CN105283806B - Photosensitive composition, cured film, colored filter and its manufacturing method, solid-state imager and image display device - Google Patents

Photosensitive composition, cured film, colored filter and its manufacturing method, solid-state imager and image display device Download PDF

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Publication number
CN105283806B
CN105283806B CN201480030200.XA CN201480030200A CN105283806B CN 105283806 B CN105283806 B CN 105283806B CN 201480030200 A CN201480030200 A CN 201480030200A CN 105283806 B CN105283806 B CN 105283806B
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group
pigment
compound
resin
represented
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CN105283806A (en
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稻部阳树
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Fujifilm Corp
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Fujifilm Corp
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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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • C09B1/20—Preparation from starting materials already containing the anthracene nucleus
    • C09B1/206—Dyes with amino groups substituted by heterocyclic radicals
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/02—Monoazo dyes prepared by diazotising and coupling from diazotised o-amino-hydroxy compounds
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/32—Monoazo dyes prepared by diazotising and coupling from coupling components containing a reactive methylene group
    • C09B29/33—Aceto- or benzoylacetylarylides
    • C09B29/335—Aceto- or benzoylacetylarylides free of acid groups
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
    • C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
    • 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
    • C09B48/00—Quinacridones
    • 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
    • C09B57/004—Diketopyrrolopyrrole dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Nonlinear Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)

Abstract

The present invention provides a kind of photosensitive composition, cured film, colored filter and its manufacturing method, solid-state imager and image display device, the photosensitive composition contains: (A) pigment, (B) alkaline pigment derivative, (C) phosphate dispersing agent represented by the following general formula (II), (D) by compound (x) represented by the following general formula (IV) and resin made of compound (y) combined polymerization with ethylene unsaturated double-bond, (E) Photoepolymerizationinitiater initiater, and (F) polymerizable compound.Patternability after the irregular colour (color spot) of photosensitive composition of the invention or the ageing stability and then PCD of color spot is excellent.

Description

Photosensitive composition, cured film, colored filter and its manufacturing method, Solid-state imager and image display device
Technical field
The present invention relates to one kind be suitable for production liquid crystal display element (liquid crystal display (Liquid Crystal Display, )) or solid-state imager (charge coupled cell (Charge-coupled Device, CCD), complementary metal-oxide LCD Semiconductor (Complementary Metal-Oxide-Semiconductor, CMOS) etc.) etc. used in colored filter Photosensitive composition, the colored filter with the painted areas as made by the composition and have institute State the solid-state imager of colored filter, Organic Light Emitting Diode (Light Emitting Diode, LED) uses liquid crystal display The image display devices such as device.
Background technique
In recent years, along with personal computer (personal computer), particularly the hair of big picture LCD TV Exhibition, there is the increased tendency of needs of liquid crystal display (LCD), particularly colour liquid crystal display device.Due to further higher image quality Requirement, also it is desirable to organic electroluminescent (Electroluminescence, EL) display it is universal.On the other hand, due to number Universal, the solid-state image pickups such as ccd image sensor of word camera (digital camera), mobile phone with camera The needs of element also constantly increase.
As these displays or the key element (key device) of optical element, using colored filter, further The requirement of higher image quality is continuously improved with the requirement for reducing (cost down) to cost.Such colored filter is generally configured with red Color (R), green (G) and blue (B) trichromatic colored pattern, in display element or photographing element, playing will be passed through Light is divided into trichromatic effect.
For colorant used in colored filter, the following characteristic of common prescription.
That is, it needs to following characteristic: having preferred dichroism in terms of color reprodubility；There is no lead to liquid crystal display Light scattering that the contrast of device reduces or cause solid-state imager irregular colour color spot sense optical concentration it is uneven The optical perturbations such as property；Under used environmental condition fastness, such as heat resistance, light resistance, moisture-proof it is good；Mole Absorptivity is big and can realize filming etc..
Therefore, colorant usually uses pigment.
Forming liquid crystal display element (LCD) or solid-state imager (CCD, CMOS etc.) and organic LED liquid crystal display It is real usually after the step of being coated with photosensitive composition on substrate used in device when colored filter The step of row is carried out the step of pattern exposure and is developed using alkaline-based developer.At this point, sometimes in coating coloring phototonus After the step of resin combination, middle during being exposed before development step place several days.It usually will be after such coating Placement be known as be coated with after postpone (Post Coating Delay, PCD).Its reason is: manufacturing sometimes in colored filter In the process, storage in advance is coated with the substrate of photosensitive composition, vacates exposure development device, then one goes forward side by side In the case where the subsequent exposure development step of row, processing can be effectively performed.
Due to background as described above, photosensitive composition is required after PCD in the formation of colored pattern Aspect does not also cause problem.Specifically, Fig. 1 be self-reference substrate above on substrate be coated with photosensitive composition after The schematic diagram that colored pattern 1 is observed is formed by when being exposed the situation of development immediately.Herein, by colored pattern shape As rectangle.For photosensitive composition, it is desirable that also keep the formation of such rectangular patterns after PCD.
However, the type of view photosensitive composition is different, as shown in Fig. 2, the colored pattern 1 after PCD sometimes Significantly collapse.
Such as a kind of photosensitive coloring composition is recorded in patent document 1 and patent document 2, contain comprising specific Resin of the acrylic monomer of structure as combined polymerization ingredient.
In addition, a kind of color compositions are recorded in patent document 3 and patent document 4, containing containing specific structure The alkali compounds of triazine ring and the phosphate dispersing agent of specific structure.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2004-101728 bulletin
[patent document 2] Japanese Patent Laid-Open 2007-212654 bulletin
[patent document 3] Japanese Patent Laid-Open 2007-231106 bulletin
[patent document 4] Japanese Patent Laid-Open 2007-231107 bulletin
Summary of the invention
[the invention project to be solved]
It is recorded in patent document 1 and patent document 2, copolymerization is used as by using the acrylic monomer for containing specific structure The resin of synthesis point can get the excellent coloured compositions such as dispersion stabilization, but the color when colored filter is made is not There is the leeway further improved in terms of (color spot) or the ageing stability of color spot.It is believed that its reason is: for patent For photosensitive composition as being recorded in document 1, patent document 2, dispersion resin to the absorption of pigment particles not Stablize, make composition for a long time through when during, it is de- from pigment particles surface to be adsorbed in the dispersion resin on pigment particles surface From.Therefore speculate, make composition for a long time through when during, pigment particles cause secondary aggregation and pigment particle size becomes thick Greatly, cause through when after colored filter color spot deterioration.
In addition, being recorded in patent document 3 and patent document 4, by using the alkalization containing triazine ring of specific structure The phosphate dispersing agent of object and specific structure is closed, can get the excellent color compositions such as dispersion stabilization.However, patent document 3 and patent document 4 in, ageing stability, and then the PCD of irregular colour (color spot) or color spot still when being used as colored filter There are also the leeway further improved for the aspect of patternability afterwards.It is believed that its reason is: for patent document 3, patent The resulting coloring phototonus resin group of the color compositions by the phosphate dispersing agent containing specific structure as being recorded in document 4 For closing object, the poor compatibility of each ingredient of composition is constituted, forms one of film during placement (PCD) after coating It is divided into the raw mutually separation of distribution, is significantly collapsed by the resulting colored pattern of exposure development thereafter.
To solve the problem of the present invention, and it is related to the ageing stability and then PCD of a kind of irregular colour (color spot) or color spot The excellent photosensitive composition of patternability afterwards, utilizes the hardening of the photosensitive composition Film, colored filter, the manufacturing method of colored filter, solid-state imager and image display device.
[means to solve the problem]
The present inventor et al. is studied in detail, as a result, it has been found that, by using set phosphate dispersing agent and set Resin binder, can to solve the problem.
Specifically, solving the project by following 1 > of means <, preferably 2 > of means <~17 > of means <.
A kind of photosensitive composition of 1 > of <, contains: (A) pigment, (B) alkaline pigment derivative, (C) are following Phosphate dispersing agent represented by logical formula (II), (D) by compound (x) represented by the following general formula (IV) and have ethylene not It is saturated resin, (E) Photoepolymerizationinitiater initiater and (F) polymerizable compound made of compound (y) combined polymerization of double bond,
[changing 1]
In logical formula (II), R3Indicate that number average molecular weight is 400~30000 polyester construction, y indicates 1 or 2；In y For 2 situation when, multiple R3It may be the same or different respectively；
In logical formula (IV), R4Indicate hydrogen atom or methyl, R5Indicate the alkylidene of carbon number 2 or 3, R6Expression hydrogen atom can The alkyl of carbon number 1~20 containing phenyl ring, n indicate 1~15 integer；
When n is 2 or more situation, multiple R5It may be the same or different respectively.
2 > of < photosensitive composition according to documented by 1 > of <, wherein (B) alkaline pigment derivative It is the compound with amino.
3 > of < photosensitive composition according to documented by 2 > of < 1 > or <, wherein described (A) pigment is choosing In group composed by free red pigment, viridine green and yellow uitramarine.
4 > of < photosensitive composition according to documented by any one of 3 > of < 1 > to <, wherein described logical In formula (II), the R3The number average molecular weight of represented polyester construction is 1900~10000.
5 > of < photosensitive composition according to documented by any one of 4 > of < 1 > to <, wherein described logical In formula (II), the R3Represented polyester construction is that two or more different internal ester monomer ring-opening polymerisations are resulting poly- Ester structure.
6 > of < photosensitive composition according to documented by any one of 5 > of < 1 > to < also contains (G) In Side chain has the resin of polymeric double bond.
7 > of < photosensitive composition according to documented by 6 > of <, wherein (G) has polymerization in side chain Property double bond resin be resin made of reacting compound (b) with copolymer (a), the compound (b) is with can be with hydroxyl The functional group of reaction and ethylene unsaturated double-bond, the copolymer (a) are the polymerizable monomer (p) with 2~6 hydroxyls With the copolymer of other polymerizable monomers (q).
8 > of < photosensitive composition according to documented by any one of 7 > of < 1 > to <, wherein relative to 100 mass parts of (A) pigment, (D) is by compound (x) represented by logical formula (IV) and has ethylene unsaturated double The content of resin made of compound (y) combined polymerization of key is 5 mass parts~80 mass parts.
9 > of < photosensitive composition according to documented by any one of 8 > of < 1 > to <, wherein described Color sensation photosensitive resin composition is that described (A) pigment, (B) alkaline pigment derivative and (C) is made to lead to formula (II) institute table After the phosphate dispersing agent dispersion shown, (D) described in allotment is by compound (x) represented by logical formula (IV) and has ethylene insatiable hunger Resin made of compound (y) combined polymerization with double bond forms.
10 > of < photosensitive composition according to documented by any one of 9 > of < 1 > to < is for shape At the painted areas of colored filter.
A kind of cured film of 11 > of < is to make the coloring phototonus tree according to documented by any one of 10 > of < 1 > to < Oil/fat composition hardens.
A kind of manufacturing method of colored filter of 12 > of <, comprising the following steps: will be according to any in 10 > of < 1 > to < The step of photosensitive composition documented by is applied on support and forms coloring photosensitive combination layer；It will The step of coloring photosensitive combination layer exposure is at pattern-like；And unexposed portion is developed and removes and forms colored pattern The step of.
A kind of manufacturing method of colored filter of 13 > of <, comprising the following steps:
The photosensitive composition according to documented by any one of 10 > of < 1 > to < is applied on support And the step of forming coloring photosensitive combination layer；
In the step of forming photoresist layer on the coloring photosensitive combination layer；
The step of making the photoresist pattern layers and being exposed and developing, obtaining resist pattern；With And
The resist pattern is come to carry out dry-etching to the coloring photosensitive combination layer as etching mask Step.
A kind of colored filter of 14 > of < is the colored filter with the cured film according to documented by 11 > of <.
A kind of colored filter of 15 > of < is with the manufacture of the colored filter according to documented by 13 > of < 12 > or < Method is fabricated.
A kind of solid-state imager of 16 > of < has the colored filter according to documented by 15 > of < 14 > or <.
A kind of image display device of 17 > of < has the colored filter according to documented by 15 > of < 14 > or <.
[The effect of invention]
According to the present invention, it is possible to provide the pattern after the ageing stability of a kind of irregular colour (color spot) or color spot and then PCD The excellent photosensitive composition of formative utilizes the cured film of the photosensitive composition, colored filter Mating plate, the manufacturing method of colored filter, solid-state imager and image display device.
Detailed description of the invention
Fig. 1 is to be exposed development immediately after coating photosensitive composition on substrate above self-reference substrate Situation when be formed by the schematic diagram that colored pattern observed.
Fig. 2 is self-reference substrate top to the coating photosensitive composition on substrate and is exposed after PCD The schematic diagram that colored pattern is observed is formed by when the situation of development.
The explanation of symbol
1: colored pattern
Specific embodiment
Hereinafter, the contents of the present invention will be described in detail.In addition, in the specification of the present application, so-called "~" is to wrap It is used containing numerical value documented by its front and back as the meaning of lower limit value and upper limit value.In addition, so-called organic EL member of the invention Part refers to organic electroluminescent device.
In the present specification, so-called total solid content refers to and removes from the total composition of photosensitive composition The gross mass of the resulting ingredient of solvent.
In the statement of group (atomic group) in the present specification, not recording the statement for being substituted and being unsubstituted includes not Group with substituent group, and also comprising the group with substituent group.For example, so-called " alkyl ", not only takes comprising not having The alkyl (alkyl being unsubstituted) of Dai Ji, and include the alkyl (alkyl being substituted) with substituent group.
In addition, " radioactive ray " so-called in this specification, such as refer to representated by the bright-line spectrum of mercury vapor lamp, excimer laser Far ultraviolet, extreme ultraviolet (EUV light (Extreme Ultraviolet)), X-ray, electron beam etc..In addition, in the present invention So-called light refers to actinic ray or radioactive ray." exposure " so-called in this specification then refers not only to benefit as long as no special instructions The exposure of the far ultraviolet representated by mercury vapor lamp, excimer laser, X-ray, EUV light etc., utilizes the grains such as electron beam, ion beam Drawing for beamlet is also included in exposure.
In addition, " (methyl) acrylate " indicates acrylate and two kinds or any of methacrylate in this specification Kind, " (methyl) acrylic acid " indicates that acrylic acid and two kinds or any of methacrylic acid, " (methyl) acryloyl group " indicate propylene Acyl group and two kinds or any of methylacryloyl.
In addition, in the present specification, " monomer " and " monomer (monomer) " is identical meanings.Monomer in this specification Refer to that with oligomer and polymer phase differentiation, weight average molecular weight be 2,000 compounds below.In the present specification, institute Polymerizable compound is called, refers to the compound with polymerizable functional groups, can be monomer is also polymer.So-called polymerism official Energy base, refers to the group for participating in polymerization reaction.
Weight average molecular weight and number average molecular weight can utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) it finds out.
In the present specification, the Me in chemical formula indicates that methyl, Et indicate that ethyl, Pr indicate that propyl, Bu indicate butyl, Ph indicates phenyl.
" step " word in this specification, refers not only to independent step, in the feelings that can not clearly distinguish with other steps When shape, as long as may achieve the predictive role of the step, it is also included in the term.
The present invention is formed in view of the situation, and its purpose is to provide a kind of coloured compositions that color characteristics are excellent.
In the present specification, weight average molecular weight and number average molecular weight are to measure resulting polyphenyl second by GPC Alkene scaled value defines.In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) for example can by with Under type is found out: being used HLC-8220 (Tosoh (stock) manufacture), is used (the east super (TSKgel Super) AWM-H of tsk gel Cao's (stock) manufacture, 6.0mmID × 15.0cm) it is used as tubing string, use the lithium bromide N-Methyl pyrrolidone (N- of 10mmol/L Methyl pyrrolidinone, NMP) solution is as eluent.
< photosensitive composition >
Photosensitive composition (hereinafter sometimes referred to " composition of the invention ", " coloring compositions of the invention Object ") it is characterized in that containing phosphate point represented by: (A) pigment, (B) alkaline pigment derivative, (C) the following general formula (II) Compound (x) represented by the following general formula (IV) and the compound (y) with ethylene unsaturated double-bond are copolymerized by powder, (D) Resin made of conjunction, (E) Photoepolymerizationinitiater initiater and (F) polymerizable compound.
[changing 2]
In logical formula (II), R3Indicate that number average molecular weight is 400~30000 polyester construction, y indicates 1 or 2.In y For 2 situation when, multiple R3It may be the same or different respectively.
In logical formula (IV), R4Indicate hydrogen atom or methyl, R5Indicate the alkylidene of carbon number 2 or 3, R6Expression hydrogen atom can The alkyl of carbon number 1~20 containing phenyl ring, n indicate 1~15 integer.
When n is 2 or more situation, multiple R5It may be the same or different respectively.
By using composition of the invention, the ageing stability of irregular colour (color spot) or color spot, the in turn figure after PCD Case formative becomes excellent.Though the reasons why can get such effect of the invention is uncertain, reason can be presumed as follows.
It could be speculated that if (C) is led to phosphate dispersing agent represented by formula (II) and (D) for change represented by logical formula (IV) It closes object (x) to be used in combination with resin made of compound (y) combined polymerization with ethylene unsaturated double-bond, then (C) leads to formula (II) institute The phosphate dispersing agent of expression can get following effect: dispersing agent is strongly adsorbed in pigment particles, inhibits along with composition Through when color spot deteriorate.In addition speculate that its reason is: (D) is by compound (x) represented by logical formula (IV) and has ethylene Resin made of compound (y) combined polymerization of property unsaturated double-bond is functioned as expanding material (compatibilizer), Inhibit the phenomenon that occur mutually to separate during the placement (PCD) of each ingredient of composition composition after coating., it can be said that thus originally Patternability after the irregular colour (color spot) of invention or the ageing stability and then PCD of color spot becomes excellent.
Hereinafter, composition of the invention is described in detail.
< < (A) pigment > >
Composition of the invention contains (A) pigment.Pigment used in the present invention is preferably selected from by red pigment, green In group composed by pigment and yellow uitramarine, previously known various inorganic pigments or organic pigment can be used.The pigment Preferably high-transmission rate.
Inorganic pigment can enumerate metallic compound represented by metal oxide, metallic complex salt etc., specific enumerable: carbon The black, black pigments such as titanium is black, the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the metal Composite oxides.
Organic pigment can for example be enumerated:
Color index (Color Index, C.I.) pigment yellow 11, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment Yellow 53, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 99, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. Pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 167, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 199；
C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 43, C.I. pigment orange 71；
C.I. pigment red 81, C.I. paratonere 105, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 155, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. face Expect red 209, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 270；
C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 32, C.I. pigment violet 39；
C.I. pigment blue 1, C.I. pigment blue 2, C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. pigment blue 22, C.I. pigment blue 60, C.I. pigment blue 66；
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58；
C.I. pigment brown 25, C.I. pigment brown 28；
C.I. pigment black 1 etc..
The pigment preferably used in the present invention can be enumerated below.However, the present invention is not limited to these pigment.
C.I. pigment yellow 11, C.I. pigment yellow 24, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 154, C.I. face Expect yellow 167, C.I. pigment yellow 180, C.I. pigment yellow 185,
C.I. pigment orange 36, C.I. pigment orange 71,
C.I. pigment red 122, C.I. paratonere 150, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 177, C.I. paratonere 209, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264,
C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 32,
C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. pigment blue 22, C.I. pigment blue 60, C.I. pigment blue 66,
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58,
C.I. pigment black 1.
These organic pigments can be used alone or use multiple combinations to adjust light splitting or improve colour purity. The combined concrete example described below.Such as can be used: as red pigment anthraquione pigmentss, be pigment, diketo Pyrrolopyrrole system pigment is individually a kind of or these pigment at least one yellow with bisazo system yellow uitramarine, isoindoline system Color pigment, quinophthalone system yellow uitramarine are mixing of red pigment etc..Such as anthraquione pigmentss can enumerate C.I. paratonere 177, it is that pigment can enumerate C.I. paratonere 155, C.I. paratonere 224, diketopyrrolopyrrolecocrystals system pigment can be enumerated C.I. paratonere 254, the mixing for the aspect of color decomposition, preferably with C.I. pigment yellow 13 9.In addition, red face The mass ratio of material and yellow uitramarine is preferably 100:5~100:50.The mass ratio is to be difficult to inhibit in 100:4 situation below The light transmission of 400nm~500nm, in addition, dominant wavelength is inclined to short wavelength in the case that the mass ratio is 100:51 or more It moves, color decomposition ability can not be improved sometimes.The especially described mass ratio it is most suitable be 100:10~100:30 range.In addition, In the case where red pigment combination with one another, required light splitting can correspond to adjust.
The halogenated phthalocyanines system pigment in addition, viridine green can be used alone, or use halogenated phthalocyanines system pigment and double The mixing of azo system yellow uitramarine, quinophthalone system yellow uitramarine, azomethine system yellow uitramarine or isoindoline system yellow uitramarine.Example Such as, such example is preferably C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37, C.I. naphthol green 58 and C.I. pigment Huang 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185 Mixing.The mass ratio of viridine green and yellow uitramarine is preferably 100:5~100:150.The mass ratio is especially preferably The range of 100:30~100:120.
Blue pigment can be used alone phthualocyanine pigment, or use the phthualocyanine pigment and dioxazines system violet pigment Mixing.Such as preferably C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment Preferably 100:0~100:100, more preferably 100:10 or less.
In addition, black carbon, titanium, iron oxide, titanium oxide can be used alone or as a mixture in black pigment.It is used by these mixing Situation when, preferably carbon and the black combination of titanium, the carbon and the black mass ratio of titanium of the situation are preferably 100:0~100:60's Range.
In addition, pigment of the invention also can be used the following general formula (A2) represented by azo pigments, its tautomer, this A little salt or hydrate.
General formula (A2)
[changing 3]
In general formula (A2), G indicates hydrogen atom, fatty group, aryl or heterocycle, R1Indicate the ammonia that there can be substituent group Base, aliphatic oxygroup, fatty group, aryl or heterocycle, R2Indicate substituent group.
A indicates the heterocycle for the atom for having more than at least one of nitrogen-atoms, oxygen atom and sulphur atom.
M indicates that 0~5 integer, n indicate 1~4 integer.
The situation expression of n=2 passes through R1、R2, A or G dimer.
The situation expression of n=3 passes through R1、R2, A or G trimer.
The situation expression of n=4 passes through R1、R2, A or G tetramer.
General formula (A2) does not have ionic hydrophily base.
In general formula (A2), A preferably indicates either one or two of the following general formula (A-1)~general formula (A-32).General formula (A-1)~logical In formula (A-32), R51~R59Separately indicate that hydrogen atom, substituent group, adjacent substituent group can also mutually be bonded and form 5 Member ring~6 member rings.* the binding site with the azo group of general formula (A2) is indicated.
[changing 4]
Azo pigments has specific structure represented by general formula (A2), thus can show that tinting strength, tinting power, color equal color are special The excellent characteristic of property, and also show the characteristic of the excellent in te pins of durability such as light resistance, ozone resistance.For example, using general formula is contained (A2) red pattern that the coloured composition of the invention of the azo pigments represented by is formed by colored filter shows work The more good dichroism for red.Herein, so-called " the good dichroism as red ", such as refer to following property At least one.The dichroism for all meeting following 3 properties is especially excellent.
The transmissivity of the wave-length coverage of 650nm~750nm is high.
In the wave-length coverage of 540nm or more, transmittance graph sharply (sharp) rises.
Transmissivity less than the wave-length coverage of 540nm (especially 350nm~400nm) is low.
