CN106661343B

CN106661343B - The manufacturing method of coloured composition and its application and pigment polymer

Info

Publication number: CN106661343B
Application number: CN201580037421.4A
Authority: CN
Inventors: 原彰宏; 伊藤纯一; 原田昌之; 出井宏明; 鲛岛贤; 金子祐士; 尾田和也
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2014-08-29
Filing date: 2015-07-23
Publication date: 2019-07-30
Anticipated expiration: 2035-07-23
Also published as: WO2016031442A1; JPWO2016031442A1; TWI695037B; KR20190035929A; KR102027797B1; CN106661343A; KR20170016954A; JP6279745B2; TW201607995A

Abstract

The present invention provides the manufacturing method of a kind of coloured composition and its application and pigment polymer.The light resistance of the coloured composition, migrating property and flatness are excellent comprising by the pigment polymer and polymerizable compound represented by general formula (1).In general formula (1), P indicates that the concatenating group of n valence, Q indicate that the polymer chain containing the repetitive unit with pigmentary structures, the average value of the number of the repetitive unit with pigmentary structures of n Q are two or more, and n indicates 3~10 integer.P-(Q)_n…(1)。

Description

The manufacturing method of coloured composition and its application and pigment polymer

Technical field

The present invention relates to a kind of coloured compositions.More particularly to one kind is suitable for solid state photo element, image display device The coloured composition of chromatic filter Deng used in.Moreover, it relates to which a kind of filtered using the colour of coloured composition Light device, solid state photo element and image display device.In addition, being formed the present invention also relates to a kind of using the pattern of coloured composition Method, the manufacturing method of chromatic filter, the manufacturing method of pigment polymer (multimer).

Background technique

In recent years, the mobile phone because of digital camera, with camera is universal, therefore charge-coupled device (Charge Coupled Device, CCD) demand of the solid state photos element such as imaging sensor increases substantially.As these displays or light The Primary Component for learning element, using chromatic filter, and the requirement of further high sensitivityization miniaturization improves.Such colour Optical filter is generally configured with the colored pattern of 3 primary colors of red (R), green (G) and blue (B), and performance makes through photodegradation into 3 primary colors Effect.

For colorant used in chromatic filter, common prescription is had the property that.That is, it needs to color again There are preferred optical absorption characteristics in terms of existing property and light resistance is good etc..

On the other hand, disclosing in patent document 1 a kind of includes 2~9 in a molecule with for pigment The pigment dispersing agent at the position of absorption property.As the position with the absorption property for pigment, can enumerate: organic pigment knot Structure, heterocycle structure, acidic groups, the base with basic nitrogen atom, urea groups, carbamate groups, the base with coordinating oxygen atom, Alkyl, alkoxysilane group, epoxy group, isocyanate group, hydroxyl, ionic functional group of 4 or more carbon number etc..

Existing technical literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2008-222950 bulletin

Summary of the invention

Subject to be solved by the invention

In the coloured composition for chromatic filter etc., it is desirable that light resistance, migrating property, the further of flatness change It is kind.

Furthermore patent document 1 relates to the invention of pigment dispersing agent.Record in patent document 1 can be used it is organic Pigmentary structures are as the position with the absorption property for pigment, but pigment dispersing agent does not have color preferably, therefore has There is the structure that absorbance must be selected small the position of the absorption property of pigment.In addition, in patent document 1, also without becoming Pigment dispersing agent is used as to the record of the motivation of colorant.

The present invention is winner in view of the situation, and its purpose is to provide a kind of light resistance, migrating property and flatness are excellent Different coloured composition.In addition, the purpose of the present invention is to provide a kind of chromatic filter, pattern forming method, colorized optical filterings Manufacturing method, the manufacturing method of solid state photo element, image display device and pigment polymer of device.

Technical means to solve problem

It is that the present inventor is studied in detail as a result, discovery contains the repetitive unit with pigmentary structures by using n Polymer chain be bonded to the pigment polymer on the concatenating group of n valence, can get light resistance, migrating property and flatness it is excellent Color composition, so as to complete the present invention.Therefore, the present invention provides following person.

<1>a kind of coloured composition comprising by the pigment polymer and polymerizable compound represented by general formula (1)；

P-(Q)_n…(1)

In general formula (1), P indicates the concatenating group of n valence,

Q indicates the polymer chain containing the repetitive unit with pigmentary structures,

The average value of the number of the repetitive unit with pigmentary structures of n Q is two or more,

N indicates 3~10 integer.

<2>coloured composition according to<1>, wherein by the pigment polymer represented by general formula (1) by general formula (2) table Show；

[changing 1]

In general formula (2), A¹Indicate the concatenating group of n valence,

B¹Indicate singly-bound ,-O- ,-S- ,-CO- ,-NR- ,-O₂C-、-CO₂,-NROC- or-CONR-,

R indicates hydrogen atom, alkyl or aryl,

C¹Indicate the concatenating group of singly-bound or divalent,

S indicates sulphur atom,

N indicates 3~10 integer.

<3>coloured composition according to<2>, wherein A¹To include the aliphatic that can have oxygen atom on main chain The combined base of one or more of alkyl, aromatic series ring group and heterocycle.

<4>coloured composition according to any one of<1>to<3>, wherein pigment polymer is in 400nm~800nm In interior maximum absorption wavelength is 5 or more by the ratio absorbance represented by following formula (A λ)；

E=A/ (c × 1) ... (A λ)

In formula (A λ), E indicates the ratio absorbance in the maximum absorption wavelength in 400nm~800nm,

A indicates the absorbance in the maximum absorption wavelength in 400nm~800nm,

L indicates the element length that unit is indicated by cm,

C indicates the concentration of the pigment polymer in the solution that unit is indicated by mg/ml.

<5>coloured composition according to any one of<1>to<4>, wherein the total solid relative to coloured composition Ingredient contains 1 mass of mass %~50 % of pigment polymer.

<6>coloured composition according to any one of<1>to<5>, wherein pigment polymer is makes by general formula (3) institute The compound of expression carries out free radical polymerization institute winner with the compound with pigmentary structures and radically polymerizable group.

P⁰-(SH)_n…(3)

In general formula (3), P⁰Indicate the concatenating group of n valence,

SH indicates mercapto,

N indicates 3~10 integer.

<7>coloured composition according to any one of<1>to<6>, further includes the pigment other than pigment polymer.

<8>coloured composition according to any one of<1>to<7>, further includes Photoepolymerizationinitiater initiater.

<9>coloured composition according to any one of<1>to<8>, wherein Q, which has to be originated from, is selected from triarylmethane color Element, xanthene pigment, anthraquinone pigment, anthocyanidin, the sour inner salt pigment in side, quinophthalone pigment, phthalocyanine dye, sub- phthalocyanine dye, The pigmentary structures of azopigment and the pigment in two pyrroles's methylene pigments.

<10>coloured composition according to any one of<1>to<9>, wherein Q contains selected from the repetition with acidic group One or more of unit and the repetitive unit with polymerism base.

<11>coloured composition according to any one of<1>to<10>, wherein Q is selected from (methyl) acrylic acid series tree One of rouge, phenylethylene resin series and (methyl) acrylic/styrene system resin.

<12>a kind of chromatic filter is formed using the coloured composition according to any one of<1>to<11>.

<13>a kind of pattern forming method comprising: the coloured composition according to any one of<1>to<11>is answered The step of being used to support on body to form coloring compositions nitride layer；The step of coloring compositions nitride layer is exposed into pattern-like；And it will The step of exposing into the unexposed portion development removal of the coloring compositions nitride layer of pattern-like and forming colored pattern.

<14>a kind of pattern forming method comprising: the coloured composition according to any one of<1>to<11>is answered It is used to support on body to form coloring compositions nitride layer, and the step of making it harden and form coloring layer；Light is formed on coloring layer The step of causing resist layer；And photoresist layer being patterned by being exposed and developing obtain resist pattern The step of；And resist pattern is formed to the step of colored pattern as etching mask to coloring layer progress dry-etching Suddenly.

<15>a kind of manufacturing method of chromatic filter comprising according to pattern forming method described in<13>or<14>.

<16>a kind of solid state photo element comprising the chromatic filter according to<12>or by according to described in<15> Chromatic filter manufacturing method chromatic filter obtained.

<17>a kind of image display device comprising the chromatic filter according to<12>or by according to described in<15> Chromatic filter manufacturing method chromatic filter obtained.

<18>a kind of manufacturing method of pigment polymer comprising compound represented by making by general formula (3), with there is color The compound of plain structure and radically polymerizable group carries out free radical polymerization.

P⁰-(SH)_n…(3)

In general formula (3), P⁰Indicate the concatenating group of n valence,

SH indicates mercapto,

N indicates 3~10 integer.

The effect of invention

According to the present invention, it is possible to provide a kind of light resistance, migrating property and the excellent coloured composition of flatness.In addition, can mention For a kind of chromatic filter, pattern forming method, the manufacturing method of chromatic filter, solid state photo element, image display device And the manufacturing method of pigment polymer.

Specific embodiment

Hereinafter, the contents of the present invention are described in detail.

In the statement of base (atomic group) in the present specification, not recording the statement for being substituted and being unsubstituted includes not have The base (atomic group) of substituted base, and also comprising the base (atomic group) with substituent group.For example, so-called " alkyl ", is not only wrapped Containing the alkyl (alkyl being unsubstituted) without substituent group, also comprising the alkyl (alkyl being substituted) with substituent group.

In the present specification, light refers to actinic ray or radioactive ray.In addition, " actinic ray " or " radioactive ray " refers to for example The bright-line spectrum of mercury vapor lamp, using excimer laser as the far ultraviolet of representative, extreme ultraviolet (extreme ultraviolet (Extreme Ultraviolet, EUV) light), X-ray, electron beam etc..

In the present specification, as long as in advance without special instruction, " exposure " not only comprising using mercury vapor lamp bright-line spectrum, Using excimer laser as the exposure of the progress such as the far ultraviolet of representative, X-ray, EUV light, the particles such as electron beam, ion beam are utilized The description of Shu Jinhang is also contained in exposure.

In the present specification, the numberical range indicated using "~" refers to that numerical value documented by the front and back comprising "~" is made For lower limit value and the range of upper limit value.

In the present specification, so-called total solid content, refer to from the total composition of coloured composition remove solvent after at The gross mass divided.

In the present specification, " (methyl) acrylate " indicates the two or any of acrylate and methacrylate Person, " (methyl) acrylic " indicate acrylic and methacrylic acid group the two or any one, " (methyl) allyl " table Show allyl and methacrylic the two or any one, " (methyl) acryloyl group " indicates acryloyl group and methacryl The two of base or any one.

In the present specification, so-called polymerizable compound refers to the compound with polymerizable functional groups, can be monomer, It can also be polymer.So-called polymerizable functional groups refer to the base for participating in polymerization reaction.

In the present specification, the Me in chemical formula indicates that methyl, Et indicate that ethyl, Pr indicate that propyl, Bu indicate butyl, Ph Indicate phenyl.

In the present specification, " step " this term refers not only to independent step, even if can not be bright with other steps In the case of really being distinguish, as long as reaching the expected effect of the step, also it is contained in this term.

In the present specification, weight average molecular weight and number average molecular weight, which are used as, passes through gel permeation chromatography (Gel Permeation Chromatography, GPC) resulting polystyrene scaled value is measured to define.In the present specification, weight Amount average molecular weight (Mw) and number average molecular weight (Mn) can for example be found out in the following way: use (the east HLC-8220 Cao's (Tosoh) (share) manufacture), and TSK surpassed into gel (TSKgel Super) AWM-H (Tosoh (share) manufactures, in 6.0mm Diameter (Inner Diameter, ID) × 15.0cm) it is used as tubing string, by the lithium bromide N-Methyl pyrrolidone (N- of 10mmol/L Methylpyrrolidinone, NMP) solution be used as eluent.

Coloured composition of the invention contains the pigment polymer and polymerism chemical combination represented by aftermentioned (1) by general formula Object.

By being set as the composition, it is possible to provide light resistance, migrating property and the excellent coloured composition of flatness.

The reasons why can get such effect is still not clear, but be believed that aftermentioned (1) by general formula represented by pigment poly Body because n is bonded on the concatenating group of n valence containing the polymer chains of the repetitive unit with pigmentary structures, therefore with linear chain structure Pigment polymer is compared, and the mutual winding of polymer chain with pigmentary structures can be reduced.Thus, it is believed that pigment polymer is difficult With cohesion, the excellent film of flatness can get.In addition, it is believed that because pigmentary structures are fed in polymer chain, therefore pigment is difficult With diffusion, migrating property is also excellent.In addition, it is believed that the absorption property by the way that pigment polymer is made, with other molecules such as pigment It is promoted, easily causes intermolecular energy movement, thus light resistance is also excellent.

In addition, for example when using photoetching process to carry out pattern formation, can reduce the polymer chain with pigmentary structures that This winding, therefore the infiltration of developer solution can be made to become well, developing powder is fast, and development residue can also be made to be difficult to generate.Hereinafter, The present invention is described in detail.

<<by the pigment polymer represented by general formula (1)>>

Coloured composition of the invention contain by the following general formula (1) represented by pigment polymer (hereinafter, sometimes referred to simply as " pigment polymer (A) ").

Preferably there are maximum absorption wavelengths in the range of 400nm~800nm for pigment polymer (A).Of the invention In coloured composition, pigment polymer (A) is for example functioned as colorant.

P-(Q)_n…(1)

In general formula (1), P indicates the concatenating group of n valence,

N indicates 3~10 integer.

<<<concatenating group P>>>

In general formula (1), P indicates the concatenating group of n valence.

As the concatenating group of n valence, including include 1~100 carbon atoms, 0~10 nitrogen-atoms, 0~50 oxygen The base of atom, 1~200 hydrogen atoms and 0~20 sulphur atoms, can be unsubstituted, and can also further have substituent group.

The concatenating group of n valence represented by P includes preferably 1~60 carbon atoms, 0~10 nitrogen-atoms, 0~40 The base of a oxygen atom, 1~120 hydrogen atoms and 0~10 sulphur atoms.It more preferably include 1~50 carbon atoms, 0 A~10 nitrogen-atoms, 0~30 oxygen atoms, 1~100 hydrogen atoms and 0~7 sulphur atoms base.And then it is more excellent It is selected as comprising 1~40 carbon atoms, 0~8 nitrogen-atoms, 0~20 oxygen atoms, 1~80 hydrogen atoms and 0 The base of~5 sulphur atoms.

The concatenating group of n valence represented by P is preferably the concatenating group derived from polyalcohol.

In the present invention, it is preferably indicated by general formula (2) by the pigment polymer represented by general formula (1).

[changing 2]

In general formula (2), A¹Indicate the concatenating group of n valence,

R indicates hydrogen atom, alkyl or aryl,

C¹Indicate the concatenating group of singly-bound or divalent,

S indicates sulphur atom,

N indicates 3~10 integer.

Furthermore the structure of the following formula (2a) in addition to the Q in general formula (2) is equivalent to the concatenating group P in general formula (1).* it indicates With the binding site of Q.

[changing 3]

In general formula (2), A¹Indicate the concatenating group of n valence.

As the concatenating group of n valence, preferably comprising that can have aliphatic alkyl, the aromatic ring of oxygen atom on main chain The combined base of one or more of base and heterocycle.

As aliphatic alkyl, alkylidene, alkenylene can be enumerated.The carbon number of alkylidene is for example preferably 1~60, more preferably It is 1~30.The carbon number of alkenylene is for example preferably 1~60, more preferably 1~30.

As the aliphatic alkyl on main chain with oxygen atom, can enumerate by-(OR^x1)_m-、-(R^x1O)_mRepresented base. Aliphatic alkyl on main chain with oxygen atom can be straight chain, branch, cricoid any.Furthermore so-called main chain refers to connection The skeleton part of base does not include substituent group.

R^x1Indicate alkylidene or alkenylene.M indicates 1 or more integer, when m is 2 or more, m R^x1Can be identical, it can also It is different.

R^x1The carbon number of represented alkylidene is preferably 1~20, and more preferably 1~10, and then more preferably 1~5.Alkylene Base can be straight chain, branch, cricoid any.

R^x1The carbon number of represented alkenylene is preferably 2~20, and more preferably 2~10, and then more preferably 2~5.Sub- alkene Base can be straight chain, branch, cricoid any.

Aromatic series ring group can be monocycle, can also be polycyclic.As aromatic ring, for example, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus,Ring, Sanya phenyl ring, fluorenes ring, cyclohexyl biphenyl etc., preferably phenyl ring.

Heterocycle is preferably 5 member rings or 6 member rings.Heterocycle can be monocycle, can also be polycyclic.As contained in heterocycle Hetero atom, nitrogen-atoms, oxygen atom, sulphur atom can be illustrated.Preferably nitrogen-atoms.Heteroatomic quantity is preferably 1~3.As Heterocycle, such as cyanuric acid ring, triazine ring, oxane ring, pyrrole ring, furan nucleus, thiphene ring, imidazole ring, oxazole ring, thiophene can be enumerated Azoles ring, pyridine ring, pyridine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, different benzo furan Mutter ring, quinolizine ring, quinoline ring, phthalazines ring, naphthyridines ring, quinoxaline ring, quinoline oxazoline ring, isoquinolin ring, carbazole ring, phenanthridines ring, Acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, coffee dislike thiophene ring, phenthazine ring, coffee piperazine ring, preferably cyanuric acid Ring, triazine ring, oxane ring.

A¹The concatenating group of represented n valence preferably enumerate on main chain the alkyl that can have oxygen atom, aromatic series ring group, Can have on heterocycle, main chain can have in the alkyl of oxygen atom and the combination of aromatic series ring group, main chain the alkyl of oxygen atom with The combination etc. of heterocycle.

As A¹For can have on aromatic series ring group, heterocycle, main chain the combination of the alkyl of oxygen atom and aromatic series ring group, Or can have on main chain oxygen atom alkyl and heterocycle combination when concatenating group P (formula (2a)), such as can enumerate with Lower person.

[changing 4]

In formula, X indicates the alkyl that can have oxygen atom on main chain,

R indicates hydrogen atom, alkyl or aryl,

C¹Indicate the concatenating group of singly-bound or divalent,

S indicates sulphur atom,

N indicates 3 or more integer.

* the binding site with Q is indicated.

In general formula (2), B¹Indicate singly-bound ,-O- ,-S- ,-CO- ,-NR- ,-O₂C-、-CO₂,-NROC- or-CONR-, it is excellent It is selected as singly-bound ,-O- ,-CO- ,-O₂C-、-CO₂,-NROC- or-CONR-.

R indicates hydrogen atom, alkyl or aryl.

The carbon number of alkyl represented by R is preferably 1~30, and more preferably 1~10.Alkyl can be straight chain, branch, cricoid It is any.

The carbon number of aryl represented by R is preferably 6~30, and more preferably 6~12.

R is preferably hydrogen atom or alkyl, more preferably hydrogen atom.

In general formula (2), C¹Indicate the concatenating group of singly-bound or divalent.

As the concatenating group of divalent, preferably alkylidene, arlydene, oxyalkylene group, more preferably alkylidene or oxyalkylene Base.

Alkylidene, oxyalkylene group carbon number be preferably 1~30, more preferably 1~10.Alkyl, oxyalkylene group can for straight chain, It is branch, cricoid any.

The carbon number of arlydene is preferably 6~30, and more preferably 6~12.

The concrete example of the concatenating group of n valence represented by following presentation P.But in the present invention, not by these concrete examples Limitation.

[changing 5]

[changing 6]

[changing 7]

The concatenating group of n valence preferably described (P-1)~(P-8), (P-16)~(P-20), (P-22)~(P-32).

<<<polymer chain Q>>>

Polymer chain represented by Q indicates the polymer chain containing the repetitive unit with pigmentary structures, and n Q's has The average value of the number of the repetitive unit of pigmentary structures is two or more.The n contained in general formula (1) or general formula (2) Q, each described Q contain more than two repetitive units with pigmentary structures.Represented by general formula (1) or general formula (2) Pigment polymer contains 2n or more the repetitive unit with pigmentary structures.N Q can be identical, can also be different.

It is 2~20 that polymer chain represented by Q, which preferably has the average value of the repetitive unit of pigmentary structures, more excellent It is selected as 2~15, and then more preferably 2~10.

The average value of the number of repetitive unit with pigmentary structures can pass through nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) it finds out.Specifically, the repetition of the concatenating group of the n valence for example represented by by P and polymer chain Q The peak area ratio of unit, finds out the number of the repetitive unit in general formula (1).Secondly, making described value divided by n, thus can calculate The number of repetitive unit in polymer chain Q.

The weight average molecular weight of polymer chain Q is preferably 1,000~100,000, more preferably 1000~30000, special It You Xuanwei 1000~10000.

Pigmentary structures possessed by each repetitive unit can be identical pigmentary structures, can also be identical for skeleton, but substituent group, The different pigmentary structures such as central metal can also be the different pigmentary structures of skeleton.

In addition, cation, which can be located at polymer chain Q with anion, to be had when pigmentary structures have cation with anion The same intramolecular of some pigmentary structures, may be alternatively located at outside the molecule of pigmentary structures.Furthermore so-called same point in pigmentary structures There is cation and anion in sub, refer to the case where cation and anion are bonded via covalent bond.In addition, it is so-called There is anion outside the molecule of pigmentary structures, refer to that cation is not bonded with anion via covalent bond, and as other Compound there are the case where.Hereinafter, the extramolecular anion of pigmentary structures is also referred to as counter-anion.

As long as polymer chain represented by Q includes pigmentary structures, and not specially provided, it is preferably selected from (methyl) propylene One of acid system resin, phenylethylene resin series and (methyl) acrylic/styrene system resin.

Furthermore so-called (methyl) acrylic resin, refers to the resin for containing (methyl) acrylic resin as principal component. So-called (methyl) acrylic resin that contains refers in (methyl) acrylic resin as principal component, preferably contains 50 matter Measure % or more (methyl) acrylic resin, more preferably contain 60 mass % or more, particularly preferably containing 70 mass % with On.

In addition, so-called phenylethylene resin series, refer to the resin for containing styrene resin as principal component.It is so-called to contain benzene second Olefine resin refers in phenylethylene resin series as principal component, preferably the styrene resin containing 50 mass % or more, more excellent It is selected as containing 60 mass % or more, particularly preferably contains 70 mass % or more.

In addition, so-called (methyl) acrylic/styrene system resin, refers to containing (methyl) acrylic resin and styrene resin Resin of the rouge as principal component.So-called (methyl) acrylic resin and the styrene resin of containing refers to as principal component in (first Base) in acrylic/styrene system resin, preferably total (methyl) acrylic resin and styrene containing 50 mass % or more Resin more preferably contains 60 mass % or more, particularly preferably contains 70 mass % or more.

Hereinafter, polymer chain Q is described in detail.

<<<<skeleton structure of the repetitive unit with pigmentary structures>>>>

As the skeleton structure of the repetitive unit with pigmentary structures, and it is not specially provided, preferably by Japan Patent spy It opens shown in No. 2013-28764 0276~paragraph of paragraph 0304 by general formula (A), general formula (B) and general formula (C) institute table At least one of the Component units shown is as skeleton, or preferably by the pigment polymer represented by general formula (D).Japan Patent The record of special open 2013-28764 0276~paragraph of paragraph 0304 can be incorporated into present specification.

In the present invention, it is preferred to for containing by the repetitive unit represented by the following general formula (a1-1).

In addition, constituting the total preferred of the repetitive unit with pigmentary structures in all repetitive units of polymer chain Q For 5 moles of %~60 mole %, more preferably 10 moles of %~50 mole %, and then more preferably 20 moles of %~40 are rubbed You are %.

[changing 8]

In general formula (a1-1), Q¹Indicate the concatenating group of trivalent, L¹Indicate the concatenating group of singly-bound or divalent, D¹Indicate pigment knot Structure, " * " indicate the associative key with main chain.

In general formula (a1-1), Q¹Indicate the concatenating group of trivalent.Q¹To be formed by concatenating group by polymerization, and refers to and to be formed It is equivalent to the part that the repetitive unit of main chain is formed by using polymerization reaction.Furthermore become by the position represented by 2 " * " Repetitive unit.

As Q¹, as long as the concatenating group formed by the well known monomer that may be polymerized, then there is no particular restriction, especially Preferably by the concatenating group represented by following (XX-1)~following (XX-24), more preferably free (XX-1) and (XX-2) institute table (methyl) the acrylic acid series coupling chain that shows, by represented by (XX-10)~(XX-17) polystyrene coupling chain, by (XX-18) and (XX-19) and in ethylene base system coupling chain represented by (XX-24) it selects, and then preferably free (XX-1) and (XX-2) institute (methyl) the acrylic acid series coupling chain that indicates, by represented by (XX-10)~(XX-17) polystyrene coupling chain, by (XX-24) It is selected in represented ethylene base system coupling chain, and then more preferably by (methyl) acrylic acid represented by (XX-1) and (XX-2) It is coupling chain and by the polystyrene coupling chain represented by (XX-11).

(XX-1) in~(XX-24), the position and L represented by by * are indicated¹Connection.

Me indicates methyl.In addition, the R in (XX-18) and (XX-19) indicates the alkyl or phenyl of hydrogen atom, carbon number 1~5.

[changing 9]

[changing 10]

In general formula (a1-1), L¹Separately indicate the concatenating group of singly-bound or divalent.

As the concatenating group of divalent, indicate carbon number 1~30 be substituted or be unsubstituted alkylidene (such as methylene, Ethylidene, trimethylene, propylidene, butylidene etc.), arlydene (such as the sub- benzene for being substituted or being unsubstituted of carbon number 6~30 Base, naphthylene etc.), the heterocycle ,-CH=CH- ,-O- ,-the S- ,-C (=O)-,-CO that are substituted or are unsubstituted₂-、-NR-、- CONR-、-O₂C-、-SO-、-SO₂And these two or more is linked and the concatenating group that is formed.In addition, L¹For containing Have the composition of anion it is also preferred that.L¹More preferably singly-bound or alkylidene, and then more preferably singly-bound or-(CH₂)_n(n is 1~5 Integer).Herein, R separately indicates hydrogen atom, alkyl, aryl or heterocycle.

