CN107918246A - Colored curable resin composition - Google Patents

Abstract

The present invention relates to colored curable resin composition.Colored curable resin composition includes colouring agent, resin, polymerizable compound and polymerization initiator, and the colouring agent includes triarylmethane colouring agent, xanthene dye and anthraquinone dye.

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin composition.

Background technology

As the colored curable resin for forming in liquid crystal display device etc. or solid photographic device etc. the colour filter included Composition, Japanese patent application discloses to have recorded in 2015-199912 publications to be contaminated comprising triarylmethane dye and xanthene Expect the colored curable resin composition as colouring agent.

The content of the invention

The present invention provides following [1]~[5].

[1] colored curable resin composition, which contain toner, resin, polymerizable compound and polymerization initiator,

The colouring agent includes triarylmethane colouring agent, xanthene dye and anthraquinone dye.

[2] colored curable resin composition as described in [1], wherein, the content of the anthraquinone dye is relative to described It is 0.5~50 mass parts for 100 mass parts of triarylmethane colouring agent.

[3] colored curable resin composition as described in [2], wherein, the content of the anthraquinone dye is relative to described It is 1.0~13.5 mass parts for 100 mass parts of triarylmethane colouring agent.

[4] colour filter, it is formed as the colored curable resin composition any one of [1]~[3].

[5] display device, it includes the colour filter described in [4].

Embodiment

The colored curable resin composition of the present invention includes colouring agent (A), resin (B), polymerizable compound (C) and gathers Close initiator (D).The colored curable resin composition of the present invention preferably comprises solvent (E) and/or levelling agent (leveling Agent) (F), also can further include antioxidant (H), other compositions.Colouring agent (A) includes triarylmethane colouring agent (Aa1), xanthene dye (Aa2) and anthraquinone dye (Aa3).The colored curable resin composition of the present invention is due to above-mentioned Form, therefore the colour filter of high contrast (contrast) can be manufactured.

＜ colouring agents (A) ＞

Colouring agent (A) includes triarylmethane colouring agent (Aa1), xanthene dye (Aa2) and anthraquinone dye (Aa3).Also may be used It is (following to be sometimes referred to as comprising the dyestuff different from triarylmethane dye (Aa1), xanthene dye (Aa2) and anthraquinone dye (Aa3) For " dyestuff (Aa4) ".).

(triarylmethane colouring agent (Aa1))

Triarylmethane colouring agent (Aa1) is included in the coloring of compound of the intramolecular with triarylmethane skeleton Agent.As the colouring agent, dyestuff and pigment or color lake pigment can be enumerated.As triarylmethane colouring agent (Aa1), they (below, are referred to as " chemical combination by the compound and its dynamic isomer preferably represented comprising formula (A-I) sometimes Thing (A-I) ".) dyestuff.

When using compound (A-I), the containing ratio of the compound (A-I) in triarylmethane colouring agent (Aa1) is preferred For more than 50 mass %, more preferably more than 70 mass %, more preferably more than 90 mass %.Wherein, as triaryl Methane colorant (Aa1), preferably using only compound (A-I).

[in formula (A-I), [Y²]^m-Represent the anion of m valencys.

R⁴¹~R⁴⁴Independently of one another represent hydrogen atom, can substituted carbon number 1~20 saturated hydrocarbyl, forming Be inserted between the carbon atom of the alkyl of carbon number 2~20 aerobic atom group, can substituted aryl or can substituted virtue Alkyl.R⁴¹With R⁴²It can be bonded and together form ring, R with the nitrogen-atoms that they are bonded⁴³With R⁴⁴Can be bonded and with their institutes The nitrogen-atoms of bonding together forms ring.

R⁴⁵~R⁵²Independently of one another represent hydrogen atom, halogen atom, nitro, hydroxyl, carbon number 1~8 saturated hydrocarbyl, Or the group of aerobic atom is inserted between the carbon atom of alkyl of carbon number 2~8 is formed, or R⁴⁶With R⁵⁰Can mutual key Close and formation-O- ,-NH- ,-S- or-SO₂-。

Y¹Representing can substituted aryl or can substituted heteroaryl.

When the compound that formula (A-I) represents includes multiple cations, multiple cations can be identical structure each other, Can also be different structures.

M represents arbitrary natural number.]

[Y²]^m-Represent the anion of m valencys.As by [Y²]^m-The anion of expression, as long as it can be formed with dye cations The anion of counter ion, is not particularly limited, preferably containing boron anion, anion containing aluminium, fluo anion, chlorine the moon from The halide anions such as son, and contain the moon selected from least one of the group being made of tungsten, molybdenum, silicon and phosphorus element and oxygen atom Ion.

As containing boron anion and anion containing aluminium, for example, the anion of formula (4) expression can be enumerated.

[in formula (4), W¹And W²The compound represented independently of one another from the proton property the given substituent containing 2 monovalencies is released The group released proton and formed.M represents boron or aluminium.]

On formula (4), as the compound of the proton property the given substituent containing 2 monovalencies, can enumerate containing 2 monovalencies The proton property given substituent (such as hydroxyl, carboxyl etc.) compound, for example, dihydroxy naphthlene can be enumerated, can have substituent 2,2 '-'-biphenyl diphenol, can the 3- hydroxy-2-naphthoic acids with substituent, can the 2- hydroxyl -1- naphthoic acids with substituent, Can the 1- hydroxy-2-naphthoic acids with substituent, can the dinaphthol with substituent, can the salicylic acid with substituent, can have The diphenylglycollic acid of substituted base or the mandelic acid can with substituent.

The group for discharging proton from the compound and being formed refers to that proton is all given from multiple protons in the compound The property given substituent dissociate and formed there is O^-And/or COO^-Group.

As above-claimed cpd, preferably can the catechol with substituent, can 2, the 3- dihydroxy with substituent Naphthalene, can be with substituent 2,2 '-'-biphenyl diphenol, can the 3- hydroxy-2-naphthoic acids with substituent, can the 2- with substituent Hydroxyl -1- naphthoic acids, can the 1- hydroxy-2-naphthoic acids with substituent, can the dinaphthol with substituent, can be with substituent Salicylic acid, can be with substituent diphenylglycollic acid or can the mandelic acid with substituent.

In above-mentioned each compound, as substituent, saturated hydrocarbyl (alkyl, cycloalkyl etc.), halogen atom, hydroxyl can be enumerated Base, amino, nitro, alkoxy etc..

As the salicylic acid can with substituent, can enumerate：Salicylic acid, 3- cresotinic acids, 3- tert-butyl salicylic acids, 3- Methoxysalicylic acid, 3-Nitrosalicylic Acid, 4- trifluoromethyls salicylic acid, 3,5- di-tert-butyl salicylic acids, 3- aminosalicylic acids, 4- The mono amino salicylic acids such as aminosalicylic acid, 5-aminosalicylic acid, 6- aminosalicylic acids；3- hydroxyls salicylic acid (2,3- dihydroxy benzenes Formic acid), 4- hydroxyls salicylic acid (2,4- dihydroxy-benzoic acids), 5- hydroxyls salicylic acid (2,5- dihydroxy-benzoic acids), 6- hydroxyl water The monohydroxy salicylic acids such as poplar acid (2,6- dihydroxy-benzoic acids)；The dihydroxies such as 4,5- dihydroxy salicylic acids, 4,6- dihydroxy salicylic acids Base salicylic acid；3- chloro-salicylic acids, 4- chloro-salicylic acids, 5- chloro-salicylic acids, 6- chloro-salicylic acids, 3- bromo ortho-oxybenzoic acids, 4- bromo ortho-oxybenzoic acids, 5- The monohaloalkyl salicylic acids such as bromo ortho-oxybenzoic acid, 6- bromo ortho-oxybenzoic acids；3,5- dichlorosalicylic acids, 3,5- dibromosalicylic acids, 3,5- diiodo- bigcatkin willows The dihalo salicylic acid such as acid；The three halo salicylic acids such as tri- chloro-salicylic acids of 3,5,6-；Etc..

As the diphenylglycollic acid can with substituent, can enumerate by following compound of structural formula expression etc..

As the mandelic acid can with substituent, can enumerate by following compound of structural formula expression etc..

The anion represented as formula (4), is preferably enumerated being expressed from the next, with the substituent described in table 1 Anion (BC-1)~anion (BC-24) and respectively by formula (BC-25), formula (BC-26), formula (BC-27) and formula (BC- 28) anion (BC-25)~anion (BC-28) represented etc..

[in formula, M represents boron or aluminium.]

[table 1]

Anion	R61	R62	R63	R64
					Anion (BC-1)	H	H	H	H
Anion (BC-2)	OH	H	H	H
					Anion (BC-3)	H	OH	H	H
Anion (BC-4)	H	H	OH	H
					Anion (BC-5)	H	H	H	OH
Anion (BC-6)	Cl	H	H	H
					Anion (BC-7)	H	Cl	H	H
Anion (BC-8)	H	H	Cl	H
					Anion (BC-9)	H	H	H	Cl
Anion (BC-10)	Br	H	H	H
					Anion (BC-11)	H	Br	H	H
Anion (BC-12)	H	H	Br	H
					Anion (BC-13)	H	H	H	Br
Anion (BC-14)	NH2	H	H	H
					Anion (BC-15)	H	NH2	H	H
Anion (BC-16)	H	H	NH2	H
					Anion (BC-17)	H	H	H	NH2
Anion (BC-18)	H	tBu	H	tBu
					Anion (BC-19)	H	Cl	H	Cl
Anion (BC-20)	H	Br	H	Br
					Anion (BC-21)	H	I	H	I
Anion (BC-22)	H	OH	OH	H
					Anion (BC-23)	OH	H	OH	H
Anion (BC-24)	Cl	Cl	H	Cl

[in formula (BC-25), M represents boron or aluminium.]

[in formula (BC-26), M represents boron or aluminium.]

[in formula (BC-27), M represents boron or aluminium.]

[in formula (BC-28), M represents boron or aluminium.]

The anion represented as formula (4), preferred anionic (BC-1), anion (BC-2), anion (BC-3), it is cloudy from Sub (BC-25), anion (BC-26), more preferably anion (BC-27), anion (BC-1), anion (BC-2), anion (BC-25), further preferred anion (BC-1), anion (BC-2).For containing any anion in above-mentioned anion The compound that represents of formula (A-I) for, have the excellent tendency of dissolubility in organic solvent.

As fluo anion, for example, formula (6), (7), (8), the group of (9) expression can be enumerated.

[in formula (6), W³And W⁴The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of one another, alternatively, W³With W⁴It is integrally formed and represents the fluorinated alkanes hydrocarbon diyl (alkanediyl) of carbon number 1~4.]

[in formula (7), W⁵、W⁶And W⁷The fluoro-alkyl of fluorine atom or carbon number 1~4 is represented independently of one another.]

[in formula (8), Y^aRepresent the fluorinated alkanes hydrocarbon diyl of carbon number 1~4.]

[in formula (9), Y^bRepresent the fluoro-alkyl of carbon number 1~4.]

It is preferably perfluoroalkyl as the fluoro-alkyl of carbon number 1~4 in formula (6), (7) and (9).It is complete as this Fluoroalkyl, can enumerate-CF₃、-CF₂CF₃、-CF₂CF₂CF₃、-CF(CF₃)₂、-CF₂CF₂CF₂CF₃、-CF₂CF(CF₃)₂、-C(CF₃)₃。

In formula (6) and (8), as the fluorinated alkanes hydrocarbon diyl of carbon number 1~4, perfluoroalkane hydrocarbon diyl can be enumerated, Preferably enumerate-CF₂-、-CF₂CF₂-、-CF₂CF₂CF₂-、-C(CF₃)₂-、-CF₂CF₂CF₂CF₂- etc..

As formula (6) represent anion (hereinafter sometimes referred to " anion (6) "), can enumerate respectively by formula (6-1)~ The anion (hereinafter sometimes referred to " anion (6-1) "~" anion (6-6) ") that formula (6-6) represents.

The anion (hereinafter sometimes referred to " anion (7) ") represented as formula (7), can enumerate the anion of following formula expression (7-1)。

As formula (8) represent anion (hereinafter sometimes referred to " anion (8) "), can enumerate respectively by formula (8-1)~ The anion (hereinafter sometimes referred to " anion (8-1) "~" anion (8-4) ") that formula (8-4) represents.

As formula (9) represent anion (hereinafter sometimes referred to " anion (9) "), can enumerate respectively by formula (9-1)~ The anion (hereinafter sometimes referred to " anion (9-1) "~" anion (9-4) ") that formula (9-4) represents.

As [Y²]^m-, be preferably fluo anion, polyoxoanion, more preferably formula (6) represent anion, [PW₁₂O₄₀]^3-、[P₂W₁₈O₆₂]^6-、[SiW₁₂O₄₀]^4-And [W₁₀O₃₂]^4-, it is more preferably what formula (6-1)~formula (6-5) represented Anion, [PW₁₂O₄₀]^3-And [P₂W₁₈O₆₂]^6-, anion and [PW that particularly preferably formula (6-2) represents₁₂O₄₀]^3-。

M represents arbitrary natural number, and with anion [Y²]^m-Possessed negative electrical charge is equal.For cation side m and Speech, with anion [Y²]^m-The mode equal with the electric charge of cation is determined.M is preferably 1~10 natural number.

R⁴¹~R⁴⁴The saturated hydrocarbyl of the carbon number 1~20 of expression can be appointing in straight-chain, branched and ring-type What.In addition, the carbon number of the saturated hydrocarbyl is preferably 1~10, more preferably 1~8, more preferably 1~6 are especially excellent Elect 1~4 as.

As the saturated hydrocarbyl of above-mentioned straight-chain or branched, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, The straight-chain alkyls such as octyl group, nonyl, decyl；The branched-chain alkyls such as isopropyl, isobutyl group, 2- ethylhexyls.Straight-chain or side chain The carbon number of the saturated hydrocarbyl of shape is preferably 1~8, more preferably 1~6, more preferably 1~4.

Above-mentioned cricoid saturated hydrocarbyl is either monocyclic can also be polycyclic.As the cricoid saturated hydrocarbyl, can lift Go out cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, adamantyl etc..The carbon number of cyclic saturated hydrocarbon base is preferably 3~10, more Preferably 6~10.

