CN106987154A

CN106987154A - The manufacture method of dyestuff lysate, colored curable resin composition, colour filter and the display device for including above-mentioned dyestuff lysate

Info

Publication number: CN106987154A
Application number: CN201710025846.4A
Authority: CN
Inventors: 赤坂哲郎; 金奉建; 嘉村亮平
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2016-01-14
Filing date: 2017-01-13
Publication date: 2017-07-28
Anticipated expiration: 2037-01-13
Also published as: CN106987154B; KR20170085452A; TWI739780B; JP2017128709A; JP6889543B2; TW201736523A; KR102114958B1

Abstract

The present invention provides the manufacture method of the excellent xanthene dye lysate of ageing stability, includes colored curable resin composition, colour filter and the display device of above-mentioned dyestuff lysate.The present invention relates to the manufacture method of dyestuff lysate, it is characterised in that includes：In the presence of an organic at least one kind of process being stirred in the salt of (a) xanthene dye and (b) selected from organic acid and the compound containing silicon atom.

Description

The manufacture method of dyestuff lysate, the colored curable for including above-mentioned dyestuff lysate Resin combination, colour filter and display device

Technical field

The present invention relates to the manufacture method of dyestuff lysate.

Background technology

In order to be carried out using reflected light or transmitted light in the field such as in fibrous material, liquid crystal display device, ink-jet Color is shown, has used dyestuff.As such dyestuff, it is known that being represented for example with xanthene skeleton, by following formula (Rb) Rhodamine B (non-patent literature 1).

Prior art literature

Non-patent literature

Non-patent literature 1：Thin Tian Fengzhu " reactive monoazo dyestuffs chemistry ", (strain) skill report hall, the 1st edition, in May, 1973, page 274

The content of the invention

The invention problem to be solved

In such use use xanthene dye when, from equably implement coloring from the viewpoint of, xanthene dye generally with The state of lysed solution is used in organic solvent.But, xanthene dye itself is difficult to dissolve in organic solvent, in addition If the solution containing xanthene dye preserved in such a state, it is known even if 1 week or so also due to rheological parameters' change with time and Produce precipitate.Dyestuff lysate containing precipitate is not used to such use, and this is problem.

In such a case, the present invention makees in the method for providing the excellent xanthene dye lysate of manufacture ageing stability For the problem of invention.

Means for solving the problems

The present invention has main points following in terms of.

[1] manufacture method of dyestuff lysate, it is characterised in that include：(a) xanthene is contaminated in the presence of an organic At least one kind of process being stirred in material and the salt of (b) selected from organic acid and the compound containing silicon atom.

[2] manufacture method of the dyestuff lysate described in [1], wherein, after above-mentioned agitating procedure, also comprising separation of solid and liquid Process.

[3] manufacture method of the dyestuff lysate described in [1] or [2], wherein, above-mentioned organic acid is selected from aliphatic carboxylic Acid, aromatic carboxylic acid, aliphatic sulfonic, alicyclic series sulfonic acid, aromatic sulphonic acid, by following formula (h1) represent compound and by It is at least one kind of in the compound that following formula (h2) is represented, constitute above-mentioned aliphatic carboxylic acid, above-mentioned aromatic carboxylic acid, above-mentioned fat Hydrogen atom beyond the acid proton of race's sulfonic acid and above-mentioned aromatic sulphonic acid can be replaced by halogen atom or hydroxyl etc., in composition State-the CH of aliphatic carboxylic acid, aliphatic sulfonic and above-mentioned alicyclic series sulfonic acid₂- can be replaced by-CO-.

[in formula (h1), X^h1And X^h2The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of each other, or, X^h1With X^h2 With reference to and form the fluorianted alkylene of carbon number 2~4.

In formula (h2), X^h3~X^h5The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of each other.]

[4] manufacture method of the dyestuff lysate described in any one of [1]~[3], wherein, it is above-mentioned containing silicon atom Compound is the compound represented by following formula (j).

R^h2-Si-(R^h1)₃ (j)

[in formula (j),

R^h1Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R^h1Can phase each other Together also can be different,

R^h2Represent the substituent of 1 valency.]

[5] manufacture method of the dyestuff lysate described in any one of [1]~[4], wherein, above-mentioned organic solvent is Asia The carboxylate of alkylene glycol monoalkyl ether, the aliphatic alcohol with ketone carbonyl or their mixed solvent.

[6] manufacture method of the dyestuff lysate described in any one of [1]~[5], wherein, above-mentioned xanthene dye is under State formula (1a) expression.

[in formula (1a),

R¹~R⁴Independently of each other represent hydrogen atom, can have substituent carbon number 1~20 1 valency saturated hydrocarbyl, can have The aromatic hydrocarbyl of 1 valency of the carbon number 6~10 of substituted base or the group represented by formula (ii).

*-R⁵⁰-Si(R²⁹)₃ (ii)

(in formula (ii), R²⁹Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R²⁹ Can with it is mutually the same can also be different.

R⁵⁰The alkylidene of carbon number 1~10 is represented ,-the CH of the alkylidene is constituted₂- can be by-O- ,-CO- ,-NR¹¹-、- OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- will not be replaced simultaneously For group of the same race ,-the CH of end in addition₂- will not also be replaced.

* the bonding end with nitrogen-atoms is represented.)

R¹~R⁴In, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴Can be with The ring containing nitrogen-atoms is formed together.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, in addition end- CH₂- will not also be replaced.

R⁵Expression-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰。

R⁶And R⁷The alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

M represents 0~5 integer.When m is more than 2, multiple R⁵Can be with identical also different.

A represents 0 or 1 integer.

X represents halogen atom.

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺, 4 R¹¹Can be with identical also different.

R⁸Represent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be by halogen atom Substitution.

R⁹And R¹⁰Hydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, should Contained-CH in saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、-COO-、-OCONH-、-NHCOO-、-CONH- Or-NHCO- is replaced, R⁹And R¹⁰It can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, abut- CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- will not also be replaced.

R¹¹Represent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.]

[7] manufacture method of the dyestuff lysate described in any one of [1]~[6], wherein, above-mentioned xanthene dye is served as reasons The compound that following formula (1d) is represented.

[in formula (1d),

R^1d~R^4dIndependently of each other represent hydrogen atom, can have substituent carbon number 1~20 1 valency saturated hydrocarbyl, can The aromatic hydrocarbyl of 1 valency of the carbon number 6~10 with substituent or the group represented by formula (ii), R^1d~R^4dMiddle at least one For the group represented by formula (ii).

*-R⁵⁰-Si(R²⁹)₃ (ii)

R⁵⁰The alkylidene of carbon number 1~10 is represented ,-the CH of the alkylidene is constituted₂- can be by-O- ,-CO- ,-NR^11d-、- OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- will not be replaced simultaneously For group of the same race ,-the CH of end in addition₂- will not also be replaced.

* the bonding end with nitrogen-atoms is represented.)

R^1d~R^4dIn, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, R^1dAnd R^2dThe ring containing nitrogen-atoms, R can be formed together^3dAnd R^4dCan one Rise and form the ring containing nitrogen-atoms.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- Also it will not be replaced.

R^5dExpression-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Zd⁺、-CO₂H、-CO₂ ^-Zd⁺、-CO₂R^8d、-SO₃R^8dOr-SO₂NR^9dR^10d。

R^6dAnd R^7dThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

Md represents 0~5 integer.When md is more than 2, multiple R^5dCan be with identical also different.

D represents 0 or 1 integer.

Xd represents halogen atom.

Zd⁺Represent⁺N(R^11d)₄、Na⁺Or K⁺, 4 R^11dCan be with identical also different.

R^8dRepresent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be by halogen atom Substitution.

R^9dAnd R^10dHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9dAnd R^10dIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, Adjacent-CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- will not also be replaced.

R^11dRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.]

[8] colored curable resin composition, it is characterised in that molten comprising the dyestuff described in any one of [1]~[7] Solve liquid, resin (B), polymerizable compound (C) and polymerization initiator (D).

[9] colour filter formed as the colored curable resin composition described in [8].

[10] display device, it includes the colour filter described in [9].

The effect of invention

According to the manufacture method of dyestuff lysate of the present invention, in obtained dye solution, it can suppress with warp Shi Bianhua and produce foreign matter, therefore be stable for rheological parameters' change with time.Therefore, manufactured dyestuff lysate can be applied to The extensive purposes such as dyestuff of color solidification compound.

Embodiment

The manufacture method of dyestuff lysate of the present invention, it is characterised in that include：It is right in the presence of an organic (a) at least one kind of process being stirred in the salt of xanthene dye and (b) selected from organic acid and the compound containing silicon atom.

By to xanthene dye (a) and as at least one kind of in the salt selected from organic acid and the compound containing silicon atom (b) be stirred, so as to play xanthene dye (a) individually in the case of the effect of ageing stability that can not play Really.

The manufacture method ＞ of ＜ dyestuff lysates

The dyestuff lysate obtained in the present invention is selected from the salt of organic acid comprising (a) xanthene dye, (b) and contains silicon atom Compound at least one kind of and organic solvent.Moreover, the dyestuff lysate passes through in the presence of an organic to (a) xanthene At least one kind of be stirred in the salt of dyestuff and (b) selected from organic acid and the compound containing silicon atom and obtain.

＜ xanthene dyes (a) ＞

The xanthene dye (a) used in the present invention is the dyestuff of the compound included in intramolecular with xanthene skeleton, is made For xanthene dye (a), the compound represented by formula (1a) is preferably comprised (hereinafter sometimes referred to " compound (1a) ".) dyestuff. Compound (1a) can be its dynamic isomer.

[in formula (1a),

*-R⁵⁰-Si(R²⁹)₃ (ii)

(R²⁹Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R²⁹Can phase each other Together can also be different.

* the bonding end with nitrogen-atoms is represented.)

R¹~R⁴In, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴Can be together Form the ring containing nitrogen-atoms.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- It will not be replaced.

A represents 0 or 1 integer.

X represents halogen atom.

In formula (1a) ,-SO₃ ^-In the presence of, its number is 1.

It is used as R¹~R⁴In carbon number 6~10 1 valency aromatic hydrocarbyl, can for example include phenyl, tolyl, diformazan Phenyl, mesitylene base, propyl group phenyl and butyl phenyl etc..

The aromatic hydrocarbyl of 1 valency of the carbon number 6~10 can have substituent.The substitution that can have as the aromatic hydrocarbyl Base, can include halogen atom ,-R⁸、-OH、-OR⁸、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、- SO₃R⁸Or-SO₂NR⁹R¹⁰, preferably these substituents replace hydrogen atom contained in aromatic hydrocarbyl.In these, substitution is used as Base, preferably-R⁸、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺With-SO₂NR⁹R¹⁰, more preferably-R⁸、-SO₃ ^-Z⁺With-SO₂NR⁹R¹⁰.It is used as this feelings - R under condition⁸, the more preferably saturated hydrocarbyl of 1 valency of carbon number 1~10, the alkyl of further preferred carbon number 1~5.In addition, being used as this - SO in the case of kind₃ ^-Z⁺, preferably-SO₃ ^-+N(R¹¹)₄。

It is used as R¹~R⁴And R⁸~R¹¹In carbon number 1~20 1 valency saturated hydrocarbyl, can for example include methyl, ethyl, The straight-chain alkane such as propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl Base；Point branched-chain alkyl such as isopropyl, isobutyl group, isopentyl, neopentyl, 2- ethylhexyls；Cyclopropyl, cyclopenta, cyclohexyl, The ester ring type saturated hydrocarbyl of the carbon numbers such as suberyl, cyclooctyl, tricyclodecyl 3~20.

Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, end in addition - CH₂- will not also be replaced.

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-O-, for example, can include following group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-CO-, for example, can include following group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- by-NR¹¹- the group that substituted for, for example, can include following group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-OCO-, for example, can include following group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-COO-, for example, can include following group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-OCONH-, for example, can include following base Group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-NHCOO-, for example, can include following base Group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-CONH-, for example, can include following base Group (* represents bonding end).

It is used as-CH contained in the saturated hydrocarbyl₂- the group that substituted for Bei-NHCO-, for example, can include following base Group (* represents bonding end).

R¹~R⁴In the saturated hydrocarbyl in contained hydrogen atom for example can be by the virtue of the carbon number 6~10 as substituent Fragrant race's alkyl or halogen atom substitution.As can be by R¹~R⁴Saturated hydrocarbyl hydrogen atom substitution carbon number 6~10 aromatic series Alkyl, can be included and as R¹~R⁴In carbon number 6~10 the same group of group that illustrates of aromatic hydrocarbyl.

R⁹And R¹⁰In the saturated hydrocarbyl in contained hydrogen atom for example can be former by the hydroxyl as substituent or halogen Son substitution.

It is used as R¹And R²The ring and R formed together³And R⁴The ring formed together, for example, can include following ring.

It is used as-OR⁸, for example, can include methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan Alkoxies such as base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide etc..

It is used as-CO₂R⁸, can for example include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Alkoxy carbonyl such as hexyloxy carbonyl and eicosane epoxide carbonyl etc..

It is used as-SR⁸, for example, can include methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl Alkyl alkylthio base such as sulfanyl and eicosyl sulfanyl etc..

It is used as-SO₂R⁸, for example, can include methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems Alkyl sulphonyl such as base sulfonyl and eicosyl sulfonyl etc..

It is used as-SO₃R⁸, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy Alkyloxysulfonyls such as sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR⁹R¹⁰, for example, can include

Sulfamoyl；

N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- isopropylsulfamoyls base, N- butyl Sulfamoyl, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyl groups sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl propyls) sulfamoyl, N- (1,2- dimethyl propyls) sulfamoyl, N- (2,2- dimethyl propyls) sulfamoyl, N- (1- methyl butyls) sulfamoyl, N- (2- methyl butyls) sulfamoyl, N- (3- Methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyls base, N- hexyls sulfamoyl, N- (1,3- dimethylbutyls) sulfamoyl, N- (3,3- dimethylbutyls) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (1,4- diformazans Base amyl group) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethylhexanyls) ammonia sulphur The N-1 such as acyl group and N- (1,1,2,2- tetramethyl butyls) sulfamoyl replaces sulfamoyl；

N, N- DimethylsuIfamoyl, N, N- ethyl-methyls sulfamoyl, N, N- diethyl aminos sulfonyl, N, N- propyl group first Base sulfamoyl, N, N- isopropyl methyls sulfamoyl, N, N- tertbutyl methyls sulfamoyl, N, N- butyl ethyl sulfonamides Base, N, the double N, N-2 such as (1- methyl-propyls) sulfamoyl and N, N- hept-ylmethyl sulfamoyl the substitution sulfamoyls of N- etc..

It is used as R⁵, preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H and-SO₂NHR⁹, more preferably-SO₃ ^-、- SO₃ ^-Z⁺、-SO₃H and-SO₂NHR⁹。

M is preferably 1~4, more preferably 1 or 2.

As compound (1a), preferred formula (1a) is middle by (R⁵)_mThe phenyl of base substitution is formula (R⁵- 1)~formula (R⁵- 37) The compound of any one, more preferably formula (R⁵- 1)~formula (R⁵- 25) compound of any one, more preferably formula (R⁵- 1)~formula (R⁵- 5) compound of any one, particularly preferably formula (R⁵- 1) compound.Further, formula (R⁵- 1)~formula (R⁵- 37) in, R⁴⁰And R⁴¹The branch's chain state of the saturated hydrocarbyl, preferably carbon number 6~12 of 1 valency of carbon number 1~20 is represented independently of each other Alkyl, more preferably 2- ethylhexyls.

It is used as R⁶And R⁷In carbon number 1~6 alkyl, the group of carbon number 1~6 in the above-mentioned alkyl enumerated can be included.

It is used as R⁶And R⁷, preferred hydrogen atom.

R⁹And R¹⁰3~10 member heterocyclic ring containing nitrogens can be represented together with nitrogen-atoms.As the heterocycle, for example, it can include following Nitrogen heterocyclic ring.

It is used as R¹¹In carbon number 7~10 aralkyl, benzyl, phenylethyl and phenyl butyl etc. can be included.

Z⁺For⁺N(R¹¹)₄、Na⁺Or K⁺, it is preferably⁺N(R¹¹)₄。

As above-mentioned⁺N(R¹¹)₄, preferably 4 R¹¹Middle at least two is the saturated hydrocarbyl of 1 valency of carbon number 5~20.In addition, 4 R¹¹Total carbon number be preferably 20~80, more preferably 20~60.Exist in compound (1a)⁺N(R¹¹)₄In the case of, such as Fruit R¹¹For these groups, then few foreign can be formed by the colored curable resin composition of the invention of inclusion compound (1a) Colour filter.

X is the halogen atom, preferably chlorine atom or bromine atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atom, more preferably For chlorine atom.

A is 0 or 1, preferably 0.

In addition, R¹~R⁴The group represented by following formula (ii) can be represented.

*-R⁵⁰-Si(R²⁹)₃ (ii)

(R²⁹Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R²⁹Can phase each other Together also can be different.

R⁵⁰The alkylidene of carbon number 1~10 is represented ,-the CH of the alkylidene is constituted₂- can be by-O- ,-CO- ,-NR¹¹-、- OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- substitutions.But, adjacent-CH₂- will not be replaced simultaneously For group of the same race ,-the CH of end in addition₂- will not also be replaced.

* the bonding end with nitrogen-atoms is represented.)

R²⁹Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R²⁹Can phase each other Together also can be different.

As by R²⁹The alkyl of the carbon number 1~4 of expression, can include methyl, ethyl, propyl group and butyl.

As by R²⁹The alkoxy of the carbon number 1~4 of expression, can include methoxyl group, ethyoxyl, propoxyl group and tert-butoxy Deng.

It is used as R²⁹, the preferably alkoxy of the alkoxy of hydroxyl and carbon number 1~4, more preferably carbon number 1~4, further preferred first Base, ethyl, methoxyl group and ethyoxyl, particularly preferred methoxyl group and ethyoxyl.

