CN105593311A

CN105593311A - Colored composition, cured film, color filter, method for producing color filter, solid state imaging element, and liquid crystal display device

Info

Publication number: CN105593311A
Application number: CN201480052638.8A
Authority: CN
Inventors: 樋口聡; 加藤隆志; 藤田明徳
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2013-09-30
Filing date: 2014-08-04
Publication date: 2016-05-18
Anticipated expiration: 2034-08-04
Also published as: TW201512315A; CN105593311B; JP2015092217A; KR20160047561A; WO2015045622A1; JP6147181B2; TWI634162B; KR101855237B1

Abstract

Provided are: a colored composition having excellent heat resistance, excellent solvent resistance and an excellent voltage retention rate; a cured film; a color filter; a method for producing a color filter; a solid state imaging element; and a liquid crystal display device. The colored composition according to the present invention comprises: a coloring agent which contains a triarylmethane structure having a crosslinking group and a cation and having a molecular weight of 2000 or less and a counter anion; and a polymerizable compound.

Description

Manufacture method, solid photographic element and the liquid crystal indicator of coloured composition, cured film, colored filter, colored filter

Technical field

The manufacture method, the solid that the present invention relates to a kind of coloured composition, cured film, colored filter, colored filter are taken the photographShadow element and liquid crystal indicator.

Background technology

In the past, colored filter is to manufacture in the following way: make organic pigment or inorganic pigment disperse to form by containingPigment dispensing composition and polyfunctional monomer, polymerization initiator, alkali soluble resin and other compositions optionally andMake coloured composition, then use described coloured composition, utilize photoetching process, ink-jet method etc. to form colored pattern, fromAnd manufacture colored filter.

In recent years, colored filter has in liquid crystal display cells (LiquidCrystalDisplay, LCD) purposes not onlyBe used for monitor, and expand the tendency of purposes to TV (Television, TV). Along with the tendency of described purposes expansion,For colored filter, in colourity, contrast etc., require the look characteristic of height. In addition, for imageing sensor (solidPhotographic element) colored filter of purposes, require similarly the minimizing of look inequality, the raising isochrome characteristic of look capacity of decompositionFurther raising.

But, in existing Pigments system, easily produce because of the oversize grain of pigment there is scattering, because of dispersion stabilizationBad and cause the problems such as viscosity rise, be usually difficult to further improve contrast, brightness.

Therefore, in the past, as colouring agent, just studying and not only using pigment, and using dyestuff (for example, with reference to patent documentation1). If use dyestuff as colouring agent, can pass through the excitation of dyestuff self or the vividness of its form and aspect, improve imageForm and aspect or the brightness of demonstration image when demonstration, and because oversize grain disappears, so useful aspect raising contrast.

The example of dyestuff is known to be had: phthalocyanine (phthalocyanine) dyestuff, two pyrroles's methylene (dipyrromethene) dyeMaterial, pyrimidine azo (pyrimidineazo) dyestuff, pyrazoles azo (pyrazoleazo) dyestuff, xanthene (xanthene)The compound that dyestuff, triarylmethane (triarylmethane) dyestuff etc. have multiple pigment precursor is (for example, with reference to patent documentation2～patent documentation 8).

Prior art document

Patent documentation

Patent documentation 1: Japanese patent laid-open 6-75375 communique

Patent documentation 2: Japanese Patent Laid-Open 2008-292970 communique

Patent documentation 3: Japanese Patent Laid-Open 2007-039478 communique

Patent documentation 4: Japanese patent laid-open 9-157536 communique

Patent documentation 5: Japanese Patent Laid-Open 2013-25194 communique

Patent documentation 6: Japanese Patent Laid-Open 2012-201694 communique

Patent documentation 7: Japanese Patent Laid-Open 2012-108469 communique

Patent documentation 8: Japanese Patent Laid-Open 2000-095805 communique

Summary of the invention

The problem that invention will solve

As middle coloured compositions using such as colored filters, require heat resistance, solvent resistance and voltage retention herein,More excellent person.

The object of the invention is to solve described problem, and object is for providing a kind of heat resistance, solvent resistance and voltage retentionExcellent coloured composition. Problem of the present invention is being used colour cell particularly in providing a kind of as blue color filter (bluefilter)Compound and useful coloured composition.

The technological means of dealing with problems

Based on described situation, this case inventor has carried out active research, found that, by will comprise have bridging property base andCation and molecular weight are that triarylmethane structure below 2000 and the colouring agent of anti-lotus anion are allocated in composition,Can solve described problem.

Particularly, by following means<1>, be preferably pass through<2>～<14>solve described problem.

<1>coloured composition, it comprises colouring agent and polymerizable compound, described colouring agent comprise have crosslinkedProperty base and cation and molecular weight are triarylmethane structure and the anti-lotus anion below 2000.

<2>as<1>as described in coloured composition, wherein having bridging property base and cation and molecular weight is below 2000Triarylmethane structure be represented by general formula (TP1) and/or general formula (TP2),

[changing 1]

(in general formula (TP1) and general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl;Rtp₅、Rtp₆、Rtp₈、Rtp₉And Rtp₁₁Represent independently respectively substituting group; Rtp₇Represent hydrogen atom, alkyl, aryl orNRtp₇₁Rtp₇₂；Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₁₀Represent hydrogen atom, alkylOr aryl; A, b and c represent respectively 0～4 integer independently; Be 2 above in the situation that at a, b and c, Rtp₆、Rtp₇And Rtp₈In two can mutually link and form ring; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in have crosslinkedProperty base).

<3>as<1>or<2>as described in coloured composition, wherein anti-lotus anion is to be selected from:

Be selected from fluorine anion, cl anion, bromine anions, iodine anion, cyanide ion, cross chlorate anions anion, boronHydrochlorate anion, pF^6-And SbF^6-In at least one; And

Be selected from-SO₃ ^-、-COO^-、-PO₄ ^-, represented structure and the following general formula (A2) of following general formula (A1) be representedStructure at least one.

General formula (A1)

[changing 2]

(in general formula (A1), R¹And R²Difference expression-SO independently₂-or-CO-)

General formula (A2)

[changing 3]

(in general formula (A2), R³Expression-SO₂-or-CO-; R⁴And R⁵Difference expression-SO independently₂-,-CO-or-CN).

<4>as<1>to<3>in coloured composition as described in any one, wherein anti-lotus anion be contained in contain crosslinkedIn the compound of property base.

<5>as<1>to<3>in coloured composition as described in any one, wherein anti-lotus anion is contained in repetitiveIn.

<6>as<1>as described in coloured composition, wherein having bridging property base and cation and molecular weight is below 2000Triarylmethane structure be represented by general formula (TP1A) or general formula (TP2A).

[changing 4]

(in general formula (TP1) and general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl;Rtp₅、Rtp₆、Rtp₈、Rtp₉And Rtp₁₁Represent independently respectively substituting group; Rtp₇Represent hydrogen atom, alkyl, aryl orNRtp₇₁Rtp₇₂；Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₁₀Represent hydrogen atom, alkylOr aryl; A, b and c represent respectively 0～4 integer independently; Be 2 above in the situation that at a, b and c, Rtp₆、Rtp₇And Rtp₈In two can mutually link and form ring; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in have crosslinkedProperty base; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂At least one can replace through general formula (P))

General formula (P)

[changing 5]

(in general formula (P), L represents singly-bound or bivalence linking base; X¹Be selected from-SO₃ ^-、-COO^-、-PO₄ ^-, bagIn the group that contains the group of the represented structure of following general formula (A1) and comprise the represented structure of following general formula (A2)At least one;

General formula (A1)

[changing 6]

General formula (A2)

[changing 7]

<7>as<1>to<6>in coloured composition as described in any one, it also comprises Photoepolymerizationinitiater initiater.

<8>as<1>to<7>in coloured composition as described in any one, it is used to form the dyed layer of colored filter.

<9>a painted cured film, it is by as<1>to<8>in coloured composition sclerosis as described in any one form.

<10>colored filter, it comprises as<9>as described in painted cured film.

<11>manufacture method for colored filter, it comprises the following steps: will be as<1>to<8>in any one instituteThe coloured composition of stating is imparted on support and forms coloured composition layer; Described coloured composition layer is exposed into pattern-like;And unexposed portion is developed and removed and formation colored pattern.

<12>manufacture method for colored filter, it comprises the following steps: will be as<1>to<8>in any one instituteThe coloured composition of stating is imparted on support and forms coloured composition layer, hardens and forms dyed layer; At dyed layerUpper formation photoresist layer; By exposing and developing, photoresist layer is carried out to patterning and obtains photoresistance pattern; Or by photoresistance patternAs etching mask, dyed layer is carried out to dry-etching.

<13>colored filter, it is to utilize as<11>or<12>as described in the manufacture method of colored filterManufacture.

<14>solid photographic element or an image display device, it comprises as<10>as described in colored filter orUtilize as<11>or<12>as described in the colored filter made of the manufacture method of colored filter.

The effect of invention

According to the present invention, can provide the coloured composition of a kind of heat resistance, solvent resistance and voltage retention excellence.

Detailed description of the invention

Below, content of the present invention is elaborated. In addition, in this description, so-called "～", is to comprise before itRear recorded numerical value uses as the implication of lower limit and higher limit.

In this description, so-called all solids composition, refers in whole compositions of coloured composition and removes the one-tenth that solvent formsThe gross mass of dividing.

In the statement of the group (atomic group) in this description, do not record the statement that is substituted and is unsubstituted and not only compriseDo not there is substituent group (atomic group), and comprise and there is substituent group (atomic group). For example, what is called" alkyl ", not only comprises and does not have substituent alkyl in (alkyl being unsubstituted), and comprise have substituentAlkyl (alkyl being substituted).

In addition, the what is called " radioactive ray " in this description, for example, refer to bright-line spectrum, PRK institute's generation of mercury vapor lampThe far ultraviolet, extreme ultraviolet line (extremeultravioletlight, EUV light), X ray, electron beam of table etc. In addition,So-called light in the present invention, refers to actinic ray or radioactive ray. What is called " exposure " in this description, as long as without saying especiallyBright, not only refer to exposing to the sun that far ultraviolet, X ray, EUV light of utilizing mercury vapor lamp, PRK representative etc. carry outLight, and utilize drawing of the particle beams such as electron beam, ion beam to be also contained in exposure.

In addition, in this description, " (methyl) acrylate " represent acrylate and methacrylate the two or appointOne, " (methyl) acrylic acid " represents acrylic acid and methacrylic acid the two or any one, " (methyl) acryloyl group "Represent acryloyl group and methacryl the two or any one.

In addition, in this description, " single amount body " is identical with " monomer (monomer) " implication. List in this descriptionAmount body is different from oligomer and polymer, refers to that weight average molecular weight is the compound below 2,000. In this description,So-called polymerizable compound, refers to the compound with polymerizable functional groups, can be single amount body, also can be polymer. So-calledPolymerizable functional groups, refers to the group that participates in polymerisation.

In this description, the Me in chemical formula represents methyl, and Et represents ethyl, and Pr represents propyl group, and Bu represents butyl,Ph represents phenyl.

In this description, the term of " step " not only comprises independently step, even if cannot clearly distinguish with other stepsSituation, as long as reach the desired effect of described step, be also contained in this term.

As long as no special instructions, the weight average molecular weight in the present invention refers to and utilizes gel permeation chromatography (GelPermeationChromatography, GPC) value measured. GPC can be to the polymer of gained, by removing solventSeparate, the solid constituent of gained is diluted to 0.1 quality % with oxolane, utilize HLC-8020GPC (eastern Cao (thigh)Manufacture), and TSKgelSuperMultiporeHZ-H (eastern Cao (thigh) manufactures, 4.6mmID × 15cm) series connection is linked3 persons of forming measure as tubing string. As condition, can establish sample solution concentration is that 0.35 quality %, flow velocity are 0.35ML/min, sample injection rate are that 10 μ L, mensuration temperature are 40 DEG C, use refractive index (RefractiveIndex, RI) to detectDevice carries out.

Coloured composition of the present invention is characterised in that: comprise colouring agent and polymerizable compound, described colouring agent comprises and hasBridging property base and cation and molecular weight are triarylmethane structure and the anti-lotus anion below 2000.

By being made as this kind of formation, can provide the coloured composition of heat resistance, solvent resistance and voltage retention excellence.

Below, with the order of the 1st example and the 2nd example, colouring agent is described.

The 1st example is the situation beyond following the 2nd illustrated example. For example can be set forth in and there is bridging property baseAnd cation and molecular weight are not have covalent bond in the bond part of triarylmethane structure below 2000 and anti-lotus anionSituation.

The 2nd example can be enumerated: anti-lotus anion is below 2000 with having bridging property base and cation and molecular weightThe triarylmethane skeleton part of triarylmethane structure is directly carried out the situation of covalency bond; Or anti-lotus anion and three virtuesMethylmethane skeleton portion is divided the situation of carrying out covalency bond via concatenating group.

The 1st example of colouring agent

Below, taking have bridging property base and cation and molecular weight as the triarylmethane structure below 2000, anti-He Yin fromThe order of son describes.

" triarylmethane structure "

The bridging property base that triarylmethane structure has can use and can carry out crosslinked bridging property by free radical, acid, heatBase. Particularly, can enumerate: group, (methyl) acrylic, styryl, the ethene with ethene unsaturated double-bondBase, pi-allyl, ring-type ether etc., be preferably and be selected from (methyl) acrylic, styryl, vinyl and pi-allyl extremelyFew a kind of, be more preferably selected from least one in (methyl) acrylic, styryl and vinyl, and then (first more preferablyBase) acrylic and styryl.

Ring-type ether is for example preferably epoxy radicals, oxa-cyclobutyl etc., more preferably epoxy radicals.

The molecular weight with bridging property base and cationic triarylmethane structure is below 2000, is preferably 300～1500,More preferably 300～900.

The triarylmethane structure that has bridging property base and cation and molecular weight and be below 2000 is preferably by following general formula(TP1) and/or general formula (TP2) represented.

[changing 8]

(in general formula (TP1) and general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl;Rtp₅、Rtp₆、Rtp₈、Rtp₉And Rtp₁₁Represent independently respectively substituting group; Rtp₇Represent hydrogen atom, alkyl, aryl orNRtp₇₁Rtp₇₂；Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₁₀Represent hydrogen atom, alkylOr aryl; A, b and c represent respectively 0～4 integer independently; Be 2 above in the situation that at a, b and c, Rtp₆、Rtp₇And Rtp₈In two can mutually link and form ring; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in have crosslinkedProperty base. )

In general formula (TP1), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl, be preferably hydrogen atom orAlkyl.

The carbon number of alkyl is preferably 1～10, and more preferably 1～5, and then more preferably 1～3. Alkyl can be straight chain shape, dividesAny of shape and ring-type, but be preferably straight chain shape or branch-like. Alkyl can have substituting group, but be preferably withoutReplace. The substituting group that alkyl can have can enumerate aftermentioned substituting group cohort A item in cited substituting group.

The carbon number of aryl is preferably 6～18, and more preferably 6～12, and then more preferably 6. The substituting group that aryl can have canEnumerate aftermentioned substituting group cohort A item in cited substituting group.

In general formula (TP1), Rtp₇Represent hydrogen atom, alkyl, aryl or NRtp₇₁Rtp₇₂, be preferably hydrogen atom orNRtp₇₁Rtp₇₂, more preferably NRtp₇₁Rtp₇₂。

The carbon number of alkyl is preferably 1～10, and more preferably 1～5, and then more preferably 1～3. Alkyl can be straight chain shape, dividesAny of shape and ring-type, but be preferably straight chain shape. The substituting group that alkyl can have can be enumerated aftermentioned substituting group cohort AItem in cited substituting group. The carbon number of aryl is preferably 6～18, and more preferably 6～12, and then more preferably 6.

Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl, be preferably hydrogen atom or alkyl.

The carbon number of alkyl is preferably 1～10, and more preferably 1～8, and then more preferably 1～6. Alkyl can be straight chain shape, dividesAny of shape and ring-type, but be preferably straight chain shape or branch-like. Alkyl is preferably and is unsubstituted. Alkyl can haveSubstituting group can enumerate aftermentioned substituting group cohort A item in cited substituting group. The carbon number of aryl is preferably 6～18, moreBe preferably 6～12, and then more preferably 6. The substituting group that aryl can have can enumerate aftermentioned substituting group cohort A item in listedThe substituting group of lifting.

In general formula (TP1), Rtp₅、Rtp₆And Rtp₈Represent independently respectively substituting group. Substituting group can be enumerated aftermentioned and replaceCited substituting group in the item of base cohort A. Be particularly preferably the straight chain of carbon number 1～5 or the alkyl of branch, carbon number 1～5Aryl, carboxyl or the sulfo group of thiazolinyl, carbon number 6～15, so more preferably the straight chain of carbon number 1～5 or the alkyl of branch,Thiazolinyl, phenyl or the carboxyl of carbon number 1～5. Be particularly preferably Rtp₅And Rtp₆Be the alkyl of carbon number 1～5 independently respectively.In addition, Rtp₈Be preferably two thiazolinyl bond and form ring mutually. Ring is preferably phenyl ring.

In general formula (TP1), a, b and c represent that respectively 0～4 integer, particularly a and b are preferably expression 0 independentlyOr 1, more preferably represent 0. C is preferably and represents 0～2, more preferably represents 0 or 1.

In general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl, in general formula (TP1)Rtp₁～Rtp₄Implication is identical, and preferable range is also identical.

In general formula (TP2), Rtp₅And Rtp₆Represent independently respectively substituting group, with the Rtp in general formula (TP1)₅And Rtp₆Implication is identical, and preferable range is also identical.