R⁴¹~R⁴⁴The hydrogen atom of saturated hydrocarbyl can be substituted base and substituted.As the substituent, can enumerate through taking Generation or unsubstituted amino or halogen atom.As the amino being substituted, dialkyl amidos such as dimethylamino etc. can be enumerated, are made For halogen atom, fluorine atom, chlorine atom, bromine atoms, iodine atom can be enumerated.Be substituted as hydrogen atom or unsubstituted amino or The saturated hydrocarbyl of person's halogen atom substitution, such as the group of following formula expression can be enumerated.In following formula, * represents the connection with nitrogen-atoms Key.

As R⁴¹~R⁴⁴Between the methylene (carbon atom) of alkyl in the group of expression, in composition carbon number 2~20 Group inserted with oxygen atom, for example, the group of following formula expression can be enumerated.In following formula, * represents the connecting key with nitrogen-atoms.Its In, as it is described form alkyl methylene between be inserted into aerobic atom group, preferably carbon number 2~10 group, more It is preferred that the group of carbon number 2~6.The alkyl for being inserted into oxygen atom is preferably straight chained alkyl.In addition, the carbon atom between oxygen atom Number is preferably 1~4, more preferably 2~3.

R⁴¹~R⁴⁴In, the carbon number of aryl is preferably 6~20, and more preferably 6~10, the carbon number of aralkyl is excellent Elect 7~20 as, more preferably carbon number is 7~10.

As R⁴¹~R⁴⁴Aryl, phenyl, naphthyl, toluyl groups etc. can be enumerated.

As R⁴¹~R⁴⁴Aralkyl in aryl, phenyl, naphthyl etc. can be enumerated, as aralkyl, above-mentioned virtue can be enumerated Group obtained from the connecting key of base is bonded with alkane diyl.The carbon number of above-mentioned alkane diyl is preferably 1~ 10, more preferably 1~5, are preferably straight-chain alkane diyl.As above-mentioned alkane diyl, specifically, methylene can be enumerated Base, ethylidene, propylidene, butane diyl, pentane diyl etc., as aralkyl, can enumerate benzyl, phenethyl, menaphthyl, naphthalene second Base etc..

In R⁴¹~R⁴⁴In aryl and aralkyl in the group of expression, as substituent, can enumerate fluorine atom, chlorine atom, The halogen atoms such as iodine atom；The alkoxy of the carbon numbers such as methoxyl group, ethyoxyl 1~6；Hydroxyl；The carbon numbers such as methyl sulphonyl 1 ~6 alkyl sulphonyl；The alkoxy carbonyl of the carbon numbers such as methoxycarbonyl, ethoxy carbonyl 2~6；Etc..

As can substituted aryl concrete example, can enumerate following formula expression group.In following formula, * is represented and nitrogen-atoms Connecting key.

As can substituted aralkyl, can enumerate and methylene, ethylidene etc. are bonded with the connecting key of above-mentioned aryl Group obtained from alkylidene.

As R⁴¹With R⁴²The ring and R for being bonded and together being formed with the nitrogen-atoms that they are bonded⁴³With R⁴⁴Into line unit Merge the ring together formed with the nitrogen-atoms that they are bonded, 5 yuan of rings such as pyrrolidine ring can be enumerated；Morpholine ring, piperidine ring, piperazine 6 yuan of rings such as ring；Etc..

From the aspect of the easy degree of synthesis, R⁴¹~R⁴⁴Can substituted carbon number 1 it is preferred that being each independently ~20 saturated hydrocarbyl, can substituted aryl or can substituted aralkyl, be more preferably each independently carbon number 1 The group that~8 saturated hydrocarbyl or following formula represents.In following formula, * represents the connecting key with nitrogen-atoms.

R⁴⁵~R⁵²The saturated hydrocarbyl of expression can be any in straight-chain, branched and ring-type, be preferably chain.Make For R⁴⁵~R⁵²The saturated hydrocarbyl of expression, can enumerate as R⁴¹~R⁴⁴The saturated hydrocarbyl of expression and the carbon atom in the group that illustrates The group of number 1~8.

The group of aerobic atom, more preferably carbon number are inserted between the methylene (carbon atom) of alkyl is formed as this 2~8 alkyl.The alkyl for being inserted into oxygen atom is preferably straight chained alkyl, and the carbon number between oxygen atom is preferably 1~4, more Preferably 2~3.For example, the group of following formula expression can be enumerated.In following formula, * represents the connecting key with carbon atom.

From the aspect of the easy degree of synthesis, R⁴⁵~R⁵²It is preferred that it is former to be each independently hydrogen atom, halogen atom or carbon The saturated hydrocarbyl of subnumber 1~8 is more preferably each independently hydrogen atom, methyl, fluorine atom or chlorine atom.

R⁴⁶With R⁵⁰It can be mutually bonded and form-O- ,-NH- ,-S- or-SO₂-。

Y¹Representing can substituted aryl or can substituted heteroaryl.

Can be any in monocyclic and fused rings as aryl, can enumerate phenyl, tolyl, xylyl, naphthyl, The aromatic hydrocarbyl of the carbon numbers such as anthryl, phenanthryl, xenyl, terphenyl 6~20.

Heteroaryl is the substituent from heteroaromatic.Above-mentioned heteroaromatic can be in monocyclic and fused rings It is any, it is preferably 5~10 yuan of rings, more preferably 5~9 yuan of rings.

As monocyclic heteroaromatic, can enumerate：

5 yuan of rings containing nitrogen-atoms such as pyrrole ring, oxazole rings, pyrazole ring, imidazole ring, thiazole ring；

5 yuan of rings containing oxygen atom, sulphur atom such as furan nucleus, thiphene ring；

6 yuan of rings containing nitrogen-atoms such as pyridine ring, pyrimidine ring, pyridazine ring, pyridine ring；Etc..

As the heteroaromatic of fused rings, can enumerate：

The fused rings containing nitrogen-atoms such as indole ring, benzimidazole ring, benzothiazole ring, quinoline ring；

The ring containing oxygen atom, sulphur atom such as benzofuran ring；Etc..

As can substituted heteroaryl, more preferably formula (Ab2-x1) represent group.

[ring T²Represent heteroaromatic.

R⁵³And R⁵⁴Independently of one another represent can substituted carbon number 1~20 saturated hydrocarbyl, form carbon number Be inserted between the carbon atom of 2~20 alkyl aerobic atom group, can substituted aryl or can substituted aralkyl, Or hydrogen atom.

R⁵⁵Represent hydrogen atom, carbon number 1~20 saturated hydrocarbyl or can substituted aryl.

K1 represents 0 or 1.

* the connecting key with carbocation is represented.]

Ring T²Represent heteroaromatic, preferably represent the heteroaromatic of carbon number 2~9.

It should be noted that R⁵³~R⁵⁵Detailed content it is as described later.

As compound (A-I), the compound that more preferably formula (A-II) represents.

[in formula (A-II), [Y²]^m-、R⁴¹~R⁵²And the implication of m is same as above.

R⁵³And R⁵⁴Independently of one another represent hydrogen atom, can substituted carbon number 1~20 saturated hydrocarbyl, forming Be inserted between the carbon atom of the alkyl of carbon number 2~20 aerobic atom group, can substituted aryl or can substituted virtue Alkyl.R⁵⁵Represent hydrogen atom, carbon number 1~20 saturated hydrocarbyl or can substituted aryl.

X represents oxygen atom ,-NR⁵⁷- or sulphur atom.

R⁵⁷Represent the alkyl of hydrogen atom or carbon number 1~10.

When the compound that formula (A-II) represents includes multiple cations, multiple cations can be identical knot each other Structure or different structures.]

As R⁵³And R⁵⁴, can enumerate and R⁴¹~R⁴⁴The same group of the group of middle illustration.

As R⁵⁵The saturated hydrocarbyl of the carbon number 1~20 of expression, can enumerate and be used as R⁴¹~R⁴⁴Saturated hydrocarbyl and example The same group of the group that shows.Wherein, it is preferably the alkyl of the alkyl of carbon number 1~10, more preferably carbon number 1~8, The alkyl of the more preferably alkyl of carbon number 1~6, particularly preferably carbon number 1~4.

As R⁵⁵It is representing, above-mentioned that the group of aerobic atom is inserted between the carbon atom of alkyl is formed, it can enumerate and R⁴¹~ R⁴⁴The same group of the group of middle illustration.The alkyl for being inserted into oxygen atom is preferably straight chained alkyl.In addition, the carbon between oxygen atom is former Subnumber is preferably 1~4, more preferably 2~3.

In R⁵⁵In, the carbon number of aryl is preferably 6~20, and more preferably 6~10.As the aryl, can enumerate and pin To R⁴¹~R⁴⁴And the same group of aryl illustrated, it is preferably phenyl.

In R⁵⁵In, as substituent possessed by aryl, the halogen atoms such as fluorine atom, chlorine atom, iodine atom can be enumerated；Methoxy The alkoxy of the carbon numbers such as base, ethyoxyl 1~6；Hydroxyl；Amino-sulfonyl；The alkane of the carbon numbers such as methyl sulphonyl 1~6 Base sulfonyl；The alkoxy carbonyl of the carbon numbers such as methoxycarbonyl, ethoxy carbonyl 2~6；Etc..

From the aspect of the easy degree of synthesis, R⁵⁵The saturated hydrocarbyl of carbon number 1~10 or it can preferably be substituted Aryl, more preferably carbon number 1~8 alkyl or can by halogen atom, the alkoxy of carbon number 1~4, hydroxyl or The aryl of methyl sulphonyl substitution, the group that more preferably following formula represents.In following formula, * represents the connection with carbon atom Key.

R⁵⁷The preferably alkyl of carbon number 1~4, more preferably methyl.

X represents oxygen atom ,-NR⁵⁷- or sulphur atom.As the cyclic structure comprising X, for example, the base of following formula expression can be enumerated Group.In formula, R⁵³~R⁵⁵Implication difference it is same as above, * is represented and the connecting key of carbocation.Wherein, as X, preferably For oxygen atom or sulphur atom, more preferably sulphur atom.

The cation having as formula (A-I), can enumerate sun that formula (A-I-1) represents, with the substituent shown in table 2 1~cation of ion 27.

[table 2]

In table 2, Ph1~Ph12 refers to the group that following formula represents.

It is more excellent as the cation in formula (A-I), preferably 1~cation of cation 6, cation 11 and cation 12 Elect cation 1, cation 2 and cation 12 as.

When the compound that formula (A-II) represents includes multiple cations, multiple cations can be identical knot each other Structure or different structures.

(xanthene dye (Aa2))

Xanthene dye (Aa2) is included in the dyestuff of compound of the intramolecular with xanthene skeleton.As xanthene dye (Aa2), can enumerating C.I. CI 45430s, (record omission following, by C.I. acid reds, only records numbering.Other are similarly.)、 52nd, 87,92,94,289,388, C.I. acid violets 9,30,102, C.I. alkali red 1:1s (rhodamine 6G), 2,3,4,8, C.I. alkalescence Red 10 (rhodamine Bs), 11, C.I. alkaline purple 1s 0,11,25, C.I. solvent reds 218, C.I. mordant rouges 27, C.I. active reds 36 Xanthene dye described in (rose red b (Rose Bengal B)), Sulforhodamine G, Japanese Unexamined Patent Publication 2010-32999 publications And xanthene dye described in No. 4492760 publications of Japanese Patent No. etc..Wherein, the Xanthones being preferably dissolvable in water in organic solvent Ton dyestuff.

In them, as xanthene dye (Aa2), the compound preferably represented comprising formula (1a) and its dynamic isomer (it is following, they are referred to as " compound (1a) " sometimes.) dyestuff.When using compound (1a), in xanthene dye (A2) The content of compound (1a) be preferably more than 50 mass % more preferably more than 70 mass %, more preferably 90 matter Measure more than %.Wherein, as xanthene dye (A2), preferably using only compound (1a).

[in formula (1a), R¹~R⁴Independently of one another represent hydrogen atom, carbon number 1~20 univalent saturated hydrocarbon radical or can The monovalence aromatic hydrocarbyl of carbon number 6~10 with substituent, the hydrogen atom contained in the saturated hydrocarbyl can be by carbon atom The aromatic hydrocarbyl or halogen atom of number 6~10 substitute, and the hydrogen atom contained in the aromatic hydrocarbyl can be by carbon number 1~3 Alkoxy substitutes ,-the CH contained in above-mentioned saturated hydrocarbyl₂- it can be replaced-O- ,-CO- or-NR¹¹-。R¹And R²It can be integrally formed And the ring for including nitrogen-atoms is formed, R³And R⁴It can be integrally formed and form the ring comprising nitrogen-atoms.

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 one another.

M represents 0~5 integer.When m is more than 2 integer, multiple R⁵It may be the same or different.

A represents integer 0 or 1.

X0 represents halogen atom.

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

Z⁺Represent⁺N(R¹¹)₄、Na⁺Or K⁺。

R⁹And R¹⁰Hydrogen atom is represented independently of one another or there can be the monovalence saturated hydrocarbons of the carbon number 1~20 of substituent The base ,-CH contained in the saturated hydrocarbyl₂- it can be replaced-O- ,-CO- ,-NH- or-NR⁸-, R⁹And R¹⁰It can bond together and be formed The heterocycle of 3~10 yuan of rings comprising nitrogen-atoms.

⁺N(R¹¹)₄In 4 R¹¹Hydrogen atom, the univalent saturated hydrocarbon radical or carbon of carbon number 1~20 are represented independently of one another The aralkyl of atomicity 7~10.]

As expression R¹~R⁴Monovalence aromatic hydrocarbyl, phenyl, toluyl groups, xylyl, mesitylene can be enumerated Base (mesityl group), propyl group phenyl and butyl phenyl etc..