So-called substituent group of the invention, as long as the group that can be replaced, such as can enumerate: fatty group, virtue Base, heterocycle, acyl group, acyloxy, acyl amino, aliphatic oxygroup, aryloxy group, heterocyclic oxy group, aliphatic Epoxide carbonyl, virtue Epoxide carbonyl, heterocyclyloxycarbonyl, carbamyl, aliphaticsulfonyl, aryl sulfonyl, heterocyclicsulfonyl, aliphatic sulphonyl It is base oxygroup, aryl sulfonyl oxygroup, heterocyclicsulfonyl oxygroup, sulfamoyl, aliphatic sulfoamido, aryl-sulfonyl amino, miscellaneous Cyclic sulfonamides base, amino, aliphatic amines, arylamino, heterocyclic amino group, aliphatic Epoxide carbonyl amino, aryloxycarbonyl ammonia Base, heterocyclyloxycarbonyl amino, aliphatic sulfonamido base, aryl sulfonyl kia, aliphatic sulfenyl, arylthio, hydroxyl, cyano, Sulfo group, carboxyl, aliphatic oxygroup amino, aryloxyamino, carbamyl amino, sulphamoylamino, halogen atom, sulfonamides Base carbamyl, carbamyl sulfamoyl, two aliphatic oxygroup phosphinyls, two aryloxy group phosphinyls etc..Hereinafter, so-called " take Group described in the item of Dai Ji " refers to the substituent group.
Fatty group represented by G can also have substituent group, can be saturation also be unsaturated.
The preferred substituents that fatty group represented by G can have are hydroxyl, aliphatic oxygroup, carbamyl, aliphatic Epoxide carbonyl, aliphatic sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.
Fatty group represented by G is preferably the fatty group of total carbon atom number 1~8, more preferably total carbon atom number 1~ 6 alkyl, such as methyl, ethyl, cyclohexyl can be enumerated etc..
In general formula (A2), aryl represented by G can also contracting ring, can also have substituent group, as long as substitutive group be it is upper Then can be any group described in the item of substituent group described in text and the group that can be replaced, preferred substituent group be nitro, Halogen atom, aliphatic oxygroup, carbamyl, aliphatic Epoxide carbonyl, aliphatic sulfenyl, amino, aliphatic amines, acyl group ammonia Base, carbamyl amino.Aryl represented by G is preferably the aryl of carbon number 6~12, more preferably total carbon atom number 6~10 Aryl, such as phenyl, 4- nitrobenzophenone, 4- acetvlaminophenvl, 4- methanesulfonylphenYl can be enumerated etc..
In general formula (A2), heterocycle represented by G can also have substituent group, can be saturation be also it is unsaturated, can also contract Ring.It can be any as long as substitutive group is the group that described in the item of substituent group described above and can be replaced Group, preferred substituent group are halogen atom, hydroxyl, aliphatic oxygroup, carbamyl, aliphatic Epoxide carbonyl, analiphatic sulphur Base, amino, aliphatic amines, acyl amino, carbamyl amino.Heterocycle represented by G is preferably total carbon atom number 2~12 With carbon atom be bonded heterocycle, more preferably with carbon atom bond total carbon atom number 2~10 5 yuan~6 yuan of heterocycle Base, such as 2- tetrahydrofuran base, 2- pyrimidine radicals (2-pyrimidyl) can be enumerated etc..
G is preferably hydrogen atom.Its reason is that intramolecular hydrogen bond easy to form or intramolecular intersect hydrogen bond.
R1Represented amino can also have substituent group, as long as substitutive group is in the item of substituent group described above Group that is described and being replaced, then can be any group, and substituent group can preferably enumerate fatty group, aryl, heterocycle etc..
These substituent groups can also also have a substituent group, the substituent group be preferably fatty group, hydroxyl, have amido bond, The substituent group of ehter bond, Epoxide carbonyl key, thioether bond etc., be easy for forming the viewpoint of the intermolecular interactions such as intermolecular hydrogen bonding and Speech, the substituent group of the key more preferably with hetero atom and hydrogen atom.
R1Represented amino is preferably the amino being unsubstituted, alkyl amino, the entire carbon atom of total carbon atom number 1~10 The dialkyl amido (dialkyl group can also mutually be bonded and form 5 member rings~6 member rings) of number 2~10, total carbon atom number 6~12 Arylamino, total carbon atom number 2~12 are that saturation can also be unsaturated heterocyclic amino group, the ammonia being more preferably unsubstituted Base, the alkyl amino of total carbon atom number 1~8, the dialkyl amido of total carbon atom number 2~8, total carbon atom number 6~10 aryl Amino, total carbon atom number 2~12 are that saturation can also be unsaturated heterocyclic amino group, such as can enumerate methylamino, N, N- Dimethylamino, N- phenyl amino, N- (2- pyrimidine radicals) amino etc..
And then preferably the arylamino of total carbon atom number 6~13 and total carbon atom number 2~12 are that saturation can also be Unsaturated heterocyclic amino group.
In R1For arylamino situation when, substituent group on aryl preferably relative to the binding site with amino and With the situation of substituent group in contraposition, most preferably only in contraposition with the situation of substituent group.As long as the substituent group is upper It then can be any group, can preferably enumerate: total carbon is former described in the item of substituent group described in text and the group that can be replaced Fatty group (such as methyl, ethyl, allyl, (different) propyl, (uncle) of subnumber 1~7, more preferably total carbon atom number 1~4 Butyl etc.), the aliphatic oxygroup (such as methoxyl group, ethyoxyl, (different) propoxyl group, allyloxy etc.) of total carbon atom number 1~7, Halogen atom (such as fluorine, chlorine, bromine etc.), carbamyl (such as the carbamyl, N- phenyl carbamyl of total carbon atom number 1~7 Base, N- methylcarbamoyl etc.), uride base (such as the uride of total carbon atom number 1~7, more preferably total carbon atom number 1~4 Base, N- methyl uride base, N, N- dimethyl uride base, N-4- pyridyl group uride base, N- phenyl uride base etc.), nitro, total carbon The heterocycle (such as imidazoles ketone group) with aryl contracting ring of atomicity 1~7, hydroxyl, total carbon atom number 1~7, more preferably total carbon The aliphatic sulfenyl (such as methyl mercapto, ethylmercapto group, (different) rosickyite base, allyl sulfenyl, (uncle) butylthio etc.) of atomicity 1~4, always Acyl amino (such as acetyl ammonia (acetoamino) base, propiono of carbon atom number 2~7, more preferably total carbon atom number 2~4 Amino, pivaloyl group amino, benzoyl-amido etc.), total carbon atom number 2~7, more preferably total carbon atom number 2~4 Aliphatic Epoxide carbonyl amino (such as methyloxycarbonylamino, propoxy carbonylamino etc.), it is total carbon atom number 2~7, more excellent It is selected as the aliphatic Epoxide carbonyl (such as methoxycarbonyl, ethoxy carbonyl etc.) of total carbon atom number 2~4, total carbon atom number 2~ 7, be more preferably total carbon atom number 2~4 acyl group (can be aliphatic Oxo, can also be aryl carbonyl, can also be heterocyclecarbonyl, There can also be substituent group, as long as substitutive group is the base that described in the item of substituent group described above and can be replaced Group, then can be any group.The preferably acyl group of total carbon atom number 2~7, the more preferably acyl group of total carbon atom number 2~4, example Acetyl group, propiono, benzoyl, 3- pyridine carbonyl can such as be enumerated) etc..
The situation on aligning is replaced in relative to the binding site with amino in the substituent group on the aryl of arylamino When, because substituent group is located at the end of molecule, therefore the intermolecular interactions such as intermolecular hydrogen bonding easy to form, therefore form and aspect smarten (sharp).When the substituent group on aryl also has the situation of substituent group, preferably fatty group, hydroxyl, have amido bond, The substituent group of ehter bond, Epoxide carbonyl key, thioether bond etc., be easy for forming the viewpoint of the intermolecular interactions such as intermolecular hydrogen bonding and Speech, the substituent group of the key more preferably with hetero atom and hydrogen atom.
In R1For heterocyclic amino group situation when, as long as substituent group is described in the item of substituent group described above and can be into The group that row replaces can be then any group, is preferably advisable with substituent group identical with the situation of the arylamino, miscellaneous When substituent group in ring group also has the situation of substituent group, preferably fatty group, hydroxyl, have amido bond, ehter bond, oxygroup carbonyl The substituent group of base key, thioether bond etc. is easy for for the viewpoint to form the intermolecular interactions such as intermolecular hydrogen bonding, more preferably The substituent group of key with hetero atom and hydrogen atom.
R1More preferable substituent group for arylamino, the situation of heterocyclic amino group is fatty group, aliphatic oxygroup, halogen original Son, the heterocycle of carbamyl and aryl contracting ring, aliphatic Epoxide carbonyl.Substituent group and then preferably total carbon atom number 1~4 Fatty group, the aliphatic oxygroup of total carbon atom number 1~4, halogen atom, nitro, total carbon atom number 1~4 carbamyl, The aliphatic Epoxide carbonyl of total carbon atom number 2~4.
R1Represented aliphatic oxygroup can also have substituent group, as long as substituent group is in the item of substituent group described above Group that is described and being replaced, then can be any group, preferred substituent group be hydroxyl, aliphatic oxygroup, carbamyl, Aliphatic Epoxide carbonyl, aliphatic sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.R1Aliphatic oxygen Base is preferably the alkoxy of total carbon atom number 1~8, more preferably the alkoxy of total carbon atom number 1~4, such as can enumerate methoxy Base, ethyoxyl, (uncle) butoxy, methoxy ethoxy, carbamyl methoxyl group etc..
R1Represented fatty group can also have substituent group, as long as substituent group is institute in the item of substituent group described above The group stated and can replaced, then can be any group, and preferred substituent group is hydroxyl, aliphatic oxygroup, carbamyl, rouge Fat race Epoxide carbonyl, aliphatic sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino.R1Fatty group it is excellent It is selected as the alkyl of total carbon atom number 1~8, the alkyl of more preferably total carbon number 1~4.
R1Represented aryl can also have substituent group, if substituent group be substituent group described above item described in and The group that can be replaced, then can be any group, and preferred substituent group is fatty group, aliphatic oxygroup, halogen atom, ammonia The heterocycle of formoxyl and aryl contracting ring, aliphatic Epoxide carbonyl.R1Aryl be preferably total carbon atom number 6~12 aryl, The more preferably aryl of total carbon atom number 6~10, such as phenyl, 4- aminomethyl phenyl, 3- chlorphenyl can be enumerated etc..
R1Represented heterocycle can be saturated heterocyclyl, can also be unsaturated heterocycle base, can also have substituent group, replace As long as base is the group that described in the item of substituent group described above and can be replaced, it can be any group, preferably take Dai Jiwei fatty group, aliphatic oxygroup, heterocycle, the aliphatic Epoxide carbonyl of carbamyl and miscellaneous base contracting ring.R1Heterocycle Base is preferably the heterocycle of total carbon atom number 2~10, more preferably total carbon atom number 2~8 with nitrogen-atoms bond 5 member rings~ The non aromatic heterocyclyl of 6 member rings, such as 1- piperidyl, 4- morpholinyl, 1- quinolyl (1-quinoyl), 2- pyrimidine can be enumerated Base, 4- pyridyl group etc..
R1Preferably amino, aliphatic oxygroup, with the 5 member rings~6 member rings non aromatic heterocyclyl of nitrogen-atoms bond Situation, more preferably amino, aliphatic oxygroup, and then preferably amino.
R1The preferably situation of amino.
R2As long as represented substituent group is the group that described in the item of substituent group described above and can be replaced, It can be any group, preferably fatty group, aryl, heterocycle, aliphatic Epoxide carbonyl, carboxyl, carbamyl, acyl group ammonia Base, sulfoamido, carbamyl amino, sulfamoyl, aliphatic oxygroup, aliphatic sulfenyl, cyano, halogen atom, more preferably For aliphatic Epoxide carbonyl, carbamyl, acyl amino, carbamyl amino, aliphatic oxygroup, halogen atom, particularly preferably For aliphatic oxygroup.
When these substituent groups also have the situation of substituent group, preferably fatty group, hydroxyl, have amido bond, ehter bond, The substituent group of Epoxide carbonyl key, thioether bond etc. is easy for for the viewpoint to form the intermolecular interactions such as intermolecular hydrogen bonding, more The substituent group of key preferably with hetero atom and hydrogen atom.
M is preferably 0~3 situation, more preferably 0~1 situation, and then preferably 0 situation.
N is preferably 1 or 2 situation.
R2Represented fatty group can also have substituent group, can be saturation be also it is unsaturated, substitutive group is only To be the group that described in the item of substituent group described above and can be replaced, then can be any group.R2Fatty group The preferably alkyl of total carbon atom number 1~8, the more preferably alkyl of total carbon atom number 1~6, for example, can enumerate methyl, ethyl, Isopropyl, cyclohexyl, tert-butyl etc..
R2Represented aryl can also have substituent group, as long as substitutive group is in the item of substituent group described above Group that is described and being replaced then can be any group.R2Aryl be preferably total carbon atom number 6~12 aryl, more The preferably aryl of total carbon atom number 6~10, such as phenyl, 3- methoxyphenyl, 4- Carbamoylphenyl can be enumerated etc..
R2Represented heterocycle can also have substituent group, can be saturation be also it is unsaturated, can also contracting ring, it is substitutive It can be any group as long as group is the group that described in the item of substituent group described above and can be replaced.R2It is miscellaneous Ring group is preferably the heterocycle of total carbon atom number 2~16, more preferably 5 member rings of total carbon atom number 2~12~6 member rings heterocycle Base, such as 1- pyrroles's piperidinyl, 4- morpholinyl, 2- pyridyl group, 1- pyrrole radicals, 1- imidazole radicals, 1- benzimidazolyl can be enumerated etc..
R2Represented aliphatic Epoxide carbonyl can also have substituent group, can be saturation be also it is unsaturated, it is substitutive It can be any group as long as group is the group that described in the item of substituent group described above and can be replaced.R2Rouge Fat race Epoxide carbonyl is preferably the alkoxy carbonyl of total carbon atom number 1~8, more preferably the alkoxy carbonyl of total carbon atom number 1~6 Base, such as methoxycarbonyl, isopropoxy carbonyl, carbamyl methoxycarbonyl can be enumerated etc..
R2Represented carbamyl can also have substituent group, as long as substitutive group is substituent group described above It then can be any group, preferably fatty group, aryl, heterocycle etc. described in and the group that can be replaced.R2Ammonia Formoxyl is preferably the dialkyl amino first of carbamyl, the alkylcarbamoyl group of total carbon atom number 2~9, total carbon atom number 3~10 Acyl group, the aromatic yl ammonia methanoyl of total carbon atom number 7~13, total carbon atom number 3~12 heterocycle carbamyl, more preferably ammonia first Acyl group, the alkylcarbamoyl group of total carbon atom number 2~7, the dialkyl carbamyl of total carbon atom number 3~6, total carbon atom number 7 The heterocycle carbamyl of~11 aromatic yl ammonia methanoyl, total carbon atom number 3~10, such as carbamyl, methyl ammonia first can be enumerated Acyl group, dimethylcarbamoyl, phenylcarbamoyl, 4- pyridine carbamyl etc..
R2Represented acyl amino can also have substituent group, can be aliphatic, can also be aromatic series, can also be heterocycle, It can be any base as long as substitutive group is the group that described in the item of substituent group described above and can be replaced Group.R2Acyl amino be preferably total carbon atom number 2~12 acyl amino, the more preferably acyl group ammonia of total carbon atom number 1~8 Base, and then the alkyl-carbonyl-amino of preferably total carbon atom number 1~8, for example, can enumerate acetyl-amino, benzoyl-amido, 2- pyridine carbonylamino, propanoylamino etc..
R2Represented sulfoamido can also have substituent group, can be aliphatic, can also be aromatic series, can also be heterocycle. It can be any base as long as substitutive group is the group that described in the item of substituent group described above and can be replaced Group.R2Sulfoamido be preferably total carbon atom number 1~12 sulfoamido, the more preferably sulfonamide of total carbon atom number 1~8 Base, and then the alkylsulfonamido of preferably total carbon atom number 1~8, such as methylsulfonyl amido, benzene sulfonamido, 2- can be enumerated Pyridine sulfonyl sulfonyl amido etc..
R2Represented carbamyl amino can also have substituent group, as long as substitutive group is substitution described above It then can be any group, preferably fatty group, aryl, heterocycle etc. described in the item of base and the group that can be replaced.R2 Carbamyl amino be preferably carbamyl amino, the alkylcarbamoyl group amino of total carbon atom number 2~9, total carbon atom number 3 ~10 dialkyl carbamyl amino, the aromatic yl ammonia methanoyl amino of total carbon atom number 7~13, total carbon atom number 3~12 Heterocycle carbamyl amino, more preferably carbamyl amino, the alkylcarbamoyl group amino of total carbon atom number 2~7, total carbon are former The dialkyl carbamyl amino of subnumber 3~6, the aromatic yl ammonia methanoyl amino of total carbon atom number 7~11, total carbon atom number 3~ 10 heterocycle carbamyl amino, such as can enumerate: carbamyl amino, methylcarbamoyl amino, N, N- dimethylamino first Acyl amino, phenylcarbamoyl amino, 4- pyridine carbamyl amino etc..
R2Represented sulfamoyl can also have substituent group, as long as substitutive group is substituent group described above It then can be any group, preferably fatty group, aryl, heterocycle etc. described in and the group that can be replaced.R2Ammonia Sulfonyl is preferably the dialkyl amino sulphur of sulfamoyl, the alkylsulfamoyl group of total carbon atom number 1~9, total carbon atom number 2~10 Acyl group, the ammonia aryl sulfonyl of total carbon atom number 7~13, total carbon atom number 2~12 heterocyclic sulfonamides base, more preferably ammonia sulphur Acyl group, the alkylsulfamoyl group of total carbon atom number 1~7, the dialkyl sulfamine of total carbon atom number 3~6, total carbon atom number 6 The heterocyclic sulfonamides base of~11 ammonia aryl sulfonyl, total carbon atom number 2~10, such as can enumerate: sulfamoyl, methyl ammonia Sulfonyl, N, N- DimethylsuIfamoyl, phenyl sulfamoyl base, 4- pyridine sulfamoyl etc..
R2Represented aliphatic oxygroup can also have substituent group, can be saturation also be unsaturated, substitutive group It can be any group as long as being the group that described in the item of substituent group described above and can be replaced.R2Aliphatic Oxygroup is preferably the alkoxy of total carbon atom number 1~8, more preferably the alkoxy of total carbon atom number 1~6, such as can be enumerated: first Oxygroup, ethyoxyl, isopropoxy, cyclohexyloxy, methoxy ethoxy etc..
R2Represented aliphatic sulfenyl can also have substituent group, can be saturation also be unsaturated, substitutive group It can be any group as long as being the group that described in the item of substituent group described above and can be replaced.R2Aliphatic Sulfenyl is preferably the alkyl sulfenyl of total carbon atom number 1~8, more preferably the alkyl sulfenyl of total carbon atom number 1~6, such as can be arranged It lifts: methyl mercapto, ethylmercapto group, carbamyl methyl mercapto, tertiary butylthio etc..
R2Represented halogen atom is preferably fluorine atom, chlorine atom, bromine atom, can more preferably enumerate chlorine atom.With regard to this For the aspect of The effect of invention, R2Preferably aliphatic Epoxide carbonyl, the situation of carbamyl.With regard to the side of effect of the invention For face, m is preferably 0 or 1 situation, more preferably 0 situation.
General formula represented by A (A-1)~general formula (A-32) is illustrated.General formula (A-1)~general formula (A-32) is represented Position be preferably total carbon atom number 2~15, more preferably total carbon atom number 2~12.
R51~R54As long as represented substituent group is the base that described in the item of substituent group described above and can be replaced Group, then can be any group.R51~R54Substituent group be preferably fatty group, aryl, heterocycle, aliphatic Epoxide carbonyl, ammonia Formoxyl, acyl amino, sulfoamido, aliphatic oxygroup, aliphatic sulfenyl, cyano etc., more preferably fatty group, aliphatic Epoxide carbonyl, carbamyl, aliphatic oxygroup, cyano etc..
For the aspect of effect of the invention, R51~R54Preferably hydrogen atom, fatty group, aryl, heterocycle, rouge The situation of fat race Epoxide carbonyl, carbamyl, acyl amino, sulfoamido, aliphatic oxygroup, aliphatic sulfenyl, cyano etc., more Preferably hydrogen atom, fatty group, aliphatic Epoxide carbonyl, carbamyl, aliphatic oxygroup, the situation of cyano.
R55As long as represented substituent group is the group that described in the item of substituent group described above and can be replaced, It can be any group.R55Substituent group be preferably fatty group, aryl, heterocycle etc., more preferably fatty group, aryl, In With 5 yuan~6 circle heterocyclic ring base of aromatic series containing nitrogen-atoms in the contiguous bits at the bond position of nitrogen-atoms.
For the aspect of effect of the invention, R55The preferably situation of fatty group, aryl, heterocycle, more preferably Fatty group, aryl, 5 yuan~6 circle heterocyclic ring base of aromatic series containing nitrogen-atoms in the contiguous bits for being bonded position with nitrogen-atoms Situation, and then preferably with nitrogen-atoms bond position contiguous bits on 5 yuan~6 circle heterocyclic ring of aromatic series containing nitrogen-atoms The situation of base.By making R55For with nitrogen-atoms bond position contiguous bits on 5 yuan~6 yuan of aromatic series containing nitrogen-atoms it is miscellaneous Ring group is not only easy to be stably formed the intermolecular interaction of pigment molecular, but also is easy to be stably formed intramolecular mutual Effect.Thus it is easy to constitute the stable pigment of molecules align, is showing good form and aspect, high fastness (resistance to phosgene Body heat water etc.) aspect for preferably.
For the aspect of effect of the invention, as R55And preferably with nitrogen-atoms bond position contiguous bits on 5 yuan~6 circle heterocyclic ring base of aromatic series containing nitrogen-atoms can also have substituent group, as long as substitutive group is described above takes It then can be any group described in the item of Dai Ji and the group that can be replaced.Preferred substituent group is hydroxyl, aliphatic oxygen Base, carbamyl, aliphatic Epoxide carbonyl, aliphatic sulfenyl, amino, aliphatic amines, acyl amino, carbamyl amino, Can be saturated heterocyclyl be also unsaturated heterocycle base, can also be contracting ring heterocycle, preferably total carbon atom number 2~12 with 5 yuan~6 circle heterocyclic ring base of aromatic series containing nitrogen-atoms, more preferably total carbon atom number in the contiguous bits at the bond position of nitrogen-atoms 2~10 5 yuan~6 circle heterocyclic ring base of aromatic series containing nitrogen-atoms in the contiguous bits for being bonded position with nitrogen-atoms.Such as it can Enumerate: 2- thiazolyl, 2-[4-morpholinodithio base, 2- oxazolyl, 2- benzoxazolyl, 2- pyridyl group, 2- pyrazinyl, 3- pyridazinyl, 2- pyrimidine radicals (2-pyrimidinyl), 4- pyrimidine radicals, 2- imidazole radicals, 2- benzimidazolyl, 2- triazine radical etc., these heterocycles It can also be tautomer structure together with substituent group.
For the aspect of effect of the invention, as R55And preferred aryl can also have substituent group, substitutive base As long as group is the group that described in the item of substituent group described above and can be replaced, it can be any group, preferably take Dai Jiwei hydroxyl, nitro, fatty group, aliphatic oxygroup, carbamyl, aliphatic Epoxide carbonyl, aliphatic sulfenyl, amino, Aliphatic amines, acyl amino, carbamyl amino.R55Aryl be preferably total carbon atom number 6~12 aryl, more preferably The aryl of total carbon atom number 6~10, such as phenyl, 3- methoxyphenyl, 4- Carbamoylphenyl can be enumerated etc., preferably benzene Base.
For the aspect of effect of the invention, as R55And preferred fatty group can also have substituent group, may replace As long as group be described in the item of substituent group described above and the group that can be replaced, can be any group, preferably Substituent group be hydroxyl, nitro, aliphatic oxygroup, carbamyl, aliphatic Epoxide carbonyl, aliphatic sulfenyl, amino, aliphatic Amino, acyl amino, carbamyl amino.R55Fatty group be preferably total carbon atom number 1~6 alkyl, more preferably always The fatty group of carbon atom number 1~4, such as methyl, ethyl, methoxy ethyl, carbamoyhnethyl can be enumerated etc., preferably first Base.