D¹Indicate the pigmentary structures for being originated from aftermentioned pigment compound.

<<<<pigmentary structures>>>>

As pigmentary structures, there is no particular restriction, can apply the various pigmentary structures comprising well known pigmentary structures.

About the specific pigment compound that can form pigmentary structures, in " brief guide of new edition dyestuff " (Synthetic Organic Chemistry association It can compile；Ball is kind, 1970), " Colour Index (Colour Index) " (Britain dyes worker and learns (The Society of Dyers and colourists)), " pigment handbook " (great river original etc. compile；Talk about society, 1986) etc. in it is on the books.

Such as the pigmentary structures etc. from following pigment can be enumerated, the pigment is selected from quinochrome (benzoquinones pigment, naphthoquinones Pigment, anthraquinone pigment, Anthrapyridone pigment etc.), carbon pigment (diarylmethanes pigment, triarylmethane pigment, xanthene color Element, acridine pigment etc.), quinone imines pigment (oxazines pigment, thiazine (thiazine) pigment etc.), azine (azine) pigment, poly- time Methyl pigment (oxonols pigment, merocyanine pigment, arlydene pigment, styryl pigment, anthocyanidin, the sour inner salt color in side Element, gram ketone pigment etc.), quinophthalone pigment, phthalocyanine dye, sub- phthalocyanine dye, purple cyclic ketones pigment, indigo pigment, thioindigo cyan Element, quinoline pigment, nitro pigment, nitroso pigment, two pyrroles's methylene pigments, azopigment and these metal complex are looked for Element.

Among these pigmentary structures, for dichroism, sunproof viewpoint, be preferably selected from triarylmethane pigment, Xanthene pigment, anthraquinone pigment, anthocyanidin, the sour inner salt pigment in side, quinophthalone pigment, phthalocyanine dye, sub- phthalocyanine dye, azo Pigmentary structures in pigment and two pyrroles's methylene pigments are more preferably selected from triarylmethane pigment, xanthene pigment, anthraquinone color In plain, the sour inner salt pigment in side, quinophthalone pigment, phthalocyanine dye, sub- phthalocyanine dye, azopigment and two pyrroles's methylene pigments Pigmentary structures, and then more preferably triarylmethane pigment, xanthene pigment.Color contained in polymer chain represented by Q Plain structure can be only one kind, can also be two or more.

Hereinafter, being specifically described to can be preferably used as pigmentary structures of the invention.

<<<<<triarylmethane pigment>>>>>

The preferred form of pigmentary structures in the present invention is with from triarylmethane pigment (triarylmethane chemical combination Object) part-structure person.Compound as triarylmethane pigment, represented by can enumerating by following formula (TP).So-called three virtue Methylmethane compound refers to that intramolecular has the general name of compound at the pigment position containing triarylmethane skeleton.

Formula (TP)

[changing 11]

In formula (TP), Rtp¹~Rtp⁴Separately indicate hydrogen atom, alkyl or aryl.Rtp⁵Indicate hydrogen atom, alkane Base, aryl or NRtp⁹Rtp¹⁰(Rtp⁹And Rtp¹⁰Indicate hydrogen atom, alkyl or aryl).Rtp⁶、Rtp⁷And Rtp⁸Indicate substituent group. A, b and c indicates 0~4 integer.When a, b and c are 2 or more, Rtp⁶、Rtp⁷And Rtp⁸Can be connected to each other and form ring.X^-Table Show anion structure.When there is no X^-When, Rtp¹~Rtp⁷At least one contain anion.

As Rtp¹~Rtp⁶, the preferably alkyl and phenyl of hydrogen atom, the straight chain of carbon number 1~5 or branch.Rtp⁵It is preferred that For hydrogen atom or NRtp⁹Rtp¹⁰, particularly preferably NRtp⁹Rtp¹⁰。Rtp⁹And Rtp¹⁰The preferably straight chain of hydrogen atom, carbon number 1~5 Or the alkyl or phenyl of branch.Rtp⁶、Rtp⁷And Rtp⁸Represented substituent group can be used in aftermentioned substituent group group A mono- Cited substituent group, in particular, the straight chain of preferably carbon number 1~5 or the alkyl of branch, the alkenyl of carbon number 1~5, carbon number 6~15 Aryl, carboxyl or sulfo group, the more preferably straight chain of carbon number 1~5 or the alkyl of branch, the alkenyl of carbon number 1~5, phenyl or carboxylic Base.In particular, Rtp⁶、Rtp⁸The preferably alkyl of carbon number 1~5, Rtp⁷Preferably (particularly preferably 2 adjacent alkenyls connect alkenyl Phenyl made of knot), phenyl or carboxyl.

A, b or c separately indicates 0~4 integer.In particular, it is preferably 0~2 that a and b, which is preferably respectively 0~1, c, Integer.

Work as Rtp¹~Rtp⁷At least one when containing anion, as anion, Rtp can be enumerated¹~Rtp⁷At least one A structure replaced through general formula (P).

General formula (P)

[changing 12]

In general formula (P), L indicates the concatenating group of singly-bound or divalent, X¹From selected from-SO₃ ^-、-COO^-、-PO₄ ^-, containing by following The base of structure represented by general formula (A1) and containing by being selected at least one of base of structure represented by the following general formula (A2) It selects.

General formula (A1)

[changing 13]

In general formula (A1), R¹And R²Separately expression-SO₂Or-CO-.

General formula (A2)

[changing 14]

In general formula (A2), R³Expression-SO₂Or-CO-.R⁴And R⁵Separately expression-SO₂,-CO- or-CN.

In general formula (P), L indicates the concatenating group of singly-bound or divalent.As the concatenating group of divalent, preferably expression-NR¹⁰-、- O-、-SO₂, fluorine substituted alkylene, fluorine substituted phenylene or the combined base comprising these.In particular, preferably including-NR¹⁰- With-SO₂And the combined base of fluorine substituted alkylene, the combined base comprising-O- and fluorine substituted phenylene or include-NR¹⁰- With-SO₂And the combined base of fluorine substituted phenylene.

In-NR¹⁰In, R¹⁰Indicate the alkyl of hydrogen atom or carbon number 1~5, 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 alkylenes Base is more preferably perfluorinated alkylidene.It as the concrete example of fluorine substituted alkylene, can enumerate: difluoro methylene, tetrafluoro ethylidene, six Fluorine propylidene etc..

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

In general formula (P), X¹For anion, it is preferably selected from-SO certainly₃ ^-、-COO^-, containing by the knot represented by general formula (A1) The base of structure and containing by being selected at least one of base of structure represented by general formula (A2).

It is preferably in the general formula (A1), in R containing the base by the structure represented by general formula (A1)¹And R²One of end There is fluorine to replace alkyl, more preferably R at end¹And R²One of directly with fluorine replace alkyl be bonded.The carbon number of fluorine substitution alkyl Preferably 1~10, more preferably 1~6, and then preferably 1~3, and then more preferably 1 or 2, particularly preferably 1.These alkyl More preferably perfluoroalkyl.Replace the concrete example of alkyl, preferably trifluoromethyl as fluorine.

It is preferably in the general formula (A2), in R containing the base by the structure represented by general formula (A2)³~R⁵It is at least any There is fluorine to replace alkyl, more preferably R for the end of person³~R⁵Both at least directly replace alkyl to be bonded with fluorine.In particular, Preferably in R³~R⁵At least two end have fluorine replace alkyl, more preferably R³~R⁵At least two directly and fluorine Alkyl is replaced to be bonded.Fluorine replaces the meaning of alkyl and contains person's phase by illustrated in the base of the structure represented by general formula (A1) Together, preferred range is also identical.

<<<<<xanthene pigment>>>>>

The preferred form of pigmentary structures in the present invention is to tie with the part for being originated from xanthene pigment (xanthene compound) Structure person.Xanthene compound as xanthene pigment, represented by can enumerating by following formula (J).

[changing 15]

In formula (J), R⁸¹、R⁸²、R⁸³And R⁸⁴Separately indicate the substituent group of hydrogen atom or monovalence, R⁸⁵Separately Indicate that the substituent group of monovalence, m indicate 0~5 integer.X^-Indicate counter-anion.When there is no X^-When, R⁸¹~R⁸⁵At least one It is a to contain anion.

R in formula (J)⁸¹~R⁸⁵Adoptable substituent group and substituent group cited in aftermentioned substituent group group A mono- It is identical.

R in formula (J)⁸¹With R⁸²、R⁸³With R⁸⁴And m be 2 or more when R⁸⁵It can separately mutually be bonded and shape each other At 5 yuan, 6 yuan or 7 yuan of saturated rings or 5 yuan, 6 yuan or 7 yuan of unsaturated ring.When the ring for being formed by 5 yuan, 6 yuan or 7 yuan For can be further substituted with base when, can also be by R⁸¹~R⁸⁵Illustrated in substituent group replace, taken when by more than two substituent groups Dai Shi, these substituent groups can be identical, can also be different.

R in the formula (J)⁸¹With R⁸²、R⁸³With R⁸⁴And m be 2 or more when R⁸⁵It is independently mutually bonded separately from each other And when forming 5 yuan, 6 yuan and 7 yuan of the saturated rings or 5 yuan, 6 yuan and 7 yuan of unsaturated ring without substituent group, as not 5 yuan, 6 yuan and 7 yuan of saturated rings or 5 yuan, 6 yuan and 7 yuan of unsaturated ring with substituent group, for example, can enumerate pyrrole ring, Furan nucleus, thiphene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrroles's phenazine ring, piperidine ring, cyclopentene ring, ring Hexene ring, phenyl ring, pyridine ring, pyridine ring, pyridazine ring, can preferably enumerate phenyl ring, pyridine ring.

As anion, the person can be enumerated.

In particular, preferably R⁸²And R⁸³For hydrogen atom or the alkyl that is substituted or is unsubstituted, R⁸¹And R⁸⁴To be substituted or The alkyl or phenyl being unsubstituted.In addition, R⁸⁵Preferably halogen atom, the alkyl of the straight chain of carbon number 1~5 or branch, sulfo group, sulphur Amide groups, carboxyl, amide groups, more preferably sulfo group, sulfoamido, carboxyl, amide groups.R⁸⁵It is preferably bonded to and connects with xanthene ring On the adjacency section of the carbon of knot.R⁸¹And R⁸⁴Phenyl possessed by substituent group be particularly preferably hydrogen atom, halogen atom, carbon number 1~ 5 straight chain or alkyl, sulfo group, sulfoamido, the carboxyl of branch.

Compound represented by formula (J) with xanthene skeleton can be synthesized using the method recorded in document.Specifically For, " Tet Lett (Tetrahedron Letters) " can be applied, 2003, vol.44, No.23, page 4355~the Page 4360；" tetrahedron (Tetrahedron) ", it is recorded in 2005, vol.61, No.12, page 3097~page 3106 etc. Method.

Work as X^-When indicating anion, record when aftermentioned counter-anion is different molecular can refer to.

In addition, when X is not present^-, and R⁸¹、R⁸²、R⁸³And R⁸⁴At least one when containing anion, can refer to anti-He Yin from Record when son is in same Component units.

Furthermore in pigmentary structures, cationic non-localized, therefore for example as shown below, it is present in nitrogen-atoms or xanthene On the carbon atom of ring.

[changing 16]

<<<<<anthraquinone pigment>>>>>

The preferred form of pigmentary structures in the present invention is with the part-structure person for being originated from anthraquinone pigment.As anthraquinone Pigment (anthraquinone compounds), preferably by the compound represented by the following general formula (AQ-1)~general formula (AQ-3).So-called anthraquinone Object is closed, refers to that intramolecular has the general name of compound at the pigment position containing anthraquinone skeleton.

[changing 17]

In general formula (AQ-1), A and B separately indicate amino, hydroxyl, alkoxy or hydrogen atom.Xqa indicates ORqa¹ Or NRqa²Rqa³。Rqa¹~Rqa³Separately indicate hydrogen atom, alkyl or aryl.Rq₁~Rq₄Indicate substituent group.Rq₁~ Rq₄Adoptable substituent group is identical as substituent group cited in aftermentioned substituent group group A mono-.Ra and Rb are separately Indicate hydrogen atom, alkyl or aryl.

In general formula (AQ-2), the meaning of C and D are identical as the A in general formula (AQ-1) and B.Xqb indicates ORqb¹Or NRqb²Rqb³。Rqb¹~Rqb³Separately indicate hydrogen atom, alkyl or aryl.Rq₅~Rq₈Indicate substituent group.Rq₅~Rq₈ Meaning and general formula (AQ-1) in Rq₁~Rq₄It is identical.The meaning of Rc in general formula (AQ-1) Ra or Rb it is identical.

In general formula (AQ-3), the meaning of E and F are identical as the A in general formula (AQ-1) and B.Xqc indicates ORqc¹Or NRqc²Rqc³。Rqc¹~Rqc³Separately indicate hydrogen atom, alkyl or aryl.Rq₉~Rq₁₂Meaning and general formula (AQ-1) In Rq_l~Rq₄It is identical.The meaning of Rd in general formula (AQ-1) Ra or Rb it is identical.

As the preferred range of general formula (AQ-1), general formula (AQ-2) and general formula (AQ-3), such as it can refer to Japan Patent 0045~paragraph of paragraph 0047 of special open 2013-29760 bulletin, content can be incorporated into present specification.

As anthraquinone pigment, such as it can refer to 0049~paragraph of paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0050, content can be incorporated into present specification.

<<<<<anthocyanidin>>>>>

The preferred form of pigmentary structures in the present invention is to tie with the part for being originated from anthocyanidin (cyanine compound) Structure person.As anthocyanidin, preferably by the compound (cyanine compound) represented by the following general formula (PM).In the present invention, So-called cyanine compound refers to that intramolecular has the general name of compound at the pigment position containing cyanine skeleton.

[changing 18]

In general formula (PM), ring Z1 and ring Z2 separately indicate the heterocycle that can have substituent group.L indicate 0 or more, 3 with Under integer.X^-Indicate anion.

As the preferred range of general formula (PM), such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0077~paragraph 0084, content can be incorporated into present specification.Furthermore at Japanese Patent Laid-Open 2013-29760 Any one hydrogen in 0077~paragraph of paragraph 0084 of bulletin in the concrete example of documented anthocyanidin, in anthocyanidin structure The R of atom and general formula (1)²It is bonded.

<<<<<side's acid inner salt pigment>>>>>

The preferred form of pigmentary structures in the present invention is with from the sour inner salt pigment in side (side's acid inner salt chemical combination Object) part-structure person.As the sour inner salt pigment in side, preferably by the compound represented by the following general formula (K) (in side's acid Salt compound).In the present invention, so-called side's acid inner salt compound refers to that intramolecular has containing the sour inner salt skeleton in side The general name of the compound at pigment position.

[changing 19]

In general formula (K), A and B separately indicate aryl or heterocycle.As aryl, preferably carbon number 6~48, more Preferably 6~24 aryl, such as phenyl, naphthalene can be enumerated etc..As heterocycle, the preferably heterocycle of five-membered ring or hexatomic ring Base, such as pyrrole radicals, imidazole radicals, pyrazolyl, thienyl, pyridyl group, pyrimidine radicals, pyridazinyl, triazol-1-yl, furans can be enumerated Base, thiadiazolyl group etc..

As the preferred range of general formula (K), such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0088~paragraph 0106, content can be incorporated into present specification.

As the concrete example of the sour inner salt pigment in side, such as it can refer to the section of Japanese Patent Laid-Open 2013-29760 bulletin Fall 0105.

<<<<<quinophthalone pigment>>>>>

The preferred form of pigmentary structures in the present invention is with the portion for being originated from quinophthalone pigment (quinophthalone compound) Separation structure person.As quinophthalone pigment, preferably by the compound (quinophthalone compound) represented by the following general formula (QP).At this In invention, so-called quinophthalone compound refers to that intramolecular has the general name of compound at the pigment position containing quinophthalone skeleton.

[changing 20]

In general formula (QP), Rqp₁~Rqp₆Separately indicate hydrogen atom or substituent group.Work as Rqp₁~Rqp₆At least two It is a be in contiguous bits when, can mutually be bonded and form ring, substituent group can further be had by being formed by ring above.

As the preferred range of general formula (QP), such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0110~paragraph 0114, content can be incorporated into present specification.

As the concrete example of quinophthalone pigment, such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0113 record.

<<<<<phthalocyanine dye>>>>>

The preferred form of pigmentary structures in the present invention is to tie with the part for being originated from phthalocyanine dye (phthalocyanine compound) Structure person.As phthalocyanine dye, it is however preferred to have the part of the compound (phthalocyanine compound) represented by being originated from by the following general formula (F) Structure person.In the present invention, so-called phthalocyanine compound refers to that intramolecular has the compound at the pigment position containing phthalocyanine frame General name.

[changing 21]

In general formula (F), M¹Indicate metal class, Z¹、Z²、Z³And Z⁴It separately represents to be formed containing former selected from hydrogen Atom group needed for 6 member rings that atom in son, carbon atom and nitrogen-atoms is constituted.

As the preferred range of general formula (F), such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0118~paragraph 0124, content can be incorporated into present specification.

As the concrete example of phthalocyanine dye, such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0123。

<<<<<sub- phthalocyanine dye>>>>>

The preferred form of pigmentary structures in the present invention is with the portion for being originated from sub- phthalocyanine dye (subphthalocyanine compounds) Separation structure person.As sub- phthalocyanine dye, preferably by the compound (subphthalocyanine compounds) represented by the following general formula (SP).At this In invention, so-called subphthalocyanine compounds refer to that intramolecular has the general name of compound at the pigment position containing sub- phthalocyanine frame.

[changing 22]

In general formula (SP), Z¹~Z¹²Separately indicate hydrogen atom, alkyl, aryl, hydroxyl, sulfydryl, amino, alcoxyl Base, aryloxy group, thioether group.X indicates anion.

As the preferred range of general formula (SP), such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0128~paragraph 0133, content can be incorporated into present specification.

As the concrete example of sub- phthalocyanine dye, such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0132 record.

<<<<<azopigment>>>>>

The preferred form of pigmentary structures in the present invention is to tie with the part for being originated from azopigment (azo-compound) Structure person.In the present invention, so-called azo-compound refers to that intramolecular has the total of the compound at the pigment position containing N=N base Claim.It can be suitable for selection from well known azopigment (for example, replacing azobenzene etc.) to apply as azopigment.For example, making For azopigment, record and the day of 0084~paragraph of paragraph 0134 of Japanese Patent Laid-Open 2013-41097 bulletin can refer to The record of 0029~paragraph of paragraph 0136 of this patent special open 2011-162760 bulletin, content can be incorporated into this explanation In book.

<<<<<two pyrroles's methylene pigments>>>>>

One of form of pigmentary structures of the invention is with the part-structure person for being originated from two pyrroles's methylene pigments.As Two pyrroles's methylene pigments, preferably two pyrroles's methylene compounds and from two pyrroles's methylene compounds and metal or metal Compound two pyrroles methylene metal complex compounds obtained.For example, can refer to Japan as two pyrroles's methylene pigments The record of 0033~paragraph of paragraph 0136 of open patent 2011-95732 bulletin, content, which can be incorporated into the application, to be illustrated In book.

The substituent group in following substituent group group A can also be used to replace the hydrogen in pigmentary structures in the pigmentary structures Atom.

(substituent group group A)

As the substituent group that pigmentary structures can have, can enumerate: halogen atom (such as fluorine atom, chlorine atom, bromine atom), Alkyl (the preferably straight chain of carbon number 1~48, branch or cricoid alkyl, the more preferably straight chain of carbon number 1~24, branch or Cricoid alkyl, for example, methyl, ethyl, propyl, isopropyl, butyl (preferably tert-butyl), amyl, hexyl, heptyl, octyl, 2- ethylhexyl, dodecyl, palmityl, cyclopropyl, cyclopenta, cyclohexyl, 1- norborny, 1- adamantyl), alkenyl it is (excellent Be selected as the alkenyl of carbon number 2~48, the more preferably alkenyl of carbon number 2~18, such as vinyl, allyl, 3- butene-1-yl), alkynes Base (preferably carbon number 2~20, more preferably carbon number 2~12, particularly preferably carbon number 2~8, such as propargyl, 3- penta can be enumerated Alkynyl etc.), it is aryl (the preferably aryl of carbon number 6~48, the more preferably aryl of carbon number 6~24, such as phenyl, naphthalene), miscellaneous Ring group (the preferably heterocycle of carbon number 1~32, the more preferably heterocycle of carbon number 1~18, for example, 2- thienyl, 4- pyridyl group, 2- furyl, 2- pyrimidine radicals, 1- pyridyl group, 2-[4-morpholinodithio base, 1- imidazole radicals, 1- pyrazolyl, benzotriazole -1- base), silane Base (the preferably silylation of carbon number 3~38, the more preferably silylation of carbon number 3~18, such as trimethylsilyl, triethyl group Silylation, tributyl silylation, t-butyldimethylsilyi, tertiary hexyl dimethylsilyl), hydroxyl, cyano, nitro, alkane Oxygroup (the preferably alkoxy of carbon number 1~48, the more preferably alkoxy of carbon number 1~24, such as methoxyl group, ethyoxyl, 1- fourth Oxygroup, 2- butoxy, isopropoxy, tert-butoxy, dodecyloxy, cycloalkyloxy, such as cyclopentyloxy, cyclohexyloxy), virtue Oxygroup (the preferably aryloxy group of carbon number 6~48, the more preferably aryloxy group of carbon number 6~24, such as phenoxy group, 1- naphthoxy), Heterocyclic oxy group (the preferably heterocyclic oxy group of carbon number 1~32, the more preferably heterocyclic oxy group of carbon number 1~18, such as 1- phenyl four Azoles -5- oxygroup, 2- tetrahydro-pyran oxy), siloxy (the preferably siloxy of carbon number 1~32, more preferably carbon number 1~ 18 siloxy, such as trimethyl silicane alkoxy, t-butyldimethyl silane oxygroup, diphenylmethylsilane oxygroup), acyl-oxygen Base (the preferably acyloxy of carbon number 2~48, the more preferably acyloxy of carbon number 2~24, such as acetoxyl group, pivaloyl Oxygroup, benzoyloxy, lauroyl oxygroup), alkoxy carbonyloxy group (the preferably alkoxy carbonyloxy group of carbon number 2~48, more preferably For the alkoxy carbonyloxy group of carbon number 2~24, such as ethyoxyl carbonyloxy group, tert-butoxy carbonyloxy group, cycloalkyloxy carbonyloxy group, such as Cyclohexyloxy carbonyl oxygen), aryloxy group carbonyloxy group (preferably the aryloxy group carbonyloxy group of carbon number 7~32, more preferably carbon number 7~24 Aryloxy group carbonyloxy group, such as phenoxy group carbonyloxy group), carbamoyloxy group (the preferably carbamoyloxy group of carbon number 1~48, it is more excellent It is selected as the carbamoyloxy group of carbon number 1~24, such as N, N- dimethyl carbamyl oxygroup, N- butyl carbamoyloxy group, N- phenylamino Formyloxy, N- ethyl, N-phenyl carbamoyloxy group), sulfamoyloxy (the preferably sulfamoyloxy of carbon number 1~32, it is more excellent Be selected as the sulfamoyloxy of carbon number 1~24, such as N, N- diethyl amino sulfonyloxy, N- propyl sulfamoyloxy), alkyl sulfonyl Oxygroup (the preferably alkylsulfonyloxy of carbon number 1~38, the more preferably alkylsulfonyloxy of carbon number 1~24, such as methyl sulphur Acyloxy, palmityl sulfonyloxy, cyclohexylsulfonyl oxygroup), aryl-sulfonyl oxygen (the preferably arylsulfonyl of carbon number 6~32 Oxygroup, the more preferably aryl-sulfonyl oxygen of carbon number 6~24, such as phenylsulfonyloxy group), acyl group (preferably carbon number 1~48 Acyl group, the more preferably acyl group of carbon number 1~24, such as formoxyl, acetyl group, pivaloyl group, benzoyl, myristoyl Base, cyclohexanoyl), alkoxy carbonyl (the preferably alkoxy carbonyl of carbon number 2~48, the more preferably alkoxy of carbon number 2~24 Carbonyl, such as methoxycarbonyl, ethoxy carbonyl, octadecane epoxide carbonyl, cyclohexyloxy carbonyl, 2,6- di-t-butyl -4- first Basic ring hexyloxy carbonyl), aryloxycarbonyl (the preferably aryloxycarbonyl of carbon number 7~32, the more preferably virtue of carbon number 7~24 Epoxide carbonyl, such as phenyloxycarbonyl), carbamyl (the preferably carbamyl of carbon number 1~48, more preferably carbon number 1~24 Carbamyl, such as carbamyl, N, N- diethylcarbamoyl, N- ethyl-N- octyl carbamyl, N, N- dibutylamine Formoxyl, N- propyl carbamyl, N- phenylcarbamoyl, N- Methyl-N-phenyl carbamyl, N, N- dicyclohexyl carbamyl Base), amino (the preferably amino below of carbon number 32, the more preferably amino below of carbon number 24, such as amino, methylamino, N, N- dibutylamino, tetradecyl amino, 2- ethylhexylamino, Cyclohexylamino), anilino- (the preferably benzene of carbon number 6~32 Amido, more preferably 6~24 anilino-, such as anilino-, methylphenylamine base), heterocyclic amino group (preferably carbon number 1~32 Heterocyclic amino group, more preferably 1~18 heterocyclic amino group, such as 4- pyridinylamino), carbonamido (preferably carbon number 2~48 Carbonamido, more preferably 2~24 carbonamido, such as acetamido, benzamido, myristoyl amido, front three Base acetyl group amide groups, hexamethylene alkyl amide), urea groups (the preferably urea groups of carbon number 1~32, the more preferably urea of carbon number 1~24 Base, such as urea groups, N, N- dimethyl urea groups, N- phenyl urea groups), imide (the preferably imide below of carbon number 36, more The preferably imide below of carbon number 24, such as N- succinimido, N phlhalimide base), alkoxy carbonyl Amino (the preferably alkoxycarbonyl amino of carbon number 2~48, the more preferably alkoxycarbonyl amino of carbon number 2~24, such as first Epoxide carbonyl amino, ethoxycarbonylamino group, tertbutyloxycarbonylamino, octadecane epoxide carbonylamino, cyclohexyloxy carbonyl Amino),

Aryloxycarbonylamino (the preferably aryloxycarbonylamino of carbon number 7~32, the more preferably virtue of carbon number 7~24 Epoxide carbonyl amino, such as phenoxycarbonylamino), sulfoamido (the preferably sulfoamido of carbon number 1~48, more preferably The sulfoamido of carbon number 1~24, for example, sulfonyl methane amido, butane sulfoamido, benzene sulfonamido, hexadecane sulfoamido, Hexamethylene sulfoamido), sulphamoylamino (the preferably sulphamoylamino of carbon number 1~48, more preferably carbon number 1~24 Sulphamoylamino, such as N, N- dipropyl sulphamoylamino, N- ethyl-N- dodecyl sulphamoylamino), azo group (the preferably azo group of carbon number 1~32, the more preferably azo group of carbon number 1~24, such as phenylazo, 3- pyrazolyl are even Nitrogen base), alkylthio group (the preferably alkylthio group of carbon number 1~48, the more preferably alkylthio group of carbon number 1~24, such as methyl mercapto, second Sulfenyl, pungent sulfenyl, cyclohexylthio), arylthio (the preferably arylthio of carbon number 6~48, the more preferably fragrant sulphur of carbon number 6~24 Base, such as thiophenyl), heterocyclethio (the preferably heterocyclethio of carbon number 1~32, more preferably the heterocycle sulphur of carbon number 1~18 Base, such as 2-[4-morpholinodithio sulfenyl, 2- pyridine thio, 1- phenyltetrazole sulfenyl), alkyl sulphinyl (preferably carbon number 1~32 Alkyl sulphinyl, the more preferably alkyl sulphinyl of carbon number 1~24, such as dodecane sulfinyl), aryl sulfenyl Base (the preferably aryl sulfonyl kia of carbon number 6~32, the more preferably aryl sulfonyl kia of carbon number 6~24, such as phenyl Asia sulphur Acyl group), alkyl sulphonyl (the preferably alkyl sulphonyl of carbon number 1~48, the more preferably alkyl sulphonyl of carbon number 1~24, example As methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, butyl sulfonyl, isopropelsulfonyl, 2- ethylhexyl sulfonyl, Palmityl sulfonyl, octyl sulfonyl, cyclohexylsulfonyl), aryl sulfonyl (the preferably aryl sulfonyl of carbon number 6~48, The more preferably aryl sulfonyl of carbon number 6~24, such as phenyl sulfonyl, 1- Naphthylsulfonyl), sulfamoyl (preferably carbon The sulfamoyl below of number 32, the more preferably sulfamoyl below of carbon number 24, such as sulfamoyl, N, N- dipropyl sulfonamides Base, N- ethyl-N- dodecyl sulfamoyl, N- ethyl, N-phenyl sulfamoyl, N- cyclohexylsulfamoyl), sulfo group, phosphono Base (the preferably phosphono of carbon number 1~32, the more preferably phosphono of carbon number 1~24, such as phenoxy group phosphono, octyloxy Phosphono, Phenylphosphine acyl group), sub- phosphonamino (the preferably sub- phosphonamino of carbon number 1~32, more preferably carbon number 1~ 24 sub- phosphonamino, such as diethoxy Asia phosphonamino, two octyloxy Asia phosphonaminos), alkoxy carbonyloxy group (preferably alkoxy carbonyloxy group of carbon number 5~30, more preferably the alkoxy carbonyloxy group of carbon number 5~10) etc..

