CN107918246A - Colored curable resin composition - Google Patents
Colored curable resin composition Download PDFInfo
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- CN107918246A CN107918246A CN201710920192.1A CN201710920192A CN107918246A CN 107918246 A CN107918246 A CN 107918246A CN 201710920192 A CN201710920192 A CN 201710920192A CN 107918246 A CN107918246 A CN 107918246A
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0038—Mixtures of anthraquinones
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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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
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), YaRepresent the fluorinated alkanes hydrocarbon diyl of carbon number 1~4.]
[in formula (9), YbRepresent 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), RaAnd RbRepresent the alkyl of hydrogen atom or carbon number 1~4, contain in the alkyl
Hydrogen atom can be optionally substituted by a hydroxyl group.XaAnd XbRepresent singly-bound ,-Rc-, *-Rc- O-, *-Rc- S- or *-Rc-NH-。RcRepresent 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 RaAnd Rb, 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 XaAnd Xb, 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 [5.2.1.02,6] 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 [5.2.1.02,6] 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 [5.2.1.02,6] 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 [5.2.1.02.6] 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 [5.2.1.02.6] last of the ten Heavenly stems
Base ester/(methyl) acrylic acid/N- N-cyclohexylmaleimides copolymer, (methyl) acrylic acid 3,4- epoxy group tricyclics
[5.2.1.02.6] 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 [5.2.1.02.6] 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 [5.2.1.02,6] 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.
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JP2013144724A (en) * | 2012-01-13 | 2013-07-25 | Sumitomo Chemical Co Ltd | Colored curable resin composition |
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WO2015141536A1 (en) * | 2014-03-18 | 2015-09-24 | 富士フイルム株式会社 | Colored curable resin composition, cured film, color filter, method for producing color filter, solid-state image sensor, image display device, compound, and cation |
CN105573055A (en) * | 2014-10-30 | 2016-05-11 | 住友化学株式会社 | Colored curable resin composition |
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CN102914942A (en) * | 2011-08-05 | 2013-02-06 | 住友化学株式会社 | Colored curable resin composition |
JP2013144724A (en) * | 2012-01-13 | 2013-07-25 | Sumitomo Chemical Co Ltd | Colored curable resin composition |
CN104516200A (en) * | 2013-10-07 | 2015-04-15 | 住友化学株式会社 | Colored curable resin composition |
WO2015141536A1 (en) * | 2014-03-18 | 2015-09-24 | 富士フイルム株式会社 | Colored curable resin composition, cured film, color filter, method for producing color filter, solid-state image sensor, image display device, compound, and cation |
CN105573055A (en) * | 2014-10-30 | 2016-05-11 | 住友化学株式会社 | Colored curable resin composition |
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KR102509937B1 (en) | 2023-03-15 |
JP2018059097A (en) | 2018-04-12 |
KR20180038387A (en) | 2018-04-16 |
JP6957298B2 (en) | 2021-11-02 |
CN107918246B (en) | 2022-02-25 |
TW201823374A (en) | 2018-07-01 |
TWI770067B (en) | 2022-07-11 |
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