As by R⁵⁰The alkylidene of the carbon number 1~10 of expression, can include methylene, ethylidene, trimethylene, four methylenes Base, pentamethylene, hexa-methylene, isopropylidene, isobutylidene, 2- methyl trimethylenes, isoamylidene, sub- isohesyl, Asia are different Octyl group and 2- ethyl hexylens etc., wherein it is preferred to, the alkylidene of carbon number 1~6 can be included, it is highly preferred that carbon can be included The alkylidene of number 1~4.

Constitute by R⁵⁰- the CH of the alkylidene represented₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, separately - the CH of outer end₂- will not also be replaced.

As the group represented by formula (ii), for example, it can include the group represented by following formula (ii-1)~(ii-24).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-O-, for example, can include following shown bases Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-CO-, for example, can include following shown bases Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- by-NR¹¹- the group that substituted for, can for example include it is following shown in Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-OCO-, can for example include it is following shown in Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-COO-, can for example include it is following shown in Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-OCONH-, for example, can include following shown Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-NHCOO-, for example, can include following shown Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-CONH-, can for example include it is following shown in Group (* represents bonding end).

In formula (ii), composition R is used as⁵⁰- CH₂- the group that substituted for Bei-NHCO-, can for example include it is following shown in Group (* represents bonding end).

In the case that compound (1a) has the substituent represented by formula (ii), formula (ii), preferably R are used as²⁹For hydroxyl or The substituent of the alkoxy of carbon number 1~4, more preferably R²⁹For the alkoxy of hydroxyl or carbon number 1~4, R⁵⁰For the Asia of carbon number 1~10 The substituent of alkyl, the substituent further preferably represented by following formula (i).

(in formula (i),

N represents 1~8 integer,

R¹²Represent the alkyl of hydrogen atom or carbon number 1~4, multiple OR¹²Can be with mutually the same also different.

* the bonding end with nitrogen-atoms is represented.)

N is preferably 1~6, more preferably 1~5, more preferably 1~4.

As by R¹²The alkyl of the carbon number 1~4 of expression, can include methyl, ethyl, propyl group, butyl.

It is used as R¹², preferably hydrogen atom, methyl, ethyl, propyl group, more preferably hydrogen atom, methyl, ethyl.

As the group represented by formula (i), for example, it can include the group represented by following formula (i-1)~(i-12).Make For the group represented by formula (i), preferably represented by the group of formula (i-2) expression, the group by formula (i-3) expression, by formula (i-5) Group, by formula (i-6) represent group, more preferably by formula (i-3) represent group.

According to R¹~R⁴In the presence or absence of the group represented by formula (ii), the compound represented by formula (1a) can be categorized as Without the substituent represented by formula (ii) by following formula (1a-1) represent compound and with taking for being represented by formula (ii) The Dai Ji compound represented by following formula (1a-2).Below for the compound represented by following formula (1a-1) and by following formula (1a-2) represent compound each in preferred compound be described in detail.

Formula (1a-1)：

In above-mentioned formula (1a), R¹~R⁴Represent independently of each other hydrogen atom, can have substituent carbon number 1~20 1 valency Saturated hydrocarbyl can the aromatic hydrocarbyl with 1 valency of the carbon number 6~10 of substituent, R¹~R⁴In, it is contained in the saturated hydrocarbyl - CH₂- can be by-O- ,-CO- ,-NR¹¹- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- replace, R¹ And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴The ring containing nitrogen-atoms can be formed together,

R⁵~R¹¹、m、a、X、Z⁺Compound same as described above.

Formula (1a-2)：

In above-mentioned formula (1a), R¹~R⁴Represent independently of each other hydrogen atom, can have substituent carbon number 1~20 1 valency Saturated hydrocarbyl, can have substituent carbon number 6~10 1 valency aromatic hydrocarbyl or by formula (ii) represent group, R¹~R⁴ Middle at least one is the group represented by formula (ii).R¹~R⁴In, contained-CH in the saturated hydrocarbyl₂- can by-O- ,-CO- ,- NR¹¹- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- replace, R¹And R²It can form former containing nitrogen together The ring of son, R³And R⁴The ring containing nitrogen-atoms can be formed together,

R⁵~R¹¹、R²⁹、R⁵⁰、m、a、X、Z⁺Compound same as described above.

As the compound represented by formula (1a-1), the compound for example preferably represented by following formula (1b) is (below sometimes Referred to as " compound (1b) ".).Compound (1b) can be its dynamic isomer.

[in formula (1b),

R^1b~R^4bRepresent there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent independently of each other,

R^1b~R^4bIn, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11b-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, R^1bAnd R^2bThe ring containing nitrogen-atoms, R can be formed together^3bAnd R^4bCan one Rise and form the ring containing nitrogen-atoms.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- Also it will not be replaced.

R^5bExpression-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Zb⁺、-CO₂H、-CO₂ ^-Zb⁺、-CO₂R^8b、-SO₃R^8bOr-SO₂NR^9bR^10b。

R^6bAnd R^7bThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

Mb represents 0~5 integer.When mb is more than 2, multiple R^5bCan be with identical also different.

B represents 0 or 1 integer.

Xb represents halogen atom.

Zb⁺Represent⁺N(R^11b)₄、Na⁺Or K⁺, 4 R^11bCan be with identical also different.

R^8bRepresent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be by halogen atom Substitution.

R^9bAnd R^10bHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11b-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9bAnd R^10bIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, it is adjacent - the CH connect₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- will not also be replaced.

R^11bRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.]

In formula (1b) ,-SO₃ ^-In the presence of, its number is 1.

It is used as R^1b~R^4bAnd R^8b~R^11bIn carbon number 1~20 1 valency saturated hydrocarbyl, can for example include methyl, second The straight chains such as base, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl and eicosyl Shape alkyl；Point branched-chain alkyl such as isopropyl, isobutyl group, isopentyl, neopentyl and 2- ethylhexyls；Cyclopropyl, cyclopenta, ring The ester ring type saturated hydrocarbyl of the carbon numbers such as hexyl, suberyl, cyclooctyl and tricyclodecyl 3~20.

Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11b-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, end in addition - CH₂- will not also be replaced.

R^1b~R^4bIn the saturated hydrocarbyl in contained hydrogen atom can be by for example as the carbon number 6~10 of substituent Aromatic hydrocarbyl or halogen atom substitution.As can be by R^1b~R^4bSaturated hydrocarbyl hydrogen atom substitution carbon number 6~10 virtue Fragrant race's alkyl, can be included and as R¹~R⁴In carbon number 6~10 the same group of group that illustrates of aromatic hydrocarbyl.

R^9bAnd R^10bIn the saturated hydrocarbyl in contained hydrogen atom can be former by the hydroxyl or halogen for example as substituent Son substitution.

In compound (1b), preferably R^1b~R^4bMiddle R^1bWith R^2b、R^3bWith R^4bRespectively identical saturated hydrocarbyl, for example, excellent Select R^1bWith R^2b、R^3bWith R^4bThe respectively combination of straight-chain alkyl, more preferably R^1bWith R^2b、R^3bWith R^4bRespectively carbon number 1~5 Straight-chain alkyl combination, more preferably R^1bWith R^2b、R^3bWith R^4bRespectively in methyl, ethyl, propyl group, butyl 2 kinds of combination.

It is used as R^1bAnd R^2bThe ring and R formed together^3bAnd R^4bThe ring formed together, for example, can include following ring.

It is used as-OR^8b, for example, can include methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan Alkoxies such as base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide etc..

It is used as-CO₂R^8b, can for example include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Alkoxy carbonyl such as hexyloxy carbonyl and eicosane epoxide carbonyl etc..

It is used as-SR^8b, for example, can include methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl Alkyl alkylthio base such as sulfanyl and eicosyl sulfanyl etc..

It is used as-SO₂R^8b, for example, can include methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems Alkyl sulphonyl such as base sulfonyl and eicosyl sulfonyl etc..

It is used as-SO₃R^8b, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen Alkyloxysulfonyls such as base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR^9bR^10b, for example, can include：

Sulfamoyl；

N- Methylsulfamoyls, N- ethylsulfamovls, N- propylsulfamovs, N- isopropylsulfamoyls base, N- butyl Sulfamoyl, N- isobutyl groups sulfamoyl, N- sec-butyls sulfamoyl, N- tert-butyl groups sulfamoyl, N- amyl groups sulfamoyl, N- (1- ethyl propyls) sulfamoyl, N- (1,1- dimethyl propyls) sulfamoyl, N- (1,2- dimethyl propyls) sulfamoyl, N- (2,2- dimethyl propyls) sulfamoyl, N- (1- methyl butyls) sulfamoyl, N- (2- methyl butyls) sulfamoyl, N- (3- Methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyls base, N- hexyls sulfamoyl, N- (1,3- dimethylbutyls) sulfamoyl, N- (3,3- dimethylbutyls) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyls) sulfamoyl, N- (1,4- diformazans Base amyl group) sulfamoyl, N- octyl groups sulfamoyl, N- (2- ethylhexyls) sulfamoyl, N- (1,5- dimethylhexanyls) ammonia sulphur The N-1 such as acyl group, N- (1,1,2,2- tetramethyl butyls) sulfamoyl replace sulfamoyl；

N, N- DimethylsuIfamoyl, N, N- ethyl-methyls sulfamoyl, N, N- diethyl aminos sulfonyl, N, N- propyl group first Base sulfamoyl, N, N- isopropyl methyls sulfamoyl, N, N- tertbutyl methyls sulfamoyl, N, N- butyl ethyl sulfonamides Base, N, N- double (1- methyl-propyls) sulfamoyl, N, the N such as N- hept-ylmethyl sulfamoyls, N-2 substitution sulfamoyls etc..

It is used as R^5b, preferably-CO₂H、-CO₂ ^-Zb⁺、-CO₂R^8b、-SO₃ ^-、-SO₃ ^-Zb⁺、-SO₃H or-SO₂NHR^9b, more preferably- SO₃ ^-、-SO₃ ^-Zb⁺、-SO₃H or-SO₂NHR^9b。

Mb preferably 1~4, more preferably 1 or 2.

In compound (1b), by (R^5b)_mbThe phenyl of base substitution is preferably above-mentioned (R⁵- 1)~(R⁵- 37) any one, More preferably (R⁵- 1)~(R⁵- 25) any one, more preferably (R⁵- 1)~(R⁵- 5), it is particularly preferably (R⁵-1)。

It is used as R^6bAnd R^7bIn carbon number 1~6 alkyl, the alkyl of carbon number 1~6 in the above-mentioned alkyl enumerated can be included. Wherein, as R^6b、R^7b, preferred hydrogen atom.

R^9bAnd R^10b3~10 member heterocyclic ring containing nitrogens can be represented together with nitrogen-atoms.As the heterocycle, can for example include with Under heterocycle.

It is used as R^11bIn carbon number 7~10 aralkyl, benzyl, phenylethyl and phenyl butyl etc. can be included.

Zb⁺For⁺N(R^11b)₄、Na⁺Or K⁺, it is preferably⁺N(R^11b)₄。

As above-mentioned⁺N(R^11b)₄, preferably 4 R^11bMiddle at least two is the saturated hydrocarbyl of 1 valency of carbon number 5~20.In addition, 4 Individual R^11bTotal carbon number be preferably 20~80, more preferably 20~60.

As Xb, the halogen atoms such as fluorine atom, chlorine atom, bromine atoms and iodine atom can be included, it is preferable that can include Chlorine atom and bromine atoms, it is highly preferred that chlorine atom can be included.

B is 0 or 1, preferably 0.

In addition, as the compound represented by formula (1a-1), such as the compound preferably represented by following formula (1c) is (following Sometimes referred to as " compound (1c) ".).Compound (1c) can be its dynamic isomer.

[in formula (1c),

R^1cAnd R^4cThe alkyl, the alkyl alkylthio base of carbon number 1~4 or carbon number 1~4 of carbon number 1~4 are represented independently of each other Alkyl sulphonyl.

P and q represent 0~5 integer independently of each other.When p is more than 2, multiple R^1cCan with identical also different, q be 2 with When upper, multiple R^4cCan be with identical also different.

R^2cAnd R^3cHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent,

R^2c、R^3cIn, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11c-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, separately - the CH of outer end₂- will not also be replaced.

R^1cAnd R^2cThe ring containing nitrogen-atoms, R can be formed together^3cAnd R^4cThe ring containing nitrogen-atoms can be formed together.

R^5cExpression-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Zc⁺、-CO₂H、-CO₂ ^-Zc⁺、-CO₂R^8c、-SO₃R^8cOr-SO₂NR^9cR^10c。

R^6cAnd R^7cThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other.

Mc represents 0~5 integer.When mc is more than 2, multiple R^5cCan be with identical also different.

C represents 0 or 1 integer.

Xc represents halogen atom.

Zc⁺Represent⁺N(R^11c)₄、Na⁺Or K⁺, 4 R^11cCan be with identical also different.

R^8cRepresent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be by halogen atom Substitution.

R^9cAnd R^10cHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11c-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9cAnd R^10cIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, it is adjacent - the CH connect₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- will not also be replaced.

R^11cRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.]

In formula (1c) ,-SO₃ ^-In the presence of, its number is 1.

It is used as R^1cAnd R^4cIn carbon number 1~4 alkyl, methyl, ethyl, propyl group, butyl, isopropyl, isobutyl can be included Base, sec-butyl, tert-butyl group etc..

It is used as R^1cAnd R^4cIn carbon number 1~4 alkyl alkylthio base, methylsulfanyl, Ethylsulfanyl, third can be included Base sulfanyl, butyl sulfanyl and isopropyl sulfanyl etc..

It is used as R^1cAnd R^4cIn carbon number 1~4 alkyl sulphonyl, methyl sulphonyl, ethylsulfonyl, third can be included Base sulfonyl, butyl sulfonyl and isopropelsulfonyl etc..

R^1cAnd R^4cThe preferably alkyl of carbon number 1~4, more preferably methyl.

P and q are preferably 0~2 integer, preferably 1 or 2.

It is used as R^2c、R^3cAnd R^8c~R^11cIn carbon number 1~20 1 valency saturated hydrocarbyl, can for example include methyl, second Base, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl and eicosyl etc. it is straight Chain-like alkyl；Point branched-chain alkyl such as isopropyl, isobutyl group, isopentyl, neopentyl and 2- ethylhexyls；Cyclopropyl, cyclopenta, The ester ring type saturated hydrocarbyl of the carbon numbers such as cyclohexyl, suberyl, cyclooctyl and tricyclodecyl 3~20.

Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11c-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, end in addition - CH₂- will not also be replaced.

R^2cAnd R^3cIn the saturated hydrocarbyl in contained hydrogen atom for example can be by the carbon number 6~10 as substituent Aromatic hydrocarbyl or halogen atom substitution.As can be by R^2cAnd R^3cSaturated hydrocarbyl hydrogen atom substitution carbon number 6~10 virtue Fragrant race's alkyl, can be included and as R¹~R⁴In carbon number 6~10 the same group of group that illustrates of aromatic hydrocarbyl.

R^9cAnd R^10cIn the saturated hydrocarbyl in contained hydrogen atom can be former by the hydroxyl or halogen for example as substituent Son substitution.

It is used as-OR^8c, for example, can include methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan Alkoxies such as base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide etc..

It is used as-CO₂R^8c, can for example include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Alkoxy carbonyl such as hexyloxy carbonyl and eicosane epoxide carbonyl etc..

It is used as-SR^8c, for example, can include methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl Alkyl alkylthio base such as sulfanyl and eicosyl sulfanyl etc..

It is used as-SO₂R^8c, for example, can include methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems Alkyl sulphonyl such as base sulfonyl and eicosyl sulfonyl etc..

It is used as-SO₃R^8c, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen Alkyloxysulfonyls such as base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR^9cR^10c, for example, can include：

Sulfamoyl；

It is used as R^5c, preferably-CO₂H、-CO₂ ^-Zc⁺、-CO₂R^8c、-SO₃ ^-、-SO₃ ^-Zc⁺、-SO₃H or-SO₂NHR^9c, more preferably- SO₃ ^-、-SO₃ ^-Zc⁺、-SO₃H or-SO₂NHR^9c。

Mc preferably 1~4, more preferably 1 or 2.

In compound (1c), by (R^5c)_mcThe phenyl of base substitution is preferably above-mentioned (R⁵- 1)~(R⁵- 37) any one, More preferably (R⁵- 1)~(R⁵- 25) any one, more preferably (R⁵- 1)~(R⁵- 5), it is particularly preferably (R⁵-1)。

It is used as R^6cAnd R^7cIn carbon number 1~6 alkyl, the alkyl of carbon number 1~6 in the above-mentioned alkyl enumerated can be included. Wherein, as R^6c、R^7c, preferred hydrogen atom.

R^9cAnd R^10c3~10 member heterocyclic ring containing nitrogens can be represented together with nitrogen-atoms.As the heterocycle, can for example include with Under heterocycle.

It is used as R^11cIn carbon number 7~10 aralkyl, benzyl, phenylethyl, phenyl butyl etc. can be included.

Zc⁺For⁺N(R^11c)₄、Na⁺Or K⁺, it is preferably⁺N(R^11c)₄。

As above-mentioned⁺N(R^11c)₄, preferably 4 R^11cMiddle at least two is the saturated hydrocarbyl of 1 valency of carbon number 5~20.In addition, 4 Individual R^11cTotal carbon number preferably 20~80, more preferably 20~60.

Xc is the halogen atom, preferably chlorine atom or bromine atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atom, more preferably For chlorine atom.

C is 0 or 1, more preferably 0.

In addition, as the compound represented by formula (1a-2), such as the compound preferably represented by following formula (1d) is (following Sometimes referred to as " compound (1d) ".).Compound (1d) can be its dynamic isomer.

[in formula (1d),

R^1d~R^4dIndependently of each other represent hydrogen atom, can have substituent carbon number 1~20 1 valency saturated hydrocarbyl, can The aromatic hydrocarbyl of 1 valency of the carbon number 6~10 with substituent or the group represented by formula (ii), R^1d~R^4dIn at least 1 Individual is the group represented by formula (ii).

*-R⁵⁰-Si(R²⁹)₃ (ii)

* the bonding end with nitrogen-atoms is represented.)

D represents 0 or 1 integer.

Xd represents halogen atom.