In general formula (A2), R55The situation of either one or two of preferably following (Y-1)~(Y-13), in order to be easy to obtain intramolecular Hydrogen bond structure, the situation of either one or two of following (Y-1)~(Y-6) of more preferably 6 member rings, and then preferably following (Y-1), (Y-3), the situation of either one or two of (Y-4), (Y-6), the situation of especially preferably following (Y-1) or (Y-4).General formula (Y-1)~ * in general formula (Y-13) indicates the bond position with the N atom of pyrazole ring.Y1~Y11Indicate hydrogen atom or substituent group.(Y-13) In G11Expression may make up the non-metallic atom group of 5 yuan~6 circle heterocyclic rings, G11Represented heterocycle can be unsubstituted, and can also be had Substituted base, heterocycle can be that monocycle is also contracting ring.Formula (Y-1)~formula (Y-13) can also be tautomerism together with substituent group Body structure.
[changing 5]
Y1~Y11As long as represented substituent group is the base that described in the item of substituent group described above and can be replaced Group, then can be any group.Y1~Y11Substituent group be preferably fatty group, aryl, heterocycle, aliphatic Epoxide carbonyl, ammonia Formoxyl, acyl amino, sulfoamido, aliphatic oxygroup, aliphatic sulfenyl, cyano etc., more preferably fatty group, aliphatic Oxygroup, aliphatic sulfenyl, cyano etc..Y1~Y11In, 2 adjacent substituent groups can also form 5 member rings~6 member rings.
For the aspect of effect of the invention, Y1~Y11Preferably hydrogen atom, fatty group, aryl, heterocycle, fat The situation of race's Epoxide carbonyl, carbamyl, acyl amino, sulfoamido, aliphatic oxygroup, aliphatic sulfenyl, cyano etc., it is more excellent It is selected as hydrogen atom, fatty group, aliphatic Epoxide carbonyl, carbamyl, aliphatic oxygroup, the situation of cyano.
For the aspect of effect of the invention, the A in general formula (A2) is preferably 5 membered ring heterocyclics for the aspect of form and aspect Situation, more preferably nitrogenous or 5 circle heterocyclic ring of sulfur-bearing situation, and then preferably contain 2 or more heteroatomic 5 circle heterocyclic rings Situation.
R56~R57、R59As long as represented substituent group is that described in the item of substituent group described above and can be replaced Group, then can be any group.R56~R57、R59Substituent group be preferably fatty group, aryl, heterocycle, aliphatic oxygroup Carbonyl, carbamyl, acyl amino, sulfoamido, aliphatic oxygroup, aliphatic sulfenyl, cyano etc., more preferably aliphatic Base, aliphatic oxygroup, aliphatic sulfenyl, cyano etc..
For the aspect of effect of the invention, R56~R57、R59Preferably fatty group, aryl, heterocycle, aliphatic The situation of Epoxide carbonyl, carbamyl, acyl amino, sulfoamido, aliphatic oxygroup, aliphatic sulfenyl, cyano etc., more preferably For fatty group, aliphatic oxygroup, the situation of aliphatic sulfenyl, cyano.
R58As long as represented substituent group is the group that described in the item of substituent group described above and can be replaced, It can be any group.For the aspect of effect of the invention, R58The preferably substituent group of heterocycle, Hammett (Hammett) The electro base of drawing that the electro base of drawing that constant σ p value is 0.2 or more, more preferably σ p value are 0.3 or more.The upper limit is that σ p value is The 1.0 electro bases of drawing below.
R as the electro base of drawing that σ p value is 0.2 or more58Concrete example can enumerate: acyl group, acyloxy, carbamyl Base, alkoxy carbonyl, aryloxycarbonyl, cyano, nitro, dialkylphosphono, diaryl phosphin acyl group, diaryl phosphinyl, alkane Base sulfinyl, aryl sulfonyl kia, alkyl sulphonyl, aryl sulfonyl, sulfonyl oxygroup, acyl mercapto, sulfamoyl, sulphur Cyanic acid ester group, thiocarbonyl, halogenated alkyl, halogenated alkoxy, halogen aryloxy, halogenated alkyl amino, halogenated alkyl sulfenyl, warp σ p value draws aryl replaced electro base, heterocycle, halogen atom, azo group or selenium cyanate for other of 0.20 or more Base.
In addition, for the aspect of effect of the invention, R58The situation of preferably described (Y-1)~(Y-13), in order to hold Intramolecular hydrogen bond structure, the situation of either one or two of following (Y-1)~(Y-6) of more preferably 6 member rings are easily obtained, and then is preferably The situation of either one or two of (Y-1), (Y-3), (Y-4), (Y-6), the situation of especially preferably described (Y-1) or (Y-4).
It is enumerated in the heterocycle of (A-1)~(A-32) as the A in general formula (A2), as long as with the carbon that is bonded to azo group The adjacent atom of atom is hetero atom, then has the tendency that light fastness, hot fastness are got higher, by that will have such structure feature Pigment be used for colored filter, can get and show the colored filter of high contrast, therefore it is preferred that.
For the aspect of effect of the invention, azo pigments represented by general formula (A2) is preferably following scenario described: G is hydrogen Atom, R1For amino or the saturated heterocyclyl being bonded with nitrogen-atoms, m is 0 or 1, when m is 1 situation, R2For aliphatic oxygroup Carbonyl, carbamyl or aliphatic oxygroup, A are (A-1), (A-10)~(A-17), (A-20)~(A-23), (A-27), (A- 28), either one or two of (A-30)~(A-32), and n is 1 or 2.
More preferably following scenario described: G is hydrogen atom, R1For amino or with nitrogen-atoms be bonded saturated heterocyclyl, m be 0 or 1, when m is 1 situation, R2For aliphatic Epoxide carbonyl, carbamyl or aliphatic oxygroup, A is (A-1), (A-10), (A- 11), any of (A-13)~(A-17), (A-20), (A-22)~(A-23), (A-27), (A-28), (A-30)~(A-32) It is a, and n is 1 or 2.
And then preferably following scenario described: G is hydrogen atom, R1For amino or with nitrogen-atoms be bonded saturated heterocyclyl, m 0, A be (A-10), (A-11), (A-13)~(A-17), (A-20), (A-22)~(A-23), (A-27), (A-28), (A-30)~ Either one or two of (A-32), and n is 1 or 2.
Especially preferably following scenario described: G is hydrogen atom, R1For amino, m 0, A be (A-16)~(A-17), (A-20), (A-28), either one or two of (A-32), n are 1 or 2；Especially preferably G is hydrogen atom, R1It is (A-16) and n for amino, m 0, A For 1 or 2 situation.
For the aspect of effect of the invention, azo pigments represented by general formula (A2) is more preferably the following general formula (A3) Represented azo pigments.
For the azo pigments represented by general formula (A3), make Z or R using azo group55It is formed and is handed over the hydroxyl of naphthalene nucleus Pitch hydrogen bond, improve the flatness of pigment structure, intramolecular, intermolecular interaction become strong, as a result light fastness, hot fastness, Solvent resistance etc. is significantly increased, therefore it is preferred that.
Hereinafter, azo pigments represented by mutual-through type (A3), its tautomer, these salt or hydrate are subject in detail Explanation.
General formula (A3)
[changing 6]
In general formula (A3), R21、R22、R55、R59, m and n respectively with R defined in general formula (A2)1、R2、R55、 R59, m and n be Identical meanings.Z indicates that the σ p value of Hammett is 0.2 or more the electro base of drawing.The situation expression of n=2 passes through R21、R22、R55、 R59Or the dimer of Z.The situation expression of n=3 passes through R21、R22、R55、R59Or the trimer of Z.The situation expression of n=4 passes through R21、R22、R55、R59Or the tetramer of Z.General formula (A3) does not have ionic hydrophily base.
The substituent group that the σ p value of Hammett represented by Z is 0.2 or more can enumerate the R of general formula described above (A2)58's Group described in explanation.
The R of azo pigments represented by general formula (A3)21、R22、R55、R59, m, n preferred substituent group, range and general formula (A2) R1、R2、R55、R59, m and n it is identical.
For the aspect of effect of the invention, Z is preferably acyl group, carbamyl, alkoxy carbonyl, cyano, alkyl sulphur Acyl group, sulfamoyl, more preferably carbamyl, alkoxy carbonyl, cyano, the especially preferably situation of cyano.
For the aspect of effect of the invention, azo pigments represented by general formula (A3) is preferably following scenario described: R21For There can be the amino of substituent group, m is 0 or 1, when m is 1 situation, R22For aliphatic Epoxide carbonyl, carbamyl or aliphatic Oxygroup, R55For 5 yuan~6 circle heterocyclic ring base of aromatic series containing nitrogen-atoms, R in the contiguous bits at bond position59For hydrogen atom or rouge Fat race base, Z is acyl group, carbamyl, alkoxy carbonyl, cyano, alkyl sulphonyl or sulfamoyl, and n is 1 or 2.
More preferably following scenario described: R21For that can have the amino of substituent group, m 0, R55For any of (Y-1)~(Y-13) It is a, R59For hydrogen atom or fatty group, Z is carbamyl, alkoxy carbonyl or cyano, and n is 1 or 2.
And then preferably following scenario described: R21For that can have the amino of substituent group, m 0, R55For appointing for (Y-1)~(Y-6) One, R59For hydrogen atom or fatty group, Z is carbamyl, alkoxy carbonyl or cyano, and n is 1 or 2.
Especially preferably following scenario described: R21For that can have the amino of substituent group, m 0, R55For (Y-1), (Y-4) or (Y- 6), R59For hydrogen atom, Z is cyano, and n is 1 or 2.
For the aspect of effect of the invention, azo pigments represented by general formula (A2) or general formula (A3) is preferably " total Carbon number/azo group number " is 40 hereinafter, more preferably 30 or less.For the aspect of effect of the invention, general formula (A2) Or it is 700 or less that azo pigments represented by general formula (A3), which is preferably " molecular weight/azo group number ",.With regard to effect of the invention Aspect for, azo pigments represented by general formula (A2) or general formula (A3) preferably without sulfo group, carboxyl isoiony replace The situation that base replaces.
For azo-compound represented by the general formula (A2) in other forms, preferably A is (A-1)~(A-9), (A- 11)~(A-13), (A-17), (A-20)~(A-23), (A-27), (A-28), (A-30)~(A-32), more preferably (A- 11)~(A-13), (A-17), (A-20)~(A-23), (A-27), (A-28), (A-30)~(A-32), and then preferably (A- 17), (A-20), (A-22)~(A-23), (A-27), (A-28), (A-31), (A-32), and then more preferably (A-20), (A- 28), (A-32), especially preferably (A-20).In addition, being in turn preferably the R of (A-20)56For R59。
In the present invention, the tautomer of azo pigments represented by general formula (A2) or general formula (A3) is also included within its range It is interior.General formula (A2) or general formula (A3) be from chemical structure can use a variety of tautomers in the form of canonical structure table Show, can also be the tautomer other than documented structure, moreover it is possible to containing there are many in the form of the mixture of tautomer It uses.
For example, the azo pigments represented by general formula (A2), it is contemplated that azo-hydrazone represented by the following general formula (A1') Tautomer.
In the present invention, following general formula (A1') institute table of the tautomer as azo pigments represented by general formula (A2) The pigment shown is also included within the scope of its.
General formula (A1')
[changing 7]
In general formula (A1'), G, R1、R2, m, n and A respectively with G, R in general formula (A2)1、R2, m, n be identical meanings.
In azo pigments represented by general formula (A2), as described above as the general formula example of especially preferred azo pigments can arrange Lift azo pigments represented by the following general formula (A4-1)~general formula (A4-4).Azo pigments represented by the general formula (A2) is preferred For azo pigments represented by the following general formula (A4-1)~general formula (A4-4).
Hereinafter, azo pigments represented by mutual-through type (A4-1)~general formula (A4-4), its tautomer, these salt or Hydrate is described in detail.
[changing 8]
In general formula (A4-1)~general formula (A4-4), R1、R2, m and n respectively with the R in general formula (A2)1、R2, m and n be identical Meaning.X indicates that carbon atom or nitrogen-atoms, Ax and X and the carbon atom of adjoining are formed together 5 yuan~6 circle heterocyclic ring base of aromatic series, Bx It is formed together 5 yuan~6 circle heterocyclic ring base of aromatic series with adjacent carbon atom, specifically, expression is defined by the A of general formula (A2) (A-1)~(A-32) in corresponding group.Yx and nitrogen-atoms and the carbon atom of adjoining are formed together heterocycle, indicate by general formula (A2) R55Corresponding group in defined heterocycle.R23Indicate the R of general formula (A2) defined51、R54、R57、R58Deng substitution In base, it is equivalent to the substituent group for removing the resulting group of carbonyl from corresponding substituent group.R'1Indicate self-drifting (A2) defined R1Amino in remove the corresponding substituent group of-NH-.
The azo pigments represented by the general formula (A2), general formula (A3), general formula (A4-1)~general formula (A4-4), can think To a variety of tautomers.
In addition, azo pigments represented by general formula (A2) preferably has to form intramolecular hydrogen bond or molecule in the present invention The interior substituent group for intersecting hydrogen bond.Substituent group more preferably with the formation intramolecular hydrogen bond of at least more than one, particularly preferably For the substituent group for intersecting hydrogen bond with the formation intramolecular of at least more than one.
The factor of the preferably described structure can be enumerated: constitute azo pigments as shown in general formula (A4-1)~general formula (A4-4) The nitrogen-atoms of heterocycle contained by structure, the hydrogen atom of the hydroxyl of naphthalene substituent group and oxygen atom and azo group are mutual as it The carbonyl that replaces on the nitrogen-atoms of the hydrazone group of tautomeric or the azo ingredient contained by azo pigments structure, naphthalene substituent group The nitrogen-atoms intramolecular easy to form of the hydrogen atom and oxygen atom and azo group or the hydrazone group as its tautomer of hydroxyl Intersect hydrogen bond.
As a result, the flatness of molecule improves, interaction is further increased between Intramolecular, general formula (A4-1)~logical The crystallinity of azo pigments represented by formula (A4-4) gets higher (higher order structure easy to form), and the requirement performance as pigment is Light fastness, thermal stability, hydrothermal stability, water resistance, gas resistance and/or solvent resistance are significantly increased, therefore become Preferred example.
It is also preferably general formula (A3), general formula (A4-1) for azo pigments represented by general formula (A2) for the viewpoint Pigment represented by pigment represented by~general formula (A4-4), more preferably general formula (A3), general formula (A4-1) or general formula (A4-2), Especially preferably azo pigments represented by general formula (A3).
The concrete example of azo pigments used in the present invention for example can refer to Japanese Patent Laid-Open 2011-162760 bulletin 0094~paragraph of paragraph 0116 in the compound recorded, its content is incorporated into this specification.
In addition, pigment of the invention can also be used represented by the following general formula (1A), general formula (1B) and the general formula (1C) The pigment of one or more of quinophthalone compound (hereinafter sometimes referred to " specific quinophthalone compound ").By using quinophthalone Compound has the effect that brightness is high and contrast is high, and tinting strength, tinting power is excellent, colored filter coloured composition Lowering viscousity is excellent.
General formula (1A)
[changing 9]
General formula (1B)
[changing 10]
General formula (1C)
[changing 11]
In general formula (1A)~general formula (1C), R14~R28、R29~R43、R44~R60Separately indicate hydrogen atom, halogen Atom, the alkyl that can have substituent group, the alkoxy that can have substituent group, the aryl ,-SO that can have substituent group3H； -COOH； And 1 valence of these acidic groups~trivalent metal salt；Alkylammonium salt, the phthalimide methyl that can have substituent group or can Sulfamoyl with substituent group.
Herein, halogen atom can enumerate fluorine, chlorine, bromine, iodine.
In addition, can have the alkyl of substituent group in addition to methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, It other than the straight chains such as neopentyl, n-hexyl, n-octyl, stearyl, 2- ethylhexyl or branched alkyl groups, can enumerate: trichloromethyl, three Methyl fluoride, 2,2,2- trifluoroethyl, 2,2- dibromoethyl, tetra- fluoropropyl of 2,2,3,3-, 2- ethoxyethyl group, 2- butoxy second Base, 2- nitropropyl, benzyl, 4- methylbenzyl, 4- t-butylbenzyl, 4- methoxy-benzyl, 4- nitrobenzyl, 2,4- dichloro Benzyl etc. has the alkyl of substituent group.
In addition, can have the alkoxy of substituent group in addition to methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, Isobutoxy, tert-butoxy, neopentyl oxygen, 2,3- dimethyl -3- amoxy, positive hexyloxy, n-octyloxy, stearic oxygroup, 2- It other than the straight chains such as ethyl hexyl oxy or branch's alkoxy, can enumerate: trichloromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxies Base, 2,2,3,3- tetrafluoro propoxyl group, 2,2- di-trifluoromethyl propoxyl group, 2- ethoxy ethoxy, 2- Butoxyethoxy, 2- Nitro propoxyl group, benzyloxy etc. have the alkoxy of substituent group.
In addition, there can be the aryl of substituent group other than the aryl such as phenyl, naphthalene, anthryl, can enumerate: to methylbenzene Base, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4 dichloro benzene base, pentafluorophenyl group, 2- aminophenyl, 2- methyl- 4- chlorphenyl, 4- hydroxyl -1- naphthalene, 6- methyl -2- naphthalene, the chloro- 2- naphthalene of 4,5,8- tri-, anthraquinonyl (anthraquinonyl), 2- amino anthracene quinonyl etc. has the aryl of substituent group.
In addition, acidic groups can enumerate-SO3H, 1 valence~trivalent metal salt of-COOH, these acidic groups can be enumerated: sodium salt, Sylvite, magnesium salts, calcium salt, molysite, aluminium salt etc..In addition, the alkylammonium salt of acidic groups can be enumerated: octyl amine, lauryl amine, stearyl The ammonium salt of the long-chains monoalkylamine such as amine, palmityl trimethyl ammonium, dilauryl dimethyl, distearyl dimethyl ammonium etc. four Grade alkylammonium salt.
There can be the phthalimide methyl (C of substituent group6H4(CO)2N-CH2) and can have the ammonia sulphur of substituent group Acyl group (H2NSO2) in " substituent group " can enumerate: the halogen atom, can have substituent group at the alkyl that can have substituent group Alkoxy, the aryl that can have substituent group etc..
In turn, for the viewpoint of the lowering viscousity of dispersion, quinophthalone compound is more preferably general formula (1A)~general formula The R of (1C)14~R28、R29~R43、R44~R60For hydrogen atom or halogen atom.
The concrete example of quinophthalone compound can enumerate it is following shown in quinophthalone compound (a)~quinophthalone compound (r) Deng, but the present invention is not limited to these compounds.
[changing 12]
[changing 13]
[changing 14]
In addition, pigment of the invention also can be used phthalocyanine dye represented by the following general formula (1) (hereinafter sometimes referred to " special Determine phthalocyanine dye ").
General formula (1)
[changing 15]
In general formula (1), A1~A16Separately indicate hydrogen atom, halogen atom, nitro, the alkyl that there can be substituent group Or there can be the aryl of substituent group.R1And R2It separately indicates hydrogen atom, hydroxyl, the alkyl that can have substituent group, can have The aryl of substituent group or-OR3, R1With R2It can also mutually be bonded and form ring.R3It is taken for that can have the alkyl of substituent group or can have The aryl of Dai Ji.
It is exemplified below the concrete example of workable specific phthalocyanine pigment in the present invention, but is not limited to these concrete examples.
[changing 16]
[changing 17]
Diketopyrrolopyrrolecocrystals system pigment represented by following formula (2) also can be used in pigment of the invention.
[changing 18]
(in formula (2), A and B be separately hydrogen atom, fluorine atom, iodine atom, cyano, carbon number 1~12 alkyl, can Phenyl ,-CF with substituent group3、-OR1、-SR2、-N(R3)R4、-COOR5、-CONH2、-CONHR6、 -CON(R7)R8、- SO2NH2、-SO2NHR9Or-SO2N(R10)R11, R1~R11It is separately the alkyl of carbon number 1~12, there can be substituent group Phenyl or the aralkyl that can have substituent group.Wherein, A and B is not hydrogen atom simultaneously)
In specific miscellaneous diketo-pyrrolo pyrrole pigments represented by formula used in pigment of the invention (2), with regard to brightness, For the aspect of contrast and the effect for inhibiting crystallization to be precipitated, preferably also formula (2-1), formula (2-2), formula (2-3), formula (2-4). In addition, for the aspect of contrast and the effect for inhibiting crystallization to be precipitated, the R of formula (2-3), formula (2-4)6~R8Preferably carbon number 4 Above alkyl or the phenyl that can have substituent group.It is believed that these are played in high contrast and in terms of inhibiting crystallization precipitation The reasons why effect, is: due to carbonamido (carboamide group), the phenyl, tertiary fourth of the alkyl with 4 or more carbon number The cohesion of the steric effects of the bulky substituents such as base, pigment is inhibited.In addition, with carbonamido, phenyl, tert-butyl Specific miscellaneous diketo-pyrrolo pyrrole pigments will not undermine bromination diketopyrrolopyrrolecocrystals face since color characteristics are also excellent The excellent brightness of material.
[changing 19]
(in formula (2-3) and formula (2-4), R6~R8Separately for carbon number 1~12 alkyl or can have substituent group Phenyl)
It is exemplified below the concrete example of the specific miscellaneous diketo-pyrrolo pyrrole pigments of workable formula (2) in the present invention, but It is not limited to these concrete examples.
[changing 20]
[changing 21]
[changing 22]
[changing 23]
About the primary particle size of pigment, when being used as the situation of colored filter, with regard to irregular colour or contrast Viewpoint for, preferably 100nm is hereinafter, in addition, for the viewpoint of dispersion stabilization, preferably 5nm or more.The one of pigment Secondary particle size is more preferably 5nm~75nm, and then preferably 5nm~55nm, especially preferably 5nm~35nm.Of the invention Specific dispersion resin can play particularly good in the pigment combination with the primary particle size of the range with 5nm~35nm Effect.
The primary particle size of pigment can be measured using method well known to electron microscope etc..
Pigment is preferably selected from anthraquione pigmentss, diketopyrrolopyrrolecocrystals system pigment, phthualocyanine pigment, quinophthalone system face Pigment in material, isoindoline system pigment, azomethine system pigment and dioxazine pigment.It is particularly most preferably C.I. paratonere 122, C.I. paratonere 177 (anthraquione pigmentss), C.I. paratonere 254 (diketopyrrolopyrrolecocrystals system pigment), C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 15: 6 (phthualocyanine pigments), (the quinoline phthalein of C.I. pigment yellow 13 8 Ketone system pigment), C.I. pigment yellow 13 9, C.I. pigment yellow 185 (isoindoline system pigment), (the azomethine system of C.I. pigment yellow 150 Pigment), C.I. pigment Violet 23 (dioxazine pigment).
In addition, composition of the invention contains the well known dyestuff other than (A) pigment.Such as Japan Patent can be used Tekiaki 64-90403 bulletin, Japanese Patent Laid-Open No. Sho 64-91102 bulletin, Japanese Patent Laid-Open 1-94301 public affairs Report, Japanese Patent Laid-Open 6-11614 bulletin, Japan Patent spy step on No. 2592207, No. 4808501 specifications of United States Patent (USP), No. 5667920 specifications of United States Patent (USP), No. 505950 specifications of United States Patent (USP), Japanese Patent Laid-Open 5-333207 bulletin, Japanese Patent Laid-Open 6-35183 bulletin, Japanese Patent Laid-Open 6-51115 bulletin, Japanese Patent Laid-Open 6- The pigment disclosed in No. 194828 bulletins etc..Chemical structure can be used: pyrazoles azo system, pyrroles's methylene base system, anilino- azo System, triphenyl methane system, anthraquinone system, benzal base system, oxonols system, Pyrazolotriazole azo system, pyridone azo system, cyanine The dyestuff of system, phenthazine system, pyrrolo-pyrazole azomethine system etc..