The substituent that can have as the aromatic hydrocarbyl, can enumerate halogen atom ,-R⁸、-OH、-OR⁸、-SO₃ ^-、-SO₃H、- SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸Or-SO₂NR⁹R¹⁰.It is preferably-SO as substituent in them₃ ^-、- SO₃H、-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰, more preferably-SO₃ ^-Z⁺And-SO₂NR⁹R¹⁰.As-SO in this case₃ ^-Z⁺, be preferably- SO₃ ^-+N(R¹¹)₄.If R¹~R⁴, then can be by the colored curable resin group of the invention of inclusion compound (1a) for above-mentioned group Compound forms the generation of foreign matter less and the colour filter of excellent heat resistance.

As R¹And R²The ring and R for being integrally formed and being formed³And R⁴The ring for being integrally formed and being formed, for example, can enumerate Following ring.

As expression R⁸~R¹¹Univalent saturated hydrocarbon radical, methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptan can be enumerated The straight-chain alkyls such as base, octyl group, nonyl, decyl, dodecyl, cetyl, eicosyl；Isopropyl, isobutyl group, isoamyl The branched-chain alkyls such as base, neopentyl, 2- ethylhexyls；Cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, tricyclodecyl Deng the ester ring type saturated hydrocarbyl of carbon number 3~20.

It is used as-OR⁸, methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy, epoxide in heptan, pungent oxygen can be enumerated Base, 2- ethyl hexyl oxies and eicosyl epoxide etc..

It is used as-CO₂R⁸, such as can enumerate methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, oneself Epoxide carbonyl and eicosyl Epoxide carbonyl etc..

It is used as-SR⁸, can enumerate methylsulfany (methyl sulfanyl), ethylsulfanyl, butyl sulfenyl, hexyl sulfenyl, Decyltliio and eicosyl sulfenyl etc..

It is used as-SO₂R⁸, methyl sulphonyl, ethylsulfonyl, butyl sulfonyl, hexyl sulfonyl, decyl sulphonyl can be enumerated Base and eicosyl sulfonyl etc..

It is used as-SO₃R⁸, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy sulphonyl can be enumerated Base, hexyloxy sulfonyl and eicosyl epoxide sulfonyl etc..

It is used as-SO₂NR⁹R¹⁰, can enumerate：

Amino-sulfonyl；

N- methylaminosulfonyls, N- ethylaminosulfonyls, N- propylcarbamics sulfonyl, N- isopropylamino sulphonyl Base, N- butylaminos sulfonyl, N- isobutylaminos sulfonyl, N- s-butylaminos sulfonyl, N- tert-butylaminos sulfonyl, N- pentyl aminos sulfonyl, N- (1- ethyl propyls) amino-sulfonyl, N- (1,1- dimethyl propyls) amino-sulfonyl, N- (1, 2- dimethyl propyls) amino-sulfonyl, N- (2,2- dimethyl propyls) amino-sulfonyl, N- (1- methyl butyls) aminosulfonyl Base, N- (2- methyl butyls) amino-sulfonyl, N- (3- methyl butyls) amino-sulfonyl, N- clopentylaminos sulfonyl, N- oneself Base amino-sulfonyl, N- (1,3- dimethylbutyls) amino-sulfonyl, N- (3,3- dimethylbutyls) amino-sulfonyl, N- heptyl Amino-sulfonyl, N- (1- methylhexyls) amino-sulfonyl, N- (1,4- dimethyl amyl groups) amino-sulfonyl, N- octyl amino sulphurs Acyl group, N- (2- ethylhexyls) amino-sulfonyl, N- (1,5- dimethyl) hexylamino sulfonyl, N- (1,1,2,2- tetramethyls Butyl) the mono-substituted amino-sulfonyls of N- such as amino-sulfonyl；

N, N- dimethylamino-sulfonyl, N, N- ethylmethylaminos sulfonyl, N, N- diethylaminos sulfonyl, N, N- Propyl-methylamino sulfonyl, N, N- isopropylmethylaminos sulfonyl, N, N- tertbutyl methyls amino-sulfonyl, N, N- butyl Ethylaminosulfonyl, N, double (1- methyl-propyls) amino-sulfonyls of N-, the N such as N, N- hept-ylmethyl amino-sulfonyls, N- bis- take The amino-sulfonyl in generation etc..

As expression R⁹、R¹⁰Univalent saturated hydrocarbon radical in substituent, hydroxyl and halogen atom can be enumerated.

As R⁵, it is preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or SO₂NHR⁹, more preferably SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or SO₂NHR⁹。

It is preferably 1~4 as m, more preferably 1 or 2.

As expression R⁶And R⁷Carbon number 1~6 alkyl, can be that straight chain can also be side chain, can enumerate methyl, Ethyl, propyl group, butyl, amyl group, hexyl.

As expression R¹¹Aralkyl, benzyl, phenethyl, benzene butyl etc. can be enumerated.

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

As above-mentioned⁺N(R¹¹)₄, preferably 4 R¹¹In at least two be carbon number 5~20 univalent saturated hydrocarbon radical.4 R¹¹Total number of carbon atoms be preferably 20~80, more preferably 20~60.Exist in compound (1a)⁺N(R¹¹)₄Situation Under, if R¹¹For above-mentioned group, then can be formed by the colored curable resin composition of the invention of inclusion compound (1a) different The few colour filter of thing.

As the preference of compound (1a), the compound and its dynamic isomer that can enumerate formula (2a) expression (have below When they are referred to as " compound (2a) ".).When using compound (2a), compound (2a) in xanthene dye (A2) Content is preferably more than 50 mass % more preferably more than 70 mass %, more preferably more than 90 mass %.

[in formula (2a), R²¹~R²⁴Hydrogen atom ,-R are represented independently of one another²⁶Or can have substituent carbon number 6~ 10 monovalence aromatic hydrocarbyl.R²¹And R²²It can be integrally formed and form the ring comprising nitrogen-atoms, R²³And R²⁴It can be integrally formed and shape Into the ring comprising nitrogen-atoms.

R²⁵Expression-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺Or-SO₂NHR²⁶。

M1 represents 0~5 integer.When m1 is more than 2 integer, multiple R²⁵It may be the same or different.

A1 represents integer 0 or 1.

X1 represents halogen atom.

R²⁶Represent the univalent saturated hydrocarbon radical of carbon number 1~20.

Z1⁺Represent⁺N(R²⁷)₄、Na⁺Or K⁺。

⁺N(R²⁷)₄In 4 R²⁷The univalent saturated hydrocarbon radical or benzyl of carbon number 1~20 are represented independently of one another.]

As expression R²¹~R²⁴Monovalence aromatic hydrocarbyl, can enumerate and above-mentioned R¹~R⁴It is middle to be lifted as aromatic hydrocarbyl The same group of the group that goes out.The hydrogen atom contained in the aromatic hydrocarbyl can be by-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶Or- SO₂NHR²⁶Substitution.

As R²¹~R²⁴Combination, it is preferred that R²¹And R²³For hydrogen atom, R²²And R²⁴For the one of carbon number 6~10 Valency aromatic hydrocarbyl, and the hydrogen atom contained in the aromatic hydrocarbyl is by-SO₃ ^-、-SO₃H、-SO₃ ^-Z1⁺、-SO₃R²⁶Or- SO₂NHR²⁶Substitution.Further preferred combination is as follows：R²¹And R²³For hydrogen atom, R²²And R²⁴For the monovalence of carbon number 6~10 Aromatic hydrocarbyl, and the hydrogen atom contained in the aromatic hydrocarbyl is by-SO₃ ^-Z1⁺Or-SO₂NHR²⁶Substitution.

If R²¹~R²⁴, then can be by the colored curable resin group of the invention of inclusion compound (2a) for above-mentioned group Compound forms the colour filter of excellent heat resistance.

As R²¹And R²²The ring and R comprising nitrogen-atoms for being integrally formed and being formed²³And R²⁴It is integrally formed and is formed Ring comprising nitrogen-atoms, can enumerate and R¹And R²The same ring of the ring that is integrally formed and is formed.Wherein, preferred aliphat heterocycle.Make For the aliphatic heterocycle, for example, following rings can be enumerated.

As expression R²⁶And R²⁷Carbon number 1~20 univalent saturated hydrocarbon radical, can enumerate and R⁸~R¹¹It is middle to be used as saturation Alkyl and the same group of the group enumerated.

Work as R²¹~R²⁴For-R²⁶When ,-R²⁶It is preferred that it is each independently methyl or ethyl.It is used as-SO₃R²⁶And-SO₂NHR²⁶In R²⁶, be preferably carbon number 3~20 branched-chain alkyl, more preferably carbon number 6~12 branched-chain alkyl, further Preferably 2- ethylhexyls.If R²⁶, then can be by the colored curable tree of the invention of inclusion compound (2a) for above-mentioned group Oil/fat composition formation foreign matter produces few colour filter.

Z1⁺For⁺N(R²⁷)₄、Na⁺Or K⁺, it is preferably⁺N(R²⁷)₄。

As above-mentioned⁺N(R²⁷)₄, preferably 4 R²⁷In at least two be carbon number 5~20 univalent saturated hydrocarbon radical.Separately Outside, 4 R²⁷Total number of carbon atoms be preferably 20~80, more preferably 20~60.When compound (2a) contains⁺N(R²⁷)₄When, Can be by including R²⁷The production of foreign matter is formed for the colored curable resin composition of the invention of the compound (2a) of above-mentioned group Raw few colour filter.

M1 is preferably 1~4, and more preferably 1 or 2.

As the preference of compound (1a), the compound and its dynamic isomer that can enumerate formula (3a) expression (have below When they are referred to as " compound (3a) ".).When using compound (3a), compound (3a) in xanthene dye (Aa) Content is preferably more than 50 mass % more preferably more than 70 mass %, more preferably more than 90 mass %.

[in formula (3a), R³¹And R³²The univalent saturated hydrocarbon radical of carbon number 1~10, the saturated hydrocarbyl are represented independently of one another In the hydrogen atom that contains can be substituted by the aromatic hydrocarbyl of carbon number 6~10 or halogen atom, contain in the aromatic hydrocarbyl Hydrogen atom can be substituted by the alkoxy of carbon number 1~3 ,-the CH contained in above-mentioned saturated hydrocarbyl₂- it can be replaced-O- ,-CO- Or-NR¹¹-。

R³³And R³⁴Represent that the alkyl of carbon number 1~4, the alkyl sulfenyl of carbon number 1~4 or carbon are former independently of one another The alkyl sulphonyl of subnumber 1~4.

R³¹And R³³It can be integrally formed and form the ring comprising nitrogen-atoms, R³²And R³⁴It can be integrally formed and be formed former comprising nitrogen The ring of son.

P and q represents 0~5 integer independently of one another.When p is more than 2, multiple R³³It may be the same or different, when q is 2 During the above, multiple R³⁴It may be the same or different.R¹¹Represent implication same as above.]

As R³¹And R³²In univalent saturated hydrocarbon radical, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, The straight-chain alkyls such as octyl group, nonyl, decyl；The branched alkane such as isopropyl, isobutyl group, isopentyl, neopentyl, 2- ethylhexyls Base；The ester ring type saturated hydrocarbons of the carbon numbers such as cyclopropyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, tricyclodecyl 3~10 Base.

On can be used as substituent and by with aromatic hydrocarbyl, can enumerate and R¹In the identical base of aromatic hydrocarbyl Group.

As the alkoxy of carbon number 1~3, methoxyl group, ethyoxyl, propoxyl group etc. can be enumerated.

R³¹And R³²It is preferred that it is each independently the univalent saturated hydrocarbon radical of carbon number 1~3.

As expression R³³And R³⁴Carbon number 1~4 alkyl, can enumerate methyl, ethyl, propyl group, butyl, isopropyl, Isobutyl group, sec-butyl, tert-butyl group etc..

As R³³And R³⁴In carbon number 1~4 alkyl sulfenyl, methylsulfany, ethylsulfanyl, propylthio can be enumerated Base, butyl sulfenyl and isopropylsulfanyl etc..

As R³³And R³⁴In carbon number 1~4 alkyl sulphonyl, can enumerate methyl sulphonyl, ethylsulfonyl, Sulfonyl propyl base, butyl sulfonyl and isopropelsulfonyl etc..

R³³And R³⁴The preferably alkyl of carbon number 1~4, more preferably methyl.

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

As compound (1a), for example, the chemical combination represented respectively by formula (1-1)~formula (1-42), formula (1-21 ') can be enumerated Thing.It should be noted that in formula, R²⁶Represent the univalent saturated hydrocarbon radical of carbon number 1~20, be preferably carbon number 6~12 Branched-chain alkyl, more preferably 2- ethylhexyls.The compound phase that formula (1-1)~formula (1-29), formula (1-21 ') represent is worked as In compound (2a), the compound that formula (1-30)~formula (1-42) represents is equivalent to compound (3a).

It is preferably the sulfonamide compound of C.I. acid reds 289, the quaternary ammonium salt of C.I. acid reds 289, C.I. acidity in them Purple 102 sulfonamide compound or the quaternary ammonium salt of C.I. acid violets 102.As such compound, formula (1-1)~formula can be enumerated Compound that (1-8), formula (1-11) and formula (1-12) represent etc..

From the aspect of dissolubility in organic solvent is excellent, the chemical combination of preferred formula (1-30)~formula (1-39) expression Thing.

Xanthene dye (Aa2) can be commercially available xanthene dye (for example, " the Chugai Aminol of middle tank formation (strain) system Fast Pink R-H/C ", field ridge chemical industry (strain) system " Rhodamin 6G ").Can also using commercially available xanthene dye as Starting material, synthesizes with reference to Japanese Unexamined Patent Publication 2010-32999 publications.

(anthraquinone dye (Aa3))

Anthraquinone dye (Aa3) can be known material.As anthraquinone dye (Aa3), for example, can enumerate：

C.I. (following, the record of omission C.I. solvent yellows, only records numbering to solvent yellow 117.), 163,167,189,

C.I. solvent orange 77,86,

C.I. solvent red 111,143,145,146,150,151,155,168,169,172,175,181,207,222, 227th, 230,245,247,

C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60,

C.I. solvent blue 19 4,18,35,36,45,58,59,59：1、63、68、69、78、79、83、94、97、98、100、 101st, 102,104,105,111,112,122,128,132,136,139,

C.I. solvent green 3,28,29,32,33,

C.I. acid red 80,

C.I. ACID GREEN 25,27,28,41,

C.I. acid violet 34,

C.I. acid blue 25,27,40,45,78,80,112

C.I. disperse yellow 51,

C.I. disperse violet 26,27,

C.I. disperse blue 1,14,56,60,

C.I. direct indigo plant 40,

C.I. mordant rouge 3,11,

C.I. mordant dyeing indigo plant 8 etc..