In general formula (TP2), Rtp₉And Rtp₁₁Represent independently respectively substituting group, can use the item of aftermentioned substituting group cohort AIn cited substituting group.

Rtp₉Be preferably alkyl, alkoxyl and halogen atom.

Rtp₁₁Be preferably alkyl, the more preferably alkyl of carbon number 1～5, and then the alkyl of carbon number 1～3 more preferably. AlkylBe preferably straight chain shape or branch-like, more preferably straight chain shape.

In general formula (TP2), Rtp₁₀Represent substituting group, can use aftermentioned substituting group cohort A item in cited substituting group.Particularly Rtp₁₀The more preferably aryl of carbon number 6～12, more preferably phenyl.

In general formula (TP2), a, b and c represent that respectively 0～4 integer, particularly a and b are preferably expression 0 independentlyOr 1, more preferably represent 0. C is preferably and represents 0～2, more preferably represents 0.

Be preferably at Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in there is bridging property base, be particularly preferably at Rtp₇₁OrRtp₇₂In there is bridging property base.

The group with bridging property base can only comprise bridging property base, also can except bridging property base, also comprise concatenating group. HaveThe group of bridging property base is particularly preferably-L⁰-P⁰Represented group. Herein, L⁰Represent singly-bound or bivalence linking base, P¹RepresentBridging property base.

Bridging property base is identical with described bridging property base implication, and preferable range is also identical.

Bivalence linking base be preferably alkylidene, arlydene, heterocycle concatenating group ,-CH=CH-,-O-,-S-,-C (=O)-,-CO-,-NR-、-CONR-、-OC-、-SO-、-SO₂-and by two groups that form above of these moiety combinations. Herein, R dividesDo not represent independently hydrogen atom, alkyl, aryl or heterocyclic radical.

Bivalence linking base is particularly preferably alkylidene.

Alkylidene can be any of straight chain shape, branch-like and ring-type. The carbon number of alkylidene is preferably 1～30, more preferablyBe 1～20, and then more preferably 5～20, be particularly preferably 5～10. Particularly, be preferably: methylene, ethylidene,Propylidene, butylidene, hexylidene, sub-heptyl, cyclopentenylidene, cyclohexylidene etc.

The carbon number of arlydene is preferably 6～30, and more preferably 6～18, and then more preferably 6～12. Particularly, sub-virtueBase is preferably phenylene, naphthyl etc.

The cation of described triarylmethane structure as follows but not localization ground exist, the implication phase of following two kinds of structuresWith, be all contained in the present invention. In addition, cation position can be arranged in arbitrary position of molecule.

[changing 9]

[changing 10]

Substituting group cohort A:

Substituting group can be enumerated: halogen atom, alkyl, cycloalkyl, thiazolinyl, cycloalkenyl group, alkynyl, aryl, heterocyclic radical, cyanogenBase, hydroxyl, nitro, carboxyl, alkoxyl, aryloxy, silanyloxy base, heterocyclic oxy group, acyloxy, carbamyl oxygenBase, amino (comprising alkyl amino, anilino-), acyl amino, amino carbonyl amino, alkoxycarbonyl amino, arylOxygen base carbonylamino, sulfamic amino, alkyl sulfonyl-amino or arlysulfonylamino, sulfydryl, alkyl sulfenyl, virtueBase sulfenyl, heterocycle sulfenyl, sulfamic, sulfo group, alkyl sulphinyl or aryl sulfonyl kia, alkyl sulphonyl or arylSulfonyl, acyl group, aryloxy carbonyl, alkoxy carbonyl, carbamyl, arylazo base or heterocycle azo base, acylImido grpup, phosphino-, phosphinyl, phosphinyl oxygen base, phosphinyl amino, silylation etc. Below describe in detail.

Can enumerate: the alkyl of halogen atom (for example: fluorine atom, chlorine atom, bromine atoms, iodine atom), straight chain or branch(alkyl that is substituted or is unsubstituted of straight chain or branch, is preferably the alkyl of carbon number 1～30, for example methyl, ethyl,N-pro-pyl, isopropyl, the tert-butyl group, n-octyl, 2-chloroethyl, 2-cyano ethyl, 2-ethylhexyl), cycloalkyl (preferablyFor the cycloalkyl that is substituted or is unsubstituted of carbon number 3～30, for example, can enumerate cyclohexyl, cyclopenta; Multi-ring alkyl, example(be preferably the bicyclic alkyl that is substituted or is unsubstituted of carbon number 5～30, for example: dicyclo [1,2,2] as enumerated bicyclic alkylHeptane-2-base, dicyclo [2,2,2] octane-3-yl) or the group of the multiring structure such as tricyclic alkyl; Be preferably monocycle cycloalkyl,Bicyclic alkyl is particularly preferably the cycloalkyl of monocycle),

(thiazolinyl that is substituted or is unsubstituted of straight chain or branch is preferably carbon number 2～30 for the thiazolinyl of straight chain or branchThiazolinyl, for example: vinyl, pi-allyl, prenyl, geranyl, oleyl (oleyl)), cycloalkenyl group is (excellentElect the cycloalkenyl group that is substituted or is unsubstituted of carbon number 3～30 as, for example, can enumerate: 2-cyclopentene-1-base, 2-cyclohexene-1-Base; Many cycloalkenyl groups, for example: bicyclic alkenyl (is preferably the bicyclic alkenyl that is substituted or is unsubstituted of carbon number 5～30, exampleAs: dicyclo [2,2,1] hept-2-ene"-1-base, dicyclo [2,2,2] oct-2-ene-4-yl) or tricyclene base, be particularly preferably the cyclenes of monocycleBase), alkynyl (is preferably the alkynyl that is substituted or is unsubstituted of carbon number 2～30, for example: acetenyl, propargyl, threeMethyl-monosilane ethyl-acetylene base),

Aryl (be preferably the aryl that is substituted or is unsubstituted of carbon number 6～30, for example: phenyl, p-methylphenyl, naphthyl,Between chlorphenyl, adjacent hexadecanoyl group aminophenyl), heterocyclic radical (is preferably being substituted or being unsubstituted of 5 member～7 Yuan, saturatedOr the heterocyclic radical of unsaturated, aromatic series or non-aromatic, monocycle or contracting ring, more preferably ring atom be selected from carbon atom,Nitrogen-atoms and sulphur atom, and there is any the heteroatomic heterocyclic radical at least one nitrogen-atoms, oxygen atom and sulphur atom,And then more preferably 5 Yuans or the aromatic heterocycle of 6 Yuans of carbon number 3～30; For example: 2-furyl, 2-thienyl, 2-pyrrolePyridine base, 4-pyridine radicals, 2-pyrimidine radicals, 2-[4-morpholinodithio base), cyano group, hydroxyl, nitro, carboxyl,

Alkoxyl (be preferably the alkoxyl that is substituted or is unsubstituted of carbon number 1～30, for example: methoxyl group, ethyoxyl,Isopropoxy, tert-butoxy, n-octyloxy, 2-methoxy ethoxy), aryloxy (be preferably carbon number 6～30 through gettingGeneration or the aryloxy being unsubstituted, for example: phenoxy group, 2-methylphenoxy, 2,4-bis--tertiary pentyl phenoxy group, the 4-tert-butyl groupPhenoxy group, 3-nitro-phenoxy, 2-myristoyl base amino-benzene oxygen), silanyloxy base (is preferably the silane of carbon number 3～20Base oxygen base, for example: TMS oxygen base, tert-butyl group dimethylsilyl oxygen base), heterocyclic oxy group (be preferably carbon number 2～30 the heterocyclic oxy group that is substituted or is unsubstituted, heterocycle quality award from the ministry is elected heterocycle portion illustrated in described heterocyclic radical as, for example:1-phenyltetrazole-5-oxygen base, 2-tetrahydro-pyran oxy),

Acyloxy (be preferably the alkyl-carbonyl oxygen base that is substituted or is unsubstituted, carbon number 6 of formyloxy, carbon number 2～30～30 the aryl carbonyl oxygen base that is substituted or is unsubstituted, for example: formyloxy, acetoxyl group, trimethyl acetoxyl,Stearoyl-oxy, benzoyloxy, p-methoxyphenyl ketonic oxygen base), carbamoyloxy group (is preferably carbon number 1～30The carbamoyloxy group that is substituted or is unsubstituted, for example: N, N-dimethylamino formyloxy, N, N-diethyl amino formyloxy,Morpholinyl carbonyl oxygen base, N, N-bis--n-octyl amino carbonyl oxygen base, N-n-octyl carbamoyloxy group), alkoxy-carbonyl oxy(be preferably the alkoxy-carbonyl oxy that is substituted or is unsubstituted of carbon number 2～30, for example: methoxycarbonyl oxygen base, secondOxygen base ketonic oxygen base, tert-butoxycarbonyl oxygen base, n-octyl ketonic oxygen base), aryloxy ketonic oxygen base (be preferably carbon number 7～30 the aryloxy ketonic oxygen base that is substituted or is unsubstituted, for example: phenyloxycarbonyl oxygen base, to methoxyphenoxy carbonylBase oxygen base, to n-hexadecyl oxygen phenoxyl ketonic oxygen base),

Amino (be preferably amino, carbon number 1～30 the alkyl amino that is substituted or is unsubstituted, carbon number 6～30 through gettingGeneration or the arylamino being unsubstituted, the heterocyclic amino group of carbon number 0～30, for example: amino, methylamino, dimethylamino,Anilino-, N-methyl-anilino-, diphenyl amino, N-1,3,5-triazine-2-base amino), acyl amino (is preferably formoxylBeing substituted or being unsubstituted of the alkyl-carbonyl-amino that is substituted or is unsubstituted of amino, carbon number 1～30, carbon number 6～30Aryl-amino-carbonyl, for example: formoxyl amino, acetyl-amino, pivaloyl group amino, lauroyl amino,Benzoyl-amido, 3,4,5-tri--n-octyloxy phenylcarbonyl group amino), amino carbonyl amino (is preferably the warp of carbon number 1～30The amino carbonyl amino that replaces or be unsubstituted, for example: carbamyl amino, N, N-dimethylamino carbonylamino, N, N-Diethylamino carbonylamino, morpholinyl carbonyl amino), alkoxycarbonyl amino (is preferably being substituted of carbon number 2～30Or the alkoxycarbonyl amino being unsubstituted, for example: methoxycarbonyl amino, ethoxy carbonyl amino, tert-butoxycarbonylAmino, n-octadecane base oxygen base carbonylamino, N-methyl-methoxycarbonyl amino),

Aryloxy carbonylamino (is preferably the aryloxy carbonylamino that is substituted or is unsubstituted of carbon number 7～30, exampleAs: phenyloxycarbonyl amino, to chlorophenoxy carbonylamino, a n-octyloxy phenyloxycarbonyl amino), sulfamic ammoniaBase (is preferably the sulfamic amino that is substituted or is unsubstituted of carbon number 0～30, for example: sulfamic amino, N, N-Dimethylamino-sulfonyl amino, N-n-octyl amino-sulfonyl amino), alkyl sulfonyl-amino or arlysulfonylamino(be preferably carbon number 1～30 the alkyl sulfonyl-amino that is substituted or is unsubstituted, carbon number 6～30 be substituted or withoutThe arlysulfonylamino replacing, for example: methyl sulphonyl amino, butyl sulfuryl amino, phenyl sulfonyl amino, 2,3,5-Trichlorophenyl sulfuryl amino, p-methylphenyl sulfuryl amino), sulfydryl,

Alkyl sulfenyl (is preferably the alkyl sulfenyl that is substituted or is unsubstituted of carbon number 1～30, for example: methyl sulfenyl, secondBase sulfenyl, n-hexadecyl sulfenyl), artyl sulfo (is preferably the aryl sulphur that is substituted or is unsubstituted of carbon number 6～30Base, for example: phenyl sulfenyl, rubigan sulfenyl, m-methoxyphenyl sulfenyl), heterocycle sulfenyl (is preferably carbon number 2～30The heterocycle sulfenyl that is substituted or is unsubstituted, heterocycle quality award from the ministry is elected heterocycle portion illustrated in described heterocyclic radical as, for example: 2-Benzothiazolyl sulfenyl, 1-phenyltetrazole-5-base sulfenyl), sulfamic (be preferably carbon number 0～30 be substituted or withoutThe sulfamic replacing, for example: N-ethylamine sulfonyl, N-(3-dodecyl oxygen base propyl group) sulfamic, N, N-dimethylSulfamic, N-acetyl amine sulfonyl, N-benzoyl sulfamic, N-(N '-phenylamino formoxyl) sulfamic),Sulfo group,

Alkyl sulphinyl or aryl sulfonyl kia (are preferably the alkyl sulfenyl that is substituted or is unsubstituted of carbon number 1～30The aryl sulfonyl kia that is substituted or is unsubstituted of base, carbon number 6～30, for example: methylsulfinyl, ethyl sulfenylBase, phenyl sulfinyl, p-methylphenyl sulfinyl), alkyl sulphonyl or aryl sulfonyl (be preferably carbon number 1～30The alkyl sulphonyl that is substituted or is unsubstituted, the aryl sulfonyl that is substituted or is unsubstituted of carbon number 6～30, for example:Methyl sulphonyl, ethylsulfonyl, phenyl sulfonyl, p-methylphenyl sulfonyl), acyl group (is preferably formoxyl, carbonSeveral 2～30 the alkyl-carbonyl that is substituted or is unsubstituted, the aryl carbonyl that is substituted or is unsubstituted of carbon number 7～30,For example: acetyl group, pivaloyl group, 2-chloracetyl, stearyl, benzoyl, align octyloxyphenyl carbonyl),Aryloxy carbonyl (is preferably the aryloxy carbonyl that is substituted or is unsubstituted of carbon number 7～30, for example: phenoxy group carbonylBase, adjacent chlorophenoxy carbonyl, m-nitro oxygen base carbonyl, to tert-butyl group phenyloxycarbonyl),

Alkoxy carbonyl (is preferably the alkoxy carbonyl that is substituted or is unsubstituted of carbon number 2～30, for example: methoxyl group carbonylBase, ethoxy carbonyl, tert-butoxycarbonyl, n-octadecane base oxygen base carbonyl), carbamyl (is preferably carbon number 1～30The carbamyl that is substituted or is unsubstituted, for example: carbamyl, N-methylcarbamoyl, N, N-dimethylamino formylBase, N, N-bis--n-octyl carbamyl, N-(methyl sulphonyl) carbamyl), arylazo base or heterocycle azo base (excellentElect as carbon number 6～30 the arylazo base that is substituted or is unsubstituted, carbon number 3～30 be substituted or be unsubstituted assortedRing azo group (heterocycle quality award from the ministry is elected heterocycle portion illustrated in described heterocyclic radical as), for example: phenylazo, rubigan are occasionallyNitrogen, 5-ethyl sulfenyl-1,3,4-thiadiazoles-2-base azo), imide (be preferably carbon number 2～30 be substituted or without gettingThe imide in generation, for example: N-succimide, N phlhalimide), phosphino-(is preferably carbon number 2～30The phosphino-that is substituted or is unsubstituted, for example: dimethyl phosphino-, diphenylphosphino, methylphenoxy phosphino-), phosphinyl(be preferably the phosphinyl that is substituted or is unsubstituted of carbon number 2～30, for example: phosphinyl, two octyloxy phosphinyls, twoEthyoxyl phosphinyl),

Phosphinyl oxygen base (is preferably the phosphinyl oxygen base that is substituted or is unsubstituted of carbon number 2～30, for example: two phenoxy groupsPhosphinyl oxygen base, two octyloxy phosphinyl oxygen bases), phosphinyl amino (be preferably carbon number 2～30 be substituted or without gettingThe phosphinyl amino in generation, for example: dimethoxy phosphinyl amino, dimethylamino phosphinyl amino), silylation (preferablyFor example, for the silylation that is substituted or is unsubstituted of carbon number 3～30: TMS, tert-butyl group dimethylsilyl,Phenyl dimethylsilyl).

The concrete example that has bridging property base and cation and molecular weight and be the triarylmethane structure below 2000 can be enumerated followingStructure, but the present invention is not limited to these structures.

[changing 11]

[changing 12]

" anti-lotus anion "

The cationic anti-lotus anion that anti-lotus anion has for described triarylmethane structure. Anti-lotus anion can only wrapContaining anti-lotus anion, also can be used as compound structure a part and comprise.

In the situation that only comprising anti-lotus anion, can enumerate: fluorine anion, cl anion, bromine anions, iodine anion,Cyanide ion, mistake chlorate anions anion, borate anion (BF^4-Deng), PF^6-And SbF^6-Deng, be preferably borate the moonIon and PF^6-。

Situation about comprising as a part for the structure of compound about anti-lotus anion, can enumerate: with there is bridging property baseAnd cation and molecular weight are the different and situation about existing as anti-lotus anion of triarylmethane structure below 2000.

Borate anion is B (R¹⁰)^4-Represented group, R¹⁰Can illustrate fluorine atom, cyano group, fluorinated alkyl, alkoxyl,Aryloxy etc.

Situation about comprising as a part for the structure of compound about anti-lotus anion, can be contained in and have repetitiveIn a part for polymer, also can be contained in molecular weight is in the so-called low molecular compound below 2000. Close degradedIn the situation of thing, can illustrate at least one the form that comprises in the lump alkyl, aryl and bridging property base with anionic site. ThisIn invention, be particularly preferably contained in form and the anti-He Yinlizibao in the compound that contains bridging property base for anti-lotus anionBe contained in the form in repetitive, more preferably anti-lotus anion is contained in the form in repetitive.