In addition, pigment polymer can also be used in dyestuff.Pigment polymer can enumerate Japanese Patent Laid-Open 2011-213925 The compound recorded in bulletin, Japanese Patent Laid-Open 2013-041097 bulletin.
Relative to total ingredient (solid component) in addition to solvents contained by photosensitive composition, this hair The content of pigment in bright composition is preferably the 10 mass % of mass %~70, more preferably the 20 mass % of mass %~60, And then preferably 30 mass of mass %~60 %.
Pigment can also contain two or more in the present compositions only containing one kind.Containing two or more When situation, preferably its total amount becomes the range.
< < (B) alkalinity pigment derivative > >
Composition of the invention contains (B) alkaline pigment derivative.Alkaline pigment derivative is will with utilization basic group The compound for the structure that a part of pigment replaces.
Pigment to constitute alkaline pigment derivative can be enumerated: quinoline system pigment, benzimidazolone system pigment, iso-indoles Quinoline system pigment, diketopyrrolopyrrolecocrystals system pigment, azo pigment, phthualocyanine pigment, anthraquione pigmentss, quinacridone face Material, purple cyclic ketones system pigment, is pigment, thioindigo system pigment, isoindolinone pigment, quinophthalone system face at dioxazine pigment Material, reduction (threne) are pigment, metal complex system pigment etc..
Alkaline pigment derivative is preferably the alkaline pigment derivative of quinoline system, benzimidazolone system, isoindoline system, more The preferably alkaline pigment derivative of benzimidazolone system.
It can specifically illustrate: the compound recorded in Japanese Patent Laid-Open No. Sho 60-88185 bulletin, Japanese Patent Laid-Open Recorded in the compound and Japanese Patent Laid-Open 2009-86375 bulletin recorded in 2000-239554 bulletin in molecule It is interior that there is pigment mother nucleus structure and the compound of amino etc., its content is incorporated into this specification.
Basic group possessed by alkaline pigment derivative is preferably amino.
Wherein, alkaline pigment derivative is preferably pigment derivative represented by the following general formula (P1) or logical formula (I).
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A-N=N-X-Y (P1)
In general formula (P1), A indicates the ingredient that azo pigments can be formed together with X-Y.As long as the A can be with diazotising The compound that object (diazonium compound) is coupled and forms azo pigments is closed, then can arbitrarily be selected.Described in following presentation The concrete example of A, but the present invention is not limited to these concrete examples.
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In the general formula (P1), X indicates singly-bound (meaning that Y is directly bonded to-N=N-) or selected from by following structural formula table The base of the concatenating group for the divalent shown.
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In the general formula (P1), Y indicates the base indicated by the following general formula (P2).
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In general formula (P2), Z indicates low-grade alkylidene.Z expression-(CH2)b, the integer of the b expression 1~5, preferably b Indicate 2 or 3.In general formula (P2) ,-NR2Indicate the 5- or 6-membered saturated heterocyclic of low-grade alkyl amino or nitrogen atom.Institute State-NR2In the case where indicating low-grade alkyl amino ,-the NR2Expression-N (CnH2n+1)2, the integer of n expression 1~4, preferably n Indicate 1 or 2.On the other hand, in-the NR2In the case where the 5- or 6-membered saturated heterocyclic for indicating nitrogen atom ,-the NR2 The heterocycle preferably indicated by following structural formula.
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In the general formula (P2), Z and-NR2Can have low alkyl group, alkoxy as substituent group respectively.The general formula (P2) in, a indicates 1 or 2, and preferably a indicates 2.
The concrete example (1~concrete example of concrete example 22) for the compound that following presentation is indicated by the general formula (P1), but this hair It is bright to be not limited to these concrete examples.
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Logical formula (I)
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In logical formula (I), Dye indicates that the organic pigment residue of n valence, X indicate singly-bound ,-CONH-Y2-、-SO2NH-Y2Or- CH2NHCOCH2NH-Y2-(Y2Indicate the alkylidene or arlydene that can have substituent group), Y1Expression-NH- or-O- indicates 1 in n When situation, Z indicates hydroxyl, the alkoxy, (X in X and logical formula (I) of group or-NH-X-Dye represented by the following general formula (III) For identical meanings), when n indicates the situation of 2~4 integer, Z respectively indicates hydroxyl, alkoxy or the following general formula (III) institute table The group shown, R1And R2Respectively indicate the alkyl that there can be substituent group, R1With R2It can also mutually be bonded and be formed containing nitrogen-atoms Heterocycle.M indicates that 1~6 integer, n indicate 1~4 integer.When n is 2 or more situation, multiple X, Y1、R1And R2Difference can It is identical can also be different.
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In logical formula (III), Y3Expression-NH- or-O-.R1And R2Respectively indicate the alkyl that there can be substituent group, R1With R2It can also It is mutually bonded and forms the heterocycle containing nitrogen-atoms.M indicates 1~6 integer.
The organic pigment residue of Dye expression n valence.Organic pigment residue can enumerate the colour developing atom in pigment as described above Group, its similar structures or part-structure, it is specific enumerable: containing selected from the skeleton with azo group, the skeleton with urea structure, Skeleton with amide structure, the skeleton with cyclic amide structure, with containing heteroatomic 5 member ring aromatic ring and tool There is the structure of the part-structure of one or more of aromatic ring containing heteroatomic 6 member ring, Dye is to contain these organic pigments The substituent group of residue.
Dye preferably has pigment mother nucleus structure or pigment mother nucleus structure and aromatic rings or nitrogenous aromatic rings or oxygen-containing Aromatic rings or sulfur-bearing aromatic rings, amino are to be bonded to pigment mother nucleus structure, aromatic rings, nitrogenous virtue directly or with concatenating group Either one or two of fragrant ring, oxygen-containing aromatic rings, sulfur-bearing aromatic rings.It is specific enumerable: quinoline system residue, benzimidazolone system residue, different Indoline system residue, diketopyrrolopyrrolecocrystals system residue, azo system residue, phthalocyanine system residue, anthraquinone system residue, quinacridone It is residue, dioxazines system residue, purple cyclic ketones system residue, is residue, thioindigo system residue, isoindolinone system residue, quinophthalone Be residue, reduction be residue, metal complex system residue etc..
The specific enumerable copper phthalocyanine residue of organic pigment residue represented by Dye, organic pigment residue below etc..Formula In, * indicates the bond position with the X in logical formula (I).
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In these, it is however preferred to have the monoazo pigment of benzimidazolone skeleton.
X indicates singly-bound ,-CONH-Y2-、-SO2NH-Y2Or-CH2NHCOCH2NH-Y2, preferably singly-bound.
Y2Indicate the alkylidene or arlydene that there can be substituent group.The alkylidene is preferably the alkylidene of carbon number 1~10, The more preferably alkylidene of carbon number 1~6, and then the alkylidene of preferably carbon number 1~3.It is specific enumerable: methylene, ethylidene, Propylidene, butylidene, pentylidene, hexylidene etc..Alkylidene can also have substituent group, and substituent group can enumerate the item of the substituent group Described in group.
The arlydene is preferably the arlydene of carbon number 6~20, more preferably the arlydene of carbon number 6~10.It can specifically arrange Lift phenylene, naphthylene, anthrylene etc..
Alkylidene and arlydene can also have substituent group, and substituent group can enumerate group described in the item of the substituent group.
Y1Expression-NH- or-O-, preferably-NH-.
R1And R2Respectively indicate the alkyl that there can be substituent group, R1With R2It can also mutually be bonded and be formed containing nitrogen-atoms Heterocycle.
The alkyl is preferably the alkyl of carbon number 1~10, more preferably the alkyl of carbon number 1~6.It is specific enumerable: methyl, Ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, neopentyl, n-hexyl, n-octyl etc..Alkyl can also have substitution Base, substituent group can enumerate group described in the item of the substituent group.
R1And R2Preferably indicate the identical alkyl with substituent group.
The integer of m expression 1~6, preferably 1~4, more preferably 1~3.
N indicates 1~4 integer, preferably 1~3, more preferably 1 or 2.
When n indicates 1 situation, Z indicates hydroxyl, alkoxy, group or-NH-X- represented by the logical formula (III) Dye (X in X and logical formula (I) is identical meanings), when n indicates the situation of 2~4 integer, Z respectively indicates hydroxyl, alcoxyl Group represented by base or the logical formula (III).
When n indicates 1 situation, Z is preferably group or-NH-X-Dye represented by the logical formula (III), more preferably Group represented by the logical formula (III).
When n indicates the situation of 2~4 integer, Z is preferably group represented by the logical formula (III).
In logical formula (III), Y3Expression-NH- or-O-, preferably-NH-.Y3It preferably indicates and the Y in logical formula (I)1It is identical Group.
R in logical formula (III)1And R2The alkyl that there can be substituent group is respectively indicated, with the R in logical formula (I)1And R2For phase Same meaning, preferred scope are also identical.R in logical formula (III)1And R2Preferably indicate the identical alkyl with substituent group.Separately Outside, lead to the R in formula (III)1And R2It preferably indicates and the R in logical formula (I)1And R2The identical alkyl with substituent group.
The integer of m expression 1~6, preferably 1~4, more preferably 1~3.M is preferably indicated and the m phase in logical formula (I) Same integer.
It is described below the present invention used in alkalinity pigment derivative concrete example, but the present invention is not limited to these specifically Example.
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Relative to total solid content, the content of (B) alkaline pigment derivative in the present invention be preferably 0.5 mass % with Upper, 40 mass % are hereinafter, more preferably 1 mass % or more, 15 mass % or less.
In addition, relative to 100 mass parts of (A) pigment, the content of (B) alkalinity pigment derivative be preferably 0.5 mass parts with It is upper, 50 below the mass, more than more preferably 1 mass parts, 25 below the mass.
Alkaline pigment derivative can also contain two or more in the present compositions only containing one kind.Containing When two or more situations, preferably its total amount becomes the range.
< < (C) leads to phosphate dispersing agent > > represented by formula (II)
Composition of the invention contains (C) and leads to phosphate dispersing agent represented by formula (II).By containing the phosphate Dispersing agent, dispersing agent be strongly adsorbed in pigment particles, can inhibit along with composition through when color spot deteriorate.In addition, In When the color compositions recorded in patent document 3 and patent document 4 are directly used in the situation of photosensitive composition, (C) poor compatibility of ingredient and other compositions, through when color spot slightly become larger, the patternability after PCD is excessively poor, but this In invention, described problem is eliminated and being used in combination with (D) ingredient.
Logical formula (II)
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In logical formula (II), R3Indicate that number average molecular weight is 400~30000 polyester construction, y indicates 1 or 2.In y For 2 situation when, multiple R3It may be the same or different respectively.
R3Indicate that number average molecular weight is 400~30000 polyester construction, when y is 2 situation, multiple R3Difference can It is identical can also be different.The number average molecular weight of the polyester construction is more preferably 1900~10000, and then preferably 400~ 3000, especially preferably 2000~3000.Lack pigment-dispersing ability in the situation less than 400, therefore is not available.
Polyester construction can be enumerated: by the resulting polyester base of internal ester monomer ring-opening polymerisation, have styryl, acryloyl group, The polyester construction of cyanoacrylate acyl group, methylacryloyl, vinyl ether etc., it is preferably that internal ester monomer ring-opening polymerisation is resulting Polyester base.
Phosphate dispersing agent represented by logical formula (II) can be R3For the phosphate of single kind, it is possible to use a variety of to include Different R3Phosphate.In addition, can be individually a kind of for the phosphate dispersing agent of y=1, it can also be the phosphate dispersing agent of y=1 With the mixture of the phosphate dispersing agent of y=2.
The phosphate represented by logical formula (II), if the phosphate dispersing agent of the phosphate dispersing agent and y=2 of y=1 In the presence of than for 100:0~100:30, then pigment-dispersing becomes good and preferred.
In addition, if the R of phosphate dispersing agent represented by logical formula (II)3It is 400~10000 for number average molecular weight Polyester construction, then pigment-dispersing becomes good and preferred.More preferably 400~3000.
In turn, if the R of phosphate dispersing agent represented by logical formula (II)3For two or more different internal ester monomers are opened The resulting polyester construction of cyclopolymerization, then effect of the invention becomes excellent, very preferably.
In turn, lead to the R of phosphate dispersing agent represented by formula (II)3Preferably by the following general formula (11) represented by.
General formula (11)
R12-O-R13-(O-R14)S
(in formula, R12Indicate alkylidene, R13Indicate the polyol structure of ternary or more, R14Indicate acryloyl group, cyano third Enoyl-, methylacryloyl, s indicate 2 or more)
R12The preferably alkylidene below of carbon number 8.In addition, s is preferably 2 or more for the viewpoint of pigment-dispersing.In When the situation, R14Mutually different group can also be used.S is more preferably 2~5, especially preferably 2.
R13Polyalcohol more than ternary used can be enumerated: glycerol, propyl alcohol, pentaerythrite, dipentaerythritol etc..It is especially excellent It is selected as ternary~hexahydroxylic alcohols.
The acid value of phosphate dispersing agent is preferably 10mgKOH/g~300mgKOH/g, more preferably 30mgKOH/g~200 MgKOH/g, and then preferably 40mgKOH/g~150mgKOH/g.
The manufacture of phosphate dispersing agent can be manufactured using well known method, such as can refer to Japanese Patent Laid-Open 2007- The record of 0037~paragraph of paragraph 0051 of No. 231107 bulletins, its content is incorporated into this specification.
Relative to total solid content, the content of the phosphate dispersing agent in composition of the invention be preferably 1 mass %~ 30 mass %, the more preferably 2 mass % of mass %~20, and then preferably 4 mass of mass %~15 %.
In addition, the content of (C) phosphate dispersing agent is preferably 5 mass parts~60 matter relative to 100 mass parts of (A) pigment Measure part, more preferably 9 mass parts~40 mass parts.
Phosphate dispersing agent can also contain two or more in the present compositions only containing one kind.Containing two Kind or more situation when, preferably its total amount become the range.
Other than described, other dispersing agents can also be contained, Japanese Patent Laid-Open 2013-073104 bulletin can also be contained 0338~0333 in the dispersing agent recorded, these contents are incorporated into present specification.
< < (D) is by compound (x) represented by logical formula (IV) and with the compound (y) of ethylene unsaturated double-bond Resin > > made of combined polymerization
Composition of the invention contains (D) for compound (x) represented by logical formula (IV) and has ethylene unsaturated double Resin made of compound (y) combined polymerization of key (hereinafter also referred to specific resin adhesive).In patent document 1 or patent document In 2, (D) ingredient plays a role as so-called dispersing agent.In contrast, (D) ingredient is as expanding material in the present application And it plays a role.Its reason can be presumed as follows.That is, polyester is residual for (C) ingredient (phosphate dispersing agent) of the invention Base is easy cohesion crystallization each other, has and other compositions (such as (E) polymerization initiator or (F) polymerism for constituting composition Close object etc.) occur mutually to separate and the only tendency of the cohesion of (C) ingredient, crystallization.It could be speculated that if adding (D) ingredient, (D) wherein Sterically bulky aromatic rings position (leads to-Ph-R of compound (x) represented by formula (IV) contained by ingredient6Represented Part) it enters in the polyester residue moiety of (C) ingredient and prevents the mutual cohesion crystallization of polyester residue, it as a result plays and inhibits (C) effect mutually separated occurs for ingredient.
In addition, the color compositions recorded in the patent document 3 or patent document 4 are directly used in coloring phototonus When the situation of resin combination, as described above, there is (C) phosphate dispersing agent mutually to separate with the other compositions generation for constituting composition Tendency described problem is eliminated by allotment (D) ingredient but in the present invention, can effectively inhibit and constitute each of composition There is a situation where mutually separate during the placement (PCD) of ingredient after coating.
Logical formula (IV)
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In logical formula (IV), R4Indicate hydrogen atom or methyl, R5Indicate the alkylidene of carbon number 2 or 3, R6Expression hydrogen atom can The alkyl of carbon number 1~20 containing phenyl ring, n indicate 1~15 integer.When n is 2 or more situation, multiple R5It can be identical It can be different.
R6Indicate the alkyl of hydrogen atom or the carbon number 1~20 containing phenyl ring.R6Represented alkyl is that carbon number is 1~20 Alkyl, the preferably alkyl of carbon number 1~10.R6Represented alkyl can be enumerated: methyl, ethyl, propyl, butyl, amyl, oneself Base, heptyl, octyl, nonyl, decyl etc..
R6The represented alkyl containing phenyl ring can be enumerated: 1- phenylethyl, 1- phenyl propyl, 1- phenyl butyl, 1- benzene Base amyl, 1- Phenylhexyl, 1- phenylheptyl, 1- phenyl octyl, 1- phenyl nonyl, 1- phenyl decyl, benzyl, 2- phenyl (different) Propyl etc..
In these, preferably benzyl, 2- phenyl (different) propyl.
Compound (x) can be enumerated: modified (methyl) acrylate of the ethylene oxide (Ethylene Oxide, EO) of phenol, The EO or propylene oxide (Propylene Oxide, PO) of p -cumylphenol are modified (methyl) acrylate, the EO of nonyl phenol changes Property (methyl) acrylate, modified (methyl) acrylate of PO of nonyl phenol etc..In these compounds, resin is just sufficiently obtained (D) for the aspect as the function of expanding material, modified (methyl) acrylic acid of the EO or PO of especially preferably p -cumylphenol Ester.
Compound (y) with ethylene unsaturated double-bond can be enumerated: (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid (different) propyl ester, (methyl) acrylic acid (different) butyl ester, (methyl) acrylic acid (different) Pentyl ester, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) Cyclohexyl acrylate, (methyl) glycidyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid phosphinylidyne Oxygroup ethyl ester, (methyl) acrylic acid phosphinylidyne oxygroup propyl ester, the chloro- 2- acid phosphorus acyloxy ethyl ester of (methyl) acrylic acid -3-, acid Property phosphinylidyne oxygroup polyethyleneglycol (methyl) acrylate etc..
The ratio of compound (x) in (D) resin of the invention is the 0.1 mass % of mass %~50, more preferably 10 matter Measure the mass of %~35 %.If the ratio of compound (x) is less than 10 mass %, the effect as expanding material of resin (D) is reduced, If the effect as expanding material of resin (D) further decreases, therefore not good enough and then less than 0.1 mass %.In addition, if being more than Then hydrophobicity becomes larger 35 mass %, and the developability of photosensitive composition reduces sometimes, or leads to residue, and if then more It is substantially reduced in compatibility of the 50 mass % then with other constituents in photosensitive composition, also causes sometimes The precipitation of monomer or Photoepolymerizationinitiater initiater.
The weight average molecular weight (Mw) of (D) resin (copolymer) of the invention is preferably 5000~100000, more preferably It is 10000~50000.
In addition, in order to make monomer or resin react with each other and improve the sensitivity of photosensitive composition, it can be at this Ethylene double bond is imported on the side chain of (D) resin (copolymer) of invention.Specifically, there is hydroxyl isoreactivity in resin When the situation of functional group, by having (methyl) glycidyl acrylate, 2- (methyl) acryloxy isocyanate etc. The compound of the functional group and ethylene unsaturated group that react with the reactive functional group react, and ethylene is imported on side chain Property double bond.
(D) manufacture of resin can be manufactured using well known method, such as can refer to Japanese Patent Laid-Open 2004-101728 The record of 0041~paragraph of paragraph 0045 of number bulletin, its content is incorporated into this specification.
Relative to total solid content, the content of (D) resin of composition of the invention is preferably 1 matter of mass %~50 Measure %, the more preferably 3 mass % of mass %~40, and then preferably 5 mass of mass %~30 %.
In addition, the content of (D) resin is preferably 5 mass parts~80 mass parts, more excellent relative to 100 mass parts of (A) pigment It is selected as 10 mass parts~70 mass parts.By the way that the content of (D) resin is set as 5 mass parts relative to 100 mass parts of (A) pigment ~80 mass parts, (D) resin are effectively functioned as expanding material rather than are functioned as dispersing agent, effect of the invention Become excellent.
(D) resin can also contain two or more in the present compositions only containing one kind.Containing two or more Situation when, preferably its total amount become the range.
< (E) Photoepolymerizationinitiater initiater >
For the viewpoint for further increasing sensitivity, composition of the invention contains Photoepolymerizationinitiater initiater.
As long as the Photoepolymerizationinitiater initiater has the ability for the polymerization for causing aftermentioned polymerizable compound, special limit is had no System, can suitably select from well known Photoepolymerizationinitiater initiater.Such as preferably have to ultraviolet ray range to luminous ray photosensitive Property.In addition, can also also be able to be to generate the activating agent of living radical with certain effects occur through light activated sensitizer Cause the initiator as cationic polymerization according to the type of monomer.
In addition, the Photoepolymerizationinitiater initiater preferably contains at least one in about 300nm~800nm (more preferably 330nm ~500nm) in the range of at least about 50 molecule absorptivity compound.
The Photoepolymerizationinitiater initiater can for example be enumerated: halogenation hydrocarbon derivative (such as with triazine skeleton, have oxadiazoles Skeleton etc.), oxidation acylphosphanes (acyl phosphine oxide) etc. acylphosphine compounds, six aryl bisglyoxalines, oxime it is derivative The oxime compounds such as object, organic peroxide, sulphur compound, ketone compound, aromatic series salt, ketoxime ether, aminoacetophenone chemical combination Object, hydroxy acetophenone etc..
In addition, being preferably selected from for the viewpoint for exposing sensitivity by trihalomethyl group triaizine compounds, benzil diformazan Base ketal compound, alpha-hydroxyacetone compounds, α-aminoketone compound, acylphosphine compounds, phosphine oxide compound, metallocene Close object, oxime compound, triarylimidazoles dimer, compound, benzothiazole compound, benzophenone cpd, acetophenone Compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halogenated methyl oxadiazole compound, 3- aryl substitution perfume Compound in group composed by legumin compound.
Commercially available product can also be used in trihalomethyl group triaizine compounds, such as TAZ-107 (green (midori) chemistry can also be used Company's manufacture).
Especially when composition of the invention to be used to make the situation for the colored filter that solid-state imager has, Fine pattern must be formed with the shape of sharp (sharp), it is therefore important that hardenability in unexposed portion without residue Develop on ground.For such viewpoint, Photoepolymerizationinitiater initiater especially preferably uses oxime compound.Especially in solid-state image pickup member In part formed fine pattern situation when, hardening with exposure when use step printing, but sometimes the exposure machine because of halogen And it is damaged, it is necessary to the additive amount of Photoepolymerizationinitiater initiater be inhibited low, if therefore in view of being most preferably in terms of these When forming the fine pattern such as solid-state imager, use oxime compound as (E) Photoepolymerizationinitiater initiater.
The halogenation hydrocarbon derivative with triazine skeleton, the ketone compound and it is described other than Photoepolymerizationinitiater initiater can The compound recorded in 0074~paragraph of paragraph 0077 referring to Japanese Patent Laid-Open 2013-077009 bulletin, by its content It is incorporated into this specification.
Photoepolymerizationinitiater initiater also preferably uses hydroxy acetophenone compound, aminoacetophenone compounds and acylphosphanes Close object.More specifically, the aminoacetophenone system recorded in Japanese Patent Laid-Open 10-291969 bulletin such as also can be used The oxidation acylphosphanes series initiators recorded in No. 4225898 initiator, Japanese Patent No. bulletins.
