CN104861691A - Dye and colored curable resin composition - Google Patents

Dye and colored curable resin composition Download PDF

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Publication number
CN104861691A
CN104861691A CN201510085192.5A CN201510085192A CN104861691A CN 104861691 A CN104861691 A CN 104861691A CN 201510085192 A CN201510085192 A CN 201510085192A CN 104861691 A CN104861691 A CN 104861691A
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carbonatoms
group
formula
methyl
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CN104861691B (en
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芦田彻
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Sumitomo Chemical Co Ltd
Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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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
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/007—Squaraine dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • 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
    • 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
    • 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
    • G03F7/09—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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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Filters (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a dye and a colored curable resin composition. The dye comprises a group containing silicon atoms, and comprises a squarylium skeleton.

Description

Dye well colored curable resin composition
Technical field
The present invention relates to dye well colored curable resin composition.
Background technology
Squaraine dye (ス Network ア リ リ ウ system dyestuff) is used in the fields such as picture photosensitive body.
In Japanese Laid-Open Patent Publication 60-248652 publication, as squaraine dye, recite the compound represented by formula (II-0).
Summary of the invention
The present invention includes following invention.
[1] dyestuff, it has group containing Siliciumatom and the sour skeleton in the side of having.
[2] dyestuff Gen Ju [1], the group containing Siliciumatom is for containing-Si (R 14) 3group,
Wherein, R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4,3 R 14can distinguish identical also can be different.
[3] according to [1] or the dyestuff described in [2], wherein, the group of the group containing Siliciumatom represented by formula (iia),
*-L 1-Si(R 14) 3(iia)
In formula (iia), R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4,3 R 14can distinguish identical also can be different,
L 1represent the alkylidene group of carbonatoms 1 ~ 8 ,-the CH comprised in this alkylidene group 2-can be replaced by Sauerstoffatom,
* bonding end is represented.
[4] according to dyestuff according to any one of [1] ~ [3], its compound represented by formula (IIa),
In formula (II), R 1, R 2, R 111and R 112separately represent that hydrogen atom, halogen atom, hydroxyl maybe can have the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20, Sauerstoffatom or sulphur atom can be inserted between the carbon atom forming this saturated hydrocarbyl,
R 3, R 4, R 113and R 114separately represent hydrogen atom or hydroxyl,
R 5, R 6, R 15and R 16separately represent: hydrogen atom; Group containing Siliciumatom; The saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 can be had, Sauerstoffatom or sulphur atom can be inserted between the carbon atom forming this saturated hydrocarbyl; Maybe can have substituent phenyl, wherein, R 5, R 6, R 15and R 16in at least 1 be group containing Siliciumatom.
[5] dyestuff Gen Ju [4], wherein, the group of the group containing Siliciumatom represented by formula (iia),
*-L 1-Si(R 14) 3(iia)
In formula (iia), R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4,3 R 14can distinguish identical also can be different,
L 1represent the alkylidene group of carbonatoms 1 ~ 8 ,-the CH comprised in this alkylidene group 2-can be replaced by Sauerstoffatom,
* bonding end is represented.
[6] according to [4] or the dyestuff according to any one of [5], wherein, the group of substituent phenyl represented by formula (i) can be had,
In formula (i), R 12represent hydrogen atom, the saturated hydrocarbyl of 1 valency of carbonatoms 1 ~ 20 or the undersaturated alkyl of 1 valency of carbonatoms 2 ~ 20, m represents the integer of 1 ~ 5, when m is more than 2, and multiple R 12can distinguish identical also can be different, * represents the bonding end with nitrogen-atoms.
[7] according to dyestuff according to any one of [1] ~ [6], its compound represented by formula (II),
In formula (II), R 1aand R 2aseparately represent that hydrogen atom, halogen atom, hydroxyl maybe can have the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20, Sauerstoffatom or sulphur atom can be inserted between the carbon atom forming this saturated hydrocarbyl,
R 3aand R 4aseparately represent hydrogen atom or hydroxyl,
R 5aand R a6in a group represented by formula (ii), another is hydrogen atom, can has the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20, can insert Sauerstoffatom or sulphur atom between the carbon atom forming saturated hydrocarbyl; Or the group represented by formula (i),
In formula (i), R 12represent hydrogen atom, the saturated hydrocarbyl of 1 valency of carbonatoms 1 ~ 20 or the undersaturated alkyl of 1 valency of carbonatoms 2 ~ 20, m represents the integer of 1 ~ 5, when m is more than 2, and multiple R 12can distinguish identical also can be different, * represents the bonding end with nitrogen-atoms,
In formula (ii), n represents the integer of 1 ~ 8, R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4, * represents the bonding end with nitrogen-atoms, 3 R 14can distinguish identical also can be different.
[8] tinting material, it contains [1] ~ [7] according to any one of dyestuff.
[9] tinting material Gen Ju [8], it is also containing yellow ultramarine.
[10] tinting material Gen Ju [9], wherein, yellow ultramarine is be selected from least a kind of pigment in C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 185.
[11] colored curable resin composition, it contains [8] ~ [10] according to any one of tinting material, resin, polymerizable compound and polymerization starter.
[12] film, it is formed by the colored curable resin composition described in [11].
[13] colour filter, it is formed by the photosensitive composition described in [11].
[14] display unit, the colour filter that it contains described in [13].
Dyestuff of the present invention is excellent to the solvability of organic solvent, and the colour filter formed by the colored curable resin composition containing this dyestuff is excellent in thermotolerance.
Embodiment
The present invention has group containing Siliciumatom and the dyestuff of the sour skeleton in the side of having.
As the group containing Siliciumatom, the substituting group that trialkylsilanyloxy, trialkoxysilyl etc. have silicon alkoxyl group can be enumerated.
As trialkylsilanyloxy, the trialkylsilanyloxy that trimethyl silicane alcoxyl base, triethyl silicane oxygen base etc. have the alkyl of carbonatoms 1 ~ 8 (preferably 1 ~ 4) can be enumerated.
As trialkoxysilyl, the trialkoxysilyl that trimethoxysilyl, triethoxysilyl etc. have the alkoxyl group of carbonatoms 1 ~ 8 (preferably 1 ~ 4) can be enumerated.
As the group with silicon alkoxyl group, also can enumerate the group of ester ring type hydrocarbon and the silicon alkoxyl group with carbonatoms 3 ~ 10, described later have in the saturated hydrocarbyl of carbonatoms 1 ~ 20, insert Sauerstoffatom, the group of sulphur atom and the group of silicon alkoxyl group, these groups can also have halogen atom, alkylamino and dialkyl amido (following, to be referred to as by these substituted-aminos " (two) alkylamino ") etc.
In dyestuff of the present invention, the group containing Siliciumatom is preferably containing-Si (R 14) 3group, be more preferably formula (iia):
*-L 1-Si(R 144) 3(iia)
Represented group.
-Si (R 14) 3in, R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4.3 R 14can distinguish identical also can be different.
As R 14represented alkyl, can enumerate methyl, ethyl, propyl group, butyl.
As R 14represented alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-, butoxy.
R 14be preferably the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4, be more preferably hydrogen atom, methyl, ethyl, propyl group, methoxyl group, oxyethyl group or propoxy-, more preferably hydrogen atom, methyl, ethyl, methoxy or ethoxy.
Preferably 3 R 14identical.
In formula (iia), R 144represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4.
L 1represent the alkylidene group of carbonatoms 1 ~ 8.-the CH comprised in this alkylidene group 2-can be replaced by Sauerstoffatom.* the bonding end with nitrogen-atoms is represented.