R^9dAnd R^10dHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is replaced, R^9dAnd R^10dIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, it is adjacent - the CH connect₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- will not also be replaced.

In formula (1d) ,-SO₃ ^-In the presence of, its number is 1.

It is used as R^1d~R^4dIn carbon number 6~10 1 valency aromatic hydrocarbyl, can for example include phenyl, tolyl, two Tolyl, mesitylene base, propyl group phenyl and butyl phenyl etc..

The substituent that can have as the aromatic hydrocarbyl, can include halogen atom ,-R^8d、-OH、-OR^8d、-SO₃ ^-、- SO₃H、-SO₃ ^-Zd⁺、-CO₂H、-CO₂R^8d、-SR^8d、-SO₂R^8d、-SO₃R^8dOr-SO₂NR^9dR^10d, preferably these substituents are by fragrance Contained hydrogen atom substitution in race's alkyl.In these, substituent, preferably-SO are used as₃ ^-、-SO₃H、-SO₃ ^-Zd⁺With- SO₂NR^9dR^10d, more preferably-SO₃ ^-Zd⁺With-SO₂NR^9dR^10d.It is used as-SO in this case₃ ^-Zd⁺, preferably-SO₃ ^-+N(R^11d)₄。

It is used as R^1d~R^4dAnd R^8d~R^11dIn carbon number 1~20 1 valency saturated hydrocarbyl, can for example include methyl, second The straight-chains such as base, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl Alkyl；Point branched-chain alkyl such as isopropyl, isobutyl group, isopentyl, neopentyl, 2- ethylhexyls；Cyclopropyl, cyclopenta, hexamethylene The ester ring type saturated hydrocarbyl of the carbon numbers such as base, suberyl, cyclooctyl, tricyclodecyl 3~20.

Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, end in addition - CH₂- will not also be replaced.

R^1d~R^4dIn the saturated hydrocarbyl in contained hydrogen atom can be by for example as the carbon number 6~10 of substituent Aromatic hydrocarbyl or halogen atom substitution.As can be by R^1d~R^4dSaturated hydrocarbyl hydrogen atom substitution carbon number 6~10 virtue Fragrant race's alkyl, can be included and as R^1d~R^4dIn carbon number 6~10 the same group of group that illustrates of aromatic hydrocarbyl.

R^9dAnd R^10dIn the saturated hydrocarbyl in contained hydrogen atom for example can be former by the hydroxyl as substituent or halogen Son substitution.

It is used as R^1dAnd R^2dThe ring and R formed together^3dAnd R^4dThe ring formed together, for example, can include following ring.

R^1d~R^4dMiddle at least one is the group represented by formula (ii), is used as other R^1d~R^4d, preferably methyl, ethyl, Propyl group, 1- aminomethyl phenyls, 1,5- 3,5-dimethylphenyls, more preferably methyl, ethyl, propyl group.

It is used as-OR^8d, for example, can include methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, oxygen in heptan Alkoxies such as base, octyloxy, 2- ethyl hexyl oxies and eicosane epoxide etc..

It is used as-CO₂R^8d, can for example include methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, Alkoxy carbonyl such as hexyloxy carbonyl and eicosane epoxide carbonyl etc..

It is used as-SR^8d, for example, can include methylsulfanyl, Ethylsulfanyl, butyl sulfanyl, hexyl sulfanyl, decyl Alkyl alkylthio base such as sulfanyl and eicosyl sulfanyl etc..

It is used as-SO₂R^8d, for example, can include methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, the last of the ten Heavenly stems Alkyl sulphonyl such as base sulfonyl and eicosyl sulfonyl etc..

It is used as-SO₃R^8d, for example, can include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tertiary fourth oxygen Alkyloxysulfonyls such as base sulfonyl, hexyloxy sulfonyl and eicosane epoxide sulfonyl etc..

It is used as-SO₂NR^9dR^10d, for example, can include：

Sulfamoyl；

It is used as R^5d, preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R^8d、-SO₃ ^-、-SO₃ ^-Zd⁺、-SO₃H or-SO₂NHR^9d, more preferably- SO₃ ^-、-SO₃ ^-Zd⁺、-SO₃H or-SO₂NHR^9d。

Md preferably 1~4, more preferably 1 or 2.

As compound (1d), in formula (1d), it is also preferred that by (R^5d)_mdThe phenyl of base substitution is above-mentioned formula (R⁵- 1)~ (R⁵- 37) any one, more preferably (R⁵- 1)~(R⁵- 25) any one, more preferably (R⁵- 1)~(R⁵- 5), especially Preferably (R⁵-1)。

It is used as R^6dAnd R^7dIn carbon number 1~6 alkyl, the alkyl of carbon number 1~6 in the above-mentioned alkyl enumerated can be enumerated.Its In, it is used as R^6d、R^7d, preferred hydrogen atom.

R^9dAnd R^10d3~10 member heterocyclic ring containing nitrogens can be represented together with nitrogen-atoms.As the heterocycle, can for example include with Under heterocycle.

It is used as R^11dIn carbon number 7~10 aralkyl, benzyl, phenylethyl, phenyl butyl etc. can be included.

Zd⁺For⁺N(R^11d)₄、Na⁺Or K⁺, it is preferably⁺N(R^11d)₄。

As above-mentioned⁺N(R^11d)₄, preferably 4 R^11dMiddle at least two is the saturated hydrocarbyl of 1 valency of carbon number 5~20.In addition, 4 Individual R^11dTotal carbon number preferably 20~80, more preferably 20~60.

Xd is the halogen atom, preferably chlorine atom or bromine atoms such as fluorine atom, chlorine atom, bromine atoms or iodine atom, more preferably For chlorine atom.

D is 0 or 1, more preferably 0.

In addition, R^1d~R^4dIn the substituent and the formula (1a) that are represented by formula (ii) in detailed description substituent it is same.

In above-mentioned xanthene dye (1d), as preferred compound, for example, it can include and be represented by following formula (2d) Compound：

[in formula (2d),

R^1d~R^4dIndependently of each other represent hydrogen atom, can have substituent carbon number 1~10 1 valency saturated hydrocarbyl, can Phenyl with substituent or the group by formula (ii) expression, R^1d~R^4dMiddle at least one is the group represented by formula (ii).

*-R⁵⁰-Si(R²⁹)₃ (ii)

R⁵⁰The alkylidene of carbon number 1~10 is represented ,-the CH of the alkylidene is constituted₂- can be by-O- ,-CO- ,-NR^11d-、- OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- are substituted.But, adjacent-CH₂- will not be replaced simultaneously For group of the same race ,-the CH of end in addition₂- will not also be replaced.

* the bonding end with nitrogen-atoms is represented.)

R^1d~R^4dIn, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, R^1dAnd R^2dThe ring containing nitrogen-atoms, R can be formed together^3dAnd R^4dCan To form the ring containing nitrogen-atoms together.But, adjacent-CH₂- group of the same race will not be replaced by simultaneously, in addition end- CH₂- will not also be replaced.

D represents 0 or 1 integer.

Xd represents halogen atom.

R^9dAnd R^10dHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, Contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、-OCONH-、-NHCOO-、- CONH- or-NHCO- is substituted, R^9dAnd R^10dIt can be combined with each other and be formed the heterocycle of 3~10 yuan of rings containing nitrogen-atoms.But, Adjacent-CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- will not also be replaced.

It is highly preferred that being the compound represented by following formula (3d).

[in formula (3d),

R^1d~R^4dIndependently of each other represent hydrogen atom, can have substituent carbon number 1~10 1 valency saturated hydrocarbyl, can Phenyl with substituent or the group by formula (i) expression, R^1d~R^4dMiddle at least one is the group represented by formula (i).

(in formula (i),

N represents 1~8 integer,

* the bonding end with nitrogen-atoms is represented.)

D represents 0 or 1 integer.

Xd represents halogen atom.

As the preferred compound of above-mentioned xanthene dye (1a), for example, it can include by following formula (I-1)~(I-170) The compound of expression.Further, in formula, R⁴⁰Represent the branched chain of the saturated hydrocarbyl, preferably carbon number 6~12 of 1 valency of carbon number 1~20 Shape alkyl, more preferably 2- ethylhexyls.

Wherein as xanthene dye (1a), more preferably for example in R¹~R⁴It is middle to there is 1 substitution represented by formula (ii) Base, remaining group are the compound of the saturated hydrocarbyl of 1 valency of the carbon number 1~20 can with substituent (for example, compound (I- 1)~(I-4), (I-13)~(I-16), (I-25)~(I-28), (I-37)~(I-40), (I-55)~(I-110), (I- 117), (I-120) etc.), in R¹~R⁴It is middle to have 2 substituents represented by formula (ii), remaining group to have substituent Carbon number 1~20 1 valency saturated hydrocarbyl compound (for example, compound (I-49)~(I-54), compound (I-111)~ (I-116), compound (I-119), (I-121), (I-122)), in R¹~R⁴In have 2 xylyls compound (for example, Compound (I-124)~(I-146), (I-151), (I-153), (I-155), (I-156) etc.), in R¹~R⁴In there are 2 first The compound (for example, compound (I-147), (I-150), (I-152), (I-154) etc.) of phenyl, R¹~R⁴It is all to have The compound (for example, compound (I-160)~(I-170) etc.) of the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent.

More preferably compound (I-1)~(I-4), (I-13)~(I-16), (I-25)~(I-28), (I-50), (I-51), (I-53), (I-54), (I-119), (I-121), (I-122), (I-124)~(I-147), (I-150)~(I- 156), (I-160)~(I-167).

Xanthene dye (a) can use commercially available xanthene dye (for example, " Chugai of middle tank formation (strain) manufacture Aminol Fast Pink R-H/C ", field ridge chemical industry (strain) manufacture " Rhodamin 6G ").In addition, also can be with Commercially available xanthene dye is as initial feed, with reference to the synthesis of Japanese Unexamined Patent Publication 2010-32999 publications.

As such xanthene dye (a), for example, it can include the C.I. CI 45430s (note of C.I. acid reds omitted below Carry, only record sequence number.Other are similarly.), the C.I. acid red dyes such as 52,87,92,94,289,388；C.I. acid violet 9, 30th, the acid purple dyes of the C.I. such as 102；C.I. alkali red 1:1 (rhodamine 6G), 2,3,4,8,10 (rhodamine Bs), the C.I. such as 11 are alkaline Red；C.I. C.I. basic purple dyes such as alkaline purple 10,11,25；C.I. the grade of solvent red 218 C.I. solvent red dyes；C.I. The grade C.I. mordant dyeing reds of mordant rouge 27；C.I. C.I. active red dyes such as active red 36 (rose red b)；Sulfo rhodamine G；Day Xanthene dye described in this JP 2010-32999 publications；With the xanthene described in No. 4492760 publications of Japanese Patent No. Dyestuff etc..

Xanthene dye (a) preferably 0.1~20 mass %, more preferably 0.5~15 matter in the mass % of dyestuff lysate 100 Measure %, more preferably 1~10 mass %.

The salt ＞ of ＜ organic acids

As the salt of the organic acid used in the present invention, for example, selected from aliphatic carboxylic acid, aromatic carboxylic acid, aliphatic sulphur Acid, alicyclic series sulfonic acid, aromatic sulphonic acid, the compound represented by following formula (h1) and the compound represented by following formula (h2) In at least one kind of organic acid salt, constitute above-mentioned aliphatic carboxylic acid, above-mentioned aromatic carboxylic acid, above-mentioned aliphatic sulfonic and on Stating the hydrogen atom beyond the acid proton of aromatic sulphonic acid can be replaced by halogen atom or hydroxyl etc., constitute above-mentioned aliphatic carboxylic - the CH of acid, aliphatic sulfonic and above-mentioned alicyclic series sulfonic acid₂- can be replaced by-CO-.

Aliphatic carboxylic acid refers to the compound R with carboxyl (- COOH)²¹(COOH)_x(x is more than 1 integer, more preferably For 1,2 or 3, more preferably 1 or 2) in R²¹For the carboxylic acid or formic acid of aliphatic alkyl.As such aliphatic carboxylic acid, Such as can include the saturated fatty acid of carbon number 1~25, the unsaturated carboxylic acid of carbon number 1~25.It is used as the full of carbon number 1~25 And aliphatic acid, the fat such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, laurate can be illustrated Fat race monocarboxylic acid；Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid etc..In addition, being used as carbon number 1 ~25 unsaturated carboxylic acid, can illustrate oleic acid, linoleic acid, leukotrienes, eicosatetraenoic acid, docosahexaenoic acid, 20 Carbon 5 alkene acid, fumaric acid, maleic acid etc..

Aromatic carboxylic acid refers to the compound R with carboxyl (- COOH)²²(COOH)_x(x is more than 1 integer, more preferably For 1,2 or 3, more preferably 1 or 2) in R²²For the carboxylic acid of aromatic hydrocarbyl.It is used as R²², can include can have substituent Carbon number 6~10 aromatic hydrocarbyl, more preferably can have carbon number 1~10 1 valency saturated hydrocarbyl phenyl.As so Aromatic carboxylic acid, can for example include benzoic acid, toluic acid, mesitylenic acid, diethylbenzene formic acid, dipropyl benzene first Acid, dibutyl benzoic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), naphthalenedicarboxylic acid etc..

As alicyclic series sulfonic acid, cyclohexanesulfonic, 4- methyl cyclohexanes alkyl sulfonic acid, bicyclic [2.2.1]-hept- 2- can be included Alkene -5- sulfonic acid etc..

Aliphatic sulfonic refers to sulfo group (- SO₃H compound R)²³(SO₃H)_x(x is more than 1 integer, more preferably 1st, 2 or 3, more preferably 1 or 2) in R²³For the sulfonic acid of aliphatic alkyl.As such aliphatic sulfonic, for example, it can arrange Enumerate the fat such as methanesulfonic acid, ethyl sulfonic acid, propane sulfonic acid, fourth sulfonic acid, penta sulfonic acid, own sulfonic acid, sulfonic acid in heptan, pungent sulfonic acid, nonyl sulfonic acid, last of the ten Heavenly stems sulfonic acid Fat race list sulfonic acid；Methane-disulfonic acid, ethane disulfonic acid, propanedisulfonic acid, butane disulfonic acid, pentane disulfonic acid, hexane disulfonic acid Etc. aliphatic disulfonic acid etc..

Aromatic sulphonic acid refers to sulfo group (- SO₃H compound R)²⁴(SO₃H)_x(x is more than 1 integer, more preferably 1st, 2 or 3, more preferably 1 or 2) in R²⁴For the sulfonic acid of aromatic hydrocarbyl.As such aromatic sulphonic acid, for example, it can arrange Enumerate benzene sulfonic acid, toluenesulfonic acid, DBSA, naphthalene sulfonic acids, naphthalenedisulfonic acid etc..

Constitute the acid of above-mentioned aliphatic carboxylic acid, above-mentioned aromatic carboxylic acid, above-mentioned aliphatic sulfonic and above-mentioned aromatic sulphonic acid Hydrogen atom beyond property can be replaced by halogen atom or hydroxyl.As can be by above-mentioned aliphatic carboxylic acid, above-mentioned aromatic series The halogen atom of hydrogen atom substitution beyond acid proton in carboxylic acid, above-mentioned aliphatic sulfonic and above-mentioned aromatic sulphonic acid, can F, Cl, Br, I are included, wherein it is preferred that fluorine.As these acid, can illustrate lactic acid, malic acid, citric acid, salicylic acid, 3,5- bis-- Tert-butyl salicylic acid etc..

Constitute-the CH of above-mentioned aliphatic carboxylic acid, aliphatic sulfonic and above-mentioned alicyclic series sulfonic acid₂- can be replaced by-CO-, As these acid, 10- camphorsulfonic acids etc. can be illustrated.

In addition, in above-mentioned formula (h1), X^h1And X^h2The independently of one another fluoro-alkyl of fluorine atom or carbon number 1~4.In addition, In above-mentioned formula (h2), X^h3~X^h5The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of each other.

As the fluoro-alkyl of above-mentioned carbon number 1~4, can for example include it is following shown in substituents, wherein it is preferred that *- CF₂CF₃, *-CF₂CF₂CF₃With *-CF₂CF₂CF₂CF₃, more preferably *-CF₂CF₂CF₃With *-CF₂CF₂CF₂CF₃。

In addition, with regard to X^h1And X^h2For, X^h1With X^h2It can combine and be formed the fluorianted alkylene of carbon number 2~4.It is used as carbon number 2 ~4 fluorianted alkylene, such as preferably by *-(CF₂)_nThe substituent that-* is represented (in formula, n is 2~4 integer).

As the salt of above-mentioned various organic acids, the alkali metal salt such as can include lithium salts, sodium salt, sylvite, cesium salt；Calcium The alkali earth metal salts such as salt；The metal salts such as zinc salt, mantoquita；Quaternary ammonium salt etc..

As the salt of such organic acid, such as preferably as there is substitution shown in following formula (h0-1)~(h0-21) Shown in compound and following formula (h2-1)~(h2-8) shown in the salt of the benzoic acid of base, following formula (h1-1)~(h1-8) Compound.

As the salt of organic acid, wherein it is preferred that by the salt of the compound of above-mentioned formula (h0-13) expression, by above-mentioned formula (h1) table The compound shown or the compound represented by above-mentioned formula (h2), zinc salt, double (the fluoroform sulphurs of more preferably above-mentioned formula (h0-13) Acyl group) imine lithium or three (trifyl) methylene ylide lithiums.

＜ contains the compound ＞ of silicon atom

As the compound containing silicon atom, for example, it can include the compound represented by following formula (j).In the present invention, Also " condensation product " of the compound represented by following formula (j) is included in " compound containing silicon atom ".

R^h2-Si-(R^h1)₃ (j)

In formula (j),

R^h2Represent the substituent of 1 valency.

It is used as R^h1In carbon number 1~4 alkyl, can for example include methyl, ethyl, propyl group and butyl, these can be Straight-chain or branch-like.

It is used as R^h1In carbon number 1~4 alkoxy, can for example include methoxyl group, ethyoxyl, propoxyl group and butoxy. From contributing to ageing stability, preferably methoxyl group and ethyoxyl, more preferably ethyoxyl.