Hydroxy acetophenone series initiators can be used: gorgeous good solid (IRGACURE) -184, Da Luoka (DAROCUR) -1173, gorgeous Good solid (IRGACURE) -500, gorgeous good solid (IRGACURE) -2959, (trade name: being Bath to gorgeous good solid (IRGACURE) -127 Husband (BASF) company manufacture).Aminoacetophenone series initiators can be used: as commercially available product gorgeous good solid (IRGACURE) -907, Gorgeous good solid (IRGACURE) -369 and gorgeous good solid (IRGACURE) -379, gorgeous good solid (IRGACURE)-OXE379 (trade name: For the manufacture of BASF (BASF) company).Aminoacetophenone series initiators also can be used absorbing wavelength and 365nm or 405nm isometric The compound recorded in the Japanese Patent Laid-Open 2009-191179 bulletin of wave source matching (matching).In addition, acylphosphanes Gorgeous good solid (IRGACURE) -819 or Da Luoka (DAROCUR)-TPO (commodity as commercially available product also can be used in series initiators Name: being the manufacture of BASF (BASF) company).
Photoepolymerizationinitiater initiater can more preferably enumerate oxime compound.Japanese Patent Laid-Open can be used in the concrete example of oxime compound The compound recorded in the compound recorded in 2001-233842 bulletin, Japanese Patent Laid-Open 2000-80068 bulletin, day The compound recorded in this patent special open 2006-342166 bulletin.In addition, oxime compound can be enumerated: " Britain's chemistry can will (Journal of the Chemical Society, J.C.S.) Poole gold proceedings (Perkin) II " (1979) pp.1653- 1660, " Britain's chemistry can will (Journal of the Chemical Society, J.C.S.) Poole gold proceedings (Perkin) II " (1979) pp.156-162, " photopolymer science and technology periodical (Journal of Photopolymer Science and Technology) " (nineteen ninety-five) pp.202-232, remember in Japanese Patent Laid-Open 2000-66385 bulletin The compound of load, Japanese Patent Laid-Open 2000-80068 bulletin, Japanese patent special table 2004-534797 bulletin, Japan are specially The compound etc. recorded in each bulletin of sharp special open 2006-342166 bulletin.
Commercially available product it may also be preferred to use gorgeous good solid (IRGACURE)-OXE01 (manufacture of BASF (BASF) company), gorgeous good (Gu IRGACURE)-OXE02 (manufacture of BASF (BASF) company), TR-PBG-304 (Changzhou potenxin Materials Co., Ltd system It makes).
Preferably the oxime compounds such as 9 oxime derivate as Photoepolymerizationinitiater initiater of the invention can refer to Japan Patent spy The compound recorded in 0080~paragraph of paragraph 0116 of 2013-077009 bulletin is opened, its content is incorporated to this specification In.
Oxime compound has maximum absorption wavelength in the wave-length coverage of 350nm~500nm, preferably in 360nm~480 There is absorbing wavelength, the absorbance height of especially preferably 365nm and 455nm in the wave-length coverage of nm.
For the viewpoint of sensitivity, the 365nm or the molar absorption coefficient under 405nm of oxime compound be preferably 1,000~ 300,000, more preferably 2,000~300,000, especially preferably 5,000~200,000.
Well known method can be used to measure for the molar absorption coefficient of compound, specifically, for example preferably using purple Outer visible spectrophotometer (- 5 (Carry-5) spectrophotometers in the card of Varian (Varian) company manufacture (spectrophotometer)) it, is measured using ethyl acetate solvent with the concentration of 0.01g/L.
Photoepolymerizationinitiater initiater used in the present invention optionally also can be used in combination two or more.
In the present compositions contain (E) Photoepolymerizationinitiater initiater situation when, relative to composition total solid at Point, the content of (E) Photoepolymerizationinitiater initiater be preferably 0.1 mass % or more, 50 mass % hereinafter, more preferably 0.5 mass % with Upper, 30 mass % hereinafter, be preferably 1 mass % or more, 20 mass % or less in turn.It can get in the range better Sensitivity and patternability.
< < (F) polymerizable compound > >
Composition of the invention contains (F) polymerizable compound.In the present invention, can be used can by free radical, acid, heat The well known polymerizable compound being crosslinked, such as can enumerate containing ethylene unsaturated bond, cyclic ether (epoxy, oxa- ring Butane), the polymerizable compound of methylol etc..For the viewpoint of sensitivity, (F) polymerizable compound is to be preferably chosen to have At least one, preferably more than two terminal ethylene unsaturated bonds compound in.Wherein, preferably more than 4 functions Multifunctional polymerizable compound, and then multifunctional polymerizable compounds more than preferably 5 functions.
Such compound group is well-known in this industrial field, can be without particular limitation using these changes in the present invention Close object.These compounds may be, for example, any of following chemical form: monomer, prepolymer, that is, dimer, trimer and oligomerization Object or these mixture and these oligomer etc..Polymerizable compound of the invention can be used alone one kind, can also be simultaneously With two or more.
More specifically, the example of monomer and its prepolymer can be enumerated: unsaturated carboxylic acid (such as acrylic acid, metering system Acid, itaconic acid, butenoic acid, methacrylate, maleic acid etc.) or its esters, amides and these polymer, preferably not The amides of the ester and unsaturated carboxylic acid of saturated carboxylic acid and aliphatic polybasic alcoholic compound and aliphatic polybasic amine compounds, with And these polymer.In addition, it may also be preferred to use following reactant: having the nucleophilic substitutions such as hydroxyl or amino, sulfydryl The esters of unsaturated carboxylic acids or amides and simple function of base or the addition reaction of polyfunctional isocyanate's class or epoxies, Huo Zheyu Simple function or the dehydration condensation object of polyfunctional carboxylic acid etc..In addition, following reactant it is also preferred that: have isocyanate group or The esters of unsaturated carboxylic acids or amides and simple function or polyfunctional alcohols, amine, mercaptan of the electrophilicities substituent group such as epoxy group The addition reaction of class, and then esters of unsaturated carboxylic acids or amide with detachments substituent groups such as halogen radical or tosyloxies Class and simple function or polyfunctional alcohols, amine, thio-alcohol substituted reactant.In addition, also can be used and replace as other examples The unsaturated carboxylic acid and made of vinyl benzenes derivative, vinethene, the allyl ether etc. such as be substituted for unsaturated phosphonic acids, styrene Compound group.
It, can also be by the numbered paragraphs of Japanese Patent Laid-Open 2009-288705 bulletin as these particular compound [0095] compound recorded in~numbered paragraphs [0108] is preferably used in the present invention.
In addition, the polymerizable compound be also preferably have at least one can carry out the vinyl of addition polymerization and With the compound with ethylene unsaturated group of 100 DEG C or more of boiling point under normal pressure.Its example can refer to Japan Patent spy The compound recorded in the paragraph 0124 of 2013-077009 bulletin is opened, its content is incorporated into this specification.
In addition, under normal pressure with 100 DEG C or more boiling point and have at least one can carry out the ethylene of addition polymerization The compound of unsaturated group is also preferably that numbered paragraphs [0254]~paragraph of Japanese Patent Laid-Open 2008-292970 bulletin is compiled The compound recorded in number [0257].
Other than described, 0126~paragraph of paragraph 0129 of Japanese Patent Laid-Open 2013-077009 bulletin can refer to Free radical polymerization monomer represented by the general formula (MO-1) of middle record~general formula (MO-5), its content is incorporated to this specification In.
In addition, following compound also is used as the polymerizable compound: in Japanese Patent Laid-Open 10-62986 public affairs The addition of ethylene oxide on the polyfunctional alcohol recorded together as general formula (1) and general formula (2) with its concrete example in report or It is subject to compound made of (methyl) acroleic acid esterification after propylene oxide.
Wherein, the polymerizable compound is preferably dipentaerythritol triacrylate (commercially available product Ka Yala get (KAYARAD)D-330；NIPPON PHARMACEUTICAL CO., LTD manufacture), dipentaerythritol tetraacrylate (commercially available product Ka Yala Obtain (KAYARAD) D-320；NIPPON PHARMACEUTICAL CO., LTD manufacture), dipentaerythritol five (methyl) acrylate (commercially available product For Ka Yala get (KAYARAD) D-310；NIPPON PHARMACEUTICAL CO., LTD manufacture), dipentaerythritol six (methyl) acrylate (commercially available product is Ka Yala get (KAYARAD) DPHA；NIPPON PHARMACEUTICAL CO., LTD's manufacture, A-DPH-12E；The village Xin Zhong chemistry Company manufacture) and these (methyl) acryloyl group by glycol residue, diol residues structure.This also can be used A little oligomer types.The form of the preferred polymerizable compound described below.
The polymerizable compound can also be polyfunctional monomer, and can also have the acidic groups such as carboxyl, sulfonic group, phosphate. As long as ethylene compound to have unreacted carboxyl as the situation of mixture, can be utilized directly, depending on needing as described above It reacts non-aromatic carboxylic acid anhydrides with the hydroxyl of the ethylene compound and import acidic group.In the situation, institute The concrete example of the non-aromatic carboxylic acid anhydrides used can be enumerated: tetrabydrophthalic anhydride, alkylation tetrabydrophthalic anhydride, six Hydrogen phthalic anhydride, alkylation hexahydrophthalic anhydride, succinic anhydride, maleic anhydride.
In the present invention, the monomer with acidic group is the ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid, preferably React non-aromatic carboxylic acid anhydrides with the unreacted hydroxyl of aliphatic polyhydroxy compound and the polyfunctional monomer with acidic group, Aliphatic polyhydroxy compound is pentaerythrite and/or dipentaerythritol especially preferably in its ester.Commercially available product for example may be used Enumerate M-510, M-520 etc. as modified by polyacid acrylate oligomers of East Asia synthesis limited liability company manufacture.
These monomers can be used alone one kind, but for manufacture view, it is difficult to use single compound, therefore can also mix It closes using two or more.In addition, optionally can also and with without acidic group polyfunctional monomer with acidic group multifunctional list Body is as monomer.
The preferred acid number of polyfunctional monomer with acidic group be 0.1mgKOH/g~40mgKOH/g, especially preferably 5 MgKOH/g~30mgKOH/g.If the acid value of polyfunctional monomer is too low, the dissolution characteristics that develop are reduced, and are manufactured or are grasped if excessively high It becomes difficult and photopolymerization reduced performance, the hardenability such as surface smoothness of pixel are deteriorated.Therefore, and with two or more acid The situation of the different polyfunctional monomer of base or and when with the situation of the polyfunctional monomer without acidic group, preferably with overall Mode of the acidic group of polyfunctional monomer in the range adjusts.
In addition, containing the multi-functional monomer with caprolactone structure as polymerizable monomer is also preferred configuration.
As long as the multi-functional monomer with caprolactone structure has caprolactone structure in its intramolecular, special limit is had no It is fixed, such as the modified multifunctional (methyl) acrylate of 6-caprolactone can be enumerated, modified multifunctional (methyl) third of the 6-caprolactone Olefin(e) acid ester is by by trimethylolethane, two-trimethylolethanes, trimethylolpropane, two-trimethylolpropanes, season penta The polyalcohols such as tetrol, dipentaerythritol, tripentaerythritol, glycerol, two glycerol, trimethylol melamine and (methyl) acrylic acid And 6-caprolactone is esterified and is obtained.Wherein, can refer to the paragraph 0135 of Japanese Patent Laid-Open 2013-077009 bulletin~ Its content is incorporated into this specification by the compound recorded in paragraph 0153.
The commercially available product of such polymerizable compound can for example be enumerated: the manufacture of Sartomer (Sartomer) company has The tetrafunctional acrylate SR-494 of 4 inferior ethoxyl chains, NIPPON PHARMACEUTICAL CO., LTD's manufacture have 6 sub- amoxys Six functional acrylate DPCA-60 of chain, trifunctional acrylate TPA-330 with 3 sub- isobutoxy chains etc..
In addition, the polymerizable compound is also preferably Japan Patent examined patent publication 48-41708 bulletin, Japan Patent spy Open clear 51-37193 bulletin, Japanese Patent Laid-fair 2-32293 bulletin, in Japanese Patent Laid-fair 2-16765 bulletin Propenoic methyl carbamate class or Japan Patent examined patent publication 58-49860 bulletin, Japan Patent examined patent publication 56- as record The tool that No. 17654 bulletins, Japan Patent examined patent publication 62-39417 bulletin, Japan Patent examined patent publication 62-39418 bulletin are recorded There is the carbamate compounds class of ethylene oxide pastern bone frame.In turn, by using Japanese Patent Laid-Open No. Sho 63-277653 public affairs The intramolecular tool recorded in report, Japanese Patent Laid-Open No. Sho 63-260909 bulletin, Japanese Patent Laid-Open 1-105238 bulletin There are the addition polymerization compounds of amino structure or sulfide based structural as the polymerizable compound, it is non-to can get film speed The curable adhensive compositions of Chang Youyi.
The commercially available product of the polymerizable compound can be enumerated: urethane oligomer UAS-10, carbamate oligomerization Object UAB-140 (manufacture of adret state basic policy paper pulp company), " UA-7200 " (manufacture of chemical company, the village Xin Zhong), DPHA-40H (Japan The manufacture of chemical drug company), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufacture of common prosperity society), three hydroxyl first Base propane triacrylate (commercially available product A-TMPT；The manufacture of chemical company, the village Xin Zhong) etc..
About cyclic ether (epoxy, oxetanes), such as having epoxy group, bisphenol A type epoxy resin is JER-827、 JER-828、JER-834、JER-1001、JER-1002、JER-1003、JER-1055、JER-1007、JER- 1009, JER-1010 (the above are Japanese epoxy resin (stock) manufactures), Epiclon (EPICLON) 860, Epiclon (EPICLON) 1050, Epiclon (EPICLON) 1051, (the above are DIC (DIC) for Epiclon (EPICLON) 1055 (stock) manufacture) etc.；Bisphenol f type epoxy resin is JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER- 4010 (the above are Japanese epoxy resin (stock) manufactures), Epiclon (EPICLON) 830, Epiclon (EPICLON) 835 (the above are DIC (DIC) (stock) manufactures), LCE-21, RE-602S (the above are Japanese chemical drug (stock) manufactures) etc.；Phenol phenol Novolac type epoxy resin is that (the above are Japanese epoxy resin by JER-152, JER-154, JER-157S70, JER-157S65 (stock) manufacture), Epiclon (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N- 775 (the above are DIC (DIC) (stock) manufactures) etc.；Cresol novolak type epoxy resin is Epiclon (EPICLON) N- 660, Epiclon (EPICLON) N-665, Epiclon (EPICLON) N-670, Epiclon (EPICLON) N-673, Chinese mugwort ratio Clone (EPICLON) N-680, Epiclon (EPICLON) N-690, (the above are DIC by Epiclon (EPICLON) N-695 (DIC) (stock) manufactures), EOCN-1020 (the above are Japanese chemical drug (stock) manufactures)；Aliphatic epoxy resin can be enumerated: Ai Dike Resin (ADEKA RESIN) EP-4080S, Ai Dike resin (ADEKA RESIN) EP-4085S, Ai Dike resin (ADEKA RESIN) EP-4088S (the above are Ai Dike (ADEKA) (stock) manufactures), (Celloxide) 2021P, Sai Luo West Germany, Sai Luo West Germany (Celloxide) 2081, Sai Luo West Germany (Celloxide) 2083, Sai Luo West Germany (Celloxide) 2085, EHPE-3150 (2, 1,2- epoxy -4- (2- oxiranyl) hexamethylene addition product of bis- (the hydroxymethyl) -1- butanol of 2-), Ai Boli obtains (EPOLEAD) PB 3600, Ai Boli obtain (EPOLEAD) PB 4700 (the above are Daicel (Daicel) chemical industry (stock) systems Make), for that Cauer (Denacol) EX-211L, for that Cauer (Denacol) EX-212L, for that Cauer (Denacol) EX- 214L, for that Cauer (Denacol) EX-216L, for that Cauer (Denacol) EX-321L, for that Cauer (Denacol) EX- 850L (the above are rapids chemical conversion (Nagase Chemtex) (stock) manufactures of length), Ai Dike resin (ADEKA RESIN) EP- 4000S, Ai Dike resin (ADEKA RESIN) EP-4003S, Ai Dike resin (ADEKA RESIN) EP-4010S, Ai Dike Resin (ADEKA RESIN) EP-4011S (the above are Ai Dike (ADEKA) (stock) manufactures), NC-2000, NC-3000, NC- 7300, XD-1000, EPPN-501, EPPN-502 (the above are Ai Dike (ADEKA) (stock) manufactures), JER-1031S (Japanese ring Oxygen resin (stock) manufacture) etc..Such polymerizable compound is suitable for being formed the situation of pattern using dry etching method.
About these polymerizable compounds, structure, exclusive use or and the application methods such as use, additive amount details It can be according to the final performance design of photosensitive composition come any setting.It is excellent such as the viewpoint of sensitivity It is selected as the structure more than the unsaturated group content of each molecule, is preferably two functions or more in the case where more.In addition, just improve by Color sensation photosensitive resin composition is formed by for the viewpoint of hardening film strength, with more than trifunctional being advisable, in turn, is passed through And (such as acrylate, methacrylate, styrenic, the second different with function radix difference polymerism base Alkene ether based compound) it is also effective to adjust the method for both sensitivity and intensity.In turn, and with more than trifunctional and ethylene oxide chain Long different polymerizable compound is preferred for following aspect: the developability of adjustable photosensitive composition, can Obtain excellent pattern Forming ability.
In addition, for (such as Photoepolymerizationinitiater initiater, being divided with the other compositions contained by photosensitive composition Granular media, alkali soluble resin etc.) compatibility, dispersibility, polymerizable compound select using method be also important factor, Such as by using low-purity compound or and compatibility can be improved with two or more sometimes.In addition, with regard to raising and support Deng hard surface adhesion viewpoint for, specific structure also may be selected.
(F) polymerism relative to the total solid content in photosensitive composition, in composition of the invention The content of compound is preferably the 0.1 mass % of mass %~90, and then the preferably 1.0 mass % of mass %~50, particularly preferably For 2.0 mass of mass %~30 %.
< < other compositions > >
Composition of the invention, can also be in the range of not undermining effect of the invention, also other than each ingredient There are the other compositions such as resin, organic solvent, the crosslinking agent of polymeric double bond in side chain containing (G).
(G) has the resin-of polymeric double bond in side chain
In the present invention, and then optionally there is the resin of polymeric double bond (hereinafter also referred in side chain containing (G) " (G) resin ").By also containing (G) in resin of the side chain with polymeric double bond, composition of the invention can be made more effective Ground hardening.Polymeric double bond is preferably (methyl) acrylate.
(G) as long as there is polymeric double bond in side chain in resin of the side chain with polymeric double bond, special limit is had no System preferably makes compound (b) with the functional group and ethylene unsaturated double-bond that can be reacted with hydroxyl and with 2~6 Resin made of the polymerizable monomer (p) of a hydroxyl is reacted with the copolymer (a) of other polymerizable monomers (q).
(G), which is constituted, in the polymerizable monomer (p) with 2~6 hydroxyls of resin of the side chain with polymeric double bond is Compound with 2 or more and 6 hydroxyl and ethylene unsaturated double-bonds below, such as the following general formula (1) institute can be used The monomer of expression.
General formula (1)
[changing 56]
(in formula, R1And R4Respectively indicate the alkyl of hydrogen atom, carbon number 1~5 being substituted, R2Indicate the Asia of carbon number 1~4 Alkyl, R3Indicate that the alkylidene or singly-bound of carbon number 1~4, n indicate 2 or more, 6 integers below)
Monomer represented by the general formula (1) can enumerate the monoesters etc. of the polyalcohol with ethylene unsaturated double-bond, excellent It is selected as glycerol list (methyl) acrylate.
Other polymerizable monomers (q) are can be with the polymerism of polymerizable monomer (p) combined polymerization with 2~6 hydroxyls Monomer, such as can enumerate: (methyl) acrylic acid, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid third Ester, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, the tertiary fourth of (methyl) acrylic acid Ester, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid phenoxy group second Ester, (methyl) acrylic acid-2-ethyl caproite, (methyl) isobornyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (first Base) (methyl) esters of acrylic acid such as tetrahydrofurfuryl acrylate；N-vinyl pyrrolidone；Styrene and its derivatives, Alpha-Methyl The phenylethylenes such as styrene；(methyl) acrylamide, methylol (methyl) acrylamide, alkoxy methylol (methyl) propylene The acrylic amides such as amide, diacetone (methyl) acrylamide；(methyl) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, acetic acid Other vinyl compounds such as vinyl acetate；And polymethyl methacrylate macromonomer, Group-capped Polystyrene Macromer etc. are big Molecule monomer class etc..These monomers can be used alone one kind, or be used in mixed way two or more.
In addition, the combined polymerization of polymerizable monomer (p) and other polymerizable monomers (q) with 2~6 hydroxyls is than preferred For the 5 mass %:95 mass mass % of %~5 of mass %~95, the more preferably 30 mass %:70 mass of mass %~70 %~ 30 mass %.When the combined polymerization of polymerizable monomer (p) is than situation less than 5 mass %, the ethylene that can be imported is unsaturated double Bond number is few, and the numerical value of double bond equivalent (double bond equivalent defined in following formula) becomes larger, and can not obtain sufficient sensitivity.In polymerism When the combined polymerization of monomer (p) is than situation more than 95 mass %, a large amount of ethylene unsaturated double-bond, but polymerism list can be imported The ratio of body (q) is lower, therefore is difficult to maintain the physical property such as dispersion stabilization, dissolubility, chemical-resistant.
The manufacture of the copolymer (a) of polymerizable monomer (p) and other polymerizable monomers (q) with 2~6 hydroxyls can It is manufactured using well known method, such as can refer to the record of the paragraph 0013 of Japanese Patent Laid-Open 2005-156930 bulletin, Its content is incorporated into this specification.
It (G) is by making with the functional group and ethylene that can be reacted with hydroxyl in resin of the side chain with polymeric double bond The compound (b) of unsaturated double-bond is reacted with the copolymer (a) and is obtained.With the functional group and ethylene that can be reacted with hydroxyl The compound (b) of property unsaturated double-bond as the functional group that can be reacted with hydroxyl, isocyanate group, carboxyl etc. can be enumerated, especially It is for reactive aspect, preferably isocyanate group.
The specific enumerable 2- acryloyl ethyl isocyanide of compound with isocyanate group and ethylene unsaturated double-bond Acid esters, 2- methylacryloyl ethyl isocyanate etc..In addition, the compound tool with carboxyl and ethylene unsaturated double-bond Body can enumerate acrylic acid, methacrylic acid, maleic anhydride.
The amount for the ethylene unsaturated double-bond being directed into copolymer (a) by hydroxyl is " double by resulting resin Key equivalent " indicates.So-called double bond equivalent, becomes the standard of double bond amount contained in molecule, identical photosensitive if molecular weight Property resin, then the import volume of the smaller then double bond of the numerical value of double bond equivalent more becomes more.
[double bond equivalent]=[molecular weight of constitutional repeating unit]/[double key number in constitutional repeating unit]
The double bond equivalent of (G) resin of the invention is preferably 200~2,000, more preferably 300~900.In (G) resin Situation of the double bond equivalent less than 200 when, the ratio for importing the polymerizable monomer (p) of ethylene unsaturated double-bond is got higher, can not Make an adequate amount of polymerizable monomer (q) combined polymerization for maintaining various characteristics.In the situation more than 2,000, ethylene is unsaturated Double key number is few, therefore can not obtain sufficient sensitivity.
In addition, for the aspect of the favorable dispersibility of composition of the invention, the weight averaged molecular of (G) resin Measuring (Mw) is preferably 2000~200000, and more preferably 5000~50000.
Copolymer (a), with there is the anti-of the compound (b) of functional group and ethylene unsaturated double-bond that can be reacted with hydroxyl It should can be carried out using well known method, such as can refer to the paragraph 0016 of Japanese Patent Laid-Open 2005-156930 bulletin It records, its content is incorporated into this specification.
Relative to total solid content, (G) in composition of the invention has containing for the resin of polymeric double bond in side chain The amount preferably 0.1 mass % of mass %~50, the more preferably 0.3 mass % of mass %~40, and then preferably 0.5 mass %~ 30 mass %.
(G) in side chain there is the resin of polymeric double bond can also contain only containing one kind in the present compositions It is two or more.When containing two or more situations, preferably its total amount becomes the range.