These substituent groups can be further substituted.In addition, when with more than two substituent groups, it can be identical, it can also not Together.In addition, can also be interconnected in the conceived case and form ring.

Details see also such as Japanese Patent Laid-Open 2013-29760 bulletin 0027~paragraph of paragraph 0038, Its content can be incorporated into present specification.

<<<<counter-anion>>>>

When pigmentary structures include cation and counter-anion, as counter-anion, there is no particular restriction, but just resistance to For hot viewpoint, the preferably anion of non-nucleophilic.As the counter-anion of non-nucleophilic, preferably Japan Patent Documented well known non-nucleophilic anion during the paragraph 0075 of special open 2007-310315 bulletin is equal.Herein, so-called non- Nucleophilicity refers to the property that will not carry out nucleophillic attack to pigment due to heating.

As counter-anion, be preferably selected from azochlorosulfonate acid anion, carboxylate anion, sulfonyl acid imide yin from Sub, bis- (alkyl sulphonyl) imide anions, three (alkyl sulphonyl) methide anions, carboxylate anion, four virtues Ylboronic acid salt anionic ,-CON^-CO-、-CON^-SO₂-、BF₄ ^-、PF₆ ^-、SbF₆ ^-、B^-(CN)₃OCH₃At least one of.More preferably For selected from azochlorosulfonate acid anion, sulfonyl imide anion, bis- (alkyl sulphonyl) imide anions, three (alkyl sulfonyls Base) methide anion, carboxylate anion, four aryl boric acid salt anionics, BF₄ ^-、PF₆ ^-And SbF₆ ^-In at least one Kind.

Among these, as counter-anion, represented by more preferably having by following (AN-1)~following (AN-5) The non-nucleophilic anion of structure.

[changing 23]

In formula (AN-1), X¹And X²Separately indicate the alkyl of fluorine atom or the carbon number 1~10 with fluorine atom.X¹ And X²It can mutually be bonded and form ring.

X¹And X²Separately indicate the alkyl of fluorine atom or the carbon number 1~10 with fluorine atom, preferably fluorine atom or The alkyl of carbon number 1~10 with fluorine atom, the more preferably perfluoroalkyl of carbon number 1~10, and then more preferably carbon number 1~4 Perfluoroalkyl, particularly preferably trifluoromethyl.

[changing 24]

In formula (AN-2), X³、X⁴And X⁵Separately indicate the alkyl with fluorine atom of fluorine atom or carbon number 1~10.

X³、X⁴And X⁵Independently, meaning and X¹And X²Identical, the meaning of preferred range is also identical.

[changing 25]

X⁶-SO₃ ^-

(AN-3)

In formula (AN-3), X⁶Indicate the alkyl with fluorine atom of carbon number 1~10.

X⁶The preferably perfluoroalkyl of carbon number 1~10, the more preferably perfluoroalkyl of carbon number 1~4.

[changing 26]

(AN-4)

In formula (AN-4), X⁷Indicate the alkylidene with fluorine atom of carbon number 1~10.

X⁷The preferably perfluorinated alkylidene of carbon number 1~10, the more preferably perfluorinated alkylidene of carbon number 1~4.

[changing 27]

In formula (AN-5), Ar¹、Ar²、Ar³And Ar⁴Separately indicate aryl.

Ar¹、Ar²、Ar³And Ar⁴It is preferably separately the aryl of carbon number 6~20, more preferably carbon number 6~14 Aryl, and then the aryl of more preferably carbon number 6~10.

Ar¹、Ar²、Ar³And Ar⁴Represented aryl can have substituent group.When with substituent group, halogen original can be enumerated Son, alkyl, aryl, alkoxy, carbonyl, carbonyloxy group, carbamyl, sulfo group, sulfoamido, nitro etc., preferably halogen atom And alkyl, more preferably fluorine atom, alkyl, and then the perfluoroalkyl of more preferably fluorine atom, carbon number 1~4.

Ar¹、Ar²、Ar³And Ar⁴It is more preferably separately with halogen atom and/or to contain the alkane of halogen atom The phenyl of base, and then the more preferably phenyl with fluorine atom and/or the alkyl containing fluorine atom.

In addition, the counter-anion of non-nucleophilic is preferably-B (CN)_n1(OR^a)_4-n1(R^aIndicate carbon number 1~10 alkyl or The aryl of carbon number 6~10, n1 indicate 1~4 integer).The R of alkyl as carbon number 1~10^aThe preferably alkane of carbon number 1~6 Base, the more preferably alkyl of carbon number 1~4.The R of aryl as carbon number 6~10^aPreferably phenyl, naphthalene.

N1 is preferably 1~3, and more preferably 1~2.

In turn, in addition the counter-anion of non-nucleophilic is preferably-PF₆R^P _(6-n2) ^-(R^PIndicate the alkyl fluoride of carbon number 1~10 Base, n2 indicate 1~6 integer).R^PThe preferably alkyl with fluorine atom of carbon number 1~6, the more preferably tool of carbon number 1~4 There are the alkyl of fluorine atom, and then the perfluoroalkyl of more preferably carbon number 1~3.

N2 is preferably 1~4 integer, and more preferably 1 or 2.

The quality of every 1 molecule of non-nucleophilic counter-anion is preferably 100~1,000, more preferably 200~500.

Pigment polymer (A) can only contain a kind of non-nucleophilic counter-anion, can also contain two or more.

Hereinafter, indicating the concrete example of the counter-anion of non-nucleophilic, but the present invention is not limited to this.

[changing 28]

[changing 29]

[changing 30]

[changing 31]

Following presentation can be preferably used as the concrete example of the repetitive unit with pigmentary structures of the invention.The present invention is certain It is not limited to these concrete examples.

[changing 32]

[changing 33]

[changing 34]

<<<<other things answer unit>>>>

Except it is described with the repetitive unit of pigmentary structures in addition to, polymer chain Q can also contain other repetitive units.Other are heavy Multiple unit can contain the functional groups such as polymerism base, acidic group.It can be free of functional group.Preferably containing selected from the repetition with acidic group One or more of unit and the repetitive unit with polymerism base, more preferably containing the repetitive unit with acidic group.

As polymerism base, the well known polymerism base that can be crosslinked by free radical, acid, heat can be used, such as The base containing ethylene unsaturated bond, cyclic ether group (epoxy group, oxetanyl), methylol etc. can be enumerated, is preferably contained There are the base of ethylene unsaturated bond, more preferably (methyl) acryloyl group.(methyl) acryloyl group can for example make (methyl) propylene Acid glycidyl ester and (methyl) acrylic acid 3,4- epoxy group-cyclohexylmethyl are reacted to import.

All repetitive units when polymer chain Q contains the repetitive unit with polymerism base, relative to polymer chain Q 100 moles, such as preferably 5 moles~50 moles of the ratio of the repetitive unit with polymerism base, more preferably 10 moles~ 40 moles.

As acidic group, carboxyl, sulfonic group, phosphate can be illustrated.Acidic group can also contain two or more only containing one kind.

All repetitive units 100 when polymer chain Q contains the repetitive unit with acidic group, relative to polymer chain Q Mole, the ratio of the repetitive unit with acidic group is for example preferably 5 moles~50 moles, more preferably 10 moles~40 moles.

As other functional groups, the base for the duplicate alkylene oxide group chain being unsubstituted comprising 2~20, lactone can be enumerated The development accelarations base such as base, anhydride group, amide groups, cyano, chain alkyl and cyclic alkyl, aralkyl, aryl, polyalkylene oxide base, The hydrophilic and hydrophobics such as hydroxyl, maleimide base, amino adjust base etc., can be suitable for importing.

In the base for the duplicate alkylene oxide group chain being unsubstituted comprising 2~20, the repeat number of alkylene oxide group chain is excellent It is selected as 2~10, more preferably 2~15, and then more preferably 2~10.1 alkylene oxide group chain is by-(CH₂)_nO- It indicating, n is integer, and n is preferably 1~10, more preferably 1~5, and then more preferably 2 or 3.

Indicate the concrete example of other repetitive units, but the present invention is not limited to this.

[changing 35]

[changing 36]

[changing 37]

<<<polymer chain without pigmentary structures>>>

Pigment polymer (A) can also have the polymer chain without pigmentary structures.

As the polymer chain for being free of pigmentary structures, institute in other repetitive units comprising the polymer chain Q can be enumerated The polymer chain of the repetitive unit of explanation.

<<the various properties of pigment polymer (A)>>

The weight average molecular weight of pigment polymer (A) is preferably 1000~100000.Lower limit is for example more preferably 3000 More than, and then preferably 4000 or more, and then more preferably 5000 or more.The upper limit is more preferably 50000 hereinafter, more preferably 20000 hereinafter, be more preferably 15000 or less in turn.If weight average molecular weight is the range, migrating property is better.Into And developability is promoted, and can be further reduced the generation of development residue.

The acid value of pigment polymer (A) is preferably 10mgKOH/g or more.Lower limit is more preferably 15mgKOH/g or more, in turn More preferably 20mgKOH/g or more.The upper limit is more preferably 200mgKOH/g hereinafter, particularly preferably 150mgKOH/g or less.If Acid value is 10mgKOH/g or more, then developability is promoted, and can be further reduced the generation of development residue.

The method etc. that the measuring method of the ratio absorbance of pigment polymer (A) can be for example listed below: use is for pigment Polymer (A) has sufficient deliquescent solvent, adjusts in such a way that the maximum absorbance in 400nm~800nm becomes 1.0 The concentration of solution containing pigment polymer (A), and the solution is measured at 25 DEG C using the unit that optical path length is 1cm Absorbance.Solvent when measuring than absorbance can be suitable for having sufficient dissolubility person using for pigment polymer (A).As Preferred solvent can be enumerated: tetrahydrofuran, methanol, isopropanol, dimethyl sulfoxide, acetonitrile, ethyl acetate, hexane, toluene, water, The concentrated sulfuric acid, methanesulfonic acid etc..Tetrahydrofuran is utilized when tetrahydrofuran has sufficient dissolubility.

In maximum absorption wavelength in 400nm~800nm by the ratio absorbance represented by following formula (A λ) be preferably 5 with On, more preferably 10 or more, and then more preferably 20 or more, particularly preferably 30 or more.It, can if being 5 or more than absorbance Suitably it is used as colorant.

E=A/ (c × 1) ... (A λ)

A indicates the absorbance in the maximum absorption wavelength in 400nm~800nm,

L indicates the element length that unit is indicated by cm,

Pigment polymer (A) is preferably dyestuff.So-called dyestuff refers to have tangible solubility in water or organic solvent Pigment, the organic solvent solubility dyestuff being particularly preferably dissolved in organic solvent below.

As organic solvent, esters (such as 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, lactic acid second can be enumerated Ester, butyl acetate, 3- methoxy methyl propionate etc.), ethers (such as methylcellosolve acetate, ethyl cellosolve acetate, third Glycol monomethyl ether, propylene glycol methyl ether acetate etc.), ketone (methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone etc.), fragrance Race's hydro carbons (such as toluene, dimethylbenzene etc.) preferably dissolves the 1 mass % of mass %~50, more preferably for these organic solvents To dissolve the 5 mass % of mass %~40,10 mass of mass %~30 % are particularly preferably dissolved.By within the said range, When coloured composition of the invention to be applied to the production of chromatic filter etc., coating planar becomes suitable, in addition, can be into one Step reduction concentration decline as caused by the dissolution after being coated with other colors.

In coloured composition of the invention, can be used alone a kind of pigment polymer (A), can also and with two or more.

The content of pigment polymer (A) in coloured composition of the invention is (excellent with other aftermentioned pigments in consideration Be selected as pigment) etc. containing ratio after set.

As the mass ratio (pigment polymer (A)/pigment) of the pigment polymer relative to pigment, preferably 0.1~5, More preferably 0.2~2, and then more preferably 0.3~1.

Relative to the total solid content in coloured composition, pigment polymer (A) in coloured composition of the invention Content is preferably the 1.0 mass % of mass %~50, more preferably the 5.0 mass % of mass %~30, particularly preferably 10 mass % ~25 mass %.

<<synthetic method of pigment polymer (A)>>

By the manufacturing method of the pigment polymer represented by the general formula (1), there is no particular restriction, but can be by making one point Multi-functional thiol's compound with 3~10 mercaptos in son and the change with pigmentary structures and radically polymerizable group It closes object and carries out the method for free radical polymerization to manufacture.Hereinafter, by the compound with pigmentary structures and radically polymerizable group Referred to as " free-radical polymerised pigment compound ".

In free-radical polymerised pigment compound, as pigmentary structures, the person can be enumerated.In free-radical polymerised color In plain compound, as radically polymerizable group, vinyl, (methyl) allyl, (methyl) acryloyl group etc. can be enumerated and contained The base of ethylene unsaturated bond.

More specifically, compound represented by preferably making by general formula (3) and free-radical polymerised pigment compound into The method of row free radical polymerization.

p⁰-(SH)_n…(3)

In general formula (3), P⁰Indicate the concatenating group of n valence,

SH indicates mercapto,

N indicates 3~10 integer.

In general formula (3), P⁰Including comprising 1~100 carbon atoms, 0~10 nitrogen-atoms, 0~50 oxygen atoms, The base of 1~200 hydrogen atoms and 0~20 sulphur atoms, can be unsubstituted, and can also further have substituent group.

P⁰The concatenating group of represented n valence preferably include 1~60 carbon atoms, 0~10 nitrogen-atoms, 0~ The base of 40 oxygen atoms, 1~120 hydrogen atoms and 0~10 sulphur atoms.It more preferably include 1~50 carbon originals The base of son, 0~10 nitrogen-atoms, 0~30 oxygen atoms, 1~100 hydrogen atoms and 0~7 sulphur atoms.In turn More preferably comprising 1~40 carbon atoms, 0~8 nitrogen-atoms, 0~20 oxygen atoms, 1~80 hydrogen atoms and The base of 0~5 sulphur atoms.

P⁰The concatenating group of represented n valence is preferably the concatenating group derived from polyalcohol.

By the compound represented by general formula (3) be preferably by general formula (4) represented by compound.

A⁰-(B⁰-C⁰-SH)_n…(4)

In general formula (4), A⁰Indicate the concatenating group of n valence,

B⁰Indicate singly-bound ,-O- ,-S- ,-CO- ,-NR- ,-O₂C-、-CO₂,-NROC- or-CONR-,

R indicates hydrogen atom, alkyl or aryl,

C⁰Indicate the concatenating group of singly-bound or divalent,

SH indicates mercapto,

N indicates 3~10 integer.

A in general formula (4)⁰、B⁰And C⁰Meaning respectively with the A in mutual-through type (2)¹、B¹And C¹Illustrated range is identical, Preferred form is also identical.

As the concrete example by the compound represented by general formula (3), compound below can be enumerated.

[changing 38]

[changing 39]

[changing 40]

Among described, with regard to raw material it is acquired, synthesis easiness, for the deliquescent viewpoint of various solvents, Particularly preferred compound is preferably (SH-1)~(SH-8), (SH-16)~(SH-20), (SH-22)~(SH-32).

The free radical polymerization of multi-functional thiol's compound and free-radical polymerised pigment compound is for example using following Method and obtain: make multi-functional thiol's compound and free-radical polymerised pigment compound be dissolved in solvent appropriate, and to Free-radical generating agent is wherein added, the method (mercaptan-ene reaction method) of addition is then carried out at about 50 DEG C~100 DEG C.

As the example of solvent appropriate used in mercaptan-ene reaction method, multi-functional thiol's compound can correspond to And free-radical polymerised pigment compound dissolubility and arbitrarily select.

Such as it can enumerate: methanol, ethyl alcohol, propyl alcohol, isopropanol, 1- methoxy-2-propanol, 1- methoxyl group -2- propyl-acetic acid Ester, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methoxypropylacetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydro Furans, dimethylformamide, chloroform, toluene.These solvents can also be use mixing two or more.

In addition, as free-radical generating agent, it is bis- (isobutyronitrile) using such as 2,2 '-azos (Azobisisobutyronitrile, AIBN), 2,2 '-azos pair-(2,4 '-methyl pentane nitrile), 2,2 '-azobisisobutylonitriles acid The azo-compound of dimethyl ester, such as the peroxide of benzoyl peroxide, and the persulfate of such as potassium peroxydisulfate, ammonium persulfate Deng.

<<polymerizable compound>>

Coloured composition of the invention contains polymerizable compound.As polymerizable compound, can be used can pass through freedom Base, acid, heat and the well known compound being crosslinked.Such as it can enumerate containing base, cyclic ether with ethylene unsaturated bond The compound of (epoxy group, oxetanes) base, methylol etc..As the base with ethylene unsaturated bond, ethylene can be enumerated Base, (methyl) allyl, (methyl) acryloyl group etc..In the present invention, polymerizable compound is preferably trifunctional~six functions (methyl) acrylate compounds.

Polymerizable compound may be, for example, monomer, prepolymer (i.e. dimer, tripolymer and oligomer) or these mixing The chemical forms such as object and these polymer it is any.

As monomer, the example of prepolymer, can enumerate unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, Crotonic acid, iso-crotonic acid, maleic acid etc.) or its esters, amides and these polymer, preferably unsaturated carboxylic The amides of acid and the ester of aliphatic polybasic alcoholic compound and unsaturated carboxylic acid and aliphatic polybasic amine compounds and these Polymer.In addition, can also properly use esters of unsaturated carboxylic acids with the nucleophilic substitutions base such as hydroxyl, amino, sulfydryl or Amides, the addition reaction with simple function or polyfunctional isocyanate's class or epoxies, or with simple function or polyfunctional Dehydration condensation object of carboxylic acid etc..In addition, the unsaturated carboxylic acid with electrophilicities substituent groups such as isocyanate group, epoxy groups Ester or amides and simple function or polyfunctional alcohols, amine, thio-alcohol reactant, there is halogen or tosyloxy etc. The esters of unsaturated carboxylic acids or amides of detachment substituent group and simple function or polyfunctional alcohols, amine, thio-alcohol reactant Also it is suitable for.In addition, it is possible to use be substituted for the vinyl benzenes such as unsaturated phosphonic acids, styrene derivative, vinyl ethers, allyl ether Deng heterogeneous compound group replace the unsaturated carboxylic acid.

As these specific compound, in the present invention, Japanese Patent Laid-Open 2009- can also be properly used Documented compound in the paragraph [0095] of No. 288705 bulletins~paragraph [0108].

In addition, polymerizable compound is to have containing the more than one base with ethylene unsaturated bond and under normal pressure Have the compound of 100 DEG C or more of boiling point it is also preferred that.As the example of the compound, such as it can refer to Japanese Patent Laid-Open 0254~paragraph of paragraph of the paragraph 0227 of 2013-29760 bulletin, Japanese Patent Laid-Open 2008-292970 bulletin Documented compound in 0257, content can be incorporated into present specification.

Polymerizable compound is preferably that (commercially available product is Ka Yala get (KAYARAD) D- to dipentaerythritol triacrylate 330；NIPPON PHARMACEUTICAL CO., LTD manufacture), dipentaerythritol tetraacrylate (commercially available product be Ka Yala get (KAYARAD) D-320；NIPPON PHARMACEUTICAL CO., LTD manufacture), dipentaerythritol five (methyl) acrylate (commercially available product Ka Yala get (KAYARAD)D-310；NIPPON PHARMACEUTICAL CO., LTD's manufacture), (commercially available product is dipentaerythritol six (methyl) acrylate Ka Yala get (KAYARAD) DPHA；NIPPON PHARMACEUTICAL CO., LTD's manufacture, A-DPH-12E；The manufacture of chemical company, the village Xin Zhong), And structure of these (methyl) acryloyl group between ethylene glycol, diol residues is (for example, by Sartomer (Sartomer) institute, company commercially available SR454, SR499).These oligomer type can also be used.Following presentation preferably polymerize The form of property compound.

Polymerizable compound can also have the acidic groups such as carboxyl, sulfonic group, phosphate.As the polymerism chemical combination with acidic group The ester of object, preferably aliphatic polyhydroxy compound and unsaturated carboxylic acid more preferably makes aliphatic polyhydroxy compound not The hydroxyl of reaction is reacted and the ester with acidic group with non-aromatic carboxylic acid anhydrides, particularly preferably in the ester, aliphatic Polyol is pentaerythrite and/or dipentaerythritol person.As commercially available product, such as it can enumerate and be synthetically produced as East Asia Modified by polyacid acrylate oligomers M-510, M-520 etc..

The preferred acid value of polymerizable compound with acidic group is 0.1mgKOH/g~40mgKOH/g, particularly preferably 5mgKOH/g~30mgKOH/g.If the acid value of polymerizable compound is 0.1mgKOH/g or more, the dissolution characteristics that develop are good, It is if 40mgKOH/g hereinafter, then advantageous in terms of manufacture or processing.In turn, photopolymerization is functional and hardenability is excellent.

As polymerizable compound, has and be originated from cyclic ester and (such as caprolactone, valerolactone can be enumerated etc., particularly preferably Caprolactone) the compound of structure be also preferred form.

As the compound with the structure from caprolactone, as long as intramolecular has the structure from caprolactone, simultaneously It is not particularly limited, such as can enumerate by by trimethylolethane or two-trimethylolethanes, trimethylolpropane, two-three hydroxyls The polyalcohols such as methylpropane, pentaerythrite, dipentaerythritol, tripentaerythritol, glycerol, two glycerol, trimethylol melamine The modified multifunctional (methyl) acrylate of 6-caprolactone for being esterified and being obtained with (methyl) acrylic acid and 6-caprolactone.Its In, preferably by the following general formula (Z-1) represented by have from caprolactone structure compound.

[changing 41]

In general formula (Z-1), 6 R be by the following general formula (Z-2) represented by base or 6 R in 1~5 be By the base represented by the following general formula (Z-2), remaining as by the base represented by the following general formula (Z-3).

[changing 42]

In general formula (Z-2), R¹Indicate that hydrogen atom or methyl, m indicate that 1 or 2 number, " * " indicate associative key.

[changing 43]

In general formula (Z-3), R¹Indicate that hydrogen atom or methyl, " * " indicate associative key.

Be originated from caprolactone structure polymerizable compound for example as Ka Yala get (KAYARAD) DPCA series and It is commercially available by Japanese chemical drug (share), it can enumerate: DPCA-20 (in the formula (Z-1)~formula (Z-3), m=1, by formula (Z-2) institute table Quantity=2 of the base shown, R¹Be the compound of hydrogen atom), DPCA-30 (in the formula (Z-1)~formula (Z-3), m=1, by (Z-2) quantity=3 of the base represented by, R¹Be the compound of hydrogen atom), the DPCA-60 (formula (Z-1)~formula (Z-3) In, m=1, quantity=6 by the base represented by formula (Z-2), R¹Be the compound of hydrogen atom), the DPCA-120 (formula (Z- 1) in~formula (Z-3), m=2, quantity=6 by the base represented by formula (Z-2), R¹It is the compound of hydrogen atom) etc..