As R 144represented alkyl, can enumerate methyl, ethyl, propyl group, butyl.
As R 144represented alkoxyl group, can enumerate methoxyl group, oxyethyl group, propoxy-, butoxy.
R 144preferred hydrogen atom, methyl, ethyl, propyl group, methoxyl group, oxyethyl group or propoxy-, be more preferably hydrogen atom, methyl, ethyl, methoxy or ethoxy.Preferably 3 R 144identical.
As L 1represented alkylidene group, can enumerate methylene radical, ethylidene, propane-1,3-bis-base, propane-1,2-bis-base, butane-Isosorbide-5-Nitrae-two base, butane-1,3-bis-base, pentane-1,5-bis-base, hexane-1,6-bis-base, heptane-1,7-bis-base, octane-1,8-bis-base etc.
L 1be preferably the alkylidene group of carbonatoms 1 ~ 4.
As the group represented by formula (iia), such as following shown group can be enumerated.Wherein, the group represented by group ~ formula (ii-6) represented by preferred formula (ii-1).
(* represents the bonding end with nitrogen-atoms or carbon atom.)
As dyestuff of the present invention, the silicon alkoxyl groups such as such as there is trimethyl silicane alcoxyl base, triethyl silicane oxygen base, trimethoxysilyl, triethoxysilyl can be enumerated and the dyestuff of the sour skeleton in the side of having.
As dyestuff of the present invention, the compound be preferably represented by formula (IIa) (below, is also recited as compound (IIa) sometimes.), the compound (following, to be sometimes also recited as compound (II)) more preferably represented by formula (II).Compound (IIa) and compound (II) also comprise its tautomer respectively.
[in formula (II), R 1, R 2, R 111and R 112separately represent that hydrogen atom, halogen atom, hydroxyl maybe can have the saturated hydrocarbyl (can insert Sauerstoffatom or sulphur atom between the carbon atom forming this saturated hydrocarbyl) of 1 valency of substituent carbonatoms 1 ~ 20.
R 3, R 4, R 113and R 114separately represent hydrogen atom or hydroxyl.
R 5, R 6, R 15and R 16separately represent hydrogen atom, group containing Siliciumatom, (can insert Sauerstoffatom or sulphur atom between the carbon atom forming this saturated hydrocarbyl) maybe can have substituent phenyl can to have the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20.Wherein, R 5, R 6, R 15and R 16in at least 1 be group containing Siliciumatom.]
[in formula (II), R 1aand R 2aseparately represent that hydrogen atom, halogen atom, hydroxyl maybe can have the saturated hydrocarbyl (can insert Sauerstoffatom or sulphur atom between the carbon atom forming this saturated hydrocarbyl) of 1 valency of substituent carbonatoms 1 ~ 20.
R 3aand R 4aseparately represent hydrogen atom or hydroxyl.
R 5aand R 6ain a group represented by formula (ii), another is hydrogen atom, can has the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 (can insert Sauerstoffatom or sulphur atom between the carbon atom forming saturated hydrocarbyl) or the group represented by formula (i).
(in formula (i), R 12represent hydrogen atom, the saturated hydrocarbyl of 1 valency of carbonatoms 1 ~ 20 or the undersaturated alkyl of 1 valency of carbonatoms 2 ~ 20, m represents the integer of 1 ~ 5.When m is more than 2, multiple R 12can distinguish identical also can be different.* the bonding end with nitrogen-atoms is represented.)
(n, R 14and * is identical with above-mentioned definition.)]
In this specification sheets, representative ring is with the positive charge of divalent.
As the halogen atom in formula (IIa) and formula (II), fluorine atom, chlorine atom, bromine atoms and atomic iodine can be enumerated.
As the saturated hydrocarbyl of 1 valency in formula (IIa) and formula (II),
Can enumerate: the straight-chain alkyl of the carbonatomss 1 ~ 20 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, hexadecyl and eicosyl;
The branched-chain alkyl of the carbonatomss 3 ~ 20 such as sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, isopentyl, neo-pentyl and 2-ethylhexyl;
The ester ring type saturated hydrocarbyl of the carbonatomss 3 ~ 20 such as cyclopropyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group and three ring decyls.
As the substituting group that the saturated hydrocarbyl of 1 valency in formula (IIa) and formula (II) has, (two) alkylamino of halogen atom, hydroxyl and carbonatoms 1 ~ 8 can be enumerated.
As this halogen atom, fluorine atom, chlorine atom, bromine atoms and atomic iodine can be enumerated.
As this (two) alkylamino, methylamino, ethylamino, n-propyl amino, n-butylamino, n-pentyl amino, dimethylamino, diethylamino, dipropylamino, ethylmethylamino etc. can be enumerated.
As having substituent above-mentioned saturated hydrocarbyl, the group such as represented by following formula can be enumerated.
(* represents bonding end.)
In formula (IIa) and formula (II), as the group inserting aerobic atom or sulphur atom between the carbon atom of saturated hydrocarbyl forming above-mentioned 1 valency, the group such as represented by following formula can be enumerated.
(* represents bonding end.)
R 1, R 2, R 1a, R 2a, R 111and R 112separately be preferably the alkyl of hydrogen atom, hydroxyl and carbonatoms 1 ~ 4, more preferably hydrogen atom, hydroxyl and methyl, more preferably hydrogen atom.
In compound (IIa), R 5, R 6, R 15and R 16in at least 1 represent containing the group of Siliciumatom.R 5, R 6, R 15and R 16in at least 1 be preferably group represented by formula (iia),
R 5and R 6in at least 1 group represented by formula (iia), R 15and R 16in at least 1 be preferably group represented by formula (iia).
In compound (IIa), the group containing Siliciumatom is preferably the group represented by formula (iia), is more preferably the group represented by formula (ii).
In compound (IIa), substituent phenyl can be had and be preferably group represented by formula (i).
Compound (IIa) is more preferably: the group of the group containing Siliciumatom represented by formula (iia) and can have the compound (following, to be sometimes called by this compound " compound (IIb) ") of the formula (IIa) of the group of substituent phenyl represented by formula (i).
In compound (II), preferred R 5aand R 6ain a group represented by formula (iia), another is hydrogen atom, can has the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 (can insert Sauerstoffatom or sulphur atom between the carbon atom forming saturated hydrocarbyl) or the group represented by formula (i)
More preferably R 5aand R 6ain a group represented by formula (ii), another is hydrogen atom, can have the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 (can insert Sauerstoffatom or sulphur atom between the carbon atom forming saturated hydrocarbyl) or the group represented by formula (i).
R 5, R 6, R 5a, R 6a, R 15and R 16in, as the substituting group that phenyl can have, the unsaturated alkyl of the saturated hydrocarbyl of 1 valency of carbonatoms 1 ~ 20,1 valency of carbonatoms 2 ~ 20 can be enumerated.
As the saturated hydrocarbyl of 1 valency in this substituting group, the alkyl of the carbonatomss 1 ~ 20 such as preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.
As the unsaturated alkyl of 1 valency in this substituting group, the thiazolinyl of the carbonatomss 2 ~ 20 such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base can be enumerated.
In formula (i), as R 12the unsaturated alkyl of 1 represented valency, can enumerate the thiazolinyl of the carbonatomss 2 ~ 20 such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene base, decene base.
As R 12the saturated hydrocarbyl of 1 represented valency, the alkyl of the carbonatomss 1 ~ 20 such as preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl.
