan-fatty acid ester class dispersion agent, polyester dispersion agent, acrylic dispersants etc., as dispersing auxiliary, can list pigment derivative etc.

Such dispersion agent can be bought by commerce and obtain, for example can list respectively the Disperbyk-2000 as acrylic dispersants, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324(is above to be Bi Ke chemistry (BYK) company product) etc., Disperbyk-161 as the polyurethanes dispersion agent, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182(is above to be Bi Ke chemistry (BYK) company product), Solsperse76500(Lubrizol Corp. product) etc., Solsperse-24000(Lubrizol Corp. product as polyethyleneimine: amine dispersion agent) etc., as the Ajisper-PB821 of polyester dispersion agent, Ajisper-PB822, Ajisper-PB880, Ajisper-PB881(is above to be Ajinomoto Fine-Techno company product) etc.

In addition, as above-mentioned pigment derivative, particularly, can list the sulfonic acid of copper phthalocyanine, diketopyrrolopyrrolecocrystals, quinophthalone etc.

Consider that from the angle of the black matrix of the pixel that forms briliancy height and purity of color excellence or opacifying property excellence (A) tinting material contains proportional to be 5～70 quality % usually, to be preferably 5～60 quality % in the solids component of coloured composition.Here said solids component refers to (C) described later solvent composition in addition.

-(B) polymkeric substance-

Coloured composition of the present invention contains aforementioned (B1) particular polymers or (B2) particular polymers, and these polymkeric substance also play a role as cure component when playing a role as binder resin.In this manual, reaching (B1) particular polymers (B2), particular polymers is referred to as (B) polymkeric substance.

(B2) particular polymers pass through at least compound in following formula (2) expression with quadribasic acid two anhydride reactants and must polymkeric substance (below be also referred to as " (B2 ') polymkeric substance ".) upper adduction has the operation of (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical and obtain.

(changing 3)

(in the formula (2),

R ^1aAnd R ^1bRepresent independently of each other hydrogen atom or alkyl.

R ^3aAnd R ^3bRepresent independently of each other hydrogen atom or methyl.

K1 and k2 represent 0～4 integer independently of each other.

M1 and m2 represent 0～3 integer independently of each other.

N1 and n2 represent 0～10 integer independently of each other.

P1 and p2 represent 1～4 integer independently of each other.〕

At first, the compound of formula (2) expression described.

Ring Z ¹And ring Z ²Represent independently of each other monocyclic or condensed ring formula hydrocarbon ring, as the monocyclic alkyl, such as listing the monocyclic hydrocarbon such as benzene.As condensed ring formula hydrocarbon, be 8～20 thick two ring type hydrocarbon such as carbon numbers such as can listing indenes, naphthalene; The condensed ring formula hydrocarbon that the three-ring type such as anthracene, phenanthrene is above etc.As condensed ring formula hydrocarbon, preferred carbon number is 10～16 thick two ring type hydrocarbon.Wherein, be preferably benzene, naphthalene, anthracene.Ring Z ¹And ring Z ²Can be identical, also can be different.

R ^1aAnd R ^1bRepresent independently of each other hydrogen atom or alkyl, as alkyl, preferred carbon number is 1～6 alkyl, particularly, can list methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, amyl group, isopentyl, hexyl etc.Wherein, preferred carbon number is 1～4 alkyl, more preferably methyl.R ^1aAnd R ^1bCan be identical, also can be different.

K1 and k2 represent 0～4 integer independently of each other, but are preferably 0 or 1, more preferably 0.In addition, k1, k2 are 2 when above, the R of a plurality of existence ^1a, R ^1bTo each other both can be identical, also can be different.

To R ^1a, R ^1bThe position of substitution without particular restriction, can replace at any carbon atom that consists of on the phenyl ring of fluorene skeleton.

R ^2aAnd R ^2bRepresent independently of each other alkyl, alkoxyl group, acyl group, carbalkoxy, halogen atom, nitro or cyano group, as alkyl, can list alkyl, cycloalkyl, aryl, aralkyl etc.

As aforesaid alkyl, preferred carbon number is 1～20 alkyl, particularly, and except at R ^1aAnd R ^1bBeyond the alkyl shown in the middle example, can list heptyl, octyl group, decyl, dodecyl etc.In these alkyl, more preferably carbon number is 1～8 alkyl, and especially preferred carbon number is 1～6 alkyl.

As aforementioned cycloalkyl, preferred carbon number is 5～10 cycloalkyl, particularly, can exemplify out cyclopentyl, cyclohexyl, suberyl, ring octyl group etc.In these cycloalkyl, preferred carbon number is 5～8 cycloalkyl, and more preferably carbon number is 5 or 6 cycloalkyl.

As aforementioned aryl, preferred carbon number is 6～10 aryl, particularly, can list phenyl, alkyl phenyl etc.As alkyl phenyl, such as listing aminomethyl phenyl, 3,5-dimethylphenyl etc.In these aryl, more preferably carbon number is 6～8 aryl, especially is preferably phenyl.As aforementioned aminomethyl phenyl, such as listing o-tolyl, a tolyl, p-methylphenyl etc., as aforementioned 3,5-dimethylphenyl, such as listing xylyl etc.

As aforementioned aralkyl, preferred carbon number is 7～14 aralkyl, particularly, can list carbon number be on 6～10 the aryl in conjunction with on carbon number be the group that 1～4 alkyl forms, more specifically, can list benzyl, styroyl etc.In these aralkyl, more preferably carbon number be on 6～8 the aryl in conjunction with on carbon number be the group that 1～2 alkyl forms.

As aforementioned alkoxyl group, preferred carbon number is 1～4 alkoxyl group, particularly, can list methoxyl group, oxyethyl group, butoxy etc.

As aforementioned acyl group, preferred carbon number is 1～6 acyl group, particularly, can list ethanoyl etc.

As aforementioned carbalkoxy, preferred carbon number is 1～4 carbalkoxy, particularly, can list methoxycarbonyl, ethoxycarbonyl, butoxy carbonyl etc.

As aforementioned halogen atom, can list fluorine atom, chlorine atom, bromine atoms, iodine atom etc.

In these groups, as R ^2aAnd R ^2bBe preferably alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, more preferably carbon number be 1～6 alkyl, carbon number be 5～8 cycloalkyl, carbon number be 6～10 aryl, at carbon number be on 6～8 the aryl in conjunction with on carbon number be that group, carbon number that 1～2 alkyl forms are 1～4 alkoxyl group, especially preferred carbon number is that 1～4 alkyl, carbon number are that 6～8 aryl, carbon number are 1～4 alkoxyl group.R ^2aAnd R ^2bBoth can be identical, also can be different.

M1 and m2 represent 0～3 integer independently of each other, are preferably 0～2 integer, more preferably 0 or 1, especially be preferably 0.In addition, m1, m2 are 2 when above, the R of a plurality of existence ^2a, R ^2bTo each other both can be identical, also can be different.

To R ^2a, R ^2bThe position of substitution without particular restriction, can the ring Z ¹And ring Z ²On any carbon atom on replace.

R ^3aAnd R ^3bRepresent independently of each other hydrogen atom or methyl.R ^3aAnd R ^3bDuring a plurality of the existence, to each other both can be identical, also can be different.

P1 and p2 but are preferably 1～3 integer independently of each other in 1～4 scope, and more preferably 1 or 2.In addition, to the position of substitution of the group that contains hydroxyl without particular restriction, can be at ring Z ¹And ring Z ²On any carbon atom on replace.

N1 and n2 represent 0～10 integer independently of each other, are preferably 0～4 integer, more preferably 0～2 integer.In addition, n1, n2 are 2 when above, and (many) alkylidene groups oxygen base can be made of same alkoxyl group, also can be made of different types of alkoxyl group.As the combination of different types of alkoxyl group, for example can list oxyethyl group and propylidene oxygen base.

In the compound of aforementioned formula (2) expression, can be listed as following formula (4) and formula (5) expression are shown compound as the example that is more suitable for.

(changing 4)

(in the formula (4), R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, k1, k2, m1, m2, n1, n2, p1 and p2 and aforementioned synonym.But m1+p1 is the integer below 4, and m2+p2 is the integer below 4.〕

(changing 5)

(in the formula (5), R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, k1, k2, m1, m2, n1, n2, p1 and p2 and aforementioned synonym.But m1+p1 is the integer below 5, and m2+p2 is the integer below 5.〕

As the compound of formula (4) expression, be preferably two (hydroxy alkoxy base naphthyl) the fluorenes classes, 9 of 9,9-, two (many alkoxyl groups of hydroxyl naphthyl) the fluorenes classes of 9-.

As 9, two (hydroxy alkoxy base naphthyl) the fluorenes classes of 9-, for example can list 9, two (6-(2-the hydroxyl-oxethyl)-2-naphthyls of 9-) fluorenes, 9, two (6-(2-hydroxyl the propoxy-)-2-naphthyls of 9-) fluorenes, 9, two (5-(2-the hydroxyl-oxethyl)-1-naphthyls of 9-) fluorenes, 9, two (5-(2-hydroxyl the propoxy-)-1-naphthyls of 9-) fluorenes etc.