Anthraquinone dye is preferably the dyestuff that can be dissolved in organic solvent.

Anthraquinone dye is more preferably blueness, purple or red.

It is preferably the compound (hereinafter sometimes referred to " compound that formula (1b) represents as anthraquinone dye (Aa3) (1b)”。)。

[in formula (1b), R⁹¹And R⁹²Independently of one another represent hydrogen atom, can have substituent carbon number 1~10 fat Fat race alkyl, the alicyclic type hydrocarbon of carbon number 3~10 or the group of formula (1b ') expression can with substituent.]

[in formula (1b '), R⁹³Represent alkyl, the halogen atom ,-SO of carbon number 1~6₃H、-CO₂H、-CO₂R⁹⁴、- NHCOR⁹⁴、-SO₃R⁹⁴Or-SO₂NR⁹⁴R⁹⁵。

R⁹⁴Represent can by the saturated hydrocarbyl for the carbon number 1~10 that halogen atom, hydroxyl or amino substitutes or can by halogen original The alicyclic type hydrocarbon of the carbon number 3~10 of son, hydroxyl or amino substitution.

R⁹⁵Represent the saturated hydrocarbyl of hydrogen atom or carbon number 1~10.

R represents 0~5 integer.When r is more than 2, multiple R⁹³It may be the same or different.

X⁹¹Represent the alkane diyl of singly-bound or carbon number 1~6.]

When compound (1b) contains-SO₃H and/or-CO₂During H, they can forming salt (such as sodium salt, sylvite).

As R⁹¹And R⁹²The aliphatic alkyl of expression, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, The carbon numbers such as octyl group, nonyl, decyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, isopentyl, neopentyl, 2- ethylhexyls 1~10 alkyl.

The substituent contained as above-mentioned aliphatic alkyl, can enumerate hydroxyl, halogen atom etc..

As R⁹¹、R⁹²And R⁹⁴The alicyclic type hydrocarbon of expression, it is pungent can to enumerate cyclopropyl, cyclopenta, cyclohexyl, suberyl, ring The cycloalkyl of the carbon numbers such as base, tricyclodecyl 3~10.

The substituent contained as above-mentioned alicyclic type hydrocarbon, can enumerate hydroxyl, halogen atom etc..

As R⁹³The alkyl of expression, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, isopropyl, isobutyl group, secondary Butyl, the tert-butyl group, isopentyl, neopentyl etc..

As R⁹⁴And R⁹⁵The saturated hydrocarbyl of expression, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, pungent The alkyl of the carbon numbers such as base, nonyl, decyl 1~10.

It is used as-CO₂R⁹⁴, methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxy can be enumerated Carbonyl and eicosyl Epoxide carbonyl etc..

It is used as-NHCOR⁹⁴, N- acetyl-aminos, N- propanoylaminos, N- bytyries amino, N- isobutyryl ammonia can be enumerated Base, N- pivaloyl group amino etc..

It is used as-SO₃R⁹⁴, methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxy sulphonyl can be enumerated Base, hexyloxy sulfonyl and eicosyl epoxide sulfonyl etc..

It is used as-SO₂NR⁹⁴R⁹⁵, N- methylaminosulfonyls, N- ethylaminosulfonyls, N- propylcarbamic sulphonyl can be enumerated Base, N- iso-propylaminosulfonyls, N- butylaminos sulfonyl, N- isobutylaminos sulfonyl, N- s-butylaminos sulfonyl, N- tert-butylaminos sulfonyl, N- pentyl aminos sulfonyl, N- (1- ethyl propyls) amino-sulfonyl, N- (1,1- dimethyl propylenes Base) amino-sulfonyl, N- (1,2- dimethyl propyls) amino-sulfonyl, N- (2,2- dimethyl propyls) amino-sulfonyl, N- (1- Methyl butyl) amino-sulfonyl, N- (2- methyl butyls) amino-sulfonyl, N- (3- methyl butyls) amino-sulfonyl, N- rings penta Base amino-sulfonyl, N- Cyclohexylaminos sulfonyl, N- hexylaminos sulfonyl, N- (1,3- dimethylbutyls) aminosulfonyl Base, N- (3,3- dimethylbutyls) amino-sulfonyl, N- heptyl amino-sulfonyl, N- (1- methylhexyls) amino-sulfonyl, N- (1,4- dimethyl amyl groups) amino-sulfonyl, N- octyl aminos sulfonyl, N- (2- ethylhexyls) amino-sulfonyl, N- (1,5- Dimethyl) hexylamino sulfonyl, N- (1,1,2,2- tetramethyl butyls) amino-sulfonyl, N- (5- Aminopentyls) aminosulfonyl The mono-substituted amino-sulfonyls of the N- such as base；N, N- dimethylamino-sulfonyl, N, N- ethylmethylaminos sulfonyl, N, N- diethyls Base amino-sulfonyl, N, N- propyl-methylaminos sulfonyl, N, N- isopropylmethylaminos sulfonyl, N, N- tertbutyl methyl ammonia Base sulfonyl, N, N- butyl ethyls amino-sulfonyl, N, N- double (1- methyl-propyls) amino-sulfonyl, N, N- hept-ylmethyl amino Dibasic amino-sulfonyl of the N such as sulfonyl, N- etc..

As expression X⁹¹Alkane diyl, methylene, ethylidene, propane -1,3- diyl, propane -1,2- bis- can be enumerated Base, butane -1,4- diyls, pentane -1,5- diyls, hexane -1,6- diyls, ethane -1,1- diyls, butane -1,3- diyls, 2- first Base propane -1,3- diyls, 2- methylpropane -1,2- diyls, pentane -1,4- diyls, 2- methybutane -1,4- diyls etc..

As compound (1b), the compound that formula (3-1)~formula (3-11) represents can be enumerated.

As anthraquinone dye (Aa3), more preferably C.I. solvent blues 45.If above-mentioned anthraquinone dye, then can not only be formed more Film, the pattern of high contrast, additionally it is possible to formed foreign matter generation less, the film of excellent in light-resistance, pattern.

(dyestuff (Aa4))

Dyestuff (Aa4) as long as with triarylmethane colouring agent (Aa1), xanthene dye (Aa2) and anthraquinone dye (Aa3) Different dyestuffs, is not particularly limited.As dyestuff (Aa4), can enumerate oil-soluble dyes, acid dyes, basic-dyeable fibre, Direct dyes, mordant dye, the ammonium salt of acid dyes, the dyestuff such as sulfamide derivative of acid dyes.Specifically, can enumerate It is classified as dyestuff in Colour Index (The Society of Dyers and Colourists publication) (i.e. beyond pigment) Compound, the known dye described in Dyeing Note (Shikisensha CO., LTD.).According to chemical constitution not Together, can enumerate azo dyes, cyanine dyes, phthalocyanine dye, naphthoquinone dyestuff, quinoneimine dye, methine dyes, azo methine dyes, Side's acid (squarylium) dyestuff, acridine dye, styryl dye, coumarine dye, quinoline dye and nitro dye etc.. It is preferably organic solvent-soluble dyestuff in them.

Specifically, can enumerate：

C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99,162；

C.I. solvent red 125,130；

C.I. solvent orange 2,7,11,15,26,56；

C.I. solvent blue 37,67,70,90；

C.I. the C.I. solvent dyes such as solvent green 34,35；

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, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,57,66,73,80,88, 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、 308、312、315、316、339、341、345、346、349、382、383、394、401、412、417、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 6,7；

C.I. Blue VRS 8,29,59,60,70,72,74,82,87,92,102,113,117,120,126,130,131, 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 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 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107；

C.I. direct 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 1,2,6,8,15,22,25,57,71,76,78,80,81,84,85,86,90,93,94,95,97, 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. alkali blue 3,9,19,24,25,28,29,40,41,54,58,59,64,65,66,67,68；

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

C.I. mordant rouge 2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38, 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 2,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44,49, 53、61、74、77、83、84；

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

(pigment (Ab))

The colored curable resin composition of the present invention can include pigment (Ab).As pigment (Ab), it is not particularly limited, Known pigment can be used, (The Society of Dyers and Colourists go out in Colour Index for example, can enumerate Version) in be classified as the pigment of pigment (Pigment).

As pigment (Ab), can enumerate：

C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117, 125th, the yellow uitramarine such as 128,137,138,139,147,148,150,153,154,166,173,194,214；

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

C.I. pigment blue 15,15：3、15：4、15：6th, the blue pigment such as 60；C.I. pigment violet 1,19,23,29,32,36, 38 grade violet pigments；

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..

Pigment (Ab) is preferably blue pigment, and more preferably phthalocyanine color is Ji triazine dioxin pigment, is more preferably selected from By C.I. pigment blue 15s：6 and at least one of the group of pigment Violet 23 composition.

For pigment (Ab), as needed, following processing can be implemented：Rosin processing；Using being imported with acidic-group Or the surface treatment of the progress such as pigment derivative of basic group；The grafting carried out using high-molecular compound etc. to surface of pigments Processing；Handled using the micronized of the progress such as sulfuric acid particles method；Using the progress such as organic solvent, water, for removing impurity Carrying out washing treatment；Or utilize the progress such as ion-exchange, removing ionic impurity processing etc..The particle diameter of preferred pigments point It is ununiform.

By making pigment contain pigment dispersing agent and carrying out decentralized processing, so as to which it is made in pigment dispersing agent solution In dispersed state dispersible pigment dispersion.Pigment can individually carry out decentralized processing, can also mix a variety of pigment Close and carry out decentralized processing.

As above-mentioned pigment dispersing agent, cationic system, anionic system, nonionic system, both sexes, Polyester, polynary can be enumerated Pigment dispersing agent of amine system, acrylic acid series etc. etc..Above-mentioned pigment dispersing agent, which can be used alone, can also make two or more combination With.As pigment dispersing agent, trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), FLOREN (common prosperity society chemistry (strain) can be enumerated System), Solsperse (ZENECA company systems), EFKA (BASF (strain) systems), AJISPER (Ajinomoto Fine-Techno Co., Inc. systems), Disperbyk (Bi Ke chemical companies system) etc..

When using pigment dispersing agent when, its usage amount for 100 mass parts of pigment be preferably 100 mass parts with Under, 50 is below mass part more preferably more than 5 mass parts.If the usage amount of pigment dispersing agent is within the above range, existing can Obtain the tendency of the dispersible pigment dispersion in homogeneously dispersed state.

In this specification, unless otherwise specified, the compound illustrated as each component can be used alone or will Multiple combinations and use.

For the total amount of solid state component, the containing ratio of the colouring agent (A) in colored curable resin is preferably 5 matter Measure below 70 mass % of more than %, more preferably below 60 mass % of more than 5 mass %, more preferably more than 5 mass % Below 50 mass %.If the containing ratio of colouring agent (A) is within the above range, desired light splitting, colour saturation can be obtained.

In this specification, " total amount of solid state component " refers to remove from the colored curable resin composition of the present invention molten The total amount of component after agent (E).The total amount of solid state component and the content equivalent to each component for the total amount of solid state component It can be measured for example, by analysis method known to liquid chromatogram or gas-chromatography etc..

In colouring agent (A), as expected the containing ratio of each dyestuff can be divided suitably to select, but from height can be formed It is preferably following scope from the aspect of the film of contrast, pattern.

The containing ratio of triarylmethane colouring agent (Aa1) in colouring agent (A) is preferably more than 0.5 mass %, 98 matter Measure below %, more preferably more than 61 mass %, below 97 mass %, more preferably more than 81 mass %, 96 mass % Below.

The containing ratio of xanthene dye (Aa2) in colouring agent (A) is preferably more than 0.1 mass %, below 80 mass %, more Preferably more than 0.5 mass %, below 40 mass %, more preferably more than 1 mass %, below 20 mass %.

The containing ratio of anthraquinone dye (Aa3) in colouring agent (A) is preferably more than 0.1 mass % more preferably 0.5 matter Measure more than %, more preferably more than 1.0 mass %.The containing ratio of anthraquinone dye (Aa3) is preferably below 50 mass %, more Preferably below 30 mass %, more preferably below 10 mass %.

In colouring agent (A), relative to 100 mass parts of triarylmethane colouring agent (Aa1), the content of anthraquinone dye (Aa3) Preferably 0.5~50 mass parts, more preferably 1.0~35 mass parts, more preferably 1.0~13.5 mass parts, further More preferably 1.2~13.1 mass parts.

Content by making anthraquinone dye (Aa3) within the above range, can form film, the pattern of more high contrast.

＜ resins (B) ＞

As resin (B), it is not particularly limited, is preferably alkali soluble resins (B).Alkali soluble resins (B) is (following to be sometimes referred to as For " resin (B) ") it is the copolymer for including following construction units, the construction unit is derived from selected from by unsaturated carboxylic acid and not At least one of the group of saturated carboxylic acid acid anhydride composition monomer (a).

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

Resin [K1] is selected from the monomer (a) of at least one of the group being made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides (hereinafter sometimes referred to " (a) "), the monomer (b) with the ring-type ether structure containing carbon number 2~4 and ethylenic unsaturated bond The copolymer that (hereinafter sometimes referred to " (b) ") is formed；

(but it is different with (a) and (b) for resin [K2] (a), (b) and the monomer (c) that can be copolymerized from (a).) (below sometimes Referred to as " (c) ") formed copolymer；

The copolymer that resin [K3] (a) is formed with (c)；

Resin [K4] make copolymer that (a) and (c) are formed reacted with (b) obtained from resin；

Resin [K5] make copolymer that (b) and (c) are formed reacted with (a) obtained from resin；

Resin [K6] makes (b) to be reacted with the copolymer that (c) is formed and (a) and further make itself and carboxylic acid anhydride reactant Obtained from resin.