At anti-lotus anion as a part for the structure of compound and comprising, anion quality award from the ministry is elected as and is selected from -SO₃ ^-、-COO^-、-PO₄ ^-, in the represented structure of following general formula (A1) and the represented structure of following general formula (A2)At least one.

General formula (A1)

[changing 13]

(in general formula (A1), R¹And R²Difference expression-SO independently₂-or-CO-. )

In general formula (A1), be preferably R¹And R²At least one expression-SO₂-, more preferably R¹And R²The two expression-SO₂-。

Described general formula (A1) is more preferably represented by following general formula (A1-1).

General formula (A1-1)

[changing 14]

(in general formula (A1-1), R¹And R²Difference expression-SO independently₂-or-CO-; X¹And X²Represent independently respectivelyAlkylidene or arlydene. )

In general formula (A1-1), R¹And R²With the R in general formula (A1)¹And R²Implication is identical, and preferable range is also identical.

At X¹Represent that in the situation of alkylidene, the carbon number of alkylidene is preferably 1～8, more preferably 1～6. At X¹Represent sub-In the situation of aryl, the carbon number of arlydene is preferably 6～18, and more preferably 6～12, and then more preferably 6. At X¹HaveIn substituent situation, be preferably through fluorine atom and replace.

X²Represent alkyl or aryl, be preferably alkyl. The carbon number of alkyl is preferably 1～8, and more preferably 1～6, Jin ErgengBeing preferably 1～3, is particularly preferably 1. At X²Have in substituent situation, be preferably through fluorine atom and replace.

General formula (A2)

[changing 15]

(in general formula (A2), R³Expression-SO₂-or-CO-; R⁴And R⁵Difference expression-SO independently₂-,-CO-or-CN. )

In general formula (A2), be preferably R³～R⁵At least one expression-SO₂-, more preferably R³～R⁵At least two tablesShow-SO₂-。

The concrete example of anti-lotus anion as the part of the structure of compound and in situation about comprising is R-SO₃ ^-、R-COO^-Or R-PO₄ ^-, also can illustrate R for halogen atom, the alkyl that can replace through halogen atom, can replace through halogen atomThe situation of aryl.

The concrete example of the compound that in addition, comprises the represented group of described general formula (A1) can illustrate: R¹With halogen atom,The alkyl that can replace through halogen atom, the aryl that can replace through halogen atom carry out the compound of bond.

The concrete example of the compound that in addition, comprises the represented group of described general formula (A2) can illustrate: R⁴And R⁵Be respectivelyThe situation of halogen atom, the alkyl that can replace through halogen atom, the aryl that can replace through halogen atom.

It is particularly preferably following form. For comprising the compound of the represented group of general formula (A1-1), and general formula (A1-1)In R¹And R²Expression-SO₂-，X¹And X²At least one represent the form of alkylidene or arlydene. For comprising general formula (A2)The compound of represented group, and R in general formula (A2)⁴And R⁵Carry out bond with the alkyl replacing through halogen atomForm.-PO₄ ^-Or-SO₃ ^-As the part of the structure of compound and the form comprising. Cl anion, cyanide ion,BF^4-Or pF^6-。

The concrete example of other anti-lotus anion can be enumerated following example, but the present invention is not limited to these examples. This explanationIn book, following other the concrete example of anti-lotus anion is called to " anti-lotus anion A ".

[changing 16]

[changing 17]

Below, to anti-lotus anion be contained in the situation in the compound that contains bridging property base, anti-lotus anion is contained in repetitionSituation in unit is elaborated.

Bridging property base can be enumerated and can carry out crosslinked bridging property base by free radical, acid, heat, with described triarylmethane knotThe bridging property base implication that structure has is identical, and preferable range is also identical.

The quantity of the bridging property base in the compound that contains bridging property base is preferably 1～3, and more preferably 1.

In addition, direct bond between bridging property base and anti-lotus anion, also can be via concatenating group bond, but be preferably throughThe bond by concatenating group.

The concrete example that anti-lotus anion is contained in the situation in the compound that contains bridging property base is preferably by following general formula (B)Represented.

General formula (B)

[changing 18]

(in general formula (B), P represents bridging property base; L represents singly-bound or bivalence linking base; Anion (anion) tableShow described anti-lotus anion. )

In general formula (B), P represents bridging property base, can enumerate described bridging property base.

In general formula (B), in the situation that L represents bivalence linking base, be preferably: the alkylidene of carbon number 1～30 (for example:Methylene, ethylidene, trimethylene, propylidene, butylidene etc.), the arlydene of carbon number 6～30, heterocycle concatenating group ,-CH=CH-,-O-、-S-、-C(＝O)-、-CO-、-NR-、-CONR-、-OC-、-SO-、-SO₂-and by two of these moiety combinations withOn the concatenating group that forms. Herein, R represents respectively hydrogen atom, alkyl, aryl or heterocyclic radical independently.

Concatenating group is particularly preferably for (to be preferably the alkylidene of carbon number 1～10-(CH₂) n-(integer that n is 1～10)), carbonSeveral 6～12 arlydene (being preferably phenylene, naphthyl) ,-NH-,-CO-,-O-and-SO₂Two of-combinations form aboveConcatenating group.

" other functional groups "

At anti-lotus anion as a part for the structure of compound and comprising, also can have beyond bridging property baseOther functional groups. Described in other functional groups can enumerate, have in the repetitive that comprises cationic triarylmethane structure saidOther bright functional groups, preference also implication is identical. Comprise as a part for the structure of compound at anti-lotus anionIn situation, the quantity of the polymerism base in compound is preferably 1～3, and more preferably 1.

At anti-lotus anion as a part for the structure of compound and comprising, the quantity of the acidic group in compound is excellentElect 1～3 as, more preferably 1.

Below illustrate that anti-lotus anion is contained in the concrete example in the situation in the compound that contains bridging property base, but the present invention alsoBe not limited to these examples.

[changing 19]

The molecular weight of the compound that contains bridging property base is preferably 200～2000, and more preferably 200～500.

Be contained in the situation (below also referred to as anion polymer) in repetitive at anti-lotus anion, can be on side chainThere is anti-lotus anion, also can on main chain, there is anti-lotus anion, also can there is anti-lotus on the two at main chain and side chainAnion.

Anion polymer is preferably by following general formula (C) and/or following general formula (D) represented.

General formula (C)

[changing 20]

(in general formula (C), X¹Represent the main chain of repetitive; L¹Represent singly-bound or bivalence linking base; Anion (anion)Represent described anti-lotus anion. )

In general formula (C), X¹Represent the main chain of repetitive, the concatenating group that ordinary representation forms by polymerisation, exampleAs be preferably (methyl) acrylic acid series, polystyrene, ethene base system etc. In addition, two represented positions of * become repetition listUnit.

At L¹Represent, in the situation of bivalence linking base, to be preferably: alkylidene (methylene, the ethylidene, three of carbon number 1～30Methylene, propylidene, butylidene etc.), the arlydene (phenylene, naphthyl etc.) of carbon number 6～30, heterocycle concatenating group ,-CH=CH-,-O-、-S-、-C(＝O)-、-CO-、-NR-、-CONR-、-OC-、-SO-、-SO₂-and by two of these moiety combinations withOn the concatenating group that forms. Herein, R represents respectively hydrogen atom, alkyl, aryl or heterocyclic radical independently.

L¹It is particularly preferably singly-bound or the alkylidene of carbon number 1～10 (is preferably-(CH₂) n-(integer that n is 5～10)),The arlydene (being preferably phenylene, naphthyl) of carbon number 6～12 ,-NH-,-CO₂-,-O-and-SO₂Two of-combinations above andThe bivalence linking base becoming.

X¹And L¹The concrete example of combination can enumerate following (XX-1)～(X-30), but the present invention is not limited to theseExample. In addition anion polymer being connected by the position shown in * and described anti-lotus anion in (XX-1)～(X-30),Knot.

[changing 21]

In addition, X¹And L¹The concrete example of combination be also preferably following example. In following concrete example, n represent 1～9 wholeNumber. In addition, be illustrated in by the position shown in * and described anti-lotus anion and link.

[changing 22]

General formula (D)

[changing 23]

(in general formula (D), L²And L³Represent independently respectively singly-bound or bivalence linking base; Anion (anion) representsDescribed anti-lotus anion. )

In general formula (D), at L²And L³Represent, in the situation of bivalence linking base, to be preferably alkylidene, the carbon of carbon number 1～30Several 6～30 arlydene, heterocycle concatenating group ,-CH=CH-,-O-,-S-,-C (=O)-,-CO₂-、-NR-、-CONR-、-O₂C-、-SO-、-SO₂-and by two concatenating groups that form above of these moiety combinations. Herein, R represents respectively independentlyHydrogen atom, alkyl, aryl or heterocyclic radical.

L²Be preferably the arlydene (being particularly preferably phenylene) of carbon number 6～12. The arlydene of carbon number 6～30 is preferably through fluorineAtom replaces.

L³The group that is preferably the arlydene that comprises carbon number 6～12 (being particularly preferably phenylene) and the combination of-O-, is preferablyThe arlydene of at least one carbon number 6～12 replaces through fluorine atom.

The polymeric macromolecule of formation anion only can preferably use and be made up of the dye composition composition with bridging property baseHomopolymers (separately polymer), also can preferably use and the copolymer (co-polymer) of other polymerizable compounds,More preferably homopolymers (polymer separately).

The polymeric molecular weight of anion be preferably weight average molecular weight be 3,000～30,000 and molecular weight distribution withMw/Mn counts 0.8～3.0, more preferably weight average molecular weight be 5,000～20,000 and molecular weight distribution with Mw/MnCount 1～2.5.

Forming in the polymeric situation of anion, can add chain-transferring agent. Chain-transferring agent is preferably alkyl hydrosulfide, is preferablyThe alkyl hydrosulfide of carbon number below 10 or the alkyl hydrosulfide replacing through ether ester group. Especially more preferably logP value be 5 withUnder alkyl hydrosulfide.

In anion polymer, the contained polymeric raw material of anion has the anionic monomer compound of bridging property baseAmount is preferably below 5%, more preferably below 1%.

In anion polymer, contained content of halide ions is preferably below 10ppm～3000ppm, and more preferably 10Ppm～2000ppm, and then 10ppm～1000ppm more preferably.

The polymeric concrete example of anion is below shown, but the present invention is not limited to these examples.

[changing 24]

Following concrete example represents the unsegregated state of anion structure, and the state that anion structure separates is certainly also in the present inventionScope in.

[changing 25]

[changing 26]

[changing 27]

[changing 28]

[changing 29]

Be in high molecular situation at anti-lotus anion, also can there are other repetitives.

Contain in the polymeric situation of anion at anti-lotus anion, with respect to the whole weights in the colouring agent using in the present invention100 moles of multiple unit, the polymeric amount of anion is preferably 1 mole～50 moles, more preferably 10 moles～30 moles.

In addition, also comprise the repetitive with polymerism base at anion polymer, with respect to all repeating list100 moles, unit, described in there is the repetitive of polymerism base amount be for example preferably 10 moles～50 moles, more preferably10 moles～30 moles.

The repetitive with polymerism base can be enumerated concrete example as described below. But the present invention is not limited to these examplesSon.

[changing 30]

[changing 31]

[changing 32]

Also comprise the repetitive with acidic group at anion polymer, with respect to 100 moles of whole repetitives,The ratio of the repetitive that contains the repetitive with acidic group is for example preferably 10 moles～50 moles, more preferably 10 rubsYou～30 moles.

In addition, also can comprise the repetitive with following functional group: lactone, acid anhydrides, acid amides ,-COCH₂CO-、The development accelaration bases such as cyano group, long-chain and cyclic alkyl, aralkyl, aryl, polyalkylene oxide base, hydroxyl, maleoyl-AsiaThe hydrophilic and hydrophobic such as amido, amino is adjusted the functional groups such as base.

The concrete example of other repetitives is below shown, but the present invention is not limited thereto.

[changing 33]

" concrete example of colouring agent "

The concrete example of the colouring agent of the 1st example using in the present invention is below shown, but is not limited to these examples.

In following compound, have the bridging property base and cation and molecular weight of (D-21) is the triarylmethane below 2000Only there is the quantity suitable with the repetitive of anti-lotus anion in structure.

[changing 34]

[changing 35]

The 2nd example of colouring agent

The 2nd example of colouring agent is preferably that to have bridging property base and cation and molecular weight be the triaryl below 2000Methane structure is represented by general formula (TP1A) or general formula (TP2A).

[changing 36]

(in general formula (TP1) and general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl;Rtp₅、Rtp₆、Rtp₈、Rtp₉And Rtp₁₁Represent independently respectively substituting group; Rtp₇Represent hydrogen atom, alkyl, aryl orNRtp₇₁Rtp₇₂；Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₁₀Represent hydrogen atom, alkylOr aryl; A, b and c represent respectively 0～4 integer independently; Be 2 above in the situation that at a, b and c, Rtp₆、Rtp₇And Rtp₈In two can mutually link and form ring; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in have crosslinkedProperty base; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂At least one can replace through general formula (P). )

General formula (P)

[changing 37]

(in general formula (P), L represents singly-bound or bivalence linking base, X¹Be selected from-SO₃ ^-、-COO^-、-PO₄ ^-, bagIn the group that contains the group of the represented structure of following general formula (A1) and comprise the represented structure of following general formula (A2)At least one.

General formula (A1)

[changing 38]

General formula (A2)

[changing 39]

In general formula (TP1A) and general formula (TP2A), except Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂At least one can be throughBeyond the aspect that general formula (P) replaces, with have the bridging property base and cation and molecular weight of described the 1st example be 2000Following triarylmethane structure implication is identical, and preferable range is also identical.

In general formula (P), L represents singly-bound or bivalence linking base. In the situation that L represents bivalence linking base, be preferablyAt least one hydrogen atom of the group of below enumerating is through X¹The bivalence linking base replacing.

Alkyl, cycloalkyl, thiazolinyl, cycloalkenyl group, alkynyl, aryl, heterocyclic radical, carboxyl, alkoxyl, aryloxy, siliconAlkyl oxy, heterocyclic oxy group, acyloxy, carbamoyloxy group, amino (comprising alkyl amino, anilino-), acyl amino,Amino carbonyl amino, alkoxycarbonyl amino, aryloxy carbonylamino, sulfamic amino, alkyl sulfonyl-amino orArlysulfonylamino, alkyl sulfenyl, artyl sulfo, heterocycle sulfenyl, sulfamic, sulfo group, alkyl sulphinyl or virtueBase sulfinyl, alkyl sulphonyl or aryl sulfonyl, acyl group, aryloxy carbonyl, alkoxy carbonyl, carbamyl,Arylazo base or heterocycle azo base, imide, phosphino-, phosphinyl, phosphinyl oxygen base, phosphinyl amino, silaneBase, ether, thioether group.

Alkyl is preferably the alkyl that is substituted or is unsubstituted of carbon number 1～30, for example, be preferably from methyl, ethyl, positive thirdIn base, isopropyl, the tert-butyl group, n-octyl, 2-chloroethyl, 2-cyano ethyl, 2-ethylhexyl, remove that a hydrogen forms twoValency alkyl. In order to make these alkyl become divalence, X¹Can be directed into arbitrary position.

Cycloalkyl is preferably the cycloalkyl that is substituted or is unsubstituted of carbon number 3～30. For example can enumerate cyclohexyl, cyclopenta.In addition, also can enumerate multi-ring alkyl, for example bicyclic alkyl (is preferably the dicyclo that is substituted or is unsubstituted of carbon number 5～30Alkyl, for example: dicyclo [1,2,2] heptane-2-base, dicyclo [2,2,2] octane-3-yl) or the group of the multiring structure such as tricyclic alkyl.Being preferably cycloalkyl, the bicyclic alkyl of monocycle, is particularly preferably the cycloalkyl of monocycle. In order to make these cycloalkyl become divalence,X¹Can be directed into arbitrary position.

Thiazolinyl can be straight chain shape, also can be branch-like. Thiazolinyl is preferably the thiazolinyl that is substituted or is unsubstituted of carbon number 2～30.Be particularly preferably for example vinyl, pi-allyl, prenyl, geranyl, oleyl. In order to make these thiazolinyls become twoValency, X¹Can be directed into arbitrary position.

Cycloalkenyl group is preferably the cycloalkenyl group that is substituted or is unsubstituted of carbon number 3～30. For example can enumerate 2-cyclopentene-1-base,2-cyclohexene-1-base; Many cycloalkenyl groups, for example bicyclic alkenyl, is preferably the bicyclic alkenyl of carbon number 5～30, for example, be dicyclo [2,2,1]Hept-2-ene"-1-base, dicyclo [2,2,2] oct-2-ene-4-base or tricyclene base are particularly preferably the cycloalkenyl group of monocycle. In order to make these ringsThiazolinyl becomes divalence, X¹Can be directed into arbitrary position.

Alkynyl is preferably the alkynyl that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably acetenyl, propargyl, threeMethyl-monosilane ethyl-acetylene base. In order to make these alkynyls become divalence, X¹Can be directed into arbitrary position.

Aryl is preferably the aryl that is substituted or is unsubstituted of carbon number 6～30. For example be preferably phenyl, p-methylphenyl, naphthaleneBase, a chlorphenyl, adjacent hexadecanoyl group aminophenyl. In order to make these aryl become divalence, X¹Can be directed into arbitrary position.

Heterocyclic radical be preferably being substituted or being unsubstituted of 5 member～7 Yuan, saturated or unsaturated, aromatic series or non-aromatic,The heterocyclic radical of monocycle or contracting ring. More preferably ring atom is selected from carbon atom, nitrogen-atoms and sulphur atom, and has at least oneAny heteroatomic heterocyclic radical in individual nitrogen-atoms, oxygen atom and sulphur atom, and then 5 members of carbon number 3～30 more preferablyOr the aromatic heterocycle of 6 Yuans. For example be preferably 2-furyl, 2-thienyl, 2-pyridine radicals, 4-pyridine radicals, 2-pyrimidine radicals,2-[4-morpholinodithio base. In order to make these heterocyclic radicals become divalence, X¹Can be directed into arbitrary position.