As 9, two (many alkoxyl groups of hydroxyl naphthyl) the fluorenes classes of 9-, be preferably 9, two (hydroxyl dialkoxy naphthyl) the fluorenes classes of 9-, particularly, can list 9,9-pair 6-(2-(2-hydroxyl-oxethyl) oxyethyl group)-the 2-naphthyl } fluorenes, 9,9-pair 6-(2-(2-hydroxyl propoxy-) propoxy-)-the 2-naphthyl } fluorenes, 9,9-pair 5-(2-(2-hydroxyl-oxethyl) oxyethyl group)-the 1-naphthyl } fluorenes, 9,9-two { 5-(2-(2-hydroxyl propoxy-) propoxy-)-1-naphthyl } fluorenes etc. 9, two (hydroxyl two C2-4 alkoxyl group naphthyls) fluorenes of 9-etc.

Compound as formula (5) expression, be preferably two (hydroxy alkoxy base phenyl) the fluorenes classes, 9 of 9,9-, two (many alkoxyl groups of hydroxyl dialkyl phenyl organic) the fluorenes classes, 9 of 9-, two (hydroxy alkoxy base aryl phenyl) the fluorenes classes, 9 of 9-, two (many alkoxy aryls of hydroxyl phenyl) the fluorenes classes of 9-.

As 9, two (hydroxy alkoxy base phenyl) the fluorenes classes of 9-, for example can list 9, two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes of 9-, 9, two (4-(the 2-hydroxyl propoxy-) phenyl) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (4-(2-hydroxyl the propoxy-)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (the 4-(2-hydroxyl-oxethyl)-3 of 9-, the 5-3,5-dimethylphenyl) fluorenes, 9, two (4-(2-hydroxyl-oxethyl) phenoxyethyl alcohol) fluorenes of 9-, 9, two (4-(the 2-hydroxyl propoxy-) phenoxyethyl alcohol) fluorenes of 9-, 9, two (4-(2-the hydroxyl-oxethyl)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (4-(2-hydroxyl the propoxy-)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (the 4-(2-hydroxyl-oxethyl)-2 of 9-, the 5-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl propoxy-)-2 of 9-, the 5-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl-oxethyl)-3 of 9-, the 6-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl propoxy-)-2 of 9-, the 6-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl-oxethyl)-2 of 9-, the 4-3,5-dimethylphenyl) fluorenes, 9, two (the 3-(2-hydroxyl propoxy-)-2 of 9-, the 4-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl-oxethyl)-3 of 9-, the 4-3,5-dimethylphenyl) fluorenes, 9, two (the 2-(2-hydroxyl propoxy-)-3 of 9-, the 4-3,5-dimethylphenyl) fluorenes etc. 9, two (hydroxy alkoxy alkyl phenyl) the fluorenes classes of 9-.

As two (the many alkoxyl phenyls of hydroxyl) the fluorenes classes of 9,9-, be preferably two (hydroxyl dialkoxy phenyl) the fluorenes classes of 9,9-.As its object lesson, can list 9, two (4-(the 2-hydroxyl diethoxy) phenyl) fluorenes of 9-, 9, two (4-(the 2-hydroxyl dipropoxy) phenyl) fluorenes of 9-, 9, two (4-(2-hydroxyl the diethoxy)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (4-(2-hydroxyl the dipropoxy)-3-aminomethyl phenyl) fluorenes of 9-, 9, two (the 4-(2-hydroxyl diethoxy)-3 of 9-, the 5-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl diethoxy)-2 of 9-, the 5-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl dipropoxy)-2 of 9-, the 5-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl diethoxy)-3 of 9-, the 6-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl dipropoxy)-2 of 9-, the 6-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl diethoxy)-2 of 9-, the 4-3,5-dimethylphenyl) fluorenes, 9, two (the 3-(2-hydroxyl dipropoxy)-2 of 9-, the 4-3,5-dimethylphenyl) fluorenes, 9, two (the 4-(2-hydroxyl diethoxy)-3 of 9-, the 4-3,5-dimethylphenyl) fluorenes, 9, two (2-(2-hydroxyl dipropoxy)-3,4-3,5-dimethylphenyl) fluorenes of 9-etc.

As 9, two (hydroxy alkoxy base aryl phenyl) the fluorenes classes of 9-, can list 9, two (4-(2-the hydroxyl-oxethyl)-3-phenyl) fluorenes, 9 of 9-, two (4-(2-hydroxyl the propoxy-)-3-phenyl of 9-) fluorenes, 9, two (4-(2-hydroxyl propoxy-)-3-tolyl phenyl of 9-) fluorenes etc. 9, two (the hydroxy alkoxy base aryl phenyl) fluorenes of 9-, be preferably two (2-hydroxyl-oxethyl aryl phenyl) fluorenes of 9,9-etc.

As 9, two (many alkoxy aryls of hydroxyl phenyl) the fluorenes classes of 9-, be preferably 9, two (hydroxyl dialkoxy aryl phenyl) the fluorenes classes of 9-particularly, can list 9,9-two { 4-(2-(2-hydroxyl-oxethyl) oxyethyl group)-3-phenyl } fluorenes etc. 9, two (hydroxyl dialkoxy aryl phenyl) the fluorenes classes of 9-are preferably two (2-(2-hydroxyl-oxethyl) the oxyethyl group aryl phenyls of 9,9-) fluorenes etc.

Among the present invention, the compound as above-mentioned formula (2) expression can use the compound of making by well-established law, but also can use BPEF, BOPPEF, BNFEO(is above is Osaka combustion gas chemical company product) etc. commercially available product.

Then, the quadribasic acid dianhydride is described.

As the quadribasic acid dianhydride, for example can list the butane tetracarboxylic acid dianhydride, the pentane tetracarboxylic dianhydride, the hexane tetracarboxylic dianhydride, the tetramethylene tetracarboxylic dianhydride, the pentamethylene tetracarboxylic dianhydride, the hexanaphthene tetracarboxylic dianhydride, the suberane tetracarboxylic dianhydride, the norbornane tetracarboxylic dianhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, the phenyl ether tetracarboxylic dianhydride, 5-(2,5-diketo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, 4-(2,5-diketo tetrahydrofuran (THF)-3-yl)-1,2,3,4-naphthane-1, the 2-dicarboxylic acid anhydride, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 4,4 '-(hexafluoro isopropyl alkene) two anhydride phthalic acids, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride etc.These compounds can use in independent or two or more mixing.Wherein, preferred pyromellitic acid anhydride, 5-(2,5-diketo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride.

Then, (B2 ') polymkeric substance and the reaction with (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical are described.

As having (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical, without particular restriction, get final product so long as have respectively the more than one compound that contains oxygen saturation heterocyclic radical and more than one (methyl) acryl in the molecule.Here, " contain the oxygen saturation heterocyclic radical " and refer to the saturated heterocyclyl that has Sauerstoffatom as the heteroatoms that consists of heterocycle.The binding site that contains oxygen saturation heterocyclic radical and (methyl) acryl that has in (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical is unrestricted.

As containing the oxygen saturation heterocyclic radical among the present invention, the preferred atomicity that consists of ring is 3～7 ring-type ether, particularly, can list Oxyranyle, oxa-cyclobutyl, 3,4-epoxycyclohexyl, tetrahydrofuran base etc.Wherein, consider from reactive angle, be preferably Oxyranyle, oxa-cyclobutyl, 3, the 4-epoxycyclohexyl.

As having (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical, the compound of following formula (3-1), formula (3-2), formula (3-3) expression for example can example be shown.

(changing 6)

(changing 7)

(changing 8)

((3-1), in the formula (3-2), formula (3-3),

R ⁴Expression hydrogen atom or methyl.

R ⁵The group of expression singly-bound or following formula (6) expression.

R ⁶The expression carbon number is 1～6 alkyl.〕

(changing 9)

(in the formula (6), q, r, s represent 0～9 integer independently of each other.

But q, r, s are not 0 simultaneously ,-C ₂H ₄The O-base ,-C ₃H ₆The O-base reaches-C ₄H ₈The O-base can be with the random order combination.〕

In the formula (6) ,-C ₂H ₄The O-base refers to comprise ethylidene and ethane-1, the linking group of 1-two bases ,-C ₃H ₆The O-base refers to comprise propane-1,1-two bases, propane-1,2-two bases, propane-1,3-two bases, propane-2, the linking group of 2-two bases.In addition ,-C ₄H ₈The O-base refers to comprise butane-1,2-two bases, butane-1,3-two bases, butane-Isosorbide-5-Nitrae-two base, butane-2,2-two bases, butane-2, the linking group of 3-two bases etc.

As R ⁶, preferred carbon number is 1～4 alkyl, its object lesson can be enumerated group as hereinbefore.