As (a), specifically, can enumerate：

Acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to vinyl benzoic acid Deng unsaturated monocarboxylic；

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl neighbours benzene two Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, 1,4- The unsaturated carboxylic acids such as cyclohexene dioctyl phthalate；

Methyl -5- norbornene -2,3- dioctyl phthalate, 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；

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

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

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

In them, in terms of the copolyreaction, from the aspect of deliquescent in alkaline aqueous solution of obtained resin, It is preferred that acrylic acid, methacrylic acid, maleic anhydride etc..

(b) refer to the ring-type ether structure containing such as carbon number 2~4 (for example, selected from by oxirane ring, oxa- ring Butane ring and tetrahydrofuran ring group into group in it is at least one kind of) and ethylenic unsaturated bond polymerizable compound.

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

In this specification, " (methyl) acrylic acid " is to represent in the group being made of acrylic acid and methacrylic acid extremely It is a kind few.The statement such as " (methyl) acryloyl group " and " (methyl) acrylate " also has same implication.

As (b), such as the monomer (b1) containing Oxyranyle and ethylenic unsaturated bond can be enumerated (below sometimes referred to as For " (b1) "), the monomer (b2) (hereinafter sometimes referred to " (b2) ") containing oxetanyl and ethylenic unsaturated bond, contain Monomer of tetrahydrofuran base and ethylenic unsaturated bond (b3) (hereinafter sometimes referred to " (b3) ") etc..

As (b1), it is at least partially epoxidized and obtains for example, the unsaturated aliphatic hydrocarbon with straight-chain or branched can be enumerated Structure monomer (b1-1) (hereinafter sometimes referred to " (b1-1) "), have ester ring type unsaturated hydrocarbons be at least partially epoxidized obtained from knot The monomer (b1-2) (hereinafter sometimes referred to " (b1-2) ") of structure.

As (b1-1), can enumerate (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl ether, an ethene Base benzyl glycidyl ether, to vinylbenzyl glycidyl ether, Alpha-Methyl-neighbour's vinylbenzyl glycidyl ether, Alpha-Methyl- Between vinylbenzyl glycidyl ether, Alpha-Methyl-to vinylbenzyl glycidyl ether, double (the glycidyl epoxide first of 2,3- Base) styrene, double (glycidyl oxy methyl) styrene of 2,4-, double (glycidyl oxy methyl) styrene of 2,5-, 2,6- double (glycidyl oxy methyl) styrene, 2,3,4- tri- (glycidyl oxy methyl) styrene, 2,3,5- tri- (glycidyl oxy methyl) styrene, 2,3,6- tri- (glycidyl oxy methyl) styrene, 3,4,5- tri- (shrink sweet Oil base epoxide methyl) styrene, 2,4,6- tri- (glycidyl oxy methyl) styrene etc..

As (b1-2), vinylcyclohexene list oxide (vinyl cyclohexene monoxide), 1 can be enumerated, 2- epoxy group -4- vinyl cyclohexanes (such as, CELLOXIDE 2000；Daicel Corporation systems), (methyl) propylene Sour 3,4- epoxycyclohexanecarboxylates (such as, CYCLOMER A400；Daicel Corporation systems), (methyl) acrylic acid 3, 4- epoxycyclohexanecarboxylates (such as, CYCLOMER M100；Daicel Corporation systems), formula (II) represent compound And compound of formula (III) expression etc..

[in formula (II) and formula (III), R^aAnd R^bRepresent the alkyl of hydrogen atom or carbon number 1~4, contain in the alkyl Hydrogen 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 carbon The alkane diyl of atomicity 1~6.* the connecting key with O is represented.]

As the alkyl of carbon number 1~4, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, uncle can be enumerated Butyl etc..

Alkyl obtained from being optionally substituted by a hydroxyl group as hydrogen atom, can enumerate hydroxymethyl, 1- hydroxyethyls, 2- hydroxyl second Base, 1- hydroxypropyls, 2- hydroxypropyls, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxyls Base butyl, 2- hydroxybutyls, 3- hydroxybutyls, 4- hydroxybutyls etc..

As R^aAnd R^b, hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls are preferably enumerated, is more preferably lifted Go out hydrogen atom, methyl.

As the alkane diyl of carbon number 1~6, can enumerate methylene, ethylidene, propane -1,2- diyl, propane - 1,3- diyls, butane -1,4- diyls, pentane -1,5- diyls, hexane -1,6- diyls etc..

As X^aAnd X^b, preferably enumerate singly-bound, methylene, ethylidene, *-CH₂- O- and *-CH₂CH₂- O-, is more preferably lifted Go out singly-bound, *-CH₂CH₂- O- (* represents the connecting key with O).

The compound represented as formula (II), can enumerate the chemical combination of any one of formula (II-1)~formula (II-15) expression Thing etc..Wherein, it is preferably formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~formula (II-15) compound represented, the chemical combination that more preferably formula (II-1), formula (II-7), formula (II-9) or formula (II-15) represent Thing.

The compound represented as formula (III), can enumerate the change of any one of formula (III-1)~formula (III-15) expression Compound etc..Wherein, it is preferably formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III- 11) compound that~formula (III-15) represents, more preferably formula (III-1), formula (III-7), formula (III-9) or formula (III-15) The compound of expression.

The compound that the compound and formula (III) that formula (II) represents represent can be used alone respectively, also can be by formula (II) table The compound that the compound and formula (III) shown represent is used in combination.By they and used time, with molar basis, what formula (II) represented The containing ratio for the compound that compound and formula (III) represent is preferably 5：95~95：5, more preferably 10：90~90：10, into One step is preferably 20：80~80：20.

As (b2), the monomer more preferably containing oxetanyl He (methyl) acryloxy., can as (b2) Enumerate 3- methyl -3- methacryloxymethyls oxetanes, 3- methyl -3- acryloyloxymethyls oxetanes, 3- ethyl -3- methacryloxymethyls oxetanes, 3- ethyl -3- acryloyloxymethyls oxetanes, 3- first Base -3- methacryloxyethyls oxetanes, 3- methyl -3- acryloyl-oxyethyls oxetanes, 3- ethyls -3- Methacryloxyethyl oxetanes, 3- ethyl -3- acryloyl-oxyethyl oxetanes etc..

As (b3), the monomer more preferably containing tetrahydrofuran base He (methyl) acryloxy.As (b3), specifically For, tetrahydrofurfuryl acrylate (for example, VISCOAT V#150, Osaka Organic Chemical Industry (strain) system), metering system can be enumerated Sour tetrahydrochysene chaff ester etc..

As (b), the reliability of heat resistance, chemical proofing from the colour filter that can be further improved etc. From the aspect of, it is preferably (b1).In addition, from the aspect of the excellent storage stability of colored curable resin composition, more Preferably (b1-2).

As (c), for example, can enumerate：

(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Zhong Ding Ester, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) third Olefin(e) acid lauryl, (methyl) stearyl acrylate base ester, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) Acrylic acid 2- methyl cyclohexyls, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base esters (and in the art, as Trivial name, is referred to as " (methyl) acrylic acid Bicvclopentyl ester ".In addition, it is sometimes referred to as " (methyl) acrylic acid tricyclodecyl Ester ".), (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decene -8- base esters (in the art, as trivial name, are referred to as " (methyl) acrylic acid double cyclopentenyl ester ".), (methyl) acrylic acid Bicvclopentyl epoxide ethyl ester, (methyl) isobomyl acrylate Ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) acrylic acid benzene (methyl) acrylate such as ester, (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 Ester；

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- tert-butoxycarbonyls, 5- cyclohexyloxy carbonyls are double Bicyclic [2.2.1] hept-2-ene" of ring [2.2.1] hept-2-ene", 5- phenyloxycarbonyls, 5,6- double (tert-butoxycarbonyls) are bicyclic The bicyclic unsaturated compounds 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, 3- dimaleoyl imino benzene Formic acid-N- succinimide esters, 4- maleimidobutyric acid-N- succinimide esters, 6- maleimidocaproic acid-N- ambers The dicarbapentaborane acyls such as amber imide ester, 3- maleimidoproprionic acid-N- succinimide esters, N- (9- acridinyls) maleimide Imine derivative；

Styrene, α-methylstyrene, m-methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3- dimethyl -1,3- butadiene etc..

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

In resin [K1], for the ratio from the construction unit of each component, the whole of resin [K1] is being formed In construction unit, it is preferred that

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

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

It is further preferred that

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

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

If the ratio of the construction unit of resin [K1] is within the above range, there are the guarantor of colored curable resin composition Deposit stability, formed colored pattern when developability and obtained colour filter excellent solvent resistance tendency.

Resin [K1] refers to such as document " experimental method of Polymer Synthesizing ", and (big Jin Longhangzhu publishing houses (strain) chemistry is same The printing of people the 1st edition the 1st time distribution on March 1st, 1972) described in method and the document described in citation manufacture.

Specifically, following methods can be enumerated：(a) and (b), polymerization initiator and solvent by ormal weight etc. are added to anti- Answer in container, replace oxygen by using such as nitrogen and form deoxidizing atmosphere, heated and kept the temperature while agitating.It is above-mentioned poly- Close initiator and solvent etc. to be not particularly limited, material usually used in this field can be used.As polymerization initiator, can lift Go out such as azo-compound (2,2 '-azobis isobutyronitrile, 2,2 '-azo double (2,4- methyl pentane nitrile) etc.), organic peroxy Thing (benzoyl peroxide etc.), as solvent, as long as can dissolve each monomer solvent, can enumerate as the present invention The solvent (E) of color hardening resin composition and solvent for recording below etc..

It should be noted that for obtained copolymer, the solution after reaction can be used directly, it is possible to use carry out Concentration or diluted solution, the product that also the methods of passing through reprecipitation can be used to take out in the form of the solid (powder).Especially, When carrying out the polymerization, the solvent contained in the colored curable resin composition by using the present invention, can as solvent Solution after reaction is directly used in the preparation of the colored curable resin composition of the present invention, therefore, it is possible to simplify the present invention Colored curable resin composition manufacturing process.

In resin [K2], for the ratio from the construction unit of each component, the whole of resin [K2] is being formed In construction unit, it is preferred that

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

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

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

It is further preferred that

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

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

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

If the ratio of the construction unit of resin [K2] is within the above range, there are the guarantor of colored curable resin composition Developability and the solvent resistance of obtained colour filter, heat resistance and mechanical strength when depositing stability, forming colored pattern is excellent Different tendency.

Resin [K2] for example can be same according to the method recorded with the manufacture method as resin [K1] mode make Make.

In resin [K3], for the ratio from the construction unit of each component, the whole of resin [K3] is being formed In construction unit, it is preferred that

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

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

It is further preferred that

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

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

Resin [K3] for example can be same according to the method recorded with the manufacture method as resin [K1] mode make Make.

Resin [K4] can be manufactured by following manner：The copolymer of (a) and (c) are obtained, makes carbon possessed by (b) former The cyclic ether of subnumber 2~4 carries out addition with carboxylic acid possessed by (a) and/or carboxylic acid anhydrides.

First, the mode same according to the method recorded with the manufacture method as resin [K1] manufactures (a) and (c) Copolymer.At this time, the ratio from the construction unit of each component is preferably identical with the ratio enumerated in resin [K3] Ratio.

Next, make being had from the carboxylic acid of (a) and/or a part for carboxylic acid anhydrides with (b) in above-mentioned copolymer The cyclic ether of carbon number 2~4 reacted.

Atmosphere in flask is and then replaced into air by nitrogen after copolymer of the manufacture (a) with (c), is added into flask (b), the catalyst (three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor of the reaction of carboxylic acid or carboxylic acid anhydrides and cyclic ether are catalyzed (quinhydrones etc.) etc., when such as 60~130 DEG C reactions 1~10 are small, thus can manufacture resin [K4].

For 100 moles of (a), the usage amount of (b) is preferably 5~80 moles, more preferably 10~75 moles.It is logical Crossing makes it within the range, thus storage stability there are colored curable resin composition, developability when forming pattern, And the solvent resistance of obtained pattern, heat resistance, the harmony of mechanical strength and susceptibility become good tendency.Due to ring The reactivity height of shape ether, be not easy remaining unreacted (b), therefore, as (b) for resin [K4], is preferably (b1), into one Step is preferably (b1-1).

For 100 mass parts of total amount of (a), (b) and (c), the usage amount of above-mentioned catalysts is preferably 0.001~5 mass parts.For 100 mass parts of total amount of (a), (b) and (c), the usage amount of above-mentioned polymerization inhibitor is preferred For 0.001~5 mass parts.

The reaction conditions such as charging process, reaction temperature and time are contemplated that manufacturing equipment, the caloric value produced by polymerization Suitably adjusted Deng next.It should be noted that can be in the same manner as polymerizing condition, consideration manufacturing equipment, the fever produced by polymerization Amount etc. suitably adjusts charging process, reaction temperature.

For resin [K5], as the first step, according to the operation same with the manufacture method of above-mentioned resin [K1], obtain To the copolymer of (b) and (c).Same as abovely, for obtained copolymer, the solution after reaction can be used directly, It can also be used and carried out concentration or diluted solution, also can be used by being taken out the methods of reprecipitation in the form of solid (powder) Product.

For the ratio from the construction unit of (b) and (c), relative to the entire infrastructure for forming above-mentioned copolymer Total molal quantity of unit, is preferably respectively,

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

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

It is further preferred that

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

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

And then under conditions of same with the manufacture method of resin [K4], make to come possessed by (b) and the copolymer of (c) Come from (b) cyclic ether, with (a) possessed by carboxylic acid or carboxylic acid anhydrides reacted, this makes it possible to obtain resin [K5].

For 100 moles of (b), the usage amount with (a) of above-mentioned copolymer reaction is preferably 5~80 moles.By In the reactivity of cyclic ether it is high, be not easy remaining unreacted (b), therefore, as (b) for resin [K5], be preferably (b1), More preferably (b1-1).

Resin [K6] be make resin [K5] further reacted with carboxylic acid anhydrides obtained from resin.

Make by the reaction of cyclic ether and carboxylic acid or carboxylic acid anhydrides and produce hydroxyl, reacted with carboxylic acid anhydrides.

