CN101548203B - Photosensitive color resin composition for color filter, color filter, liquid crystal display, and organic el display - Google Patents

Photosensitive color resin composition for color filter, color filter, liquid crystal display, and organic el display Download PDF

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CN101548203B
CN101548203B CN2008800010167A CN200880001016A CN101548203B CN 101548203 B CN101548203 B CN 101548203B CN 2008800010167 A CN2008800010167 A CN 2008800010167A CN 200880001016 A CN200880001016 A CN 200880001016A CN 101548203 B CN101548203 B CN 101548203B
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color
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weight
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CN101548203A (en
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田中俊行
水上润二
土谷达格
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei 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
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography

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  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention provides a photosensitive color resin composition for color filters, which is excellent in image-forming property even when a colorant has a high concentration, while having an excellent balance between sensitivity and solubility. This photosensitive color resin composition for color filters is also excellent in sharpness of a pixel edge and adhesion. Specifically disclosed is a photosensitive color resin composition for color filters, which contains an alkali-soluble resin (A) obtained by reacting a reaction product of an epoxy resin (a) represented by the general formula (1-a) below and an unsaturated group-containing carboxylic acid (b) with a polybasic acid and/or an anhydride thereof (c), a photopolymerization initiator (B), and a colorant (C). The alkali-soluble resin (A) has a weight average molecular weight of not less than 3,300 but not more than 50,000. (1-a) (In the formula, n represents an average value which is a number of 0-10; R<41> represents a hydrogen atom, a halogen atom, an alkyl group having 1-8 carbon atoms, a cycloalkyl group having 3-10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group; and G represents a glycidyl group.).

Description

Photosensitive color resin composition for color, color filter, liquid crystal indicator and organic EL display panel
Technical field
The present invention relates to photosensitive color resin composition for color, color filter, liquid crystal indicator and organic electroluminescent (EL) display screen.At length say, even the present invention relates under the concentration condition with higher of colorant, also have excellent imaging, sensitivity and deliquescent balance excellent and the sharpening property of pixel edge and photosensitive color resin composition for color of adaptation excellence and uses thereof.
Background technology
In the past, as the autofrettage of the color filter that has used pigment, known had decoration method, electro-deposition method, ink-jet method, a pigment dispersing method etc.
When utilizing pigment dispersing manufactured color filter, in the colored resin composition that dispersion pigment such as utilizing spreading agent forms, add resin glue, Photoepolymerizationinitiater initiater, photopolymerization monomer etc. usually, the photosensitive color resin combination after such sensitized is coated on the glass substrate; After carrying out drying, use mask to make public, and develop; Form colored pattern thus; Then it is heated, thereby pattern is fixed, form pixel.Repeat these operations according to each color, thereby form color filter.
The photosensitive color resin combination that is used for the imaging of such color filter requires to have sufficient resolution, with characteristics such as good adaptation, the development residue of substrate is few.In addition, in recent years, people require at the bottom of the high resin black of the high pixel of colour saturation and optical concentration always.Therefore, require the photosensitive color resin combination when containing colorants such as a large amount of pigment and carbon black, to have excellent above-mentioned characteristic.
Generally, because photosensitive polymer combination is supplied in the photo-mask process that will pass through coating, drying, exposure, developing procedure, so in these operations, often require: the part of removing in developing procedure does not produce residue or scum silica frost; Remove part and have sufficient dissolubility; Improve pixels such as sharpening degree formation property of pattern edge.But, use the high photosensitive color resin combination of content of the colorant of above-mentioned that kind form pixel and black matrix (below, sometimes pixel and black matrix are closed and are called " pattern ".) situation under, very easily produce following problem: produce residue, scum silica frost in the developing procedure on unexposed the substrate; Unexposed can not obtain fine solubility; The sharpening degree of pattern edge is relatively poor; The photocuring of exposure portion is not enough, so surface smoothing property is relatively poor; Or the like.