R 12be preferably the alkyl of hydrogen atom or carbonatoms 1 ~ 4, be more preferably hydrogen atom, methyl or ethyl.
As the group represented by formula (i), group below can be enumerated.
(* represents the bonding end with nitrogen-atoms.)
In formula (II), n is preferably the integer of 1 ~ 6, is more preferably the integer of 1 ~ 4.
R 5, R 6, R 5aand R 6aduring the group of represented group respectively beyond expression (iia), group represented by formula (ii), be preferably hydrogen atom, the saturated hydrocarbyl of carbonatoms 1 ~ 20, the group represented by formula (i), be more preferably hydrogen atom.
As following formula
(R 5and R 6represent the meaning same as described above respectively, * represents the bonding end with carbon atom)
Represented group,
(R 5aand R 6arepresent the meaning same as described above respectively, * represents the bonding end with carbon atom) represented by group, group etc. below can be enumerated.
As the group had containing Siliciumatom and the dyestuff of the sour skeleton in the side of having, can the compound represented by compound ~ (AII-75) represented by enumerative (AII-1).
In the present invention, easily obtaining in raw material, the compound represented by compound ~ formula (AII-6) more preferably represented by formula (AII-4) and the compound represented by compound ~ formula (AII-33) represented by formula (AII-31).
Compound (II) can be manufactured by the method for the method recorded based on Japanese Unexamined Patent Publication 2002-363434 publication, specifically, can by making the compound represented by formula (IV-1) and square acid (3,4-dihydroxyl-3-cyclobutene-1,2 diketone) reaction manufacture compound (II).
(in formula, R 1a~ R 6arepresent the meaning same as described above respectively.)
The usage quantity of side's acid is preferably more than 0.5 mole and less than 0.8 mole relative to the compound 1 mole represented by formula (IV-1), is more preferably more than 0.55 mole and less than 0.6 mole.
Temperature of reaction is preferably 30 DEG C ~ 180 DEG C, is more preferably 80 DEG C ~ 140 DEG C.Reaction times is preferably 1 hour ~ 12 hours, is more preferably 3 hours ~ 8 hours.
From the viewpoint of yield, preferably react in organic solvent.As organic solvent, the hydrocarbon solvent such as toluene, dimethylbenzene can be enumerated; The halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, chloroform; The alcoholic solvents such as methyl alcohol, ethanol, Virahol, butanols; The nitro-hydrocarbon solvents such as oil of mirbane; The ketone solvents such as methyl iso-butyl ketone (MIBK); The amide solvents such as 1-Methyl-2-Pyrrolidone; Deng, also can be used in combination by them.The wherein mixed solvent of preferred butanols and toluene.The usage quantity of organic solvent is preferably more than 30 mass parts relative to compound 1 mass parts represented by formula (IV-1) and below 200 mass parts, is more preferably more than 50 mass parts and below 150 mass parts.
The method obtained as the compound (II) of target compound from reaction mixture is not particularly limited, and can adopt known various method.After can enumerating such as cooling, filtration obtains the method for the crystallization of precipitation.Preferably with water etc. wash, the then crystallization that obtains of dry filter.In addition as required, can be refined further by known methods such as recrystallizations.
< tinting material >
Tinting material of the present invention contains: have the group containing Siliciumatom and the dyestuff of the sour skeleton in the side of having (following, to be called by this tinting material " tinting material (A) ").
Tinting material (A), except dyestuff of the present invention, in order to mix colours, namely in order to adjust dichroism, can also contain other dyestuffs (A2), pigment (P) or their mixture.
As dyestuff (A2), the dyestuffs such as oil-soluble colourant, matching stain, the amine salt of matching stain or the sulfone amide derivative of matching stain can be enumerated, the compound being such as classified as dyestuff in color index (カ ラ ー イ Application デ ッ Network ス) (The Society of Dyers and Colourists publishes), the known dyestuff recorded in dyeing notes (Se Ran society) can be enumerated.In addition, according to chemical structure, coumarine dye can be enumerated, containing golden azoic dyestuff, pyridone azo dyes, barbituric acid azoic dyestuff, quinophthalone dyestuff, methine dyestuff, cyanine dye, anthraquinone dye, triphenhlmethane dye, xanthene dye and phthalocyanine pigment etc.These dyestuffs can be used alone also that two or more kinds may be used.
Specifically, (following, the record of omission C.I. solvent yellow, only records numbering can to enumerate C.I. solvent yellow 4.)、14、15、23、24、38、62、63、68、82、94、98、99、162；
C.I. solvent orange 2,7,11,15,26,56; Deng C.I. solvent dye,
C.I. turmeric 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. von Muller's indicator 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169,173; Deng C.I. matching stain,
C.I. direct 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. direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107; In C.I. substantive dyestuff,
C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;
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; Deng C.I. mordanting dye etc.
As dyestuff (A2), preferred coumarine dye, containing yellow dyess such as golden azoic dyestuff, pyridone azo dyes, barbituric acid azoic dyestuff, quinophthalone dyestuff, methine dyestuff, cyanine dyes.
The content of dyestuff of the present invention is generally 3 ~ 99.9 quality % relative to the total amount of tinting material, is preferably 4 ~ 50 quality %, is more preferably 5 ~ 30 quality %.If the content of dyestuff of the present invention is in above-mentioned scope, then brightness when making colour filter is high, thus preferably.
As pigment (P), be not particularly limited and can use known pigment, the pigment being such as classified as pigment in color index (The Society of Dyers and Colourists publishes) can be enumerated.
As pigment (P), the yellow ultramarines such as C.I. Pigment Yellow 73 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214 can be enumerated;
C.I. pigment Orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigmentss such as 73;
C.I. pigment Green 7,36, the veridians such as 58.
As pigment (P), the yellow ultramarines such as preferred C.I. Pigment Yellow 73 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214; And
C.I. pigment Green 7,36, the veridians such as 58,
More preferably C.I. pigment yellow 13 8,150,185 and C.I. pigment green 36,58, further preferred C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 185.By containing above-mentioned pigment, the optimizing of transmitted spectrum is easy, and the photostabilization of colour filter and chemical-resistant become good.
< colored curable resin composition >
Colored curable resin composition of the present invention contains tinting material (A), resin (B), polymerizable compound (C) and polymerization starter (D).Solvent (E) can also be contained.
In this manual, if illustrative compound does not have special stipulation as each composition, just can use separately or by multiple combination.
In colored curable resin composition of the present invention, the content of tinting material (A) is preferably 5 ~ 60 quality % relative to the total amount of solids component, is more preferably 8 ~ 55 quality %, more preferably 10 ~ 50 quality %.If the content of tinting material (A) is in above-mentioned scope, colour density when then making colour filter is abundant, and resin (B), the polymerizable compound (C) containing necessary amount in composition can be made, therefore can form the sufficient pattern of physical strength.Herein, in this specification sheets, " total amount of solids component " refers to from the total amount of colored curable resin composition except the amount after the content of desolventizing.The total amount of solids component and can being measured by known analytical procedure such as such as liquid phase chromatography or vapor-phase chromatography etc. with the content relative to its each composition.
< resin (B) >
Resin (B), although be not particularly limited, is preferably alkali soluble resin.As resin (B), following resin [K1] ~ [K6] etc. can be enumerated.