Wherein, as R^h1, the alkoxy of further preferred hydroxyl or carbon number 1~4, the alcoxyl of particularly preferred carbon number 1~4 Base.

R^h2For the substituent of 1 valency.It is used as R^h2, the preferably saturated hydrocarbyl of carbon number 1~10, the aromatic hydrocarbon of carbon number 6~10 Base or, comprising selected from vinyl, epoxy radicals, methylacryloyl, acryloyl group, amino, isocyanurate group, urea groups, mercapto The substituent of at least one kind of functional group in base, thioether group and NCO.R^h2In the above-mentioned functional group contained preferably with containing There are the Si atoms in the compound (j) of silicon atom via the saturated hydrocarbyl or carbon number 6~10 of singly-bound or the divalent of carbon number 1~10 The aromatic hydrocarbyl of divalent is combined.

It is used as R^h2Carbon number 1~10 saturated hydrocarbyl, preferably carbon number 2~9 saturated hydrocarbyl, more preferably carbon number 4~8 Saturated hydrocarbyl, more preferably amyl group, hexyl, heptyl or octyl group.The hydrogen atom for constituting above-mentioned saturated hydrocarbyl can be by fluorine The halogen atoms such as atom, chlorine atom or *-Si (R^h3)₃(in above-mentioned formula, R^h3For the alkoxy of carbon number 1~4) etc. substituent take Generation.

R^h2The aromatic hydrocarbyl of carbon number 6~10 be, for example, phenyl.

It is used as R^h2In contained carbon number 1~10 divalent saturated hydrocarbyl, preferably carbon number 1~8 saturated hydrocarbyl, more preferably For the saturated hydrocarbyl of the saturated hydrocarbyl of carbon number 1~5, more preferably carbon number 1~3.

It is used as R^h2In contained carbon number 6~10 divalent aromatic hydrocarbyl, such as preferred phenylene.

It is used as such R^h2, such as preferably following shown substituents, wherein, it is used as R^h2, preferred 3- methacryloxypropyls Base propyl group, N- methyl -3- aminopropyls, N- phenyl -3- aminopropyls and octyl group.

As such compound containing silicon atom, silane coupler and silane compound can be included.

As silane coupler, the second such as can include vinyltrimethoxy silane, VTES Alkenyl system silane coupler；2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- glycidoxypropyls two Methoxy silane, 3- glycidoxypropyltrimewasxysilanes, 3- glycidoxypropyls diethoxy silane, The epoxy silane couplers such as 3- glycidoxypropyl triethoxysilanes；The benzene such as p- styryl trimethoxy silane Ethene base system silane coupler；3- methacryloyloxypropyl methyls dimethoxysilane, 3- methacryloxypropyls Trimethoxy silane, 3- methacryloyloxypropyl methyls diethoxy silane, the ethoxy of 3- methacryloxypropyls three (methyl) acryloyl base system silane coupler such as base silane, 3- acryloxypropyl trimethoxy silanes；N-2- (amino second Base) -3- amino propyl methyls dimethoxysilane, N-2- (amino-ethyl) -3- TSL 8330s, 3- aminopropans Base trimethoxy silane, APTES, 3- triethoxysilyls-N- (1,3- dimethyl-Aden Base) the amino system such as propyl group amine, N- methyl -3- TSL 8330s, N- phenyl -3- TSL 8330s Silane coupler；The urea groups such as 3- ureidopropyltrialkoxysilanes system silane coupler；3- mercaptopropyi methyl dimethoxy epoxide silicon The sulfydryl such as alkane, 3-mercaptopropyi trimethoxy silane system silane coupler；Double (triethoxysilylpropyltetrasulfide) four thioethers etc. Thioether system silane coupler；The isocyanates system such as 3- NCO propyl-triethoxysilicanes silane coupler etc..

In addition, as silane compound, can for example include MTMS, dimethyldimethoxysil,ne, Phenyltrimethoxysila,e, MTES, dimethyldiethoxysilane, phenyl triethoxysilane, propyl group three Methoxy silane, propyl-triethoxysilicane, hexyl trimethoxy silane, hexyl triethoxysilane, octyl group trimethoxy silicon Double (the trimethyoxysilanes of alkane, octyltri-ethoxysilane, decyl trimethoxy silane, decyl triethoxysilane, 1,6- Base) alkoxy silane such as hexane etc..

Wherein as the compound containing silicon atom, preferably (methyl) acryloyl base system silane coupler, amino system silane Coupling agent, alkoxy silane, more preferably 3- methacryloyloxypropyl methyls dimethoxysilane, 3- methacryloxypropyls Base propyl trimethoxy silicane, 3- methacryloyloxypropyl methyls diethoxy silane, 3- methacryloxypropyls Triethoxysilane, 3- TSL 8330s, APTES, N- methyl -3- aminopropyls Trimethoxy silane, N- phenyl -3- TSL 8330s, propyl trimethoxy silicane, propyl-triethoxysilicane, Hexyl trimethoxy silane, hexyl triethoxysilane, octyl group trimethoxy silane, octyltri-ethoxysilane, decyl front three TMOS, more preferably 3- methacryloxypropyl trimethoxy silanes, N- methyl -3- aminopropyl trimethoxies Base silane, N- phenyl -3- TSL 8330s, hexyl trimethoxy silane, hexyl triethoxysilane, octyl group three Methoxy silane, octyltri-ethoxysilane, particularly preferably 3- methacryloxypropyl trimethoxy silanes, N- first Base -3- TSL 8330s, N- phenyl -3- TSL 8330s, octyl group trimethoxy silane.

Relative to the mass parts of xanthene dye (a) 100, usage amount preferably 20~500 mass of the compound containing silicon atom Part, more preferably 50~300 mass parts, more preferably 80~200 mass parts.

Further, as (b) composition, the situation that the salt of organic acid and both compounds containing silicon atom are applied in combination Under, relative to the mass parts of xanthene dye 100, the usage amount of the salt of organic acid represents preferably 1~50 mass parts with total, more preferably For 5~40 mass parts, more preferably 10~30 mass parts.In addition, the usage amount (total) 100 of the salt relative to organic acid Mass parts, usage amount preferably 200~1000 mass parts of the compound containing silicon atom, more preferably 300~800 mass parts, More preferably 400~700 mass parts.

＜ organic solvents ＞

As the organic solvent used in the present invention, as long as the solvent that above-mentioned xanthene dye (a) can be dissolved, then simultaneously It is not particularly limited, for example, can includes ester solvent (including-COO-, the solvent without-O- in intramolecular), ether solvents (in molecule It is interior to include-O-, the solvent without-COO-), ether-ether solvent (in solvent of the intramolecular comprising-COO- and-O-), ketone solvent (point - CO-, the solvent without-COO- are included in sub), alcoholic solvent is (in intramolecular comprising OH, without the molten of-O- ,-CO- and-COO- Agent), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc..

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be included Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester, gamma-butyrolacton etc..

As ether solvents, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two can be included Alcohol single-butyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propane diols Single ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl butanols, four Hydrogen furans, oxinane, 1,4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG) methyl ethyl ether, two Glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole etc..

As ether-ether solvent, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, ethoxy can be enumerated Base methyl acetate, ethyoxyl ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethyoxyls Methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, second Sour 3- methoxybutyls, acetic acid 3- methyl -3- methoxybutyls, propylene glycol monomethyl ether, propylene glycol monoethyl second Acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diglycol monotertiary Monoethyl ether acetate, diethylene glycol monobutyl ehter acetic acid esters, dipropylene glycol methyl ether acetic acid esters etc..

As ketone solvent, diacetone alcohol (4- hydroxy-4-methyl-2-pentanones), acetone, 2- butanone, 2-HEPTANONE, 3- can be enumerated Heptanone, 4- heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc..

As alcoholic solvent, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols, glycerine can be enumerated Deng.

As aromatic hydrocarbon solvents, benzene,toluene,xylene, 1,3,5- trimethylbenzenes etc. can be enumerated.

As amide solvent, DMF, DMA, 1-METHYLPYRROLIDONE can be enumerated Deng.

These solvents can only use a kind, can be also used in mixed way a variety of.Wherein, preferably use ether-ether solvent, ketone solvent, Alcoholic solvent and their mixed solvent, more preferably using ether-ether solvent, ketone solvent and their mixed solvent.

It is used as ether-ether solvent, preferably propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, propane diols list third The carboxylic of the alkylene glycol monoalkyl ethers such as base ether acetic acid ester, ethylene glycol single methyl ether acetic acid esters and ethylene glycol monomethyl ether acetate Acid esters, more preferably propylene glycol monomethyl ether.

It is used as ketone solvent, the preferably aliphatic alcohol with ketone carbonyl, more preferably diacetone alcohol (4- hydroxy-4-methyls -2- Pentanone)

The making ＞ of ＜ dyestuff lysates

In the present invention, as (b) composition, at least one kind of of the salt of organic acid and the compound containing silicon atom can be used, can Only using a kind in the salt selected from organic acid and the compound containing silicon atom, also by the salt selected from organic acid and silicon can be contained Two or more in the compound of atom is used in combination.As the occupation mode of such (b) composition, for example, it can include using organic The mode of the salt of acid, mode, the compound by the salt of organic acid and containing silicon atom for only using the compound containing silicon atom Both mode being applied in combination etc..

In using the mode of the salt of organic acid, mode only using the compound containing silicon atom, to including (a) xanthene The preparation method of the composition (mixture) of dyestuff and these (b) compositions is not particularly limited, and is used as the preparation of above-mentioned composition Method, for example, can include the method that (a) xanthene dye is added in the mixed solution comprising (b) composition and organic solvent； Method of (b) composition etc. is added in mixed solution comprising (a) xanthene dye and organic solvent.

In the mode that the salt of organic acid and both compounds containing silicon atom are applied in combination, to xanthene (a) and The adding method of compound containing silicon atom is not particularly limited, for example, can include and be added in the presence of the salt of organic acid The method of (referred to as agitating procedure 1) addition xanthene dye (a) after compound and stirring containing silicon atom；In the salt of organic acid In the presence of add xanthene dye (a) and after stirring the compound of (be referred to as agitating procedure 2) addition containing silicon atom method；Having Method of addition xanthene dye (a) and the compound containing silicon atom etc. in the presence of the salt of machine acid.

In above-mentioned agitating procedure 1~2, mixing time is, for example, more than 30 minutes, preferably more than 1 hour, more preferably 2 More than hour, the upper limit is not particularly limited, usually less than 20 hours.

In addition, in order to improve dissolubility of the compound containing silicon atom for organic solvent, silicon atom can be being contained Mixture is warming up to 30~60 DEG C in any one before the addition of compound or after addition.

Included what is so obtained in the salt of (a) xanthene dye and (b) selected from organic acid and the compound containing silicon atom At least one kind of composition stir in the presence of an organic.

Mixing time is not particularly limited, for example, it is preferable to more than 1 hour, it is more preferably more than 3 hours, further excellent Elect more than 5 hours as, particularly preferably more than 10 hours, preferably less than 100 hours, more preferably less than 90 hours, further Preferably less than 80 hours, particularly preferably less than 60 hours, be still more preferably less than 40 hours, further particularly preferably For less than 30 hours.

In addition, by xanthene dye (a) only with the case of the salt treatment of organic acid, mixing time such as preferably 2 hours with On, more preferably more than 3 hours, preferably less than 80 hours, more preferably less than 60 hours, more preferably 40 hours with Under, particularly preferably less than 30 hours.

In addition, by xanthene dye (a) only with the compound containing silicon atom or, by the salt of organic acid with it is former containing silicon In the case of both compounds of son combined treatment, mixing time, more preferably such as preferably more than 5 hours, 10 hours are used as More than, preferably less than 30 hours, more preferably less than 20 hours.

Whipping temp is not particularly limited, for example, it is preferable to more than -10 DEG C, more preferably more than 0 DEG C, further preferred 10 More than DEG C, particularly preferred more than 20 DEG C, preferably less than 80 DEG C, more preferably less than 70 DEG C, further preferred less than 60 DEG C.

＜ solid-liquid separation process ＞

In the present invention, after above-mentioned agitating procedure, the solid-liquid separation process for insoluble matter to be removed can be implemented.As solid Liquid is separated, for example, can include filtering, centrifugation and combinations thereof, from easy to operate, the present invention particularly preferably Implement filtering.As the method for filtering, such as can include natural filtration, pressure filtration, be filtered under diminished pressure.

Filtration adjuvant can be used in filtering.Filtration adjuvant can be used in precoating, any usage of body feed.Make For filtration adjuvant, atlapulgite, silica, diatomite, Celite, pearlite, cellulose, activated carbon, oxidation can be included Aluminium, magnesium silicate, aluminium hydroxide, hydrotalcite, alumina silicate, magnalium system solid solution, dawsonite etc..

＜ colored curable resin compositions ＞

Dyestuff lysate (A1) can be used as dyestuff, especially, can be used as in the colour filter of the display devices such as liquid crystal display The colouring agent of the colored curable resin composition used.

The xanthene dye formed in dyestuff lysate (A1) contained in the colored curable resin composition of the colour filter (a) content, relative to the total amount of the solid constituent of colored curable resin composition, preferably more than 0.025 mass % and 48 Below quality %, more preferably more than 0.08 mass % and below 42 mass %, further preferred more than 0.1 mass % and 30 matter Measure below %.

" total amount of solid constituent " refers to solvent from the colored curable resin composition of the present invention in this specification (E) total amount of the composition after removing.The total amount of solid constituent and content relative to its each composition can for example use liquid Analysis means known to phase chromatogram or gas-chromatography etc. are determined.

The present invention colored curable resin composition comprising colouring agent (A), resin (B), polymerizable compound (C) and Polymerization initiator (D).

Colouring agent (A) preferably comprises pigment (P) in addition to dyestuff lysate (A1).And then, it can include and be dissolved with dyestuff The different dyestuff (A2) of contained xanthene dye (a) in liquid (A1).

The content of xanthene dye (a) in colouring agent (A), relative to colouring agent (A) total amount, preferably 0.01 mass % with Upper and below 90 mass %, more preferably more than 0.1 mass % and below 80 mass %.

＜ pigment (P) ＞

As pigment (P), it is not particularly limited, known pigment can be used, for example, can includes in colour index (The Society of Dyers and Colourists are published) in be categorized as the compound of pigment.

As pigment, can for example including C.I. pigment yellows 1, (sequence is only recorded in the record of C.I. pigment yellows omitted below Number.)、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、 139th, the yellow uitramarine such as 147,148,150,153,154,166,173,194,214；

C.I. the orange pigment such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73；

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,175,176,177,180,192,209, 215th, the red pigment such as 216,224,242,254,255,264,265；

C.I. pigment blue 15,15：3、15：4、15：6th, the green pigment such as 60,80；

C.I. the violet pigment such as pigment violet 1,19,23,29,32,36,38；

C.I. the viridine green such as pigment Green 7,36,58；

C.I. the brown such as pigment brown 23,25；

C.I. black pigment such as pigment black 1,7 etc..

These pigment can be used alone, and can also be used in mixed way two or more.

It is used as pigment, the preferably yellow uitramarine such as C.I. pigment yellow 13s 8,139,150, C.I. paratoneres 177,242,254 etc. Red pigment, C.I. pigment blue 15s, 15：3、15：4、15：6th, the green pigments such as 60 and C.I. pigment violet 1s, 19,23,29,32, 36th, the violet pigment such as 38, more preferably selected from C.I. pigment blue 15s, 15：3、15：4、15：6 and pigment Violet 23 at least one Kind, more preferably selected from C.I. pigment blue 15s：At least one of 6 and pigment Violet 23.By comprising above-mentioned pigment, making With the optimization of the transmitted spectrum of the colour filter of the colored curable resin composition of the present invention easily, colour filter is heat-resisting Property, light resistance and chemical-resistant become good.

The colored curable resin composition of the present invention preferably comprises green pigment.

For pigment, as needed, rosin processing can be implemented, the pigment for having imported acidic-group or basic group has been used The surface treatment of derivative etc., using high-molecular compound etc. to the grafting processing of surface of pigments, using sulfuric acid particles method Deng micronized processing or adopted using the cleaning treatment of the organic solvent, the water that remove impurity etc., ionic impurity is used for Removing processing with ion-exchange etc. etc..The particle diameter of preferred pigments is each homogeneous.

As above-mentioned pigment, the dispersible pigment dispersion that usable pigment is uniformly dispersed in a solvent.

Dispersible pigment dispersion can be by the way that pigment and pigment dispersing agent be obtained by mixing in a solvent.

It in above-mentioned mixing, in the case that pigment of more than two kinds is mixed, each can individually mix, a variety of will can also mix Close.

Can be any point of cation system, anion system, nonionic system and both sexes as above-mentioned pigment dispersing agent Powder, can include pigment dispersing agent of Polyester, many amine systems, acrylic acid series etc. etc..

These pigment dispersing agents can be used alone or two or more is applied in combination.As pigment dispersing agent, with trade name Represent, KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), FLORENE (common prosperity society chemistry (strain) manufacture), SOLSPERS (ゼ can be included ネカ (strain) manufacture), EFKA (BASF AG's manufacture), AJISPUR (aginomoto Off ァイ Application テ Network ノ (strain) manufactures), Disperbyk (manufacture of BYK chemical companies) etc..

As above-mentioned solvent, it is not particularly limited, can includes in the colored curable resin composition with the present invention The same solvent of solvent.

In the case of using pigment dispersing agent, its usage amount relative to the mass parts of pigment 100, preferably 100 mass parts with Under, more than more preferably 5 mass parts and below 50 mass parts.If the usage amount of pigment dispersing agent is in above-mentioned scope, tool Have the tendency of to obtain the dispersible pigment dispersion that pigment is uniformly dispersed in a solvent.

＜ dyestuffs (A2) ＞

As dyestuff (A2), can include oil-soluble dyes, acid dyes, basic-dyeable fibre, direct dyes, mordant dye, The dyestuffs such as the amine salt of acid dyes, the sulfamide derivative of acid dyes, can include such as colour index (The Society of Dyers and Colourists publish) in be categorized as dyestuff compound, dyeing notes (Se Ran societies) described in it is known Dyestuff.In addition, according to chemical constitution, azo dyes, cyanine dyes, triphenhlmethane dye, xanthene dye, phthalocyanine dye can be included Material, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azomethine dyes, squaraine dye, acridine dye, styryl dye Material, coumarine dye, quinoline dye and nitro dye etc..In these, organic solvent-soluble dyestuff is preferably used.