Particularly, owing to comprise black pigment at the bottom of the resin black, have light-proofness in the wavelength region may of broad, therefore produce more serious problem, for example (1) is difficult to make the cross-linking density of exposed portion and unexposed portion to create a difference; (2) even the part after exposure also produces the poor of cross-linking density on film thickness direction, that is, even the photoirradiated surface side is fully solidified, the basal surface side but is difficult to solidify; (3) contain the black pigment that is insoluble to developer solution in a large number, therefore be difficult to obtain high development property; Or the like.
So,, have document to propose to use and have the photosensitive color resin combination (referring to patent documentation 1) of the novolaks Epocryl of carboxyl as resin glue in order to solve such problem.But the research according to the inventor can be known; Even when using this resin glue; Also can produce following problem: for example; Because the balance of dissolubility and sensitivity is insufficient, therefore the infiltration of developer solution to exposure portion take place in unexposed dissolving, the rectilinearity of pattern edge part is lower; The adaptation of pattern and substrate is insufficient; Or the like.
The reaction product of the acryl resin that in addition, has document to propose to use to have carboxyl and the unsaturated compound that contains epoxy radicals of ester ring type is as the photosensitive polymer combination (referring to patent documentation 2) of resin glue.But, can know that according to the inventor's research even when using this resin glue, sensitivity is also insufficient, so the adaptation of pattern and substrate is relatively poor, is difficult to form high fine pattern.
In addition, the reaction product of epoxy resin, the carboxylic acid that contains unsaturated group and polynary type carboxylic acid anhydrides that in patent documentation 3, has proposed use formula (1) expression is as the photosensitive color resin composition for color (referring to patent documentation 3) of resin glue.Though the composition of putting down in writing in this document has room for improvement more excellent aspect the sharpening degree of the adaptation of substrate, pattern edge and storage stability aspect sensitivity.
Figure G2008800010167D00031
(in the formula, n representes mean value and representes 0～10 number.P, R represent that hydrogen atom, halogen atom, carbon number are 1～8 alkyl, any group in the aryl, and each P, R can be identical or inequality each other.G representes glycidyl.)
Patent documentation 1: japanese kokai publication hei 11-84126 communique
Patent documentation 2: japanese kokai publication hei 1-289820 communique
Patent documentation 3: TOHKEMY 2005-55814 communique
The object of the present invention is to provide a kind of photosensitive color resin composition for color and used the color filter of this photosensitive color resin combination and used this color filter and liquid crystal indicator and the organic el panel processed; Even said photosensitive color resin composition for color also has excellent imaging under the concentration condition with higher of colorant; Sensitivity and deliquescent balance are excellent, and the sharpening property of pixel edge, adaptation are excellent.
Summary of the invention
The inventor furthers investigate, and the result finds, has ad hoc structure and the higher resin glue of molecular weight can address the above problem through use, so that accomplished the present invention.
That is, main points of the present invention are following.
[1] a kind of photosensitive color resin composition for color; It is characterized in that; Said composition contains alkali soluble resins (A), Photoepolymerizationinitiater initiater (B) and colorant (C); Said alkali soluble resins (A) is that the reaction product through epoxy resin (a) that makes formula (1-a) expression and the carboxylic acid (b) that contains unsaturated group further obtains with polyprotonic acid and/or its acid anhydrides (c) reaction, and the weight-average molecular weight of the alkali soluble resins (A) that is obtained by polystyrene conversion through gel permeation chromatography (GPC) mensuration is 3300～50000.
Figure DEST_PATH_GSB00000152045600011
In the above-mentioned general formula (1-a), n representes mean value and representes 0～10 number.R 41Expression hydrogen atom, halogen atom, carbon number are that 1～8 alkyl, carbon number are any group in 3～10 naphthenic base, phenyl, naphthyl or the xenyl.In addition, be present in 2 above R in 1 molecule 41Can be same to each other or different to each other.G representes glycidyl.
[2] like [1] described photosensitive color resin composition for color, wherein, said composition also contains spreading agent (D).
[3] like [1] or [2] described photosensitive color resin composition for color, wherein, said composition also contains photopolymerization monomer (E).