As carboxylic acid anhydrides, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- second can be enumerated Alkenyl phthalic anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro Phthalic anhydride, bicyclic [2.2.1] hept-2-ene" -5,6- dicarboxylic acid anhydrides etc..For 1 mole of the usage amount of (a), carboxylic The usage amount of acid anhydrides is preferably 0.5~1 mole.

As resin (B), specifically, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates/(methyl) propylene can be enumerated Acid copolymer, (methyl) acrylic acid 3,4- epoxy group tricyclics [5.2.1.0^2.6] resin such as decyl ester/(methyl) acrylic copolymer [K1]；(methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) acrylic acid Ethylene oxidic ester/styrene/(methyl) acrylic copolymer, (methyl) acrylic acid 3,4- epoxy group tricyclics [5.2.1.0^2.6] last of the ten Heavenly stems Base ester/(methyl) acrylic acid/N- N-cyclohexylmaleimides copolymer, (methyl) acrylic acid 3,4- epoxy group tricyclics [5.2.1.0^2.6] decyl ester/(methyl) acrylic acid/vinyl toluene copolymer, 3- methyl -3- (methyl) acryloyloxymethyl The resins [K2] such as oxetanes/(methyl) acrylic/styrene copolymer；(methyl) benzyl acrylate/(methyl) acrylic acid Copolymer, styrene/(methyl) acrylic copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl ester/(first Base) resin [K3] such as acrylic copolymer；Make (methyl) benzyl acrylate/(methyl) acrylic copolymer and (methyl) acrylic acid Ethylene oxidic ester carry out addition obtained from resin, make (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) acrylic acid common Resin obtained from polymers and (methyl) glycidyl acrylate carry out addition, make (methyl) acrylic acid tricyclodecyl ester/(first Base) benzyl acrylate/(methyl) acrylic copolymer and (methyl) glycidyl acrylate carry out resin obtained from addition Deng resin [K4]；Make the copolymer and (methyl) third of (methyl) acrylic acid tricyclodecyl ester/(methyl) glycidyl acrylate Resin obtained from olefin(e) acid is reacted, make (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) glycidyl The resin [K5] such as resin obtained from the copolymer of ester is reacted with (methyl) acrylic acid；It will make (methyl) acrylic acid tricyclic last of the ten Heavenly stems Resin obtained from the copolymer of base ester/(methyl) glycidyl acrylate is reacted with (methyl) acrylic acid, further Resin such as resin [K6] etc. obtained from being reacted with tetrabydrophthalic anhydride.

Resin (B) is preferably selected from one kind in the group of resin [K1], resin [K2] and resin [K3] composition, more preferably One kind in the group being made of resin [K2] and resin [K3].If above-mentioned resin, then colored curable resin composition Developability it is excellent.It is more preferably resin [K2] from the viewpoint of from the adaptation of colored pattern and substrate.

The weight average molecular weight (Mw) according to polystyrene conversion meter of resin (B) is preferably 3,000~100,000, more excellent Elect 5,000~50,000 as, more preferably 5,000~30,000.If weight average molecular weight (Mw) is within the above range, deposit In following tendencies：The hardness of the film formed by the colored curable resin composition comprising the resin (B) improves, its residual film ratio Also high, favorable solubility, the resolution ratio of colored pattern improve in developer solution in unexposed portion.

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

The acid number of resin (B) is preferably 50~170mg-KOH/g, more preferably 60~150mg-KOH/g, further preferably For 70~135mg-KOH/g.Herein, acid number is measured as the amount (mg) for neutralizing 1g resins (B) required potassium hydroxide Value, such as can be titrated and be obtained by using potassium hydroxide aqueous solution.

For the total amount of solid state component, the content of resin (B) is preferably 7~65 mass %, more preferably 13~ 60 mass %, more preferably 17~55 mass %.If the content of resin (B) is within the above range, coloring can be formed Pattern, and then resolution ratio and the tendency of residual film ratio raising there are colored pattern.

＜ polymerizable compounds (C) ＞

Polymerizable compound (C) is can be under the action of the living radical and/or acid produced by polymerization initiator (D) The compound of row polymerization.As polymerizable compound (C), the compound of the ethylenic unsaturated bond with polymerism can be enumerated Deng, be preferably (methyl) acrylate compounds.

As the polymerizable compound with 1 ethylenic unsaturated bond, can enumerate nonyl phenyl carbitol acrylate, Acrylic acid 2- hydroxyl -3- phenoxy-propyls, 2- ethylhexyl carbitols acrylate, acrylic acid 2- hydroxy methacrylates, N- vinyl Pyrrolidones etc. and above-mentioned (a), (b) and (c).

As the polymerizable compound with 2 ethylenic unsaturated bonds, 1,6- hexylene glycols two (methyl) propylene can be enumerated Acid esters, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylic acid Double (acryloyl-oxyethyl) ether, 3- methyl pentanediols two (methyl) acrylate etc. of ester, bisphenol-A.

Polymerizable compound (C) is preferably the polymerizable compound with the ethylenic unsaturated bond of more than 3.It is used as this The polymerizable compound of sample, can enumerate trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, Pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid Ester, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) third Olefin(e) acid ester, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters, ethylene glycol It is modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol modified Pentaerythrite four (methyl) acrylate, propylene glycol modified dipentaerythritol six (methyl) acrylate, caprolactone modification season penta Tetrol four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc., wherein, preferably two seasons penta 4 (methyl) acrylate of alcohol five and dipentaerythritol six (methyl) acrylate.

The weight average molecular weight of polymerizable compound (C) is preferably more than 150 2, less than 900, and more preferably 250~1,500 Below.

For the total amount of solid state component, the content of polymerizable compound (C) is preferably 7~65 mass %, more excellent Elect 13~60 mass % as, more preferably 17~55 mass %.

Content ratio (the resin (B) of resin (B) and polymerizable compound (C)：Polymerizable compound (C)) in terms of quality criteria Preferably 20：80~80：20, more preferably 35：65~80：20.

If the content of polymerizable compound (C) is within the above range, there are residual film ratio during colored pattern formation and filter The tendency that the chemical proofing of color device improves.

＜ polymerization initiators (D) ＞

Polymerization initiator (D) as long as can produce living radical, acid etc. by the effect of light, heat and trigger polymerization Compound, be not particularly limited, known polymerization initiator can be used.

As polymerization initiator (D), O- acyl groups oxime compound, alkyl phenones compound, united imidazole, three can be enumerated Piperazine compound and acylphosphine oxide compound etc..

Above-mentioned O- acyl groups oxime compound is the compound of the structure represented containing formula (d1).Hereinafter, * represents connecting key.

As above-mentioned O- acyl groups oxime compound, can enumerate N- benzoyloxys -1- (4- Phenylsulfanylphenyls) butane -1- ketone - 2- imines, N- benzoyloxys -1- (4- Phenylsulfanylphenyls) octane -1- ketone -2- imines, N- benzoyloxys -1- (4- thiophenyls Phenyl) -3- cyclopenta propane -1- ketone -2- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- methyl benzoyls) -9H- clicks Azoles -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- { 2- methyl -4- (3,3- dimethyl -2,4- dioxanes Phenyl-methyl epoxide) benzoyl -9H- carbazole -3- bases] ethane -1- imines, N- acetoxyl groups -1- [9- ethyls -6- (2- first Base benzoyl) -9H- carbazole -3- bases] -3- cyclopenta propane -1- imines, N- benzoyloxys -1- [9- ethyls -6- (2- first Base benzoyl) -9H- carbazole -3- bases] -3- cyclopenta propane -1- ketone -2- imines etc..Irgacure can also be used The commercially available product such as OXE01, OXE02 (more than, BASF (strain) system), N-1919 ((strain) ADEKA systems).Wherein, O- acyl groups oxime compound It is preferably selected from by N- benzoyloxys -1- (4- Phenylsulfanylphenyls) butane -1- ketone -2- imines, N- benzoyloxy -1- (4- Phenylsulfanylphenyl) octane -1- ketone -2- imines and N- benzoyloxys -1- (4- Phenylsulfanylphenyls) -3- cyclopenta propane -1- ketone - At least one kind of in the group of 2- imines composition, more preferably N- benzoyloxys -1- (4- Phenylsulfanylphenyls) octane -1- ketone -2- is sub- Amine.If above-mentioned O- acyl groups oxime compound, then in the presence of the tendency for the colour filter for obtaining high brightness.

Abovementioned alkyl benzophenone compound is, for example, the chemical combination of the structure of structure or formula (d3) expression represented with formula (d2) Thing.In said structure, phenyl ring can have substituent.

As the compound of the structure represented with formula (d2), 2- methyl -2- morpholinoes -1- (4- methylsulfanies can be enumerated Phenyl) propane -1- ketone, 2- dimethylaminos -1- (4- morphlinophenyls) -2- benzyl butane -1- ketone, 2- (dimethylamino) - 2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] butane -1- ketone etc..Can also be used Irgacure 369, 907th, 379 the commercially available product such as (more than, BASF AG's system).

As the compound of the structure represented with formula (d3), can enumerate 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 2- hydroxy-2-methyls -1- (4- (2- hydroxyl-oxethyls) phenyl propane -1- ketone, 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyls - The oligomer, α of 2- methyl isophthalic acids-(4- isopropenyls phenyl) propane -1- ketone, α-diethoxy acetophenone, benzyl dimethyl ketal Deng.

From the aspect of susceptibility, as alkyl phenones compound, it is however preferred to have the change for the structure that formula (d2) represents Compound.

Above-mentioned united imidazole is, for example, the compound that formula (d5) represents.

[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, toluyl groups, xylyl, ethylphenyl and naphthyl can be enumerated Deng preferably enumerating phenyl.

As substituent, alkoxy of halogen atom, carbon number 1~4 etc. can be enumerated.As halogen atom, fluorine original can be enumerated Son, chlorine atom, bromine atoms, iodine atom etc., preferably enumerate chlorine atom.As the alkoxy of carbon number 1~4, methoxy can be enumerated Base, ethyoxyl, propoxyl group, butoxy etc., preferably enumerate methoxyl group.

As united imidazole, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5 can be enumerated, 5 '-tetraphenyl bisglyoxaline, 2,2 ' - Double (2,3- dichlorophenyls) -4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (referring to Japanese Unexamined Patent Publication 6-75372 publications, Japanese Unexamined Patent Publication Flat 6-75373 publications etc..), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxalines, 2,2 '-it is bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (three Alkoxyl phenyl) bisglyoxaline is (referring to Japanese Patent Publication 48-38403 publications, Japanese Unexamined Patent Application 62-174204 publications etc..)、 The imidazolium compounds that the phenyl of 4,4 ', 5,5 '-position is substituted by carbonylic alkoxy (referring to Japanese Unexamined Patent Publication 7-10913 publications etc.) Deng.Wherein, the compound and their mixture that preferably following formula represents.

As above-mentioned triaizine compounds, double (the trichloromethyl) -6- (4- methoxyphenyls) -1,3,5- tri- of 2,4- can be enumerated Double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of piperazine, 2,4-, double (trichloromethyl) -6- piperonyl -1 of 2,4-, Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of 3,5- triazines, 2,4-, double (the trichloromethyl) -6- of 2,4- Double (trichloromethyl) -6- (2- (furans -2- bases) ethene of (2- (5- methylfuran -2- bases) vinyl) -1,3,5- triazines, 2,4- Base) -1,3,5- triazines, double (trichloromethyl) -6- (2- (4- diethylamino -2- aminomethyl phenyls) the vinyl) -1,3,5- of 2,4- Double (trichloromethyl) -6- (2- (3,4- Dimethoxyphenyls) vinyl) -1,3,5- triazines of triazine, 2,4- etc..

As above-mentioned acylphosphine oxide compound, 2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. can be enumerated.

In addition, as polymerization initiator (D), benzoin, benzoin methylether, benzoin ethyl ether, benzoin isopropyl can be enumerated The benzoin compound such as ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl benzophenones, 4- Benzoyl -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6- trimethyls The benzophenone cpds such as benzophenone；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- ethyl hydrazine, camphorquinone；10- butyl -2- chlorine a word used for translations Pyridine ketone, benzil (benzil), phenylglyoxalates methyl esters, titanocenes compound etc..

They preferably trigger auxiliary agent (D1) (especially amine compounds) to combine and use with polymerization described later.

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

For 100 mass parts of total amount of resin (B) and polymerizable compound (C), polymerization initiator (D's) contains Amount is preferably 0.1~40 mass parts, more preferably 1~30 mass parts.

＜ polymerizations trigger auxiliary agent (D1) ＞

It is for promoting to trigger the poly- of the polymerizable compound of polymerization by polymerization initiator that polymerization, which triggers auxiliary agent (D1), The compound or sensitizer of conjunction.When triggering auxiliary agent (D1) comprising polymerization, usually combine and use with polymerization initiator (D).

Trigger auxiliary agent (D1) as polymerization, amine compounds, alkoxy anthracene compound, thioxanthone compounds and carboxylic acid can be enumerated Compound etc..

As above-mentioned amine compounds, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylaminos can be enumerated Methyl benzoate, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acids isopentyl ester, benzoic acid 2- dimethylaminos Ethyl ester, 4- dimethylaminobenzoic acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4 '-bis- (dimethylamino) hexichol Ketone (being commonly called as Elisabeth Micheler ketone), 4,4 '-bis- (diethylamino) benzophenone, 4,4 '-bis- (ethylmethylamino) benzophenone Deng, wherein, it is preferably 4,4 '-bis- (diethylamino) benzophenone.EAB-F (hodogaya chemical industry (strain) system) can also be used Etc. commercially available product.

As above-mentioned alkoxy anthracene compound, can enumerate 9,10- dimethoxys anthracene, 2-ethyl-9,10-dimethoxypyrene, 9,10- diethoxies anthracene, 2- ethyl -9,10- diethoxies anthracene, 9,10- dibutoxies anthracene, 2- ethyl -9,10- dibutoxy anthracenes Deng.

As above-mentioned thioxanthone compounds, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thiophenes can be enumerated Ton ketone, bis- clopenthixal ketones of 2,4-, the chloro- 4- propoxythioxanthones of 1- etc..

As above-mentioned carboxylic acid compound, thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, first can be enumerated Base ethylthiophenyl acetic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorobenzene sulphur Guanidine-acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N- naphthyls glycine, naphthalene oxygen Guanidine-acetic acid etc..