Alkali soluble resin-
Composition of the invention can also also contain alkali soluble resin as adhesive.Furthermore alkali described herein is solvable It does not include containing the ingredient in composition of the invention as dispersion. formulation in property resin.
Alkali soluble resin can suitably be selected from following alkali soluble resin, and the alkali soluble resin is linear organic High molecular polymer, and molecule (preferably using acrylic acid series copolymer, styrene based copolymer as main chain molecule) in Promote the group of alkali-soluble at least one.For the viewpoint of heat resistance, preferably polyhydroxy styrene system resin, poly- Siloxane-based resin, acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin, just control development For the viewpoint of property, preferably acrylic resin, acrylamide resin, acrylic acid/acrylamide copolymer resin.
Alkali soluble resin for example can refer to 0179~paragraph of paragraph of Japanese Patent Laid-Open 2013-077009 bulletin Its content is incorporated into this specification by the alkali soluble resin recorded in 0208.
In addition, alkali soluble resin can refer to 0558~paragraph of paragraph of Japanese Patent Laid-Open 2012-208494 bulletin The later note in 0571 ([0685]~[0700] of No. 2012/0235099 specification of corresponding U.S. Patent Application Publication No.) It carries, these contents is incorporated into present specification.
And then preferably using the 0029~paragraph of numbered paragraphs recorded in Japanese Patent Laid-Open 2012-32767 bulletin Alkali soluble resin, Japanese Patent Laid-Open 2012-208474 used in the copolymer (B) and embodiment recorded in number 0063 Adhesive tree used in the adhesive resin and embodiment recorded in 0088~numbered paragraphs of numbered paragraphs 0098 of number bulletin Rouge, Japanese Patent Laid-Open 2012-137531 bulletin 0022~numbered paragraphs of numbered paragraphs 0032 in the adhesive tree recorded 0132~section of numbered paragraphs of adhesive resin used in rouge and embodiment, Japanese Patent Laid-Open 2013-024934 bulletin Fall adhesive resin used in the adhesive resin recorded in number 0143 and embodiment, Japanese Patent Laid-Open 2011- Adhesive resin used in the 0092~numbered paragraphs of numbered paragraphs 0098 and embodiment of No. 242752 bulletins, Japan Patent are special Open the adhesive resin recorded in 0030~numbered paragraphs of numbered paragraphs 0072 of 2012-032770 bulletin.By these contents It is incorporated into present specification.
The acid value of alkali soluble resin be preferably 30mgKOH/g~200mgKOH/g, more preferably 50mgKOH/g~ 150mgKOH/g is advisable, most preferably 70mgKOH/g~120mgKOH/g.
In addition, the weight average molecular weight (Mw) of alkali soluble resin is preferably 2,000~50,000, and then preferably 5, 000~30,000, most preferably 7,000~20,000.
When situation in coloured composition containing alkali soluble resin, relative to the total solid content of coloured composition, Content of the alkali soluble resin in coloured composition is preferably the 1 mass % of mass %~15, more preferably 2 matter of mass %~12 Measure %, especially preferably 3 mass of mass %~10 %.
Composition of the invention can only contain a kind of alkali soluble resin, can also contain two or more.Containing there are two types of with On situation when, preferably its total amount become the range.
Organic solvent-
Composition of the invention can also contain organic solvent.
As long as organic solvent meets the dissolubility of each ingredient or the coating of photosensitive composition, substantially It is not particularly limited, dissolubility, coating especially preferably in view of ultraviolet absorbing agent, alkali soluble resin or dispersing agent etc. Property, safety and select.Organic solvent can be one kind, also may include two or more.
Organic solvent is preferably enumerated: as such as ethyl acetate of esters, n-butyl acetate, isobutyl acetate, first Sour pentyl ester, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, oxygen Guanidine-acetic acid Arrcostab (such as ethoxyacetic acid methyl esters, ethoxyacetic acid ethyl ester, ethoxyacetic acid butyl ester (such as methoxy menthyl acetate, first Ethoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate etc.)), 3- oxygroup propionic acid alkyl Esters (such as 3- oxygroup methyl propionate, 3- oxygroup ethyl propionate etc. (such as 3- methoxy methyl propionate, 3- methoxypropionic acid second Ester, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate etc.)), 2- oxygroup alkyl propionates class (such as 2- oxygroup propionic acid first Ester, 2- oxygroup ethyl propionate, 2- oxygroup propyl propionate etc. (such as 2- methoxy methyl propionate, 2- methoxypropionate, 2- first Oxygroup propyl propionate, 2- ethoxypropanoate, 2- ethoxyl ethyl propionate)), 2- oxygroup -2 Methylpropionic acid methyl esters and 2- oxygen Base -2 Methylpropionic acid ethyl ester (such as 2- methoxyl group -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2 Methylpropionic acid ethyl ester etc.), third Ketone acid methyl esters, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid methyl esters, 2- oxygen For ethyl butyrate etc.；And such as diethylene glycol dimethyl ether as ethers, tetrahydrofuran, glycol monoethyl ether, ethylene glycol list Ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters Deng；And as ketone such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3- heptanone；And as aromatic hydrocarbon example Such as toluene, dimethylbenzene, cyclopentanone.
For the viewpoint of dissolubility, the coated surface state of improvement ultraviolet absorbing agent and alkali soluble resin etc., this A little organic solvents also preferably mix two or more.In the situation, particularly preferably for by two kinds in following solvent Above the constituted mixed solution: the 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, ethyl cellosolve acetate, Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- methoxy methyl propionate, 2-HEPTANONE, cyclohexanone, ethyl carbitol second Acid esters, acetate of butyl carbitol, propylene glycol monomethyl ether and propylene glycol methyl ether acetate.
For the viewpoint of coating, the content of organic solvent in the composition is preferably the total solid for being set as composition Constituent concentration becomes the amount of 5 mass of mass %~80 %, and then the preferably 5 mass % of mass %~60, especially preferably 10 matter Measure the mass of %~50 %.
Crosslinking agent-
It can also supplement in the present compositions using crosslinking agent, further increase hardening made of hardening composition The hardness of film.
As long as crosslinking agent can carry out film hardening by cross-linking reaction, it is not particularly limited, such as can enumerate: (a) ring Oxygen resin；(b) melamine replaced through at least one substituent group in methylol, alkoxy methyl and pivaloyloxymethyl Compound, guanamines compound, glycoluril compounds or carbamide compound；(c) through being selected from methylol, alkoxy methyl and pivaloyloxymethyl In at least one substituent group replace oxybenzene compound, naphthol compound or hydroxyl anthracene compound.Wherein, preferably multifunctional Epoxy resin.
The details such as the concrete example about crosslinking agent can refer to the section of Japanese Patent Laid-Open 2004-295116 bulletin Fall the record of 0134~paragraph 0147.
In the present compositions when situation containing crosslinking agent, the blending amount of crosslinking agent is not particularly limited, preferably For the 2 mass % of mass %~30 of the total solid content of composition, more preferably 3 mass of mass %~20 %.
Composition of the invention can only contain a kind of crosslinking agent, can also contain two or more.Containing two or more feelings When shape, preferably its total amount becomes the range.
Polymerization inhibitor-
In the present compositions, for prevention polymerizable compound in the manufacture of the composition or in preservation Unwanted thermal polymerization, it is generally desirable to add a small amount of polymerization inhibitor.
Workable polymerization inhibitor can be enumerated in the present invention: hydroquinone, p methoxy phenol, di-t-butyl are to first Phenol, pyrogallol, tert-butyl catechol, benzoquinones, 4,4'- thiobis (3 methy 6 tert butyl phenol), 2,2'- methylene Bis- (4- methyl -6- tert-butyl phenols), N- nitroso phenylhydroxylamine Asia cerium salt etc..
In the present compositions when situation containing polymerization inhibitor, relative to the quality of all compositions, polymerization The additive amount of inhibitor is preferably from about the mass % of 0.01 mass %~about 5.
Composition of the invention can only contain a kind of polymerization inhibitor, can also contain two or more.Containing two or more Situation when, preferably its total amount become the range.
Surfactant-
In composition of the invention, for the viewpoint for further increasing coating, various surfactants can also be added. In the present invention, by deploying surfactant, and (C) ingredient and (D) ingredient described in using situation when, can more effectively send out Wave the excellent effect of the invention of PCD tolerance.About its reason, mechanism can be presumed as follows.That is, about composition of the invention The excellent reason of PCD tolerance, as described above, it is believed that its reason is: sterically bulky contained by (D) ingredient Aromatic rings the position (- Ph-R of compound (x) represented by logical formula (IV)6Represented part) enter to the polyester of (C) ingredient In residue moiety, the effect for preventing polyester residue from aggregating with one another crystallization is played, as a result the mutually separation of (C) ingredient is suppressed. It could be speculated that if adding surfactant wherein, sterically bulky aromatic rings position and (C) contained by (D) ingredient Surface-active effect is played between the polyester residue moiety of ingredient, the sterically bulky position of (D) ingredient swimmingly enters Into the polyester residue moiety of (C) ingredient.
Surfactant can be used: fluorine system surfactant, nonionic surfactants, cationic system surface-active The various surfactants such as agent, anionic surfactant, silicone-based surfactant.
For composition especially of the invention by containing fluorine system surfactant, solution properties when being prepared into coating fluid are (special It is not mobility) it further increases, therefore can further improve the uniformity of coating thickness or save fluidity.
That is, in the situation for carrying out film formation using the coating fluid for applying the composition containing fluorine system surfactant When, the interfacial tension by making to be applied face and coating fluid reduces, and is improved to the wetting quality in the face that is applied, to being applied face Coating improve.It therefore, can also be more even if in the situation with a small amount of liquid measure to form the film of several microns of (μm) left and right The film for carrying out the small uniform thickness of uneven thickness goodly is formed, in this connection effectively.
Fluorine containing ratio in fluorine system surfactant is preferably the 3 mass % of mass %~40, more preferably 5 mass %~30 Quality %, especially preferably 7 mass of mass %~25 %.Fluorine containing ratio is that the fluorine system surfactant in the range is being coated with The uniformity of the thickness of film or the aspect for saving fluidity are effective, and dissolubility in the composition is also good.
Fluorine system surfactant can for example be enumerated: Mei Jiafa (Megafac) F171, Mei Jiafa (Megafac) F172, Mei Jia Method (Megafac) F173, Mei Jiafa (Megafac) F176, Mei Jiafa (Megafac) F177, Mei Jiafa (Megafac) F141, Mei Jiafa (Megafac) F142, Mei Jiafa (Megafac) F143, Mei Jiafa (Megafac) F144, Mei Jiafa (Megafac) R30, Mei Jiafa (Megafac) F437, Mei Jiafa (Megafac) F475, Mei Jiafa (Megafac) F479, Mei Jiafa (Megafac) F482, Mei Jiafa (Megafac) F554, Mei Jiafa (Megafac) F780, Mei Jiafa (Megafac) F781 (with It is upper to be manufactured for DIC (DIC) (stock)), Fu Lade (Fluorad) FC430, Fu Lade (Fluorad) FC431, Fu Lade (Fluorad) FC171 (the above are Sumitomo 3M (stock) manufactures), Sha Fulong (Surflon) S-382, Sha Fulong (Surflon) SC- 101, Sha Fulong (Surflon) SC-103, Sha Fulong (Surflon) SC-104, Sha Fulong (Surflon) SC-105, Sha Fulong (Surflon) SC1068, Sha Fulong (Surflon) SC-381, Sha Fulong (Surflon) SC-383, Sha Fulong (Surflon) S393, Sha Fulong (Surflon) KH-40 (the above are Asahi Glass (stock) manufactures) etc..
Nonionic surfactants are specific enumerable: glycerol, trimethylolpropane, trimethylolethane and these Ethoxylate and propoxylate (such as propoxylated glycerol, ethoxylated glycerol etc.), gather polyoxyethylenelauryl ether Oxygen ethylidene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, Polyethylene glycol dilaurate, polyglycol distearate, sorbitan carboxylic esters be (manufacture of BASF (BASF) company Pu Luonike (Pluronic) L10, Pu Luonike (Pluronic) L31, Pu Luonike (Pluronic) L61, Pu Luonike (Pluronic) L62, Pu Luonike (Pluronic) 10R5, Pu Luonike (Pluronic) 17R2, Pu Luonike (Pluronic) 25R2, Te Luonike (Tetronic) 304, Te Luonike (Tetronic) 701, Te Luonike (Tetronic) 704, Te Luonike (Tetronic) 901, Te Luonike (Tetronic) 904, Te Luonike (Tetronic) 150R1), rope exerts Paasche (Solsperse) 20000 (Japanese Lu Borun (Lubrizol) (stock)) etc..
Cationic system surfactant is specific enumerable: and phthalocyanine derivates (trade name: Efka (EFKA) -745, under gloomy Industry (stock) manufacture), organic siloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (stock) manufacture), (methyl) acrylic acid series (total) Polymer Pohle not Lip river (Polyflow) No.75, Pohle not Lip river (Polyflow) No.90, Pohle not Lip river (Polyflow) No.95 (common prosperity society chemistry (stock) manufacture), W001 (abundant quotient's (stock) manufacture) etc..
Anionic surfactant specific enumerable W004, W005, W017 (abundant quotient (stock) company manufacture) etc..
Silicone-based surfactant can for example be enumerated: " the east of beautiful DOW CORNING (Toray-Dow corning) (stock) manufacture in east Beautiful silicone (Toray Silicone) DC3PA ", " beautiful silicone (Toray Silicone) SH7PA in east ", " beautiful silicone (Toray in east Silicone) DC11PA ", " beautiful silicone (Toray Silicone) SH21PA in east ", " the beautiful silicone (Toray Silicone) in east SH28PA ", " beautiful silicone (Toray Silicone) SH29PA in east ", " beautiful silicone (Toray Silicone) SH30PA in east ", " east Beautiful silicone (Toray Silicone) SH8400 " is stepped figure new high-tech material (Momentive Performance Materials) " TSF-4440 ", " TSF-4300 ", " TSF-4445 ", " TSF-4460 ", " TSF-4452 " of company's manufacture, SHIN-ETSU HANTOTAI's silicone share " KP341 ", " KF6001 ", " KF6002 " of Co., Ltd's manufacture, Bi Ke chemistry (BYK Chemie) company manufacture " Bi Ke (BYK) 307 ", " Bi Ke (BYK) 323 ", " Bi Ke (BYK) 330 " etc..
One kind can be used only in surfactant, can also combine two or more.
In the present compositions when situation containing surfactant, relative to the gross mass of composition, surface is living The additive amount of property agent is preferably the 0.001 mass % of mass %~2.0, more preferably 0.005 mass of mass %~1.0 %.
Composition of the invention can only contain a kind of surfactant, can also contain two or more.Containing two or more Situation when, preferably its total amount become the range.
Other additives-
In composition of the invention, optionally adjustable various additives, such as filler, contiguity promotor, anti-oxidant Agent, ultraviolet absorbing agent, anticoalescent etc..These additives can enumerate the section of Japanese Patent Laid-Open 2004-295116 bulletin It falls and records in 0155~paragraph 0156.
In the present compositions, remember in the paragraph 0078 containing Japanese Patent Laid-Open 2004-295116 bulletin The thermal polymerization inhibitor recorded in the sensitizer or light stabilizer of load, the paragraph 0081 of the bulletin.
Ultraviolet absorbing agent specifically preferably uses following compound.
[changing 57]
-- organic carboxyl acid, organic carboxyl acid acid anhydride --
Composition of the invention can also be 1000 organic carboxyl acid and/or organic carboxyl acid acid anhydrides below containing molecular weight.
The specific enumerable aliphatic carboxylic acid of organic carboxylic acid compounds or aromatic carboxylic acid.Aliphatic carboxylic acid can for example be enumerated: The monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, Glycolic acid, acrylic acid, methacrylic acid, grass Acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, lemon health The dicarboxylic acids such as acid, maleic acid, fumaric acid, tricarboxylic acids such as 1,2,3- propanetricarboxylic acid, aconitic acid etc..In addition, aromatic carboxylic acid is for example Can enumerate: the carboxyls such as benzoic acid, phthalic acid are directly bonded to the carboxylic acid of phenyl, and are bonded carboxyl by carbon key from phenyl Carboxylic acids.In these, especially preferably 600 or less molecular weight, particularly molecular weight 50~500, specifically, for example excellent It is selected as maleic acid, malonic acid, succinic acid, itaconic acid.
Organic carboxyl acid acid anhydride can for example enumerate aliphatic carboxylic acid acid anhydride, aromatic carboxylic acid acid anhydride, specifically, can for example enumerate: second Acid anhydrides, Trichloroacetic anhydride, trifluoroacetic anhydride, tetrabydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic acid The rouge such as acid anhydride, glutaric anhydride, 1,2- cyclohexene dicarboxylic acid acid anhydride, n-octadecane base succinic anhydride, 5- norbornene -2,3- dicarboxylic anhydride Aliphatic carboxylic acid's acid anhydride.Aromatic carboxylic acid acid anhydride can for example be enumerated: phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, naphthalene two Formic anhydride etc..In these, especially preferably 600 or less molecular weight, particularly molecular weight 50~500, specifically, for example excellent It is selected as maleic anhydride, succinic anhydride, citraconic anhydride, itaconic anhydride.
In the present compositions containing organic carboxyl acid, organic carboxyl acid acid anhydride situation when, these organic carboxyl acids and/or have The additive amount of machine carboxylic acid anhydrides is the 0.01 mass % of mass %~10, preferably 0.03 mass %~5 usually in total solid content Quality %, the more preferably range of 0.05 mass of mass %~3 %.
It is 1000 organic carboxyl acid and/or organic carboxyl acid acid anhydrides below by adding these molecular weight, high pattern can be kept Adhesion, and it is further reduced the remaining of the undissolved object of composition.
The preparation method > of < photosensitive composition
Composition of the invention is prepared and mixing ingredient described above.
Furthermore when preparing composition, each ingredient for constituting composition can disposably be deployed, it can also be molten by each ingredient Solution is gradually deployed after being scattered in solvent.In addition, ordering in launching or operating condition are not particularly limited when allotment.Such as it can incite somebody to action All the components dissolve simultaneously and are scattered in solvent and prepare composition, optionally also each ingredient suitably can be made two kinds in advance Above solution dispersion liquid, and these are mixed (when coating) when in use and is prepared into composition.
Wherein, in the present invention, lead to the alkaline pigment derivative of (A) pigment, (B) and (C) represented by formula (II) After the dispersion of phosphate dispersing agent, allotment (D) is by compound (x) represented by logical formula (IV) and has ethylene unsaturated double-bond Resin made of compound (y) combined polymerization.
Preferably 0.01 μm~3.0 μm of aperture, more preferably aperture 0.05 can be used in the composition prepared as described above μm~0.5 μm or so of filter etc. is filtered after separation for using.
Composition of the invention can form heat resistance and the excellent cured film of color characteristics, therefore can be preferably used as forming coloured silk The colored pattern (coloring photosensitive combination layer) of colo(u)r filter.In addition, composition of the invention is preferably taken the photograph as solid Colored filter used in the image display devices such as element (such as CCD, CMOS etc.) or liquid crystal display device (LCD) etc. Colored pattern formed use.In turn, it also may be preferable for ground is used to print the production purposes of ink, jetted ink and coating etc..Wherein, It can be preferably used as the production purposes of the colored filter of the solid-state imagers such as CCD and CMOS.
< cured film, pattern forming method, colored filter and colored filter manufacturing method >
Then, cured film of the invention, pattern forming method and colored filter are described in detail.
Pattern forming method of the invention, will be of the invention the following steps are included: coloring photosensitive combination layer forming step Photosensitive composition assign to forming (hereinafter also referred to " the coloring of coloring photosensitive combination layer on support Composition layer ")；Step of exposure is exposed the coloring compositions nitride layer with pattern-like；And pattern forming step, it will not Exposure portion development removes and forms colored pattern.
Pattern forming method of the invention be preferably applied to be formed colored pattern possessed by colored filter (as Element).
The support of pattern is formed using pattern forming method of the invention other than the plate objects such as substrate, as long as being The support that can be applied to pattern formation, then be not particularly limited.
Hereinafter, by the manufacturing method of solid-state imager colored filter come in pattern forming method of the invention Each step be described in detail, but the present invention is not limited to the methods.
The manufacturing method of colored filter of the invention applies pattern forming method of the invention, of the invention including using Pattern forming method is the step of forming colored pattern on support.
That is, the manufacturing method of colored filter of the invention apply pattern forming method of the invention, and it is characterized in that The following steps are included: coloring photosensitive combination of the invention is applied to form coloring photosensitive combination layer on support The step of；The step of coloring photosensitive combination layer is exposed into pattern-like；And unexposed portion is developed and is removed and shape The step of at colored pattern.
In turn, optionally also settable the step of coloring compositions nitride layer is toasted (pre-bake step) and to through aobvious The step of colored pattern of shadow is toasted (rear baking procedure).Hereinafter, these steps are referred to as pattern forming step sometimes.
Colored filter of the invention can preferably be obtained using the manufacturing method.
Hereinafter, solid-state imager is referred to as " colored filter " with colored filter sometimes.
Hereinafter, the manufacturing method of the colored filter to each step of pattern forming method of the invention through the invention is come It is described in detail.
The step > of < formation coloring photosensitive combination layer
In the step of forming coloring photosensitive combination layer, formed on support using composition of the invention Color photosensitive composition layer.
Workable support for example can be used in the step: Charged Couple member is equipped on substrate (such as silicon substrate) Part (Charge Coupled Device, CCD) or complementary metal oxide semiconductor (Complementary Metal- Oxide Semiconductor, CMOS) etc. photographing elements (light receiving element) solid-state imager substrate.
The photographing element that colored pattern of the invention can be formed in solid-state imager substrate forms surface side (surface), The surface side (back side) of not formed photographing element can be formed in.
Shading can also be equipped between the colored pattern of solid-state imager or on the back side of solid-state imager substrate Film.
In addition, on support, optionally may also set up priming coat with improve with the contiguity of the layer on top, prevent substance Diffusion or the planarization for realizing substrate surface.
Slot coated, ink-jet method, rotary coating, curtain coating can be applied using the method for composition of the invention on support The various coating methods such as coating, roller coating cloth, screen printing.
The drying (prebake conditions) of the coloring photosensitive combination layer on support is coated on using hot plate (hot Plate), baking oven (oven) etc. 50 DEG C~140 DEG C at a temperature of carry out 10 seconds~300 seconds.
The step of < < is exposed coloring phototonus composition layer with pattern-like (carries out pattern shape using photoetching process At situation) > >
Step of exposure-
It is right by the mask with set mask pattern in step of exposure, such as using exposure devices such as steppers The coloring photosensitive combination layer formed in coloring photosensitive combination layer forming step carries out pattern exposure.Thus it can get hard Change film.
Workable radioactive ray (light) are especially preferably (particularly preferred using ultraviolet lights such as g ray, i rays when exposure For i ray).Exposure (light exposure) is preferably 30mJ/cm2~1500mJ/cm2, more preferably 50mJ/cm2~1000mJ/ cm2, most preferably 80mJ/cm2~500mJ/cm2。
The film thickness of cured film is preferably 1.0 μm hereinafter, more preferably 0.1 μm~0.9 μm, and then preferably 0.2 μm~ 0.8μm。
By the way that film thickness is set as 1.0 μm hereinafter, can get high analyticity, high density of access, therefore it is preferred that.
In addition, in the step, it also may be preferable for ground forms the cured film with 0.7 μm of thin film thickness below, passes through Development treatment is carried out to resulting cured film using aftermentioned pattern forming step, even if can get for film developability, surface it is thick Rough inhibition and pattern form also excellent colored pattern.
The step > > > of < < < formation colored pattern
Then alkali development processing is carried out, thus the coloring photosensitive combination of the part without light irradiation in step of exposure Layer dissolution is into alkaline aqueous solution, and only the part through photo-hardening remains.