Polymerizable compound can also be used by the following general formula (Z-4) or general formula (Z-5) represented by compound.

[changing 44]

In general formula (Z-4) and general formula (Z-5), E separately indicates-((CH₂)_yCH₂O)-or-((CH₂)_yCH(CH₃) O)-, y separately indicates that 0~10 integer, X separately indicate (methyl) acryloyl group, hydrogen atom or carboxyl.

In general formula (Z-4), (methyl) acryloyl group adds up to 3 or 4, m separately indicate 0~10 it is whole Number, the integer for adding up to 0~40 of each m.Wherein, when each m is when adding up to 0, any of X is carboxyl.

In general formula (Z-5), (methyl) acryloyl group adds up to 5 or 6, n separately indicate 0~10 it is whole Number, the integer for adding up to 0~60 of each n.Wherein, when each n is when adding up to 0, any of X is carboxyl.

In general formula (Z-4), m is preferably 0~6 integer, more preferably 0~4 integer.

In addition, total preferably 2~40 integer of each m, more preferably 2~16 integer, particularly preferably 4~8 Integer.

In general formula (Z-5), n is preferably 0~6 integer, more preferably 0~4 integer.

In addition, total preferably 3~60 integer of each n, more preferably 3~24 integer, particularly preferably 6~12 Integer.

In addition, in general formula (Z-4) or general formula (Z-5)-((CH₂)_yCH₂O)-or-((CH₂)_yCH(CH₃) O)-it is preferably oxygen The form of the end of atom side and X bond.

Can be used alone one kind by the compound represented by general formula (Z-4) or general formula (Z-5), can also and with two or more. In particular, 6 X are the form of acryloyl group preferably in general formula (Z-5).

In addition, as by compound always containing in polymerizable compound represented by general formula (Z-4) or general formula (Z-5) Amount, preferably 20 mass % or more, more preferably 50 mass % or more.

The compound represented by general formula (Z-4) or general formula (Z-5) can be synthesized by following steps: by making pentaerythrite Or dipentaerythritol makes the step of open loop skeleton bond with ethylene oxide or propylene oxide progress opening and makes The terminal hydroxyl of open loop skeleton and the step of for example (methyl) acryloyl chloride is reacted to import (methyl) acryloyl group.Each step Suddenly be well-known step, this field practitioner can be easily synthesized by general formula (Z-4) or general formula (Z-5) represented by change Close object.

Among the compound represented by general formula (Z-4) or general formula (Z-5), more preferably pentaerythritol derivative and/or Dipentaerythritol derivative.

Specifically, the compound represented by can enumerating by following formula (a)~formula (f) is (hereinafter also referred to as " illustration chemical combination Object (a)~exemplary compounds (f) "), wherein preferably exemplary compounds (a), exemplary compounds (b), exemplary compounds (e), Exemplary compounds (f).

[changing 45]

[changing 46]

It as the commercially available product by the polymerizable compound represented by general formula (Z-4) or general formula (Z-5), such as can enumerate: husky SR-494, the Japanese chemical drug share as the tetrafunctional acrylate with 4 inferior ethoxyl chains of more Ma company manufactures are limited Company's manufacture as the DPCA-60 of six functional acrylates with 6 sub- amoxy chains, as with 3 Ge Yi Aden oxygen The TPA-330 etc. of the trifunctional acrylate of base chain.

In the present invention, as polymerizable compound, it is possible to use the compound with epoxy group.As with epoxy group Compound, preferably 1 intramolecular have more than two epoxy group persons.More than two rings are had by using 1 intramolecular The compound of oxygroup, and can more effectively reach effect of the invention.In 1 intramolecular, epoxy group is preferably 2~10, more Preferably 2~5, particularly preferably 3.

In the present invention, the compound with epoxy group is preferably linked using with 2 phenyl ring by alkyl Structure person.Alkyl is preferably the alkylidene of carbon number 1~6.

In addition, epoxy group is preferably linked via concatenating group.As concatenating group, can enumerate containing selected from alkylidene, Arlydene ,-O-, by-NR '-, (R ' expression hydrogen atom can have the alkyl of substituent group or can have the aryl of substituent group, preferably Hydrogen atom) represented by structure ,-SO₂,-CO-, at least one of-O- and-S- base.

Epoxide equivalent (molecular weight/epoxy group number of=the compound with epoxy group of compound with epoxy group Amount) it is preferably 500g/eq hereinafter, more preferably 100g/eq~400g/eq, and then more preferably 100g/eq~300g/eq.It is logical It crosses and the upper limit value of the epoxide equivalent of the compound with epoxy group is set as 500g/eq hereinafter, and can get the effect.Separately Outside, for stability in practical use, the lower limit value of the epoxide equivalent of the compound with epoxy group is preferably set as 100g/ Eq or more.

Compound with epoxy group can (such as molecular weight less than 2000, in turn, molecular weight be less than for low molecular compound It 1000), can also be that (such as molecular weight is 1000 or more to high-molecular compound (macromolecule), the polymer the case where Under, weight average molecular weight be 1000 or more) any one.The weight average molecular weight of compound with epoxy group is preferably 200~100000, more preferably 500~50000.

The compound with epoxy group as the structure that 2 phenyl ring are linked by alkyl, it is preferable to which use is under State compound represented by general formula (2a).

[changing 47]

In general formula (2a), R¹~R¹⁹Separately indicate hydrogen atom, alkyl, alkoxy or halogen atom.

The R of general formula (2a)¹~R¹⁹Details can refer to the paragraph of Japanese Patent Laid-Open 2013-011869 bulletin 0036, content may be included in present specification.

In particular, R¹~R¹⁹It is preferably separately any one of hydrogen atom, methyl, ethyl or methoxyl group.In addition, more It is preferably selected from R¹³、R¹⁸And R¹⁹In more than one be methyl.And then more preferably R¹³、R¹⁸And R¹⁹For methyl, R¹~R¹²、R¹⁴ ~R¹⁷For hydrogen atom.

It can refer to the paragraph of Japanese Patent Laid-Open 2013-011869 bulletin by the compound represented by the general formula (2a) Number 0036 synthesizes.It as commercially available product, can enumerate: the VG-3101L of Pu Lintaike (Printec) limited liability company manufacture, day The NC-6000 and NC-6300 etc. of this chemical drug limited liability company manufacture.

Compound with epoxy group for example can be used by the compound represented by the following general formula (EP1).

[changing 48]

In formula (EP1), R^EP1~R^EP3Hydrogen atom, halogen atom, alkyl are respectively indicated, alkyl can be for cyclic structure Person, in addition, can also have substituent group.In addition, R^EP1With R^EP2、R^EP2With R^EP3It can mutually be bonded and form ring structure.

Q^EPIndicate singly-bound or n^EPThe organic group of valence.R^EP1~R^EP3It can be with Q^EPIt is bonded and forms ring structure.

n^EPThe integer of 2 or more expression, preferably 2~10, more preferably 2~6.But work as Q^EPWhen for singly-bound, n^EPIt is 2.

R^EP1~R^EP3、Q^EPDetails can refer to the paragraph 0087 of Japanese Patent Laid-Open 2014-089408 bulletin The record of~paragraph 0088, content can be incorporated into present specification.

The concrete example of compound illustrated below with epoxy group, but the present invention is not limited to these concrete examples.

[changing 49]

[changing 50]

As the compound with epoxy group, it also may be preferable for ground uses oligomer or the polymerization on side chain with epoxy group Object.It as such compound, can enumerate: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak-type epoxy tree Rouge, cresol novolak type epoxy resin, aliphatic epoxy resin etc..

Commercially available product can be used in these compounds, can also be obtained and importing epoxy group on the side chain to polymer.

As commercially available product, for example, bisphenol A type epoxy resin is JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japanese epoxy resin (Japan Epoxy Resins) (share) manufacture), Epiclon (EPICLON) 860, Epiclon (EPICLON) 1050, Epiclon (EPICLON) 1051, Epiclon (EPICLON) 1055 (more than, DIC (DIC) (share) manufacture) etc., bisphenol f type epoxy resin JER806, JER807, JER4004, JER4005, JER4007, JER4010 (more than, Japanese epoxy resin (share) manufacture), Epiclon (EPICLON) 830, Epiclon (EPICLON) 835 (more than, DIC (share) manufacture), LCE-21, RE-602S (more than, The manufacture of Japanese chemical drug (share)) etc., phenol novolak type epoxy resin JER152, JER154, JER157S70, JER157S65 (more than, Japanese epoxy resin (share) manufacture), Epiclon (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N-775 (more than, DIC (share) manufacture) etc., cresol novolak type Epoxy resin is Epiclon (EPICLON) N-660, Epiclon (EPICLON) N-665, Epiclon (EPICLON) N- 670, Epiclon (EPICLON) N-673, Epiclon (EPICLON) N-680, Epiclon (EPICLON) N-690, Chinese mugwort ratio Clone (EPICLON) N-695 (more than, DIC (share) manufacture), EOCN-1020 (more than, Japanese chemical drug (share) manufacture) It is Ai Dike resin (ADEKA RESIN) EP-4080S, Ai Dike resin (ADEKA RESIN) EP- Deng, aliphatic epoxy resin 4085S, Ai Dike resin (ADEKA RESIN) EP-4088S (more than, Ai Dike (ADEKA) (share) manufacture), Sai Luo West Germany (Celloxide) 2021P, Sai Luo West Germany (Celloxide) 2081, Sai Luo West Germany (Celloxide) 2083, Sai Luo West Germany (Celloxide) 2085, EHPE3150, Ai Boli obtain (EPOLEAD) PB 3600, Ai Boli obtain (EPOLEAD) PB 4700 (with On, Daicel (Daicel) chemical industry (share) manufacture), pellet receives Cauer (Denacol) EX-212L, EX-214L, EX- 216L, EX-321L, EX-850L (more than, long rapids chemical conversion (Nagase chemteX) (share) manufacture) etc..In addition to this, may be used Enumerate Ai Dike resin (ADEKA RESIN) EP-4000S, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike tree Rouge (ADEKA RESIN) EP-4010S, Ai Dike resin (ADEKA RESIN) EP-4011S (more than, Ai Dike (share) system Make), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (more than, Ai Dike (share) manufacture), JER1031S (Japanese epoxy resin (share) manufacture) etc..

In addition, also preferably using JER1031S (Mitsubishi Chemical's (share) manufacture), JER1032H60 (Mitsubishi Chemical (share) manufacture), Epiclon (EPICLON) HP-4700 (manufacture of DIC (share) company), Epiclon (EPICLON) N-695 (manufacture of DIC (share) company), Epiclon (EPICLON) 840 (manufacture of DIC (share) company), Chinese mugwort Bick (DIC (share) is public by grand (EPICLON) N660 (manufacture of DIC (share) company), Epiclon (EPICLON) HP7200 Department's manufacture) etc..

In the present invention, as polymerizable compound, as Japan Patent examined patent publication 48-41708 bulletin, Japan Patent are special Open clear 51-37193 bulletin, Japanese Patent Laid-fair 2-32293 bulletin, in Japanese Patent Laid-fair 2-16765 bulletin Documented propenoic methyl carbamate class or Japan Patent examined patent publication 58-49860 bulletin, Japan Patent examined patent publication 56- No. 17654 bulletins, are recorded in Japan Patent examined patent publication 62-39418 bulletin Japan Patent examined patent publication 62-39417 bulletin Carbamate compounds class with ethylene oxide pastern bone frame is also suitable for.In addition, by using Japanese Patent Laid-Open No. Sho 63- No. 277653 bulletins, Japanese Patent Laid-Open No. Sho 63-260909 bulletin are remembered in Japanese Patent Laid-Open 1-105238 bulletin The intramolecular of load has the addition polymerization compounds of amino structure or sulfide structure, and it is very excellent to can get film speed Coloured composition.

In addition, in the present invention, it is possible to use the compound with oxetanyl is as polymerizable compound.As Compound with oxetanyl can enumerate 0134~paragraph of paragraph of Japanese Patent Laid-Open 2008-224970 bulletin The compound recorded in 0145, content can be incorporated into this specification.As concrete example, sub- imperial oxetanes can be used (ARON OXETANE) OXT-121, OXT-221, OX-SQ, PNOX (more than, East Asia synthesizes (share) manufacture).

It as the commercially available product of polymerizable compound, can enumerate: urethane oligomer UAS-10, UAB-140 (adret state The manufacture of plan paper pulp (Sanyo Kokusaku Pulp) company), UA-7200 (manufacture of chemical company, the village Xin Zhong), DPHA-40H (day The manufacture of this chemical drug company), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufacture of common prosperity society) etc..

In coloured composition of the invention, relative to the total solid content of coloured composition, polymerizable compound contains Amount is preferably 0.1 mass of mass %~30 %.Lower limit is for example more preferably 0.5 mass % or more, and then more preferably 1 mass % More than.The upper limit is for example more preferably 20 mass % hereinafter, being more preferably 15 mass % or less in turn.Polymerizable compound can be single It is solely a kind of, can also and with two or more.When and with it is two or more when, preferably total amount becomes the range.

<<multi-functional thiol's compound>>

For the purpose of reaction for promoting polymerizable compound etc., coloured composition of the invention can also have containing intramolecular Multi-functional thiol's compound of more than two sulfydryls.Multi-functional thiol's compound is preferably the alkanethiol class of second level, especially The compound of structure represented by preferably having by the following general formula (T1).

General formula (T1)

[changing 51]

(in formula (T1), n indicates that 2~4 integer, L indicate divalent~tetravalence concatenating group)

In the general formula (T1), concatenating group L is preferably the fatty group of carbon number 2~12, and particularly preferably n is 2, L is carbon The alkylidene of number 2~12.As the concrete example of multi-functional thiol's compound, can enumerate by following structural formula (T2)~structural formulas (T4) compound represented by, particularly preferably for by the compound represented by formula (T2).The usable one kind of these multi-functional thiols, Or multiple combinations are used.

[changing 52]

When coloured composition of the invention contains multi-functional thiol's compound, relative to coloured composition total solid at Point, the content of multi-functional thiol is preferably the 0.3 mass % of mass %~8.9, more preferably 0.8 mass of mass %~6.4 %.Separately Outside, multi-functional thiol can also be added for the purpose of improved stability, foul smell, analyticity, developability, adhesion etc..

<<other pigments>>

Coloured composition of the invention contains the pigment other than the pigment polymer (A) (hereinafter also referred to as other Pigment).Other pigments preferably use any one of pigment, dyestuff, just this reason high for the tolerance of heat or light and Speech, more preferably pigment.

In other pigments, relative to the total amount of other pigments, the content of pigment is preferably 95 mass % or more, more preferably 97 mass % or more, and then more preferably 99 mass % or more.According to the form, it is easy to get the tolerance for heat or light The effect got higher.

As pigment, well known various inorganic pigments or organic pigment, preferably organic pigment before can be used.

<<<dyestuff>>>

As dyestuff, there is no particular restriction, and well known dyestuff used in chromatic filter can be used.Such as it can make With: Japanese Patent Laid-Open No. Sho 64-90403 bulletin, Japanese Patent Laid-Open No. Sho 64-91102 bulletin, Japanese Patent Laid-Open 1- No. 94301 bulletins, Japanese Patent Laid-Open 6-11614 bulletin, Japan Patent spy step on No. 2592207, United States Patent (USP) 4808501 Number No. 5667920 specification, No. 5667920 specifications of United States Patent (USP), No. 505950 specifications of United States Patent (USP), United States Patent (USP) explanations Book, Japanese Patent Laid-Open 5-333207 bulletin, Japanese Patent Laid-Open 6-35183 bulletin, Japanese Patent Laid-Open 6- Dyestuff disclosed in No. 51115 bulletins, Japanese Patent Laid-Open 6-194828 bulletin etc..As chemical structure, can be used Pyrazoles azo system, pyrroles's methylene base system, anilino- azo system, triarylmethane system, anthraquinone system, benzal base system, oxonols system, pyrrole Azoles and the dyestuff of triazole azo system, pyridone azo system, cyanine system, phenthazine system, pyrrolo-pyrazole azomethine system etc..

<<<pigment>>>

Metallic compound or carbon black as inorganic pigment, represented by can enumerating by metal oxide, metallic complex salt etc. (C.I. pigment black 7).As metallic compound, specifically, can enumerate: iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony Deng metal oxide and metal composite oxides.

As organic pigment, such as pigment can be listed below etc.:

C.I. pigment yellow 11, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 53, C.I. pigment yellow 83, C.I. Pigment yellow 93, C.I. pigment yellow 99, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 138, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 167, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 199；

C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 43, C.I. pigment orange 71；

C.I. pigment red 81, C.I. paratonere 105, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 155, C.I. paratonere 167, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 176, C.I. face Expect red 177, C.I. pigment red179, C.I. paratonere 209, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 270；

C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 32, C.I. pigment violet 39；

C.I. pigment blue 1, C.I. pigment blue 2, C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. pigment blue 22, C.I. pigment blue 60, C.I. pigment blue 66；

C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58；

C.I. pigment brown 25, C.I. pigment brown 28；

C.I. pigment black 1.

Organic pigment can be used alone or in order to light splitting adjustment or promoted excitation purity and combine various organic pigments It uses.The concrete example that following presentation preferably combines.

For example, as red pigment, the anthraquione pigmentss that can be used alone are pigment, diketopyrrolo-pyrrole system pigment, Or it can be used at least one of these pigment and bisazo system yellow uitramarine, isoindoline system yellow uitramarine, quinophthalone system yellow Color pigment or be red pigment mixing etc..For example, C.I. paratonere 177 can be enumerated as anthraquione pigmentss, as being Pigment can enumerate C.I. paratonere 155, C.I. paratonere 224, as diketopyrrolo-pyrrole system pigment, can enumerate C.I. face Expect red 254, the mixing for the viewpoint of dichroism, preferably with C.I. pigment yellow 13 9.In addition, red pigment and yellow face The mass ratio of material is preferably 100: 5~100: 50, more preferably 100: 10~100: 30 range.At mutual group of red pigment In the case where conjunction, it is adjusted in combination with required light splitting.

As viridine green, can be used alone halogenated phthalocyanines system pigment, or can be used it with bisazo system yellow uitramarine, The mixing of quinophthalone system yellow uitramarine, azomethine system yellow uitramarine or isoindoline system yellow uitramarine.For example, as such example, Preferably C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37 and C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. The mixing of pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.Viridine green and yellow uitramarine Mass ratio be preferably 100: 5~100: 150, more preferably 100: 30~100: 120 range.

As blue pigment, can be used alone phthualocyanine pigment or can be used it mixed with dioxazines system violet pigment It closes.For example, it is preferable to be C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is excellent It is selected as 100: 0~100: 100.

As the pigment of black matrix", the carbon that can be used alone, titanium be black, iron oxide, titanium oxide, or these face can be used Two or more mixing in material, preferably carbon and the black combination of titanium.In addition, carbon and the black mass ratio of titanium be preferably 100: 0~ 100: 60 range.

About the primary particle size of pigment, in the case where being used as chromatic filter purposes, with regard to irregular colour or contrast For viewpoint, preferably 100nm is hereinafter, in addition, for the viewpoint of dispersion stabilization, preferably 5nm or more.Pigment it is primary Partial size is more preferably 5nm~75nm, and then more preferably 5nm~55nm, particularly preferably 5nm~35nm.

The primary particle size of pigment can be measured by method well known to electron microscope etc..

Wherein, as pigment, anthraquinone pigment, diketopyrrolo-pyrrole pigment, phthalocyanine color, quinophthalone face are preferably selected from Pigment in material, isoindoline pigment, azomethine pigment and dioxazines pigment.In particular, preferably 177 (anthraquinone of C.I. paratonere Pigment), C.I. paratonere 254 (diketopyrrolo-pyrrole pigment), C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 15s: 6 (phthalocyanine colors), C.I. pigment yellow 13 8 (quinophthalone pigments), C.I. pigment yellow 13 9, C.I. pigment Yellow 185 (isoindoline pigments), C.I. pigment yellow 150 (azomethine pigment), C.I. pigment Violet 23 (dioxazines pigment).

When coloured composition of the invention contains other pigments, relative to the total solid content of coloured composition, other The content of pigment is preferably the 10 mass % of mass %~70, more preferably the 25 mass % of mass %~65, and then more preferably 35 The mass of quality %~55 %.

Coloured composition of the invention can also contain two or more only containing other a kind of pigments.When containing there are two types of with When upper, preferably its total amount becomes the range.

<<resin>>

Coloured composition of the invention preferably contains resin.As the resin, the resin for dispersing pigment can be enumerated (dispersion resin) or alkali soluble resin etc..

<<<dispersion resin>>>

It as dispersion resin, such as can enumerate: daiamid and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acids Ester, modified polyurethanes, modified poly ester, modified poly- (methyl) acrylate, (methyl) acrylic acid series copolymer, naphthalene sulfonic acids The macromolecule dispersing agents such as formaline condensates.

Macromolecule dispersing agent can be categorized further, as straight-chain macromolecule according to its structure, with for surface of pigments The terminal-modified type macromolecule of fixed position, with for surface of pigments fixed position graft type macromolecule, have be directed to The block type polymer of the fixed position of surface of pigments.

It as the terminal-modified type macromolecule with the fixed position for surface of pigments, such as can enumerate: Japan Patent There is phosphoric acid in end documented by Japanese Laid-Open Patent Publication 3-112992 bulletin and Japanese patent special table 2003-533455 bulletin etc. The macromolecule of base, in Japanese Patent Laid-Open 2002-273191 bulletin etc. documented by end there is sulfonic macromolecule, The macromolecule of part skeleton or heterocycle documented by Japanese Patent Laid-Open 9-77994 bulletin etc. with organic pigment Deng.It is directed in addition, being imported with two or more in macromolecule end documented by Japanese Patent Laid-Open 2007-277514 bulletin The high molecular stably dispersing of the fixed position (acidic group, basic group, the part skeleton of organic pigment or heterocycle etc.) of surface of pigments Property is also excellent, and it is preferred that.

As the graft type macromolecule with the fixed position for surface of pigments, such as polyester based resin can be enumerated etc.. Specifically, can enumerate: the flat 8-507960 bulletin of Japanese Patent Laid-Open No. Sho 54-37082 bulletin, Japanese patent special table, day The reaction product of documented poly- (low-grade alkylidene imines) and polyester, day in this patent special open 2009-258668 bulletin etc. The reaction product of documented polyallylamine and polyester, Japanese Patent Laid-Open in this patent Japanese Laid-Open Patent Publication 9-169821 bulletin etc. Documented macromonomer and nitrogen-atoms in flat 10-339949 bulletin, Japanese Patent Laid-Open 2004-37986 bulletin etc. The copolymer of monomer, Japanese Patent Laid-Open 2003-238837 bulletin, Japanese Patent Laid-Open 2008-9426 bulletin, Japan are specially The graft type macromolecule of part skeleton or heterocycle documented by sharp special open 2008-81732 bulletin etc. with organic pigment, The copolymer of documented macromonomer and the monomer containing acidic group in Japanese Patent Laid-Open 2010-106268 bulletin etc. Deng.In particular, with regard to the dispersibility of pigment dispersion, dispersion stabilization and using shown by the coloured composition of pigment dispersion It is documented particularly preferably in Japanese Patent Laid-Open 2009-203462 bulletin that there is basic group for the viewpoint of developability With the amphoteric resin of acidic group.

As macromonomer used when manufacturing graft type macromolecule using free radical polymerization, can be used well known Macromonomer can be enumerated: East Asia synthesizes the macromonomer AA-6 that (share) manufactures, and (terminal groups are the poly- of methylacryloyl Methyl methacrylate), AS-6 (polystyrene that terminal groups are methylacryloyl), (terminal groups are methacryl to AN-6S The styrene of base and the copolymer of acrylonitrile), the AB-6 butyl polyacrylate of methylacryloyl (terminal groups be), Daicel Learning pula Sai Er (Placcel) FM5 that industrial (share) manufactures, (5 moles of 6-caprolactone of 2-hydroxyethyl methacrylate are worked as Measure addition product), FA10L (the 10 molar equivalent addition product of 6-caprolactone of acrylic acid 2- hydroxy methacrylate) and Japanese Patent Laid-Open Documented Polyester macromonomer etc. in flat 2-272009 bulletin.Dispersion among these, especially with regard to pigment dispersion Property, developability shown by dispersion stabilization and coloured composition using pigment dispersion viewpoint for, it is preferably soft Property and the excellent Polyester macromonomer of said solvophilic, particularly preferably for by Japanese Patent Laid-Open 2-272009 bulletin Polyester macromonomer represented by the Polyester macromonomer of record.

As the block type polymer with the fixed position for surface of pigments, preferably Japanese Patent Laid-Open 2003- Documented block type polymer in No. 49110 bulletins, Japanese Patent Laid-Open 2009-52010 bulletin etc..