When using above-mentioned polymerization trigger auxiliary agent (D1) when, its content relative to resin (B) and polymerizable compound (C) conjunction It is preferably 0.1~30 mass parts to measure for 100 mass parts, more preferably 1~20 mass parts.If polymerization triggers auxiliary agent (D1) Amount within the range, then further can form colored pattern with high sensitive, and there are the tendency of the productivity raising of colour filter.

＜ solvents (E) ＞

Solvent (E) is not particularly limited, and solvent usually used in the field can be used.As solvent (E), ester can be enumerated Solvent (solvent comprising-COO- and without-O- in the molecule), ether solvents are (molten comprising-O- and without-COO- in the molecule Agent), ether-ether solvent (solvent comprising-COO- and-O- in the molecule), ketone solvent (be free of-COO- comprising-CO- in the molecule Solvent), alcoholic solvent (solvent comprising OH and without-O- ,-CO- and-COO- in the molecule), aromatic hydrocarbon solvents, acid amides it is molten Agent and dimethyl sulfoxide (DMSO) etc..

As ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, acetic acid second can be enumerated 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, can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propane diols Single propyl ether, propylene glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl butanols, tetrahydrofuran, oxinane, 1, 4- dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethyl Dibutyl ether, methyl phenyl ethers anisole, phenetole and methylanisole etc..

As ether-ether solvent, methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy can be enumerated Acetic acid methyl ester, ethoxy 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 methyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetic acid Ester, butyl carbitol acetate 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- heptan can be enumerated Ketone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone and isophorone etc..

As alcoholic solvent, methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols and the third three can be enumerated Alcohol etc..

As aromatic hydrocarbon solvents, benzene,toluene,xylene and mesitylene etc. can be enumerated.

As amide solvent, n,N-Dimethylformamide, n,N-dimethylacetamide and 1-methyl-2-pyrrolidinone can be enumerated Deng.

Above-mentioned solvent can be used alone, and also and can use two or more.

Wherein, it is preferably propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetic acid esters, ethyl lactate, propane diols list Methyl ether, 3- ethoxyl ethyl propionates, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol list second Ether, acetic acid 3- methoxybutyls, 3- methoxyl groups-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanones, N,N-dimethylformamide and N- Methyl pyrrolidone etc., more preferably propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol Methylether acetate, ethyl lactate, acetic acid 3- methoxybutyls, 3- methoxyl groups-n-butyl alcohol, 3- ethoxyl ethyl propionates and N- first Base pyrrolidones.

For the total amount of colored curable resin composition, the containing ratio of solvent (E) is preferably 70~95 matter Measure %, more preferably 75~92 mass %.In other words, the solid state component of colored curable resin composition is preferably 5~30 matter Measure %, more preferably 8~25 mass %.If the containing ratio of solvent (E) is within the above range, colored curable resin group is coated with Flatness during compound becomes good, in addition, colour saturation will not be insufficient when forming colour filter, therefore becomes good there are display characteristic Good tendency.

＜ levelling agents (F) ＞

As levelling agent (F), silicone based surfactants, fluorine system surfactant and having containing fluorine atom can be enumerated Machine silicon systems surfactant etc..They can have polymerizable group in side chain.

As silicone based surfactants, surfactant with siloxanes key etc. in the molecule can be enumerated.Specifically For, can enumerate Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA, Toray Silicone SH8400 (TorayDow Corning Corporation systems), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Inc. systems) etc..

As above-mentioned fluorine system surfactant, surfactant with fluorocarbon chain etc. in the molecule can be enumerated.It is specific and Speech, can enumerate Fluorad (registration mark) FC430, Fluorad FC431 (Sumitomo 3M (strain) systems), Megaface (registrars Mark) F142D, Megaface F171, Megaface F172, Megaface F173, Megaface F177, Megaface F183, Megaface F554, Megaface R30, Megaface RS-718-K (DIC (strain) systems), EFTOP (registration mark) EF301、EFTOP EF303、EFTOP EF351、EFTOP EF352(Mitsubishi Material Electronic Chemicals Co., Ltd. (strain) make), Surflon (registration mark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (strain) system) and E5844 (Daikin Fine Chemical Institute systems) etc..

As the above-mentioned silicone based surfactants containing fluorine atom, can enumerate in the molecule containing siloxanes key and Surfactant of fluorocarbon chain etc..Specifically, can enumerate Megaface (registration mark) R08, Megaface BL20, Megaface F475, Megaface F477 and Megaface F443 (DIC (strain) systems) etc..

When containing levelling agent (F), its containing ratio is preferably for the total amount of colored curable resin composition Below 0.2 mass % of more than 0.001 mass %, more preferably below 0.1 mass % of more than 0.002 mass %, further preferably For below 0.07 mass % of more than 0.005 mass %.If the containing ratio of levelling agent (F) is within the above range, colour filter can be made The flatness of device becomes good.

＜ antioxidants (H) ＞

From the viewpoint of the heat resistance and light resistance for improving colouring agent, antioxidant is preferably used alone or combined 2 Used more than kind., can as long as industrial usually used antioxidant, is not particularly limited as antioxidant To use phenol antioxidant, phosphorous antioxidant and sulfur antioxidant etc..

As above-mentioned phenol antioxidant, (the イ Le ガ ノ ッ Network ス 1010 of Irganox 1010 can be enumerated：Pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], BASF (strain) system), (the イ Le ガ ノ ッ Network ス of Irganox 1076 1076：3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid stearyl, BASF (strain) system), (the イ Le of Irganox 1330 ガノックス1330：3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl group-a, a ', a "-(mesitylene -2,4, tri- bases of 6-) three paracresol, BASF (strain) make), (the イ Le ガ ノ ッ Network ス 3114 of Irganox 3114：1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls)- 1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones, BASF (strain) system), (the イ Le ガ ノ ッ Network ス 3790 of Irganox 3790：1, 3,5- tri- ((the 4- tert-butyl group -3- hydroxyls -2,6- xylyl) methyl) -1,3,5-triazines -2,4,6 (1H, 3H, 5H)-triketones, BASF (strain) make), (the イ Le ガ ノ ッ Network ス 1035 of Irganox 1035：Double [3- (3,5- di-t-butyl -4- the hydroxyls of thio diethylene Base phenyl) propionic ester], BASF (strain) system), (the イ Le ガ ノ ッ Network ス 1135 of Irganox 1135：Double (the 1,1- dimethyl second of 3,5- Base) -4- hydroxy phenylpropionic acids C7-C9 pendant alkyl group esters, BASF (strain) system), Irganox 1520L (イ Le ガ ノ ッ Network ス 1520L：4,6- double (octylsulfo methyl)-o-cresols, BASF (strain) systems), Irganox 3125 (イ Le ガ ノ ッ Network ス 3125, BASF (strain) make), (the イ Le ガ ノ ッ Network ス 565 of Irganox 565：Double (n-octylthio) -6- (the 4- hydroxyls 3 ', 5 '-two of 2,4- Tertiary-butyl anilino) -1,3,5-triazines, BASF (strain) system), Adekastab AO-80 (ア デ カ ス タ Block AO-80：3,9- is double Four oxa-s of (2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propiono epoxide) -1,1- dimethyl ethyls) -2,4,8,10- Spiral shell (5,5) hendecane, (strain) ADEKA systems), Sumilizer BHT (ス ミ ラ イ ザ ー BHT, Sumitomo Chemical (strain) system), Sumilizer GA-80 (ス ミ ラ イ ザ ー GA-80, Sumitomo Chemical (strain) system), Sumilizer GS (ス ミ ラ イ ザ ー GS, Sumitomo Chemical (strain) is made), Cyanox 1790 (シ ア ノ ッ Network ス 1790, Cytec Corporation systems) and vitamin E (Eisai Co., Ltd. system) etc..

As above-mentioned phosphorous antioxidant, (the イ Le ガ Off ォ ス 168 of IRGAFOS 168 can be enumerated：Three (2,4- of phosphorous acid Di-tert-butyl-phenyl) ester, BASF (strain) system), (the イ Le ガ Off ォ ス 12 of IRGAFOS 12：Three [2- [[tetra- tertiary fourths of 2,4,8,10- Base dibenzo [d, f] [miscellaneous English in the heptan -6- bases of 1,3,2] Delnavs] epoxide] ethyl] amine, BASF (strain) system), 38 (イ of IRGAFOS ルガフォス38：Double (2,4- double (1,1- the dimethyl ethyl) -6- aminomethyl phenyls) ethyl esters of phosphorous acid, BASF (strain) systems), Adekastab 329K ((strain) ADEKA systems), Adekastab PEP36 ((strain) ADEKA systems), Adekastab PEP-8 ((strain) ADEKA systems), Sandstab P-EPQ (Clariant company systems), Weston 618 (ウ ェ ス ト Application 618, GE company systems), Weston 619G (ウ ェ ス ト Application 619G, GE company system), Ultranox 626 (ウ Le ト ラ ノ ッ Network ス 626, GE company systems) And Sumilizer GP (ス ミ ラ イ ザ ー GP：6- [3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propoxyl group] -2,4,8, 10- tetra-terts dibenzo [d, f] [the miscellaneous English in heptan (dioxaphosphepin) of 1.3.2] Delnavs) (Sumitomo Chemical (strain) system) Deng.

As above-mentioned sulfur antioxidant, thiodipropionate dilauryl, thio-2 acid myristyl can be enumerated The dialkyl thiodipropionate compound such as ester or thio-2 acid distearyl base ester and four [methylene (3- dodecyls are thio) Propionic acid ester group] β-alkylmercaptopropionates compound of polyalcohol such as methane etc..

＜ other compositions ＞

As needed, colored curable resin composition of the invention can include filler, other high-molecular compounds, close Close the additives known in the art such as accelerating agent, light stabilizer, chain-transferring agent.

The manufacture method ＞ of ＜ colored curable resin compositions

The colored curable resin composition of the present invention can pass through mixed colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D) and solvent (E), the levelling agent (F) used as needed, polymerization trigger auxiliary agent (D1), anti-oxidant It is prepared by agent (H) and other compositions.

Preferably, pigment when containing pigment (Ab) is mixed with part or all of solvent (E) in advance, uses pearl Grinding machine etc. makes it scattered, until the average grain diameter of pigment reaches less than 0.2 μm Zuo You.At this time, as needed, can also coordinate above-mentioned Part or all of pigment dispersing agent, resin (B).In the dispersible pigment dispersion obtained as described above, so as to regulation The mode of concentration mixes residual components, thus can prepare target coloration hardening resin composition.

On colouring agent (A), it is preferred that be dissolved in dyestuff in advance in part or all of solvent (E) so as to make Standby solution.It is preferred that filter the solution with the filter that aperture is 0.01~1 μm or so.

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

The manufacture method ＞ of ＜ colour filters

Colored pattern can be manufactured by the colored curable resin composition of the present invention.Manufacturer as the colored pattern Method, can enumerate photoetching process, ink-jet method, print process etc., preferably enumerate photoetching process.

Photoetching process is following methods：Above-mentioned colored curable resin composition is coated on substrate, be dried so as to Coloring compositions nitride layer is formed, the coloring compositions nitride layer is exposed via photomask, is then developed.In photoetching process, lead to Cross in exposure without using photomask and/or without development, so as to form the solidfied material as above-mentioned coloring compositions nitride layer Coloring film.Colored pattern, the coloring film formed as described above 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., is, for example, 0.1~30 μm, be preferably 0.1~20 μm, more preferably 0.5~6 μm.

As substrate, quartz glass, pyrex, alumina silicate glass, surface can be used through silica-coating The resin plates such as the glass plates such as soda lime glass, makrolon, polymethyl methacrylate, polyethylene terephthalate, silicon, Substrate formed with aluminium, silver, silver/copper/palldium alloy film etc. on aforesaid substrate.Other colour filters can be also formed on aforesaid substrate Device layer, resin bed, transistor, circuit etc..

The formation of each color pixel carried out using photoetching process can be carried out by known or usual device, condition.For example, It can make in the following manner.

First, colored curable resin composition is coated on substrate, by be thermally dried (prebake conditions) and/or It is dried under reduced pressure so as to which the volatile ingredients such as solvent be removed and is dried, obtains smooth coloring compositions nitride layer.

As coating method, spin-coating method, slot coated method, method for combining slot coated and spin coating etc. can be enumerated.

It is preferably 30~120 DEG C as temperature when being thermally dried, more preferably 50~110 DEG C.In addition, conduct Heating time, is preferably 10 seconds~60 minutes, more preferably 30 seconds~30 minutes.

When being dried under reduced pressure, carried out preferably under the pressure of 50~150Pa, within the temperature range of 20~25 DEG C.

The thickness of coloring compositions nitride layer is not particularly limited, and is suitably selected according to the thickness of target colour filter.

Next, coloured composition layer is exposed via the photomask for forming target coloration pattern.The light is covered Pattern on mould is not particularly limited, and the pattern suitable for intended applications can be used.

As the light source for exposure, the light source of the light of the wavelength of 250~450nm is preferably sent.For example, can will be small Blocked in the light of 350nm with the wave filter for blocking the wavelength region, or by near 436nm, near 408nm, 365nm Neighbouring light is optionally taken out with the bandpass filter (band pass filter) for taking out above-mentioned wavelength region.It is specific and Speech, as light source, can enumerate mercury lamp, light emitting diode, metal halide lamp, halogen lamp etc..

Due to can equably irradiate parallel rays to whole plane of exposure, photomask can be carried out and formed with coloring compositions The accurate contraposition of the substrate of nitride layer, therefore preferably using exposure devices such as mask aligner and steppers.

Developed by making the coloring compositions nitride layer after exposure be contacted with developer solution, so as to be formed on substrate Colored pattern.By developing, so that the unexposed portion of coloring compositions nitride layer is dissolved in developer solution and is removed.

It is preferably the alkali compounds such as potassium hydroxide, sodium acid carbonate, sodium carbonate, tetramethyl ammonium hydroxide as developer solution Aqueous solution.The concentration of above-mentioned alkali compounds in aqueous is preferably 0.01~10 mass %, more preferably 0.03~5 matter Measure %.In addition, developer solution can contain surfactant.Developing method can be sheathed submergence (puddle) method, infusion process and spray It is any in mist method etc..In addition, substrate can be tilted with any angle in development.Preferably washed after development.