As the compound of aforementioned formula (3-1) expression, such as listing (methyl) glycidyl acrylate, 2-hydroxyethyl (methyl) acrylate glycidyl ether, (methyl) vinylformic acid 2-hydroxypropyl (methyl) acrylate glycidyl ether, 3-hydroxypropyl (methyl) acrylate glycidyl ether, 4-hydroxybutyl (methyl) acrylate glycidyl ether, polyoxyethylene glycol polypropylene glycol (methyl) acrylate glycidyl ether etc.

In addition, the compound as aforementioned formula (3-2) expression for example can list (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters etc.

In addition, as the compound of aforementioned formula (3-3) expression, such as listing 3-(methacryloxy methyl)-3-methyl trimethylene oxide, 3-(methacryloxy methyl)-3-Ethyloxetane, 3-(acryloyl-oxy ylmethyl)-3-methyl trimethylene oxide, 3-(acryloyl-oxy ylmethyl)-the 3-Ethyloxetane etc.

By (B2 ') polymkeric substance with having (methyl) acrylic compound reaction of containing the oxygen saturation heterocyclic radical polymkeric substance can be directly as the use of (B2) particular polymers, also the part of residual carboxyl can be sealed with Racemic glycidol ethers etc. and use as (B2) particular polymers afterwards.By the part of sealing carboxyl, can suppress the acid number of (B2) particular polymers.

As (B2) of the present invention particular polymers, be preferably the polymkeric substance of the structural unit with following formula (1) expression.

(changing 10)

(in the formula (1), ring Z ¹, the ring Z ², R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, k1, k2, m1, m2, n1 and n2 and aforementioned synonym.

R ^aExpression has the group of (methyl) acryloxy.

R ^bExpression has the group of hydrogen atom or (methyl) acryloxy.

T and u represent 0～3 integer independently of each other.〕

Y represents to remove 4 residues behind the carboxyl from the organic compound with 4 carboxyls, particularly, can list from the quadribasic acid corresponding with aforementioned quadribasic acid dianhydride and remove 4 residues behind the carboxyl.

In the formula (1), R ^aExpression has the group of (methyl) acryloxy, can list the group that has (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical from aforementioned.

R ^bExpression hydrogen atom or (methyl) acryloxy.

T and u represent 0～3 integer independently of each other, are preferably 0～2 integer, more preferably 0 or 1, especially be preferably 0.

Ring Z in the formula (1) ¹, the ring Z ², R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, the ring Z in k1, k2, m1, m2, n1 and n2 and the formula (2) ¹, the ring Z ², R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, k1, k2, m1, m2, n1 and n2 synonym, preferred implementation is also identical.

Have in the polymkeric substance of structural unit of such formula (1) expression, can example the structural unit of following formula (1-A) and formula (1-B) expression be shown as the example that is more suitable for.

(changing 10)

(in the formula (1-A), R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, R ^a, R ^b, Y, k1, k2, m1, m2, n1, n2, t and u and aforementioned synonym.〕

(in the formula (1-B), R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, R ^a, R ^b, Y, k1, k2, m1, m2, n1, n2, t and u and aforementioned same meaning.〕

Among the present invention, the molecular weight of (B) polymkeric substance without particular restriction, but is considered from the angle of coating strength, coating or development, be preferably 1,000～200,000, more preferably 2,500～50,000.In addition, in this manual, (B) molecular weight of polymkeric substance is for gel permeation chromatography (below be abbreviated as GPC) (stripping solvent: the weight-average molecular weight that is scaled polystyrene (Mw) of tetrahydrofuran (THF)) measuring.

Among the present invention, (B) acid number of polymkeric substance is preferably 30～150mgKOH/g, but considers that from the angle of development more preferably 30～130mgKOH/g especially is preferably 50～100mgKOH/g.If acid number is excessively low, then developing powder reduces, and existence can not obtain the situation of necessary pattern.On the other hand, when acid number is too high, overdevelopment, the situation that exists pattern to peel off easily.The mg number of the required KOH of nonvolatile component 1g behind the solvent of polymers soln is removed in " acid number " in this specification sheets expression neutralization.

Among the present invention, as binder resin, also can add other resins beyond (B) polymkeric substance (below be also referred to as " (b) other polymkeric substance ".）。Thus, can improve binding property, alkali-developable, storage stability to substrate.As this polymkeric substance, without particular restriction, but preferably has the resin of the acidic functionalities such as carboxyl, phenol hydroxyl.Wherein, preferably have the polymkeric substance of carboxyl, for example can list ethylene unsaturated monomer with 1 above carboxyl (below be also referred to as " unsaturated monomer (b-1) ".But) with the multipolymer of the ethylene unsaturated monomer of other copolymerization (below be also referred to as " unsaturated monomer (b-2) ").

As the object lesson of unsaturated monomer (b-1) with the multipolymer of unsaturated monomer (b-2), such as listing disclosed multipolymer in Japanese kokai publication hei 7-140654 communique, Japanese kokai publication hei 8-259876 communique, Japanese kokai publication hei 10-31308 communique, Japanese kokai publication hei 10-300922 communique, Japanese kokai publication hei 11-174224 communique, Japanese kokai publication hei 11-258415 communique, TOHKEMY 2000-56118 communique, TOHKEMY 2004-101728 communique etc.

Among the present invention, (b) other polymkeric substance can use in independent or two or more mixing.

Among the present invention, with respect to (A) tinting material 100 mass parts, (B) content of composition is preferably 10～1, and 000 mass parts especially is preferably 20～500 mass parts.At this moment, if (B) content of composition is very few, for example existing, alkali-developable reduces the anxiety of the storage stability reduction of gained coloured composition.On the other hand, if (B) content of composition is too much, then because as film, there is the anxiety that is difficult to reach aim colour concentration in the colorant concentration relative reduce.

In addition, and during with (b) other polymkeric substance, with respect to the total amount of binder resin, (B) content of polymkeric substance is preferably more than 10 quality %, more preferably more than 15 quality %, especially preferably more than 20 quality %.

-(C) solvent-

Coloured composition of the present invention contain at least a solvent that is selected from alcohols and the ketone (below be also referred to as " solvent c1 ".), it accounts for 3～50 quality % in the solvent total amount.Can obtain thus the coloured composition of excellent storage stability.

As above-mentioned alcohols, for example can list

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

(ring) alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, isopropylcarbinol, the trimethyl carbinol, 3-methoxybutanol, octanol, 2-Ethylhexyl Alcohol, hexalin;

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

The ketols such as diacetone alcohol etc.

In these alcohols, be preferably (many) alkylene glycol monoalkyl ethers class, (ring) alkyl alcohols, especially be preferably ethylene glycol mono-n-butyl ether, dipropylene glycol list positive propyl ether, dipropylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monoethyl ether, ethanol, 3-methoxybutanol.Alcohols can use in independent or two or more mixing.

In addition, as above-mentioned ketone, such as listing methyl ethyl ketone, pimelinketone, 2-heptanone, 3-heptanone etc., wherein, be preferably pimelinketone.Ketone can use in independent or two or more mixing.

In addition, as (c1) in addition solvent (below be also referred to as " solvent (c2) "), for example can list

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetic ester, 3-methoxyl group butylacetic acid ester, 3-methyl-(many) alkylene glycol monoalkyl ethers acetate esters such as 3-methoxyl group butylacetic acid ester;

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

Propylene-glycol diacetate, 1,3 butylene glycol diacetate esters, 1, the diacetate esters classes such as 6-hexylene glycol diacetate esters;

3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, the 3-methyl-alkoxyl carboxylate classes such as 3-methoxyl group butyl 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 FCC, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, the positive butyl ester of butyric acid, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, pyruvic acid n-propyl, methyl acetoacetate, methyl aceto acetate, 2-Oxobutyric acid ethyl ester;

Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;

The acid amides such as DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone or lactams etc.

In these solvents (c2), be preferably (many) alkylene glycol monoalkyl ethers acetate esters, ethers, diacetate esters class, alkoxyl carboxylate class, especially be preferably ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxyl group butylacetic acid ester, dipropylene glycol monomethyl ether acetic ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, 1,3-butyleneglycol diacetate esters, 1,6-hexylene glycol diacetate esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate.Solvent (c2) can use in independent or two or more mixing.

In the present invention, solvent (c1) contain proportional 5～50 quality % that are preferably the solvent total amount, more preferably 10～40 quality % especially are preferably 15～35 quality %.If solvent (c1) contain proportional less than 3 quality %, then produce easily foreign matter in the coloured composition or in the cured film.On the other hand, if solvent (c1) contain the proportional 50 quality % that surpass, then the viscosity of coloured composition has easily in time and the tendency that rises.

Without particular restriction, but the total concentration of removing each composition behind the solvent of preferred coloured composition is the amount of 5～50 quality %, especially is preferably the amount of 10～40 quality % to the content of (C) solvent.Like this, the coloured composition that can obtain dispersiveness, coating, has good stability.