Resin also can be used as commercially available product and obtain, and as such concrete example, can enumerate: nanmu is melted into limited liability company's system " -101 (polyamide of Di Sipabike (Disperbyk) of " DA-7301 " made, Bi Ke chemistry (BYK Chemie) company manufacture Amine phosphate), Di Sipabike (Disperbyk) -107 (carboxylate), Di Sipabike (Disperbyk) -110 (containing acid The copolymer of base), Di Sipabike (Disperbyk) -130 (polyamide), Di Sipabike (Disperbyk) -161, Di Si Pa Bike (Disperbyk) -162, Di Sipabike (Disperbyk) -163, Di Sipabike (Disperbyk) -164, enlightening Si Pabike (Disperbyk) -165, Di Sipabike (Disperbyk) -166, Di Sipabike (Disperbyk) -170 (high-molecular copolymer) ", " BYK-P104, BYK-P105 (high molecular weight unsaturation polycarboxylic acid) ", Efka (EFKA) corporation Make " Efka (EFKA) 4047, Efka (EFKA) 4050~Efka (EFKA) 4010~Efka (EFKA) 4165 are (poly- Carbamate system), Efka (EFKA) 4330~Efka (EFKA) 4340 (block copolymer), Efka (EFKA) 4400 ~Efka (EFKA) 4402 (modified polyacrylate), Efka (EFKA) 5010 (polyesteramide), Efka (EFKA) (phthalocyanine is derivative for 5765 (high molecular weight multi-carboxylates), Efka (EFKA) 6220 (fatty acid polyester), Efka (EFKA) 6745 Object), Efka (EFKA) 6750 (azo pigments derivative) ", aginomoto microtechnic (Ajinomoto Fine-Techno) is public Take charge of " A Jisipa (Ajisper) PB821, A Jisipa (Ajisper) PB822, A Jisipa (Ajisper) of manufacture PB880, A Jisipa (Ajisper) PB881 ", " Fu Luolan (Florene) TG-710 (amino of chemical company, common prosperity society manufacture Formic acid oligomer ester), Po Lifuluo (Polyfiow) No.50E, Po Lifuluo (Polyfiow) No.300 (acrylic copolymer Object) ", " Di Sipalong (Disparlon) KS-860, Di Sipalong (Disparlon) 873SN, enlightening of Nanben Chemical Company manufacture Si Palong (Disparlon) 874, Di Sipalong (Disparlon) #2150 (aliphatic polycarboxylic acid), Di Sipalong (Disparlon) #7004 (polyether ester), Di Sipalong (Disparlon) DA-703-50, Di Sipalong (Disparlon) DA- 705, Di Sipalong (Disparlon) DA-725 ", " De Moer (Demol) RN, De Moer (Demol) N of KAO. Corp. SA's manufacture (naphthalenesulfonic acid formalin condensation polymer), De Moer (Demol) MS, De Moer (Demol) C, De Moer (Demol) SN-B (fragrance Race's sulfonic acid formalin polycondensates) ", " fiery Mo Genuo (Homogenol) L-18 (macromolecule polycarboxylic acid), Ai Maji (Emalgen) 920, Ai Maji (Emalgen) 930, Ai Maji (Emalgen) 935,985 (ethylene nonyl phenyl of Ai Maji (Emalgen) Ether), A Saita orders (Acetamin) 86 (stearic amine acetic acid esters) ", " rope of Japanese Lu Borun (Lubrizol) (share) manufacture Exert Paasche (Solsperse) 5000 (phthalocyanine derivates), rope exerts Paasche (Solsperse) 22000 (azo pigments derivative), rope Exert Paasche (Solsperse) 13240 (polyesteramine), rope exerts Paasche (Solsperse) 3000, rope exerts Paasche (Solsperse) 17000, rope exerts Paasche (Solsperse) 27000 (macromolecule that terminal part has function part), rope exerts Paasche (Solsperse) 24000, rope exerts Paasche (Solsperse) 28000, rope exerts Paasche (Solsperse) 32000, rope exerts Paasche (Solsperse) 38500 (graft type macromolecules) ", the manufacture of daylight chemistry (Nikko Chemicals) company " Nikkor (Nikol) T106 is (poly- Ethylene oxide sorbitan monooleate), Mace-Yi Ke (MYS-IEX) (polyoxyl 40 stearate) ", river, which is ground, refines " Hai Nuoai Carter (Hinoact) T-8000E etc. " of (Kawaken Fine Chemicals) (share) manufacture, SHIN-ETSU HANTOTAI's chemistry work " the organic siloxane polymer KP341 " of industry (share) the manufacture, " W001: cationic system surface-active of abundant quotient's (share) manufacture Agent, polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxy Ethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan alcohol fatty acid ester etc. are non- The anionic surfactants such as ionization series surfactant, ' W004, W005, W017 ' ", gloomy lower industry (share) manufacture " Efka (EFKA) -46, Efka (EFKA) -47, Efka (EFKA) -47EA, Efka polymer (EFKA Polymer) 100, Efka polymer (EFKA Polymer) 400, Efka polymer (EFKA Polymer) 401, Efka polymer " this Paasche of enlightening Ai De (Disperse Aid) of (EFKA Polymer) 450 ", Sheng Nuopuke (Sannopco) (share) manufacture 6, this Paasche of enlightening Ai De (Disperse Aid) 8, this Paasche of enlightening Ai De (Disperse Aid) 15, this Paasche of enlightening Ai De (Disperse Aid) macromolecule dispersing agents such as 9100 ", " Ai Dike pluronic (Adeka of Ai Dike (share) manufacture Pluronic) L31, Ai Dike pluronic (Adeka Pluronic) F38, Ai Dike pluronic (Adeka Pluronic) L42, Ai Dike pluronic (Adeka Pluronic) L44, Ai Dike pluronic (Adeka Pluronic) L61, Ai Di The bright Buddhist nun of section's pluronic (Adeka Pluronic) L64, Ai Dike pluronic (Adeka Pluronic) F68, Ai Di science popularization Gram (Adeka Pluronic) L72, Ai Dike pluronic (Adeka Pluronic) P95, Ai Dike pluronic (Adeka Pluronic) F77, Ai Dike pluronic (Adeka Pluronic) P84, Ai Dike pluronic (Adeka Pluronic) F87, Ai Dike pluronic (Adeka Pluronic) P94, Ai Dike pluronic (Adeka Pluronic) L101, Ai Di Section's pluronic (Adeka Pluronic) P103, Ai Dike pluronic (Adeka Pluronic) F108, Chinese mugwort Di Kepulang Ni Ke (Adeka Pluronic) L121, Ai Dike pluronic (Adeka Pluronic) P-123 " and Sanyo are melted into (stock Part) " her Austria Knight (Ionet) (trade name) S-20 " etc. of manufacture.

Resin can be used alone, and can also be used in combination of two or more.In addition, resin can also will have for surface of pigments Fixed position terminal-modified type macromolecule, with for surface of pigments fixed position graft type macromolecule, have needle The block type polymer of the fixed position of surface of pigments is used in combination with aftermentioned alkali soluble resin.

As alkali soluble resin, can enumerate (methyl) acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, Acid cellulose on acid/maleic acid copolymers, partial esterification acid/maleic acid copolymers etc. and side chain with carboxylic acid spreads out Biology, the resin made of modified anhydride in the polymer with hydroxyl.Particularly preferably (methyl) acrylic copolymer.Separately Outside, documented N substitution maleimide monomer copolymer, day in Japanese Patent Laid-Open 10-300922 bulletin Documented ether dimerization precursor copolymer, Japanese Patent Laid-Open 7-319161 in this patent special open 2004-300204 bulletin In bulletin documented by the alkali soluble resin containing polymerism base it is also preferred that.

In coloured composition, when containing dispersion resin, as the content of dispersion resin, relative to 100 mass of pigment Part, preferably 1 mass parts~100 mass parts.Lower limit is for example more preferably 5 mass parts or more, and then more preferably 10 mass parts More than.The upper limit is for example more preferably 80 below the mass, and then preferably 70 below the mass, and then more preferably 60 mass parts Below.

<<<alkali soluble resin>>>

Coloured composition of the invention can contain alkali soluble resin as resin.By containing alkali soluble resin, show Shadow patternability is promoted.Furthermore alkali soluble resin also is used as the dispersion resin.

As the molecular weight of alkali soluble resin, and not specially provided, weight average molecular weight (Mw) is preferably 5000~ 100,000.In addition, number average molecular weight (Mn) is preferably 1000~20,000.

It can also be linear organic polymer condensate as alkali soluble resin, it can be from molecule (preferably by acrylic acid series The molecule of copolymer, styrene based copolymer as main chain) in at least one promote alkali-soluble base alkali-soluble It is suitable for selection in resin.

Alkali soluble resin is illustrated.

As alkali soluble resin, for the viewpoint of heat resistance, preferably polyhydroxy styrene system resin, polysiloxanes It is resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin, just controls the sight of developability For point, preferably acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin.

As the base (hereinafter also referred to as acidic group) of promotion alkali-soluble, such as carboxyl, phosphate, sulfonic group, phenol can be enumerated Property hydroxyl etc., the base for preferably dissolving in organic solvent and developing using weak alkaline aqueous solution, as particularly preferred person, (methyl) acrylic acid can be enumerated.These acidic groups can be only one kind, can also be two or more.

When manufacturing alkali soluble resin, such as can be using the method using well known radical polymerization.Utilize freedom Temperature, pressure, the type of radical initiator and its amount, the type of solvent when base polymerization manufactures alkali soluble resin etc. are gathered Conjunction condition can easily be set by this field practitioner, can also experimentally rated condition.

As alkali soluble resin, with the polymer of carboxylic acid preferably on side chain, methacrylic acid copolymer can be enumerated Object, acrylic copolymer, itaconic acid copolymer, crotonic acid-copolymers, acid/maleic acid copolymers, partial esterification maleic acid Alkali-solubles phenol resin such as copolymer, phenolic varnish type resin etc. and the acid cellulose on side chain with carboxyl derive Object, addition acid anhydrides forms person in the polymer with hydroxyl.In particular, (methyl) acrylic acid with can be copolymerized with it other The copolymer of monomer is suitable as alkali soluble resin.As the other monomers that can be copolymerized with (methyl) acrylic acid, can arrange It lifts: (methyl) alkyl acrylate, (methyl) benzyl acrylate, vinyl compound etc..As (methyl) acrylic acid alkyl Ester and (methyl) benzyl acrylate can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid third Ester, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (first Base) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) toluene toluene, (methyl) propylene Sour naphthalene ester, (methyl) cyclohexyl acrylate etc., as vinyl compound, can enumerate styrene, α-methylstyrene, vinyl Toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, n-vinyl pyrrolidone, methacrylic acid tetrahydro chaff Ester, Group-capped Polystyrene Macromer, polymethyl methacrylate macromonomer etc., as Japanese Patent Laid-Open 10- Documented N substitution maleimide monomer, can enumerate N- phenylmaleimide, N- in No. 300922 bulletins Cyclohexylmaleimide etc..Furthermore these other monomers that can be copolymerized with (methyl) acrylic acid can be only one kind, It can also be two or more.

In addition, in order to promote the cross-linking efficiency of the coloured composition in the present invention, it is possible to use the alkali with polymerism base Soluble resin.As polymerism base, (methyl) allyl, (methyl) acryloyl group etc. can be enumerated.Alkali with polymerism base The soluble resin usefully alkali soluble resin etc. containing polymerism base on side chain.

Alkali soluble resin containing polymerism base is preferably following resin etc.: making following compound and contains carboxyl Acrylic resin carry out reacting obtained through urethane-modified alkali soluble resin, the compound makes different in advance Cyanic acid ester group is reacted with hydroxyl, remains 1 unreacted isocyanate group and containing polymerisms such as (methyl) acryloyl groups Base；With intramolecular there is the reacting for compound of epoxy group and polymeric double bond to be obtained by the acrylic resin containing carboxyl Alkali soluble resin；Acid pendant type Epocryl；Make the acrylic resin containing hydroxyl and has polymerism double The dibasic acid anhydride of key carries out reacting alkali soluble resin obtained；Make the acrylic resin containing hydroxyl and isocyanates and tool There is the compound of polymerism base to carry out reacting alkali soluble resin obtained；By to Japanese Patent Laid-Open 2002-229207 Resin documented by number bulletin and Japanese Patent Laid-Open 2003-335814 bulletin on side chain with ester group carries out alkali Property processing alkali soluble resin obtained, the ester group is on α or the position β with the disengaging such as halogen atom or sulfonate group Base.

It as the alkali soluble resin containing polymerism base, can enumerate: Di Anuo (Dianal) NR series (beautiful positive stock of Mitsubishi The manufacture of part Co., Ltd), (the acrylic acid polyurethane oligomer containing COOH of Buddha's Ma (Photomer) 6173 (polyurethane acrylic oligomer), Ultramar Diamond Shamrock Co., Ltd (Diamond Shamrock Co.Ltd.) Manufacture), than this Carter (Viscoat) R-264, KS Resistl06 (be Osaka Organic Chemical Industry limited liability company system Make), match Crow horse (Cyclomer) P series, pula Sai Er (Placcel) CF200 series (be Daicel chemical industry share Co., Ltd manufacture), Chinese mugwort Ba Keli (Ebecryl) 3800 (manufacture of Daicel-UCB (Daicel-UCB) limited liability company), Acker Li Qiuer (Acrycure)-RD-F (Japanese catalyst Co. manufacture) etc..

Alkali soluble resin preferably uses (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) third Olefin(e) acid benzyl ester/(methyl) acrylic acid/(methyl) acrylic acid 2- hydroxy methacrylate copolymer includes (methyl) benzyl acrylate/(first Base) acrylic acid/other monomers multiple copolymer.In addition, also preferably using carrying out 2-hydroxyethyl methacrylate It is copolymerized and winner, documented (methyl) acrylic acid 2- hydroxy propyl ester/polyphenyl in Japanese Patent Laid-Open 7-140654 bulletin Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer, acrylic acid 2- hydroxyl -3- phenoxy-propyl/poly- first Base methyl acrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/ Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polyphenyl Ethylene macromonomer/benzyl methacrylate/methacrylic acid copolymer etc..

Alkali soluble resin contain the polymer (a) for making following monomer component be polymerized it is also preferred that, the list Body ingredient contain by the following general formula (ED) represented by compound and/or by represented by the following general formula (ED2) compound (with Under, these compounds are also known as " ether dimer " sometimes).

[changing 53]

In general formula (ED), R¹And R²It separately indicates hydrogen atom or can have the alkyl of the carbon number 1~25 of substituent group.

General formula (ED2)

[changing 54]

In general formula (ED2), R indicates the organic group of hydrogen atom or carbon number 1~30.As the concrete example of general formula (ED2), can join Examine the record of Japanese Patent Laid-Open 2010-168539 bulletin.

In general formula (ED), as by R¹And R²The alkyl of the represented carbon number 1~25 with substituent group has no especially Limitation, such as can enumerate: methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, tertiary pentyl, stearyl, the moon The alkyl of the straight-chains such as Gui Ji, 2- ethylhexyl or branch-like；The aryl such as phenyl；Cyclohexyl, tert-butylcyclohexyl, two rings penta 2 The ester ring types bases such as alkenyl, adamantyl, isobornyl, adamantyl, 2- methyl -2- adamantyl；1- methoxy ethyl, 1- The alkyl that ethoxyethyl group etc. replaces through alkoxy；The alkyl etc. that benzyl etc. replaces through aryl.Among these, with regard to the sight of heat resistance For point, particularly preferably such as methyl, ethyl, cyclohexyl, benzyl be not easy because acid or it is hot due to the level-one carbon that is detached from or second level The substituent group of carbon.

It as the concrete example of ether dimer, such as can enumerate: dimethyl -2,2 '-[oxo is bis- (methylene)] double -2- propylene Acid esters, the double -2- acrylate of diethyl -2,2 '-[oxo is bis- (methylene)], two (n-propyl) -2,2 '-[bis- (methylenes of oxo Base)] double -2- acrylate, two (isopropyl) -2, the double -2- acrylate of 2 '-[oxo is bis- (methylene)], two (normal-butyl) -2, Double -2- the acrylate of 2 '-[oxo is bis- (methylene)], two (isobutyl group) -2,2 '-[oxo is bis- (methylene)] double -2- acrylic acid Ester, two (tert-butyl) -2, the double -2- acrylate of 2 '-[oxo is bis- (methylene)], two (tertiary pentyl) -2,2 '-[bis- (methylenes of oxo Base)] double -2- acrylate, two (stearyl) -2, the double -2- acrylate of 2 '-[oxo is bis- (methylene)], two (lauryl) -2, Double -2- the acrylate of 2 '-[oxo is bis- (methylene)], two (2- ethylhexyl) -2,2 '-[oxo is bis- (methylene)] double -2- third Olefin(e) acid ester, two (1- methoxy ethyl) -2,2 '-[oxo is bis- (methylene)] double -2- acrylate, two (1- ethoxyethyl groups) - Double -2- the acrylate of 2,2 '-[oxo is bis- (methylene)], the double -2- acrylate of dibenzyl -2,2 '-[oxo is bis- (methylene)], Double -2- the acrylate of diphenyl -2,2 '-[oxo is bis- (methylene)], dicyclohexyl -2,2 '-[oxo is bis- (methylene)] double -2- Acrylate, two (tert-butylcyclohexyl) -2, the double -2- acrylate of 2 '-[oxo is bis- (methylene)], two (bicyclopentadiene Base) double -2- acrylate of -2,2 '-[oxo is bis- (methylene)], two (adamantyl) -2,2 '-[oxo is bis- (methylene)] Double -2- acrylate, two (isobornyl) -2, the double -2- acrylate of 2 '-[oxo is bis- (methylene)], two adamantyl -2, Double -2- the acrylate of 2 '-[oxo is bis- (methylene)], two (2- methyl -2- adamantyls) -2,2 '-[oxo is bis- (methylene)] Double -2- acrylate etc..Among these, particularly preferably dimethyl -2, the double -2- acrylate of 2 '-[oxo is bis- (methylene)], Double -2- the acrylate of diethyl -2,2 '-[oxo is bis- (methylene)], dicyclohexyl -2,2 '-[oxo is bis- (methylene)] double -2- Acrylate, dibenzyl -2,2 '-[oxo is bis- (methylene)] double -2- acrylate.These ether dimers can be only one kind, It can be two or more.It can also be copolymerized with other monomers from the structural body by the compound represented by general formula (ED).

Alkali soluble resin contains the structural unit of the compound represented by being originated from by following formula (X)s.

[changing 55]

In formula (X), R₁Indicate hydrogen atom or methyl, R₂Indicate the alkylidene of carbon number 2~10, R₃It indicates hydrogen atom or can contain There is the alkyl of the carbon number 1~20 of phenyl ring.N indicates 1~15 integer.

In the formula (X), R₂The carbon number of alkylidene be preferably 2~3.In addition, R₃Alkyl carbon number be 1~20, preferably For 1~10, R₃Alkyl can contain phenyl ring.As by R₃The represented alkyl containing phenyl ring can enumerate benzyl, 2- phenyl (different) propyl etc..

Alkali soluble resin can refer to 0558~paragraph of Japanese Patent Laid-Open 2012-208494 bulletin paragraph, 0571 (phase [0685]~[0700] of No. 2012/0235099 specification of corresponding U.S. Patent Application Publication No.) later record, these Content can be incorporated into present specification.

In turn, it is possible to use documented 0029~paragraph of paragraph in Japanese Patent Laid-Open 2012-32767 bulletin Alkali soluble resin used in the copolymer (B) and embodiment recorded in 0063, Japanese Patent Laid-Open 2012-208474 Adhesive resin, day used in the adhesive resin and embodiment recorded in 0088~paragraph of paragraph 0098 of bulletin The adhesive resin and embodiment recorded in 0022~paragraph of paragraph 0032 of this patent special open 2012-137531 bulletin Used in adhesive resin, Japanese Patent Laid-Open 2013-024934 bulletin 0132~paragraph of paragraph 0143 in Adhesive resin used in the adhesive resin and embodiment of record, Japanese Patent Laid-Open 2011-242752 bulletin Adhesive resin used in 0092~paragraph of paragraph 0098 and embodiment, Japanese Patent Laid-Open No. 2012-032770 number The adhesive resin recorded in 0030~paragraph of paragraph 0072 of bulletin.These content, which can be incorporated into the application, to be illustrated In book.

The acid value of alkali soluble resin is preferably 30mgKOH/g~500mgKOH/g.Lower limit be more preferably 50mgKOH/g with On, and then more preferably 70mgKOH/g or more.The upper limit is more preferably 400mgKOH/g hereinafter, being more preferably 200mgKOH/ in turn G hereinafter, particularly preferably 150mgKOH/g hereinafter, also be more preferably 120mgKOH/g or less.

When coloured composition contains alkali soluble resin, relative to the total solid content of coloured composition, alkali-soluble The content of resin is preferably the 1 mass % of mass %~15, the more preferably 2 mass % of mass %~12, and then more preferably 3 matter Measure the mass of %~10 %.Coloured composition of the invention can only contain a kind of alkali soluble resin, can also contain two or more.When Containing it is two or more when, preferably its total amount become the range.

<<pigment derivative>>

Coloured composition of the invention can contain pigment derivative.

So-called pigment derivative, refers to have and replaces pigment using acidic groups, basic group, phthalimide methyl etc. A part structure compound.Preferably contain for dispersibility and the viewpoint of dispersion stabilization as pigment derivative There is the pigment derivative with acidic groups or basic group.

It as the pigment to constitute pigment derivative, can enumerate: pyrrolo-pyrrole pigments, diketopyrrolo-pyrrole face Material, azo pigments, phthalocyanine color, anthraquinone pigment, quinacridone pigment, dioxazines pigment, purple cyclic ketones pigment, pigment, thioindigo Blue pigment, isoindoline pigment, isoindolenone pigments, quinophthalone pigments, reduction (threne) pigment, metal complex pigment Deng.

As acidic groups possessed by pigment derivative, preferably sulfonic group, carboxylic acid group and its quarternary ammonium salt, more preferably Carboxylic acid group and sulfonic group, particularly preferably sulfonic group.As basic group possessed by pigment derivative, preferably amino, especially Preferably three-level amino.

Relative to the gross mass of pigment, the content of pigment derivative is preferably 1 mass %~50 mass %, and more preferably 3 The mass of quality %~30 %.Pigment derivative can also contain two or more only containing one kind.It is excellent when containing two or more Its total amount is selected as the range.

<<Photoepolymerizationinitiater initiater>>

Coloured composition of the invention can contain Photoepolymerizationinitiater initiater in turn.

As Photoepolymerizationinitiater initiater, as long as having the ability for starting the polymerization of polymerizable compound, special limit is had no System can be suitable for selection from well known Photoepolymerizationinitiater initiater.For example, it is preferable to for there is sense for ultraviolet range to luminous ray Photosensitiveness person.In addition, the activating agent of living radical can be generated to generate certain effect with through light activated sensitizer, it can also The initiator for starting cationic polymerization such as to correspond to the type of monomer.

In addition, Photoepolymerizationinitiater initiater preferably contains at least one following compound, the compound about 300nm~ At least there is about 50 molecule absorptivity in the range of 800nm (more preferably 330nm~500nm).

As Photoepolymerizationinitiater initiater, such as can enumerate: halogenation hydrocarbon derivative (such as with triazine skeleton person, have dislike two Azoles skeleton person etc.), the oxime compounds, organic peroxy such as acylphosphine compounds, six aryl bisglyoxalines, the 9 oxime derivate such as acylphosphine oxide Compound, sulphur compound, ketone compound, aromatic series salt, ketoxime ether, aminoacetophenone compounds, hydroxy acetophenone etc..

In addition, being preferably selected from for the viewpoint for exposing sensitivity by trihalomethyl triaizine compounds, benzyl dimethyl contracting Ketone compound, alpha-hydroxyacetone compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide compound, metallocene chemical combination Object, oxime compound, triallyl imidazole dimer, compound, benzothiazole compound, benzophenone cpd, acetophenone Compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halogen methyl oxadiazole compound, 3- aryl substitution tonka-bean Compound in group composed by plain compound.

More preferably trihalomethyl triaizine compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide compound, Oxime compound, triallyl imidazole dimer, compound, benzophenone cpd, acetophenone compound, are particularly preferably selected Free trihalomethyl triaizine compounds, α-aminoketone compound, oxime compound, triallyl imidazole dimer, benzophenone Close at least one of group composed by object compound.

In particular, when coloured composition of the invention to be used for the production of chromatic filter of solid state photo element, because needing It to form fine pattern with sharp shape, therefore it is important that hardenability and without residue develop to unexposed portion.Just For such viewpoint, particularly preferably use oxime compound as Photoepolymerizationinitiater initiater.In particular, when the shape in solid state photo element When at fine pattern, step printing is used to harden with exposure.The exposure machine is damaged because of halogen sometimes, it is necessary to by light The additive amount of polymerization initiator also inhibits low.If considering these aspects, when such as solid state photo element forms fine pattern, As Photoepolymerizationinitiater initiater, oxime compound is particularly preferably used.In addition, by using oxime compound, and can make migrating property into One step becomes good.

As the concrete example of Photoepolymerizationinitiater initiater, such as it can refer to the paragraph of Japanese Patent Laid-Open 2013-29760 bulletin 0265~paragraph 0268, content can be incorporated into present specification.

As Photoepolymerizationinitiater initiater, hydroxy acetophenone compound, aminoacetophenone compounds and acyl can also be properly used Base phosphine compound.More specifically, such as it can also be used documented amino in Japanese Patent Laid-Open 10-291969 bulletin Documented acylphosphanes series initiators in No. 4225898 acetophenone series initiators, Japanese Patent No. bulletins.

As hydroxy acetophenone series initiators, gorgeous good solid (IRGACURE) -184, Da Luoka (DAROCUR)-can be used 1173, gorgeous good solid (IRGACURE) -500, gorgeous good solid (IRGACURE) -2959, gorgeous good solid (IRGACURE) -127 (trade name: It is the manufacture of BASF (BASF) company).

As aminoacetophenone series initiators, gorgeous good (IRGACURE) -907, gorgeous good solid of consolidating as commercially available product can be used (IRGACURE) -369 and gorgeous good solid (IRGACURE) -379 (trade name: being BASF AG's manufacture).Aminoacetophenone system The matched Japanese Patent Laid-Open 2009-191179 of the long wavelength optical light source of absorbing wavelength and 365nm or 405nm etc. can also be used in initiator Documented compound in bulletin.

As acylphosphanes series initiators, can be used as gorgeous good solid (IRGACURE) -819 of commercially available product or Da Luoka-spy General (DAROCUR-TPO) (trade name: being BASF AG's manufacture).

As Photoepolymerizationinitiater initiater, oxime compound can be more preferably enumerated.

As the concrete example of oxime compound, the chemical combination recorded in Japanese Patent Laid-Open 2001-233842 bulletin can be used In the compound recorded in object, Japanese Patent Laid-Open 2000-80068 bulletin, Japanese Patent Laid-Open 2006-342166 bulletin The compound of record.