Alkoxyl is preferably the alkoxyl that is substituted or is unsubstituted of carbon number 1～30, be for example preferably methoxyl group, ethyoxyl,Isopropoxy, tert-butoxy, n-octyloxy, 2-methoxy ethoxy. In order to make these alkoxyls become divalence, X¹Can leadEnter to arbitrary position.

Aryloxy is preferably the aryloxy that is substituted or is unsubstituted of carbon number 6～30, for example, be preferably phenoxy group, 2-Methylphenoxy, 2,4-bis--tertiary pentyl phenoxy group, 4-tert-butyl group phenoxy group, 3-nitro-phenoxy, 2-myristoyl base aminobenzene oxygenBase. In order to make these aryloxies become divalence, X¹Can be directed into arbitrary position.

Silanyloxy base is preferably the silanyloxy base that is substituted or is unsubstituted of carbon number 3～20, for example, be preferably trimethylSilanyloxy base, tert-butyl group dimethylsilyl oxygen base. In order to make these silanyloxy bases become divalence, X¹Can be directed into and appointOne position.

Heterocyclic oxy group is preferably the heterocyclic oxy group that is substituted or is unsubstituted of carbon number 2～30. Heterocycle quality award from the ministry is elected described heterocycle asIllustrated heterocycle portion in base, for example, be preferably 1-phenyltetrazole-5-oxygen base, 2-THP trtrahydropyranyl oxygen base. In order to make these assortedEpoxy radicals becomes divalence, X¹Can be directed into arbitrary position.

Acyloxy is preferably being substituted of the alkyl-carbonyl oxygen base that is substituted or is unsubstituted, carbon number 6～30 of carbon number 2～30Or the aryl carbonyl oxygen base being unsubstituted, be for example preferably formyloxy, acetoxyl group, trimethyl acetoxyl, stearoylOxygen base, benzoyloxy, p-methoxyphenyl ketonic oxygen base. In order to make these acyloxy become divalence, X¹Can be directed into and appointOne position.

Carbamoyloxy group is preferably the carbamoyloxy group that is substituted or is unsubstituted of carbon number 1～30, for example, be preferably N, N-Dimethylamino formyloxy, N, N-diethyl amino formyloxy, morpholinyl carbonyl oxygen base, N, N-bis--n-octyl amino carbonyl oxygenBase, N-n-octyl carbamoyloxy group. In order to make these acyloxy become divalence, X¹Can be directed into arbitrary position.

Alkoxy-carbonyl oxy is preferably the alkoxy-carbonyl oxy that is substituted or is unsubstituted of carbon number 2～30, for example preferredFor methoxycarbonyl oxygen base, ethoxy carbonyl oxygen base, tert-butoxycarbonyl oxygen base, n-octyl ketonic oxygen base. In order to make theseAlkoxy-carbonyl oxy becomes divalence, X¹Can be directed into arbitrary position.

Aryloxy ketonic oxygen base is preferably the aryloxy ketonic oxygen base that is substituted or is unsubstituted of carbon number 7～30, for exampleBe preferably phenyloxycarbonyl oxygen base, to methoxyphenoxy ketonic oxygen base, to n-hexadecyl oxygen phenoxyl ketonic oxygen base.In order to make these aryloxy ketonic oxygen bases become divalence, X¹Can be directed into arbitrary position.

Amino is preferably being substituted of the alkyl amino that is substituted or is unsubstituted, carbon number 6～30 of amino, carbon number 1～30Or the heterocyclic amino group of the arylamino being unsubstituted, carbon number 0～30, be for example preferably amino, methylamino, dimethylaminoBase, anilino-, N-methyl-anilino-, diphenyl amino, N-1,3,5-triazine-2-base amino. In order to make these amino become twoValency, X¹Can be directed into arbitrary position.

Acyl amino be preferably carbon number 1～30 the alkyl-carbonyl-amino that is substituted or is unsubstituted, carbon number 6～30 through gettingGeneration or the aryl-amino-carbonyl that is unsubstituted, be for example preferably formoxyl amino, acetyl-amino, pivaloyl group amino,Lauroyl amino, benzoyl-amido, 3,4,5-tri--n-octyloxy phenylcarbonyl group amino. For these acyl aminos are becomeDivalence, X¹Can be directed into arbitrary position.

Amino carbonyl amino is preferably the amino carbonyl amino that is substituted or is unsubstituted of carbon number 1～30, for example, be preferably ammoniaFormoxyl amino, N, N-dimethylamino carbonylamino, N, N-diethylamino carbonylamino, morpholinyl carbonyl amino. ForMake these amino carbonyl aminos become divalence, X¹Can be directed into arbitrary position.

Alkoxycarbonyl amino is preferably the alkoxycarbonyl amino that is substituted or is unsubstituted of carbon number 2～30, for example preferredFor methoxycarbonyl amino, ethoxy carbonyl amino, tert-butoxycarbonyl amino, n-octadecane base oxygen base carbonylamino, N-Methyl-methoxycarbonyl amino. In order to make these alkoxycarbonyl aminos become divalence, X¹Can be directed into arbitrary position.

Aryloxy carbonylamino is preferably the aryloxy carbonylamino that is substituted or is unsubstituted of carbon number 7～30, for exampleBe preferably phenyloxycarbonyl amino, to chlorophenoxy carbonylamino, a n-octyloxy phenyloxycarbonyl amino. In order to make theseAryloxy carbonylamino becomes divalence, X¹Can be directed into arbitrary position.

Sulfamic amino is preferably the sulfamic amino that is substituted or is unsubstituted of carbon number 0～30, for example, be preferably amineSulfuryl amino, N, N-dimethylamino-sulfonyl amino, N-n-octyl amino-sulfonyl amino. In order to make these amine sulphonylBase amino becomes divalence, X¹Can be directed into arbitrary position.

Alkyl sulfonyl-amino or arlysulfonylamino are preferably the alkyl sulfonyl that is substituted or is unsubstituted of carbon number 1～30The arlysulfonylamino that is substituted or is unsubstituted of base amino, carbon number 6～30. For example be preferably methyl sulphonyl amino,Butyl sulfuryl amino, phenyl sulfonyl amino, 2,3,5-trichlorophenyl sulfuryl amino, p-methylphenyl sulfuryl amino.In order to make these alkyl sulfonyl-aminos or arlysulfonylamino become divalence, X¹Can be directed into arbitrary position.

Alkyl sulfenyl is preferably the alkyl sulfenyl that is substituted or is unsubstituted of carbon number 1～30, be for example preferably methyl sulfenyl,Ethyl sulfenyl, n-hexadecyl sulfenyl. In order to make these alkyl sulfenyls become divalence, X¹Can be directed into arbitrary position.

Artyl sulfo is preferably the artyl sulfo that is substituted or is unsubstituted of carbon number 6～30, be for example preferably phenyl sulfenyl,Rubigan sulfenyl, m-methoxyphenyl sulfenyl. In order to make these alkyl sulfenyls become divalence, X¹Can be directed into arbitrary position.

Heterocycle sulfenyl is preferably the heterocycle sulfenyl that is substituted or is unsubstituted of carbon number 2～30, and heterocycle quality award from the ministry is elected described heterocycle asIllustrated heterocycle portion in base, for example, be preferably 2-[4-morpholinodithio base sulfenyl, 1-phenyltetrazole-5-base sulfenyl. In order to make theseHeterocycle sulfenyl becomes divalence, X¹Can be directed into arbitrary position.

Sulfamic is preferably the sulfamic that is substituted or is unsubstituted of carbon number 0～30, for example, be preferably N-ethylamine sulphurAcyl group, N-(3-dodecyl oxygen base propyl group) sulfamic, N, N-dimethyl amine sulfonyl, N-acetyl amine sulfonyl, N-Benzoyl sulfamic, N-(N '-phenylamino formoxyl) sulfamic. In order to make these sulfamics become divalence, X¹CanBe directed into arbitrary position.

Alkyl sulphinyl or aryl sulfonyl kia are preferably the alkyl sulfenyl that is substituted or is unsubstituted of carbon number 1～30The aryl sulfonyl kia that is substituted or is unsubstituted of base, carbon number 6～30, for example, be preferably methylsulfinyl, ethyl AsiaSulfonyl, phenyl sulfinyl, p-methylphenyl sulfinyl. In order to make these alkyl sulphinyls or aryl sulfonyl kiaBecome divalence, X¹Can be directed into arbitrary position.

Alkyl sulphonyl or aryl sulfonyl are preferably the alkyl sulphonyl that is substituted or is unsubstituted, the carbon number of carbon number 1～306～30 the aryl sulfonyl that is substituted or is unsubstituted, for example, be preferably methyl sulphonyl, ethylsulfonyl, phenyl sulphonylBase, p-methylphenyl sulfonyl. In order to make these alkyl sulphonyls or aryl sulfonyl become divalence, X¹Can be directed into arbitraryPosition.

Acyl group be preferably carbon number 2～30 the alkyl-carbonyl that is substituted or is unsubstituted, carbon number 7～30 be substituted or withoutThe aryl carbonyl replacing, be for example preferably acetyl group, pivaloyl group, 2-chloracetyl, stearyl, benzoyl,Align octyloxyphenyl carbonyl. In order to make these acyl groups become divalence, X¹Can be directed into arbitrary position.

Aryloxy carbonyl is preferably the aryloxy carbonyl that is substituted or is unsubstituted of carbon number 7～30, for example, be preferably benzeneOxygen base carbonyl, adjacent chlorophenoxy carbonyl, m-nitro oxygen base carbonyl, to tert-butyl group phenyloxycarbonyl. In order to make these arylOxygen base carbonyl becomes divalence, X¹Can be directed into arbitrary position.

Alkoxy carbonyl is preferably the alkoxy carbonyl that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably methoxyl groupCarbonyl, ethoxy carbonyl, tert-butoxycarbonyl, n-octadecane base oxygen base carbonyl. In order to make these alkoxy carbonyls become twoValency, X¹Can be directed into arbitrary position.

Carbamyl is preferably the carbamyl that is substituted or is unsubstituted of carbon number 1～30, for example carbamyl, N-methylCarbamyl, N, N-dimethylamino formoxyl, N, N-bis--n-octyl carbamyl, N-(methyl sulphonyl) carbamyl. ForMake these carbamyls become divalence, X¹Can be directed into arbitrary position.

Arylazo base or heterocycle azo base are preferably the arylazo base, the carbon that are substituted or are unsubstituted of carbon number 6～30Several 3～30 the heterocycle azo base that is substituted or is unsubstituted (heterocycle quality award from the ministry is elected heterocycle portion illustrated in described heterocyclic radical as).For example be preferably phenylazo, rubigan azo, 5-ethyl sulfenyl-1,3,4-thiadiazoles-2-base azo. In order to make these arylAzo group or heterocycle azo base become divalence, X¹Can be directed into arbitrary position.

Imide is preferably the imide that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably N-succinyl AsiaAmine, N phlhalimide base. In order to make these imides become divalence, X¹Can be directed into arbitrary position.

Phosphino-is preferably the phosphino-that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably dimethyl phosphino-, diphenylPhosphino-, methylphenoxy phosphino-. In order to make these phosphino-s become divalence, X¹Can be directed into arbitrary position.

Phosphinyl is preferably the phosphinyl that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably phosphinyl, two pungent oxygenBase phosphinyl, diethoxy phosphinyl. In order to make these phosphinyls become divalence, X¹Can be directed into arbitrary position.

Phosphinyl oxygen base is preferably the phosphinyl oxygen base that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably hexichol oxygenBase phosphinyl oxygen base, two octyloxy phosphinyl oxygen bases. In order to make these phosphinyl oxygen bases become divalence, X¹Can be directed into arbitraryPosition.

Phosphinyl amino is preferably the phosphinyl amino that is substituted or is unsubstituted of carbon number 2～30, for example, be preferably dimethoxyBase phosphinyl amino, dimethylamino phosphinyl amino. In order to make these phosphinyl amino become divalence, X¹Can be directed into and appointOne position.

Silylation is preferably the silylation that is substituted or is unsubstituted of carbon number 3～30, for example can enumerate TMS,Tert-butyl group dimethylsilyl, phenyl dimethylsilyl. In order to make these silylation become divalence, X¹Can be directed into arbitraryPosition.

In addition, in the situation that L represents bivalence linking base, be preferably expression-NR¹⁰-、-O-、-SO₂-, fluorine substituted alkylene,The group of fluorine substituted phenylene or the combination that comprises these groups. Be particularly preferably: comprise-NR¹⁰-、-SO₂And fluorine replaces alkyleneThe group of the combination of the group of the combination of base, comprise-O-and fluorine substituted phenylene or comprise-NR¹⁰-、-SO₂And fluorine replacesThe group of the combination of alkylidene.

-NR¹⁰-in, R¹⁰The alkyl that represents hydrogen atom or carbon number 1～5, is preferably hydrogen atom.

The carbon number of fluorine substituted alkylene is preferably 1～10, and more preferably 1～6, and then more preferably 1～3. These alkylidenesMore preferably perfluorinated alkylidene. The concrete example of fluorine substituted alkylene can be enumerated difluoro methylene, tetrafluoro ethylidene, hexafluoro Asia thirdBase etc.

The carbon number of fluorine substituted phenylene is preferably 6～20, and more preferably 6～14, and then more preferably 6～10. Fluorine replaces sub-The concrete example of phenyl can be enumerated tetrafluoro phenylene, hexafluoro-1-naphthylene, hexafluoro-2-naphthylene etc.

In general formula (P), X¹For anti-lotus anion, be preferably selected from be selected from-SO₃ ^-、-COO^-、-PO₄ ^-, comprise general formula (A1)At least one in the group of represented structure and the group that comprises the represented structure of general formula (A2). Herein, general formula (A1)The represented structure of represented structure and general formula (A2) is identical with illustrated person's implication in described the 1st example.

The group that comprises the represented structure of general formula (A1) is preferably in described general formula (A1), at R¹And R²WhereinThe end of one has fluorine substituted alkyl, more preferably R¹And R²Wherein one directly and fluorine substituted alkyl bond. Fluorine replaces alkaneThe carbon number of base is preferably 1～10, and more preferably 1～6, and then more preferably 1～3, further and then more preferably 1 or 2,Be particularly preferably 1. More preferably perfluoroalkyl of these alkyl. The concrete example of fluorine substituted alkyl is preferably trifluoromethyl.

The group that comprises the represented structure of general formula (A2) is preferably in described general formula (A2), at R³～R⁵At leastThe end of any one has fluorine substituted alkyl, more preferably R³～R⁵At least both are directly and fluorine substituted alkyl bonds. Special excellentElect as at R³～R⁵At least both end there is fluorine substituted alkyl, more preferably R³～R⁵At least both directly and fluorine getSubstituted alkyl bond. In the group of the fluorine substituted alkyl structure represented with comprising general formula (A1), illustrated person's implication is identical, excellentSelect scope also identical.

In addition, X¹Concrete example can enumerate described anti-lotus anion A. In described situation, form anti-lotus anion A'sL bond in any hydrogen atom or halogen atom and general formula (P).

There is bridging property base and cation and molecular weight and be triarylmethane structure below 2000 at general formula (TP1A) and logicalIn formula (TP2A), can be at Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in there is bridging property base, and described in there is friendshipThe Rtp of connection property base₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any can and then replace through general formula (P).

In addition, in general formula (TP1A) and general formula (TP2A), can only there is a place in the part replacing through general formula (P),Also more than can there are two places. In the case of the part replacing through general formula (P) exists more than two places, in colouring agent, exceptIn triarylmethane structure, beyond contained cation, also there is the cation of the quantity corresponding with the quantity of anti-lotus anion.

Below, the concrete example of the colouring agent of the 2nd example using in the present invention is shown, but is not limited to these examples.

[changing 40]

[changing 41]

[changing 42]

[changing 43]

[changing 44]

The triarylmethane dye using in the present invention can contain separately one or combination contains two or more.

With respect to all solids composition of coloured composition of the present invention, the content of described triarylmethane dye is preferably 10Quality %～60 quality %, more preferably 10 quality %～40 quality %.

" other coloring compounds "

Coloured composition of the present invention also can comprise one or more kinds of described colouring agents be triarylmethane dye withOther outer coloring compounds. Other coloring compounds can be enumerated dye composition, pigment compound and these compoundsDispersion.

Dye composition brings the compound of impact as long as form and aspect on rendered image not, can be any structure, for exampleCan enumerate: azo system (for example solvent yellow 16 2), anthraquinone system (are for example remembered in Japanese Patent Laid-Open 2001-10881 communiqueThe anthraquinone compounds carrying), phthalocyanine system (phthalocyanine compound of for example recording in United States Patent (USP) 2008/0076044A1), oxa-Anthracene system (for example C.I. acid red 289 (C.I.Acid.Red289)), (for example C.I. Acid Blue 7 (C.I. of triarylmethane systemAcidBlue7), C.I. acid blue 83 (C.I.AcidBlue83), C.I. acid blue 90 (C.I.AcidBlue90), C.I.Solvent blue 38 (C.I.SolventBlue38), C.I. acid violet 17 (C.I.AcidViolet17), C.I. acid violet 49 (C.I.AcidViolet49), C.I. acid green 3 (C.I.AcidGreen3)), methine dyes etc.