Furthermore it is preferred that toasted after being carried out to obtained colored pattern.It is preferably 150~250 DEG C as rear baking temperature, More preferably 160~235 DEG C.It is preferably 1~120 minute as post-bake times, more preferably 10~60 minutes.

By the colored curable resin composition of the present invention, the colour filter of high contrast can be manufactured.The colour filter conduct Colour filter for display device (liquid crystal display device, organic el device, Electronic Paper etc.) and solid photographic device is useful.

Embodiment

Hereinafter, by embodiment, colored curable resin composition of the invention is described in more detail.

Unless otherwise specified, " % " and " part " in embodiment is quality % and mass parts.

(synthesis example 1：The synthesis of triarylmethane colouring agent (A-I-18))

Following reaction carries out under nitrogen atmosphere.Methylphenylamine is added into the flask with condenser pipe and agitating device After 15.3 parts of (Tokyo chemical conversion industry (strain) system) and 60 parts of n,N-Dimethylformamide, mixed solution is subjected to ice cooling.In ice After adding 5.7 parts of 60% sodium hydride (Tokyo chemical conversion industry (strain) system) bit by bit through 30 minutes under cooling, room is being warming up to When stirring 1 is small while warm.Add 4,4 '-difluoro benzophenone (Tokyo chemical conversion industry (strain) bit by bit into reaction solution System) 10.4 parts, and be stirred at room temperature 24 it is small when.After reaction solution is added bit by bit into 200 parts of frozen water, in being stored at room temperature 15 it is small when, water is removed by decantation, so as to obtain the sticky solid of residue form.Methanol 60 is added into the sticky solid Part after, be stirred at room temperature 15 it is small when.After the solid that leaching is separated out, purified using column chromatography.Will be purified faint yellow Solid is dried in 60 DEG C under reduced pressure, obtains the compound that 9.8 parts of formula (C-I-18) represents.

Following reaction carries out under nitrogen atmosphere.Formula (B-I-7) is added into the flask with condenser pipe and agitating device After 20 parts of 10 parts of compound and toluene that 8.2 parts of compound, the formula (C-I-18) of expression represent, 12.2 parts of phosphorus oxychloride is added, And when 95~100 DEG C of stirrings 3 are small.Next, after reaction mixture is cooled to room temperature, it is diluted for 170 parts with isopropanol. Next, the reaction solution after dilution is injected into 300 parts of saturated salt solution, 30 points of 100 parts of toluene and stirring are then added Clock.Next, stopping stirring, 30 minutes are stood, so as to be separated into organic layer and water layer.After with liquid separation operation, water layer is given up, With 300 parts of washing organic layers of saturated salt solution.After adding suitable saltcake to organic layer and stir 30 minutes, filtered and will It is dried, and obtains organic layer.The solvent in obtained organic layer is distilled off with evaporimeter, obtains bluish violet solid.Into one Step is under reduced pressure dried the bluish violet solid in 60 DEG C, obtains the compound that 18.4 parts of formula (A-II-18) represents.

Following reaction carries out under nitrogen atmosphere.Formula (A-II- is added into the flask with condenser pipe and agitating device 18) after 8 parts of the compound of expression, 396 parts of methanol, 30 minutes are stirred at room temperature so as to prepare blue solution.Next, to blueness After adding 396 parts of water in solution, further it is stirred at room temperature 30 minutes, obtains reaction solution.

53 parts of water is put into beaker, Keggin-type phosphotungstic acid (Aldrich system) is further put into the water 11.8 parts and 53 parts of methanol, are mixed in room temperature, prepare Salkowski's solution.

Obtained Salkowski's solution is added dropwise in the reaction solution prepared before when small through 1.Further it is stirred at room temperature After 30 minutes, filtered and obtain blue solid.By obtained blue solid add into 200 parts of methanol and make its scattered 1 After hour, repeat 2 filter operations.By the blue solid operated by this put into 200 parts of water and make its scattered 1 After hour, repeat 2 filter operations.The blue solid obtained through the operation is dried in 60 DEG C under reduced pressure, is obtained The triarylmethane colouring agent (A-I-18) represented to 17.1 parts of formulas (A-I-18).

(synthesis example 2：The synthesis of xanthene dye (1-38))

By 20 parts of the compound that formula (1x) represents and N- propyl group -2,6- dimethylanilines (and the pure medicine of light under the conditions of lucifuge Industrial (strain) system) 200 parts of mixing, by obtained solution when 110 DEG C of stirrings 6 are small.Obtained reaction solution is cooled to room temperature, so Add it to afterwards in the mixed liquor of 800 parts of water and 50 parts of 35 weight % hydrochloric acid, be stirred at room temperature 1 it is small when, as a result separate out Crystal.It is dried after the crystal separated out is obtained in the form of the residue of suction filtration, obtains the xanthene dye (1- of formula (1-38) expression 38)。

(synthesis example 3：The synthesis of resin B 1)

Suitable nitrogen is flowed into the flask with reflux condenser, dropping funel and mixer so as to form nitrogen Atmosphere, adds 305 parts of ethyl lactate, is heated to 70 DEG C while agitating and keeps the temperature.Next, by 46 parts of acrylic acid and propylene Sour 3,4- epoxy groups tricyclic [5.2.1.0^2.6] decyl ester (compound that the compound and formula (II-1) for representing formula (I-1) represent According to molar ratio computing with 50:50 are mixed.) 240 parts be dissolved in 185 parts of ethyl lactate and prepare solution, leaked using dropping liquid The lysate is added dropwise to insulation as in 70 DEG C of flask by bucket through 4 when small.

On the other hand, polymerization initiator 2,2 '-azo will be dissolved with 225 parts of ethyl lactate using another dropping funel The solution that 30 parts of double (2,4- methyl pentane nitriles) through 4 it is small when be added dropwise in flask.In the completion of dropwise addition of the solution of polymerization initiator Afterwards, when 70 DEG C of holdings 4 are small, it is cooled to room temperature afterwards, obtains weight average molecular weight (Mw) as 9.1 × 10³, it is dispersion degree 2.1, solid 1 solution of resin B that state component is 26 mass %, solid state component acid number is 120mg-KOH/g.Resin B 1 has following shown knots Structure unit.

(synthesis example 4：The synthesis of resin B 2)

Suitable nitrogen is flowed into the flask with reflux condenser, dropping funel and mixer so as to be replaced into nitrogen Atmosphere, adds 371 parts of propylene glycol methyl ether acetate, is heated to 85 DEG C while agitating.Next, through 4 it is small when propylene is added dropwise Acid 54 parts, acrylic acid 3,4- epoxy group tricyclics [5.2.1.0^2,6] decyl ester (compound and formula (II-1) for representing formula (I-1) The compound of expression is according to molar ratio computing with 50:50 mixing.) 225 parts, 81 parts of vinyltoluene (isomer mixture), the third two The mixed solution that 80 parts of alcohol methyl ether acetate.

On the other hand, through 5 it is small when be added dropwise 2,2- azos double (2,4- methyl pentane nitriles) be dissolved in propane diols list first for 30 parts Mixed solution obtained from 160 parts of ether acetic acid ester.After completion of dropwise addition, when mutually synthermal holding 4 is small, room is subsequently cooled to Temperature, obtains the copolymerization that Type B viscosity (23 DEG C) is 246mPas, solid state component is 37.5 mass %, solution acid number is 43mg-KOH/g Thing (resin B 2).The weight average molecular weight (Mw) of resin B 2 is 1.1 × 10⁴, dispersion degree 2.01.Resin B 2 has following structure Unit.

The weight average molecular weight (Mw) of the resin obtained in synthesis example 3,4 and the measure of number-average molecular weight (Mn) use GPC method Carried out according to the following conditions.

Device：K2479 ((strain) Shimadzu Seisakusho Ltd. system)

Column：SHIMADZU Shim-pack GPC-80M

Column temperature：40℃

Solvent：THF (tetrahydrofuran)

Flow velocity：1.0mL/min

Detector：RI

Correction standard substance：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500 (Tosoh Corporation systems)

By the ratio between the weight average molecular weight (Mw) obtained above according to polystyrene conversion meter and number-average molecular weight (Mn) (Mw/Mn) it is used as dispersion degree.

(preparation example 1：The preparation of dispersion liquid (1))

By 10 parts of the triarylmethane colouring agent (A-I-18) obtained in synthesis example 1, dispersant (BYK (registration mark)- LPN6919 (BYK Japan KK systems)) 2 parts, 4 parts of resin B 2 (being scaled solid state component) obtaining in synthesis example 4 and propane diols 84 parts of mixing of methyl ether acetate, it is using ball mill that triarylmethane colouring agent (A-I-18) is fully dispersed, thus divided Dispersion liquid (1).

(preparation example 2：The preparation of dispersion liquid (2))

By pigment (C.I. pigment blue 15s：6) 12 parts, 2 parts of acrylic acid series pigment dispersing agent and propylene glycol methyl ether acetate 80.5 parts of mixing, it is using ball mill that pigment is fully dispersed, thus obtain dispersion liquid (2).

(embodiment 1~8, comparative example 1~3)

(preparation of colored curable resin composition)

Following substances are mixed so as to obtain colored curable resin composition with the number shown in table 3, the material is：

Dispersion liquid (1) (the triarylmethane colouring agent (A-I-18) for including 10 mass %),

Xanthene dye (1-38),

Anthraquinone dye (C.I. solvent blues 45；Savinyl Blue RS；Clariant company systems),

Dispersion liquid (2),

(B) resin：Resin B 1,

(C) polymerizable compound：Dipentaerythritol acrylate (KAYARAD (registration mark) DPHA；Japanese chemical drug (strain) makes),

(D) polymerization initiator：N- benzoyloxys -1- (4- Phenylsulfanylphenyls) octane -1- ketone -2- imines (Irgacure (registration mark) OXE 01；BASF (strain) makes)

(F) levelling agent：Polyether modified silicon oil (Toray Silicone SH8400：Toray·Dow Corning Corporation systems),

(E) solvent：Ethyl lactate (EL),

(E) solvent：Propylene glycol methyl ether acetate (PGMEA).

[table 3]

The making ＞ of ＜ colored patterns

Using spin-coating method 5cm square glass substrate (EAGLE 2000；Corning Incorporated's system) on be coated with colored curable After resin combination, 3 minutes prebake conditions are carried out in 100 DEG C, so as to obtain coloring compositions nitride layer., will be formed with after placing cooling Interval between the substrate and quartz glass photomask of coloring compositions nitride layer is set to 100 μm, uses exposure machine (TME- 150RSK；TOPCON CORPORATION systems), under air atmosphere, with 150mJ/cm²Light exposure (on the basis of 365nm) Carry out light irradiation.As photomask, the light formed with 100 μm of lines Yu intermittent pattern (line-and-space pattern) is used Mask.Coloring compositions nitride layer after light is irradiated is comprising nonionic surfactants 0.12% and potassium hydroxide 0.04% In 24 DEG C of immersion developments 60 seconds in water system developer solution, after washing, toast, obtain after being carried out 30 minutes in 230 DEG C in an oven Colored pattern.

＜ film thickness measuring ＞

For obtained colored pattern, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) system)) measure Thickness.The results are shown in table 4.It should be noted that on the colored curable tree being obtained by mixing with the number shown in table 3 The colouring agent (A) contained in oil/fat composition, it is each obtained from being converted in a manner of the total amount of colouring agent (A) is 100 The content of component is shown in Table 4.

＜ chromaticity evaluations ＞

For obtained colored pattern, colorimeter (OSP-SP-200 is used；Olympus system) measure light splitting, use C light Xy chromaticity coordinates (x, y) and tristimulus values Y in the XYZ color specification systems of the characterisitic function measure CIE in source.The value of Y is bigger, represents bright Degree is higher.The results are shown in table 4.

＜ contrasts evaluate ＞

When in exposure without using photomask in addition to, carry out the same operation made from colored pattern, make coloring Film.For obtained coloring film, contrast meter (CT-1 is used；Hu Ban Electric Applicance Co., Ltd system, color evaluating BM-5A； Topcon company systems, light source；F-10, light polarizing film；Pot slope motor (strain) is made), blank value is set to 30000 and measures contrast. If the contrast for colouring film is high, it is believed that colored pattern is similarly high contrast.The results are shown in table 4.

[table 4]

According to embodiment 1~3 and the colored curable resin composition of comparative example 2, obtained chromaticity coordinate y for 0.095, Chromaticity coordinate x is colored pattern similar in 0.136~0.139 and colourity.In addition, in embodiment 1~3, than comparative example 2 Speech, has obtained the colored pattern of high brightness, and then obtained showing the coloring film of high contrast.

According to embodiment 4~8 and the colored curable resin composition of comparative example 1,3, having obtained chromaticity coordinate y is 0.095th, chromaticity coordinate x is colored pattern similar in 0.150~0.153 and colourity.In addition, in embodiment 4~8, than comparing For example 1,3, the colored pattern of high brightness has been obtained, and then has obtained showing the coloring film of high contrast.

From the foregoing, it can be understood that by the colored curable resin composition of the present invention, the colored pattern of high contrast can be made. The display characteristic of colour filter that is obtained by the colored curable resin composition of the present invention is excellent, material as liquid crystal display device Material is useful.

Claims (5)

1. colored curable resin composition, which contain toner, resin, polymerizable compound and polymerization initiator,

The colouring agent includes triarylmethane colouring agent, xanthene dye and anthraquinone dye.

2. colored curable resin composition as claimed in claim 1, wherein, the content of the anthraquinone dye is relative to described It is 0.5~50 mass parts for 100 mass parts of triarylmethane colouring agent.

3. colored curable resin composition as claimed in claim 2, wherein, the content of the anthraquinone dye is relative to described It is 1.0~13.5 mass parts for 100 mass parts of triarylmethane colouring agent.

4. colour filter, it is formed by colored curable resin composition according to any one of claims 1 to 3.

5. display device, it includes the colour filter described in claim 4.