Specifically, C.I. solvent yellows 4,14,15,23,24,38,62,63,68,82,94,98,99,162 can be included；

C.I. solvent red 45,49,125,130,218；

C.I. solvent orange 2,7,11,15,26,56；

C.I. solvent blue 4,5,37,67,70,90；

C.I. C.I. solvent dyes of solvent green 1,4,5,7,34,35 etc.；

C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98, 99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、 161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、 212、214、220、221、228、230、232、235、238、240、242、243、251；

C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66, 73、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、182、 183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、 274、277、280、281、289、308、312、315、316、339、341、345、346、349、382、383、388、394、401、 412、417、418、422、426；

C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108, 169、173；

C.I. acid violet 6B, 7,9,17,19,30,102；

C.I. Blue VRS, 7,9,15,18,22,29,42,59,60,62,70,72,74,82,83,86,87,90,92, 93、100、102、103、104、113、117、120、126、130、131、142、147、151、154、158、161、166、167、 168、170、171、184、187、192、199、210、229、234、236、242、243、256、259、267、285、296、315、 335；C.I. the C.I. acid dyes such as acid green 1,3,5,9,16,50,58,63,65,80,104,105,106,109；

C.I. directly Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98, 102、108、109、129、136、138、141；

C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177, 179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250；

C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107；

C.I. directly purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104；

C.I. directly indigo plant 1,2,6,8,15,22,25,41,57,71,76,78,80,81,84,85,86,90,93,94,95, 97、98、99、100、101、106、107、108、109、113、114、115、117、119、120、137、149、150、153、155、 156、158、159、160、161、162、163、164、165、166、167、168、170、171、172、173、188、189、190、 192、193、194、195、196、198、199、200、201、202、203、207、209、210、212、213、214、222、225、 226、228、229、236、237、238、242、243、244、245、246、247、248、249、250、251、252、256、257、 259、260、268、274、275、293；

C.I. the C.I. such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82 directly contaminates Material；

C.I. C.I. disperse dyes such as disperse yellow 54,76；

C.I. alkali red 1:1,10；

C.I. alkali blue 1,3,5,7,9,19,24,25,26,28,29,40,41,54,58,59,64,65,66,67,68；

C.I. the grade of Viride Nitens 1 C.I. basic-dyeable fibres；

C.I. active yellow 2,76,116；

C.I. reactive orange 16；

C.I. the grade of active red 36 C.I. reactive dye；

C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65；

C.I. mordant rouge 1,2,4,9,12,14,17,18,19,22,23,24,25,26,27,30,32,33,36,37,38, 39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95；

C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47, 48；

C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53,58；

C.I. mordant dyeing indigo plant 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44, 49、53、61、74、77、83、84；

C.I. C.I. mordant dyes such as viridon 1,3,4,5,10,15,26,29,33,34,35,41,43,53；

C.I. the grade of vat green 1 C.I. reducing dyes etc..

Wherein, preferably cyan dye, cudbear and orchil.

These dyestuffs can be properly selected according to the spectrophotometric spectra of desired colour filter.These dyestuffs can be used alone, Also two or more may be used.

Relative to the total amount of solid constituent, the containing ratio of colouring agent (A) is preferably more than 1 mass % more preferably 5 matter Measure more than %, more preferably preferably below 70 mass %, more preferably below 60 mass %, below 50 mass %.Such as The containing ratio of fruit colouring agent (A) is in above-mentioned scope, then to result in desired light splitting, colour saturation.

＜ resins (B) ＞

As resin (B), it is not particularly limited, preferably alkali soluble resin (B).Alkali soluble resin (B) (has below When be referred to as " resin (B) ") be containing from least one monomer (a) selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides The copolymer of construction unit.

As such resin (B), following resin [K1]~[K6] etc. can be included.

Resin [K1]：With from (following selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides monomer (a) Construction unit sometimes referred to as " (a) ") and from ring-type ether structure and the monomer of ethylenic unsaturated bond with carbon number 2~4 (b) copolymer of the construction unit of (hereinafter sometimes referred to " (b) ")；

Resin [K2]：With the construction unit from (a) and the construction unit from (b) and from can be with (a) copolymerization Monomer (c) is (but, different from (a) and (b).) (hereinafter sometimes referred to " (c) ") construction unit copolymer；

Resin [K3]：Copolymer with the construction unit from (a) and the construction unit from (c)；

Resin [K4]：With making (b) addition in the construction unit of the construction unit from (a) and structure list from (c) The copolymer of member；

Resin [K5]：With making (a) addition in the construction unit of the construction unit from (b) and structure list from (c) The copolymer of member；

Resin [K6]：With making (a) addition in the construction unit from (b) and then make the construction unit of carboxylic acid anhydrides addition With the copolymer of the construction unit from (c).

As (a), specifically, acrylic acid, methacrylic acid, crotonic acid, o-, m-, p- vinyl benzoic acid can be enumerated Deng unsaturated monocarboxylic class；

The adjacent benzene two of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, 1,4- The unsaturated dicarboxylic class such as cyclohexene dicarboxylic acid；

Methyl -5- ENB -2,3- dicarboxylic acids, bicyclic [2.2.1] hept-2-ene" of 5- carboxyls, 5,6- dicarboxyls are bicyclic [2.2.1] hept-2-ene", 5- carboxyl -5- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] the hept- 2- of 5- carboxyl -5- ethyls Alkene, 5- carboxyl -6- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- carboxyl -6- ethyls etc. contain carboxyl Bicyclic unsaturated compound class；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- vinylphthalic acids acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride, 5,6- The unsaturated dicarboxylic anhydrides such as bicyclic [2.2.1] the hept-2-ene" acid anhydride of dicarboxyl；

Mono succinate [2- (methyl) acryloyl-oxyethyl] ester, phthalic acid list [2- (methyl) acryloxy second Base] more than 2 yuan of the polybasic carboxylic acid such as ester single [(methyl) acryloxyalkyl] esters of unsaturation；

The such unsaturated esters of acrylic acid containing hydroxyl and carboxyl in same molecule of α-(hydroxymethyl) acrylic acid Deng.

It is excellent in terms of copolyreaction, the deliquescent aspect of obtained resin in aqueous alkali in these Select acrylic acid, methacrylic acid, maleic anhydride etc..

As (b), the ring-type ether structure with carbon number 2~4 can be included (for example, selected from oxirane ring, oxa- ring fourth It is at least one kind of in alkane ring and tetrahydrofuran ring) and ethylenic unsaturated bond polymerizable compound.

(b) cyclic ether and the monomer of (methyl) acryloxy preferably with carbon number 2~4.

It should illustrate, in this specification, " (methyl) acrylic acid " represents at least 1 in acrylic acid and methacrylic acid Kind.The statement of " (methyl) acryloyl group " and " (methyl) acrylate " etc. also has the same meaning.

As (b), the monomer (b1) with epoxy ethyl and ethylenic unsaturated bond can be enumerated (hereinafter sometimes referred to " (b1) "), the monomer (b2) (hereinafter sometimes referred to " (b2) ") with oxetanylmethoxy and ethylenic unsaturated bond, with tetrahydrochysene furan Mutter monomer (b3) (hereinafter sometimes referred to " (b3) ") of base and ethylenic unsaturated bond etc..

As (b1), the structure that the unsaturated aliphatic hydrocarbon for example with straight-chain or branch's chain state is at least partially epoxidized can be enumerated Monomer (b1-1) (hereinafter sometimes referred to " (b1-1) "), the monomer (b1- for the structure being at least partially epoxidized with ester ring type unsaturated hydrocarbons 2) (hereinafter sometimes referred to " (b1-2) ").

As (b1-1), can enumerate (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, It is (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, o- vinylbenzyl glycidyl base ether, m- Vinylbenzyl glycidyl base ether, p- vinylbenzyl glycidyl base ether, Alpha-Methyl-o- vinylbenzyl glycidyl Base ether, Alpha-Methyl-m- vinylbenzyl glycidyl base ether, Alpha-Methyl-p- vinylbenzyl glycidyl base ether, 2,3- are double Double (glycidoxypropyl methyl) styrene of (glycidoxypropyl methyl) styrene, 2,4-, double (the glycidoxypropyl first of 2,5- Base) styrene, 2,6- double (glycidoxypropyl methyl) styrene, 2,3,4- tri- (glycidoxypropyl methyl) styrene, 2, 3,5- tri- (glycidoxypropyl methyl) styrene, 2,3,6- tri- (glycidoxypropyl methyl) styrene, 3,4,5- tri- (shrink Glycerine epoxide methyl) styrene, 2,4,6- tri- (glycidoxypropyl methyl) styrene etc..

As (b1-2), can enumerate vinylcyclohexene monoxide, 1,2- epoxy -4- vinyl cyclohexanes (for example, CELLOXIDE 2000；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates are (for example, CYCLOMER A400；(strain) Daicel manufacture), (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates are (for example, CYCLOMER M100；(strain) is big Match fine jade manufacture), the compound represented by formula (II) and the compound etc. represented by formula (III).

[in formula (II) and formula (III), R^aAnd R^bRepresent hydrogen contained in the alkyl of hydrogen atom or carbon number 1~4, the alkyl Atom can be optionally substituted by a hydroxyl group.

X^aAnd X^bRepresent singly-bound, *-R^c-, *-R^c- O-, *-R^c- S- or *-R^c-NH-。

R^cRepresent the alkylidene of carbon number 1~6.

* the bonding end with O is represented.]

As the alkyl of carbon number 1~4, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tertiary fourth can be included Base etc..

The alkyl being optionally substituted by a hydroxyl group as hydrogen atom, can include hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls, 1- hydroxypropyls, 2- hydroxypropyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxyl fourths Base, 2- hydroxybutyls, 3- hydroxybutyls, 4- hydroxybutyls etc..

It is used as R^aAnd R^b, can preferably include hydrogen atom, methyl, ethyl, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyl second Base, can more preferably include hydrogen atom, methyl.

As the alkylidene of carbon number 1~6, methylene, ethylidene, propane -1,2- diyl, propane -1,3- bis- can be included Base, butane -1,4- diyls, pentane -1,5- diyls, hexane -1,6- diyls etc..

It is used as X^aAnd X^b, can preferably include singly-bound, methylene, ethylidene, *-CH₂- O- and *-CH₂CH₂- O-, more Singly-bound, *-CH can preferably be included₂CH₂- O- (* represents the bonding end with O).

As the compound represented by formula (II), it can include what is represented by any one of formula (II-1)~formula (II-15) Compound etc..Wherein, preferably by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~ The compound that formula (II-15) is represented, the chemical combination more preferably represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) Thing.

As the compound represented by formula (III), any one expression by formula (III-1)~formula (III-15) can be included Compound etc..Wherein, preferably by formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) compound that~formula (III-15) is represented, more preferably by formula (III-1), formula (III-7), formula (III-9) or formula (III-15) compound represented.

The compound represented by formula (II) and the compound represented by formula (III) can each be used alone, can also The compound represented by the compound represented by formula (II) and by formula (III) is used in combination.In the case of by them and use, by formula (II) The containing ratio of the compound of expression and the compound represented by formula (III) is with molar basis, preferably 5：95~95：5, more Preferably 10：90~90：10, more preferably 20：80~80：20.

As (b2), the monomer more preferably with oxetanylmethoxy He (methyl) acryloxy.As (b2), it can enumerate 3- methyl -3- methacryloxymethyls oxetanes, 3- methyl -3- acryloyloxymethyls oxetanes, 3- second Base -3- methacryloxymethyls oxetanes, 3- ethyl -3- acryloyloxymethyls oxetanes, 3- methyl -3- Methacryloxyethyl oxetanes, 3- methyl -3- acryloyl-oxyethyls oxetanes, 3- ethyl -3- methyl Acryloyl-oxyethyl oxetanes, 3- ethyl -3- acryloyl-oxyethyl oxetanes etc..

As (b3), the monomer more preferably with tetrahydrofuran base He (methyl) acryloxy.As (b3), specifically Ground, can include tetrahydrofurfuryl acrylate (for example, VISCOAT V#150, Osaka Organic Chemical Industry (strain) are manufactured), methyl-prop Olefin(e) acid tetrahydrochysene chaff ester etc..

As (b), in the side for the reliability that can further improve heat resistance, the chemical-resistant of obtained colour filter etc. Face, be preferably (b1).And then, in terms of the excellent storage stability of colored curable resin composition, more preferably (b1-2).

As (c), can include (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 12 Arrcostab, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) acrylic acid ring pentyl ester, (methyl) acrylic acid Cyclohexyl, (methyl) acrylic acid 2- methyl cyclohexyls, the ring [5.2.1.0 of (methyl) acrylic acid three^2_,6] decane -8- base esters are (in the skill In art field, as trivial name, it is referred to as " the bicyclic pentyl ester of (methyl) acrylic acid ".In addition, being sometimes referred to as the " ring of (methyl) acrylic acid three Last of the ten Heavenly stems ester ".), the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decene -8- base esters are (in the technical field, as trivial name, referred to as " (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate ".), the bicyclic amoxy ethyl ester of (methyl) acrylic acid, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) benzyl acrylate, (methyl) propargylacrylate, (methyl) phenyl acrylate, (methyl) esters of acrylic acids such as (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate；

(methyl) acrylic acid containing hydroxyl such as (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters Esters；

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate；

Bicyclic [2.2.1] hept-2-ene", 5- methyl bicycles [2.2.1] hept-2-ene", bicyclic [2.2.1] hept-2-ene" of 5- ethyls, Bicyclic [2.2.1] hept-2-ene" of 5- hydroxyls, bicyclic [2.2.1] hept-2-ene" of 5- hydroxymethyls, 5- (2 '-hydroxyethyl) are bicyclic Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- methoxyl groups, bicyclic [2.2.1] hept-2-ene" of 5- ethyoxyls, 5,6- dihydroxies Bicyclic [2.2.1] hept-2-ene" of base, bicyclic [2.2.1] hept-2-ene"s of 5,6- bis- (hydroxymethyl), 5,6- bis- (2 '-hydroxyethyl) are double Bicyclic [2.2.1] hept-2-ene" of ring [2.2.1] hept-2-ene", 5,6- dimethoxys, bicyclic [2.2.1] the hept- 2- of 5,6- diethoxies Bicyclic [2.2.1] hept-2-ene" of alkene, 5- hydroxy-5-methyl bases, bicyclic [2.2.1] hept-2-ene" of 5- hydroxyl -5- ethyls, 5- hydroxyl first Bicyclic [2.2.1] hept-2-ene" of base -5- methyl bicycles [2.2.1] hept-2-ene", 5- t-butoxy carbonyls, 5- cyclohexyloxy carbonyls Bicyclic [2.2.1] hept-2-ene" of bicyclic [2.2.1] hept-2-ene", 5- phenyloxycarbonyls, 5,6- double (t-butoxy carbonyls) are bicyclic The bicyclic unsaturated compound classes such as double (cyclohexyloxy carbonyl) bicyclic [2.2.1] hept-2-ene"s of [2.2.1] hept-2-ene", 5,6-；

N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, N- succinimides base- 3- maleimidobenzoyls salt, N- succinimide base -4- maleimidobutyrates salt, N- succinimide base -6- Malaysias The dicarbapentaborane such as acid imide caproate, N- succinimide base -3- maleimidopropionic acids salt, N- (9- acridinyls) maleimide Imine derivative class；

Styrene, α-methylstyrene, m- methyl styrene, p-methylstyrene, vinyltoluene, p- methoxyl group Styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinylacetate, 1, 3- butadiene, isoprene, 2,3- dimethyl -1,3- butadiene etc..

In these, from copolyreaction and heat resistance aspect, optimization styrene, vinyltoluene, (methyl) third Olefin(e) acid benzyl ester, the ring [5.2.1.0 of (methyl) acrylic acid three^2,6] decane -8- base esters, N-phenylmaleimide, N- cyclohexyl Malaysia Acid imide, N- benzyl maleimides, bicyclic [2.2.1] hept-2-ene".

In resin [K1], the ratio of the construction unit from each monomer is constituting the entire infrastructure unit of resin [K1] In, it is preferably

Construction unit from (a)：2~60 moles of %

Construction unit from (b)：40~98 moles of %,

More preferably

Construction unit from (a)：10~50 moles of %

Construction unit from (b)：50~90 moles of %.

If in resin [K1] there is colored curable resin composition in the ratio of construction unit in above-mentioned scope The tendency of the excellent solvent resistance of developability and obtained colour filter when storage stability, formation colored pattern.

Resin [K1] being capable of bibliography《The experimental method of Polymer Synthesizing》(the big chemical same people of Jin Longhangzhu publishing houses (strain) 1st edition the 1st printing distribution on March 1st, 1972) described in method and citation described in the document manufacture.

As the specific manufacture method of resin [K1], method can be listed below：By by (a) and (b) of ormal weight, poly- Close initiator and solvent etc. to be fitted into reaction vessel, replaced oxygen with nitrogen, so as to form deoxidizing atmosphere, heat and protect while stirring Temperature.

It should illustrate, be not particularly limited for polymerization initiator as used herein and solvent etc., the field can be used In usually used material.As polymerization initiator, azo-compound (2,2 '-azodiisobutyronitrile, 2,2 '-azo can be enumerated Two (2,4- methyl pentane nitriles) etc.), organic peroxide (benzoyl peroxide etc.), as solvent, as long as each monomer is dissolved , can enumerate as solvent (E) solvent described later of colored curable resin composition of the present invention etc..

It should illustrate, for obtained copolymer, reacted solution can be used as former state, it is possible to use concentration dilutes Solution, it is possible to use the product taken out using the method such as reprecipitation as solid (powder).Especially, during the polymerization, as Contained solvent in solvent, the colored curable resin composition by using the present invention, can as former state will be reacted molten Liquid is used in the preparation of the colored curable resin composition of the present invention, therefore, it is possible to make the colored curable resin of the present invention The manufacturing process of composition simplifies.