-linking agent-

In the present invention, can further improve solidified nature by adding linking agent.Linking agent refers to have the compound of the polymerizable groups more than 2.As polymerizable groups, such as listing ethene unsaturated group, epoxy ethyl, oxa-cyclobutyl, N-alkoxy methyl amino etc.In the present invention, as linking agent, be preferably the compound (not comprising above-mentioned (B) composition) with (methyl) acryloxy more than 2 or the compound with 2 above N-alkoxy methyl amino.

As above-mentioned object lesson with compound (not comprising above-mentioned (B) composition) of (methyl) acryloxy more than 2, can enumerate multifunctional (methyl) acrylate that the aliphatic polyhydroxy compound of sening as an envoy to gets with the reaction of (methyl) vinylformic acid, multifunctional (methyl) acrylate of caprolactone modification, multifunctional (methyl) acrylate of oxirane modification, make (methyl) acrylate with hydroxyl and polyfunctional isocyanate reaction and multifunctional urethane (methyl) acrylate, make (methyl) acrylate with hydroxyl and anhydride reaction and multifunctional (methyl) acrylate with carboxyl etc.

Here, as above-mentioned aliphatic polyhydroxy compound, for example can list the divalence aliphatic polyhydroxy compound as ethylene glycol, propylene glycol, polyoxyethylene glycol, polypropylene glycol; The aliphatic polyhydroxy compound that the trivalent of glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and so on is above.As above-mentioned (methyl) acrylate with hydroxyl, such as listing (methyl) vinylformic acid 2-hydroxy methacrylate, TriMethylolPropane(TMP) two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, glycerine dimethacrylate etc.As above-mentioned polyfunctional isocyanate, such as listing tolylene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc.As acid anhydrides, for example can list the acid anhydrides such as the dihydric acid of succinyl oxide, maleic anhydride, Pyroglutaric acid, itaconic anhydride, Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride and so on, aforementioned quadribasic acid dianhydride.

In addition, as multifunctional (methyl) acrylate of above-mentioned caprolactone modification, for example can list the compound of record in paragraph (0015)～(0018) of Japanese kokai publication hei 11-44955 communique.As multifunctional (methyl) acrylate of above-mentioned oxirane modification, can list with dihydroxyphenyl propane two (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide, with isocyanuric acid three (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide, with trimethylolpropane tris (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide, with tetramethylolmethane three (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide, with tetramethylolmethane four (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide, with Dipentaerythritol five (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide, with Dipentaerythritol six (methyl) acrylate after at least a modification that is selected from oxyethane and the propylene oxide etc.

In addition, as above-mentioned compound with the N-alkoxy methyl amino more than 2, have the trimeric cyanamide structure such as listing, the compound of benzene guanamine structure, urea structure etc.Wherein, trimeric cyanamide structure, benzene guanamine structure refer to have 1 above triazine ring or phenyl substituted triazine ring as the chemical structure of basic framework, are the concepts that also comprises trimeric cyanamide, benzene guanamine or their condenses.Object lesson as the compound with the N-alkoxy methyl amino more than 2 can list N, N, N ', N ', N ' ', N ' '-six (alkoxy methyl) trimeric cyanamide, N, N, N ', N '-four (alkoxy methyl) benzene guanamine, N, N, N ', N '-four (alkoxy methyl) glycoluril etc.

In these linking agents, be preferably make the above aliphatic polyhydroxy compound of trivalent with the reaction of (methyl) vinylformic acid multifunctional (methyl) acrylate, caprolactone modification multifunctional (methyl) acrylate, multifunctional urethane (methyl) acrylate, have multifunctional (methyl) acrylate, the N of carboxyl, N, N ', N ', N ' ', N ' '-six (alkoxy methyl) trimeric cyanamide, N, N, N ', N '-four (alkoxy methyl) benzene guanamine.High from the intensity of pigmented layer, the surface smoothness of pigmented layer is excellent and be difficult for the generation spot at substrate and the light shield layer of unexposed section, the angle of the residual grade of film is considered, in multifunctional (methyl) acrylate that aliphatic polyhydroxy compound more than making trivalent gets with the reaction of (methyl) vinylformic acid, especially preferred Viscoat 295, pentaerythritol triacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate, in having multifunctional (methyl) acrylate of carboxyl, especially preferably make pentaerythritol triacrylate and succinyl oxide the reaction and compound, the compound that makes the reaction of Dipentaerythritol five acrylate and succinyl oxide and get.

In the present invention, linking agent can use in independent or two or more mixing.

With respect to (A) tinting material 100 mass parts, the content of the linking agent among the present invention is preferably 10～1, and 000 mass parts especially is preferably 20～500 mass parts.At this moment, if the content of linking agent is very few, then may can not get sufficient solidified nature.On the other hand, if the content of linking agent is too much, then when giving alkali-developable to coloured composition of the present invention, there is alkali-developable to reduce, on the substrate of unexposed section or light shield layer, occur easily the tendencies such as spot, film be residual.

-Photoepolymerizationinitiater initiater-

Can add Photoepolymerizationinitiater initiater in the coloured composition of the present invention.Thus, can give the coloured composition radiation-sensitive.The Photoepolymerizationinitiater initiater that uses among the present invention is the compound that produces the spike of the polymerization that can cause (B) composition and any linking agent that adds by the exposure of visible rays, ultraviolet ray, far ultraviolet rays yue, electron beam, X ray isoradial.

As such polymerization starter, such as listing thioxanthone compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class, O-acyl group oxime compounds, salt compounds, bitter almond oil camphor compounds, benzophenone compound, α-cyclohexadione compounds, polycyclic quinone compound, diazonium compounds, imide sulfonates compounds, salt compounds etc.

In the present invention, Photoepolymerizationinitiater initiater can use in independent or two or more mixing.As Photoepolymerizationinitiater initiater; preferably contain and be selected from least a in thioxanthone compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class, the O-acyl group oxime compounds; consider from the angle good with (B) polymer phase capacitive, that foreign matter is difficult to occur, especially preferably contain O-acyl group oxime compounds.

Among the present invention in the preferred Photoepolymerizationinitiater initiater, object lesson as the thioxanthone compounds, can list thioxanthone, CTX, 2-methyl thioxanthone, ITX, ITX, 2,4-two clopenthixal ketones, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-di-isopropyl thioxanthone etc.

In addition, as the object lesson of above-mentioned acetophenone compounds, can list 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-(4-methyl-benzyl)-the 2-(dimethylamino)-1-(4-morpholino phenyl) butane-1-ketone etc.

In addition, as the object lesson of above-mentioned bisglyoxaline compounds, can list 2,2 '-two (2-chloro-phenyl-s)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4 dichloro benzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.

In addition, when using the bisglyoxaline compounds as Photoepolymerizationinitiater initiater, consider from the angle that can improve sensitivity, preferred and use hydrogen donor." hydrogen donor " described here refers to supply with to the free radical that is produced by the bisglyoxaline compounds by exposure the compound of hydrogen atom.As hydrogen donor, such as listing the thio-alcohol hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole; The amine hydrogen donors such as 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone.In the present invention, hydrogen donor can use by independent or two or more mixtures, considers from the angle that can further improve sensitivity, preferably more than one thio-alcohol hydrogen donor and more than one amine hydrogen donor is used in combination.

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

In addition; object lesson as O-acyl group oxime compounds; can list 1; the 2-acetyl caproyl; 1-(4-(thiophenyl) phenyl)-; the 2-(O-benzoyl oximes); ethyl ketone; 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-; 1-(O-ethanoyl oxime); ethyl ketone; 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9H-carbazole-3-yl)-; 1-(O-ethanoyl oxime); ethyl ketone; 1-(9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-DOX base) anisoyl }-9H-carbazole-3-yl)-, 1-(O-ethanoyl oxime) etc.As the commercially available product of O-acyl group oxime compounds, can use to be ADEKA company product more than NCI-831, the NCI-930() etc.In these compounds; angle from the susceptibility of coloured composition; be preferably ethyl ketone, 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base anisoyl)-9H-carbazole-3-yl)-, 1-(O-ethanoyl oxime), NCI-831, NCI-930.

In the present invention, when using the Photoepolymerizationinitiater initiater beyond the bisglyoxaline compounds such as acetophenones chemical combination, may be used sensitizing agent.As this class sensitizing agent; for example can list 4; 4 '-two (dimethylamino) benzophenone, 4; 4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino Propiophenone, EDMAB, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2, two (the 4-diethylamino benzylidene) pimelinketone of 5-, 7-diethylamino-3-(4-diethylamino benzoyl) tonka bean camphor, 4-(diethylamino) cinnamophenone etc.In addition, in the present invention, can improve by the multi-functional thiol who has added the chain-transfer agent effect sensitivity of coloured composition.As this class chain-transfer agent, for example can list trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), 2,4,6-tri-thiol s-triazine, 2-(N, N-dibutylamino)-4,6-dimercapto s-triazine etc.

In the present invention, with respect to total 100 mass parts of (B) composition and any linking agent that adds, the content of Photoepolymerizationinitiater initiater is preferably 0.01～120 mass parts, more preferably 1～100 mass parts, especially be preferably 7～50 mass parts, be particularly preferably 10～30 mass parts.At this moment, if the content of Photoepolymerizationinitiater initiater is very few, the insufficient anxiety of curing that then exists exposure to produce, on the other hand, and if content is too much, the tendency that then exists the pigmented layer that forms when developing, to come off from substrate easily.