Resin [K1]; Be selected from least a kind (Ba) (hereinafter sometimes referred to " (Ba) ") in unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and there is the multipolymer of the cyclic ether structure of carbonatoms 2 ~ 4 and the monomer (Bb) (hereinafter sometimes referred to " (Bb) ") of ethylenic unsaturated bond;
Resin [K2]; (Ba), (Bb) and can from the multipolymer of the monomer of (Ba) copolymerization (Bc) (but different with (Ba) and (Bb)) (hereinafter sometimes referred to " (Bc) ");
Resin [K3]; (Ba) with the multipolymer of (Bc);
Resin [K4]; Make the copolymer reaction of (Bb) and (Ba) and (Bc) and the resin that obtains;
Resin [K5]; Make the copolymer reaction of (Ba) and (Bb) and (Bc) and the resin that obtains;
Resin [K6]; Make the copolymer reaction of (Ba) and (Bb) and (Bc), then the resin reacting with carboxylic acid anhydride and obtain.
As (Ba), the such as unsaturated monocarboxylic acid such as vinylformic acid, methacrylic acid, β-crotonic acid, o-, m-, p-vinyl benzoic acid can be enumerated;
Toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-tetrahydrobenzene dioctyl phthalate;
Methyl-5-norbornylene-2, the carboxylic dicyclo unsaturated compound such as 3-dioctyl phthalate, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene";
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-Tetra Hydro Phthalic Anhydride, 1,2, the unsaturated dicarboxylic acid acid anhydrides such as 3,6-Tetra Hydro Phthalic Anhydride, dimethyl tetrahydro Tetra hydro Phthalic anhydride, 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" acid anhydrides;
Unsaturated list [(methyl) acryloxyalkyl] ester of the polycarboxylic acid of mono succinate [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc. more than 2 yuan;
The unsaturated acrylate etc. of hydroxyl and carboxyl is contained in same a part as α-(hydroxymethyl) vinylformic acid.
In them, from viewpoint, the deliquescent viewpoint of gained resin in alkali aqueous solution of copolyreaction, preferred vinylformic acid, methacrylic acid, maleic anhydride etc.
(Bb) polymerizable compound of cyclic ether structure (such as, being selected from least a kind in oxyethane ring, trimethylene oxide ring and tetrahydrofuran (THF) ring) and the ethylenic unsaturated bond with carbonatoms 2 ~ 4 is referred to.
(Bb) preferably there is the cyclic ether of carbonatoms 2 ~ 4 and the monomer of (methyl) acryloxy.
In this specification sheets, " (methyl) vinylformic acid " represents at least a kind that is selected from vinylformic acid and methacrylic acid.The statement such as " (methyl) acryl " and " (methyl) acrylate " also has same implication.
As (Bb), the monomer with Oxyranyle and ethylenic unsaturated bond, the monomer with propylene oxide base and ethylenic unsaturated bond can be enumerated, there is the monomer etc. of tetrahydrofuran base and ethylenic unsaturated bond.
As (Bb), can improve further the colour filter obtained thermotolerance, chemical-resistant etc. reliability in, preferably there is the monomer of Oxyranyle and ethylenic unsaturated bond.
As (Bc), can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-methyl cyclohexyl, (methyl) vinylformic acid three ring [5.2.1.0 2,6] decane-8-base ester (in the art, as popular name, is called " (methyl) vinylformic acid Bicvclopentyl ester ".In addition, be sometimes referred to as " (methyl) vinylformic acid three ring decyl ester "), (methyl) vinylformic acid three ring [5.2.1.0 2,6] decene-8-base ester (in the art, as popular name, be called " (methyl) vinylformic acid double cyclopentenyl ester "), (methyl) acrylate such as (methyl) vinylformic acid dicyclo pentyloxy ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid adamantane esters, (methyl) allyl acrylate, (methyl) vinylformic acid propargyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid naphthalene ester, (methyl) benzyl acrylate;
(methyl) acrylate of the hydroxyls such as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester;
The dicarboxylic diesters such as ethyl maleate, DEF, diethyl itaconate;
Dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-methoxyl group dicyclo [2.2.1] hept-2-ene", 5-oxyethyl group dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxyl dicyclo [2.2.1] hept-2-ene", 5,6-bis-(hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-bis-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen base carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5,6-bis-(tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene", the dicyclo unsaturated compounds such as 5,6-bis-(cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene",
The dicarbonyl imides derivatives such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridyl) maleimide;
Vinylbenzene, alpha-methyl styrene, a vinyl toluene, p-methylstyrene, Vinyl toluene, to methoxy styrene, vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylamide, Methacrylamide, vinyl-acetic ester, 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene etc.
In them, from the view point of copolyreaction and thermotolerance, optimization styrene, Vinyl toluene, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, dicyclo [2.2.1] hept-2-ene" etc.
As resin (B), 3,4-epoxycyclohexyl-methyl (methyl) acrylate/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 can be enumerated 2.6] resin [K1] such as decyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/vinylbenzene/(methyl) acrylic copolymer, 3,4-epoxy three ring [5.2.1.0 2.6] resin [K2] such as decyl acrylate/(methyl) vinylformic acid/N-N-cyclohexylmaleimide multipolymer, 3-methyl-3-(methyl) acryloyloxymethyl trimethylene oxide/(methyl) vinylformic acid/styrol copolymer, the resins [K3] such as (methyl) benzyl acrylate/(methyl) acrylic copolymer, vinylbenzene/(methyl) acrylic copolymer, make (methyl) glycidyl acrylate and (methyl) benzyl acrylate/(methyl) acrylic copolymer addition and the resin that obtains, make (methyl) glycidyl acrylate and ester/vinylbenzene in the last of the ten Heavenly stems/(methyl) the acrylic copolymer addition of (methyl) vinylformic acid three ring and the resin that obtains, make (methyl) glycidyl acrylate and ester in the last of the ten Heavenly stems/(methyl) benzyl acrylate/(methyl) the acrylic copolymer addition of (methyl) vinylformic acid three ring and the resins [K4] such as the resin that obtains, make the resin of the copolymer reaction of (methyl) vinylformic acid and (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, make the resins [K5] such as the resin of the copolymer reaction of (methyl) vinylformic acid and (methyl) vinylformic acid three ring ester/vinylbenzene in the last of the ten Heavenly stems/(methyl) glycidyl acrylate, the resins [K6] etc. such as the resin that (methyl) vinylformic acid is reacted with Tetra Hydro Phthalic Anhydride further with the resin of the copolymer reaction of (methyl) vinylformic acid three ring ester in the last of the ten Heavenly stems/(methyl) glycidyl acrylate.
Wherein, as resin (B), preferred resin [K1] and resin [K2].
Can by reference to the method such as recorded in document " laboratory method of Polymer Synthesizing " (the grand row in large Tianjin work sale room (strain) chemistry is with people's the 1st edition the 1st printing distribution on March 1st, 1972) and the citing document recorded in the publication to manufacture resin [K1].
The multipolymer obtained can directly use reacted solution, also can use the solution after concentrated or dilution, can also use the material taken out with the form of solid (powder) by methods such as redeposition.Particularly by using the solvent comprised in colored curable resin composition of the present invention as solvent when this polymerization, reacted solution directly can be used in the preparation of colored curable resin composition of the present invention, therefore can simplify the manufacturing process of colored curable resin composition of the present invention.
The weight-average molecular weight of the polystyrene conversion of resin (B) is preferably 3,000 ~ 100,000, is more preferably 5,000 ~ 50,000, and more preferably 5,000 ~ 30,000.If molecular weight is in above-mentioned scope, then the hardness that there is colour filter improves, and residual film ratio is also high, unexposed portion to the favorable solubility of developing solution, the tendency that the resolving power of colored pattern improves.
The molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) is preferably 1.1 ~ 6, is more preferably 1.2 ~ 4.
The acid number of resin (B) is preferably 50 ~ 170mg-KOH/g, is more preferably 60 ~ 150mg-KOH/g, more preferably 70 ~ 135mg-KOH/g.Herein acid number be as in order in and the amount (mg) of potassium hydroxide needed for resin (B) 1g and the value that measures, such as can carry out titration to obtain by use potassium hydroxide aqueous solution.
The content of resin (B) is preferably 7 ~ 65 quality % relative to the total amount of solids component, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.If the content of resin (B) is in above-mentioned scope, then there is the tendency of resolving power and the residual film ratio raising that can form colored pattern, in addition colored pattern.
< polymerizable compound (C) >
The compound that polymerizable compound (C) is living radical by being produced by polymerization starter (D) and/or acid and can be polymerized, the compound etc. of the ethylenic unsaturated bond such as with polymerizability can be enumerated, be preferably (methyl) acrylic compound.
Wherein, polymerizable compound (C) preferably has the polymerizable compound of more than 3 ethylenic unsaturated bonds.As such polymerizable compound, such as trimethylolpropane tris (methyl) acrylate can be enumerated, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2-(methyl) acrylyl oxy-ethyl) isocyanuric acid ester, glycol-modified tetramethylolmethane four (methyl) acrylate, glycol-modified Dipentaerythritol six (methyl) acrylate, propylene glycol modified tetramethylolmethane four (methyl) acrylate, propylene glycol modified Dipentaerythritol six (methyl) acrylate, caprolactone modification tetramethylolmethane four (methyl) acrylate, caprolactone modification Dipentaerythritol six (methyl) acrylate etc.
Wherein, preferred Dipentaerythritol five (methyl) acrylate and Dipentaerythritol six (methyl) acrylate.
The weight-average molecular weight of polymerizable compound (C) is preferably 150 ~ 2,900, is more preferably 250 ~ 1,500.
The content of polymerizable compound (C) is preferably 7 ~ 65 quality % relative to the total amount of solids component, is more preferably 13 ~ 60 quality %, more preferably 17 ~ 55 quality %.If the content of polymerizable compound (C) is in above-mentioned scope, then also exist colored pattern formed time residual film ratio and colour filter chemical-resistant improve tendency.
< polymerization starter (D) >
Polymerization starter (D), as long as just can be not particularly limited by the compound of the dissociation produces active free radical, acid etc. of light, heat also initiated polymerization, can use known polymerization starter.As the polymerization starter producing living radical, such as O-acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and united imidazole can be enumerated.
As O-acyl group oxime compound, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) butane-1-ketone-2-imines can be enumerated, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl)-3-cyclopentyl propane-1-ketone-2-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-{2-methyl-4-(3, 3-dimethyl-2, 4-dioxolyl methyl oxygen base) benzoyl }-9H-carbazole-3-base] ethane-1-imines, N-acetoxyl group-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-imines, N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopentyl propane-1-ketone-2-imines etc.The commercially available product such as irgacure (registered trademark) OXE01, OXE02 (more than, BASF AG's system), N-1919 (ADEKA Inc.) can be used.Wherein, O-acyl group oxime compound is preferably selected from least a kind in N-benzoyloxy-1-(4-Phenylsulfanylphenyl) butane-1-ketone-2-imines, N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines and N-benzoyloxy-1-(4-Phenylsulfanylphenyl)-3-cyclopentyl propane-1-ketone-2-imines, is more preferably N-benzoyloxy-1-(4-Phenylsulfanylphenyl) octane-1-ketone-2-imines.If these O-acyl group oxime compounds, be then in the tendency of the colour filter that can obtain high brightness.
As abovementioned alkyl benzophenone compound, 2-methyl-2-morpholino-1-(4-methylthio group phenyl) propane-1-ketone can be enumerated, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl] butane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl propane-1-ketone, 1-hydroxycyclohexylphenylketone, the oligopolymer of 2-hydroxy-2-methyl-1-(4-pseudoallyl phenyl) propane-1-ketone, α, α-diethoxy acetophenone, benzil dimethyl ketal etc.The commercially available products such as irgacure (registered trademark) 369,907,379 (more than, BASF AG's system) can be used.
As above-mentioned triaizine compounds, can 2 be enumerated, two (the trichloromethyl)-6-(4-p-methoxy-phenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl group naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(5-methyl furan-2-base) vinyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(furans-2-base) vinyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-(2-(3 of 4-, 4-Dimethoxyphenyl) vinyl)-1, 3, 5-triazine etc.
As above-mentioned acylphosphine oxide compound, 2,4,6-trimethylbenzoyldiphenyl oxide compound etc. can be enumerated.The commercially available products such as irgacure (registered trademark) 819 (BASF AG's system) can be used.
As above-mentioned united imidazole, can 2 be enumerated, 2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-dichlorophenyl)-4,4 ' 5,5 '-tetraphenyl bisglyoxaline is (with reference to Japanese Unexamined Patent Publication 6-75372 publication, Japanese Unexamined Patent Publication 6-75373 publication etc.), 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chloro-phenyl-)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (with reference to Japanese Patent Publication 48-38403 publication, Japanese Laid-Open Patent Publication 62-174204 publication etc.), 4,4 ', 5, the imidazolium compounds that the phenyl of 5 '-position be instead of by carbonylic alkoxy is (with reference to Japanese Unexamined Patent Publication 7-10913 publication etc.) etc.
Be further used as polymerization starter (D), the bitter almond oil camphor compounds such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, benzoin isobutyl ether can be enumerated; Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2, the benzophenone cpds such as 4,6-tri-methyl benzophenone; The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone; 10-butyl-2-chloro-acridine, dibenzoyl, phenylglyoxalates methyl esters, two cyclopentadiene titanium compounds etc.
As acidic polymerization starter, can enumerate: salt or nitrobenzyl tosylat, the benzoin tosylate etc. such as 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, phenylbenzene iodine tosilate, phenylbenzene iodine hexafluoro antimonate.
As polymerization starter (D); be preferably the polymerization starter containing at least one be selected from O-acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and united imidazole, be more preferably the polymerization starter containing O-acyl group oxime compound.
The content of polymerization starter (D) is preferably 0.1 ~ 30 mass parts relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), is more preferably 1 ~ 20 mass parts.If the content of polymerization starter (D) is in above-mentioned scope, then the tendency that the time shutter shortens owing to there is high-sensitivity, therefore the productivity of colour filter improves.
< solvent (E) >
Solvent (E) is not particularly limited, and can use solvent usually used in this field.Such as ester solvent can be enumerated and (in molecule, contain-COO-, containing the solvent of-O-), ether solvents is (containing-O-in molecule, containing the solvent of-COO-), ether-ether solvent (solvent containing-COO-and-O-in molecule), ketone solvent be (containing-CO-in molecule, containing the solvent of-COO-), alcoholic solvent (containing OH in molecule, not containing the solvent of-O-,-CO-and-COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide (DMSO) etc.
As ester solvent, methyl lactate, ethyl lactate, n-Butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, Isoamyl Acetate FCC, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, methyl aceto acetate, ethyl cyclohexyl alcohol ester, gamma-butyrolactone etc. can be enumerated.
As ether solvents, ethylene glycol monomethyl ether can be enumerated, 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, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl butanol, tetrahydrofuran (THF), tetrahydropyrans, 1, 4-diox, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl ether, Diethylene Glycol dipropyl ether, dibutyl ethylene glycol ether, methyl-phenoxide, phenyl ethyl ether, methylanisole etc.