In resin [K2], the ratio of the construction unit from each monomer is constituting the entire infrastructure unit of resin [K2] In, it is preferably：

Construction unit from (a)：2~45 moles of %

Construction unit from (b)：2~95 moles of %

Construction unit from (c)：1~65 mole of %,

More preferably：

Construction unit from (a)：5~40 moles of %

Construction unit from (b)：5~80 moles of %

Construction unit from (c)：5~60 moles of %.

If there is colored curable resin composition in above-mentioned scope in the ratio of the construction unit of resin [K2] Solvent resistance, heat resistance and the mechanical strength of developability and obtained colour filter when storage stability, formation colored pattern Excellent tendency.

Resin [K2], can be with the manufacture method note as resin [K1] in addition to further using (c) of ormal weight The method of load is similarly manufactured.

In resin [K3], the ratio of the construction unit from each monomer is constituting the entire infrastructure unit of resin [K3] In, it is preferably：

Construction unit from (a)：2~60 moles of %

Construction unit from (c)：40~98 moles of %,

More preferably：

Construction unit from (a)：10~50 moles of %

Construction unit from (c)：50~90 moles of %.

Resin [K3] is in addition to replacing (b) and using (c), the side that can be recorded with the manufacture method as resin [K1] Method is similarly manufactured.

Resin [K4] can make the cyclic ether and (a) for the carbon number 2~4 that (b) have by obtaining (a) and (c) copolymer The carboxylic acid and/or the carboxylic acid anhydrides addition that have and manufacture.

First, (a) and (c) copolymerization can be manufactured in the same manner as the method for the manufacture method record as resin [K1] Thing.Under this situation, the ratio of the construction unit from each monomer is preferably the ratio identical with being enumerated in resin [K3] Ratio.

Next, make the cyclic ether of the carbon number 2~4 that (b) have and the carboxylic acid in above-mentioned copolymer from (a) and/or The part reaction of carboxylic acid anhydrides.

Then (a) and the copolymer of (c) manufacture, are replaced into air, by (b), carboxylic acid or carboxylic by atmosphere in flask by nitrogen Catalysts (such as three (dimethylaminomethyl) phenol) and polymerization inhibitor (such as quinhydrones) of acid anhydrides and cyclic ether etc. Load in flask, for example, being reacted 1~10 hour at 60~130 DEG C, so as to manufacture resin [K4].

Relative to 100 moles of (a), preferably 5~80 moles, more preferably 10~75 moles of the usage amount of (b).By making it As the scope, developability when there is the storage stability of colored curable resin composition, forming pattern and obtain The solvent resistance of pattern, heat resistance, the balance of mechanical strength and sensitivity become good tendency.Due to the reactivity of cyclic ether Height, unreacted (b) is difficult remaining, therefore as (b) of resin [K4] is used for, preferably (b1), more preferably (b1-1).

Relative to (a), (b) and (c) mass parts of total amount 100, the usage amounts preferably 0.001 of above-mentioned catalysts~ 5 mass parts.Relative to the mass parts of total amount 100 of (a), (b) and (c), usage amount preferably 0.001~5 matter of above-mentioned polymerization inhibitor Measure part.

For reaction conditions such as feed process, reaction temperature and times, it can be considered that the heat release that manufacturing equipment, polymerization are produced Amount etc. is suitably adjusted.Further, in the same manner as polymerizing condition, it can be considered that thermal discharge that manufacturing equipment, polymerization are produced etc., suitably Ground adjustment feed process, reaction temperature.

It is identical with the manufacture method of above-mentioned resin [K1] as the first stage for resin [K5], obtain (b) with (c) copolymer.As described above, the copolymer obtained can use reacted solution as former state, it is possible to use concentration or The solution of dilution, it is possible to use the product taken out using methods such as reprecipitations as solid (powder).

Ratio from (b) He the construction unit of (c), relative to the conjunction for the entire infrastructure unit for constituting above-mentioned copolymer Molal quantity is counted, is preferably respectively

Construction unit from (b)：5~95 moles of %

Construction unit from (c)：5~95 moles of %,

More preferably

Construction unit from (b)：10~90 moles of %

Construction unit from (c)：10~90 moles of %.

And then, under conditions of same with the manufacture method of resin [K4], by make carboxylic acid or carboxylic acid anhydrides that (a) have with (b) reaction of the cyclic ether from (b) having with the copolymer of (c), so as to obtain resin [K5].

Relative to 100 moles of (b), preferably 5~80 moles of the usage amount with (a) of above-mentioned copolymer reaction.Due to ring The reactivity of shape ether is high, and unreacted (b) is difficult remaining, therefore as (b) of resin [K5] is used for, preferably (b1), more preferably (b1-1)。

Resin [K6] is the resin for further making carboxylic acid anhydrides be reacted with resin [K5].Make carboxylic acid anhydrides with by cyclic ether with The hydroxyl reaction that the reaction of carboxylic acid or carboxylic acid anhydrides is produced.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- can be included Vinylphthalic acid acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl four Bicyclic [2.2.1] hept-2-ene" acid anhydride of hydrogen phthalic anhydride, 5,6- dicarboxyls etc..1 mole of usage amount relative to (a), carboxylic acid anhydrides Preferably 0.5~1 mole of usage amount.

As resin (B), specifically, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) acrylic acid can be enumerated Copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] resin [K1] such as last of the ten Heavenly stems ester/(methyl) acrylic copolymer； (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid shrink sweet Grease/styrene/(methyl) acrylic copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/(methyl) Acrylic acid/N- N-cyclohexylmaleimides copolymer, the ring [5.2.1.0 of (methyl) acrylic acid 3,4- epoxies three^2.6] last of the ten Heavenly stems ester/(first Base) acrylic acid/vinyl toluene copolymer, 3- methyl -3- (methyl) acryloyloxymethyls oxetanes/(methyl) propylene The resins such as acid/styrol copolymer [K2]；(methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) third The resins such as olefin(e) acid copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl/(methyl) acrylic copolymer [K3]；Make (methyl) glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic copolymer addition Resin, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/styrene/(methyl) acrylic copolymer The resin of addition, make (methyl) glycidyl acrylate and (methyl) acrylic acid tricyclodecyl/(methyl) acrylic acid benzyl The resins [K4] such as the resin of ester/(methyl) acrylic copolymer addition；Make (methyl) acrylic acid and (methyl) acrylic acid three The resin of the copolymer reaction of ring last of the ten Heavenly stems ester/(methyl) glycidyl acrylate, make (methyl) acrylic acid and (methyl) third The resins [K5] such as the resin of copolymer reaction of olefin(e) acid tricyclodecyl/styrene/(methyl) glycidyl acrylate；Make (methyl) acrylic acid and the tree of the copolymer reaction of (methyl) acrylic acid tricyclodecyl/(methyl) glycidyl acrylate Resins [K6] such as the resin that fat further reacts with tetrabydrophthalic anhydride etc..

Resin (B) is preferably selected from one kind in resin [K1], resin [K2] and resin [K3], more preferably selected from resin One kind in [K2] and resin [K3].If these resins, then the developability of colored curable resin composition is excellent.From From the viewpoint of the adaptation of colored pattern and substrate, further preferred resin [K2].

The weight average molecular weight of the polystyrene conversion of resin (B) is preferably 3000~100000, more preferably 5000~ 50000, more preferably 5000~30000.If molecular weight is in above-mentioned scope, exist hardness of film improve, it is residual The tendency that film rate is also high, unexposed portion is improved for the favorable solubility of developer solution, the resolution ratio of colored pattern.

The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) is preferably 1.1~6, more preferably For 1.2~4.

The acid number (solid constituent) of resin (B) is preferably 50~170mg-KOH/g, more preferably 60~150mg-KOH/g, More preferably 70~135mg-KOH/g.Wherein, acid number is the amount as the potassium hydroxide needed for neutralization resin (B) 1g (mg) value determined, for example, can be titrated and be obtained by using potassium hydroxide aqueous solution.

Relative to the total amount of solid constituent, the content of resin (B) is preferably 7~65 mass %, more preferably 13~60 matter Measure %, more preferably 17~55 mass %.If the content of resin (B) can form color-patch map in above-mentioned scope Case, the tendency that the resolution ratio with colored pattern and residual film ratio are improved in addition.

＜ polymerizable compounds (C) ＞

Polymerizable compound (C) is can to utilize the living radical produced by polymerization initiator (D) and/or acid polymerization Compound, is preferably (methyl) acroleic acid esterification such as the compound that can include the ethylenic unsaturated bond with polymerism Compound.

As the polymerizable compound with 1 ethylenic unsaturated bond, nonyl phenyl carbitol acrylate, third can be enumerated Olefin(e) acid 2- hydroxyl -3- phenoxy-propyls, 2- ethylhexyl carbitols acrylate, acrylic acid 2- hydroxy methacrylates, N- vinylpyridines Pyrrolidone etc. and above-mentioned (a), (b) and (c).

As the polymerizable compound with 2 ethylenic unsaturated bonds, 1,6- hexylene glycols two (methyl) acrylic acid can be enumerated It is ester, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, double Phenol A double (acryloyl-oxyethyl) ether, 3- methyl pentanediols two (methyl) acrylate etc..

Wherein, polymerizable compound (C) is preferably the polymerizable compound with the ethylenic unsaturated bond of more than 3.Make For such polymerizable compound, for example, it can include trimethylolpropane tris (methyl) acrylate, (first of pentaerythrite three Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, the four seasons penta 4 Alcohol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanides Urea acid esters, glycol-modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylic acid Ester, propylene glycol modified pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, oneself Lactone-modified pentaerythrite four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc., wherein, It is preferred that (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate.

The weight average molecular weight of polymerizable compound (C) be preferably more than 150 and less than 2900, more preferably more than 250 and Less than 1500.

Relative to the total amount of solid constituent, the content of polymerizable compound (C) is preferably 7~65 mass %, more preferably 13~60 mass %, more preferably 15~55 mass %.

Content ratio [the resin (B) of resin (B) and polymerizable compound (C)：Polymerizable compound (C)] with quality criteria Meter, preferably 20：80~80：20, more preferably 35：65~80：20.

If the content of polymerizable compound (C) is in above-mentioned scope, residual film ratio when being formed with colored pattern And the tendency that the chemical-resistant of colour filter is improved.

＜ polymerization initiators (D) ＞

Polymerization initiator (D) triggers polymerization as long as living radical, acid etc. can be produced using light, the effect of heat Compound, then be not particularly limited, known polymerization initiator can be used.

As polymerization initiator (D), can enumerate O- acyl groups oxime compound, alkyl phenyl assimilation compound, united imidazole, Triaizine compounds and acylphosphine oxide compound etc..

Above-mentioned O- acyl groups oxime compound is the compound with the structure represented by formula (d1).Hereinafter, * represents bonding end.

As above-mentioned O- acyl groups oxime compound, for example, it can include N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) Butane -1- ketone -2- imines, N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines, N- benzoxies Base -1- (4- Phenylsulfanyls phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- first Base benzoyl) -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- bis- Methyl -2,4- dioxolyls methoxyl group) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines and N- benzoyloxys -1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines etc..It can be used The commercially available product such as Irgacure OXE01, OXE02 (being manufactured above for BASF AG), N-1919 (ADEKA Corp.'s manufacture).Its In, O- acyl group oxime compounds are preferably selected from N- benzoyloxys -1- (4- Phenylsulfanyls phenyl) butane -1- ketone -2- imines, N- Benzoyloxy -1- (4- Phenylsulfanyls phenyl) octane -1- ketone -2- imines and N- benzoyloxys -1- (4- Phenylsulfanyls Phenyl) at least one kind of in -3- cyclopenta propane -1- ketone -2- imines, more preferably N- benzoyloxys -1- (4- Phenylsulfanyls Phenyl) octane -1- ketone -2- imines.If these O- acyl group oxime compounds, it is intended to obtain the colour filter of high brightness.

Abovementioned alkyl phenyl ketone compound is with the part-structure represented by formula (d2) or by the part of formula (d3) expression The compound of structure.In these part-structures, phenyl ring can have substituent.

As the compound with the structure represented by formula (d2), 2- methyl -2- morpholinoes -1- (4- methyl can be included Methyldisulfanylphenyl) propane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyls butane -1- ketone and 2- (dimethyl Amino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] butane -1- ketone etc..Irgacure can be used 369th, the commercially available product of 907,379 (being manufactured above for BASF AG) etc..

As the compound with the structure represented by formula (d3), can include 2- hydroxy-2-methyl -1- phenyl-propanes - 1- ketone, 2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) phenyl] propane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- hydroxyls The oligomer, α of base -2- methyl isophthalic acids-(4- isopropenyls phenyl) propane -1- ketone, α-diethoxy acetophenone and benzil diformazan Base ketal etc..

From sensitivity aspect, alkyl phenyl assimilation compound, the preferably chemical combination with the structure represented by formula (d2) are used as Thing.

As above-mentioned united imidazole, it can include by compound of formula (d5) expression etc..

[in formula (d5), R¹³~R¹⁸Represent there can be the aryl of the carbon number 6~10 of substituent.]

As the aryl of carbon number 6~10, phenyl, tolyl, xylyl, ethylphenyl and naphthyl etc. can be included, it is excellent Elect phenyl as.

As substituent, halogen atom, alkoxy of carbon number 1~4 etc. can be included.As halogen atom, it can include Fluorine atom, chlorine atom, bromine atoms, iodine atom etc., preferably chlorine atom.As the alkoxy of carbon number 1~4, methoxy can be included Base, ethyoxyl, propoxyl group, butoxy etc., preferably methoxyl group.

As united imidazole, for example, it can include 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl connection miaow Azoles, 2,2 '-bis- (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (for example, referring to Japanese Unexamined Patent Publication 6-75372 Publication, Japanese Unexamined Patent Publication 6-75373 publications etc..), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2, 2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxalines (for example, With reference to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc..) and 4,4 ', the benzene of 5,5 '-position United imidazole (for example, referring to Japanese Unexamined Patent Publication 7-10913 publications etc.) that base is replaced by alkoxy carbonyl group etc..Wherein, it is excellent Select the compound represented by following formula and their mixture.

As above-mentioned triaizine compounds, for example, double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3 of 2,4- can be included, Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of 5- triazines, 2,4-, double (the trichloromethyl) -6- peppers of 2,4- Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of base -1,3,5- triazines, 2,4-, double (three chloromethanes of 2,4- Base) -6- [2- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, double (trichloromethyl) -6- [2- (furans -2- of 2,4- Base) vinyl] -1,3,5- triazines, double (the trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) vinyl] of 2,4- - 1,3,5- triazines and double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) the vinyl] -1,3,5- triazines of 2,4- etc..

As above-mentioned acylphosphine oxide compound, TMDPO etc. can be included.

And then, as polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzene can be included even The benzoin compound such as relation by marriage isopropyl ether, benzoin isobutyl ether；Benzophenone, o- benzoyl methyl benzoate, 4- phenyl Benzophenone, -4 '-dimethyl diphenyl sulfide of 4- benzoyls, 3,3 ', 4,4 '-four (tert-butyl crosses oxygen carbonyl) benzophenone, The benzophenone cpds such as 2,4,6- tri-methyl benzophenones；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- EAQs and camphorquinone； 10- butyl -2- chloro-acridines ketone, benzil, phenylglyoxalates methyl esters and titanocenes compound etc..

These are preferably applied in combination with the initiation auxiliary agent (D1) (particularly amine) described later that polymerize.

Polymerization initiator (D) is preferably to include to be selected from alkyl phenyl assimilation compound, triaizine compounds, acylphosphine oxide chemical combination The polymerization initiator of at least one of thing, O- acyl groups oxime compound and united imidazole, more preferably comprising O- acyl group oximes The polymerization initiator of compound.

The content of polymerization initiator (D), relative to the mass parts of total amount 100 of resin (B) and polymerizable compound (C), Preferably 0.01~40 mass parts, more preferably 0.05~35 mass parts, more preferably 0.1~32 mass parts, it is especially excellent Elect 1~30 mass parts as.

＜ polymerizations trigger auxiliary agent (D1) ＞

Polymerization triggers the polymerization that auxiliary agent (D1) is the polymerizable compound for having triggered polymerization for promotion polymerization initiator Compound or sensitizer.In the case of triggering auxiliary agent (D1) comprising polymerization, generally it is applied in combination with polymerization initiator (D).

Trigger auxiliary agent (D1) as polymerization, amines, alkoxy anthracene compound, thioxanthone compounds and carboxylic can be included Acid compound etc..

As above-mentioned amines, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminos can be included Yl benzoic acid methyl esters, EDMAB, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminos Base ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylaminos) two Benzophenone (common name Michler's keton), 4,4 '-bis- (diethylamino) benzophenone and 4,4 '-bis- (ethylmethylamino) benzophenone Deng, wherein it is preferred to 4,4 ' can be included-bis- (diethylamino) benzophenone.EAB-F (hodogaya chemical industry can be used (strain) manufacture) etc. commercially available product.

As above-mentioned alkoxy anthracene compound, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxys can be included Anthracene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene and the fourth oxygen of 2- ethyls -9,10- two Base anthracene etc..

As above-mentioned thioxanthone compounds, ITX, ITX, 2,4- diethyl can be included Thioxanthones, the clopenthixal ketones of 2,4- bis- and the chloro- 4- propoxythioxanthones of 1- etc..

As above-mentioned carboxylic acid compound, Phenylsulfanyl acetic acid, methyl phefzylsulfanyl acetic acid, ethylphenyl can be included Sulfanyl acetic acid, Methylethyl phenyl sulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenyl sulfanyl acetic acid, Dimethoxyphenyl sulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenyl sulfanyl acetic acid, N-phenylglycine, benzene oxygen Base acetic acid, naphthalene sulfenyl acetic acid, N- naphthyls glycine and naphthoxy acetic acid etc..

In the case where triggering auxiliary agent (D1) using these polymerizations, its content is relative to resin (B) and polymerizable compound (C) the mass parts of total amount 100 are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.If polymerization triggers auxiliary agent (D1) amount within the range, can be tended to improve with more high sensitivity formation colored pattern, the productivity ratio of colour filter.