Pigment compound can enumerate: perylene (perylene), purple cyclic ketones (perinone), quinacridone (quinacridone),Quinacridone quinone (quinacridonequinone), anthraquinone, anthanthrone (anthanthrone), benzimidazolone(benzimidazolone), bisazo (disazo) condensation, bisazo, azo, indanthrone (indanthrone), phthaleinCyanines, triaryl carbon (triarylcarbonium), dioxazine (dioxazine), amino anthraquinones, diketopyrrolo-pyrrole(diketopyrrolopyrrole), indigo (indigo), thioindigo (thioindigo), isoindoline (isoindoline),Isoindolinone (isoindolinone), pyranthrone (pyranthrone) or iso-violanthrone (isoviolanthrone) etc.More specifically, for example, can enumerate: the perylene compound pigment such as paratonere 190, paratonere 224, pigment violet 29, pigment orange43 or the purple cyclic ketones compound pigment such as paratonere 194, pigment violet 19, pigment violet 42, pigment red 122, paratonere 192,The quinacridone compound pigment of paratonere 202, Pigment Red 207 or paratonere 209, paratonere 206, pigment orange 48,Or the quinacridone naphtoquinone compounds pigment such as pigment orange 49, the anthraquinone compounds pigment such as pigment yellow 147, paratonere 168 embeddings such as anthracene such as gradeAnthraquinone compounds pigment, pigment brown 25, pigment violet 32, pigment orange 36, pigment Yellow 12 0, pigment yellow 180, pigment yellow 181,The benzimidazolone compound pigment such as pigment orange 62 or paratonere 185, pigment yellow 93, pigment yellow 94, pigment yellow 95,Pigment Yellow 12 8, pigment yellow 166, pigment orange 34, pigment orange 13, pigment orange 31, paratonere 144, paratonere 166, faceExpect the disazo condensation such as red 220, paratonere 221, paratonere 242, paratonere 248, paratonere 262 or pigment brown 23Compound pigment, the bis-azo compound pigment such as pigment yellow 13, pigment yellow 83 or pigment yellow 188, paratonere 187, faceExpect that red 170, pigment yellow 74, pigment yellow 150, pigment red 48, paratonere 53, pigment orange 64 or paratonere 247 etc. are evenNitrogen compound pigment, the indanthrone compound pigment such as pigment blue 60, pigment Green 7, pigment green 36, naphthol green 37, naphthol green58, the phthalocyanine compound pigment such as pigment blue 16, alizarol saphirol 75 or pigment blue 15, alizarol saphirol 56 or pigment Blue-61 etc. threeAryl carbon compound pigment, the dioxazine compound pigment such as pigment Violet 23 or pigment violet 37, paratonere 177 amino anthracenes such as gradeNaphtoquinone compounds pigment, paratonere 254, paratonere 255, paratonere 264, paratonere 272, pigment orange 71 or pigment orange73 pigment such as compound such as diketopyrrolo-pyrrole such as grade, pigment Red 88 pigment such as compound such as thioindigo such as grade, pigment yellow 13 9, pigment orange 66Deng isoindoline compounds pigment, the isoindoline ketonic compound pigment such as pigment yellow 109 or pigment orange 61, pigment orange 40,Or the pyranthrone compound pigment such as pigment red 21 6, or the iso-violanthrone compound pigment such as pigment violet 31.

In the present invention, be preferably the green colored materials to cyan, be preferably: pigment Green 7, pigment green 36, naphthol green 37,The phthalocyanine compound pigment such as naphthol green 58, pigment blue 16, alizarol saphirol 75 or pigment blue 15, alizarol saphirol 56 or alizarol saphirol61 pigment such as carbon compound such as triaryl such as grade, the dioxazine compound pigment such as pigment Violet 23 or pigment violet 37, paratonere 177Deng amino anthraquinones compound pigment, paratonere 254, paratonere 255, paratonere 264, paratonere 272, pigment orange 71,Or the diketopyrrolo-pyrrole compound pigment such as pigment orange 73, pigment Red 88 pigment such as compound such as thioindigo such as grade, pigment yellow 13 9, faceExpect orange 66 pigment such as isoindoline compounds such as grade, the isoindoline ketonic compound pigment such as pigment yellow 109 or pigment orange 61, pigmentOrange 40 or the pyranthrone compound pigment such as pigment red 21 6, or the iso-violanthrone compound pigment such as pigment violet 31.

In the situation that allocating described dyestuff or pigment as dispersion, can be according to Japanese patent laid-open 9-197118 public affairsThe record of report, Japanese Patent Laid-Open 2000-239544 communique is adjusted.

The content of described material or pigment can use in the scope that does not undermine effect of the present invention, with respect to colour cell of the present inventionThe all solids composition of compound, is preferably 0.5 quality %～70 quality %. In addition, be preferably with absorption intensity than (450nmThe absorption of absorption/650nm) mode that becomes 0.95～1.05 scope makes an addition in coloured composition.

" polymerizable compound "

Coloured composition of the present invention contains polymerizable compound. Polymerizable compound for example can be enumerated has at least one etheneThe addition polymerization compound of property unsaturated double-bond.

Particularly, be selected from the compound that there is at least one, is preferably plural end ethene unsaturated bond. ThisPlanting compound cohort is the person of being widely known by the people in described industrial field, in the present invention, can use without particular limitation these compounds.These compounds can be for example monomer, and prepolymer is dimer, trimer and oligomer, or their mixture and itAny of the chemical form such as (being total to) polymer.

The example of monomer and (being total to) polymer thereof can be enumerated: unsaturated carboxylic acid (for example: acrylic acid, methacrylic acid, clothingHealth acid, butenoic acid, methacrylate, maleic acid etc.) or its ester class, amide-type and their (being total to) polymer,Be preferably: the ester of unsaturated carboxylic acid and aliphatic polyol compound and unsaturated carboxylic acid and aliphatic multivalence aminesAmide-type and their (being total to) polymer. In addition, be also applicable to using to there is the nucleophilicity such as hydroxyl or amino, sulfydrylThe addition reaction of substituent esters of unsaturated carboxylic acids or amide-type and simple function or polyfunctional isocyanate's class or epoxiesThing, or with dehydration condensation thing of simple function or polyfunctional carboxylic acid etc. In addition, there is NCO or epoxy radicals etc.Adding of the substituent esters of unsaturated carboxylic acids of electrophilicity or amide-type and simple function or polyfunctional alcohols, amine, thio-alcoholBecome reactant, so have the substituent esters of unsaturated carboxylic acids of the detachment such as halogen radical or tosyloxy or amide-type andThe substituted reactant of simple function or polyfunctional alcohols, amine, thio-alcohol is also applicable to. In addition, as other examples, also canReplace described unsaturated carboxylic acid and use the compound cohort that is substituted by unsaturated phosphonic acids, styrene, vinyl ethers etc.

As the concrete example of the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid, acrylate for example can be enumerated:Glycol diacrylate, triethylene glycol diacrylate, 1,3-BDO diacrylate, tetramethylene glycol diacrylateEster, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropaneThree (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylate, hexanediyl ester, Isosorbide-5-Nitrae-cyclohexanediol dipropylOlefin(e) acid ester, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythrite fourAcrylate, dipentaerythritol diacrylate, dipentaerythritol acrylate, D-sorbite triacrylate, sorbSugar alcohol tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanide ureaAcid esters, polyester acrylic oligomer ester, isocyanuric acid oxirane (ethyleneoxide, EO) modification triacrylate etc.

In addition, methacrylate for example can be enumerated: tetramethylene glycol dimethylacrylate, triethylene glycol dimethyl propyleneOlefin(e) acid ester, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methylAcrylate, ethylene glycol dimethacrylate, 1,3-BDO dimethylacrylate, hexanediol dimethacrylate,Dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, two seasons pentaTetrol dimethylacrylate, dipentaerythritol hexamethyl acrylate, D-sorbite trimethyl acrylic ester, D-sorbiteTetramethyl acrylate, two [to (3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two-[to (methyl-propAlkene acyloxy ethyoxyl) phenyl] dimethylmethane etc.

And then itaconate for example can be enumerated: ethylene glycol bisthioglycolate itaconate, propane diols diitaconate, 1,3-BDO twoItaconate, BDO diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, sorbSugar alcohol four itaconates etc., in addition, butenoate for example can be enumerated: ethylene glycol bisthioglycolate butenoate, tetramethylene glycol two fourthsOlefin(e) acid ester, pentaerythrite dibutene acid esters, D-sorbite four dibutene acid esters etc., methacrylate for example can be enumerated: second twoAlcohol diisobutylene acid esters, pentaerythrite diisobutylene acid esters, D-sorbite tetra methylacrylate etc., in addition, maleic acidEster for example can be enumerated: ethylene glycol bisthioglycolate maleate, triethylene glycol two maleates, pentaerythrite two maleics twoAcid esters, D-sorbite four maleates etc.

The example of other esters for example also can be applicable to using: Japan Patent examined patent publication 51-47334 communique, Japanese Patent Laid-Open are clearThe aliphatic alcohol that 57-196231 communique is recorded is ester class, the clear 59-5240 communique of Japanese Patent Laid-Open, Japanese Patent Laid-OpenWhat clear 59-5241 communique, Japanese patent laid-open 2-226149 communique were recorded has aromatic series pastern bone frame person, and Japan speciallyWhat profit Unexamined Patent 1-165613 communique was recorded contains amino person etc. And then described ester monomer also can be used as mixture.

In addition, be also applicable to be with the amido formate that the addition reaction of isocyanates and hydroxyl is manufactured be addition polymerizationCompound, this kind of concrete example for example can be enumerated: in a part of recording in Japan Patent examined patent publication 48-41708 communique, containThe vinyl amine carbamate compounds of more than two polymerism vinyl etc., it is to have more than two isocyanic acid at a partIn the polyisocyanate compounds of ester group, the represented vinyl monomer that contains hydroxyl of the following general formula of addition (A) forms.

CH₂＝C(R)COOCH₂CH(R′)OH…(A)

[in general formula (A), R and R ' represent respectively H or CH independently₃。]

In addition, polymerizable compound is also preferably: (commercially available product is the sub-rad of card to dipentaerythritol triacrylate(KAYARAD) D-330; Chemical drug limited company of Japan manufactures), (commercially available product is dipentaerythritol tetraacrylateBlock sub-rad (KAYARAD) D-320; Chemical drug limited company of Japan manufactures), dipentaerythritol five (methyl) propylene(commercially available product is card sub-rad (KAYARAD) D-310 to acid esters; Chemical drug limited company of Japan manufactures), two seasons penta 4(commercially available product is card sub-rad (KAYARAD) DPHA to alcohol six (methyl) acrylate; Chemical drug limited company of Japan systemMake) and (methyl) acryloyl groups of these compounds via the structure of ethylene glycol, propane diols residue. Also can use these changesThe oligomer type of compound.

About these polymerizable compounds, its structure, be use separately or and the details of the using method such as use, addition canAt random set according to the final performance design of coloured composition. For example, with regard to the viewpoint of sensitivity, be preferably eachThe structure that the unsaturated group content of molecule is many, be preferably as a rule 2 officials can more than. In addition, just improve painted sclerosisThe viewpoint of film strength, being preferably 3 officials can above person, and then, for example, by by different different functional number polymerism bases (Acrylate, methacrylate, distyryl compound, vinyl ether compound) person in addition and be used for regulating sensitivity withThe two method of intensity is also effective. In addition, for coloured composition in contained other compositions (for example photopolymerization causesAgent, colouring agent (pigment), binder polymer etc.) compatibility, dispersiveness, the choice for use method of polymerizable compoundAlso be important essential factor, for example, sometimes can be by the use of low-purity compound or two or more and be used for improving compatibility.In addition, with regard to improving the viewpoint with the adhesion of the hard surface of substrate etc., also can select specific structure.

Obtain with regard to the viewpoint of effect of the present invention poly-in all solids composition of coloured composition with regard to further producing effectThe content of closing property compound is preferably 10 quality %～80 quality %, and more preferably 15 quality %～75 quality %, are particularly preferably20 quality %～60 quality %.

Composition of the present invention can only comprise a kind of polymerizable compound, also can comprise two or more. Comprise two or moreIn situation, being preferably its total amount becomes described scope.

" Photoepolymerizationinitiater initiater "

Coloured composition of the present invention is preferably and contains at least one Photoepolymerizationinitiater initiater. Photoepolymerizationinitiater initiater gathers as long as can makeClosing property compound carry out polymerization person, and there is no particular restriction, is preferably according to characteristic, efficiency of initiation, absorbing wavelength, obtainsThe viewpoints such as property, cost are selected.

Photoepolymerizationinitiater initiater for example can be enumerated: be selected from Lu in Jia oxadiazole compound and halogenated methyl-s-triazineAt least one active halogen compound, 3-aryl substituted cumarin compound, cough up fen dimer, benzophenone cpd, benzene secondKetonic compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt, oxime compound etc. The concrete example of Photoepolymerizationinitiater initiaterCan enumerate the example of recording in paragraph [the 0070]～paragraph [0077] of Japanese Patent Laid-Open 2004-295116 communique. Wherein,Rapidly with regard to aspect etc., be preferably oxime compound or bisglyoxaline based compound with regard to polymerisation.

Oxime compound (below also referred to as " oxime is Photoepolymerizationinitiater initiater ") is not particularly limited, for example, can enumerate: JapanNote in open patent 2000-80068 communique, WO02/100903A1, Japanese Patent Laid-Open 2001-233842 communique etc.The oxime compound carrying.

The concrete example of oxime compound can be with reference to the record of the paragraph 0053 of Japanese Patent Laid-Open 2013-182215 communique, instituteStating content is incorporated in this description.

In addition, in the present invention, with regard to the painted viewpoint during with regard to sensitivity, ageing stability, rear heating, oxime compound moreBe preferably following general formula (1) or the represented compound of general formula (2).

[changing 45]

(in general formula (1), R and X represent respectively the substituting group of monovalence, and A represents divalent organic base, and Ar represents aryl; nIt is 1～5 integer. )

With regard to the aspect of high-sensitivity, R is preferably acyl group, particularly, is preferably acetyl group, propiono, benzene firstAcyl group, toluyl groups.

Just improve sensitivity, suppress because of heating through time the painted aspect that causes, A is preferably the alkylene being unsubstitutedBase, the alkylidene for example, replacing through alkyl (methyl, ethyl, the tert-butyl group, dodecyl), for example, through thiazolinyl (etheneBase, pi-allyl) replace alkylidene, through aryl (for example phenyl, p-methylphenyl, xylyl, cumenyl, naphthyl,Anthryl, phenanthryl, styryl) alkylidene that replaces.

Just improve sensitivity, suppress because of heating through time the painted aspect that causes, Ar is preferably and is substituted or without gettingThe phenyl in generation. The in the situation that of substituted-phenyl, its substituting group is for example preferably fluorine atom, chlorine atom, bromine atoms, iodine atomDeng halogen radical.

With regard to improving the aspect of absorption efficiency in solvent solubility and long wavelength region, X is preferably: can have substituentAlkyl, can there is substituent aryl, can there is substituent thiazolinyl, can there is substituent alkynyl, can there is substituting groupAlkoxyl, can there is substituent aryloxy, can there is substituent alkyl sulfide oxygen base, can there is substituent arylSulphur oxygen base, can there is substituent amino. In addition, the n in general formula (1) is preferably 1～2 integer.

[changing 46]

In general formula (2), R¹⁰¹Represent alkyl, alkanoyl, enoyl-, aroyl, alkoxy carbonyl, aryloxycarbonyl,Heterocyclic oxy group carbonyl, heteroaryl oxygen base carbonyl, alkyl sulfide carbonyl, aryl thiocarbonyl group, heterocycle thiocarbonyl group, heteroaryl thiocarbonyl groupOr CO-CO-Rf. Rf represents carbon-ring type aromatic series base or hetero ring type aromatic series base.

R¹⁰²Represent alkyl, aryl or heterocyclic radical, these also can be substituted.

R¹⁰³And R¹⁰⁴Represent independently respectively alkyl, aryl or heterocyclic radical, these groups can so that through halogen atom, alkaneThe institutes such as base, aryl, alkoxyl, alkyl-carbonyl replace.

R¹⁰⁵～R¹¹¹Represent independently respectively hydrogen atom, halogen atom, alkyl, aryl, heterocyclic radical, alkoxyl, aroyl,4-hetaroylpyrazol, alkyl sulfenyl, aroyl sulfenyl, 4-hetaroylpyrazol, alkyl-carbonyl, aryl carbonyl, heteroaryl carbonyl, alcoxylBase carbonyl, aryloxycarbonyl, heterocyclic oxy group carbonyl, nitro, amino, sulfonic group, hydroxyl, carboxylic acid group, amide groups, ammoniaFormoxyl or cyano group.

Be preferably R¹⁰⁵～R¹¹¹In one or two be substituting groups of electrophilic, nitro, cyano group, halogen radical,Alkyl-carbonyl or aryl carbonyl, its reason is to obtain has higher indurative coloured composition.

Below enumerate the represented concrete example with fluorene structured compound of described general formula (2). But described in being not limited toCompound.

[changing 47]

What described general formula (2) was represented have fluorene structured compound for example can be according to No. WO2014/050738, International PublicationThe synthetic method of recording in handbook is synthesized.

The concrete example of bisglyoxaline based compound can be with reference to Japanese Patent Laid-Open 2013-182213 communique paragraph 0061～paragraph0070 record, described content is incorporated in this description.

In addition, in coloured composition of the present invention, except described Photoepolymerizationinitiater initiater, also can use Japanese Patent Laid-OpenOther known Photoepolymerizationinitiater initiaters of recording in the paragraph numbering 0079 of 2004-295116 communique.