In the present invention, it as the oxime compound that can be properly used, such as can enumerate: 3- Benzoyloxyimino fourth Alkane -2- ketone, 3- Acetyloxyimino butane -2- ketone, 3- propionyloxy iminobutanes -2- ketone, 2- Acetyloxyimino Pentane -3- ketone, 2- Acetyloxyimino -1- phenyl-propane -1- ketone, 2- Benzoyloxyimino -1- phenyl-propane -1- Ketone, 3- (4- tosyloxy) iminobutanes -2- ketone and 2- ethyoxyl carbonyloxy group imino group -1- phenyl-propane -1- ketone Deng.

In addition, can also enumerate: " Britain's chemistry meeting will, Charles Bell gold transactions II (J.C.S.Perkin II) " (1979) Pp.1653-1660, " Britain's chemistry meeting will, Charles Bell gold transactions II " (1979) pp.156-162, " photopolymer science and skill Art magazine (Journal of Photopolymer Science and Technology) " (nineteen ninety-five) pp.202-232, day The compound recorded in this patent special open 2000-66385 bulletin, Japanese Patent Laid-Open 2000-80068 bulletin, Japan are specially Li Tebiao 2004-534797 bulletin, Japanese Patent Laid-Open 2006-342166 bulletin each bulletin in documented compound Deng.

Commercially available product can also properly use gorgeous good solid (IRGACURE)-OXE01 (BASF AG's manufacture), gorgeous good solid (IRGACURE)-OXE02 (BASF AG's manufacture).In addition, it is possible to use (Changzhou electronic strong new material has TR-PBG-304 The manufacture of limit company), Ai Dike Acker your (Adeka Arkls) NCI-831 and Ai Dike Acker your (Adeka Arkls) NCI- 930 (manufactures of Chinese mugwort Dicon A/S).

In addition, as the oxime compound other than the record, it is possible to use be linked with the Japan Patent of oxime on the position N of carbazole Documented compound in special table 2009-519904 bulletin, the United States Patent (USP) that miscellaneous substituent group is imported on benzophenone position Documented compound in No. 7626957 bulletin, the Japanese Patent Laid-Open 2010-15025 that nitro is imported on pigment position Compound, the published International patent 2009-131189 bulletin recorded in number bulletin and U.S. Patent Publication 2009-292039 In documented ketoxime compounds, same intramolecular contain in No. 7556910 bulletins of United States Patent (USP) of triazine skeleton and oxime skeleton Documented compound has the Japan Patent of good sensitivity special with absorption maximum at 405nm and for g ray source Open the compound etc. recorded in 2009-221114 bulletin.

It preferably for example can refer to 0274~paragraph of paragraph 0275 of Japanese Patent Laid-Open 2013-29760 bulletin, in Appearance can be incorporated into present specification.

Specifically, as oxime compound, preferably by the compound represented by following formula (OX-1).Furthermore the N-O of oxime Key can be the oxime compound of (E) body, can also be the oxime compound of (Z) body, can also be the mixture of (E) body and (Z) body.

[changing 56]

In general formula (OX-1), R and B separately indicate that the substituent group of monovalence, A indicate that the organic group of divalent, Ar indicate Aryl.

In general formula (OX-1), as the substituent group by the monovalence represented by R, the preferably nonmetallic atom group of monovalence.

It as the nonmetallic atom group of monovalence, can enumerate: alkyl, aryl, acyl group, alkoxy carbonyl, aryloxycarbonyl, miscellaneous Ring group, alkylthiocarbonyl, arylthiocarbonyl etc..In addition, these bases can also have more than one substituent group.In addition, described take Dai Ji can also be further substituted with by other substituent groups.

As substituent group, can enumerate: halogen atom, aryloxy group, alkoxy carbonyl or aryloxycarbonyl, acyloxy, acyl group, Alkyl, aryl etc..

In general formula (OX-1), as the substituent group by the monovalence represented by B, preferably aryl, heterocycle, aryl carbonyl, Or heterocyclecarbonyl.These bases can have more than one substituent group.As substituent group, the substituent group can be illustrated.

In general formula (OX-1), as the organic group by the divalent represented by A, the preferably alkylidene of carbon number 1~12, sub- ring Alkyl, alkynylene.These bases can have more than one substituent group.As substituent group, the substituent group can be illustrated.

Following presentation is by the concrete example of the compound represented by general formula (OX-1), but the present invention is not limited to these are specific Example.

[changing 57]

Oxime compound is that have maximum absorption wave elder in the wavelength region of 350nm~500nm, preferably in 360nm There is maximum absorption wave elder, the high oxime of the absorbance in particularly preferably 365nm and 405nm in the wavelength region of~480nm Compound.

For the viewpoint of sensitivity, molar absorption coefficient of the oxime compound in 365nm or 405nm be preferably 1,000~ 300,000, more preferably 2,000~300,000, particularly preferably 5,000~200,000.

Well known method can be used to measure for the molar absorption coefficient of compound, such as is preferably divided using UV, visible light Photometer ((Carry) -5 spectrophotometer (spectrophotometer) in the card of Varian (Varian) manufacture), and utilize Ethyl acetate solvent is measured with the concentration of 0.01g/L.

Photoepolymerizationinitiater initiater used in the present invention can optionally combine two or more use.

When coloured composition of the invention contains Photoepolymerizationinitiater initiater, relative to the total solid content of coloured composition, The content of Photoepolymerizationinitiater initiater is preferably the 0.1 mass % of mass %~50, more preferably the 0.5 mass % of mass %~30, in turn More preferably 1 mass of mass %~20 %.In the range, more good sensitivity and patternability can get.

Composition of the invention can only contain a kind of Photoepolymerizationinitiater initiater, can also contain two or more.When containing there are two types of with When upper, preferably its total amount becomes the range.

<<other compositions>>

In addition to each ingredient, coloured composition of the invention can also in the range of lossless effect of the invention, into And contain the other compositions such as solvent, crosslinking agent, polymerization inhibitor, surfactant, organic carboxyl acid, organic carboxyl acid acid anhydride.

<<<organic solvent>>>

Coloured composition of the invention can also contain solvent.

As long as solvent meets the dissolubility of each ingredient or the coating of coloured composition, substantially it is not particularly limited, but Preferably consider that pigment polymer (A), the dissolubility of polymerizable compound etc., coating, safety select.

As solvent,

As esters, for example, can suitably enumerate ethyl acetate, acetic acid-N-butyl, isobutyl acetate, cyclohexyl acetate, Amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Ethoxyacetic acid Arrcostab (such as: ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester (such as methoxyacetic acid first Ester, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc.)), 3- oxygroup propionic acid Alkyl esters (such as: 3- oxygroup methyl propionate, 3- oxygroup ethyl propionate etc. (such as 3- methoxy methyl propionate, 3- methoxy propyl Acetoacetic ester, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate etc.)), 2- oxygroup alkyl propionates class (such as: 2- oxygroup third Sour methyl esters, 2- oxygroup ethyl propionate, 2- oxygroup propyl propionate etc. (such as 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- ethoxypropanoate, 2- ethoxyl ethyl propionate)), 2- oxygroup -2 Methylpropionic acid methyl esters and 2- oxygroup -2 Methylpropionic acid ethyl ester (such as 2- methoxyl group -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2 Methylpropionic acid ethyl ester etc.), Methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2- Oxobutyric etc.,

As ethers, such as it can suitably enumerate diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol Single ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl two Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.,

As ketone, such as can suitably enumerate methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-HEPTANONE, 3- heptanone etc., with And

As aromatic hydrocarbon, such as it can suitably enumerate toluene, dimethylbenzene etc..

It, will for the viewpoint of the dissolubility of pigment polymer (A), polymerizable compound etc., the improvement for being coated with planar etc. Two or more these solvents mixing it is also preferred that.For example, it is preferable to be following mixed solution, it includes be selected from 3- ethoxy-propionic acid Methyl esters, 3- ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- first Oxygroup methyl propionate, 2-HEPTANONE, cyclopentanone, cyclohexanone, ethylcarbitol acetate, acetate of butyl carbitol, propylene glycol first It is two or more in ether and propylene glycol methyl ether acetate.

For the viewpoint of coating, the content of solvent is preferably that the total solid content concentration of coloured composition becomes 5 matter Measure the amount of the mass of %~80 %.Lower limit is for example more preferably 5 mass % or more, and then more preferably 10 mass % or more.The upper limit Such as more preferably 60 mass % hereinafter, be more preferably 50 mass % or less in turn.

Coloured composition of the invention can only contain a kind of solvent, can also contain two or more.When containing two or more, Preferably its total amount becomes the range.

<<<crosslinking agent>>>

Coloured composition of the invention can also contain crosslinking agent.By containing crosslinking agent, it also can further improve and obtained Cured film hardness.

As crosslinking agent, as long as film hardening person can be carried out by cross-linking reaction, then it is not particularly limited.Such as it can arrange It lifts: (a) epoxy resin；(b) through replacing selected from least one of methylol, alkoxy methyl and pivaloyloxymethyl substituent group Melamine compound, guanamines compound, glycoluril compounds or carbamide compound；(c) through selected from methylol, alkoxy methyl, And oxybenzene compound, naphthol compound or hydroxyl anthracene compound that at least one of pivaloyloxymethyl substituent group replaces.Wherein, Preferably polyfunctional epoxy resin.

The details of concrete example about crosslinking agent etc. can refer to Japanese Patent Laid-Open 2004-295116 bulletin The record of 0134~paragraph of paragraph 0147, content can be incorporated into present specification.

When coloured composition of the invention contains crosslinking agent, the content of crosslinking agent is simultaneously not specially provided, but relative to The total solid content of color composition, the preferably 2 mass % of mass %~30, more preferably 3 mass of mass %~20 %.

Coloured composition of the invention can only contain a kind of crosslinking agent, can also contain two or more.When containing two or more When, preferably its total amount becomes the range.

<<<polymerization inhibitor>>>

In coloured composition of the invention, in order to prevent in the manufacturing process of coloured composition or during preservation The unwanted thermal polymerization of polymerizable compound, it is generally desirable to add a small amount of polymerization inhibitor.

It as polymerization inhibitor, can enumerate: hydroquinone, p methoxy phenol, di-t-butyl-paracresol, biphenyl 3 phenol (pyrogallol), tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-6-tert-butylphenol), N- nitroso phenylhydroxylamine cerous salt etc..

When coloured composition of the invention contains polymerization inhibitor, relative to the quality of coloured composition, Inhibition of polymerization The content of agent is preferably from about 0.01 mass of mass %~5 %.

Coloured composition of the invention can only contain a kind of polymerization inhibitor, can also contain two or more.There are two types of containing When above, preferably its total amount becomes the range.

<<<surfactant>>>

In coloured composition of the invention, for further promoting the viewpoint of coating, various surfaces can also be added Activating agent.As surfactant, it can be used fluorine system surfactant, nonionic surfactants, cationic system surface living The various surfactants such as property agent, anionic surfactant, silicone-based surfactant.

For example, (especially being flowed as coating fluid come characteristics of liquids when preparing by containing fluorine system surfactant Property) further promoted.That is, when using the coloured composition containing fluorine system surfactant to form film, make to be applied face with The interfacial tension of coating fluid declines, and is thus improved for being applied the wetability in face, and the coating for being applied face It is promoted.Therefore, even if can also more appropriately carry out thickness just in the case where forming several μm or so of film with a small amount of liquid measure For the viewpoint that uneven small film in homogeneous thickness is formed effectively.

Fluorine the containing ratio suitably 3 mass % of mass %~40, more preferably 5 mass % in fluorine system surfactant~ 30 mass %, particularly preferably 7 mass of mass %~25 %.Fluorine containing ratio is that the fluorine system surfactant in the range just applies For the uniformity of the thickness of cloth film or the viewpoint of province's fluidity effectively, the dissolubility in coloured composition is also good.

It as fluorine system surfactant, such as can enumerate: Mei Jiafa (Megafac) F171, Mei Jiafa (Megafac) F172, Mei Jiafa (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F177, Mei Jiafa (Megafac) F141, Mei Jiafa (Megafac) F142, Mei Jiafa (Megafac) F143, Mei Jiafa (Megafac) F144, beauty Good method (Megafac) R30, Mei Jiafa (Megafac) F437, Mei Jiafa (Megafac) F475, Mei Jiafa (Megafac) F479, Mei Jiafa (Megafac) F482, Mei Jiafa (Megafac) F554, Mei Jiafa (Megafac) F780, Mei Jiafa (Megafac) F781 (more than, DIC (share) manufacture), Fu Luode (Fluorad) FC430, Fu Luode (Fluorad) FC431, Fu Luode (Fluorad) FCl71 (more than, Sumitomo 3M (Sumitomo 3M) (share) manufacture), Sha Fulong (Surflon) S-382, Sha Fu Grand (Surflon) SC-101, Sha Fulong (Surflon) SC-103, Sha Fulong (Surflon) SC-104, Sha Fulong (Surflon) SC-105, Sha Fulong (Surflon) SC1068, Sha Fulong (Surflon) SC-381, Sha Fulong (Surflon) SC-383, Sha Fu Grand (Surflon) S393, Sha Fulong (Surflon) KH-40 (more than, Asahi Glass (share) manufacture), PF636, PF656, PF6320, PF6520, PF7002 (manufacture of Ou Nuofa (OMNOVA) company) etc..

As nonionic surfactants, specifically, can enumerate: glycerol, trimethylolpropane, trimethylolethane And these ethoxylate and propoxylate (such as glycerol propoxylate, glycerol ethoxylate etc.), polyoxy second Alkene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, ethylene nonyl Phenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan alcohol fatty acid ester (BASF AG Pluronic (Pluronic) L10, L31, L61, L62,10R5,17R2,25R2 of manufacture, Te Luoke (Tetronic) 304, 701,704,901,904,150R1), rope exerts Paasche (Solsperse) 20000 (Japanese Lu Borun (Lubrizol) (share)) Deng.

As cationic system surfactant, specifically, can enumerate: phthalocyanine derivates (trade name: Efka (EFKA) -745, gloomy lower industry (share) manufacture), organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (share) manufacture), (methyl) acrylic acid series (co) polymerization body Po Lifuluo (Polyflow) No.75, No.90, No.95 (common prosperity society chemistry (share) Manufacture), W001 (abundant quotient's (share) manufacture) etc..

As anionic surfactant, specifically, can enumerate: W004, W005, W017 (abundant quotient's (share) company Manufacture) etc..

It as silicone-based surfactant, such as can enumerate: " the beautiful silicone in east of beautiful DOW CORNING (share) manufacture in east (Toray Silicone) DC3PA ", " beautiful silicone (Toray Silicone) SH7PA in east ", " beautiful silicone (Toray in east Silicone) DC11PA ", " beautiful silicone (Toray Silicone) SH21PA in east ", " the beautiful silicone (Toray Silicone) in east SH28PA ", " beautiful silicone (Toray Silicone) SH29PA in east ", " beautiful silicone (Toray Silicone) SH30PA in east ", " east It is public to step figure new high-tech material (Momentive Performance Materials) by beautiful silicone (Toray Silicone) SH8400 " Take charge of " TSF-4440 ", " TSF-4300 ", " TSF-4445 ", " TSF-4460 ", " TSF-4452 " of manufacture, SHIN-ETSU HANTOTAI's silicon benefit light " KP341 ", " KF6001 ", " KF6002 " of (Shinetsu silicone) limited liability company manufacture, Bi Ke chemical company system " BYK307 " that makes, " BYK323 ", " BYK330 " etc..

When containing surfactant in coloured composition of the invention, relative to the gross mass of coloured composition, table The content of face activating agent is preferably the 0.001 mass % of mass %~2.0, more preferably 0.005 mass of mass %~1.0 %.

Composition of the invention can only contain a kind of surfactant, can also contain two or more.When containing two or more When, preferably its total amount becomes the range.

<<<organic carboxyl acid, organic carboxyl acid acid anhydride>>>

Coloured composition of the invention can also contain organic carboxyl acid, and/or organic carboxyl acid acid anhydride.Organic carboxyl acid, organic carboxyl acid The molecular weight of acid anhydride is preferably 1000 or less.As organic carboxyl acid and the concrete example of organic carboxyl acid acid anhydride, such as it can refer to Japan Patent 0338~paragraph of paragraph 0340 of special open 2013-29760 bulletin, content can be incorporated into present specification.

When coloured composition of the invention contains organic carboxyl acid, and/or organic carboxyl acid acid anhydride, relative to coloured composition The content of total solid content, organic carboxyl acid and/or organic carboxyl acid acid anhydride is preferably the 0.01 mass % of mass %~10, more preferably The 0.03 mass % of mass %~5, and then more preferably 0.05 mass of mass %~3 %.

Coloured composition of the invention can only contain a kind of organic carboxyl acid and/or organic carboxyl acid acid anhydride respectively, can also contain two Kind or more.When containing two or more, preferably its total amount becomes the range.

In coloured composition of the invention, optionally adjustable various additives, such as filler, contiguity promotor, Antioxidant, ultraviolet absorbing agent, anticoalescent etc..As these additives, Japanese Patent Laid-Open 2004-295116 can be enumerated Recorded person in 0155~paragraph of paragraph 0156 of number bulletin, these content can be incorporated into present specification.

In coloured composition of the invention, the paragraph 0078 containing Japanese Patent Laid-Open 2004-295116 bulletin In documented sensitizer or light stabilizer, the bulletin paragraph 0081 in documented thermal polymerization preventing agent.

Coloured composition of the invention is prepared by mixing the ingredient.

When preparing coloured composition, each ingredient for constituting coloured composition can be disposably deployed, it can also be molten by each ingredient Solution is successively deployed after being scattered in solvent.In addition, there is no particular restriction for ordering in launching or operating condition when being deployed.Example Such as, all the components can be dissolved simultaneously and is scattered in solvent to prepare composition, can also be suitable for first system by each ingredient optionally At two or more solution dispersion liquids, these solution dispersion liquids are mixed as composition system (when coating) when in use It is standby.

In order to remove foreign matter or reduction defect etc., coloured composition of the invention is preferably filtered using filter. As filter, as long as the filter since before for filtration applications etc., then can use without particular limitation.Such as it can It enumerates and utilizes fluororesin such as polytetrafluoroethylene (PTFE) (Polytetrafluoroethylene, PTFE), nylon-6, nylon-6,6 is equal poly- Amide system resin, the polyolefin resins such as polyethylene, polypropylene (Polypropylene, PP) (high density contains super high molecular weight) Deng filter.Among these raw material, preferably polypropylene (include high density poly propylene).

Suitably 0.01 μm~7.0 μm or so of the aperture of filter, preferably 0.01 μm~3.0 μm or so, more preferably It is 0.05 μm~0.5 μm or so.By being set as the range, can certainly remove hinder in the next steps it is uniform and smooth The fine foreign matter of the preparation of coloured composition.

When a fitter is used, different filters can also be combined.At this point, utilizing the filtering of the first filter It can only carry out 1 time, can also carry out 2 times or more.

In addition, the first different filter of aperture can also be combined in the range.Aperture herein can join According to the nominal value of filter manufacturer.As commercially available filter, such as can be from Japan quite that (Pall) limited liability company, love More Bang get Ke Japan (Advantec Toyo) limited liability companies, the limited public affairs of Japan Ying Tege (Nihon Entegris) share Department (former Japan Mi Keli (Mykrolis) limited liability company) or damp microstrainer (Kitz Microfilter) share in north are limited It is selected in various filters provided by company etc..

Second of filter, which can be used, is formed by filter with material identical with the first described filter etc..

For example, the filtering using the first filter can be carried out only in dispersion liquid, after mixing other compositions, the is carried out 2 filterings.

Coloured composition of the invention, therefore can be suitably because that can form the good cured film of light resistance, migrating property, flatness It is used to form the coloring layer of chromatic filter.In addition, coloured composition of the invention can suitably be used as charge coupled cell (CCD), complementary metal oxide film semiconductor (Complementary Metal Oxide Semiconductor, CMOS) etc. The colored pattern of chromatic filter used in the image display devices such as solid state photo element or liquid crystal display device etc. is formed Use coloured composition.In turn, the production purposes of printing ink, ink-jet ink and coating etc. can also be suitably used as.Wherein, it can fit Manufacture preferably for chromatic filters of solid state photos element such as CCD and CMOS.

Then, for chromatic filter of the invention, pattern forming method and chromatic filter, via its manufacturing method It is described in detail.In addition, being also illustrated to the manufacturing method for the chromatic filter for using pattern forming method of the invention.

Chromatic filter of the invention is winner using coloured composition of the invention.

Coloured composition of the invention is applied to form coloring compositions on supporter by pattern forming method of the invention Nitride layer, and unwanted part is removed, to form colored pattern.

Pattern forming method of the invention can suitably be applied to the formation of the colored pattern of chromatic filter.

Pattern forming method of the invention can be formed using so-called photoetching process to carry out pattern, and dry-etching can also be used Method is formed to carry out pattern.

That is, the first form of the manufacturing method of chromatic filter of the invention includes: to answer coloured composition of the invention The step of being used to support on body to form coloring compositions nitride layer, by coloring compositions nitride layer exposure at the step of pattern-like and will The step of unexposed portion's development removes and forms colored pattern.It optionally may also set up the step toasted to coloring compositions nitride layer Suddenly (pre-bake step) and the step of toasted to developed colored pattern (rear baking procedure).

In addition, the second form of the manufacturing method of chromatic filter of the invention includes: by coloured composition of the invention Applied to forming coloring compositions nitride layer on supporter, and the step of making it harden and form coloring layer；It is formed on coloring layer The step of photoresist layer；And photoresist layer being patterned by being exposed and developing obtain resist figure The step of case；And resist pattern is formed to the step of colored pattern as etching mask to coloring layer progress dry-etching Suddenly.

Chromatic filter of the invention can suitably be obtained using the manufacturing method.These are chatted in detail below It states.

<<the step of forming coloring compositions nitride layer>>

In the step of forming coloring compositions nitride layer, coloured composition of the invention is applied to be formed on supporter Color composition layer.

As supporter, such as it may be used on substrate (such as silicon substrate) and is provided with the solid state photos such as CCD or CMOS member The solid state photo component substrate of part (light receiving element).

Colored pattern in the present invention can be formed in the solid state photo element forming face side (table of solid state photo component substrate Face), non-solid photographic element can also be formed in and form surface side (back side).

In order to improve with the contiguity of the layer on top, prevent the diffusion of substance or for the planarization of substrate surface, depending on needing Priming coat can also be set on supporter.

As towards the method for applying coloured composition of the invention on supporter, slot coated, ink-jet method, rotation can be used The various methods such as coating, cast coat, roller coating, silk screen print method.

Applied to the coloring compositions nitride layer on supporter drying (prebake conditions) can by hot plate, baking oven etc., 50 DEG C~ It is carried out 10 seconds~300 seconds at a temperature of 140 DEG C.

<<using photoetching process come (the first form) the case where carrying out pattern formation>>

<<<step of exposure>>>

Then, the coloring compositions nitride layer that will be formed on supporter is exposed at pattern-like (step of exposure).Such as use step Into exposure devices such as machines, the coloring compositions nitride layer being formed on supporter is carried out across the mask with defined mask pattern Exposure, thus can carry out pattern exposure.Exposed portion can be made to harden as a result,.

As the radioactive ray (light) that can be used in exposure, it is preferable to (especially excellent using ultraviolet lights such as g ray, i rays It is selected as i ray).Exposure (light exposure) is for example preferably 30mJ/cm²~1500mJ/cm², more preferably 50mJ/cm²~ 1000mJ/cm², most preferably 80mJ/cm²~500mJ/cm²。

The film thickness of cured film is preferably 1.0 μm hereinafter, more preferably 0.1 μm~0.9 μm, and then more preferably 0.2 μm~ 0.8μm.By the way that film thickness is set as 1.0 μm hereinafter, being easy to get high analyticity, high density of access.

<<<pattern forming step>>>

Then, removal is developed into unexposed portion to form colored pattern (pattern forming step).The development in unexposed portion is gone It is carried out except developer solution can be used.The coloring compositions nitride layer in the unexposed portion in step of exposure is dissolved out into developer solution as a result, and Only remain the part through photo-hardening.

As developer solution, it is generally desirable to not aobvious to the hurtful organic basic such as the solid state photo element of substrate or circuit Shadow liquid.

The temperature of developer solution is for example preferably 20 DEG C~30 DEG C.Developing time is preferably 20 seconds~180 seconds.In addition, in order to Residue removal is promoted, following step can also be repeated as many times: be shaken off developer solution every 60 seconds, and then supply development again Liquid.

As alkaline agent used in developer solution, such as ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, hydrogen-oxygen can be enumerated Change tetramethyl-ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide benzyltrimethylammon.um, gallbladder The organic basic compounds such as alkali, pyrroles, piperidines, 1,8- diazabicyclo-[5,4,0] -7- hendecene.As developer solution, preferably The 0.001 mass % of mass %~10 is become with concentration to use, preferably becomes the mode of 0.01 mass of mass %~1 %, benefit Alkaline aqueous solution made of being diluted with pure water to these alkaline agents.

In addition, inorganic base can also be used in developer solution, as inorganic base, such as preferably sodium hydroxide, potassium hydroxide, Sodium carbonate, sodium bicarbonate, sodium metasilicate, sodium metasilicate etc..

Furthermore when having used the developer solution comprising such alkaline aqueous solution, usually after development, carried out using pure water clear Wash (elution).

After development, preferably heated (rear baking) after implementing drying.If forming the color-patch map of multiple color Case then can be repeated in step for various colors to manufacture cured film.It can get chromatic filter as a result,.

Baking is to realize the heat treatment after fully hardened development afterwards, heating temperature is for example preferably 100 DEG C~ 240 DEG C, more preferably 200 DEG C~240 DEG C.

The heating mechanisms such as hot plate or convection oven (hot air circulation type drying machine), high frequency heating machine can be used, to become institute The mode for stating condition, baking is handled after being carried out by continous way or batch-type to the film after development.

<<using dry etching method come (the second form) the case where carrying out pattern formation>>

The coloring compositions nitride layer being formed on supporter hardening can be made to form coloring layer, then, by patterned light It causes resist layer as mask, and carries out the pattern shape using dry etching method to coloring layer obtained using etching gas At.