＜ solvents (E) ＞

Solvent (E) is not particularly limited, solvent usually used in the field can be used.Can for example ester output be enumerated molten Agent (intramolecular include-COO-, the solvent without-O-), ether solvents (intramolecular include-O-, the solvent without-COO-), Ether-ether solvent (in solvent of the intramolecular comprising-COO- and-O-), ketone solvent (include-CO-, molten without-COO- in intramolecular Agent), alcoholic solvent (intramolecular include OH, the solvent without-O- ,-CO- and-COO-), aromatic hydrocarbon solvents, amide solvent and Dimethyl sulfoxide (DMSO) etc..

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be included Ester, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, fourth Acid butyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Hexacyclonic Acid Ester and gamma-butyrolacton etc..

As ether solvents, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, second two can be included Alcohol single-butyl ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propane diols Single ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl butanols, four Hydrogen furans, oxinane, 1,4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG) methyl ethyl ether, two Glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole etc..

As ether-ether solvent, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, ethoxy can be enumerated Base methyl acetate, ethyoxyl ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- ethyoxyls Methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyls -2 Methylpropionic acid ethyl ester, 3- Methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyls acetic acid esters, propylene glycol monomethyl ether, propane diols list ethyl It is ether acetic acid ester, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, two sweet Alcohol list monoethyl ether acetate, diethylene glycol monobutyl ehter acetic acid esters and dipropylene glycol methyl ether acetic acid esters etc..

As ketone solvent, 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- can be included Heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone and isophorone etc..

As alcoholic solvent, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols and sweet can be included Oil etc..

As aromatic hydrocarbon solvents, benzene,toluene,xylene and 1,3,5- trimethylbenzenes etc. can be included.

As amide solvent, DMF, DMA and N- crassitudes can be included Ketone etc..

These solvents can be used alone, and also two or more may be used.

Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3- ethoxy-propionic acid second Ester, ethylene glycol single methyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, carbiphene, 3- methoxybutyl second Acid esters, 3- methoxyl groups-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanones, DMF and 1-METHYLPYRROLIDONE etc., More preferably propylene glycol monomethyl ether, 4- hydroxy-4-methyl-2-pentanones, propylene glycol monomethyl ether, ethylene glycol monobutyl Ether, dipropylene glycol methyl ether acetic acid esters, ethyl lactate, 3- methoxybutyls acetic acid esters, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl groups Methyl propionate, 3- ethoxyl ethyl propionates and 1-METHYLPYRROLIDONE.

Relative to the total amount of colored curable resin composition, the content of solvent (E) is preferably 70~95 mass %, more excellent Elect 75~92 mass % as.In other words, the solid constituent of colored curable resin composition is preferably 5~30 mass %, more excellent Elect 8~25 mass % as.If the content of solvent (E) is in above-mentioned scope, flatness during coating becomes good, in addition Colour saturation will not be not enough when foring colour filter, therefore becomes good tendency with display characteristic.

＜ levelling agents (H) ＞

As levelling agent (H), silicone based surfactants, fluorine system surfactant can be included and with fluorine atom Silicone based surfactants etc..These can have polymerizable group in side chain.

As silicone based surfactants, the surfactant that there is siloxanes key in intramolecular etc. can be included.Tool Body, can include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names：Dong Li-DOW CORNING (strain) manufacture), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (モメ Application ティ Block パフォーマ Application スマテリア Le ズジャパ Application contracts commercial firm systems Make) etc..

As above-mentioned fluorine system surfactant, the surfactant that there is fluorocarbon chain in intramolecular etc. can be included.Tool Body, Off ロラー De (registration mark) FC430, FC431 (Sumitomo 3M (strain) manufactures), (registration of メガ Off ァッ Network can be included Trade mark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC (strain) manufactures), エ Off トップ (registration mark) EF301, EF303, EF351, EF352 (Mitsubishi Materials electronics chemical conversion (strain) manufacture), サー Off ロ Application (registrars Mark) ((strain) ダイキ Application Off ァイ Application ケミカ Le is ground by S381, S382, SC101, SC105 (Asahi Glass (strain) manufacture) and E5844 Study carefully manufactured) etc..

As the above-mentioned silicone based surfactants with fluorine atom, can include has siloxanes key in intramolecular With the surfactant of fluorocarbon chain etc..Specifically, メガ Off ァッ Network (registration mark) R08, BL20, F475, F477 can be included With F443 (DIC (strain) manufactures) etc..

In the case of levelling agent (H), its content is preferably relative to the total amount of colored curable resin composition More than 0.001 mass % and below 0.2 mass %, more preferably more than 0.002 mass % and below 0.1 mass %, further Preferably more than 0.005 mass % and below 0.07 mass %.If the content of levelling agent (H), can in above-mentioned scope Enough making the flatness of colour filter becomes good.

＜ antioxidants (J) ＞

From the viewpoint of the heat resistance and light resistance for improving colouring agent, preferably antioxidant is used alone or by 2 Combination of the above is planted to use.As antioxidant, as long as the industrial antioxidant typically used, then be not particularly limited, energy Enough using phenol antioxidant, phosphorous antioxidant and sulphur system antioxidant etc..

As above-mentioned phenol antioxidant, (the Irganox 1010 of イ Le ガノッ Network ス 1010 can be included：Pentaerythrite Four [3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic esters], BASF (strain) manufacture), イ Le ガノッ Network ス 1076 (Irganox 1076：Octadecyl -3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester, BASF (strain) manufacture), イ Le ガノックス1330(Irganox 1330：3,3 ', 3 ", 5,5 ', 5 "-six-tert-butyl-a, a ', a "-(mesitylene -2, The bases of 4,6- tri-) three-p-Cresol, BASF (strain) manufacture), (Irganox 3114 of イ Le ガノッ Network ス 3114:1,3,5- tri- (3, 5- di-tert-butyl -4- hydroxybenzyls) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, BASF (strain) manufacture), イ Le ガノックス3790(Irganox 3790:1,3,5- tri- ((4- tert-butyl -3- hydroxyl -2,6- xylyls) methyl) -1,3,5- Triazine -2,4,6 (1H, 3H, 5H)-triketone, BASF (strain) manufacture), (Irganox1035 of イ Le ガノッ Network ス 1035：Thio two Ethylenebis [3- (3,5- di-tert-butyl -4- hydroxy phenyls) propionic ester], BASF (strain) manufacture), イ Le ガノッ Network ス 1135 (Irganox 1135：Double (1,1- the dimethyl ethyls) -4- hydroxyls of benzenpropanoic acid, 3,5-, C7-C9 pendant alkyl groups ester, BASF (strain) systems Make), イ Le ガノッ Network ス 1520L (Irganox1520L：Double (pungent the butylthiomethyl)-o-cresols of 4,6-, BASF (strain) manufactures), イ Le ガノッ Network ス 3125 (Irganox 3125, BASF (strain) are manufactured), (Irganox 565 of イ Le ガノッ Network ス 565:2, Double (n- pungent sulfenyl) -6- (4- hydroxyls -3 ', 5 '-di-tert-butyl benzene amido) -1,3,5- triazines of 4-, BASF (strain) manufactures), アデカスタブAO-80(アデカスタブAO-80:Double (2- (the 3- (3- tert-butyl -4- hydroxy-5-methyl bases phenyl) third of 3,9- Acyloxy) -1,1- dimethyl ethyls) -2,4,8,10- four oxaspiro (5,5) hendecane, (strain) ADEKA manufacture), スミライザー BHT (Sumilizer BHT, Sumitomo Chemical (strain) manufacture), スミライザー GA-80 (Sumilizer GA-80, Sumitomo Learn (strain) manufacture), スミライザー GS (Sumilizer GS, Sumitomo Chemical (strain) manufacture), シアノッ Network ス 1790 (Cyanox1790, the manufacture of (strain) サイテッ Network) and vitamin E (エーザイ (strain) manufactures) etc..

As above-mentioned phosphorous antioxidant, (the Irgafos 168 of イ Le ガ Off ォス 168 can be included：Three (2,4- bis-- Tert-butyl phenyl) phosphite ester, BASF (strain) manufacture), (Irgafos 12 of イ Le ガ Off ォス 12：Three [2- [[2,4,8,10- Four-tert-butyl dibenzo [d, f] [1,3,2] dioxa phosphine -6- bases] oxygen] ethyl] amine, BASF (strain) manufacture), イ Le ガ Off ォス38(Irgafos 38：Double (double (1,1- the dimethyl ethyls) -6- aminomethyl phenyls of 2,4-) ethyl ester phosphorous acid, BASF (strain) systems Make), アデカスタ Block 329K ((strain) ADEKA manufactures), アデカスタ Block PEP36 ((strain) ADEKA manufactures), アデカスタ Block PEP-8 ((strain) ADEKA manufactures), Sandstab P-EPQ (manufacture of Network ラリア Application ト companies), ウェスト Application 618 (Weston 618, the manufacture of GE companies), ウェスト Application 619G (manufacture of Weston 619G, GE companies), ウ Le トラノッ Network ス 626 (Ultranox 626, the manufactures of GE companies) and スミライザー GP (Sumilizer GP：6- [3- (3- tert-butyl -4- hydroxyls Base -5- aminomethyl phenyls) propoxyl group] four-tert-butyls of -2,4,8,10- dibenzo [d, f] [1.3.2] dioxaphosphepin cycloheptene) (Sumitomo Chemical (strain) manufacture) etc..

As above-mentioned sulphur system antioxidant, for example, it can include dilauryl thiodipropionate, myristyl or two hard The polyalcohol such as the dialkyl dipropionate compound of aliphatic radical etc. and four [methylene (3- dodecylthios) propionic ester] methane β-alkylmercaptopropionates compound etc..

＜ other compositions ＞

The colored curable resin composition of the present invention, as needed, can include filler, other macromolecule chemical combination Known additive in the technical fields such as thing, closely sealed accelerator, light stabilizer, chain-transferring agent.

The manufacture method ＞ of ＜ colored curable resin compositions

The colored curable resin composition 0 of the present invention can be by by dyestuff lysate (A1), resin (B), polymerism Compound (C), polymerization initiator (D) and solvent (E) and use as needed, levelling agent (H), polymerization trigger auxiliary agent (D1), antioxidant (J) and other compositions are mixed and prepared.

The colored curable resin composition 1 of the present invention can be by by dyestuff lysate (A1), dyestuff (A2), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E) and use as needed, levelling agent (H), polymerization Trigger auxiliary agent (D1), antioxidant (J) and other compositions mixing and prepare.

The colored curable resin composition 2 of the present invention can be by by dyestuff lysate (A1), resin (B), polymerism Compound (C), polymerization initiator (D), colourless metal complex (F) and solvent (E) and use as needed, levelling Agent (H), polymerization trigger auxiliary agent (D1), antioxidant (J) and other compositions mixing and prepared.

In the case of comprising pigment (P), pigment is preferably mixed with part or all of solvent (E) in advance, uses bead mill Machine etc. makes it scattered until the average grain diameter of pigment turns into less than 0.2 μm Zuo You.Now, above-mentioned pigment point can be coordinated as needed Part or all of powder, resin (B).By mixing remaining composition in the dispersible pigment dispersion so obtained with as rule Fixed concentration, can prepare the colored curable resin composition of target.

It is preferred that the colouring agents (A) such as dyestuff lysate (A1), dyestuff (A2) to be dissolved in a part or complete for solvent (E) in advance Solution is prepared in portion.It is preferred that the solution is filtered with the filter in 0.01~1 μm or so of aperture.

It is preferred that mixed colored curable resin composition is filtered with the filter in 0.01~10 μm or so of aperture.

The manufacture method ＞ of ＜ colour filters

As by the present invention colored curable resin composition manufacture colored pattern method, can include photoetching process, Ink-jet method, print process etc., can preferably include photoetching process.Photoetching process is to be coated on above-mentioned colored curable resin composition Substrate, dries and forms coloring compositions nitride layer, the method for exposing the coloring compositions nitride layer via photomask and developing.Photoetching process In, by without using photomask and/or not developing in exposure, so as to form the solidification as above-mentioned coloring compositions nitride layer The coloring film of thing.Colored pattern, the coloring film so formed is colour filter of the invention.

The thickness of the colour filter of making is not particularly limited, can suitably be adjusted according to purpose, purposes etc., be usually 0.1~30 μm, more preferably preferably 0.1~20 μm, 0.5~6 μm.

As substrate, quartz glass, pyrex can be used, alumina silicate glass, silica has been carried out to surface The tree of glass plate, makrolon, polymethyl methacrylate, the polyethylene terephthalate of the soda-lime glass of coating etc. etc. Fat plate, silicon and the product that aluminium, silver, silver/copper/palldium alloy film etc. are formd on aforesaid substrate.Can shape on these substrates Into other color-filter layer, resin bed, transistor and circuit etc..

Using photolithographic each color pixel formed can known or usual device, under the conditions of carry out.For example, can It is as described below to make.

First, colored curable resin composition is coated on substrate, passes through heat drying (prebake) and/or decompression Dry, so that the volatile ingredients such as solvent be removed and dried, obtain smooth coloring compositions nitride layer.

As coating method, spin-coating method, slot coated method, slit and method of spin coating etc. can be included.

Preferably 30~120 DEG C, more preferably 50~110 DEG C of temperature when being thermally dried.In addition, as the heat time, Preferably 10 seconds~60 minutes, more preferably 30 seconds~30 minutes.

In the case of being dried under reduced pressure, enter preferably under 50~150Pa pressure, under 20~25 DEG C of temperature range OK.

The thickness of coloured composition layer is not particularly limited, can be properly selected according to the thickness of the colour filter of target.

Next, for coloring compositions nitride layer, being exposed via the photomask of the colored pattern for forming target.To this Pattern on photomask is not particularly limited, and the pattern being consistent with the purposes of target can be used.

As the light source for exposure, the light source of the light of 250~450nm wavelength is preferably produced.Will not for example, can be used Light to 350nm is blocked with the wave filter for blocking the wave-length coverage, or using by near 436nm, near 408nm, 365nm Neighbouring light is optionally taken out with the bandpass filter for taking out these wave-length coverages.Specifically, as light source, it can include Mercury vapor lamp, light emitting diode, metal halide lamp, Halogen lamp LED etc..

Due to can equably irradiate parallel rays to plane of exposure entirety, carry out photomask and form coloring compositions nitride layer Substrate correct contraposition, therefore preferably use the exposure devices such as mask aligner and stepper.

Developed by making the coloring compositions nitride layer after exposure be contacted with developer solution, so as to form color-patch map on substrate Case.By development, the unexposed portion of coloring compositions nitride layer dissolves and is removed in developer solution.As developer solution, preferably for example The aqueous solution of the alkali compounds such as potassium hydroxide, sodium acid carbonate, sodium carbonate, tetramethyl ammonium hydroxide.These alkali compounds Concentration in the aqueous solution is preferably 0.01~10 mass %, more preferably 0.03~5 mass %.And then, developer solution can include table Face activating agent.

Developing method can be any of sheathed immersion method, infusion process and spray-on process etc..And then, it can make base in development Plate tilts arbitrary angle.

Preferably washed after development.

And then, the colored pattern that preferred pair is obtained is bakeed after carrying out.As rear stoving temperature, preferably 150~250 DEG C, more It is preferred that 160~235 DEG C.It is used as rear baking time, more preferably preferably 1~120 minute, 10~60 minutes.

By using the colored curable resin composition of the present invention, the extra high colour filter of lightness can be manufactured.The filter Color device can be used as being used for display device (for example, liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state imager Colour filter.

Embodiment

Embodiment is exemplified below to further illustrate the present invention, but the present invention is not limited fundamentally by following embodiments System, is suitably changed to implement also to be possible certainly in the range of main contents described later before being adapted to, they In the technical scope for being included in the present invention.It should illustrate, hereinafter, as long as no special instructions, " part " expression " mass parts ", " % " expression " quality % ".

The present invention is specifically described below based on embodiment, but the present invention is not limited by these embodiments.In example, table Show % and part of content or even usage amount, be then quality criteria as long as no special instructions.

[embodiment 1]

Propylene glycol monomethyl is added in 25 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture) Ether acetic acid ester (hereinafter abbreviated as PGMEA.(strain) Daicel is manufactured)/diacetone alcohol (hereinafter abbreviated as DAA.KHネオケム (strain) manufacture)=10/90 (weight ratio) 450 parts of mixed solvent (hereinafter abbreviated as mixed solvent A), be stirred at room temperature 10 points Clock, completes dissolving.25 parts of the compound represented by formula (I-1) is added, and then has been stirred at room temperature 13 hours.It is molten what is obtained 3.2 parts of Celite535 (the pure medicine of woods industrial (strain) manufacture) is added in liquid, and then has been stirred at room temperature 1 hour.Make to obtain is molten Liquid is filtered by paulownia mountain filter paper No.5C.Obtained filtrate is set further to be filtered under nitrogen 0.05MPa pressurizations by PTFE film disc type Device PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, have obtained dyestuff 470.0 parts of lysate (A1-1).

[embodiment 2]

The mixing that 450 parts are added in 25 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture) is molten Agent A, is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-119) is added, and then at room temperature Stir 13 hours.3.2 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added in obtained solution, and then in room temperature Under stirred 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5B, obtained solution is further filtered by paulownia mountain Paper No.5C is filtered.Obtained filtrate is further passed through into PTFE film disc filter PTAW04700 under nitrogen 0.05MPa pressurizations (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, has obtained dyestuff lysate (A1- 2) 470.0 parts.

[embodiment 3]

PGMEA is added in 5.0 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture), and ((strain) is big Match fine jade manufacture) 470 parts, it is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-155) is added, is entered And it has been stirred at room temperature 13 hours.5.3 parts of Celite535 (the pure medicine of woods industrial (strain) manufacture) is added in obtained solution, And then be stirred at room temperature 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5C.Obtained filtrate is further Nitrogen 0.05MPa pressurization under by ultra-high molecular weight polyethylene (UPE) film disc filter CWUA04700 (1 μm), CWAZ04700 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, has obtained 470.0 parts of dyestuff lysate (A1-3).