Preferably developer solution does not cause organic alkali development of damage (damage) to the photographing element of bottom or circuit etc. Liquid.Development temperature is usually 20 DEG C~30 DEG C, is 20 seconds~90 seconds before developing time.In order to further remove residue, in recent years Also to there is the case where implementing 120 seconds~180 seconds.In turn, it in order to further increase residue removal, also repeats the steps of sometimes Several times: getting rid of developer solution every 60 seconds, further supply developer solution again.
Alkaline agent used in developer solution can for example be enumerated: ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, tetramethylphosphonihydroxide hydroxide Base ammonium, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide benzyltrimethylammon.um, choline, pyrrole It coughs up, the organic basic compounds such as piperidines, 1,8- diazabicyclo-[5.4.0] -7- hendecene, it is preferable to using utilizing pure water These alkaline agents are diluted in such a way that concentration becomes 0.001 mass of mass %~10 %, preferably 0.01 mass of mass %~1 % Made of alkaline aqueous solution as developer solution.
Furthermore inorganic base can also be used in developer solution, inorganic basis as preferably sodium hydroxide, potassium hydroxide, sodium carbonate, Sodium bicarbonate, sodium metasilicate, sodium metasilicate etc..
Furthermore using the developer solution comprising such alkaline aqueous solution situation when, usually after development using pure water into Row cleaning (elution).
Then, heated (rear baking) after preferably implementing drying.If forming the colored pattern of multiple color, Then can each color sequentially repeating said steps manufacture hardening epithelium one by one.Thus it can get colored filter.
Baking is to make to harden the heat treatment after completely developing, usually in 100 DEG C~240 DEG C, preferably 200 afterwards DEG C~240 DEG C at carry out thermmohardening processing.
The heating mechanisms such as hot plate or convection oven (hot air circulation type drying machine), high frequency heating machine can be used, to become The mode of the condition carries out the rear baking processing to the coated film after development with continous way or batch.
The step of < < forms the step of photoresist layer, obtains the step of resist pattern and carry out dry-etching (situation of pattern formation is carried out using dry etching method) > >
Dry-etching can use etching gas using patterned photoresist layer as mask to carry out.It is specific and Speech, is coated with the radiation sensitive compositions of eurymeric or minus on coloring layer, and makes it dry, and photoresist is consequently formed Layer.In the formation of photoresist layer, preferably further implement prebake conditions processing.The formation process of photoresist layer is outstanding Preferably it implements the heat treatment (postexposure bake (Post-Exposure Bake, PEB)) after exposure, adding after development It is heat-treated the form of (rear baking processing).
The radiation sensitive compositions of eurymeric for example can be used in photoresist.The radiation sensitive compositions of the eurymeric Induction ultraviolet light (g ray, h ray, i ray), the far ultraviolet comprising excimer laser etc., electron beam, ion beam can be used And the eurymeric anti-corrosion agent composition suitable for positive light anti-etching agent of the radioactive ray such as X ray.In radioactive ray, preferably g is penetrated Line, h ray, i ray, wherein preferably i ray.
Specifically, the radiation sensitive compositions of eurymeric preferably contain quinone di-azido compound and alkali soluble resin Composition.The radiation sensitive compositions of eurymeric containing quinone di-azido compound and alkali soluble resin utilize following feelings Condition: quinonediazide group, which is decomposed, due to the irradiation of the light of 500nm wavelength below generates carboxyl, is as a result become by the insoluble state of alkali For alkali-soluble.The parsing power of the positive light anti-etching agent is obviously excellent, therefore can be used for making integrated circuit (Integrated Circuit, IC) or the integrated circuits such as large scale integrated circuit (Large Scale Integration, LSI).Two Azide of quinone Naphthalene quinone di-azido compound can be enumerated by closing object.Commercially available product can for example enumerate " FHi622BC " (Fujiphoto electronic material The manufacture of (Fujifilm Electronic Materials) company) etc..
The thickness of photoresist layer is preferably 0.1 μm~3 μm, and preferably 0.2 μm~2.5 μm, and then preferably 0.3 μ M~2 μm.Furthermore the coating side of coloring layer already described above can be used come the formation of the photoresist layer carried out using coating Method suitably carries out.
Then, photoresist layer is exposed, developed, the resist equipped with resist through hole group is consequently formed Pattern (patterned photoresist layer).There is no particular restriction for the formation of resist pattern, can be by previously known photoetching Suitably optimization carries out technology.By exposure, development, resist through hole group is set in photoresist layer, by Resist pattern as etching mask used in subsequent etching is set on coloring layer by this.
The exposure of photoresist layer can carry out in the following manner: by set mask pattern, to eurymeric or bear The radiation sensitive compositions of type implement exposure using g ray, h ray, i ray etc., preferably i ray.After exposure, pass through benefit Development treatment is carried out with developer solution, and correspondingly removes photoresist with the region of colored pattern to be formed.
If the developer solution does not impact the coloring layer containing colorant, and by the exposure portion of positive-workingresist and The unhardened portion of negative resist is dissolved, then can be used, such as combination or the alkaline aqueous solution of various organic solvents can be used. Alkali compounds is preferably become 0.001 mass of mass %~10 %, preferably 0.01 mass % with concentration by alkaline aqueous solution The mode of~5 mass % dissolves and the alkaline aqueous solution for preparing.Alkali compounds can for example be enumerated: sodium hydroxide, potassium hydroxide, Sodium carbonate, sodium metasilicate, sodium metasilicate, ammonium hydroxide, ethamine, diethylamine, dimethylethanolamine, tetramethyl ammonium hydroxide, hydroxide four Ethyl ammonium, choline, pyrroles, piperidines, 1,8- diazabicyclo [5.4.0] -7- hendecene etc..In addition, using alkaline aqueous solution When situation as developer solution, usually implement cleaning treatment using water after development.
Then, using resist pattern as etching mask, by dry in a manner of forming through hole group in coloring layer Formula etching is patterned.Colored pattern is consequently formed.Through hole group is set in coloring layer with chessboard trellis.Therefore, 1st coloring picture of the 1st colored pattern with chessboard trellis and with multiple square shapes in coloring layer equipped with through hole group Element.
Just make pattern section formed closer to rectangle viewpoint or be further reduced damage to support viewpoint and Speech, dry-etching are preferably carried out by following form.
Preferably comprise the etching in the 1st stage, the etching and overetched form in the 2nd stage, the etching in the 1st stage Use fluorine-based gas and oxygen (O2) mixed gas, be etched until the region (depth) that support does not expose, institute State the 2nd stage be etched in the etching in the 1st stage after, use nitrogen (N2) and oxygen (O2) mixed gas, be etched Until the region (depth) that preferably support exposes is nearby, the overetch is carried out after support exposing.Hereinafter, Specific method and the etching in the 1st stage, the etching in the 2nd stage and overetch to dry-etching are illustrated.
Dry-etching is to find out etching condition in advance using following methods to carry out.
(1) etch-rate (nm/min) of the etching in the 1st stage and the etch-rate of the etching in the 2nd stage are calculated respectively (nm/min).(2) it calculates and is lost in the etching for etching the time, 2 stage of Ji of required thickness in the etching in the 1st stage respectively Carve the time of required thickness.(3) implement the etching in the 1st stage according to the etching period calculated in (2).(4) according to institute The etching period of calculating in (2) is stated to implement the etching in the 2nd stage.Alternatively, being detected by terminal (end point) to determine to lose The time is carved, implements the etching in the 2nd stage according to the etching period determined.(5) for the total ascent time of (3), (4) It calculates the overetch time, implements overetch.
For it will process rectangular viewpoint as the organic material for being eclipsed engraved film, the etching step in the 1st stage Used in mixed gas preferably contain fluorine-based gas and oxygen (O2).In addition, the etching step in the 1st stage is by being set as It is etched the form until the region that support does not expose, can avoid the damage of support.In addition, it is avoided that support Damage viewpoint for, the etching step in the 2nd stage and the overetch step are preferably that the etching in the 1st stage walks After being etched through until the region that support does not expose in rapid using fluorine-based gas and the implementation of the mixed gas of oxygen, nitrogen is used And the mixed gas of oxygen is etched.
The ratio of etch quantity in the etching step of etch quantity and the 2nd stage in the etching step in the 1st stage is important It is to be determined in a manner of not undermining the resulting rectangularity of etching process in the etching step by the 1st stage.Furthermore total etching Measure the latter's in (summation of the etch quantity in the etching step in the 1st stage and the etch quantity in the etching step in the 2nd stage) Ratio is preferably greater than 0% and for 50% range below, more preferably 10%~20%.So-called etch quantity, refers to according to quilt The amount that the film thickness of the remaining of etching-film and the difference of the film thickness before etching are calculated.
In addition, etching preferably comprises overetch processing.Overetch processing sets overetch ratio preferably to carry out.Separately Outside, overetch ratio is preferably calculated according to the etch processes time initially carried out.Overetch ratio can arbitrarily be set, and just be tieed up It holds the elching resistant of photoresist and is etched for the aspect of the rectangularity of pattern, preferably at the etching in etching step The 30% of the time is managed hereinafter, more preferably 5%~25%, especially preferably 10%~15%.
Then, resist pattern (i.e. etching mask) remaining after etching is removed.The removal of resist pattern is preferably The following steps are included: assigning stripper or solvent in resist pattern and resist pattern being adjusted to removable state Step；And the step of being removed resist pattern using ejected wash water.
In the step of resist pattern is adjusted to removable state by imparting stripper or solvent in resist pattern Such as can enumerate: assign stripper or solvent at least in resist pattern, be allowed to stagnate the set time and carry out leaching set it is aobvious The step of shadow.The time for stagnating stripper or solvent, there is no particular restriction, and preferably tens seconds to a few minutes.
In addition, the step of being removed resist pattern using ejected wash water can for example enumerate: the spray of self-spray formula or fountain Nozzle is penetrated to resist pattern jet cleaning water, the step of resist pattern is removed.Ejected wash water preferably uses pure water.Separately Outside, injection nozzle can be enumerated: in its spray regime comprising entire support injection nozzle or be movable injection nozzle And its movable range includes the injection nozzle of entire support.It, can be against corrosion in removal when injection nozzle is movable situation It is 2 times mobile or more until self-supporting body central part to support end in the step of agent pattern to carry out jet cleaning water, thus more have Effect ground removal resist pattern.
Stripper usually contains organic solvent, can also also contain inorganic solvent.Organic solvent can for example be enumerated: 1) hydrocarbon system Close object, 2) halogenated hydrocarbon based compound, 3) alcohol based compound, 4) ether or acetal based compound, 5) ketone or aldehyde based compound, 6) ester Based compound, 7) polyalcohol based compound, 8) carboxylic acid or its acid anhydrides based compound, 9) phenol system compound, 10) nitrogenous compound, 11) sulfur-containing compound, 12) fluorochemical.Stripper preferably contains nitrogenous compound, more preferably nitrogenous containing non-annularity Compound and cyclic nitrogen compound.
Non-annularity nitrogenous compound is preferably the non-annularity nitrogenous compound with hydroxyl.Specifically, can for example enumerate: Monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, N- ehtylethanolamine, N, N- dibutylethanolamine, N- butylethanolamine, Monoethanolamine, diethanol amine, triethanolamine etc., preferably monoethanolamine, diethanol amine, triethanolamine, more preferably monoethanol Amine (H2NCH2CH2OH).In addition, cyclic nitrogen compound can be enumerated: isoquinolin, imidazoles, N-ethylmorpholine, epsilon-caprolactams, quinoline Quinoline, 1,3- dimethyl -2- imidazolidinone, α-methylpyridine, beta-picoline, γ-picoline, pipecoline, 3- methyl Piperidines, 4- methyl piperidine, piperazine, piperidines, pyrazine, pyridine, Pyrrolizidine, n-methyl-2-pyrrolidone, N- phenylmorpholine, 2,4- Lutidines, 2,6- lutidines etc., preferably n-methyl-2-pyrrolidone, N-ethylmorpholine, more preferably N- first Base -2-Pyrrolidone (NMP).
Stripper preferably contains non-annularity nitrogenous compound and cyclic nitrogen compound, wherein more preferably containing work For non-annularity nitrogenous compound selected from least one of monoethanolamine, diethanol amine and triethanolamine with as cyclic annular nitrogenous Compound is selected from least one of n-methyl-2-pyrrolidone and N-ethylmorpholine, and then preferably contains monoethanolamine With N- methyl -2- pyrrolidones.
When using stripper to be removed, as long as the resist pattern that will be formed on the 1st colored pattern removes i.e. Can, that is, it is convenient for when being attached with the situation as the deposit (precipitate) of etch products on the side wall of the 1st colored pattern, it is described Deposit can also be removed completely.So-called deposit, made of referring to that etch products attachment is piled up on the side wall of coloring layer.
Stripper preferably relative to 100 mass parts of stripper rather than the content of cyclic nitrogen compound is 9 mass parts Above, 11 below the mass, and relative to 100 mass parts of stripper and the content of cyclic nitrogen compound be 65 mass parts with Above, 70 below the mass.In addition, stripper preferably utilizes pure water by non-annularity nitrogenous compound and cyclic nitrogen compound Mixture dilution made of.
Furthermore the manufacturing method of the present invention optionally may also comprise the manufacture as solid-state imager colored filter The step of method and known step are as other than described.Such as step is formed carrying out the coloring photosensitive combination layer Suddenly, after step of exposure and pattern forming step, optionally may also comprise makes to be formed by colored pattern by heating and/or exposing The cure step of hardening.
In addition, using composition of the invention situation when, such as sometimes generate apparatus for coating blowing unit nozzle or Blocking with pipe portion or the pollution etc. adhered to caused by settling drying because of coloured composition or pigment in coating machine.Cause This preferably will be related with this composition described above in order to efficiently clean the pollution caused by composition of the invention Solvent be used as cleaning solution.In addition, Japanese Patent Laid-Open 7-128867 bulletin, Japanese Patent Laid-Open 7-146562 public affairs Report, Japanese Patent Laid-Open 8-278637 bulletin, Japanese Patent Laid-Open 2000-273370 bulletin, Japanese Patent Laid-Open 2006-85140 bulletin, Japanese Patent Laid-Open 2006-291191 bulletin, Japanese Patent Laid-Open 2007-2101 bulletin, day The cleaning solution recorded in this patent special open 2007-2102 bulletin, Japanese Patent Laid-Open 2007-281523 bulletin etc. can also It is preferably used for the cleaning removal of composition of the invention.
In described, preferably alkylene glycol monoalkyl ethers carboxylate and alkylene glycol monoalkyl ethers.
These solvents can be used alone can also be used in mixed way it is two or more.When mixing two or more situations, preferably Solvent with hydroxyl is mixed with the solvent for not having hydroxyl.The quality of solvent and the solvent for not having hydroxyl with hydroxyl Than being 1/99~99/1, preferably 10/90~90/10, more preferably 20/80~80/20.Especially preferably propylene glycol list first Ether acetic acid ester (Propyleneglycol monomethylether acetate, PGMEA) and propylene glycol monomethyl ether The mixed solvent of (Propyleneglycol monomethylether, PGME) and its ratio are 60/40.Furthermore in order to improve Cleaning solution can also add surface-active related with this composition described above to the permeability of pollutant in cleaning solution Agent.
Colored filter of the invention is because using composition of the invention, therefore it is excellent to be exposed tolerance (margin) Exposure, and the pattern form for being formed by colored pattern (colored pixels) is excellent, coarse or development section the residue of patterned surfaces It is inhibited, therefore color characteristics become excellent.
Colored filter of the invention can be preferably used as the solid-state imagers such as CCD, CMOS, particularly suitable for more than 100 High-resolution CCD or CMOS as ten thousand pixels etc..Solid-state imager colored filter of the invention, which can be used, for example, as, matches The colour being placed between the acceptance part and the lenticule to carry out optically focused (microlens) for each pixel for constituting CCD or CMOS Optical filter.
Furthermore the film thickness of the colored pattern (colored pixels) of colored filter of the invention is preferably 2.0 μm hereinafter, more excellent 1.0 μm are selected as hereinafter, being in turn preferably 0.7 μm or less.
In addition, the size (pattern width) of colored pattern (colored pixels) is preferably 2.5 μm hereinafter, more preferably 2.0 μm Hereinafter, especially preferably 1.7 μm or less.
[solid-state imager]
Solid-state imager of the invention has colored filter of the invention already described above.Solid-state image pickup of the invention The composition of element is to have the composition of colored filter of the invention, as long as the structure functioned as solid-state imager At being then not particularly limited, such as composition can be listed below.
So-called solid-state imager is following composition: having on support and constitutes solid-state imager (ccd image sensing Device, cmos image sensor etc.) light area multiple photodiodes (photodiode) and the biography comprising polysilicon etc. Transmission pole, the acceptance part opening on the photodiode and the transmission electrode with only photodiode includes tungsten etc. Photomask, have on photomask formed in a manner of covering photomask entire surface and photodiode acceptance part comprising nitrogen The element protection film of SiClx etc. has solid-state imager colored filter of the invention on the element protection film.
In turn, there can also be optically focused for (side of close support) on the element protection layer and under colored filter Mechanism (such as lenticule etc..It is same as below) composition or colorized optical filtering on piece have optically focused mechanism composition etc..
[image display device]
Colored filter of the invention cannot be only used for the solid-state imager, and can be used for liquid crystal display device or The image display devices such as organic EL display device, the purposes particularly suitable for liquid crystal display device.Has colorized optical filtering of the invention The liquid crystal display device of piece can show following image: show the high resolution image that the tone of image is good and display characteristic is excellent.
About the definition of display device or the details of each display device, it is e.g. recorded in " electronic console element (the clear husband of assistant assistant wood writes, the census of manufacturing meeting (stock), nineteen ninety distribution) ", " (she blows along chapter work, industry books display device (stock), 1989 issue) " etc. in.In addition, being e.g. recorded in " next-generation liquid crystal display skill about liquid crystal display device Art (Uchida Tatsuo edits, census of manufacturing meeting (stock), issues for 1994) " in.The applicable liquid crystal display device of the present invention has no Especially limitation, such as can be applied to the liquid crystal display dress for the various modes recorded in " the next-generation LCD Technology " It sets.
Colored filter of the invention can also be used in colorful film transistor (Thin Film Transistor, TFT) side The liquid crystal display device of formula.About the liquid crystal display device of colored TFT mode, it is e.g. recorded in " color TFT-LCD display (vertical publish (stock) is issued for 1996 altogether) " in.In turn, it is also possible to apply the invention to the drivings of the transverse electric fields such as coplanar switching (IPS) The visual angles such as the pixels partitioning schemes such as mode, more quadrants vertically oriented (Multi-domain Vertical Alignment, MVA) Through widened liquid crystal display device or STN Super TN (Super Twisted Nematic, STN), twisted nematic (Twisted Nematic, TN), vertically oriented (Vertical Alignment, VA), optical compensation tilt (Optically Compensated Splay, OCS), fringing field switching (Fringe Field Switching, FFS) and reflective optic mend Repay bending (Reflective-Optically Compensated Bend, R-OCB) etc..
In addition, colored filter of the invention can also be used in bright and fine colorful optical filter array (Color- Filter On Array, COA) mode.In the liquid crystal display device of COA mode, the requirement characteristic to color filter layers is removed Common as described above requires other than characteristic, also needs requirement characteristic, the i.e. low dielectric to interlayer dielectric normal sometimes Several and resistance to removing fluidity.In colored filter of the invention, because of the dyestuff polymer for using form and aspect excellent, therefore colour purity, Transmitance etc. is good and the excellent hue of colored pattern (pixel), therefore can provide a kind of high resolution and long durability of backside protective sheet excellent COA mode liquid crystal display device.Furthermore it, can also be in color filter layers in order to meet the requirement characteristic of low-k Upper setting resin coating.
About these image display patterns, be e.g. recorded in " electroluminescent (Electroluminescence, EL), etc. Gas ions display panel (Plasma Display Panel, PDP), liquid crystal display (Liquid Crystal Display, LCD) new advancement-in display-technology and market (investigate by the beautiful research center (Toray Research Center) in east Department, 2001 issue) " page 43 etc. in.
Have the liquid crystal display device of colored filter of the invention other than colored filter of the invention, is by electricity Electrode substrate, light polarizing film, phase difference film, backlight, spacer (spacer), visual angle ensure that the various components such as film are constituted.The present invention Colored filter can be applied in the liquid crystal display device that component well known to these is constituted.About these components, such as Be be recorded in " the liquid crystal display periphery material of ' 94-chemicals market (and island Itou Kentaro, CMC (stock), 1994 issue) ", " (the good Ji of table, Fuji Kai Meilai are always ground (stock), are sent out within 2003 for the status of 2003 liquid crystal relevant markets and in the future prospect (last volume) Row) " in.
It is to be recorded in " Society for Information Display's minutes (SID meeting Digest) " 1380 about backlight (2005) page 18~page 24 (island health is abundant) in the December, 2005 number of (A. modern wild (A.Konno) et al.) or monthly magazine " display " And in described document page 25~page 30 (Yagi spark gap is grand bright) etc..
If colored filter of the invention is used for liquid crystal display device, when three waves with previously known cold-cathode tube , it can be achieved that high contrast when long tube combines, and then by the way that the LED light source (RGB-LED) of red, green, blue to be set as Backlight, it is possible to provide brightness height, the in addition good liquid crystal display device of the high color reprodubility of colour purity.
[embodiment]
It is exemplified below embodiment and then the present invention is illustrated.Material shown in embodiment below, usage amount, Ratio, process content, processing sequence etc. can then be suitably changed without departing from purport of the invention.Therefore, the scope of the present invention It is not limited to concrete example as shown below.Furthermore as long as no special instructions, then " % " and " part " is quality criteria.
The synthesis > of < (C) phosphate dispersing agent
(synthesis example 1)
In the reaction vessel for being equipped with condenser pipe, nitrogen ingress pipe, blender in three neck round bottom flask, laurel is added 18.6 g of alcohol (manufacture of Na Kalai science and technology (Nacalai Tesque) limited liability company), 6-caprolactone monomer 57.1g (He Guangchun The manufacture of medicine limited liability company), butyl titanate 0.06g (Tokyo be melted into limited liability company manufacture), using nitrogen to reaction After being replaced in container, heating stirring 3 hours at 120 DEG C.It utilizes1H- nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) confirm the disappearance of internal ester monomer.After until reaction solution is cooled to room temperature, with orthophosphoric acid (orthophosphoric acid) converts content as 116% polyphosphoric acid 8.45g mixing, slowly heats up, heats at 80 DEG C Stirring 6 hours obtains the R in logical formula (II)3Number average molecular weight be 760, y=1 and y=2 are 100:12 there are ratio Phosphate dispersing agent (C-1).The acid value of resulting phosphate dispersing agent is 166.
(2~synthesis example of synthesis example 4)
The type additive amount of monohydric alcohol and the kind of used internal ester monomer used in being changed as described in Table 1 Class additive amount obtains phosphate dispersing agent (C-2)~phosphate using method identical with the synthesis example 1 in addition to this Dispersing agent (C-4).
In the table 1, so-called R3Number average molecular weight, indicate the number average molecular weight of logical formula (II).
The synthesis > of < (D) specific resin adhesive
(synthesis example 5)
Hold in the reaction for being equipped with thermometer, condenser pipe, nitrogen ingress pipe, agitating device on detachable four-hole boiling flask In device, propylene glycol methyl ether acetate is added, 80 DEG C are heated to when importing nitrogen in the reaction vessel, mutually synthermal Under from drop tube with 2 hours dropwise addition benzyl methacrylate 123.3g, methacrylic acid 17.2g, p -cumylphenol epoxy second Alkane modification acrylate (East Asia synthesizes limited liability company's manufacture " Aronix (Aronix) M110 ") 31.0g, azo are double different The mixture of butyronitrile 10.0g carries out polymerization reaction.
After until resulting resin solution is cooled to room temperature, samples about 3g and heat drying is after twenty minutes at 180 DEG C Nonvolatile component is measured, adds propylene glycol in such a way that nonvolatile component becomes 40 mass % in the resin solution synthesized in advance Acetic acid esters obtains the solution of resin binder (D-1).