Specifically, the radiation sensitive compositions of eurymeric or minus are coated on coloring layer, and make it dry, thus Form photoresist layer.In the forming process of photoresist layer, preferably and then implement prebake conditions processing.In particular, making For the formation process of photoresist layer, it is generally desirable to the heat treatment after implementing exposure, (the rear baking of the heat treatment after development Processing) form.

As photoresist layer, such as preferably, use feeling answers ultraviolet light (g ray, h ray, i ray), comprising standard The radiation sensitive compositions of the eurymeric of the radioactive ray such as far ultraviolet, electron beam, ion beam and the X-ray of molecular laser etc..It puts Among ray, preferably g ray, h ray, i ray, wherein more preferably i ray.

Specifically, the radiation sensitive compositions as eurymeric, preferably solvable containing quinone di-azido compound and alkali The composition of property resin.The radiation sensitive compositions of eurymeric containing quinone di-azido compound and alkali soluble resin are to utilize Quinonediazide group is decomposed by the light irradiation of 500nm wavelength below and generates carboxyl, is as a result become from the insoluble state of alkali Alkali-soluble person.The positive light anti-etching agent is used for integrated circuit (Integrated because parsing power is significantly excellent Circuit, IC) or the integrated circuits such as large scale integrated circuit (Large Scale Integration, LSI) production.As Quinone di-azido compound can enumerate naphthalene quinone di-azido compound.As commercially available product, such as " FHi622BC " (Fuji's glue can be enumerated The manufacture of piece electronic material (Fujifilm Electronic Materials) company) etc..

As the thickness of photoresist layer, preferably 0.1 μm~3 μm, more preferably 0.2 μm~2.5 μm, so that it is more excellent It is selected as 0.3 μm~2 μm.Furthermore the painting in already described coloring layer can be used in the coating method of the radiation sensitive compositions of eurymeric Cloth method and suitably carry out.

Then, photoresist layer is exposed and is developed, be consequently formed and be provided with the against corrosion of resist through hole group Agent pattern (patterned photoresist layer).There is no particular restriction for the formation of resist pattern, can be suitable for known before being allowed to Photoetching technology optimize to carry out.Resist through hole group is set in photoresist layer by exposure and imaging, Thus resist pattern used in next etching as etching mask is set on coloring layer.

The exposure of photoresist layer can carry out in the following way: across defined mask pattern, utilize g ray, h Ray, i ray etc., preferably i ray implement exposure to the radiation sensitive compositions of eurymeric or minus.After exposure, using aobvious Shadow liquid carries out development treatment, thus removes photoresist in conjunction with the region of colored pattern to be formed.

As developer solution, as long as impacting not against chromatograph, and keep the exposure portion of positive-workingresist and minus against corrosion The unhardened portion dissolution person of agent, may be used any developer solution.Such as the combination of various solvents or the aqueous solution of alkalinity can be used. As the aqueous solution of alkalinity, the 0.001 mass % of mass %~10 is appropriately become with concentration, preferably becomes 0.01 mass % The mode of~5 mass % dissolves alkaline aqueous solution prepared by alkali compounds.Alkali compounds can for example be enumerated: hydroxide Sodium, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium metasilicate, ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, tetramethylphosphonihydroxide hydroxide base Ammonium, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8- diazabicyclo [5,4,0] -7- hendecene etc..Furthermore work as use When alkaline aqueous solution, usually implement cleaning treatment using water after development.

Then, using resist pattern as etching mask, dry type is utilized in a manner of forming through hole group on coloring layer Etching is to be patterned.Colored pattern is formed as a result,.Through hole group is for example preferably set to coloring layer in chessboard trellis On.The 1st colored pattern made of through hole group is arranged on coloring layer as a result, has the of multiple quadrangles in chessboard trellis 1 colored pixels.

As dry-etching, just forms the viewpoint of pattern section closer to rectangle or be further reduced for supporter For the viewpoint of damage, carried out preferably by form below.

It preferably include the form of following etching: using fluorine-based gas and oxygen (O₂) mixed gas, be etched The etching in the 1st stage until the region (depth) that supporter does not expose；After the etching in the 1st stage, nitrogen is used Gas (N₂) and oxygen (O₂) mixed gas, be etched until preferably supporter expose region (depth) nearby until The etching in the 2nd stage；And the over etching (over etching) carried out after supporter exposing.Hereinafter, to dry-etching Specific method and the etching in the 1st stage, the etching in the 2nd stage and over etching be illustrated.

Dry-etching is carried out after finding out etching condition in advance using following methods.

(1) etch-rate (nm/min) in the etching in the 1st stage and the etching in the etching in the 2nd stage are calculated respectively Rate (nm/min).

(2) etching using the 1st stage is calculated respectively to etch the time of desired thickness and utilize for the 2nd stage It etches to etch the time of desired thickness.

(3) etching period calculated according to (2) implements the etching in the 1st stage.

(4) etching period calculated according to (2) implements the etching in the 2nd stage.Or terminal can also be used Detection implements the etching in the 2nd stage according to the etching period determined to determine etching period.

(5) overetch time is calculated relative to the total ascent time of (3) and (4), and implements over etching.

Mixed gas used in etching step as the 1st stage will just add as the organic material for being eclipsed engraved film It preferably include fluorine-based gas and oxygen (O for the rectangular viewpoint of work₂).In addition, by by the etching step in the 1st stage It is set as being etched the form until the region that supporter does not expose, and can avoid the damage of supporter.In addition, just Being etched through the region that supporter does not expose using fluorine-based gas and the implementation of the mixed gas of oxygen in the etching step in 1 stage is After only, for the viewpoint for avoiding the damage of supporter, the etching step and over etching in the 2nd stage are preferably a step using nitrogen And the mixed gas of oxygen is etched.

The ratio of etch quantity in the etching step in the 1st stage and the etch quantity in the etching step in the 2nd stage is important It is to be determined in such a way that the etching process in the lossless etching step by the 1st stage is formed by rectangularity.Furthermore total etch quantity The ratio of the latter in (summation of the etch quantity in the etching step in the 1st stage and the etch quantity in the etching step in the 2nd stage) Rate is preferably greater than 0% and for 50% range below, more preferably 10%~20%.So-called etch quantity refers to that basis is eclipsed The amount that the film thickness of the remaining of engraved film and the difference of the film thickness before etching are calculated.

In addition, etching is preferably handled comprising over etching.After over etching processing preferably setting over etching ratio It carries out.In addition, over etching ratio is preferably calculated according to the time of the etching process initially carried out.Over etching ratio can It arbitrarily sets, but for maintaining the viewpoint of the elching resistant of photoresist and the rectangularity for being etched pattern, preferably 30% of etch processes time in etching step is hereinafter, more preferably 5%~25%, and particularly preferably 10%~15%.

Then, resist pattern (i.e. etching mask) remaining after the etching is removed.The removal of resist pattern is preferred To include following step: stripper or solvent being assigned to resist pattern, and form the shape that can remove resist pattern The step of state；And the step of being removed resist pattern using ejected wash water.

It assigns as by stripper or solvent to resist pattern, and forms the step that can remove the state of resist pattern Suddenly, it such as can enumerate: stripper or solvent are at least assigned to resist pattern, and stop the defined time to carry out covering liquid The step of formula is developed.As stripper or solvent residence time is made, there is no particular restriction, but preferably tens seconds~rather Clock.

In addition, the step of as resist pattern is removed using ejected wash water, such as can enumerate: self-spray formula or fountain Injection nozzle towards resist pattern jet cleaning water, and the step of resist pattern is removed.As ejected wash water, it is preferable to Use pure water.In addition, can enumerate as injection nozzle: entire supporter includes injection nozzle or work in its spray regime For movable injection nozzle and its movable range includes the injection nozzle of entire supporter.When injection nozzle is movable, In the step of removing resist pattern, movement is more than twice until self-supporter central part to supporter end and injection is clear Thus wash water can more effectively remove resist pattern.

Stripper usually contains organic solvent, can contain inorganic solvent in turn.It as organic solvent, such as can enumerate: 1) Hydrocarbon system compound, 2) halogenated hydrocarbon based compound, 3) alcohol based compound, 4) ether based compound or acetal based compound, 5) ketone system Close object or aldehyde based compound, 6) ester based compound, 7) polyalcohol based compound, 8) carboxylic acid based compound or its acid anhydrides system chemical combination Object, 9) phenol system compound, 10) nitrogenous compound, 11) sulfur-containing compound, 12) fluorochemical.As stripper, preferably contain There is nitrogenous compound, more preferably contains non-annularity nitrogenous compound and cyclic nitrogen compound.

As non-annularity nitrogenous compound, it is however preferred to have the non-annularity nitrogenous compound of hydroxyl.Specifically, for example may be used Enumerate monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N- ehtylethanolamine, N, N- dibutylethanolamine, N- butyl alcohol Amine, monoethanolamine, diethanol amine, triethanolamine etc., preferably monoethanolamine, diethanol amine, triethanolamine, more preferably single second Hydramine (H₂NCH₂CH₂OH).In addition, as cyclic nitrogen compound, isoquinolin, imidazoles, N-ethylmorpholine, ε-can be enumerated in oneself Amide, quinoline, 1,3- dimethyl -2- imidazolidinone, α-methylpyridine, beta-picoline, γ-picoline, pipecoline, 3- methyl piperidine, 4- methyl piperidine, piperazine, piperidines, pyrazine, pyridine, Pyrrolizidine, n-methyl-2-pyrrolidone, n-phenylmorpholine Quinoline, 2,4- lutidines, 2,6- lutidines etc., preferably n-methyl-2-pyrrolidone, N-ethylmorpholine, more preferably For n-methyl-2-pyrrolidone (N-Methyl-2-Pyrrolidone, NMP).

Stripper preferably contains non-annularity nitrogenous compound and cyclic nitrogen compound, wherein more preferably containing work For containing selected from least one of monoethanolamine, diethanol amine and triethanolamine, and as ring-type for non-annularity nitrogenous compound Nitrogen compound is selected from least one of n-methyl-2-pyrrolidone and N-ethylmorpholine, and then more preferably containing single second Hydramine and n-methyl-2-pyrrolidone.

When being removed using stripper, as long as will be formed in the resist pattern removal on colored pattern, i.e., It, can also be incomplete when box lunch is attached on the side wall of colored pattern as the deposit (deposited matter) of etch products Ground removes deposit.So-called deposit refers to that etch products are adhered to and are piled up on the side wall of coloring layer and winner.

As stripper, it is generally desirable to which the content of non-annularity nitrogenous compound is 9 mass relative to 100 mass parts of stripper Part or more, 11 below the mass, the content of cyclic nitrogen compound relative to 100 mass parts of stripper be 65 mass parts or more, 70 below the mass.In addition, stripper is preferably to utilize pure water to non-annularity nitrogenous compound and cyclic nitrogen compound Mixture is diluted and winner.

The manufacturing method of chromatic filter of the invention can optionally have as solid state photo element chromatic filter Manufacturing method well known to step as other than described the step of.For example, the coloring compositions nitride layer shape can also carried out After step, step of exposure and pattern forming step, optionally comprising making to be formed by color-patch map by heating and/or exposing The cure step of case hardening.

In addition, in order to efficiently clean the nozzle of apparatus for coating blowing unit or blocking with pipe portion, by coloured composition or The dry caused pollution etc. of attachment precipitating of the pigment in coating machine, preferably by with coloured composition phase of the invention The solvent of pass is used as cleaning solution.In addition, Japanese Patent Laid-Open 7-128867 bulletin, Japanese Patent Laid-Open can be properly used Flat 7-146562 bulletin, Japanese Patent Laid-Open 8-278637 bulletin, Japanese Patent Laid-Open 2000-273370 bulletin, Japanese Patent Laid-Open 2006-85140 bulletin, Japanese Patent Laid-Open 2006-291191 bulletin, Japanese Patent Laid-Open 2007- Remembered in No. 2101 bulletins, Japanese Patent Laid-Open 2007-2102 bulletin, Japanese Patent Laid-Open 2007-281523 bulletin etc. The cleaning solution of load.

Among described, preferably alkylene glycol monoalkyl ethers carboxylate and alkylene glycol monoalkyl ethers.

These solvents can be used alone, and can also be use mixing two or more.When by two or more mixing, preferably will Solvent with hydroxyl is mixed with the solvent for not having hydroxyl.The mass ratio of solvent and the solvent for not having hydroxyl with hydroxyl It is 1/99~99/1, preferably 10/90~90/10, more preferably 20/80~80/20.Particularly preferably propylene glycol monomethyl ether second Acid esters (Propylene Glycol Monomethyl Ether Acetate, PGMEA) and propylene glycol monomethyl ether (Propylene Glycol Monomethyl Ether, PGME) mixed solvent, and its ratio be 60/40.Furthermore in order to promote cleaning solution pair In the permeability of pollutant, the surfactant relevant to coloured composition of the invention can also be added into cleaning solution.

Chromatic filter of the invention is because using coloured composition of the invention, therefore light resistance, migrating property, flatness are excellent It is different.

Chromatic filter of the invention may be suitably used to the solid state photos element such as CCD, CMOS, particularly suitable to be such as more than High-resolution CCD of 1000000 pixels or CMOS etc..Solid state photo element chromatic filter of the invention, which can be used, for example, as, matches Set the chromatic filter between the lenticule in the light receiver for constituting each pixel of CCD or CMOS and for optically focused.

The film thickness of colored pattern (colored pixels) in chromatic filter of the invention is preferably 2.0 μm hereinafter, more preferably For 1.0 μm hereinafter, being more preferably 0.7 μm or less in turn.

In addition, the size (pattern width) as colored pattern (colored pixels), preferably 2.5 μm hereinafter, more preferably 2.0 μm hereinafter, particularly preferably 1.7 μm or less.

Solid state photo element of the invention has the chromatic filter of the invention.As solid state photo member of the invention The composition of part, as long as the composition for having chromatic filter of the invention and functioning as solid state photo element, then have no It is particularly limited to, such as the composition that can be listed below.

The composition is as follows: having on supporter and constitutes solid state photo element (ccd image sensor, cmos image biography Sensor etc.) optical receiving region multiple optical diodes and transfer electrode comprising polysilicon etc., in optical diode and transfer electricity The extremely upper photomask comprising tungsten etc. with the light receiver opening only to optical diode, has on photomask to cover shading The device protective film comprising silicon nitride etc. that the entire surface of film and the mode of optical diode light receiver are formed is protected in device There is solid state photo element chromatic filter of the invention on film.

In turn, can also be following composition etc.: on device protecting layer and under chromatic filter (close to supporter it Side) there is optically focused mechanism (such as lenticule etc..It is same as below) composition, or with optically focused mechanism on chromatic filter It constitutes.

Chromatic filter of the invention can be used for the images such as liquid crystal display device or organic electroluminescence display device and method of manufacturing same and show Device.Purposes particularly suitable for liquid crystal display device.The liquid crystal display device for having chromatic filter of the invention can be shown The tone of high resolution image, the display image of the high resolution image is good and display characteristic is excellent.

About the definition of display device or the details of each display device, for example " (assistant assistant wood is clear for electron display device Husband write, the census of manufacturing meeting (Kogyo Chosakai Publishing) (share) nineteen ninety issue) ", " (she blows suitable display device Chapter write, industry books (Sangyo Tosho) (share) 1989 issue) " etc. in it is on the books.In addition, being filled about liquid crystal display It sets, has note in such as " next-generation LCD technology (Uchida Tatsuo edits, and issues for census of manufacturing meeting (share) 1994) " It carries.Liquid crystal display device of the invention can be applied, and there is no particular restriction, such as can be applied to " the next-generation liquid crystal display skill Art " in documented various modes liquid crystal display device.

Chromatic filter of the invention can also be used for colorful film transistor (Thin Film Transistor, TFT) side The liquid crystal display device of formula.About the liquid crystal display device of colored TFT mode, for example " color TFT-LCD display is (vertical altogether (share) 1996 is published to issue) " in it is on the books.In turn, it is can also be applied to coplanar switching (In-Plane Switching, IPS) etc. transverse electric fields driving method, multidomain vertical orientation (Multi-Domain Vertical Alignment, MVA) etc. pixels partitioning scheme etc. the visual angle liquid crystal display device or STN Super TN (Super that are extended Twisted Nematic, STN), twisted nematic (Twisted Nematic, TN), vertical orientation (Vertical Alignment, VA), optical compensation inclination (Optically Compensated Splay, OCS), fringing field switch (Fringe Field Switching, FFS) and optical compensation curved (the Reflective Optically Compensated of reflection Bend, R-OCB) etc..

In addition, the chromatic filter in the present invention is also available for bright and fine color filter array (Color- Filter On Array, COA) mode.Requirement characteristic in the liquid crystal display device of COA mode, for color filter layer Except it is as described above it is common require characteristic in addition to, it is sometimes desirable to the requirement characteristic for interlayer dielectric, i.e. low-k And resistance to removing fluidity.Chromatic filter of the invention can provide high resolution and long durability is excellent because light resistance etc. is excellent The liquid crystal display device of different COA mode.Furthermore it, can also be in chromatic filter in order to meet the requirement characteristic of low-k Resin coating is set on layer.

About these image display patterns, for example " EL, plasma display panel (Plasma Display Panel, PDP), the new advancement-in LCD display-technology and market (investigate by the beautiful research center (Toray Research Center) in east Research department 2001 issues) " page 43 etc. in it is on the books.

Have the liquid crystal display device of the chromatic filter in the present invention in addition to the chromatic filter in the present invention, also wraps The various components such as film are ensured containing electrode base board, light polarizing film, phase difference film, backlight, distance piece, visual angle.Colored filter of the invention Light device can be applied in the liquid crystal display device comprising these well known components.About these components, in such as " ' 94 liquid crystals Show the market (island Itou Kentaro CMC (share) 1994 issue) of device periphery material chemicals ", " 2003 liquid crystal correlation cities (Biao Liangji Fuji Kai Meilai always grinds (Fuji Chimera Research to the status and vision of the future (last volume) of field Institute) (share), 2003 issue) " in it is on the books.

About backlight, in " Society of Information Display conference summary (SID (The Society for Information Display) meeting Digest) " 1380 (2005) (A. modern wild (A.Konno) et al.) or " display monthly magazine (Monthly Display) " page 18 of in December, 2005 number~page 24 (island health is abundant), " display monthly magazine " in December, 2005 number the 25th It is on the books in page~page 30 (Yagi spark gap is grand bright) etc..

If the chromatic filter in the present invention is used for liquid crystal display device, as three with well known cold-cathode tube before Wavelength tube can realize high contrast when combining, in turn, by by light emitting diode (the Light Emitting of red, green, blue Diode, LED) light source as backlight can provide that brightness is high, excitation purity is high and the good liquid crystal display dress of colorrendering quality It sets.

[embodiment]

Hereinafter, the present invention is further illustrated by embodiment, it is but as long as the present invention is without departing from its purport, then and unlimited Due to embodiment below.Furthermore as long as " % " and " part " is quality criteria in advance without special instruction.

[changing 58]

<<synthesis of intermediary 1>>

By 31 parts of 3,6- dichloro sulfo group fluorane (DCSF) (middle tank formation manufacture), 67 parts of 2,6-DIPA, chlorination 17 parts of zinc, 120 parts of sulfolane additions are into flask, and 200 degree of temperature lower stirring 8 hours outside.Thereafter, place be cooled to room temperature for Only, the reaction solution is added dropwise in 600 parts of 2N hydrochloric acid water, and filters out crystallization be precipitated.It is right using 600 parts of acetonitrile of 40 degree After crystallization carries out dispersion cleaning, leaching is carried out, then progress blowing drying in 10 hours, and 42.5 parts of acquisition (yield: 82%) Intermediary 1.

<<synthesis of intermediary 2>>

11 parts of intermediary 1 and 50 parts of phosphorous oxychloride are added and stirred 4 hours into flask, and at 60 DEG C.It places cold But until room temperature, the reaction solution is added dropwise in 150 parts of ice water, and is stirred 30 minutes.Filter out crystallization obtained, and benefit It is cleaned with 20 parts of water.Thereafter, it is dissolved in crystallization obtained in 150 parts of chloroform, and carries out diatomite filtering.It utilizes 5% 100 parts of saline solution, 100 parts of 15% saline solution carry out liquid separation cleaning to filtrate.The filtrate is being done using sodium sulphate It after dry, is concentrated under reduced pressure, and obtains 12.1 parts of (yields: intermediary 2 91%).

<<synthesis of intermediary 3>>

15 parts of phenyl-pentafluoride sulfonic acid chloride, 300 parts of tetrahydrofuran (Tetrahydrofuran, THF) are added into flask, and Interior temperature is cooled to -10 DEG C.In such a way that reaction solution maintains 0 DEG C below, 6.8 parts of 28% ammonium hydroxide is added dropwise thereto.After dropwise addition, After being stirred 1 hour at 0 DEG C, reaction solution is filtered.Filtrate obtained is concentrated under reduced pressure, after THF is removed, addition 100 parts of water, and be stirred.Solid obtained is filtered, blowing drying in 10 hours is carried out after being washed, and is obtained 11.7 parts of (yields: intermediary 3 84%).

<<synthesis of intermediary 4>>

15 parts of intermediary 3,4.9 parts of 2 mercapto ethanol, 100 parts of methanol are added in flask, and carried out at room temperature Stirring.In such a way that the temperature of reaction solution is no more than 30 DEG C, 6.5 parts of triethylamine are added dropwise thereto.At room temperature to the reaction Liquid stirs 1 hour, after being concentrated under reduced pressure, adds 90 parts of ethyl acetate, 80 parts of saturated salt solution, saturated sodium bicarbonate thereto 10 parts of water, and carry out liquid separation operation.After being extracted using 90 parts of ethyl acetate to water layer, added into organic layer obtained Magnesium sulfate.After being filtered, filtrate is concentrated under reduced pressure, then progress blowing drying in 10 hours, and 17 parts of acquisition (yield: 92%) intermediary 4.

<<synthesis of intermediary 5>>

Intermediary 4,25 parts of the acrylic acid 2- isocyanatoethyl methacrylate (AOI, Showa electrician manufacture), dibutyl hydroxyl of 49 parts of addition 0.2 part of base toluene (BHT), 95 parts of dimethyl acetamide, 0.1 part of Nai Sitai (Neostann) U-600 (the chemical conversion manufacture of day east), and It is stirred 1 hour at 85 DEG C.Then, 500 parts of ethyl acetate, 500 parts of saturated salt solution are added thereto and carry out liquid separation operation. After adding sodium sulphate into organic layer obtained, filtered out, and filtrate is concentrated under reduced pressure.It is right using 170 parts of chloroform It after solid obtained carries out suspension cleaning, is filtered, drying is then blowed, thus to obtain 60 parts of (yields: 84%) Intermediary 5.

<<synthesis of xanthene compound (A-xt-1)>>

5 parts of intermediary 5,50 parts of methylene chloride, 3.4 parts of triethylamine are added in flask, and are stirred at room temperature It mixes.10.8 parts of intermediary 2 is added thereto, and is stirred at room temperature 2 hours.After reaction, 200 parts of chloroform, pure is added 500 parts of water, 200 parts of saturated salt solution, and carry out liquid separation operation.Sodium sulphate is added into organic layer obtained, is dehydrated Afterwards, it is filtered out, and filtrate is concentrated under reduced pressure.It is dissolved in solid obtained in chloroform, utilizes chloroform/ethyl acetate Solvent is simultaneously refined using column chromatography, thus to obtain 12.5 parts of (yields: A-xt-1 86%).

< xanthene compound (A-xt-2), xanthene compound (A-xt-4), xanthene compound (A-xt-6), xanthene compound (A-xt-7), xanthene compound (A-xt-9), xanthene compound (A-xt-12), xanthene compound (A-xt-15) synthesis example >

Copy xanthene compound (A-xt-1) the Lai Hecheng xanthene compound (A-xt-2), xanthene compound (A-xt- 4), xanthene compound (A-xt-6), xanthene compound (A-xt-7), xanthene compound (A-xt-9), xanthene compound (A-xt- 12), xanthene compound (A-xt-15).

[synthesis of pigment polymer S-1]

[changing 59]

Under stream of nitrogen gas, by multi-functional thiol (compound of the structure of (SH-1), SC Organic Chemical Industry (stock Part) manufacture) 1.0 parts, 13.7 parts of xanthene compound (A-xt-1), 2.1 parts of methacrylic acid (MAA) and 9.0 parts of cyclohexanone it is mixed It closes solution and is heated to 80 DEG C.Bis- (isobutyric acid) dimethyl ester [V-601 of 2,2 '-azos are added thereto；And pure medicine manufacture] 0.254 After part, heating stirring 2 hours at 80 DEG C.And then after adding 0.254 part of V-601, heating stirring 2 hours at 80 DEG C, into And heating stirring 2 hours at 90 DEG C.After until being cooled to room temperature, 30.7 parts of cyclohexanone, Tetrabutylammonium bromide (TBAB) are added 0.32 part, 1.8 parts of glycidyl methacrylate (GMA), and heating stirring 18 hours at 80 DEG C.Until being cooled to room temperature Afterwards, reaction solution is added dropwise in the mixed solvent of 250 parts of hexane, 250 parts of ethyl acetate and carries out reprecipitation, and it is more to obtain pigment Aggressiveness S-1.

The weight average molecular weight (polystyrene scaled value) of pigment polymer S-1 is 14500, by using 0.1N hydrogen-oxygen Change the titration of sodium water solution, acid value 40mgKOH/g.

In addition, measuring using NMR (nuclear magnetic resonance), the repetitive unit with pigmentary structures of polymer chain Q is calculated Quantity average out to 4.5.Prepare the S-1's of the pigment polymer containing 0.01mg/ml in addition, being dissolved in tetrahydrofuran (THF) Solution (concentration adjusted in such a way that maximum absorbance becomes 1.0) measures institute using optical path length for the unit of 1cm Absorbance of the solution at 25 DEG C is stated, as a result maximum absorption wavelength (λ max) is 535nm, and the ratio of maximum absorption wavelength (λ max) is inhaled Luminosity is 44.