[embodiment 4]

The mixing that 450 parts are added in 25 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture) is molten Agent A, is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-160) is added, and then at room temperature Stir 13 hours.3.2 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added in obtained solution, and then in room temperature Under stirred 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5C.By obtained filtrate further in nitrogen 0.05MPa Pressurization is lower to pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) is manufactured) filtering, obtain 470.0 parts of dyestuff lysate (A1-4).

[embodiment 5]

The mixing that 450 parts are added in 25 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture) is molten Agent A, is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-161) is added, and then at room temperature Stir 13 hours.3.2 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added in obtained solution, and then in room temperature Under stirred 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5C.By obtained filtrate further in nitrogen 0.05MPa Pressurization is lower to pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) is manufactured) filtering, obtain 470.0 parts of dyestuff lysate (A1-5).

[embodiment 6]

445.7 parts of mixed solvent A is added in 25 parts of the compound represented by formula (I-1), 30 points are stirred at room temperature Clock, completes dissolving.3- methacryloxypropyl trimethoxy silanes (KBM-503 is added in obtained solution：SHIN-ETSU HANTOTAI Learn (strain) manufacture) 25 parts, and then be stirred at room temperature 15 hours.(the pure medicines of woods of Celite 535 are added in obtained solution Industrial (strain) manufacture) 5.3 parts, and then be stirred at room temperature 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5B, Obtained filtrate is further filtered by paulownia mountain filter paper No.5C.Obtained filtrate is further led under nitrogen 0.05MPa pressurizations Cross PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) systems Make) filtering, obtain 485 parts of dyestuff lysate (A1-6).

[embodiment 7]

Adding PGMEA in 5.0 parts of three (trifyl) methide lithiums (central nitre (strain) manufacture), ((strain) is big Match fine jade manufacture) 470 parts, it is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-155) is added, is entered And it has been stirred at room temperature 13 hours.キョーワー De 700SEN-S (consonance chemical industry (strain) is added in obtained solution Manufacture) 5.3 parts, and then be stirred at room temperature 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5C.By what is obtained Filtrate further passes through ultra-high molecular weight polyethylene (UPE) film disc filter CWUA04700 (1 μ under nitrogen 0.05MPa pressurizations M), CWAZ04700 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, has obtained dyestuff lysate (A1-7) 470.0 Part.

[embodiment 8]

The mixing that 450 parts are added in 25 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture) is molten Agent A, is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-161) is added, and then at room temperature Stir 13 hours.3.2 parts of キョーワー De 2000 (consonance chemical industry (strain) manufacture) is added in obtained solution, is entered And it has been stirred at room temperature 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5C.Obtained filtrate is further existed Nitrogen 0.05MPa pressurizations are lower to pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) are manufactured) filtering, obtain 470.0 parts of dyestuff lysate (A1-8).

[embodiment 9]

The mixing that 450 parts are added in 25 parts of double (trifyl) imine lithiums (Tokyo chemical conversion industry (strain) manufacture) is molten Agent A, is stirred at room temperature 10 minutes, completes dissolving.25 parts of the compound represented by formula (I-1) is added, and then is stirred at room temperature Mix 13 hours.3.2 parts of キョーワー De 500SH (consonance chemical industry (strain) manufacture) is added in obtained solution, and then It has been stirred at room temperature 1 hour.Obtained solution is filtered by paulownia mountain filter paper No.5C.By obtained filtrate further in nitrogen 0.05MPa pressurizations are lower to pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) are manufactured) filtering, obtain 470.0 parts of dyestuff lysate (A1-9).

[embodiment 10]

445.7 parts of mixed solvent A is added in 25 parts of the compound represented by formula (I-1), 30 have been stirred at room temperature Minute, complete dissolving.3- methacryloxypropyl trimethoxy silanes (KBM-503 is added in obtained solution：SHIN-ETSU HANTOTAI Chemical (strain) manufacture) 25 parts, and then be stirred at room temperature 15 hours.キョーワー De 500SH is added in obtained solution 5.3 parts of (consonance chemical industry (strain) manufacture), and then be stirred at room temperature 1 hour.Obtained solution is passed through into paulownia mountain filter paper No.5B is filtered, and obtained filtrate is further filtered by paulownia mountain filter paper No.5C.By obtained filtrate further in nitrogen 0.05MPa pressurizations are lower to pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) are manufactured) filtering, obtain 485 parts of dyestuff lysate (A1-10).

[embodiment 11]

In double (3,5- di-tert -s butyl salicylate) zinc (BONTRON (registration mark) E-84 (オリエ Application ト chemical industry (strain) is manufactured)) 450 parts of mixed solvent A is added in 25 parts, it is stirred at room temperature 10 minutes, completes dissolving.Add by formula (I- 161) 25 parts of the compound represented, and then be stirred at room temperature 13 hours.キョーワー De is added in obtained solution 2000 3.2 parts of (consonance chemical industry (strain) manufacture), and then be stirred at room temperature 1 hour.Obtained solution is passed through into paulownia mountain Filter paper No.5C is filtered.Obtained filtrate is further passed through into PTFE film disc filter under nitrogen 0.05MPa pressurizations PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, have obtained dyestuff molten Solve 470.0 parts of liquid (A1-11).

[comparative example 1]

15 parts of the compound represented by formula (I-155) is added in 485 parts of PGMEA (manufacture of (strain) Daicel), in room temperature Under stirred 50 hours.The compound represented by formula (I-155) is not completely dissolved, and solution is suspended.Obtained solution is passed through Paulownia mountain filter paper No.5C is filtered, but dried residue weight has 12 parts, it is known that have dissolution residual substance.

[comparative example 2]

25 parts of the compound represented by formula (I-1) is added in 475 parts of mixed solvent A, is stirred at room temperature 15 hours, 5.3 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added, and then has been stirred at room temperature 1 hour.By obtained solution Filtered by paulownia mountain filter paper No.5B, obtained solution is further filtered by paulownia mountain filter paper No.5C.Obtained filtrate is entered One step passes through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) under nitrogen 0.05MPa pressurizations (Japanese イ Application テグリス (strain) manufacture) filtering, has obtained 485 parts of dyestuff lysate (A1-R2).

[comparative example 3]

25 parts of the compound represented by formula (I-160) is added in 475 parts of mixed solvent A, 15 are stirred at room temperature small When, 5.3 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added, and then be stirred at room temperature 1 hour.It is molten by what is obtained Liquid is filtered by paulownia mountain filter paper No.5C.Obtained filtrate is further filtered under nitrogen 0.05MPa pressurizations by PTFE film disc type Device PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, have obtained dyestuff 485 parts of lysate (A1-R3).

[comparative example 4]

25 parts of the compound represented by formula (I-161) is added in 475 parts of mixed solvent A, 15 are stirred at room temperature small When, 5.3 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added, and then be stirred at room temperature 1 hour.It is molten by what is obtained Liquid is filtered by paulownia mountain filter paper No.5C.Obtained filtrate is further filtered under nitrogen 0.05MPa pressurizations by PTFE film disc type Device PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, have obtained dyestuff 485 parts of lysate (A1-R4).

[comparative example 5]

25 parts of the compound represented by formula (I-119) is added in 475 parts of mixed solvent A, 15 are stirred at room temperature small When, 5.3 parts of Celite 535 (the pure medicine of woods industrial (strain) manufacture) is added, and then be stirred at room temperature 1 hour.It is molten by what is obtained Liquid is filtered by paulownia mountain filter paper No.5B, and obtained solution is further filtered by paulownia mountain filter paper No.5C.By obtained filtrate Further pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μ under nitrogen 0.05MPa pressurizations M) (Japanese イ Application テグリス (strain) manufacture) filtering, has obtained 485 parts of dyestuff lysate (A1-R5).

[comparative example 6]

25 parts of the compound represented by formula (I-161) is added in 475 parts of mixed solvent A, 15 are stirred at room temperature small When, 5.3 parts of キョーワー De 2000 (consonance chemical industry (strain) manufacture) is added, and then be stirred at room temperature 1 hour.Will Obtained solution is filtered by paulownia mountain filter paper No.5C.By obtained filtrate further under nitrogen 0.05MPa pressurizations by PTFE film Disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, are obtained 485 parts of dyestuff lysate (A1-R6) is arrived.

[comparative example 7]

25 parts of the compound represented by formula (I-1) is added in 475 parts of mixed solvent A, is stirred at room temperature 15 hours, 5.3 parts of キョーワー De 500SH (consonance chemical industry (strain) manufacture) is added, and then has been stirred at room temperature 1 hour.Will The solution arrived is filtered by paulownia mountain filter paper No.5B, and obtained solution is further filtered by paulownia mountain filter paper No.5C.It will obtain Filtrate further nitrogen 0.05MPa pressurization under pass through PTFE film disc filter PTAW04700 (1 μm), S4422M022Y11 (0.05 μm) (Japanese イ Application テグリス (strain) manufacture) filtering, has obtained 485 parts of dyestuff lysate (A1-R7).

The confirmation ＞ of ＜ ageing stabilities

By the dyestuff lysate respectively obtained in embodiment 1~6 and comparative example 2~5 at -20 DEG C, 10 DEG C, 23 DEG C, 40 DEG C Take care of at each temperature, confirm the presence or absence of precipitate by visual observation after 1 week.As a result it is shown in Table 1."○" represents to confirm not analyse Go out thing, "×" represents that confirmation has precipitate.

【Table 1】

	Dyestuff lysate	-20℃	10℃	23℃	40℃
						Embodiment 1	(A1-1)	○	○	○	○
Embodiment 2	(A1-2)	○	○	○	○
						Embodiment 3	(A1-3)	○	○	○	○
Embodiment 4	(A1-4)	○	○	○	○
						Embodiment 5	(A1-5)	○	○	○	○
Embodiment 6	(A1-6)	○	○	○	○
						Embodiment 7	(A1-7)	○	○	○	○
Embodiment 8	(A1-8)	○	○	○	○
						Embodiment 9	(A1-9)	○	○	○	○
Embodiment 10	(A1-10)	○	○	○	○
						Embodiment 11	(A1-11)	○	○	○	○
Comparative example 2	(A1-R2)	×	×	×	×
						Comparative example 3	(A1-R3)	×	×	×	×
Comparative example 4	(A1-R4)	×	×	×	×
						Comparative example 5	(A1-R5)	×	×	×	×
Comparative example 6	(A1-R6)	×	×	×	×
						Comparative example 7	(A1-R7)	×	×	×	×

Industrial applicability

According to the manufacture method of dyestuff lysate of the present invention, the excellent dyestuff dissolving of ageing stability can be manufactured Liquid, therefore can suppress in obtained dyestuff lysate to generate precipitate with rheological parameters' change with time.So ageing stability is excellent Different dyestuff lysate can further be mixed and is made with resin (B), polymerizable compound (C) and polymerization initiator (D) Color hardening resin composition, colour filter, display device can be expeditiously manufactured using the colored curable resin composition.

Claims

1. the manufacture method of dyestuff lysate, comprising：Organic acid is selected to (a) xanthene dye and (b) in the presence of an organic Salt and compound containing silicon atom at least one kind of process being stirred.

2. the manufacture method of dyestuff lysate according to claim 1, wherein, after the agitating procedure, also comprising solid Liquid separation circuit.

3. the manufacture method of dyestuff lysate according to claim 1, wherein, the organic acid is selected from aliphatic carboxylic Acid, aromatic carboxylic acid, aliphatic sulfonic, alicyclic series sulfonic acid, aromatic sulphonic acid, by following formula (h1) represent compound and by It is at least one kind of in the compound that following formula (h2) is represented, constitute the aliphatic carboxylic acid, the aromatic carboxylic acid, the fat Hydrogen atom beyond the acid proton of race's sulfonic acid and the aromatic sulphonic acid can be replaced by halogen atom or hydroxyl, constitute described - the CH of aliphatic carboxylic acid, aliphatic sulfonic and the alicyclic series sulfonic acid₂- can be replaced by-CO-,

In formula (h1), X^h1And X^h2The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of each other, or, X^h1With X^h2With reference to And the fluorianted alkylene of carbon number 2~4 is formed,

In formula (h2), X^h3~X^h5The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of each other.

4. the manufacture method of dyestuff lysate according to claim 1, wherein, the compound containing silicon atom is served as reasons The compound that following formula (j) is represented：

R^h2-Si-(R^h1)₃ (j)

In formula (j),

R^h1Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R^h1Can with mutually the same, Can be different,

R^h2Represent the substituent of 1 valency.

5. the manufacture method of dyestuff lysate according to claim 1, wherein, the organic solvent is alkylene glycol mono The carboxylate of alkyl ether, the aliphatic alcohol with ketone carbonyl or their mixed solvent.

6. the manufacture method of dyestuff lysate according to claim 1, wherein, the xanthene dye is by following formula (1a) table Show：

In formula (1a),

R¹~R⁴Independently of each other represent hydrogen atom, can have substituent carbon number 1~20 1 valency saturated hydrocarbyl, can have take The aromatic hydrocarbyl of 1 valency of Dai Ji carbon number 6~10 or the group represented by formula (ii),

*-R⁵⁰-Si(R²⁹)₃ (ii)

In formula (ii), R²⁹Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R²⁹Can be with that This it is identical also can be different,

R⁵⁰The alkylidene of carbon number 1~10 is represented ,-the CH of the alkylidene is constituted₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、- COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, but, adjacent-CH₂- will not be replaced by simultaneously it is of the same race - the CH of group, in addition end₂- will not also be replaced,

* the bonding end with nitrogen-atoms is represented,

R¹~R⁴In, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR¹¹-、-OCO-、-COO-、-OCONH-、- NHCOO- ,-CONH- or-NHCO- are replaced, R¹And R²The ring containing nitrogen-atoms, R can be formed together³And R⁴Can be formed together containing The ring of nitrogen-atoms, but, adjacent-CH₂- group of the same race will not be replaced by simultaneously ,-the CH of end in addition₂- also will not by for Change,

R⁵Expression-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰,

R⁶And R⁷The alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other,

M represents 0~5 integer, when m is more than 2, multiple R⁵Can be with identical, also can be different,

A represents 0 or 1 integer,

X represents halogen atom,

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺, 4 R¹¹Can be with identical, also can be different,

R⁸Represent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be substituted with halogen atoms,

R⁹And R¹⁰Hydrogen atom is represented independently of each other or can have the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, the saturation Contained-CH in alkyl₂- can be by-O- ,-CO- ,-NR¹¹- ,-OCO- ,-COO- ,-OCONH- ,-NHCOO- ,-CONH- or- NHCO- is replaced, R⁹And R¹⁰The heterocycle of 3~10 yuan of rings containing nitrogen-atoms can be combined with each other and be formed, but, adjacent-CH₂- Group of the same race will not be replaced by simultaneously, in addition-the CH of end₂- will not also be replaced,

R¹¹Represent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.

7. the manufacture method of dyestuff lysate according to claim 1, wherein, the xanthene dye is by following formula (1d) The compound of expression：

In formula (1d),

R^1d~R^4dIndependently of each other represent hydrogen atom, can have substituent carbon number 1~20 1 valency saturated hydrocarbyl, can have The aromatic hydrocarbyl of 1 valency of the carbon number 6~10 of substituent or the group represented by formula (ii), R^1d~R^4dIn at least one be The group represented by formula (ii),

*-R⁵⁰-Si(R²⁹)₃ (ii)

In formula (ii), R²⁹Represent the alkoxy of hydrogen atom, hydroxyl, the alkyl of carbon number 1~4 or carbon number 1~4, multiple R²⁹Can be with that This is identical, can also be different,

R⁵⁰The alkylidene of carbon number 1~10 is represented ,-the CH of the alkylidene is constituted₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、- COO- ,-OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, but, adjacent-CH₂- will not be replaced by simultaneously it is of the same race Group the, in addition ,-CH of end₂- will not also be replaced,

* the bonding end with nitrogen-atoms is represented,

R^1d~R^4dIn, contained-CH in the saturated hydrocarbyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、- OCONH- ,-NHCOO- ,-CONH- or-NHCO- are replaced, R^1dAnd R^2dThe ring containing nitrogen-atoms, R can be formed together^3dAnd R^4dCan one Rise and form the ring containing nitrogen-atoms, but, adjacent-CH₂- group of the same race will not be replaced by simultaneously, in addition ,-the CH of end₂- Also it will not be replaced,

R^5dExpression-OH ,-SO₃ ^-、-SO₃H、-SO₃ ^-Zd⁺、-CO₂H、-CO₂ ^-Zd⁺、-CO₂R^8d、-SO₃R^8dOr-SO₂NR^9dR^10d,

R^6dAnd R^7dThe alkyl of hydrogen atom or carbon number 1~6 is represented independently of each other,

Md represents 0~5 integer, when md is more than 2, multiple R^5dIt can be the same or different,

D represents 0 or 1 integer,

Xd represents halogen atom,

Zd⁺Represent⁺N(R^11d)₄、Na⁺Or K⁺, 4 R^11dIt can be the same or different,

R^8dRepresent that hydrogen atom contained in the saturated hydrocarbyl of 1 valency of carbon number 1~20, the saturated hydrocarbyl can be taken by halogen atom Generation,

R^9dAnd R^10dHydrogen atom is represented independently of each other or there can be the saturated hydrocarbyl of 1 valency of the carbon number 1~20 of substituent, and this is satisfied With-CH contained in alkyl₂- can be by-O- ,-CO- ,-NR^11d-、-OCO-、-COO-、-OCONH-、-NHCOO-、-CONH- Or-NHCO- is replaced, R^9dAnd R^10dThe heterocycle of 3~10 yuan of rings containing nitrogen-atoms can be combined with each other and be formed, but, adjacent- CH₂- group of the same race will not be replaced by simultaneously, in addition ,-the CH of end₂- will not also be replaced,

R^11dRepresent the aralkyl of hydrogen atom, the saturated hydrocarbyl of 1 valency of carbon number 1~20 or carbon number 7~10.

8. colored curable resin composition, it is characterised in that include：Dyestuff according to any one of claim 1~7 Lysate, resin (B), polymerizable compound (C) and polymerization initiator (D).

9. the colour filter formed by colored curable resin composition according to claim 8.

10. display device, it includes colour filter according to claim 9.