The synthesis > of < resin binder 1
(synthesis example 6)
Hold in the reaction for being equipped with thermometer, condenser pipe, nitrogen ingress pipe, agitating device on detachable four-hole boiling flask In device, propylene glycol methyl ether acetate is added, 100 DEG C are heated to when importing nitrogen in the reaction vessel, in Xiang Tongwen From in drop tube with 1 hour dropwise addition benzyl methacrylate 123.3g, methacrylic acid 25.8g, azobis isobutyronitrile under degree The mixture of 10.0g carries out polymerization reaction.
After until resulting resin solution is cooled to room temperature, samples about 3g and heat drying is after twenty minutes at 180 DEG C Nonvolatile component is measured, adds propylene glycol in such a way that nonvolatile component becomes 40 mass % in the resin solution synthesized in advance Acetic acid esters obtains the solution of resin binder 1.
The synthesis > of < (G) resin
(synthesis example 7)
Hold in the reaction for being equipped with thermometer, condenser pipe, nitrogen ingress pipe, agitating device on detachable four-hole boiling flask In device, propylene glycol methyl ether acetate is added, 80 DEG C are heated to when importing nitrogen in the reaction vessel, mutually synthermal Under from drop tube with 2 hours dropwise addition benzyl methacrylate 123.3g, methacrylic acid 17.2g, glycerol monomethacrylate The mixture of ester (Glycerol monomethacrylate) 14.6g, azobis isobutyronitrile 10.0g carry out polymerization reaction.
To resulting resin solution with 3 hours dropwise addition 2- methylacryloyl ethyl isocyanate (Showa electricity at 70 DEG C " Ka Lanci (Karenz) MOI " of work limited liability company manufacture) 23.3g, dibutyl tin laurate 0.3g, cyclohexanone 90g Mixture.
After until resulting resin solution is cooled to room temperature, samples about 3g and heat drying is after twenty minutes at 180 DEG C Nonvolatile component is measured, adds propylene glycol in such a way that nonvolatile component becomes 40 mass % in the resin solution synthesized in advance Acetic acid esters obtains the solution of resin binder (G-1).
The manufacture > of < Red Pigment Dispersion composition
After the mixture of following compositions is equably stirred, is dispersed 3 hours using ball mill mixing and prepared red Color pigment dispensing composition (R-a).
[changing 58]
Composition is changed to the composition recorded in following table 2, in addition to this, using with the Red Pigment Dispersion composition (R-a) prepare identical method to prepare Red Pigment Dispersion composition (R-b)~Red Pigment Dispersion composition (R-p).
In the table 2, each mark refers to following compound.
PR254 diketopyrrolopyrrolecocrystals system red pigment (C.I. paratonere 254)
PY139 isoindoline system yellow uitramarine (C.I. pigment yellow 13 9)
PR177 anthraquinone system red pigment (C.I. paratonere 177)
PR122 quinacridone red pigment (C.I. pigment red 122)
PO71 diketopyrrolopyrrolecocrystals system orange pigment (C.I. pigment orange 71)
Red-a: the azo system red pigment Red-a of following structural formula
[changing 59]
Pigment derivative (B-2): the compound of following structural formula
[changing 60]
Pigment derivative (B-3): the compound of following structural formula
[changing 61]
Pigment derivative (B-4): the compound of following structural formula
[changing 62]
The preparation > of < viridine green dispersive composition
After the mixture of following compositions is equably stirred, is dispersed 3 hours using ball mill mixing and prepared green Color pigment dispensing composition (G-a).
[changing 63]
Component content is changed to the composition of following Table 3, in addition to this, using with the viridine green dispersive composition (G-a) prepare identical method to prepare viridine green dispersive composition (G-b)~viridine green dispersive composition (G-o).
In the table 3, each mark refers to following compound.
PG7 chlorinated copper phthalocyanine system viridine green (C.I. pigment Green 7)
PG36 halogenated copper phthalocyanine system viridine green (C.I. pigment green 36)
PG58 halogenation ZnPc system viridine green (C.I. naphthol green 58)
PY139 isoindoline system yellow uitramarine (C.I. pigment yellow 13 9)
PY150 nickel azo system yellow uitramarine (C.I. pigment yellow 150)
PY185 isoindoline system yellow uitramarine (C.I. pigment yellow 185)
Pigment derivative (B-5): the compound of following structural formula
[changing 64]
The preparation > of < Yellow Pigment Dispersion composition
After the mixture of following compositions is equably stirred, is dispersed 3 hours using ball mill mixing and prepared yellow Color pigment dispensing composition (Y-a).
[changing 65]
The preparation > of < Blue pigment dispersion composition
After the mixture of following compositions is equably stirred, using ball mill mixing dispersion 3 hours, preparation was blue Pigment dispensing composition (B-a).
[changing 66]
Component content is changed to the composition of following table 4, in addition to this, using with the Blue pigment dispersion composition (B-a) the identical method for preparing prepares Blue pigment dispersion composition (B-b)~Blue pigment dispersion composition (B-g).
In the table 4, each mark refers to following compound.
PB15:6 copper phthalocyanine system blue pigment (C.I. pigment blue 15: 6)
PV23 dioxazines system violet pigment (C.I. pigment Violet 23)
Pigment derivative (B-7): the compound of following structural formula
[changing 67]
The preparation > of < red sensitive resin combination
The mixture of following compositions is equably stirred, red sensitive resin combination (RR-a) is prepared.
Photoepolymerizationinitiater initiater (E-1): 1,2- acetyl caproyl, 1- [4- (thiophenyl)-, 2- (O- benzoyl oximes)] (BASF (BASF) company manufactures, gorgeous good solid (IRGACURE) OXE01)
Ethylene unsaturated compound (F-1): the ethylene-oxide-modified product (village Xin Zhong of dipentaerythritol hexaacrylate Learn Industries, Inc's manufacture, NK ester (NK Ester) A-DPH-12E)
Fluorine system surfactant: (big Japanese ink limited liability company manufacture, Mei Jiafa (Megafac) F-781F)
Component content is changed to the composition of following table 5, in addition to this, using with the red sensitive resin combination (RR-a) prepare identical method to prepare red sensitive resin combination (RR-b)~red sensitive resin combination (RR-v)。
< evaluates >
(evaluation of the patternability after PCD)
(1) preparation (minus) of transparent resist solution A
By following compositions mixed dissolution, transparent resist solution A is prepared.
5.20 parts of propylene glycol methyl ether acetate
52.60 parts of cyclohexanone
30.50 parts of adhesive
(benzyl methacrylate/methacrylic acid/methacrylic acid -2- hydroxy methacrylate copolymer molar ratio=60:20: 20, average molecular weight is 30200 (polystyrene conversions), 41% cyclohexanone solution)
(2) production of the glass substrate with priming coat
After carrying out ultrasonic cleaning to glass substrate (healthy and free from worry (Corning) 1737) using 0.5%NaOH water, water is carried out It washes, be dehydrated baking (200 DEG C/20 minutes).Then, using transparent resist solution A obtained in spin coater (1) by described in do Film thickness after dry is coated on cleaned glass substrate as 2 μm of mode, the heat drying 1 hour at 220 DEG C and formed Thus priming coat prepares the glass substrate with priming coat.
(3) exposure development of photosensitive composition (colored pattern is formed)
Prepare 2 with lower substrate: will resulting red sensitive resin combination (RR-a) above~red using spin coater Color sensation photosensitive resin composition (RR-v) is coated on band obtained in (2) in such a way that the film thickness after drying becomes 0.6 μm On the priming coat for having the glass substrate of priming coat, the substrate made of prebake conditions 120 seconds at 100 DEG C.
For a piece of in the substrate, i ray step-by-step movement is used immediately after being coated with red sensitive resin combination Exposure device FPA-i5+ (Canon's (Canon) (stock) manufacture), by 1.1 μm of mask of line width, to coated film with the wave of 365nm The most suitable light exposure for the block check master drawing case that the long length to form one side is 1.1 μm is irradiated.After exposure, development is used Liquid CD-2000 (Fujiphoto electronic material (Fujifilm Electronic Materials) (stock) manufacture) is with 25 DEG C, 40 Second condition develop.Thereafter, it after with flowing water elution 30 seconds, is spray-dried, obtains colored pattern.
Then, for another in the substrate, after being coated with red sensitive resin combination, in the cleaning of room temperature After placing 72 hours (PCD) in room (clean room), colored pattern is obtained using with the identical method.
Using scanning electron microscope (Scanning Electron Microscope, SEM) to so as resulting 2 Kind of colored pattern is observed, to after coating immediately (no PCD) be exposed the resulting colored pattern of development with it is laggard in PCD The shape of the resulting colored pattern of row exposure development is compared, and is evaluated by following benchmark.
A: compared with the shape of the colored pattern of no PCD, the shape of the colored pattern after PCD does not change completely
The shape of colored pattern after B:PCD is visible slightly to be changed, but no problem
The shape of colored pattern after C:PCD is collapsed, problematic
The shape of colored pattern after D:PCD is significantly collapsed
The PCD evaluation result is summarized and is shown in following table 5.
(evaluation of color spot (irregular colour))
It will resulting red sensitive resin combination (RR-a)~red sensitive resin combination above using spin coater Object (RR-v) is coated on glass substrate in such a way that the film thickness after drying becomes 0.6 μm, prebake conditions 120 seconds at 100 DEG C And obtain coloring film 1.
In addition, making by resulting red sensitive resin combination (the RR-a)~red sensitive resin combination of the main points Object (RR-v) at room temperature through when 6 months after, using spin coater by the film thickness after drying become 0.6 μm in a manner of be coated on glass On glass substrate, the prebake conditions 120 seconds at 100 DEG C and obtain coloring film 2.
Resulting each coloring film is set between the observation camera lens of optical microscopy and light source, is shone towards observation camera lens Light is penetrated, it is observed using the optical microscopy for being provided with the digital camera that multiplying power is 1000 times and transmits light state.It is being arranged The CCD that 1,280,000 pixels are carried in digital camera in optical microscopy, is shot using the digital camera in saturating Penetrate the coloring film coated surface of light state.Shooting figure seems that digital conversion is carried out in the form of the bitmap (bitmap) by 8 (bit) Made of data (digital picture) and save.
Furthermore the shooting for colouring film coated surface is carried out to optional 20 regions.In addition, being converted about through number Data, shooting image with 0~255 256 grades of concentration distribution is protected the respective brightness number of RGB three primary colors It deposits.
Then, for the digital picture saved, 0.5 μm of square being equivalent to 1 grid size in actual substrate Model split at clathrate, the brightness in a block is equalized.In the present embodiment, the number of 1,280,000 pixels is utilized Camera shoots 1000 times of optics of image, therefore 0.5 μm in actual substrate becomes the 0.5mm on shooting image, display On picture size be 452mm × 352mm, therefore total block counts in a region be 636416.
For all blocks in each region, the average bright of any 1 block and all of its neighbor block adjacent therewith is measured Degree.The block that difference by the average brightness with adjacent block is 5 or more regards as significant difference block, calculates the aobvious of whole region Write the average total number of difference block.The numerical value is smaller, and smaller with the concentration difference of adjacent block, color spot is fewer, indicates as color The characteristic of colo(u)r filter is more excellent.
The average total number of the color spot of film 1 will be coloured as the value of color spot immediately after preparation, the color spot of film 2 will be coloured Average total number as at room temperature through when 6 months after color spot value, and then will at room temperature through when 6 months after divided by rigid preparation The color spot Magnification of the value of color spot afterwards is shown in following table 5.
In the table 5, each mark refers to following compound.
Photoepolymerizationinitiater initiater (E-2): ethyl ketone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, 1- (O- acetyl group oxime) (manufacture of BASF (BASF) company, gorgeous good solid (IRGACURE) OXE02)
Photoepolymerizationinitiater initiater (E-3): 2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) Phenyl] -1- butanone (manufacture of BASF (BASF) company, gorgeous good solid (IRGACURE) 379)
Ethylene unsaturated compound (F-2): dipentaerythritol hexaacrylate and Dipentaerythritol Pentaacrylate Mixture (NIPPON PHARMACEUTICAL CO., LTD's manufacture, Ka Yala get (KAYARAD) DPHA)
Ethylene unsaturated compound (F-3): (village Xin Zhong chemical industry share is limited for trimethylolpropane trimethacrylate Company's manufacture, A-TMPT)
Ultraviolet absorbing agent: the compound of following structural formula
[changing 68]
It is learnt according to result shown in the table 5, the red sensitive resin combination (RR- of comparative example 1 and comparative example 3 R) and red sensitive resin combination (RR-t) though contain (C) phosphate in composition of the invention as an essential component Dispersing agent, but be free of the resin of (D) specific structure, therefore the patternability after PCD significantly deteriorates, color spot through Shi Zeng great Also slightly larger.In addition, the red sensitive resin combination (RR-s) and red sensitive resin combination of comparative example 2 and comparative example 4 Object (RR-u) is free of (C) phosphoric acid though the resin containing (D) specific structure in composition of the invention as an essential component Be dispersing agent, thus color spot through when increase it is very big, the patternability after PCD also has room for improvement.
It learns relative to these comparative examples, such as red sensitive resin combination of the invention shown in embodiment 1 (RR-a) containing (C) phosphate dispersing agent in composition of the invention as an essential component, and then contain (D) specific structure Resin, therefore color spot through when increase be inhibited, the patternability after PCD is also significantly improved.
In addition it also learns, use has the resin (G-1) of polymeric double bond as the implementation of (G) resin binder in side chain In 6~embodiment of example 20, the Magnification of color spot is further inhibited.
It learns using the embodiment 12 of phosphate dispersing agent (C-3), embodiment 19 and using other phosphate dispersing agents Embodiment compares, and the patternability after PCD is more excellent.
Learn using relative to 100 mass parts of (A) pigment and the content of the resin of (D) specific structure is more than 80 mass parts In the embodiment 5 of pigment dispensing composition (R-c) ", although the Magnification of color spot and patternability after PCD are more compared with comparative example It is excellent but more slightly worse compared with other embodiments.
Learn as described in Example 4 as make the alkaline pigment derivative of (A) pigment, (B) and the dispersion of (C) phosphate dispersing agent and Obtain Red Pigment Dispersion composition after, deploy (D) resin and prepare red sensitive resin combination, thus color spot through when increase It is further suppressed greatly, the patternability after PCD is further improved.
The preparation > of < green photonasty resin composition
The mixture of following compositions is equably stirred, green photonasty resin composition (GR-a) is prepared.
Component content is changed to the content of table 6, in addition to this, using with the green photonasty resin composition (GR- A) prepare identical method to prepare green photonasty resin composition (GR-b)~green photonasty resin composition (GR- u)。
About resulting green photonasty resin composition (GR-a)~green photonasty resin composition (GR-u), utilize Method same as Example 1 come carry out immediately after preparation and at room temperature through when 6 months after color spot value and PCD after pattern The evaluation of formative.Result is summarized and is shown in following table 6.
According to shown in the table 6 as a result, the green photonasty resin composition (GR-r) of comparative example 5 and comparative example 7 and Green photonasty resin composition (GR-t) though contain (C) the phosphate dispersion in composition of the invention as an essential component Agent, but be free of the resin of (D) specific structure, therefore the patternability after PCD significantly deteriorates, color spot through when increase also slightly Greatly.In addition, the green photonasty resin composition (GR-s) and green photonasty resin composition of comparative example 6 and comparative example 8 (GR-u) though the resin binder containing (D) specific structure in composition of the invention as an essential component, is free of (C) Phosphate dispersing agent, thus color spot through when increase it is very big, the patternability after PCD also has room for improvement.
It learns relative to these comparative examples, such as green photonasty resin composition of the invention shown in embodiment 21 (GR-a) containing (C) phosphate dispersing agent in composition of the invention as an essential component, and then contain (D) specific structure Resin, therefore color spot through when increase be inhibited, the patternability after PCD is significantly improved.
In addition it also learns, use has the resin (G-1) of polymeric double bond as the implementation of (G) resin binder in side chain In 26~embodiment of example 39, the Magnification of color spot is further suppressed.
It learns using the embodiment 32 of phosphate dispersing agent (C-3), embodiment 39 and using other phosphate dispersing agents Embodiment compares, and the patternability after PCD is more excellent.
Learn using relative to 100 mass parts of (A) pigment and the content of (D) resin is more than the pigment discrete sets of 80 mass parts Close object (G-c) " embodiment 25 in, although the Magnification of color spot and patternability after PCD are more excellent compared with comparative example, with Other embodiments are compared to more slightly worse.
Learn makes the alkaline pigment derivative of (A) pigment, (B) and the dispersion of (C) phosphate dispersing agent as shown in embodiment 24 Afterwards, deploy (D) resin and prepare photosensitive composition, thus color spot through when increase and further suppressed, PCD Patternability afterwards is further improved.
The preparation > of < blue-sensitive resin combination
The mixture of following compositions is equably stirred, blue-sensitive resin combination (BR-a) is prepared.
Component content is changed to the content of following table 7, in addition to this, using with the blue-sensitive resin combination (BR-a) prepare identical method to prepare blue-sensitive resin combination (BR-b)~blue-sensitive resin combination (BR-m)。
For resulting blue-sensitive resin combination (BR-a)~blue-sensitive resin combination (BR-m), utilize Method same as Example 1 come carry out immediately after preparation and at room temperature through when 6 months after color spot value and PCD after pattern The evaluation of formative.Result is summarized and is shown in following table 7.
According to shown in the table 7 as a result, the blue-sensitive resin combination (BR-l) of comparative example 9 though containing the present invention Composition in (C) phosphate dispersing agent as an essential component, but be free of the resin binder of (D) specific structure, therefore PCD Patternability afterwards significantly deteriorates, color spot through when increase it is also slightly larger.In addition, the blue-sensitive resin of comparative example 10 Composition (BR-m) is free of (C) though the resin containing (D) specific structure in composition of the invention as an essential component Phosphate dispersing agent, thus color spot through when increase it is very big, the patternability after PCD also has room for improvement.
It learns relative to these comparative examples, such as blue-sensitive resin combination of the invention shown in embodiment 40 (BR-a) containing (C) phosphate dispersing agent in composition of the invention as an essential component, and then contain (D) specific structure Resin binder, therefore at room temperature through when 6 months after color spot increase be inhibited, the patternability after PCD obtains greatly Amplitude improves.
In addition it also learns, use has the resin (G-1) of polymeric double bond as the implementation of (G) resin binder in side chain In 45~embodiment of example 52, the Magnification of color spot is further suppressed.
It learns using the embodiment 43 of phosphate dispersing agent (C-3), embodiment 51 and using other phosphate dispersing agents Embodiment compares, and the patternability after PCD is more excellent.
Learn using relative to 100 mass parts of (A) pigment and the content of (D) resin is more than the pigment discrete sets of 80 mass parts Close object (R-c) " embodiment 44 in, although the Magnification of color spot and patternability after PCD are more excellent compared with comparative example, with Other embodiments are compared to more slightly worse.
Learn makes the alkaline pigment derivative of (A) pigment, (B) and the dispersion of (C) phosphate dispersing agent as shown in embodiment 43 Afterwards, deploy (D) resin and prepare photosensitive composition, thus color spot through when increase and further suppressed, PCD Patternability afterwards is further improved.
Japanese Patent Laid-Open 2011- in addition to (B) alkaline pigment derivative in each embodiment to be changed into equivalent Other than compound 7 documented by the paragraph 0223 of No. 162760 bulletins (reprinting as follows), coloring phototonus is prepared in the same way Resin combination.The patternability of photosensitive composition obtained is evaluated, as a result confirmation can be formed Good pattern.
[changing 69]

Claims (17)

1. a kind of photosensitive composition, contains: (A) pigment, (B) alkaline pigment derivative, (C) the following general formula (II) Represented phosphate dispersing agent, (D) by compound (x) represented by the following general formula (IV) with there is ethylene unsaturated double-bond Compound (y) combined polymerization made of resin, (E) Photoepolymerizationinitiater initiater and (F) polymerizable compound,
[changing 1]
In logical formula (II), R3Indicate that number average molecular weight is 400~30000 polyester construction, y indicates 1 or 2；
When y is 2 situation, multiple R3It may be the same or different respectively；
In logical formula (IV), R4Indicate hydrogen atom or methyl, R5Indicate the alkylidene of carbon number 2 or 3, R6It indicates hydrogen atom or can contain The alkyl of the carbon number 1~20 of phenyl ring, n indicate 1~15 integer；
When n is 2 or more situation, multiple R5It may be the same or different respectively,
Relative to total solid content, the content of (C) the phosphate dispersing agent is the 1 mass % of mass %~30,
Relative to total solid content, (D) is by compound (x) represented by logical formula (IV) and has ethylene unsaturated double-bond Compound (y) combined polymerization made of resin content be 1 mass of mass %~30 %.
2. photosensitive composition according to claim 1, wherein (B) alkaline pigment derivative is that have The compound of amino.
3. photosensitive composition according to claim 1, wherein described (A) pigment is selected from by red face In group composed by material, viridine green and yellow uitramarine.
4. photosensitive composition according to claim 1, wherein in the general formula (II), the R3It is represented Polyester construction number average molecular weight be 1900~10000.
5. photosensitive composition according to claim 1, wherein in the general formula (II), the R3It is represented Polyester construction be by the two or more different resulting polyester constructions of internal ester monomer ring-opening polymerisation.
6. photosensitive composition according to any one of claim 1 to 5 also has containing (G) in side chain The resin of polymeric double bond.
7. photosensitive composition according to claim 6, wherein (G) has polymeric double bond in side chain Resin be resin made of reacting compound (b) with copolymer (a), the compound (b) with hydroxyl with can react Functional group and ethylene unsaturated double-bond, the copolymer (a) be polymerizable monomer (p) with 2~6 hydroxyls and its The copolymer of his polymerizable monomer (q).
8. photosensitive composition according to any one of claim 1 to 5, wherein relative to (A) face Expect 100 mass parts, (D) is by compound (x) represented by logical formula (IV) and with the compound of ethylene unsaturated double-bond (y) content of resin made of combined polymerization is 5 mass parts~80 mass parts.
9. photosensitive composition according to any one of claim 1 to 5, wherein the coloring phototonus tree Oil/fat composition is that described (A) pigment, (B) alkaline pigment derivative and (C) is made to lead to phosphate represented by formula (II) After dispersing agent dispersion, (D) described in allotment is by compound (x) represented by logical formula (IV) and with the change of ethylene unsaturated double-bond Resin made of object (y) combined polymerization is closed to form.
10. photosensitive composition according to any one of claim 1 to 5, is used to form colorized optical filtering The painted areas of piece.
11. a kind of cured film is to keep photosensitive composition according to any one of claim 1 to 10 hard Change.
12. a kind of manufacturing method of colored filter, comprising: by color sensation according to any one of claim 1 to 10 The step of photosensitive resin composition is applied on support and forms coloring photosensitive combination layer；By the coloring phototonus group Close the step of nitride layer exposure is at pattern-like；And the step of removing and forming colored pattern that unexposed portion develops.
13. a kind of manufacturing method of colored filter, comprising:
Photosensitive composition according to any one of claim 1 to 10 is applied to be formed on support The step of coloring photosensitive combination layer；
In the step of forming photoresist layer on the coloring photosensitive combination layer；
By the photoresist pattern layers and being exposed and develop, the step of obtaining resist pattern；And
Carry out the step of dry-etching is carried out to the coloring photosensitive combination layer for the resist pattern as etching mask.
14. a kind of colored filter has cured film according to claim 11.
15. a kind of colored filter is manufactured with the manufacturing method of colored filter according to claim 12 or 13 It forms.
16. a kind of solid-state imager has colored filter according to claim 14 or 15.
17. a kind of image display device has colored filter according to claim 14 or 15.
CN201480030200.XA 2013-08-05 2014-07-31 Photosensitive composition, cured film, colored filter and its manufacturing method, solid-state imager and image display device Active CN105283806B (en)

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