[pigment polymer S-2~pigment polymer S-52 synthesis]

Except multi-functional thiol, the type of various monomers and amount, the amount of V-601, the amount of GMA, the amount of TBAB are altered to down It states other than table, copies the synthetic method of pigment polymer S-1 and obtain pigment polymer S-2~pigment polymer S-52.

It is dissolved in each pigment polymer in tetrahydrofuran (THF), and is adjusted to wavelength in 400nm~800nm most Big absorbance becomes 1.0 concentration, the unit for the use of optical path length being 1cm, and calculates the solution according to following formula (A λ) and exist Absorbance at 25 DEG C.

E=A/ (c × 1) ... (A λ)

A indicates the absorbance in the maximum absorption wavelength in 400nm~800nm,

L indicates the element length that unit is indicated by cm,

[table 1]

The type of documented monomer in following presentation table.

[changing 60]

[changing 61]

[changing 62]

[changing 63]

Compare pigment (S ' -1), compares pigment (S ' -2), compares pigment (S ' -3): following structures

[changing 64]

(synthesis for comparing pigment (S ' -3))

[changing 65]

Triaryl methane compounds are synthesized according to documented method in Japanese Patent Laid-Open 2000-162429 bulletin (A-tp-101)。

By triaryl methane compounds (A-tp-101) (15g), hydroxyethyl methacrylate (10g), methacrylic acid (5.5g) and azobis isobutyronitrile (5g) are added in N- ethyl pyrrolidone (70g), and be stirred at room temperature come within 30 minutes into Row dissolution (is added dropwise and uses polymeric solution).

In addition, by triaryl methane compounds (A-tp-101) (15g), hydroxyethyl methacrylate (10g) and methyl Acrylic acid (5.5g) is added into container to be dissolved, and is stirred at 80 DEG C.It lasts 3 hours and is added dropwise thereto and is made Standby dropwise addition polymeric solution adds azo isobutyronitrile (2.5g) after stirring 1 hour, and then stops after reacting 2 hours.It is cooling After until room temperature, solvent is evaporated, and obtains and compares pigment 3.The weight average molecular weight (Mw) for comparing pigment 3 is 18000, By using the titration of 0.1N sodium hydrate aqueous solution, acid value 1.81mgKOH/g.

1. the preparation of anti-corrosion liquid

After the ingredient of following compositions is mixed and dissolved, it is filtered using 0.45 μm of nylon filter, thus prepares bottom Coating anti-corrosion liquid.

The composition of priming coat anti-corrosion liquid

Solvent: 19.20 parts of propylene glycol methyl ether acetate

Solvent: 36.67 parts of ethyl lactate

Alkali soluble resin: benzyl methacrylate/methacrylic acid/methacrylic acid -2- hydroxy methacrylate copolymer The 40%PGMEA of (molar ratio=60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) is molten 30.51 parts of liquid

Polymerizable compound: ((Japanese chemical drug is public by Ka Yala get (KAYARAD) DPHA for dipentaerythritol hexaacrylate Department's manufacture)) 12.20 parts

Polymerization inhibitor: 0.0061 part of p methoxy phenol

Fluorine system surfactant: F-475, DIC (share) manufacture 0.83 part

Photoepolymerizationinitiater initiater: ((Midori is learned in TAZ-107, greening to the Photoepolymerizationinitiater initiater of trihalomethyl triazine system Kagaku) chemical company manufactures) 0.586 part

2. the production of the silicon wafer substrate with priming coat

Heat within 30 minutes with 200 DEG C of silicon wafers to 6 inches (inch) in an oven.Then, by priming coat It is coated on the silicon wafer in such a way that dry film thickness becomes 1.5 μm with anti-corrosion liquid, and then carries out 1 in 220 DEG C of baking oven Hour heat drying and form priming coat, to obtain the silicon wafer substrate for having priming coat.

3. the preparation of coloured composition

The preparation of 3-1. Blue pigment dispersion liquid

(preparation of dispersible pigment dispersion P1 (C.I. pigment blue 15: 6 dispersion liquids))

Dispersible pigment dispersion P1 (C.I. pigment blue 15: 6 dispersion liquids) is prepared as follows.

That is, using ball mill (beads mill) (zirconium oxide bead, diameter 0.3mm), to C.I. pigment blue 15: 6 is (blue Color pigment；Hereinafter also referred to " PBl5:6 ") 19.4 mass parts (average primary particle diameter 55nm) and dispersion resin BY-161 (finish The manufacture of gram chemical company) 2.95 mass parts, it is calculated as with solid component conversion the alkali soluble resin J1 (methyl-props of 2.95 mass parts Olefin(e) acid benzyl ester/methacrylic acid copolymer, 30%PGMEA solution) (solution is 9.93 mass parts), 165.3 mass parts The mixed liquor that PGMEA is mixed carries out the dispersion of mixing in 3 hours.Thereafter, and then the good pressure distribution for having the mechanism of decompressor is used Machine nanometer (NANO) -3000-10 (Japanese BEE (share) manufacture), in 2000kg/cm³Pressure under with the flow of 500g/min Carry out decentralized processing.The decentralized processing is repeated 10 times, and obtains the C.I. pigment blue 15 as dispersible pigment dispersion: 6 dispersions Liquid.For C.I. pigment blue 15 obtained: 6 dispersion liquids utilize dynamic light scattering method (Microtrac Nanotrac UPA- EX150 (Ji Zhuan company (Nikkiso Co., Ltd.) manufacture)) measurement pigment average primary particle diameter, result 24nm.

Alkali soluble resin J1

[changing 66]

The preparation of 3-2. coloured composition

Dispersion, dissolution, are filtered using 0.45 μm of nylon filter after following each ingredients is mixed, thus to obtain Color composition.

Organic solvent (cyclohexanone): 17.12 parts

Alkali soluble resin 1 (following J1): 1.23 parts (solid component is 0.37 part, solid component concentration 30%)

Alkali soluble resin 2 (Povidone-Iodine Solution (Acrycure)-RD-F8 (Japanese catalyst Co. manufacture)): 0.23 part

Photoepolymerizationinitiater initiater I-2 (gorgeous good solid (IRGACURE) OXE-02):

0.975 part

The cyclohexanone solution (solid component concentration 12.3%) of pigment polymer: 24.57 parts

Dispersible pigment dispersion P1 (C.I. pigment blue 15: 6 dispersion liquids, PGMEA solution, solid component concentration 12.8%): 51.40 parts

Polymerizable compound Z-1 (the modified dipentaerythritol hexaacrylate of inferior ethoxyl, NK ESTER A-DPH-12E (manufacture of chemical company, the village Xin Zhong)): 1.96 parts

Polymerization inhibitor (p methoxy phenol): 0.0007 part

Fluorine system surfactant (F475 of DIC company manufacture, 1%PGMEA solution): 2.50 parts

4. the production of chromatic filter (colored pattern)

4-1: photolithographic production is utilized using the chromatic filter of coloured composition

The above prepared coloured composition is coated on to the priming coat of the above made silicon wafer with priming coat On, and form coloring layer (coated film).Then, using 100 DEG C of hot plate, become 1 μm with the dry film thickness of the coated film Mode carries out heat treatment (prebake conditions) in 120 seconds.

Then, using i ray step printing device FPA-3000i5+ (Canon's (Canon) (share) manufacture), Under the wavelength of 365nm, through island (Island) pattern mask for the square that pattern is 1.0 μm of each side, with 50mJ/cm²~ 1200mJ/cm²Light exposure be exposed.

Thereafter, the silicon wafer substrate for being formed with the coated film through irradiating is placed in rotary spray developing machine (DW-30 Type, chemical electron (Chemitronics) (share) manufacture) horizontal rotating table on, use CD-2000 (Fujiphoto electronics material Material (share) manufacture) covering liquid formula development in 60 seconds is carried out at 23 DEG C, and formed on the priming coat of the silicon wafer with priming coat Colored pattern.

The silicon wafer for being formed with colored pattern is fixed on horizontal rotating table in the way of vacuum chuck, utilizes rotation Device rotates silicon wafer with the revolving speed of 50rpm, and from the top of its rotation center, supplies from jetting nozzle in shape spray pure Water carries out elution processing.It is followed by spray-dried, is toasted after being carried out 300 seconds at 200 DEG C using hot plate, and obtain silicon wafer The colored pattern (chromatic filter) that the film thickness of on piece is 1 μm.

In the above manner, and obtaining and being provided with colored pattern (colour on the priming coat of the silicon wafer with priming coat Optical filter) composition the silicon wafer with colored pattern.

Thereafter, using survey long scan formula electron microscope (Scanning Electron Microscope, SEM) " S- 9260A " (Hitachi's apex scientific and technological (Hitachi High-Technologies) (share) manufacture), measures the size of colored pattern.

Become the colored pattern of 1.0 μm of light exposure using pattern dimension, carries out the evaluation of development residue.

Using scanning electron microscope, with the forming region of the colored pattern in 30000 times of multiplying power observation silicon wafer Outside (unexposed portion), it and is evaluated according to following evaluation criteria.

A: (unexposed portion) does not confirm residue completely outside colored pattern forming region.

B: outside colored pattern forming region (unexposed portion), residue is slightly confirmed, but is the journey of practical upper no problem Degree.

C: (unexposed portion) confirms residue outside colored pattern forming region.60 will be carried out at 23 DEG C of development conditions leisure Second covering liquid formula development is altered to carry out covering liquid formula development in 180 seconds at 23 DEG C, thus becomes the degree of practical upper no problem.

D: (unexposed portion) obviously confirms residue outside colored pattern forming region.

<<migrating property evaluation>>

Utilize the absorbance of the colored pattern in each chromatic filter of MCPD-3000 (big tomb electronics (share) manufactures) measurement (absorbance A).

By CT-2000L solution, (Fujiphoto electronic material (share) is manufactured in such a way that dry film thickness becomes 1 μm；It is transparent Substrate agent) be coated in the colored pattern forming face of chromatic filter, and be dried, after forming hyaline membrane, at 280 DEG C into Heat within row 5 minutes.

After heating, the transparent of colored pattern is adjacent to using MCPD-3000 (big tomb electronics (share) manufactures) measurement The absorbance (absorbance B) of film.

For the value of the absorbance B of hyaline membrane obtained, the suction relative to the colored pattern measured before heating is calculated The ratio [%] [following (formula A)] of the value of luminosity A.It is set to the finger evaluated towards the gamut of adjacent pixels (pixel) Mark.

(formula A) gamut (%)=(absorbance B/ absorbance A) × 100

A: less than 1%

B:1% or more, less than 3%

C:3% or more, less than 10%

D:10% or more

<<Investigation on Photodegradation>>

Using spin coater (three large bamboo hats with a conical crown and broad brim (Mikasa) (share) manufacture), by the above prepared coloring photosensitive combination It is coated on glass substrate, and forms film.Then, in such a way that the dry film thickness of the film becomes 0.6 μm, 100 are used DEG C hot plate carry out heat treatment (prebake conditions) in 120 seconds.Then, heating in 5 minutes is carried out at 200 DEG C, and is coated film Hardening form coloring layer.

Using Light Resistance Test device (must congratulate testing machine (Suga Test Instrument) company manufacture SX-75), 63 DEG C of black flour plate temperature, quartzy internal filters, 275nm end external filters, illumination 75mw/m²(300nm~400nm), Under conditions of humidity 50%, implement 10 hours light fastness tests to the glass substrate for being formed with coloring layer.

Utilize the color before and after spectrophotometer MCPD-3000 (big tomb electronics (share) company manufactures) measurement light fastness test Poor (Δ E*ab).Light resistance is evaluated based on the color difference (Δ E*ab) measured, and according to following evaluation criteria.It may be said that described Numerical value is smaller, and light resistance is the better.It shows the results of the evaluation in following tables.A and B is the level of no problem in actual use.

A: Δ E*ab is 3 or less

B: Δ E*ab is greater than 3 and is 5 or less

C: Δ E*ab is greater than 5 and is 10 or less

D: Δ E*ab is greater than 10

<<evaluation of flatness>>

Using spin coater (manufacture of three large bamboo hats with a conical crown and broad brim (share) company), the above prepared coloured composition 1.0mL is coated with In on 4 inch silicon wafers, and form film.Then, in such a way that the dry film thickness of the central part of the film becomes 0.60 μm, Heat treatment (prebake conditions) in 120 seconds is carried out using 100 DEG C of hot plates and forms coloring layer.

The film thickness of coloring layer is measured using optical profile type film thickness gauge (happy (Filmetrics) (share) F20 of phenanthrene).It may be said that The most thin part of film thickness (central part) and the difference of most thick part (peripheral portion) are smaller the better.Show the results of the evaluation following tables In.A and B is the level of no problem in actual use.

A: the difference of film thickness is 0.02 μm or less

B: the difference of film thickness is greater than 0.02 μm and is 0.05 μm or less

C: the difference of film thickness is greater than 0.05 μm.

<2~embodiment of embodiment 52,1~comparative example of comparative example 3>

In " preparation of 3-2. coloured composition " in embodiment 1, such as following tables change dispersible pigment dispersion, pigment poly Body (pigment), Photoepolymerizationinitiater initiater, alkali soluble resin, polymerizable compound, in addition to this, with side same as Example 1 Formula prepares coloured composition, and evaluates development residue, migrating property, light resistance, flatness in the same manner as example 1.

Furthermore 1~comparative example of comparative example 3 uses the relatively pigment S ' -1~compare pigment S ' -3 as pigment poly Body.

[table 2]

According to described as a result, migrating property, light resistance, the flatness of the coloured composition of 1~embodiment of embodiment 52 are excellent. In turn, development residue is few, and developability is excellent.

On the other hand, any one of the migrating property of 1~comparative example of comparative example 3 or flatness be not good enough.

Then, using spin coater, coloured composition obtained is coated in such a way that film thickness becomes 0.5 μm On the glass substrate of 7.5cm × 7.5cm, and hot plate is used, carry out heating for 5 minutes at 200 DEG C, and is coated the hardening of film To make coloring layer.The film thickness of the coloring layer is 0.5 μm.

Then, it is coated with positive light anti-etching agent " FHi622BC " (manufacture of Fujiphoto Electronic Materials Corp), and at 90 DEG C It is lower to implement prebake conditions processing in 1 minute, and form the photoresist layer that film thickness is 0.8 μm.

Then, using i ray stepper (Canon's (share) manufacture), with 350mJ/cm²Light exposure to photoresist Layer carries out pattern exposure, then carries out adding for 1 minute at a temperature of the temperature of photoresist layer or environment temperature become 90 DEG C Heat treatment.Thereafter, the development treatment that 1 minute is carried out using developer solution " FHD-5 " (manufacture of Fujiphoto Electronic Materials Corp), into And the rear baking implemented at 110 DEG C 1 minute is handled, and form resist pattern.The size of the resist pattern is to consider Etching conversion is poor (by the diminution for etching caused pattern width), and is formed so that one side is 1.0 μm.

Then, the glass substrate for being formed with photoresist layer is attached on 8 inch silicon wafers, is filled using dry-etching (U-621, the manufacture of apex scientific & technical corporation, Hitachi) is set, radio frequency (Radio Frequency, RF) power is set as 800W, by antenna Bias is set as 400W, and wafer bias is set as 200W, and the internal pressure of reaction chamber is set as 4.0Pa, substrate temperature is set as 50 DEG C, the gaseous species of mixed gas and flow are set as CF₄: 80mL/min, O₂: 40mL/min, Ar:800mL/min., and implement The etching process in 80 seconds the 1st stages.

Then, in the same etching reaction room, RF power is set as 600W, antenna bias is set as 100W, by chip Bias is set as 250W, and the internal pressure of reaction chamber is set as 2.0Pa, and substrate temperature is set as 50 DEG C, by the gas of mixed gas Type and flow are set as N₂: 500mL/min, O₂: 50mL/min, Ar:500mL/min (N₂/O₂/ Ar=10/1/10), and implement The etching process in 28 seconds the 2nd stages.

After carrying out dry-etching with the condition, photoresist stripper " MS230C " (Fujiphoto electronics is used Materials Co., Ltd's manufacture), implement 120 seconds lift-off processings at 50 DEG C and removes resist, and form colored pattern.And then implement Using the cleaning of pure water, rotary drying, thereafter, dehydration baking processing in 2 minutes is carried out at 100 DEG C.In the above manner and Obtain chromatic filter.

For chromatic filter obtained, migrating property, light resistance, flatness are evaluated in the same manner as example 1.

Organic solvent (cyclohexanone): 17.12 parts

Epoxy resin JER1031S (Mitsubishi Chemical's (share) manufacture, epoxide equivalent: 180-220 (g/eq.)): 4.395 parts

Dispersible pigment dispersion (referring to following tables): 51.40 parts

Polymerization inhibitor (p methoxy phenol): 0.0007 part

[table 3]

According to described as a result, embodiment 53, the migrating property of the coloured composition of embodiment 54, light resistance, flatness are excellent.

The abbreviation of documented compound is as follows in table.

Photoepolymerizationinitiater initiater: following structures

[changing 67]

Alkali soluble resin: following structures

[changing 68]

Polymerizable compound

Z-1: the modified dipentaerythritol hexaacrylate of the inferior ethoxyl, (village Xin Zhong NK ester (NK ESTER) A-DPH-12E Company manufacture)

Z-2: dipentaerythritol hexaacrylate, Ka Yala get (KAYARAD) DPHA (Japanese chemical drug corporation is made)

Z-3: ethoxylation (4) pentaerythritol tetraacrylate, SR494 (Sartomer's manufacture)

Z-4: ethoxylation (3) trimethylolpropane trimethacrylate, SR454 (Sartomer's manufacture)

Z-5: ethoxylation (6) trimethylolpropane trimethacrylate, SR499 (Sartomer's manufacture)

Z-6: Ka Yala get (KAYARAD) DPCA-60 (Japanese chemical drug corporation is made)

Z-7: three (2- hydroxyethyl) isocyanurate triacrylates, SR368 (Sartomer's manufacture)

Dispersible pigment dispersion

Dispersible pigment dispersion P2 (C.I. pigment blue 15: 6 dispersion liquids):

In the preparation of dispersible pigment dispersion P1, replace dispersion resin BY-161 using following dispersion resin D1, except this with Outside, dispersible pigment dispersion P2 is prepared using identical operation.

[changing 69]

Mw=20000, x/y=50/50 (mass ratio), n=20, acid value=100mgKOH/g

Dispersible pigment dispersion P3 (C.I. pigment blue 15: 6 dispersion liquids):

In the preparation of dispersible pigment dispersion P1, replace dispersion resin BY-161 using following dispersion resin D2, except this with Outside, dispersible pigment dispersion P3 is prepared using identical operation.

[changing 70]

Mw=20000, x/y=15/85 (mass ratio), n=20, acid value=100mgKOH/g

Dispersible pigment dispersion P4 (C.I. pigment Violet 23 dispersion liquid):

In the preparation of dispersible pigment dispersion P1, C.I. pigment Violet 23 is used to replace PB15:6 as pigment, in addition to this, By with dispersible pigment dispersion P1 prepare it is identical in a manner of prepare dispersible pigment dispersion P4.

Dispersible pigment dispersion P5 (254 dispersion liquid of C.I. paratonere):

In the preparation of dispersible pigment dispersion P1, use C.I. paratonere 254 to replace PB15:6 as pigment, except this with Outside, by with dispersible pigment dispersion P1 prepare it is identical in a manner of prepare dispersible pigment dispersion P5.

Dispersible pigment dispersion P6 (58 dispersion liquid of C.I. naphthol green):

In the preparation of dispersible pigment dispersion P1, C.I. naphthol green 58 is used to replace PB15:6 as pigment, in addition to this, By with dispersible pigment dispersion P1 prepare it is identical in a manner of prepare dispersible pigment dispersion P6.

Dispersible pigment dispersion P7 (9 dispersion liquid of C.I. pigment yellow 13):

In the preparation of dispersible pigment dispersion P1, use C.I. pigment yellow 13 9 to replace PB15:6 as pigment, except this with Outside, by with dispersible pigment dispersion P1 prepare it is identical in a manner of prepare dispersible pigment dispersion P7.

Claims

1. a kind of coloured composition comprising by the pigment polymer and polymerizable compound represented by general formula (1)；

P-(Q)_n···(1)

In general formula (1), what P indicated to derive from polyalcohol includes comprising 1~100 carbon atoms, 0~10 nitrogen-atoms, 0 The concatenating group of the n valence of the base of a~50 oxygen atoms, 1~200 hydrogen atoms and 0~20 sulphur atoms,

Q indicates containing the polymer chain by the repetitive unit represented by general formula (a1-1), n Q by general formula (a1-1) represented by Repetitive unit number average value be two or more,

N indicates 3~10 integer,

In general formula (a1-1), Q¹Indicate the concatenating group that trivalent is formed by by polymerization,

L¹Indicate singly-bound, the alkylidene of carbon number 1~30, the arlydene of carbon number 6~30, heterocycle ,-CH=CH- ,-O- ,-S- ,-C (=O)-,-CO₂-、-NR-、-CONR-、-O₂C-、-SO-、-SO₂Or these two or more is linked and formed two The concatenating group of valence, R indicate hydrogen atom, alkyl, aryl or heteroaryl,

D¹It indicates to be originated from selected from triarylmethane pigment, xanthene pigment, anthraquinone pigment, anthocyanidin, the sour inner salt pigment in side, quinoline Phthalein ketone pigment, phthalocyanine dye, sub- phthalocyanine dye, azopigment and the pigment in two pyrroles's methylene pigments pigmentary structures,

* the associative key with main chain is indicated.

2. coloured composition according to claim 1, wherein the pigment polymer is indicated by general formula (2)；

In general formula (2), A¹Indicate the concatenating group of n valence,

B¹Indicate singly-bound ,-O- ,-S- ,-CO- ,-NR- ,-O₂C-、-CO₂,-NROC- or-CONR-, R indicate hydrogen atom, alkyl Or aryl,

C¹Indicate the concatenating group of singly-bound or divalent,

S indicates sulphur atom,

The meaning of Q is identical as the Q in general formula (a1-1),

N indicates 3~10 integer.

3. coloured composition according to claim 2, wherein the A¹To include the rouge that can have oxygen atom on main chain The combined base of one or more of fat race alkyl, aromatic series ring group and heterocycle.

4. coloured composition according to any one of claim 1 to 3, wherein the pigment polymer 400nm~ In maximum absorption wavelength in 800nm is 5 or more by the ratio absorbance represented by following formula (A λ)；

E=A/ (c × l) (A λ)

A indicates the absorbance in the maximum absorption wavelength in 400nm~800nm,

L indicates the element length that unit is indicated by cm,

5. coloured composition according to any one of claim 1 to 3, wherein relative to the total solid of the coloured composition Body ingredient contains 1 mass of mass %~50 % of pigment polymer.

6. coloured composition according to any one of claim 1 to 3, wherein the pigment polymer is to make by general formula (3) compound represented by is selected from triarylmethane pigment, xanthene pigment, anthraquinone pigment, anthocyanidin, side with having to be originated from Color in sour inner salt pigment, quinophthalone pigment, phthalocyanine dye, sub- phthalocyanine dye, azopigment and two pyrroles's methylene pigments The pigmentary structures of element and the compound of radically polymerizable group carry out free radical polymerization institute winner,

P⁰-(SH)_n···(3)

In general formula (3), P⁰Indicate to derive from polyalcohol includes comprising 1~100 carbon atoms, 0~10 nitrogen-atoms, 0 The concatenating group of the n valence of the base of a~50 oxygen atoms, 1~200 hydrogen atoms and 0~20 sulphur atoms,

SH indicates mercapto,

N indicates 3~10 integer.

7. coloured composition according to any one of claim 1 to 3 further includes the color other than the pigment polymer Element.

8. coloured composition according to any one of claim 1 to 3 further includes Photoepolymerizationinitiater initiater.

9. coloured composition according to any one of claim 1 to 3, wherein the Q contains selected from the weight with acidic group Multiple one or more of unit and the repetitive unit with polymerism base.

10. coloured composition according to any one of claim 1 to 3, wherein the Q is selected from (methyl) acrylic acid series One of resin, phenylethylene resin series and (methyl) acrylic/styrene system resin.

11. a kind of chromatic filter is formed using coloured composition according to any one of claim 1 to 10.

12. a kind of pattern forming method comprising:

Coloured composition according to any one of claim 1 to 10 is applied to form coloured composition on supporter The step of layer；

The step of coloring compositions nitride layer is exposed into pattern-like；And

The step of exposure is formed into colored pattern at the unexposed portion development removal of the coloring compositions nitride layer of pattern-like.

13. a kind of pattern forming method comprising:

Coloured composition according to any one of claim 1 to 10 is applied to form coloured composition on supporter Layer, and the step of making it harden and form coloring layer；

In the step of forming photoresist layer on the coloring layer；

The step of obtaining resist pattern and being patterned the photoresist layer by being exposed and developing；With And

The resist pattern forms coloring layer progress dry-etching as etching mask to the step of colored pattern Suddenly.

14. a kind of manufacturing method of chromatic filter comprising pattern forming method according to claim 12 or 13.

15. a kind of solid state photo element comprising chromatic filter according to claim 11 or by according to claim The manufacturing method of chromatic filter described in 14 chromatic filter obtained.

16. a kind of image display device comprising chromatic filter according to claim 11 or by according to claim The manufacturing method of chromatic filter described in 14 chromatic filter obtained.

17. a kind of manufacturing method of pigment polymer, be by general formula (1) represented by pigment polymer manufacturing method, and Compound represented by including making by general formula (3), with have be originated from selected from triarylmethane pigment, xanthene pigment, anthraquinone pigment, Anthocyanidin, the sour inner salt pigment in side, quinophthalone pigment, phthalocyanine dye, sub- phthalocyanine dye, azopigment and two pyrroles's methylene The pigmentary structures of pigment in pigment and the compound of radically polymerizable group carry out free radical polymerization,

P⁰-(SH)_n···(3)

SH indicates mercapto,

N indicates 3~10 integer,

P-(Q)_n···(1)

N indicates 3~10 integer,

* the associative key with main chain is indicated.