Obtain with regard to further producing effect with regard to the viewpoint of effect of the present invention, Photoepolymerizationinitiater initiater is whole coloured compositionContent in solid constituent is preferably 3 quality %～20 quality %, and more preferably 4 quality %～19 quality %, are particularly preferably 5Quality %～18 quality %.

Composition of the present invention can only comprise a kind of Photoepolymerizationinitiater initiater, also can comprise two or more. Comprise two or moreIn situation, being preferably its total amount becomes described scope.

" organic solvent "

Coloured composition of the present invention is preferably and contains at least one organic solvent.

As long as organic solvent can meet and the dissolubility of each composition of depositing or the coating while making coloured composition, baseIn basis, there is no particular restriction, particularly preferably for considering that dissolubility, coating, the security of adhesive select.

Organic solvent can use ester class, ethers, ketone, aromatic hydrocarbon based, particularly can illustrate Japanese Patent Laid-OpenThe solvent of recording in paragraph numbering 0161～paragraph numbering 0162 of 2012-032754 communique.

With regard to the dissolubility of described each composition, and in the situation that comprising alkali-soluble polymer with regard to its dissolubility, be coated with planarThe viewpoint such as improvement, these organic solvents be also preferably mix two or more. In described situation, particularly preferably for comprising choosingFrom 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether,Butyl acetate, 3-methoxy methyl propionate, 2-HEPTANONE, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol,Two or more mixed solution in propylene glycol monomethyl ether and propylene glycol methyl ether acetate.

The all solids constituent concentration that the content of organic solvent in coloured composition is preferably in composition becomes 10 qualityThe amount of %～80 quality %, more preferably becomes the amount of 15 quality %～60 quality %.

Composition of the present invention can only comprise a kind of organic solvent, also can comprise two or more. Comprising two or more situationsUnder, being preferably its total amount becomes described scope.

" alkali-soluble adhesive "

Coloured composition of the present invention is preferably and comprises alkali-soluble adhesive. Alkali-soluble adhesive is except having alkali-solubleIn addition, be not particularly limited, be preferably and can select according to viewpoints such as heat resistance, developability, the property obtained.

Alkali-soluble adhesive is preferably wire organic high molecular polymer, and dissolves in organic solvent, can be with weak base waterSolution develops. This kind of wire organic high molecular polymer can be set forth in the polymer on side chain with carboxylic acid, for example JapanClear No. 59-44615 of open patent, No. 54-34327, Japan Patent examined patent publication, Japan Patent examined patent publication No. 58-12577, dayNo. 54-25957, this patent examined patent publication, clear No. 59-53836 of Japanese Patent Laid-Open, clear No. 59-71048 of Japanese Patent Laid-OpenMethacrylic acid co-polymer, acrylic copolymer, itaconic acid co-polymer, the butenoic acid copolymerization in each communique, recordedCompound, maleic acid co-polymer, partial esterification maleic acid co-polymer etc. similarly have carboxylic acid on side chainAcid cellulose derivative useful.

Except described compound, the alkali-soluble adhesive in the present invention also can use: in the polymer with hydroxylAddition has acid anhydrides person etc., polycarboxylated styrene be resin, polysiloxane series resin, poly-((methyl) acrylic acid 2-hydroxy methacrylate),PVP or PEO, polyvinyl alcohol etc. In addition, wire organic high molecular polymer also can be byThere is hydrophilic monomer and carry out the polymer that combined polymerization forms. Its example can be enumerated: (methyl) alkoxyalkyl acrylate,(methyl) acrylic acid hydroxyalkyl acrylate, glycerine (methyl) acrylate, (methyl) acrylamide, N hydroxymethyl acrylamide, twoLevel alkyl acrylamide or three grades of alkyl acrylamides, (methyl) propenoic acid dialkyl aminoalkyl ester, morpholine (methyl) propyleneAcid esters, NVP, N-caprolactam, vinyl imidazole, vinyl triazole, (methyl) acrylic acid first(methyl) acrylic acid of (methyl) propyl acrylate, branch or the straight chain of ester, (methyl) ethyl acrylate, branch or straight chainButyl ester or (methyl) acrylic acid phenoxy group hydroxy propyl ester etc. In addition, having hydrophilic monomer also can use and comprise fourTetrahydrofurfuryl, phosphate, phosphate-based, quarternary ammonium salt base, ethyleneoxy group chain, propylidene oxygen base chain, sulfonic group and sourceThe monomer forming in group, the morpholinyl ethyl etc. of its salt etc.

Alkali-soluble adhesive also can preferably use maleimide as shown in following formula (b1) and formula (b2) withThe co-polymer of oxirane.

Formula (b1)

[changing 48]

(in formula (b1), R¹Represent hydrogen atom, aryl or alkyl. )

R¹Represent that the alkyl in the situation of alkyl can enumerate: the having point of the straight chain-like alkyl of carbon number 1～10, carbon number 3～10The alkyl of side chain, the cyclic alkyl of carbon number 5～20 etc., more specifically, can enumerate methyl, ethyl, the tert-butyl group, hexamethyleneBase etc.

Alkyl can have substituting group, and the substituting group that can be directed in alkyl can be enumerated: phenyl, carbonyl, alkoxyl, hydroxyl,Amino etc.

R¹Represent that the aryl in the situation of aryl can enumerate: the aryl of single ring architecture, the aryl of multiring structure, contracting ring structureAryl, comprise heteroatomic heteroaryl etc. More specifically, can enumerate: phenyl, naphthyl, xenyl, benzimidazolyl,Pyridine radicals, furyl etc.

Aryl can have substituting group, and the substituting group that can be directed in aryl can be enumerated: methyl, ethyl, the tert-butyl group, cyclohexylIn alkyl, the alkoxyls such as methoxyl group, carboxyl, hydroxyl, amino, nitro, chloro, bromo etc.

Formula (b2)

[changing 49]

(in formula (b2), R²Represent hydrogen atom or methyl; R³For the alkylidene of carbon number 2 or 3, R⁴Expression hydrogen atom,Aryl or alkyl, m represents 1～15 integer. )

R⁴Represent that the alkyl in the situation of alkyl can enumerate: the having point of the straight chain-like alkyl of carbon number 1～20, carbon number 1～20The alkyl of side chain, the cyclic alkyl of carbon number 5～20 etc., more specifically, can enumerate: methyl, ethyl, the tert-butyl group, ringHexyl, 2-ethylhexyl etc.

Alkyl can have substituting group, and the substituting group that can be directed in alkyl can be enumerated: phenyl, carbonyl, alkoxyl etc.

R⁴Represent that the aryl in the situation of aryl can enumerate: the aryl of single ring architecture, the aryl of multiring structure, contracting ring structureAryl, comprise heteroatomic heteroaryl etc. More specifically, can enumerate: phenyl, naphthyl, anthryl, xenyl, benzoImidazole radicals, indyl, imidazole radicals, oxazolyl, carbazyl, pyridine radicals, furyl etc.

Aryl can have substituting group, and the substituting group that can be directed in aryl can be enumerated: nonyl, methyl, ethyl, the tert-butyl group,The alkyl such as cyclohexyl, the alkoxyls such as methoxyl group, carboxyl, hydroxyl, amino, nitro, chloro, bromo etc.

In addition, in order to improve cross-linking efficiency, alkali-soluble adhesive can have polymerism base on side chain, for example, also can useOn side chain, contain the polymer of pi-allyl, (methyl) acrylic, pi-allyl oxygen base alkyl etc. etc. The described polymerism base that containsThe example of polymer can enumerate: KS photoresistance-106 (Osaka organic chemistry industry (thigh) manufacture) of commercially available product, Sai KuluoAgate (Cyclomer) P series (Daicel (Daicel) chemical industry (thigh) manufacture) etc. In addition, in order to improve sclerosisSkin film strength, also can be used the polyethers of alcohol soluble nylon or 2,2-pair-(4-hydroxy phenyl)-propane and chloropropylene oxide etc.

In these various alkali-soluble adhesives, with regard to stable on heating viewpoint, being preferably polycarboxylated styrene is resin, poly-Siloxane-based resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide co-polymer resin, just developProperty control viewpoint, be preferably acrylic resin, acrylamide resin, acrylic acid/acrylamide co-polymer treeFat.

Particularly preferably, for thering is repetitive as shown in following general formula (2) and the co-polymer of acidic groups, more preferably can be listed asLift except general formula (2) and acidic groups, also there is the co-polymer of the represented construction unit of general formula (3).

[changing 50]

(in general formula (2), R²⁰Represent hydrogen atom or methyl, R²¹～R²⁵Represent independently that respectively hydrogen atom, halogen are formerSon, cyano group, alkyl or aryl. )

[changing 51]

(in general formula (3), R¹¹Represent hydrogen atom or methyl; R¹²And R¹³Represent independently respectively hydrogen atom or compriseAs the carbonyl of the carbon number 3～20 of part-structure, there is not R in unsaturated double-bond¹²And R¹³Both be the situation of hydrogen atom;At R¹²And R¹³At least one expression comprise in the situation of unsaturated double-bond as the carbonyl of the carbon number 3～20 of part-structure,Also can also comprise that carboxyl is as part-structure. )

Acrylic resin is preferably: comprise and be selected from (methyl) acrylic acid benzyl ester, (methyl) acrylic acid, (methyl) acrylic acid hydroxylThe co-polymer of the monomer in base ethyl ester, (methyl) acrylamide etc., or KS photoresistance-106 (Osaka organic chemistry of commercially available productIndustry (thigh) manufacture), Sai Kuluoma (Cyclomer) P series (Daicel chemical industry (thigh) manufacture) etc.

In addition, alkali-soluble adhesive also can comprise and derives from the represented ethene of following formula (X) unsaturated single amount bodyConstruction unit.

General formula (X)

[changing 52]

(in formula (X), R¹Represent hydrogen atom or methyl, R²Represent the alkylidene of carbon number 2～10, R³Represent hydrogen atomOr can comprise the alkyl of the carbon number 1～20 of phenyl ring; N represents 1～15 integer. )

In described formula (X), R²The carbon number of alkylidene be preferably 2～3. In addition, R³The carbon number of alkyl be 1～20,More preferably 1～10, R³Alkyl can comprise phenyl ring. R³The represented alkyl that comprises phenyl ring can be enumerated benzyl, 2-phenyl (different)Propyl group etc.

With regard to the viewpoint such as developability, fluid viscosity, alkali-soluble adhesive is preferably weight average molecular weight and (surveys with GPC methodFixed and polystyrene conversion value) be 1,000～200,000 polymer, more preferably 2,000～100,000 polymerizationThing is particularly preferably 5,000～50,000 polymer.

The allotment amount of alkali-soluble adhesive is preferably 10 quality %～80 quality % of all solids composition of coloured composition,More preferably 20 quality %～60 quality %.

In addition, the acid number of alkali-soluble adhesive is preferably 10mg/KOH～1000mg/KOH, and more preferably 50Mg/KOH～300mg/KOH, and then 50mg/KOH～200mg/KOH more preferably, be particularly preferably 105mg/KOH～200mg/KOH。

Composition of the present invention can only comprise a kind of alkali-soluble adhesive, also can comprise two or more. Comprise two or moreSituation under, being preferably its total amount becomes described scope.

" crosslinking agent "

Coloured composition of the present invention also can also comprise crosslinking agent.

Crosslinking agent, as long as carrying out by cross-linking reaction the crosslinking agent of film sclerosis, is not particularly limited, for example, can enumerate:(a) epoxy resin; (b) at least one substituting group institute in being selected from methylol, alkoxy methyl and acyloxy methylMelamine (melamine) compound, guanamines (guanamine) compound, glycoluril (glycoluril) chemical combination that replaceThing or urea (urea) compound; (c) at least one in being selected from methylol, alkoxy methyl and acyloxy methylOxybenzene compound, naphthol compound or hydroxyl anthracene compound that substituting group replaces. Wherein, be preferably multi-functional epoxy treeFat.

The details such as the concrete example of crosslinking agent can be with reference to the paragraph 0134～paragraph of Japanese Patent Laid-Open 2004-295116 communique0147 record, described content is incorporated in this description.

" surfactant "

Coloured composition of the present invention also can comprise surfactant. Surfactant can be nonionic system, cation system, the moonAny in ionization series, being preferably surfactant, the fluorine with ethylene oxide structure is surfactant. Be particularly preferablyHydrophile-lipophile balance (Hydrophile-LipophileBalance, HLB) value has epoxy second in 9.2～15.5 scopeThe fluorine that the surfactant of alkyl structure or Japanese patent laid-open 2-54202 communique are recorded is surfactant.

The in the situation that of containing surfactant in coloured composition of the present invention, become with respect to all solids of coloured compositionPoint, the addition of surfactant is preferably 0.0001 quality %～2.0 quality %, more preferably 0.005 quality %～1.0 matterAmount %.

Composition of the present invention can only comprise a kind of surfactant, also can comprise two or more. Comprising two or more feelingsUnder condition, being preferably its total amount becomes described scope.

Coloured composition of the present invention can and then optionally comprise fills material, antioxidant, ultra-violet absorber, anti-cohesionThe various additives such as agent, sensitizer or light stabilizer.

" dyestuff stabilization agent "

In composition of the present invention, be preferably except triarylmethane dye, also add dyestuff stabilization agent. StabilisationAgent for example can be used: the surfactants such as cation system, anion system, nonionic system, both sexes, silicone-based, fluorine system. TableIn surface-active agent, with regard to the aspect that can evenly and imperceptibly disperse, (macromolecule disperses to be preferably high molecular surfactantAgent).

Macromolecule dispersing agent for example can be enumerated: (being total to) polymer class of the esters of unsaturated carboxylic acids such as polyacrylate; Polyacrylic acidDeng (part) amine salt, (part) ammonium salt or (part) alkylamine salt of (being total to) polymer of unsaturated carboxylic acid; Contain(being total to) polymer of the esters of unsaturated carboxylic acids of the hydroxyls such as the polyacrylate of hydroxyl or their modifier; There is bridging propertyThe sulfonic acid of base or the polymer of phosphoric acid etc.

Bridging property base can be with carrying out crosslinked bridging property base by free radical, acid, heat. Particularly can enumerate (methyl)Acrylic, styryl, vinyl, ring-type ether, methylol, be preferably (methyl) acrylic, styryl, secondThiazolinyl, more preferably (methyl) acrylic and styryl.

In addition, except these surfactants, also add two fluoroform sulfimide sodium salts or following anionThe situation of salt (sodium salt, sylvite etc.) is also effective.

[changing 53]

Composition of the present invention can comprise antioxidant. Antioxidant for example can be enumerated: free radical scavenger, peroxide divideSeparate agent, ultra-violet absorber, singlet oxygen quencher (singletoxygenquencher) etc.

Free radical scavenger for example can be enumerated: phenol is that antioxidant, hindered amine are antioxidant etc. Phenol be antioxidant for exampleCan enumerate: propionic acid hydroxylphenyl ester based compound, hydroxybenzyl based compound, thiobisphenol based compound, sulphomethyl phenolBased compound, alkane two base phenol based compounds etc. Wherein, with regard to the viewpoint of the stability of look characteristic, be preferably propionic acidHydroxylphenyl ester based compound.

Peroxide decomposer is by being harmless material by being exposed to the medium peroxide breakdown producing of light, so that notThe compound of new free radical can be produced, for example, phosphorous antioxidant can be enumerated, sulphur is antioxidant etc. Wherein, with regard to look spyThe viewpoint of the stability of property, being preferably sulphur is antioxidant.

It is antioxidant, benzophenone series antioxidant that ultra-violet absorber for example can be enumerated salicylate.

Singlet oxygen quencher is to shift and make the change of singlet oxygen inactivation by deriving from the energy of oxygen of singlet stateCompound, for example, except the ethene such as tetramethyl-ethylene, cyclopentene compound, diethylamine, triethylamine, Isosorbide-5-Nitrae-diazabicycloThe amines such as octane (Isosorbide-5-Nitrae-diazabicyclooctane, DABCO), N-ethyl imidazol(e), the naphthalene that can be substituted, dimethylnaphthalene,The fused-ring aromatic compounds such as dimethoxy anthracene, anthracene, diphenylanthrancene; 1,3-diphenyl isobenzofuran, 1,2,3,4-tetra-benzeneBase-1, beyond the aromatic compounds such as 3-cyclopentadiene, Pentaphenylcyclopentadiene, also can be set forth in using in Publication about Document as singletOxygen agent carrys out illustrative compound: Harry H. Wasserman's (HarryH.wasserman) " singlet oxygen (SingletOxygen) "The 5th chapter, academic press (AcademicPress) (1979); " showing of special sieve of Nicholas J. (NicholasJ.Turro)For molecular photochemistry (ModernMolecularPhotochemistry) " the 14th chapter, Benjamin's Maeve Cummings (The of publishing companyBenjaminCummingsPublishingCo., Inc.) (1978); And " the autochromy sensitization of CMC Cinema Magnetique Communication's distributionMultifunction product for material " the 7th chapter (2002).

In addition, can enumerate and will there is the compound of sulphur atom as the metal complex of part. This kind of compound can be enumerated:Nickel complex, cobalt complex, copper complexing using two two sulfo-s-α-diketone, two phenyl two mercaptan and thiobisphenol as partThe transition metal chelate compounds such as thing, manganese complex, platinum complex.

Sulphur is that antioxidant can be enumerated thiopropionate based compound, mercaptobenzimidazole based compound. Wherein, with regard to look characteristicThe viewpoint of stability, be preferably thiopropionate based compound.

In the present invention, antioxidant can be used alone or is use mixing two or more. With respect to colouring agent 100 quality,The content of antioxidant is preferably 0.01 mass parts～20 mass parts, is particularly preferably 0.1 mass parts～10 mass parts.