-additive-

Composition of the present invention can contain various additives as required.

As additive, such as listing the weighting agents such as glass, aluminum oxide; Polyvinyl alcohol, poly-(fluoroalkyl acrylate) family macromolecule compound; The tensio-active agents such as fluorine class tensio-active agent, silicon class tensio-active agent; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, the N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, the N-(2-amino-ethyl)-the 3-TSL 8330, APTES, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, the adherence promotor such as 3-sulfydryl propyl trimethoxy silicane; The antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6 di t butyl phenol; The 2-(3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone class UV light absorber; The anti flocculants such as sodium polyacrylate; Propanedioic acid, hexanodioic acid, methylene-succinic acid, citraconic acid, fumaric acid, methylfumaric acid, 2-monoethanolamine, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1, the residue activators such as 2-butyleneglycol; Mono succinate (2-(methyl) acryloxy ethyl) ester, phthalic acid list (2-(methyl) acryloxy ethyl) ester, ω-development property improvement agent such as carboxyl polycaprolactone list (methyl) acrylate etc.

Coloured composition of the present invention can be modulated by suitable method, as its modulator approach, and for example can be by solvent, any other compositions that add are mixed together and modulate with (A)～(B) composition and (C).When using pigment as (A) tinting material, preferably pass through pigment in (C) solvent, in the presence of dispersion agent, according to circumstances and (B) part of composition is together with for example ball mill, roller mill mix while pulverizing, disperse, make dispersible pigment dispersion, then, in this dispersible pigment dispersion, add (B) composition, the solvent that further appends as required or other compositions, mix the method for modulating.When using dyestuff and pigment two side as (A) tinting material, can adopt as disclosed in the TOHKEMY 2010-132874 communique, after making dye solution pass through the 1st strainer, make itself and the in addition mixing such as dispersible pigment dispersion of modulation, the method that the coloured composition that obtains is modulated by the 2nd strainer.In addition, also can adopt at other compositions with dyestuff and above-mentioned (B) composition and as required use and be dissolved in the solvent, the solution that makes gained is by behind the 1st strainer, and the dispersible pigment dispersion of in addition modulation mixes, the method that the coloured composition of gained is modulated by the 2nd strainer.In addition, can also adopt after making dye solution pass through the 1st strainer, mix, dissolve and make the solution of gained by the 2nd strainer itself and mentioned component (B) and other compositions of using as required, mix the method that the coloured composition of gained is modulated by the 3rd strainer with the dispersible pigment dispersion of other modulation.

Colour filter and manufacture method thereof

Colour filter of the present invention possesses the pigmented layer that forms with coloured composition of the present invention.

As the method for making colour filter, the first, can list following methods.At first, on the surface of substrate, form as required light shield layer (black matrix), will form the part subregion of pixel.Then, for example be dispersed with the liquid composition of radiation-sensitive coloured composition of the present invention of red pigment in the coating of this substrate after, carry out prebake conditions, make solvent evaporation, formation is filmed.Then, be situated between by photomask to this film expose after, develop with alkaline developer, the unexposed section of filming is removed in dissolving.Afterwards, by rear baking, form the pel array that red pattern of pixels is arranged with the alignment arrangements of regulation.

Then, use green or blue each radiation-sensitive coloured composition and above-mentioned the same coating, prebake conditions, exposure, development and the rear baking of carrying out each radiation-sensitive coloured composition, on same substrate, form successively green pel array and blue pel array.Thus, can obtain substrate dispose redness, green and blue trichromatic pel array colour filter.But in the present invention, the order that forms each color pixel is not limited to said sequence.In addition, in the first method of making colour filter, as long as the pigmented layer of any one above array for using coloured composition of the present invention to form of the pel array of above-mentioned redness, green, blueness.

In addition, black matrix can be by utilizing photolithography to make to adopt sputter, evaporation the metallic film of chromium etc. of film forming become required pattern and form, but also can use the radiation-sensitive coloured composition that is dispersed with black pigment, form by method identical when forming above-mentioned pixel.

The substrate that uses during as the formation colour filter is such as listing glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.

In addition, the pre-treatment of also can be as required implementing to adopt processing, ion plating, sputter, gas-phase reaction method, the vacuum evaporations etc. such as pharmaceutical chemicals processings, plasma of silane coupling agents etc. to suit to these substrates in advance.

When being applied to radiation-ray sensitive composition on the substrate, the suitable coating method such as spray method, rolling method, method of spin coating (spin-coating method), slit die coating method, scraper coating method be can adopt, spin-coating method, slit die coating method especially preferably adopted.

Prebake conditions is usually by making up drying under reduced pressure and heat drying to carry out.Drying under reduced pressure usually proceeds to and reaches 50～200Pa.And the condition of heat drying is generally 70～110 ℃ of lower dryings about 1～10 minute.

For coating thickness, as dried thickness, be generally 0.6～8 μ m, be preferably 1.2～5 μ m.

The light source of the radioactive rays that use during as formation pixel and/or black matrix is such as listing the LASER Light Source such as the lamp source such as xenon lamp, halogen lamp, tungsten lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, argon laser, YAG laser, XeCl excimer laser, nitrogen laser.As exposure light source, also can use ultraviolet LED.The radioactive rays of optimal wavelength in 190～450nm scope.

The exposure of radioactive rays is preferably 10～10,000J/m usually ²

In addition, as above-mentioned alkaline developer, preference such as yellow soda ash, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-(5.4.0)-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-(4.3.0)-5-nonene etc.

In above-mentioned alkaline developer, also can add in right amount water-miscible organic solvents such as methyl alcohol, ethanol, tensio-active agent etc.In addition, alkali is washed after developing usually.

As the development treatment method, can adopt spray development method, spray development method, immersion development method, soak the formula of putting (covering liquid) development method etc.Development conditions is preferably carried out 5～300 seconds at normal temperatures.

The condition of rear baking is generally 180～280 ℃ of bakings about 10～60 minutes.

The thickness of the pixel that forms like this is generally 0.5～5 μ m, is preferably 1～3 μ m.

In addition, the second method as making colour filter can adopt the disclosed method that obtains each color pixel by ink-jet in Japanese kokai publication hei 7-318723 communique, TOHKEMY 2000-310706 communique etc.In the method, at first, form the next door that has shade function concurrently on the surface of substrate.Then, after the liquid composition that will for example be dispersed with the thermoset coloured composition of the present invention of red pigment by ink discharge device is sprayed onto in the next door of formation, carry out prebake conditions, make solvent evaporation.Then, after the exposure of as required this being filmed, be cured by rear baking, form red pattern of pixels.

Then, use green or each blue heat-curable composition, on same substrate, form successively the pattern of pixels of green and blue pattern of pixels with above-mentioned the same ground.Thus, obtain disposing at substrate the colour filter of redness, green and blue trichromatic pattern of pixels.But in the present invention, the order that forms each color pixel is not limited to said sequence.In addition, in the second method of making colour filter, as long as the above pigmented layer for using coloured composition of the present invention to form of any one of the pel array of above-mentioned redness, green, blueness.

In addition, interception is not only played in above-mentioned next door, also plays be used to making the coloured composition of all kinds that is sprayed onto in the zoning that the effect of colour mixture not occur, and therefore, compares with the black matrix that uses in above-mentioned the first method, and film is thicker.Therefore, the next door forms with the black radiation-ray sensitive composition usually.

The substrate that uses when forming colour filter, the light source of radioactive rays also have the method for prebake conditions, rear baking, condition identical with above-mentioned the first method.The thickness of the pixel that forms by ink-jetting style like this, and the height in next door are same degree.

After forming protective membrane as required on the pattern of pixels that obtains like this, form nesa coating by sputter.After forming nesa coating, can also further form distance piece and make colour filter.Distance piece uses radiation-ray sensitive composition to form usually, but also can make the distance piece (spacing body night) with opacifying property.At this moment, can use the radiation-ray sensitive composition that is dispersed with black colorant, but coloured composition of the present invention also can perform well in the formation of this of spacing body night.

Briliancy and the purity of color of the colour filter of the present invention that obtains like this are high, and be therefore, exceedingly useful to color liquid crystal display device, colour pick-up tube element, color sensor, organic EL, Electronic Paper etc.

Display element

Display element of the present invention possesses colour filter of the present invention.As display element, can list color liquid crystal display device, organic EL display element, Electronic Paper etc.

The color liquid crystal display device that possesses colour filter of the present invention both can be infiltration type, also can be reflection-type, can take the structure that suits.For example, colour filter can be formed on from the driving of disposing thin film transistor (TFT) with on the different substrate of substrate, make to drive with substrate and the substrate that is formed with colour filter and be the opposed structure that is situated between by liquid crystal layer, in addition, also can form colour filter with the surface of substrate in the driving of disposing thin film transistor (TFT), this substrate and be formed with the Indium sesquioxide that ITO(is doped with tin) substrate of electrode is the opposed structure that is situated between by liquid crystal layer.The latter's structure has can especially improve aperture opening ratio, the advantage of liquid crystal display device that obtain becoming clear, fine.