[4] like each described photosensitive color resin composition for color of [1]～[3]; Wherein, Said composition also contains alkali soluble resins (A '); Said alkali soluble resins (A ') is through epoxy compound that makes formula (1-a ') expression (a ') and α, β-unsaturated monocarboxylic and/or have the α of carboxyl at ester moiety, and the reaction product of β-unsaturated monocarboxylic ester (b ') and polyprotonic acid and/or its acid anhydrides (c ') react and obtain.
Figure DEST_PATH_GSB00000152045600012
[above-mentioned general formula (1-a ') in, p and q represent 0～4 integer, R independently of one another 31And R 32Represent alkyl or halogen atom independently of one another.R 33And R 34Represent alkylidene independently of one another.X and y represent the integer more than 0 independently of one another.]
[5] like each described photosensitive color resin composition for color of [1]～[4]; Wherein, Said composition also contains alkali soluble resins (A "), and said alkali soluble resins (A ") is to react through the reaction product of the epoxy compound that makes formula (1-a ") expression (a ") and the carboxylic acid that contains unsaturated group (b ") and polyprotonic acid and/or its acid anhydrides (c ") to obtain.
Figure G2008800010167D00051
[above-mentioned general formula (1-a ") in, X representes the linking group of formula (2a), (2b) or (3) expression.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
Figure G2008800010167D00052
(at above-mentioned general formula (2a) with (2b), R 1～R 4And R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
In above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure.
In above-mentioned general formula (2a), (2b) and (3), * represent with general formula (1-a ") in the position of glycidoxypropyl bonding.)]
[6] like [5] described photosensitive color resin composition for color, wherein, said polyprotonic acid and/or its acid anhydrides (c ") contain following (i) and (ii):
(i) { tetra-atomic acid and/or its acid anhydrides } and/or { dibasic acid and/or its acid anhydrides };
(ii) ternary acid and/or its acid anhydrides.
[7] like each described photosensitive color resin composition for color of [1]～[6]; Wherein, Said composition also contains alkali soluble resins (A1 "), and said alkali soluble resins (A1 ") is to obtain through this potpourri and polyprotonic acid and/or its acid anhydrides (c ") are reacted.
Figure G2008800010167D00061
[above-mentioned general formula (1-a ") in, X representes the linking group of formula (2a), (2b) or (3) expression.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
Figure G2008800010167D00062
(at above-mentioned general formula (2a) with (2b), R 1～R 4And R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
In above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure.
In above-mentioned general formula (2a), (2b) and (3), * represent with general formula (1-a ") in the position of glycidoxypropyl bonding.)]
[8] like [7] described photosensitive color resin composition for color, wherein, said polyprotonic acid and/or its acid anhydrides (c ") contain as follows (i) and (ii):
(i) { tetra-atomic acid and/or its acid anhydrides } and/or { dibasic acid and/or its acid anhydrides };
(ii) ternary acid and/or its acid anhydrides.
[9] like each described photosensitive color resin composition for color of [1]～[8], wherein, said Photoepolymerizationinitiater initiater (B) contains the oxime ester derivative class.
[10] like each described photosensitive color resin composition for color of [1]～[9], wherein, in all solids composition of photosensitive color resin combination, the content of said colorant (C) is 20～60 weight %.
[11] like each described photosensitive color resin composition for color of [1]～[10], wherein, said colorant (C) contains black pigment.
[12] a kind of color filter, this color filter have pixel or the black matrix that each described photosensitive color resin combination of use [1]～[11] forms on transparency carrier.
[13] a kind of liquid crystal indicator, this liquid crystal indicator are to use [12] described color filter to make.
[14] a kind of organic el panel, this organic el panel are to use [12] described color filter to make.
Photosensitive color resin composition for color of the present invention highly sensitive; Good with the adaptation of substrate; Even sensitivity and deliquescent balance are also excellent when containing colorant such as pigment and carbon black with high concentration; And the sharpening property of pixel edge and adaptation are excellent, can form high resolution, high meticulous pixel.According to the present invention, through using such photosensitive color resin composition for color, can access high-quality color filter, and then high-quality liquid crystal indicator and organic el panel can be provided.