Coloured composition of the present invention can contain the compound of performance as the function of curing agent.

For example can use select free aromatic amines compound, tertiary amine compound, amine salt, phosphonium salt, amidine salt, amide compound,At least one chemical combination in the cohort that the compound of mercaptan compound, block isocyanate compound and imidazole ring-containing formsThing.

Contain this kind of curing agent by coloured composition, can further produce effect and realize the hardening at subcritical temerature of colored pattern. And,Also can further improve the storage stability of coloured composition.

Coloured composition of the present invention also can add compound that more described dyestuff more easily reduces and be used as the also place where troops were originally stationed of dyestuffOnly agent. Thus, more also can suppress dyestuff when tin indium oxide (IndiumTinOxide, the ITO) sputter after pixel formsFormer fading. Particularly be preferably naphtoquinone compounds, be preferably the naphtoquinone compounds that molecular weight is the following structure of 100～800 left and right.

Coloured composition of the present invention can and then optionally comprise fills material, ultra-violet absorber, anti-flocculating agent, sensitizerOr the various additives such as light stabilizer.

[preparation method of coloured composition]

Coloured composition of the present invention is by described each composition is mixed to prepare with any composition optionally.

In addition, while preparing coloured composition, can allocate the each composition that forms coloured composition blanketly, also can be by molten each compositionSolution is successively allotment after being scattered in solvent. In addition, ordering in launching or operating condition when allotment is not subject to special restriction. For example,Whole compositions can be dissolved to be scattered in solvent simultaneously prepare composition, optionally, also each composition suitably can be made to twoKind of above Solution Dispersion liquid, when use (when coating) they are mixed to be prepared into composition.

The coloured composition of preparation can use and be preferably aperture 0.01 μ m～3.0 μ m, aperture 0.05 more preferably in this wayThe filter of about μ m～0.5 μ m etc. carries out after isolated by filtration, in.

Coloured composition of the present invention is owing to can forming the painted cured film of form and aspect and contrast excellence, so be suitable for formingLiquid crystal indicator (LCD) or solid photographic element (for example charge coupled cell (ChargeCoupledDevice, CCD),Complementary metal oxide semiconductors (CMOS) (ComplementaryMetal-OxideSemiconductor, CMOS) etc.) middle useThe colored pixels of colored filter etc., in addition, the making that can be suitable for printing-ink, jetted ink and coating etc. is usedOn the way. Be particularly suitable for the colored pixels formation purposes that liquid crystal indicator is used.

[colored filter and manufacture method thereof]

Colored filter of the present invention is by substrate, and arranges and comprise the painted of coloured composition of the present invention on described substrateRegion forms. Painted areas on substrate be by form colored filter each pixel for example red (R), green (G),Coloring films such as blue (B) forms.

Form the painted areas (color-patch map through sclerosis as long as coloured composition of the present invention being applied on substrateCase) method, colored filter of the present invention can utilize any method to form. Be preferably use of the present invention paintedComposition is made.

In addition, in the situation that manufacturing solid photographic element with coloured composition of the present invention and using colored filter, also canAdopt the manufacture method of recording in the paragraph 0359～paragraph 0371 of Japanese Patent Laid-Open 2011-252065 communique.

The manufacture method of colored filter of the present invention comprises: step (A), on substrate, application (being preferably coating)The coloured composition of stating forms dyed layer (also referred to as coloured composition layer); And step (B), make in step (A)The coloured composition layer sclerosis forming.

The step of hardening is preferably (being preferably via mask) and exposes into pattern-like, not hard with developer solution by coated filmChange portion develops and removes and formation painted areas (colored pattern). By through these steps, can form comprise of all kinds (3 looks orPerson's 4 looks) colored pattern of pixel, can obtain colored filter. In addition, in the manufacture method of colored filter of the present invention,Particularly preferably for so that be provided with the form of following steps: step (C), the colored pattern forming in step (B) is irradiated to ultravioletLine; And step (D), the colored pattern through irradiation ultraviolet radiation in step (C) is carried out to heat treated.

By method as above, the difficulty of process aspect is few, can make with high-quality and at low cost liquid crystal displayThe colored filter using in element or solid photographic element.

Below, the manufacture method of colored filter of the present invention is further specifically described.

-step (A)-

In the manufacture method of colored filter of the present invention, first, utilize required coating process, on substrate directly orBe coated with already described coloured composition of the present invention via other layers, form coated film (the painted combination that comprises coloured compositionThing layer), then, optionally carry out pre-hardening (prebake conditions (pre-bake)), make described coloured composition layer dry.

Substrate for example can be enumerated: the alkali-free glass, soda-lime glass, Pai Resi (the Pyrex) (note that in liquid crystal display cells etc., useVolume trade mark) glass, quartz glass and make these substrates that is attached with nesa coating on glass, or solid photographic elementDeng in use photo-electric conversion element substrate, such as silicone substrate or plastic base etc. In addition, also can be on these substrates shapeBecome the black matrix" of each pixel isolation, or in order the object such as to promote to connect airtight, transparent resin layer is set. In addition, on substrate,Optionally for improve with top layer the diffusion of connecting airtight, prevent material or surface planarization, primary coat also can be setLayer.

In addition, plastic base is preferably and has gas barrier layer and/or solvent resistance layer on its surface.

In addition, can use the color liquid crystal display arrangement of thin film transistor (TFT) (ThinFilmTransistor, TFT) modeThe substrate for driving that disposes thin film transistor (TFT) (TFT) (hereinafter referred to as " TFT mode liquid crystal drive substrate ") conductSubstrate, with also forming the colored pattern that uses coloured composition of the present invention to form on substrate, makes colour in described drivingOptical filter.

TFT mode liquid crystal drive for example can be enumerated with the substrate in substrate: glass, silicone, Merlon, polyester, fragrancePolyamide, polyamidoimide, polyimides etc. For these substrates, optionally, also can implement in advance to utilize silaneThe chemical treatments of coupling agent etc., Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation etc. are suitablePre-treatment. For example, can use the substrate that is formed with the passivating films such as silicon nitride film in TFT mode liquid crystal drive with the surface of substrate.

Coloured composition of the present invention directly or via other layers is applied on substrate. The method of application is preferably paintingCloth, is preferably coating processes such as utilizing rotary coating, slot coated, curtain coating coating, roller coat cloth, rod coating, ink-jet and is coated withCloth.

In application step, the method that coloured composition of the present invention is coated on substrate is not particularly limited, and is preferably slitUse gap nozzle with rotary process (slit-and-spinmethod), non-rotating rubbing method (spinlesscoatingmethod) etc.(slitnozzle) method (hereinafter referred to as gap nozzle rubbing method).

In gap nozzle rubbing method, slit and method of spin coating and non-rotating rubbing method are according to the size of coated substrates and conditionDifference, for example, in the situation that utilizing non-rotating rubbing method to be coated with the 5th generation glass substrate (1100mm × 1250mm),Be generally 500 microlitres/second～2000 microlitre/seconds from the spray volume of the coloured composition of gap nozzle, be preferably 800 microlitres/Second～1500 microlitre/seconds, in addition, coating speed is generally 50mm/ second～300mm/ second, is preferably 100mm/ second～200Mm/ second.

In addition, the solid constituent of the coloured composition using in application step is generally 10%～20%, be preferably 13%～18％。

When forming on substrate the coated film by coloured composition gained of the present invention, the thickness of described coated film(prebake conditions is processed rear) is generally 0.3 μ m～5.0 μ m, and more satisfactory is 0.5 μ m～4.0 μ m, is desirably 0.5 μ m～3.0 mostμm。

In addition, if the situation of the colored filter that solid photographic element is used, the thickness of coated film (prebake conditions is processed rear)Be preferably the scope of 0.5 μ m～5.0 μ m.

In applying step, conventionally after application, implement prebake conditions processing. Optionally, also can before prebake conditions, implement application of vacuum.In vacuum drying condition, vacuum is generally 0.1 holder (torr)～1.0 holder, is preferably 0.2 holder left and right, holder～0.5.

In addition, can use heating plate, baking oven etc., in the temperature range of 50 DEG C～140 DEG C, be preferably 70 DEG C～110 DEG CLeft and right, carries out prebake conditions processing with the condition of 10 seconds～300 seconds. In addition, prebake conditions also can and be used high frequency processing in processingDeng. High frequency is processed and also be can be used alone.

The condition of prebake conditions can be listed below condition: use heating plate or baking oven, at 70 DEG C～130 DEG C, heat 0.5 minute～About 15 minutes.

The thickness of the coloured composition layer being formed by coloured composition in addition, can suitably be selected according to object. In liquid crystal displayDevice, with in colored filter, is preferably the scope of 0.2 μ m～5.0 μ m, and then the model of 1.0 μ m～4.0 μ m more preferablyEnclose, most preferably be the scope of 1.5 μ m～3.5 μ m. In addition, with in colored filter, be preferably 0.2 at solid photographic elementThe scope of μ m～5.0 μ m, and then the scope of 0.3 μ m～2.5 μ m more preferably, most preferably be the model of 0.3 μ m～1.5 μ mEnclose.

In addition, the thickness of coloured composition layer is the thickness after prebake conditions.

-step (B)-

Then, in the manufacture method of colored filter of the present invention, for be formed in this way on substrate comprise paintedThe film (coloured composition layer) of composition, for example, expose via photomask. Applicable light or radioactive ray in exposureBeing preferably g ray, h ray, i ray, j ray, KrF light, ArF light, is particularly preferably i ray. I ray is being usedIn the situation of light irradiation, be preferably with 100mJ/cm²～10000mJ/cm²Light exposure irradiate.

In addition, other exposure light also can use: each mercury vapor lamp of super-pressure, high pressure, middle pressure, low pressure, chemical lamp,The various LASER Light Sources of carbon arc lamp, xenon lamp, metal halide lamp, visible and ultraviolet, fluorescent lamp, tungsten lamp, sunshine etc.

Use the step of exposure of LASER Light Source

Use in the Exposure mode of LASER Light Source, use ultraviolet laser as light source.

Light irradiation is preferably the ultraviolet laser that wavelength is the wave-length coverage of the scope of 300nm～380nm, just with photoresistanceThe aspect that wavelength photoreceptor is consistent, and then the ultraviolet laser of the wavelength of the scope of 300nm～360nm more preferably. ToolBody, especially can be applicable to the yttrium-aluminium-garnet (neodymium of the doping neodymium that uses the large and less expensive Solid State Laser of powerDopedyttriumaluminumgarnet, Nd:YAG) third harmonic (355nm) of laser or PRKXeCl(308nm)、XeF(353nm)。

The light exposure that is exposed thing (pattern) is 1mJ/cm²～100mJ/cm²Scope, more preferably 1mJ/cm²～50mJ/cm²Scope. If light exposure is described scope, preferred with regard to the productive aspect of pattern formation.

There is no particular restriction for exposure device, and commercially available exposure device can use this holder (Callisto) (V science and technology of Cali(V-Technology) limited company manufactures) or Ai Jisi (EGIS) (manufacture of V Science and Technology Co., Ltd.),Or DF2200G (Dainippon Screen Manufacturing Co (DainipponScreen) (thigh) manufacture) etc. In addition, described device in addition alsoBe applicable to using.

While manufacturing the colored filter that liquid crystal indicator uses, be preferably and use by close induction type exposure machine, minute surface projection exposureMachine, and mainly use the exposure of h ray, i ray. In addition, while manufacturing the colored filter that solid photographic element uses, preferablyFor utilizing stepper exposure machine, and mainly use i ray. In addition, manufacture coloured silk with TFT mode liquid crystal drive substrateWhen colo(u)r filter, the photomask using can use the pattern except being provided with to form pixel (colored pattern),Also be provided with the photomask of the pattern that forms through hole or water chestnut (horseshoe) type pit.

Can heat through the coloured composition layer of exposure in this way.

In addition, for the oxidation that suppresses the colored materials in coloured composition layer is faded, nitrogen one on one side can circulate in chamberExpose in limit.

Then,, to the coloured composition layer after exposure, utilize developer solution to develop. Thus, can form minus or eurymericColored pattern (photoresistance pattern). In development step, make the unhardened portion stripping of the coated film after exposure in developer solution, onlySclerosis part is remained on substrate.

Developer solution is as long as the coated film of the coloured composition in unhardened portion (coloured composition layer) is dissolved, but can be byThe developer solution that sclerosis portion dissolves, can use any. For example can use combination or the alkaline aqueous solution of multiple organic solvent.

Spendable already described solvent when the organic solvent using in development can be enumerated preparation coloured composition of the present invention.

Alkaline aqueous solution for example can be enumerated: by tetraethyl ammonium hydroxide, TPAOH, TBAH, threeMethyl-benzyl ammonium hydroxide, benzyltrimethylammonium hydroxide, NaOH, potassium hydroxide, sodium carbonate, sodium acid carbonate, siliconAcid sodium, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, TMAH, tetraethyl hydroxideAmmonium, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-alkali compounds such as 7-hendecene, become 0.001 with concentrationQuality %～10 quality %, the mode that is preferably 0.01 quality %～1 quality % are dissolved the alkaline aqueous solution forming. At developer solutionIn situation for alkaline aqueous solution, alkali concn can be preferably pH value become 11～13 so that more preferably pH value become11.5～12.5 mode is adjusted.

In alkaline aqueous solution, also can add appropriate water-miscible organic solvent such as such as methyl alcohol, ethanol etc. or surfactant etc.

Development temperature is generally 20 DEG C～30 DEG C, and developing time is 20 seconds～90 seconds.

Development can be any of impregnation method, spray mode, spray pattern etc., also can combine therein swing (swing)Mode, rotation mode, ultrasonic wave mode etc. Also can be before contacting with developer solution, the face that will be developed carries out with water etc. in advanceWetting, prevent from developing uneven. In addition, also can make substrate tilt to develop.

In addition, in the situation that manufacturing solid photographic element with colored filter, also use and cover liquid (puddle) development.

After development treatment, through the drip washing processing that remaining developer solution washing is removed, after implementing to be dried, in order to make to have hardenedEntirely implement heat treated (baking afterwards).

Drip washing is processed and is normally carried out with pure water, in order to economize liquid, also can utilize in final washing, to use pure water and at the beginning of washingPhase is used the method for used pure water, and in addition, also can utilize and make substrate tilt to wash, or and with ultrasonic irradiationMethod.

After after drip washing is processed, dewatering, being dried, conventionally carry out the heat treated of approximately 200 DEG C～250 DEG C. Described heating placeReason (baking afterwards) can, to the coated film after developing, be used heating plate or convection oven (hot blast to become the mode of described conditionCirculating drying machine), the heater such as high frequency heating machine, carry out with continous way or batch-type.

By according to required form and aspect number, shades of colour is carried out to above each step successively repeatedly, can make and form through multipleThe colored filter that the painted cured film (colored pattern) of color forms.

Colored filter of the present invention because contrast is high, colour saturation uneven little, look characteristic is good, so can be suitable for solidBody photographic element or liquid crystal display cells.

-step (C)-

In the manufacture method of colored filter of the present invention, the colored pattern that also can form using coloured composition especially(pixel) carries out the post-exposure of irradiating by ultraviolet ray.

-step (D)-

Be preferably for carrying out the colored pattern of post-exposure of irradiating by ultraviolet ray as above, and then carry out heating placeReason. Carry out heat treated (after so-called, baking is processed) by the colored pattern to formed, can make colored pattern further hardChange. Described heat treated can utilize such as heating plate, various heater, baking oven etc. to carry out.

Temperature when heat treated is preferably 100 DEG C～300 DEG C, and then more preferably 150 DEG C～250 DEG C. In addition, heatingTime is preferably 10 minutes～about 120 minutes.

The colored pattern obtaining in this way forms the pixel in colored filter. There is the colour of pixel of multiple form and aspectIn the making of optical filter, if according to required number of colors repeatedly carry out described step (A), step (B), withAnd step (C) or step (D) optionally.

In addition can in the time that finishing, formation, exposure, the development of every kind of monochromatic coloured composition layer (each color) carry out,Described step (C) and/or step (D), also can the formation of all coloured composition layers of required color quantity, exposure,After development finishes, carry out described step (C) and/or step (D) blanketly.

In addition, coloured composition of the present invention also can be applicable to the manufacture method of the colored filter that comprises dry-etching step.One example of this kind of manufacture method can be enumerated the manufacture method comprising the following steps: forming with coloured composition of the present inventionThe step of chromatograph; On described dyed layer, form the step of photoresist layer; By exposing and developing, described photoresist layer is carried out to figureCase and obtain the step of photoresistance pattern; And using described photoresistance pattern as etching mask, described dyed layer is carried out to dry typeEtched step. Be used for the feelings of the manufacture method of the colored filter that comprises dry-etching step at coloured composition of the present inventionUnder condition, can be photo-hardening composition, also can be thermosetting composition. The in the situation that of thermosetting composition, can useThermoinitiators, thermoinitiators is preferably the compound in a part with more than two epoxy radicals.

Utilize colored filter (colored filter of the present invention) that the manufacture method of colored filter of the present invention obtains byIn using coloured composition of the present invention, so form and aspect and contrast excellence.

Colored filter of the present invention can be used for liquid crystal display cells or solid photographic element, is particularly suitable for liquid crystal display dressThe purposes of putting. For liquid crystal indicator in the situation that, use triarylmethane dye to reach good as colouring agentForm and aspect, and can carry out the image demonstration of dichroism and contrast excellence.

As the purposes of coloured composition of the present invention, though above mainly with the formation purposes of the colored pattern of colored filterCentered by be illustrated, but also can be applicable to form, by forming, the colored pattern (pixel) of colored filter isolatesBlack matrix".