As ether-ether solvent, methoxy menthyl acetate can be enumerated, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 2-methoxy methyl propionate, 2-methoxypropionate, 2-methoxy propyl propyl propionate, 2-ethoxypropanoate, 2-ethoxyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl esters, 2-oxyethyl group-2 Methylpropionic acid ethyl ester, 3-methoxybutyl acetic ester, 3-methyl-3-methoxybutyl acetic ester, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic ester and butyl carbitol acetate etc.
As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, dipropyl ketone, 4-methyl-2 pentanone, cyclopentanone, pimelinketone, isophorone etc. can be enumerated.
As alcoholic solvent, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, hexalin, ethylene glycol, propylene glycol and glycerine etc. can be enumerated.
As aromatic hydrocarbon solvents, benzene,toluene,xylene and sym-trimethylbenzene etc. can be enumerated.
As amide solvent, DMF, N,N-dimethylacetamide and N-Methyl pyrrolidone etc. can be enumerated.
In above-mentioned solvent, from the viewpoint of coating, drying property, the boiling point preferably under 1atm is more than 120 DEG C and the organic solvent of less than 210 DEG C.As solvent, preferred propylene glycol methyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, dinethylformamide, more preferably propylene glycol methyl ether acetate, propylene glycol monomethyl ether, DMF, N-Methyl pyrrolidone and 3-ethoxyl ethyl propionate.
The content of solvent (E) is preferably 70 ~ 95 quality % relative to the total amount of colored curable resin composition of the present invention, is more preferably 75 ~ 92 quality %.In other words, the total amount of the solids component of colored curable resin composition is preferably 5 ~ 30 quality %, is more preferably 8 ~ 25 quality %.If the content of solvent (E) is in above-mentioned scope, then flatness when being coated with becomes good, and during formation colour filter, colour density can not be not enough in addition, therefore there is the tendency that display characteristic becomes good.
Other compositions of < >
Colored curable resin composition of the present invention can cause the additives well-known in the art such as auxiliary agent, flow agent, weighting agent, other macromolecular compounds, closely sealed promotor, antioxidant, photostabilizer, chain-transfer agent containing polymerization as required.
The manufacture method > of < colored curable resin composition
Colored curable resin composition of the present invention can be prepared by mixing such as tinting material (A), resin (B), polymerizable compound (C), polymerization starter (D), solvent (E) and the flow agent used as required, polymerization initiation auxiliary agent and other compositions.
Pigment (P) preferably mix with part or all of solvent (E) in advance, and the median size that use ball mill etc. is dispersed to pigment is the degree of less than 0.2 μm.Now, part or all of pigment dispersing agent, resin (B) can be coordinated as required.By mixing all the other compositions in the mode of the concentration reaching regulation in the dispersible pigment dispersion obtained like this, target coloration curable resin composition can be prepared.
Part or all that dyestuff can be dissolved in respectively in advance solvent (E) is to prepare solution.Preferably use this solution of metre filter in about 0.01 ~ 1 μm, aperture.
Preferably use the mixed colored curable resin composition of metre filter in about 0.1 ~ 10 μm, aperture.
The manufacture method > of < film
Film of the present invention is formed by colored curable resin composition of the present invention.This film can be formed by making this colored curable resin composition solidify.Film of the present invention can contain colored pattern described later.Describe the method for being solidified by this colored curable resin composition later.
The manufacture method > of < colour filter
Colour filter of the present invention is formed by colored curable resin composition of the present invention.This colour filter can be formed by making this colored curable resin composition solidify.
By being such as coated with this colored curable resin composition on substrate, then it can being made dry and form coloring compositions nitride layer, across photomask, this coloring compositions nitride layer being exposed, obtain this colour filter thus.Colour filter of the present invention can have colored pattern on film.
As the method being manufactured colored pattern by colored curable resin composition of the present invention, photolithography, ink jet method, print process etc. can be enumerated.Wherein, preferred light lithography.Photolithography is following method: above-mentioned colored curable resin composition is coated substrate, makes it dry and forms coloring compositions nitride layer, this coloring compositions nitride layer being exposed, development across photomask.In photolithography, by not using photomask when exposing and/or do not develop, the film of the cured article as above-mentioned coloring compositions nitride layer can be formed.The colored pattern formed like this, film are colour filters of the present invention.
The thickness of colour filter is not particularly limited, and suitably can regulate according to object, purposes etc., such as, 0.1 ~ 30 μm, is preferably 0.1 ~ 20 μm, more preferably 0.5 ~ 6 μm.
As substrate, silica glass, pyrex, alumina silicate glass, effects on surface can be used to have carried out the sheet glass such as the soda-lime glass of silica dioxide coating; The resin boards such as polycarbonate, polymethylmethacrylate, polyethylene terephthalate; Silicon, on aforesaid substrate, define the substrate of aluminium, silver, silver/copper/palldium alloy film etc.On these substrates, other colour filters, resin layer, transistor, circuit etc. can be formed.
Formation based on photolithographic each color pixel can be undertaken by known or usual device, condition.Such as, can make as follows.
First, by being coated on substrate by colored curable resin composition, heat drying (prebake) and/or drying under reduced pressure, remove the volatile components such as desolventizing thus and make it dry, obtaining level and smooth coloring compositions nitride layer.
As coating process, method of spin coating, slot coated method, slit and method of spin coating etc. can be enumerated.
Temperature when carrying out heat drying is preferably 30 ~ 120 DEG C, is more preferably 50 ~ 110 DEG C.In addition as heat-up time, be preferably 10 second ~ 60 minutes, be more preferably 30 second ~ 30 minutes.
When carrying out drying under reduced pressure, preferably carry out under the pressure of 50 ~ 150Pa, in the temperature range of 20 ~ 25 DEG C.
The thickness of coloring compositions nitride layer is not particularly limited, as long as suitably select according to the thickness of the colour filter of target.
Then, across the photomask for the formation of target coloration pattern, coloring compositions nitride layer is exposed.Pattern on this photomask is not particularly limited, and uses the pattern corresponding to intended applications.
As the light source used in exposure, preferably send the light source of the light of the wavelength of 250 ~ 450nm.Such as, the filter intercepts of this wavelength region may of intercepting can be used optionally to take out the light near 436nm, near 408nm, near 365nm lower than the light of 350nm or the bandpass filter of these wavelength region may of use taking-up.Specifically, mercury lamp, photodiode, metal halide lamp, halogen lamp etc. can be enumerated.
Due to can parallel rays be irradiated equably to plane of exposure entirety or carry out photomask and the correct aligned in position of substrate defining coloring compositions nitride layer, therefore preferably use the exposure apparatus such as mask aligner and step unit.
Develop by making the coloring compositions nitride layer after exposure contact with developing solution, substrate forms colored pattern.By development, the unexposed portion of coloring compositions nitride layer dissolves and is removed in developing solution.As developing solution, such as, the aqueous solution of the basic cpd such as preferred potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.Concentration in the aqueous solution of these basic cpds is preferably 0.01 ~ 10 quality %, is more preferably 0.03 ~ 5 quality %.Developing solution can also contain tensio-active agent.
Developing method can be any one in paddle board method, pickling process and spray method etc.Can also by substrate with arbitrary angular slope when developing.
Preferably wash after development.