Possess the color liquid crystal display device of colour filter of the present invention except cold cathode fluorescent tube (CCFL:Cold Cathode Fluorescent Lamp), can possess the back light unit take White LED as light source.As White LED, for example can list: display predetermined colors in combination LED, green LED and blue led, the White LED that obtains by colour mixture; Combined blue LED, red LED and green-emitting phosphor, the White LED that gets by colour mixture; Combined blue LED, red light-emitting phosphor and green emitting fluor obtain the White LED of white light by colour mixture; Obtain the White LED of white light by the colour mixture of blue led and YAG class fluor; Combined blue LED, orange luminescence fluor and green emitting fluor obtain the White LED of white light by colour mixture; Make up ultraviolet LED, red light-emitting phosphor, green emitting fluor and blue-light-emitting fluorescent material, obtain the White LED of white light etc. by colour mixture.

The color liquid crystal display device that possesses colour filter of the present invention can adopt TN(Twisted Nematic) type, STN(Super Twisted Nematic) type, IPS(In-Planes Switching) type, VA(Vertical Alignment) type, OCB(Optically Compensated Birefringence) the suitable liquid crystal mode such as type.

In addition, the organic EL display element that possesses colour filter of the present invention can be taked the structure that suits, for example for example can take disclosed structure in the Japanese kokai publication hei 11-307242 communique.

In addition, the Electronic Paper with colour filter of the present invention can be taked the structure that suits, for example for example can take disclosed structure in the TOHKEMY 2007-41169 communique.

Embodiment

Below, further embodiments of the present invention are specifically described by enumerating embodiment.But the present invention is not limited to following embodiment.

The mensuration of＜acid number 〉

Acid number to (B) polymkeric substance of obtaining in following each synthesis example is measured by following main points.Precision weighing polymers soln 0.5g is accurate to 1mg unit, divides and gets in the Glass Containers.After being diluted to 50ml with propylene glycol methyl ether acetate, add phenolphthalein, carry out titration with 0.1N ethanol potassium hydroxide aqueous solution, become peach point as terminal point take variable color.Carry out blank test by same method.Dripping quantity by the 0.1N ethanol potassium hydroxide aqueous solution of (B) polymkeric substance and blank test is calculated acid number (unit: mgKOH/g).

＜synthetic polymer 〉

Synthesis example 1((B) synthetic polymer)

In the flask of the 1000mL that possesses stirrer and cooling tube, add biphenyl tetracarboxylic dianhydride (emerging product company of space section product: trade(brand)name BPDA) 90g, 9, two (4-(2-hydroxyl-oxethyl) phenyl of 9-) fluorenes (Osaka combustion gas chemical company product: trade(brand)name BPEF) 110g, 4-dimethylaminopyridine 1g, propylene glycol methyl ether acetate 134g, heated 4 hours while stirring under nitrogen gas stream by the oil bath with 155 ℃.Then, after being cooled to 120 ℃, as stopper, add 4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base (ADEKA company product: trade(brand)name ADK STAB LA-7RD) 0.04g, further adding 4-hydroxybutyl acrylate glycidyl ether (Japan changes into company's product: trade(brand)name 4HBAGE) 80g, stirred 4 hours at 120 ℃.Then, be cooled to room temperature, add propylene glycol methyl ether acetate, making nonvolatile component is 50 quality %, obtains faint yellow transparent toughness polymers soln.The polystyrene conversion weight-average molecular weight that the CPC of resulting polymers measures is 4920, and acid number is 61mgKOH/g.This polymkeric substance is denoted as " polymkeric substance (B-1) ".

Synthesis example 2((b) other synthetic polymer)

In the flask that possesses stirrer and cooling tube, add propylene glycol methyl ether acetate 100 mass parts, and carry out nitrogen replacement.Be heated to 80 ℃, with propylene glycol methyl ether acetate 100 mass parts, methacrylic acid 15 mass parts, vinylbenzene 12 mass parts, benzyl methacrylate 41 mass parts, 2-hydroxyethyl methacrylate 15 mass parts, n-BMA 2 mass parts, N-phenylmaleimide 15 mass parts and 2, the mixing solutions of two butyronitrile 0.5 mass parts of 2 '-azo, Dipentaerythritol four (2 mercaptopropionic acid ester) 2 mass parts remains on 80 ℃ and polymerization 4 hours under same temperature.Afterwards, the temperature of reaction soln is raised to 100 ℃, repolymerization 1 hour obtains polymers soln (solid component concentration=40 quality %) thus.The Mw=24000 of resulting polymers, Mn=14800, Mw/Mn=1.60, acid number 98mgKOH/g.This polymkeric substance is denoted as " polymkeric substance (B-2) ".

Synthesis example 3((b) other synthetic polymer)

In the flask that possesses stirrer and cooling tube, add propylene glycol methyl ether acetate 100 mass parts, and carry out nitrogen replacement.Be heated to 80 ℃, under same temperature, with splashing into propylene glycol methyl ether acetate 50 mass parts, methacrylic acid 20 mass parts, vinylbenzene 10 mass parts, benzyl methacrylate 5 mass parts, 2-hydroxyethyl methacrylate 15 mass parts, 2-Ethylhexyl Methacrylate 23 mass parts, N-phenylmaleimide 12 mass parts, mono succinate (2-acryloxy ethyl) ester 15 mass parts and 2 in 1 hour, 2 '-azo two (2, the 4-methyl pentane nitrile) mixing solutions of 6 mass parts, keep this temperature, polymerization 2 hours.Afterwards, the temperature of reaction soln is raised to 90 ℃, further polymerization is 1 hour, obtains thus polymers soln (solid component concentration=40 quality %).The Mw=11000 of resulting polymers, Mn=6000, Mw/Mn=1.83, acid number 130mgKOH/g.This polymkeric substance is denoted as " polymkeric substance (B-3) ".

The modulation of＜dispersible pigment dispersion 〉

Modulation example 1

As (A) tinting material, use C.I. Pigment green 58/C.I. pigment yellow 13 8=60/40(mass ratio) mixture 15.0 mass parts, as dispersion agent, use BYK-LPN21116(Bi Ke chemistry (BYK) company product, solvent ratio (quality %): 11.1 weight parts (solid component concentration is 40 quality %) of propylene glycol methyl ether acetate/ethylene glycol mono-n-butyl ether/ethanol=48.7/50/1.3), as (b) other polymkeric substance, use polymkeric substance (B-3) solution 13.8 mass parts (solid component concentration is 40 quality %), as solvent, use propylene glycol methyl ether acetate, making solid component concentration is 25%, mix by pearl mill method, disperseed 12 hours, and be modulated into dispersible pigment dispersion (A-1).

Modulation example 2

As (A) tinting material, use C.I. Pigment red 254/C.I. Pigment red 177=60/40(mass ratio) mixture 15.0 mass parts, as dispersion agent, the BYK-LPN21116(solid component concentration that uses 11.1 weight parts is 40 quality %), as (b) other polymkeric substance, use polymkeric substance (B-3) solution 13.8 mass parts (solid component concentration is 40 quality %), as solvent, use propylene glycol methyl ether acetate, making solid component concentration is 25%, mix, disperseed 12 hours by pearl mill method, be modulated into dispersible pigment dispersion (A-2).

Modulation example 3

As tinting material, use the C.I. pigment Blue 15: mixture 15.0 mass parts 6/C.I. Blue 7=60/40(mass ratio), as dispersion agent, the BYK-LPN21116(solid component concentration that uses 11.1 mass parts is 40 quality %), as solvent, use propylene glycol methyl ether acetate and dihydroxypropane single-ether, be modulated into dihydroxypropane single-ether in the solvent total amount contain that ratio is 20%, solid component concentration is after 25%, mix, disperseed 12 hours by pearl mill method, be modulated into pigment dye mixed solution (A-3).

The modulation of＜coloured composition and evaluation 〉

Embodiment 1

The modulation of colored radiation-sensitive coloured composition

As (A) tinting material; select dispersible pigment dispersion (A-1) 210 mass parts; as (B) polymkeric substance; selective polymer (B-1) solution 11.1 mass parts (solid component concentration=50 quality %); as linking agent; select the mixture of the Japanese chemical drug product K AYARAD of company MAX-3510(dipentaerythritol acrylate and Dipentaerythritol five acrylate) 36 mass parts; as Photoepolymerizationinitiater initiater; select 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone 5.3 mass parts and ethyl ketone; 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-; 1-(O-ethanoyl oxime) 2.0 mass parts; as fluorine class tensio-active agent; the MEGAFAC F-5540.2 mass parts of selecting DIC company to produce; as solvent (C-1); select propylene glycol methyl ether acetate; as solvent (C-4); select dihydroxypropane single-ether; mix; making the ratio that contains of the solvent (C-4) in the solvent total amount is 30 quality %, is modulated into the green radiation-sensitive coloured composition (S-1) of solid component concentration 15 quality %.