The coloured composition of the processed pigment that the black matrix" on substrate can contain the black pigments such as carbon black, titanium be black by use,Through coating, exposure and each step of developing, then optionally carry out rear baking and form.

[liquid crystal indicator]

Liquid crystal display cells of the present invention and solid photographic element comprise colored filter of the present invention. More specifically, exampleAs, the inner face side by colored filter forms alignment films, makes itself and electrode base board subtend, fills up liquid crystal enter in clearance portionRow sealing is panel thereby obtain liquid crystal display cells of the present invention. In addition, for example, color by forming on photo detectorColo(u)r filter, and obtain solid photographic element of the present invention.

About the definition of liquid crystal indicator or the details of each display unit, for example, be recorded in " electron display device (assistant assistant woodClear husband, census of manufacturing meeting (thigh) nineteen ninety distribution) ", " (she blows along chapter and display device, industry books (thigh)1989 distribution) " etc. in. About liquid crystal indicator, for example, be recorded in addition, " LCD Technology of future generation (inTian Longnan edits, census of manufacturing meeting (thigh) distribution in 1994) " in. The applicable liquid crystal indicator of the present invention be there is noSpecial restriction, the liquid crystal display dress of various ways of for example, recording in " LCD Technology of future generation " described in can be applicable toPut.

Wherein, colored filter of the present invention is effective especially for the liquid crystal indicator of colored TFT mode. About colourThe liquid crystal indicator of TFT mode, for example, be recorded in " color TFT-LCD display (vertical (thigh) 1996 of publishing altogetherOK) ". And then the present invention also can be applicable to the transverse electric fields such as coplanar switching (InPlaneSwitching, IPS) and drivesThe visual angle of the pixel partitioning schemes such as mode, multidomain vertical orientation (Multi-domainVerticalAlignment, MVA) etc. is expandedLarge liquid crystal indicator, or STN Super TN (SuperTwistedNematic, STN), twisted nematic (TwistedNematic, TN), vertical orientated (VerticalAlignment, VA), the optical compensation (OpticallyCompensated that tiltsSplay, OCS), fringing field switch (FringeFieldSwitching, FFS) and anacamptics compensated bend (ReflectiveOpticallyCompensatedBend, R-OCB) etc.

In addition, colored filter of the present invention is also available for the colorful optical filter array (Color-filterOn of bright and fineArray, COA) mode.

If by colored filter of the present invention for liquid crystal display cells, with the three-wavelength pipe group of existing known cold-cathode tubeWhile closing, can realize high contrast, and then, can pass through using the LED light source of red, green, blue (RGB-LED) as backlight,Provide brightness color reproduction high and that excitation is high good liquid crystal indicator.

[solid photographic element]

Coloured composition of the present invention also can be preferably used for solid photographic element purposes. The formation of solid photographic element is for comprisingThe formation of the colored filter of manufacturing with coloured composition of the present invention, as long as performance is as the merit of solid photographic elementThe formation of energy, is not particularly limited, for example, can enumerate following formation.

On support, there is the light that is subject to of formation solid photographic element (ccd image sensor, cmos image sensor etc.)Multiple optical diodes in region and the carry electrode that comprises polysilicon etc., on described optical diode and described carry electrodeThere is the only photomask that comprises tungsten etc. of the light accepting part opening of optical diode, on photomask, there is whole of the photomask of coveringAnd the device protecting layer that comprises silicon nitride etc. that forms of the mode of optical diode light accepting part, and on described device protecting layer toolThere is the formation of solid photographic element of the present invention colored filter.

And then, also can be on described device protecting layer and under colored filter (side approaching with support) and there is optically focusedElement (such as lenticule etc.; Identical below) formation or on colored filter, there is formation of collective optics etc.

[embodiment]

Below enumerate embodiment, the present invention is further specifically described. Only otherwise depart from purport of the present invention,Material shown in embodiment, use amount, ratio, contents processing, processing sequence etc. can suitably change. Therefore, the present inventionScope be not limited to concrete example shown below. In addition, as long as no special instructions, " % " and " part " is quality-baseAccurate.

(synthesizing of Compound I-2)

According to carrying out synthetic compound I-2 in following path.

[changing 54]

(synthesizing of synthetic intermediate (compound 3))

Make compound 1 (1-naphthylamine) 17.0g (118.8mmol) and 1,2-epoxy-cyclohexane 11.65g (118.7mmol)After being dissolved in the hexafluoroisopropanol of 50mL, add hot reflux 5 hours. After confirming that reaction finishes, utilize ethyl acetate 50mLAnd water, saline solution, object is extracted in organic layer and after washing, make it concentrated. Make described crude product in hexaneAfter dissolving, recrystallization, filter, obtain thus the compound 3 (productive rate 67%) of 19.2g.

(synthesizing of synthetic intermediate (compound 4))

Make compound 3 (2.4g (10mmol)) and triethylamine 1.5g (15mmol) be dissolved in the tetrahydrochysene of 10mLIn furans (tetrahydrofuran, THF). Described solution is cooled to after 0 DEG C, drips methacrylic chloride 1.15g (11Mol). Confirm after completion of the reaction, to utilize ethyl acetate 20mL and water, saline solution, object is extracted in organic layerAnd after washing, concentrate. Utilize tubing string chromatography by described crude product purifying, the compound 4 that obtains thus 1.8g (producesRate 58%).

(synthesizing of Compound I-2)

By compound 4 (1.9g (5.8mmol)), compound 5 (1.8g (5.8mmol)), phosphorous oxychloride 1.0g(6.4mmol) be dissolved in the toluene of 6mL, heat to 90 DEG C, stir 1 hour. After confirming that reaction finishes, describedIn solution, add ethyl acetate 10mL, take out object as supernatant, described operation is carried out 3 times repeatedly, will changeCompound 6 takes out as ethyl acetate solution. In described solution, add two fluoroform sulfimide lithium salts 2.0 of adjusting separatelyThe methyl alcohol 20mL solution of g (7.0mmol). After confirming salt exchange reaction, add water 50mL, compound is extractedTo ethyl acetate layer and after concentrated, utilize tubing string chromatography to carry out purifying, obtain thus target compound I-2 (1.7g(33％))。

¹HNMR(CHCl₃)：1.25(m，16H)，1.8(s，3H)，3.6(t，8H)，3.75(bs，1H)，5.2(dt，1H)，5.55(s，1H)，6.1(s，1H)，6.2(d，1H)，6.75(d，4H)，7.2-7.5(m，9H)，7.8(d，1H)

(preparation of coloured composition (coating fluid))

Triarylmethane dye (I-1): the compound of following structure

[changing 55]

Optical polymerism compound (T-1): block sub-rad (KAYARAD) DPHA (Japanese chemical drug (thigh) manufacture, twoThe mixture of pentaerythrite five acrylate and dipentaerythritol acrylate)

Alkali-soluble adhesive (U-1): methacrylic acid benzyl ester/methacrylic acid (85/15) [mass ratio] co-polymer(weight average molecular weight: propylene glycol methyl ether acetate solution (solid constituent is 40.0 quality %) acid number (100 12,000)mgKOH/g)

Photoepolymerizationinitiater initiater (V-3): the oxime compound of following structure

[changing 56]

Solvent (X-1): propylene glycol methyl ether acetate

Solvent (X-2): 3-ethoxyl ethyl propionate

Surfactant (Z-1): Mei Jiafa (Megafac) F781-F (large Japanese ink chemical industry (thigh) is manufactured)

Except triarylmethane dye (I-1) is changed to following (I-2)～(I-21), (I-101)～(I-106) withPrepare coloured composition in the mode identical with embodiment 1 outward.

[changing 57]

[changing 58]

Except the alkali-soluble adhesive (U-1) using in embodiment 1 is changed to following alkali-soluble adhesive (U-1-1)In addition, prepare coloured composition in the mode identical with embodiment 1.

Alkali-soluble adhesive (U-1-1): methacrylic acid benzyl ester/methacrylic acid/ALMA(20/60/20) [mass ratio] co-polymer (weight average molecular weight: propylene glycol methyl ether acetate solution 20,000) (GuBody composition is 40.0 quality %) acid number (250mgKOH/g)

Except the alkali-soluble adhesive (U-1) using in embodiment 1 is changed to following alkali-soluble adhesive (U-2-1)In addition, prepare coloured composition in the mode identical with embodiment 1.

Alkali-soluble adhesive (U-2-1): GMA-MAA/ methacrylic acid/methacrylic acid cyclohexyl ester (26/38/36)[mass ratio] co-polymer (weight average molecular weight: (solid constituent is 40.0 to propylene glycol methyl ether acetate solution 3,000)Quality %) acid number (125mgKOH/g)

In addition, GMA-MAA represents following structure.

[changing 59]

Except the alkali-soluble adhesive (U-1) using in embodiment 1 is changed to following alkali-soluble adhesive (U-1-2)In addition, prepare coloured composition in the mode identical with embodiment 1.

Alkali-soluble adhesive (U-1-2): methacrylic acid benzyl ester/methacrylic acid/ALMA/N-Phenyl maleimide (15/20/30/35) [mass ratio] co-polymer (weight average molecular weight: 20,000) the third twoAlcohol methyl ether acetate solution (solid constituent is 40.0 quality %) acid number (110mgKOH/g)

Except triarylmethane dye being changed to the following comparison of recording in the embodiment 2 of WO2010-123071 communiqueBeyond compound 1, adjust coloured composition in the mode identical with embodiment 1.

Comparative compound 1

[changing 60]

Except triarylmethane dye being changed to following comparative compound 2, adjust in the mode identical with embodiment 1Coloured composition.

Comparative compound 2:(Tokyo changes into industrial group and manufactures, and goods are called Blue 7)

[changing 61]

Become 1.5～2.0 mode with the maximum absorbance under 600nm～700nm, by the coloured composition of described acquisitionThe glass substrate (1737, healthy and free from worry (Corning) company manufactures) of coating 100mm × 100mm is upper, the baking of 100 DEG CIn case, be dried 180 seconds, on substrate, make coloring film.

The coloring film of described acquisition is carried out to following evaluation.

For described coloring film, at 230 DEG C, heat after 40 minutes, measure colourity and change, be i.e. Δ Eab value. According to heatingThe UV-Vis spectrum of front and back calculates Δ Eab value. Δ Eab value is little, represents excellent in light-resistance.

To at 230 DEG C, heat the described coloring film of 20 minutes at the 1-METHYLPYRROLIDONE of 25 DEG CIn (N-methylpyrrolidone, NMP), dipping 10 minutes, measures the colourity before and after flooding, and calculates the index that look changesΔ Eab. Calculate Δ Eab value according to the UV-Vis spectrum before and after heating. In addition be the situation below 3 in the value of Δ Eab,Under, form and aspect are with low uncertainty, have excellent solvent resistance.

Upper at the glass substrate with ITO electrode (trade name: 1737, Corning Incorporated manufactures), become with dried thicknessThe mode that is 2.0 μ m is coated with coloured composition, is dried (prebake conditions) 60 seconds in the baking oven of 90 DEG C. Then, not via coveringMould, carries out 100mJ/cm²Exposure (illumination is 20mW/cm²), use alkaline-based developer (trade name: CDK-1,Fujiphoto electronic material (thigh) is manufactured) 1% aqueous solution, at 25 DEG C, develop, will wash, dried coatingFilm carries out 30 minutes heat treated (baking afterwards) in the baking oven of 230 DEG C, forms painted cured film. Then, will be formed withThe substrate of described painted cured film and only have the substrate of ITO electrode with set shape evaporation, to be mixed with the bead of 5 μ mSealant fitted, then between substrate, inject Merck (Merck) manufacture liquid crystal MJ971189 (trade name),Make liquid crystal cells.

Then, liquid crystal cells was put into the thermostat layer of 70 DEG C after 48 hours, use Dongyang Te Kenika (ToyoTechnica)The liquid crystal voltage conservation rate of manufacturing is measured system VHR-1A type (trade name), utilizes following condition determination to measure liquid crystal listThe voltage retention of unit, evaluates according to the mark shown in following benchmark. Mark is higher, and voltage retention is better.

Condition determination

Interelectrode distance: 5 μ m～15 μ m

Apply voltage pulse amplitude: 5V

Apply potential pulse frequency: 60Hz

Apply voltage pulse width: 16.67msec

* voltage retention: the value of the voltage applying in liquid crystal cells potential difference/0 after 16.7 milliseconds millisecond

* criterion

More than 90%: 5

More than 85% and be less than 90%:4

More than 80% and be less than 85%:3

More than 75% and be less than 80%:2

Be less than 75%:1

[table 1]

Known according to described result, in the present invention, can provide the painted of heat resistance, solvent resistance and voltage retention excellenceComposition.

Known on the other hand, in the coloured composition of comparative example, heat resistance, solvent resistance and voltage retention are not good.

Claims

1. a coloured composition, it comprises colouring agent and polymerizable compound, described colouring agent comprise have bridging property base andCation and molecular weight are the triarylmethane structure below 2000, and anti-lotus anion.

2. coloured composition according to claim 1, wherein said have bridging property base and cation and molecular weight and beTriarylmethane structure below 2000 is represented by general formula (TP1) and/or general formula (TP2):

[changing 1]

In general formula (TP1) and general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₅、Rtp₆、Rtp₈、Rtp₉And Rtp₁₁Represent independently respectively substituting group; Rtp₇Represent hydrogen atom, alkyl, aryl or NRtp₇₁Rtp₇₂Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₁₀Represent hydrogen atom, alkyl or aryl; A, bAnd c represents respectively 0～4 integer independently; Be 2 above in the situation that at a, b and c, Rtp₆、Rtp₇And Rtp₈InTwo can mutually link and form ring; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in there is bridging property base.

3. coloured composition according to claim 1 and 2, wherein anti-lotus anion is to be selected from: be selected from fluorine anion,Cl anion, bromine anions, iodine anion, cyanide ion, mistake chlorate anions anion, borate anion, pF^6-AndSbF^6-In at least one; And

Be selected from-SO₃ ^-、-COO^-、-PO₄ ^-, represented structure and the following general formula (A2) of following general formula (A1) be representedAt least one in structure;

General formula (A1)

[changing 2]

In general formula (A1), R¹And R²Difference expression-SO independently₂-or-CO-;

General formula (A2)

[changing 3]

In general formula (A2), R³Expression-SO₂-or-CO-; R⁴And R⁵Difference expression-SO independently₂-,-CO-or-CN.

4. according to the coloured composition described in any one in claims 1 to 3, wherein said anti-lotus anion is contained in and containsIn the compound of bridging property base.

5. according to the coloured composition described in any one in claims 1 to 3, wherein said anti-lotus anion is contained in repetitionIn unit.

6. coloured composition according to claim 1, wherein said have bridging property base and cation and molecular weight and beTriarylmethane structure below 2000 is represented by general formula (TP1A) or general formula (TP2A);

[changing 4]

In general formula (TP1) and general formula (TP2), Rtp₁～Rtp₄Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₅、Rtp₆、Rtp₈、Rtp₉And Rtp₁₁Represent independently respectively substituting group; Rtp₇Represent hydrogen atom, alkyl, aryl orIn NR₇₁Rtp₇₂；Rtp₇₁And Rtp₇₂Represent independently respectively hydrogen atom, alkyl or aryl; Rtp₁₀Represent hydrogen atom, alkylOr aryl; A, b and c represent respectively 0～4 integer independently; Be 2 above in the situation that at a, b and c, Rtp₆、Rtp₇And Rtp₈In two can mutually link and form ring; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂Any in have crosslinkedProperty base; Rtp₁～Rtp₁₁、Rtp₇₁And Rtp₇₂At least one can replace through general formula (P);

General formula (P)

[changing 5]

In general formula (P), L represents singly-bound or bivalence linking base, X¹Be selected from-SO₃-、-COO^-、-PO₄-, compriseIn the group of the represented structure of following general formula (A1) and the group that comprises the represented structure of following general formula (A2) extremelyFew a kind of;

General formula (A1)

[changing 6]

General formula (A2)

[changing 7]

7. according to the coloured composition described in any one in claim 1 to 6, it also comprises Photoepolymerizationinitiater initiater.

8. according to the coloured composition described in any one in claim 1 to 7, it is used to form the dyed layer of colored filter.

9. a painted cured film, it is to form according to the coloured composition sclerosis described in any one in claim 1 to 8.

10. a colored filter, it comprises painted cured film according to claim 9.

The manufacture method of 11. 1 kinds of colored filters, it comprises: by according to described in any one in claim 1 to 8Colour cell compound is imparted on support and forms the step of coloured composition layer; Described coloured composition layer is exposed into pattern-likeStep; And unexposed portion is developed and removed and the step of formation colored pattern.

The manufacture method of 12. 1 kinds of colored filters, it comprises: by according to described in any one in claim 1 to 8Colour cell compound is imparted on support and forms coloured composition layer, hardens and forms the step of dyed layer; DescribedOn chromatograph, form the step of photoresist layer; By exposing and developing, described photoresist layer patterning is obtained to the step of photoresistance pattern;Or using described photoresistance pattern as etching mask, described dyed layer is carried out to the step of dry-etching.

13. 1 kinds of colored filters, it is to utilize according to the manufacture method of the colored filter described in claim 11 or 12Manufacture.

14. 1 kinds of solid photographic elements, it comprises colored filter according to claim 10 or utilizes according to rightRequire the colored filter of the manufacture method made of the colored filter described in 11 or 12.

15. 1 kinds of image display devices, it comprises colored filter according to claim 10 or utilizes according to rightRequire the colored filter of the manufacture method made of the colored filter described in 11 or 12.