Further, cure after preferably the colored pattern obtained being carried out.Rear stoving temperature is preferably 150 ~ 250 DEG C, is more preferably 160 ~ 235 DEG C.After the time of curing be preferably 1 ~ 120 minute, be more preferably 10 ~ 60 minutes.
Embodiment
By embodiment, the present invention is illustrated in greater detail, but the present invention does not limit by these embodiments.In example, represent that the % of content or usage quantity and part do not have special stipulation to be exactly quality criteria.
In following synthesis example, by mass spectroscopy (LC; Agilent system 1200 type, MASS; Agilent LC/MSD type) identify the structure of compound.
Embodiment 1: the synthesis of the compound represented by formula (AII-32)
In 3-amino-phenol (Tokyo changes into industry (strain) system) 10.9 parts, add triethoxyl silane (Tokyo changes into industry (strain) system) 19 parts and acetic acid 5 parts, reflux 8 hours in tetrahydrofuran (THF) 200 parts.After reaction terminates, distillation removing tetrahydrofuran (THF), obtains the compound 29.8 parts represented by formula (AII-32-1).
By the compound 2.9 parts shown in the formula obtained (AII-32-1), squaric acid (Tokyo changes into industry (strain) system) 0.6 part, n-butyl alcohol 90 parts and toluene 60 parts mixing.For the mixture obtained, the waterside using the removing of Dean-Stark tube edge to generate is stirred 3 hours at 125 DEG C.After reaction terminates, distillation is except desolventizing, and after adding acetic acid 15 parts, instill 18% salt solution, filtration obtains the solid of precipitation.With the solid that hexanes wash filtration obtains.By the solid drying under reduced pressure obtained, obtain the compound shown in formula (AII-32) 3.4 parts.
The qualification of the compound represented by formula (AII-32)
(mass spectroscopy) ionization mode=ESI+:m/z=680.4 [M+1] +
Exact mass: 679.3
Embodiment 2: the synthesis of the compound represented by formula (AII-5)
In embodiment 1, using except aniline except replacing 3-amino-phenol, synthesizing similarly to Example 1, obtaining the compound represented by formula (AII-5).
The qualification of the compound represented by formula (AII-5)
(mass spectroscopy) ionization mode=ESI+:m/z=650.0 [M+1] +
Exact mass: 648.9
Embodiment 3: the synthesis of the compound represented by formula (AII-31)
Using except Trimethoxy silane except replacing triethoxyl silane in embodiment 1, synthesizing similarly to Example 1, obtaining the compound represented by formula (AII-31).
The qualification of the compound represented by formula (AII-31)
(mass spectroscopy) ionization mode=ESI+:m/z=597.8 [M+1] +
Exact mass: 596.8
Compound 0.35 part represented by compound represented by formula (AII-32), the compound represented by formula (AII-5) and formula (AII-31) is dissolved in chloroform respectively and volume is set to 250cm 3, with ion exchanged water by 2cm wherein 3dilute and volume is set to 100cm 3(concentration: 0.028g/L), uses spectrophotometer (quartz colorimetric utensil, optical length; 1cm) determine absorption spectrum.The maximum absorption wavelength of these compounds: λ max is respectively 688nm, 680nm, 687nm.
The mensuration > of < solubleness
About the compound represented by the compound obtained by embodiment 1 ~ 3 and formula (II-0), obtain at propylene glycol monomethyl ether (following as follows, referred to as PGME), ethyl lactate is (following, referred to as EL), solubleness in propylene glycol methyl ether acetate (hreinafter referred to as PGMEA).
In 50mL sample hose, with following ratio by compound and above-mentioned solvent, thereafter, cover tightly sample hose, make it vibrate 3 minutes at 30 DEG C with ultrasonic vibration machine.Then at room temperature to place after 30 minutes, suction filtration, its residue of visual observation.When can not confirm insolubles, judge favorable solubility and be evaluated as zero, when can confirm insolubles, judge that solvability is bad and be evaluated as ×.In Table 1 result is shown.
5 mass parts compound 0.05g, solvent 1g
3 mass parts compound 0.03g, solvent 1g
1 mass parts compound 0.01g, solvent 1g
Table 1
(synthesis of resin)
In the flask possessing reflux exchanger, dropping funnel and agitator, inject proper N and be set to nitrogen atmosphere, adding propylene glycol methyl ether acetate 100 parts, be heated to 85 DEG C while stirring.Then, by methacrylic acid 19 parts, 3,4-epoxy three ring [5.2.1.0 2,6] decane-8-base acrylate and 3,4-epoxy three ring [5.2.1.0 2,6] mixture (containing than taking molar ratio computing as the 50:50) (trade(brand)name " E-DCPA " of decane-9-base acrylate, Co., Ltd.'s Daicel system) 171 parts be dissolved in propylene glycol methyl ether acetate 40 parts and obtain solution, dripped this solution in this flask with dropping funnel with about 5 hours.On the other hand, by polymerization starter 2,2 '-azo two (2,4-methyl pentane nitrile) 26 parts is dissolved in propylene glycol methyl ether acetate 120 parts and obtains solution, with another dropping funnel with within about 5 hours, instilling the solution obtained in flask.After the dropping of polymerization starter terminates, remain on uniform temp about 3 hours, be cooled to room temperature thereafter, obtain the solution of the multipolymer (resin (B-1)) of solids component 43.5%.The weight-average molecular weight of the resin (B-1) obtained is 8000, and molecular weight distribution is 1.98, and the acid number that solids component converts is 53mg-KOH/g.
(preparation of colored curable resin composition)
Embodiment 7
By tinting material (A): the dyestuff represented by formula (AII-32) 2 parts; And
C.I. pigment yellow 13 8 25.8 parts
Resin (B): resin B 1 50 parts
Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 50 parts
Polymerization starter (D): N-1919 (ADEKA Inc.; O-acyl group oxime compound) 10 parts
Solvent (E): propylene glycol methyl ether acetate 870 parts and
N-Methyl pyrrolidone 290 parts
Flow agent (F): polyether modified silicon oil (toray silicone SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Be obtained by mixing colored curable resin composition.
Embodiment 8
By tinting material (A): the dyestuff represented by formula (AII-5) 2 parts; And
C.I. Pigment Yellow 73 150 34.1 parts
Resin (B): resin B 1 50 parts
Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 50 parts
Polymerization starter (D): N-1919 (ADEKA Inc.; O-acyl group oxime compound) 10 parts
Solvent (E): propylene glycol methyl ether acetate 870 parts and
N-Methyl pyrrolidone 290 parts
Flow agent (F): polyether modified silicon oil (toray silicone SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Be obtained by mixing colored curable resin composition.
Embodiment 9
By tinting material (A): the dyestuff represented by formula (AII-31) 2 parts; And
C.I. Pigment Yellow 73 185 10.3 parts
Resin (B): resin B 1 50 parts
Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 50 parts
Polymerization starter (D): N-1919 (ADEKA Inc.; O-acyl group oxime compound) 10 parts
Solvent (E): propylene glycol methyl ether acetate 870 parts and
N-Methyl pyrrolidone 290 parts
Flow agent (F): polyether modified silicon oil (toray silicone SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Be obtained by mixing colored curable resin composition.
Comparative example 2
By tinting material (A): the dyestuff represented by formula (II-0) 1 part; And
C.I. Pigment Yellow 73 185 10.3 parts
Resin (B): resin B 1 50 parts
Polymerizable compound (C): dipentaerythritol acrylate (KAYARAD (registered trademark) DPHA; Japan's chemical drug (strain) system) 50 parts
Polymerization starter (D): N-1919 (ADEKA Inc.; O-acyl group oxime compound) 10 parts
Solvent (E): propylene glycol methyl ether acetate 70 parts; And
N-Methyl pyrrolidone 800 parts
Flow agent (F): polyether modified silicon oil (toray silicone SH8400; The beautiful DOW CORNING in east (strain) system) 0.1 part
Be obtained by mixing colored curable resin composition.