Sensitivity is estimated

Coloured composition (S-1) is formed with the SiO that prevents the sodium ion stripping from the teeth outwards with the coating of slit die coating machine ₂After on the soda glass substrate of film, carry out 4 minutes prebake conditions at 90 ℃ hot plates, the thickness that forms after 6 prebake conditions is filming of 2.5 μ m.

Then, these substrates are cooled to room temperature after, use high voltage mercury lamp, be situated between by photomask, will comprise that the radioactive rays of each wavelength of 365nm, 405nm and 436nm are with 100,200,300,500,800 or 1000J/m ²Exposure expose to filming.Afterwards, these substrates are pressed 1kgf/cm to develop ²The developing solution that is made of 0.04 quality % potassium hydroxide aqueous solution of 23 ℃ of (nozzle directly for 1mm) ejections sprays development thus, afterwards, further 220 ℃ carry out 30 minutes after baking, form the dot pattern of 200 μ m * 200 μ m at substrate.

With the dot pattern of sem observation on figuratum each substrate of formation under each exposure, the residual film ratio (thickness before developing in the thickness after the development * 100/) that pattern forms well, calculate as the Film Thickness Ratio before and after developing is evaluated as " zero " when above 90%, pattern forms good but the part of residual film ratio less than 90% or pattern has when disappearance to be evaluated as " △ ", is evaluated as when not forming pattern " * ".Evaluation result is shown in table 3.

Evaluation of Heat Tolerance

Coloured composition (S-1) is formed with the SiO that prevents the sodium ion stripping from the teeth outwards with the coating of slit die coating machine ₂After on the soda glass substrate of film, carry out 4 minutes prebake conditions at 90 ℃ hot plates, the thickness that forms after 2 prebake conditions is filming of 2.5 μ m.

Then, this substrate is cooled to room temperature after, use high voltage mercury lamp, be situated between by photomask, will comprise that the radioactive rays of each wavelength of 365nm, 405nm and 436nm are with 1000J/m ²Exposure expose to filming.Afterwards, this substrate is pressed 1kgf/cm to develop ²The developing solution that is made of 0.04 quality % potassium hydroxide aqueous solution of 23 ℃ of (nozzle directly for 1mm) ejections sprays development thus, afterwards, further 220 ℃ carry out 30 minutes after baking, form the dot pattern of 200 μ m * 200 μ m at substrate.

To 2 substrates of gained 230 ℃, the 250 ℃ bakings of appending of carrying out respectively 60 minutes, append pattern after the baking with observation by light microscope, 230 ℃, 250 ℃ arbitrary appends that baking is lower does not observe all that foreign matter occurs, be designated as " zero ", 230 ℃ append the lower foreign of baking occur, 250 ℃ append that baking is lower observes that foreign matter occurs, be designated as " △ ", 230 ℃ are appended that baking is lower observes that foreign matter occurs, and are designated as " * ".Evaluation result is shown in table 3.

In addition, as the storage stability evaluation of coloured composition (S-1), following foreign matter evaluation and viscosity stability evaluation have been implemented.

Foreign matter is estimated

To be formed with from the teeth outwards the SiO that prevents the sodium ion stripping with the coating of slit die coating machine at 5 ℃ of coloured compositions (S-1) after leaving standstill 3 days ₂After on the soda glass substrate of the 10cm * 10cm of film, carry out 4 minutes prebake conditions at 90 ℃ hot plates, the thickness after the formation prebake conditions is filming of 2.5 μ m.With observation by light microscope gained substrate, do not observe foreign matter on filming, be designated as " zero ", foreign matter generation number on filming is designated as " △ " more than 1 below 10, observe film on foreign matter generation number more than 11, be designated as " * ".Evaluation result is shown in table 3.

Viscosity stability is estimated

Measure the viscosity of the coloured composition (S-1) that has just modulated with E type viscometer (Tokyo gauge company product).Then, coloured composition (S-1) is filled in the front glass container, under sealed state in 23 ℃ leave standstill 14 days after, again use E type viscometer (Tokyo gauge company product) to measure viscosity.Then, the increment rate of the viscosity of calculating the viscosity of preserving after 14 days when just modulating is evaluated as during increment rate less than 5% " zero ", is evaluated as " △ " during 5% above less than 10%, and 10% is evaluated as " * " when above.Evaluation result is shown in table 3.

Embodiment 2～30 and comparative example 1～14

With the kind of the dispersible pigment dispersion among the embodiment 1, polymers soln, linking agent and Photoepolymerizationinitiater initiater and addition is as shown in table 1 changes, in addition, kind and the addition of change solvent, make alcohols in the coloured composition and ketone with respect to containing of solvent total amount proportional (unit: quality %) as shown in table 2, be modulated into coloured composition (S-2)～(S-44).Then, coloured composition (S-2)～(S-44) is estimated by the method identical with embodiment 1.Evaluation result is shown in table 3.

In the table 2, solvent (C-12) reaches the composition among the BYK-LPN21116 that uses when (C-13) being conditioned pigment dispersion liquid (A-1)～(A-2) and pigment dye mixed solution (A-3).

Table 1

In the table 1, each composition is as follows.

D-1: the mixture of dipentaerythritol acrylate and Dipentaerythritol five acrylate (trade(brand)name MAX-3510, Japanese chemical drug company product)

E-1:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (trade(brand)name IRGACURE369, Ciba company product)

E-2: ethyl ketone, 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-, 1-(O-ethanoyl oxime) (trade(brand)name IRGACURE OXE02, Ciba company product)

E-3:NCI-930(trade(brand)name: NCI-930, ADEKA company product)

(table 2)

In the table 2, each composition is as follows.Wherein, solvent (C-1)～(C-3) is equivalent to solvent c2, and solvent (C-4)～(C-13) is equivalent to solvent (c1).

C-1: propylene glycol methyl ether acetate

The C-2:3-ethoxyl ethyl propionate

C-3: acetic acid 3-methoxyl group butyl ester

C-4: dihydroxypropane single-ether

C-5: propylene glycol monomethyl ether

The C-6:3-methoxybutanol

C-7: dipropylene glycol monomethyl ether

C-8: dipropylene glycol list positive propyl ether

C-9: dipropylene glycol mono-n-butyl ether

C-10: diethylene glycol monoethyl ether

C-11: pimelinketone

C-12: ethylene glycol mono-n-butyl ether

C-13: ethanol

Table 3

＜contain modulation and the evaluation of the coloured composition of pigment lake 〉

Synthesis example 4((b) other synthetic polymer)

In the flask that possesses cooling tube and stirrer, add 2,2 '-Diisopropyl azodicarboxylate, 0.5 mass parts and propylene glycol methyl ether acetate 200 mass parts, continue to add methacrylic acid 15 mass parts, N-phenylmaleimide 20 mass parts, benzyl methacrylate 55 mass parts, vinylbenzene 10 mass parts and as the tetramethylolmethane four (3-mercaptopropionic acid ester) of molecular weight regulator (Sakai chemical industrial company product: trade(brand)name PEMPII-20P) 2 mass parts, carry out nitrogen replacement.Stir lentamente afterwards, make the temperature of reaction soln rise to 80 ℃, kept this temperature 5 hours, carry out polymerization, obtain thus polymers soln (solid component concentration=33.3 quality %).The Mw=25000 of resulting polymers, Mn=12000.This polymkeric substance is called " polymkeric substance (B-4) ".

Modulation example 4

The triarylmethane class pigment lake that will represent as the following formula (7) of tinting material is (in the formula, x=1～2) pigment Blue 15 of 7.5 mass parts and 7.5 mass parts: 6, as the BYK-LPN6919(nonvolatile component of (methyl) acrylic dispersants=60%, amine value 72mgKOH/g, Bi Ke chemistry (BYK) company product) 11 mass parts and polymkeric substance (B-4) solution 10.2 mass parts, as the propylene glycol methyl ether acetate/dihydroxypropane single-ether of solvent=90/10(mass ratio) mixed solvent mix, making solid component concentration is 20%, mix by ball mill, disperseed 12 hours, and be modulated into dispersible pigment dispersion (A-4).

(changing 11)

Modulation example 5

As tinting material, use the Pigment red 254 of 1.5 mass parts, 10.5 the Pigment red 177 of mass parts and the pigment red 81 of 3 mass parts: 2(carry out the xanthene class pigment lake that the color lake forms with silicomolybdic acid), as (methyl) acrylic dispersants, use BYK-LPN21116(nonvolatile component=40%, the amine value is 29mgKOH/g, Bi Ke chemistry (BYK) company product) 11 mass parts and polymkeric substance (B-4) solution 16.8 mass parts, as solvent, use propylene glycol methyl ether acetate/dihydroxypropane single-ether=90/10(mass ratio) mixed solvent, making solid component concentration is 20%, mix by ball mill, disperseed 12 hours, and be modulated into dispersible pigment dispersion (A-5).

Modulation example 6

The triarylmethane class pigment lake that will represent as the above-mentioned formula (7) of tinting material is (in the formula, x=1～2) pigment Blue 15 of 7.5 mass parts and 7.5 mass parts: 6, as the BYK-LPN6919(nonvolatile component of (methyl) acrylic dispersants=60%, amine value 72mgKOH/g, Bi Ke chemistry (BYK) company product) 11 mass parts and polymkeric substance (B-3) solution 10.2 mass parts, as the propylene glycol methyl ether acetate/dihydroxypropane single-ether of solvent=90/10(mass ratio) mixed solvent mix, making solid component concentration is 20%, mix by ball mill, disperseed 12 hours, and be modulated into dispersible pigment dispersion (A-6).

Modulation example 7

Will be as pigment Blue-61 (triarylmethane class pigment lake) 7.5 mass parts of tinting material and the pigment Blue 15 of 7.5 mass parts: 6, as the BYK-LPN6919(nonvolatile component of (methyl) acrylic dispersants=60%, amine value 72mgKOH/g, Bi Ke chemistry (BYK) company product) 11 mass parts and polymkeric substance (B-3) solution 10.2 mass parts, as the propylene glycol methyl ether acetate/dihydroxypropane single-ether of solvent=90/10(mass ratio) mixed solvent mix, making solid component concentration is 20%, mix by ball mill, disperseed 12 hours, and be modulated into dispersible pigment dispersion (A-7).

Embodiment 31

Interpolation is as dispersible pigment dispersion (A-4) 150 mass parts of tinting material, polymkeric substance (B-1) solution 31.8 mass parts as (B) polymkeric substance, as East Asia Synesis Company product M-402(dipentaerythritol acrylate of linking agent and the mixture of Dipentaerythritol five acrylate) 40 mass parts, as the 2-benzyl of Photoepolymerizationinitiater initiater-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba company product, trade(brand)name IRGACURE369) 4 mass parts, MEGAFAC F-554(DIC company product as fluorine class tensio-active agent) 0.1 mass parts and as propylene glycol methyl ether acetate and the propylene glycol monomethyl ether of solvent, make solid component concentration be 20 quality % and dihydroxypropane single-ether proportional with respect to containing of solvent total amount be 20 quality %, be modulated into coloured composition (S-45).

Use the coloured composition (S-45) of gained, form dot pattern by the method identical with embodiment 1, carry out sensitivity evaluation, Evaluation of Heat Tolerance, the result is all good.In addition, coloured composition (S-45) is carried out foreign matter evaluation, viscosity stability evaluation by the method evaluation identical with embodiment 1, all demonstrate good result.

Embodiment 32～34

In embodiment 31, except the kind of dispersible pigment dispersion and polymers soln and amount being changed into shown in the table 4 like that, be modulated into coloured composition (S-46)～(S-48) by the method identical with embodiment 31.

Then, in embodiment 31, except using coloured composition (S-46)～(S-48) replacement coloured composition (S-45), estimate by the method identical with embodiment 31, its result, sensitivity evaluation, Evaluation of Heat Tolerance, foreign matter evaluation and viscosity stability evaluation all demonstrate good result.

Comparative example 15～18

Except the kind of the dispersible pigment dispersion among the embodiment 31 and polymers soln and amount being changed into shown in the table 4 like that, be modulated into coloured composition (S-49)～(S-52) by the method identical with embodiment 31.

Then, except replace the coloured composition (S-45) among the embodiment 13 with coloured composition (S-49)～(S-52), estimate by the method identical with embodiment 31, its result, foreign matter evaluation and viscosity stability evaluation all demonstrate good result, but sensitivity and thermotolerance are poorer than embodiment 31～34.

Table 4

In the table 4, each composition is as follows.

D-2: the mixture of East Asia Synesis Company product M-402(dipentaerythritol acrylate and Dipentaerythritol five acrylate)

E-1:2-benzyl-2 dimethylaminos-1-(4-morpholino phenyl)-butane-1-ketone (Ciba company product, trade(brand)name IRGACURE369)

＜solvent resistance evaluation 〉

The substrate with dot pattern that forms among the embodiment 1～34 was flooded 30 minutes in 25 ℃ N-Methyl pyrrolidone, with the dot pattern before and after the sem observation dipping.Its result, each substrate is all still kept the Film Thickness Ratio (thickness before the thickness behind the dipping * 100/ dipping) of good edge shape and dipping front and back all more than 95% behind dipping.

Similarly, with the substrate with dot pattern that forms in the comparative example 1～15 by method evaluation solvent resistance same as described above, its result, comparative example 1～4 and 9～12 is still kept Film Thickness Ratio (thickness before the thickness behind the dipping * 100/ dipping) before and after good edge shape and the dipping more than 95% behind dipping, and the Film Thickness Ratio less thaies 95% of comparative example 5～8 and 13～18 before and after dipping, occur dot pattern part disappearance situation or the situation that the rear dot pattern of dipping all peels off from substrate appears.

Claims

1. coloured composition is characterized in that, contains following composition (A), (B1) and (C):

(A) tinting material,

(B1) have following formula (1) expression structural unit polymkeric substance and

(C) contain at least a solvent that is selected from alcohols and the ketone,

Aforementioned alcohols and ketone contain proportional 3～50 quality % of solvent total amount that are,

(changing 1)

In the formula (1),

Ring Z ¹And ring Z ²Represent independently of each other monocyclic or condensed ring formula hydrocarbon ring,

Y represents to remove 4 residues behind the carboxyl from the organic compound with 4 carboxyls,

R ^1aAnd R ^1bRepresent independently of each other hydrogen atom or alkyl,

R ^2aAnd R ^2bRepresent independently of each other alkyl, alkoxyl group, acyl group, carbalkoxy, halogen atom, nitro or cyano group,

R ^3aAnd R ^3bRepresent independently of each other hydrogen atom or methyl,

R ^aExpression has the group of (methyl) acryloxy,

R ^bExpression has the group of hydrogen atom or (methyl) acryloxy,

K1 and k2 represent 0～4 integer independently of each other,

M1 and m2 represent 0～3 integer independently of each other,

N1 and n2 represent 0～10 integer independently of each other,

T and u represent 0～3 integer independently of each other.

2. coloured composition is characterized in that, contains following composition (A), (B2) and (C):

(A) tinting material,

(B2) pass through at least compound in following formula (2) expression with quadribasic acid two anhydride reactants and polymkeric substance on adduction have the operation of (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical and the polymkeric substance that obtains reaches

(C) contain at least a solvent that is selected from alcohols and the ketone,

(changing 2)

In the formula (2),

R ^1aAnd R ^1bRepresent independently of each other hydrogen atom or alkyl,

R ^3aAnd R ^3bRepresent independently of each other hydrogen atom or methyl,

K1 and k2 represent 0～4 integer independently of each other,

M1 and m2 represent 0～3 integer independently of each other,

N1 and n2 represent 0～10 integer independently of each other,

P1 and p2 represent 1～4 integer independently of each other.

3. coloured composition according to claim 2 is characterized in that, described have a compound that (methyl) acrylic compound that contains the oxygen saturation heterocyclic radical is each expression in following formula (3-1), formula (3-2) and the formula (3-3),

(changing 3)

(changing 4)

(changing 5)

In formula (3-1), formula (3-2) and the formula (3-3),

R ⁴Expression hydrogen atom or methyl,

R ⁵The group of expression singly-bound or following formula (6) expression,

R ⁶The expression carbon number is 1～4 alkyl,

(changing 6)

In the formula (6),

Q, r, s represent 0～9 integer independently of each other,

But q, r, s are not 0 simultaneously ,-C ₂H ₄The O-base ,-C ₃H ₆The O-base reaches-C ₄H ₈The O-base can the random order combination.

4. according to claim 2 or 3 described coloured compositions, it is characterized in that the compound of described formula (2) expression is the compound of following formula (4) expression,

(changing 7)

In the formula (4), R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, k1, k2, m1, m2, n1, n2, p1 and p2 and aforementioned synonym, but m1+p1 is the integer below 4, m2+p2 is the integer below 4.

5. according to claim 2 or 3 described coloured compositions, it is characterized in that the compound of described formula (2) expression is the compound of following formula (5) expression,

(changing 8)

In the formula (5), R ^1a, R ^1b, R ^2a, R ^2b, R ^3a, R ^3b, k1, k2, m1, m2, n1, n2, p1 and p2 and aforementioned synonym, but m1+p1 is the integer below 5, m2+p2 is the integer below 5.

6. each described coloured composition is characterized in that according to claim 1～3, as tinting material, contains pigment.

7. coloured composition according to claim 6 is characterized in that, as tinting material, contains pigment lake.

8. each described coloured composition is characterized in that according to claim 1～3, also contains the O-acyl group oxime compounds as Photoepolymerizationinitiater initiater.

9. colour filter has the pigmented layer that forms with each described coloured composition in the claim 1～3.

10. display element has colour filter claimed in claim 9.