(formation of pattern)
At glass substrate (the eagle XG of 2 inch square; Corning Incorporated's system) on, after spin-coating method coating photosensitive composition, obtain composition layer 100 DEG C of prebake 3 minutes.After cooling, be set to 100 μm by what be formed with the glass substrate of composition layer and silica glass photomask, use exposure machine (TME-150RSK; Open up Pu Kang (strain) system), under air atmosphere, with 150mJ/cm 2exposure (365nm benchmark) carried out rayed.As photomask, use the photomask defining 100 μm of live width/pitch pattern.
After above-mentioned rayed, by the film that obtains in the water system developing solution containing nonionic system tensio-active agent 0.12% and potassium hydroxide 0.04% 23 DEG C of immersion development 80 seconds, after washing, in an oven, 200 DEG C carry out 20 minutes after cure, obtain pattern.
(Evaluation of Heat Tolerance)
At 200 DEG C, 20 minutes are heated to the coated film of photosensitive composition, with colour examining machine (OSP-SP-200; OLYMPUS Inc.) measure coated film heating before and after aberration (Δ Eab*).For the coated film obtained by embodiment 7,8,9, implement above Evaluation of Heat Tolerance respectively, as a result, aberration (Δ Eab*) is 12.6 (embodiments 7), 10.2 (embodiments 8), 11.1 (embodiments 9).Implement Evaluation of Heat Tolerance similarly to comparative example 2, result, aberration (Δ Eab*) is 20.5, is aware of the excellent heat resistance of the application's dyestuff.
Utilizability in industry
Dyestuff of the present invention is excellent to the solvability of organic solvent.Therefore, because colored curable resin composition of the present invention contains dyestuff of the present invention, so the generation of foreign matter is few, the colour filter of high-quality can be made, the colour filter of excellent heat resistance can be provided in addition.

Claims (14)

1. a dyestuff, it has group containing Siliciumatom and the sour skeleton in the side of having.
2. dyestuff according to claim 1, wherein,
Group containing Siliciumatom is for containing-Si (R 14) 3group,
Wherein, R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4,3 R 14can distinguish identical also can be different.
3. dyestuff according to claim 1 and 2, wherein,
The group of group containing Siliciumatom represented by formula (iia),
*-L 1-Si(R 14) 3(iia)
In formula (iia), R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4,3 R 14can distinguish identical also can be different,
L 1represent the alkylidene group of carbonatoms 1 ~ 8 ,-the CH comprised in this alkylidene group 2-can be replaced by Sauerstoffatom,
* bonding end is represented.
4. dyestuff according to claim 1 and 2, its compound represented by formula (IIa),
In formula (II), R 1, R 2, R 111and R 112separately represent hydrogen atom, halogen atom, hydroxyl or the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 can be had, Sauerstoffatom or sulphur atom can be inserted between the carbon atom forming this saturated hydrocarbyl,
R 3, R 4, R 113and R 114separately represent hydrogen atom or hydroxyl,
R 5, R 6, R 15and R 16separately represent: hydrogen atom; Group containing Siliciumatom; The saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 can be had, Sauerstoffatom or sulphur atom can be inserted between the carbon atom forming this saturated hydrocarbyl; Or substituent phenyl can be had, wherein, R 5, R 6, R 15and R 16in at least 1 be group containing Siliciumatom.
5. dyestuff according to claim 4, wherein,
The group of group containing Siliciumatom represented by formula (iia),
*-L 1-Si(R 14) 3(iia)
In formula (iia), R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4,3 R 14can distinguish identical also can be different,
L 1represent the alkylidene group of carbonatoms 1 ~ 8 ,-the CH comprised in this alkylidene group 2-can be replaced by Sauerstoffatom,
* bonding end is represented.
6. the dyestuff according to claim 4 or 5, wherein,
The group of substituent phenyl represented by formula (i) can be had,
In formula (i), R 12represent hydrogen atom, the saturated hydrocarbyl of 1 valency of carbonatoms 1 ~ 20 or the undersaturated alkyl of 1 valency of carbonatoms 2 ~ 20, m represents the integer of 1 ~ 5, when m is more than 2, and multiple R 12can distinguish identical also can be different, * represents the bonding end with nitrogen-atoms.
7. dyestuff according to claim 1 and 2, its compound represented by formula (II),
In formula (II), R 1aand R 2aseparately represent hydrogen atom, halogen atom, hydroxyl or the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20 can be had, Sauerstoffatom or sulphur atom can be inserted between the carbon atom forming this saturated hydrocarbyl,
R 3aand R 4aseparately represent hydrogen atom or hydroxyl,
R 5aand R a6in a group represented by formula (ii), another is hydrogen atom, can has the saturated hydrocarbyl of 1 valency of substituent carbonatoms 1 ~ 20, can insert Sauerstoffatom or sulphur atom between the carbon atom forming saturated hydrocarbyl; Or the group represented by formula (i),
In formula (i), R 12represent hydrogen atom, the saturated hydrocarbyl of 1 valency of carbonatoms 1 ~ 20 or the undersaturated alkyl of 1 valency of carbonatoms 2 ~ 20, m represents the integer of 1 ~ 5, when m is more than 2, and multiple R 12can distinguish identical also can be different, * represents the bonding end with nitrogen-atoms,
In formula (ii), n represents the integer of 1 ~ 8, R 14represent hydrogen atom, hydroxyl, the alkyl of carbonatoms 1 ~ 4 or the alkoxyl group of carbonatoms 1 ~ 4, * represents the bonding end with nitrogen-atoms, 3 R 14can distinguish identical also can be different.
8. a tinting material, it contains the dyestuff described in claim 1,2 or 3.
9. tinting material according to claim 8, it is also containing yellow ultramarine.
10. tinting material according to claim 9, wherein,
Yellow ultramarine is be selected from least a kind of pigment in C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 185.
11. 1 kinds of colored curable resin compositions, it contains tinting material, resin, polymerizable compound and polymerization starter according to any one of claim 8 or 9.
12. 1 kinds of films, it is formed by colored curable resin composition according to claim 11.
13. 1 kinds of colour filters, it is formed by photosensitive composition according to claim 11.
14. 1 kinds of display unit, it contains colour filter according to claim 13.
CN201510085192.5A 2014-02-20 2015-02-17 Dyestuff and colored curable resin composition Active CN104861691B (en)

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CN109476775A (en) * 2016-07-14 2019-03-15 Dic株式会社 Activity energy-line solidifying type resin composition and metallic film silane coupling agent
CN111742016A (en) * 2018-02-26 2020-10-02 住友化学株式会社 Colored resin composition
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KR102020917B1 (en) 2016-08-17 2019-09-11 삼성에스디아이 주식회사 Core-shell dye, photosensitive resin composition including the same, and color filter
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CN109476775A (en) * 2016-07-14 2019-03-15 Dic株式会社 Activity energy-line solidifying type resin composition and metallic film silane coupling agent
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CN111742016A (en) * 2018-02-26 2020-10-02 住友化学株式会社 Colored resin composition
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CN111742016B (en) * 2018-02-26 2023-06-06 住友化学株式会社 Colored resin composition

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