Description of drawings
Fig. 1 is the schematic cross-section that an example of the organic EL that is equipped with color filter of the present invention is shown.
Embodiment
Below, embodiment of the present invention is specified, but the present invention is not limited to following embodiment, can in the scope of its main points, carry out various distortion and implement.
In addition, in the present invention, " (methyl) acrylic acid " is meant " acrylic acid and/or methacrylic acid ", for " (methyl) acrylic ester ", " (methyl) acryloyl " too.And " (many) hydroxyls " is meant " hydroxyl and/or polyhydroxy ".
In the present invention, " all solids composition " be meant, in the photosensitive color resin composition for color or after contained in the printing ink stated desolventize beyond all the components.
In the present invention, weight-average molecular weight is meant the weight-average molecular weight (Mw) that is gone out by polystyrene conversion of utilizing that GPC (gel permeation chromatography) obtains.
In addition, in the present invention, only otherwise special declaration, the amine value that the effective solid constituent of " amine value " expression converts, amine value are to use the value of representing with the weight of the KOH of the alkali number a great deal of of every 1g solid constituent of spreading agent.In addition, assay method is of the back.
[photosensitive color resin composition for color]
Photosensitive color resin composition for color of the present invention (below be also referred to as " photosensitive color resin combination " perhaps " colored resin composition ") contains alkali soluble resins (A), Photoepolymerizationinitiater initiater (B) and colorant (C) as essential composition; Preferably also contain spreading agent (D) and photopolymerization monomer (E)
Also contain other blending constituent such as other resin glues (F) except alkali soluble resins (A), organic solvent, adaptation improving agent, coating improving agent, development modifying agent, ultraviolet light absorber, anti-oxidant, silane coupling agent, surfactant, pigment derivative as required.Usually, the various materials of alkali soluble resins (A), Photoepolymerizationinitiater initiater (B), colorant (C) and use as required are used with the state that is dissolved in or be scattered in the organic solvent.
< alkali soluble resins (A) >
Alkali soluble resins (A) is further to obtain with the reaction of polyprotonic acid and/or its acid anhydrides (c) through the reaction product that makes specific epoxy resin (a) and contain the carboxylic acid (b) of unsaturated group.
(1) epoxy resin (a)
Epoxy resin (a) is represented with formula (1-a).
Figure DEST_PATH_GSB00000152045600021
[in the above-mentioned general formula (1-a), n representes mean value and representes 0～10 number.R 41Expression hydrogen atom, halogen atom, carbon number are that 1～8 alkyl, carbon number are the arbitrary group in 3～10 naphthenic base, phenyl, naphthyl or the xenyl.In addition, be present in 2 above R in 1 molecule 41Can be mutually the same, also can be different.G representes glycidyl.]
R in the general formula (1-a) 41Expression hydrogen atom, halogen atom, carbon number are that 1～8 alkyl, carbon number are the arbitrary group in 3～10 naphthenic base, phenyl, naphthyl or the xenyl, still, and from sensitivity and the consideration of dissolubility aspect, R 41Be preferably hydrogen atom or methyl especially.In addition, be present in 2 above R in 1 molecule 41Can be same to each other or different to each other.
The epoxy resin (a) of above-mentioned general formula (1-a) expression can be through for example making formula (1-a-1) expression compound and epihalohydrin in the presence of alkali metal hydroxide, react and obtain.
Figure DEST_PATH_GSB00000152045600022
(in the formula, n and R 41The expression with general formula (1-a) in identical implication.)
The compound of above-mentioned general formula (1-a-1) expression can be through for example making formula (1-a-2) expression compound and phenol in the presence of acid catalyst, carry out condensation reaction and obtain.
Figure DEST_PATH_GSB00000152045600023
(in the formula, Z representes halogen atom, hydroxyl or lower alkoxy.R 41The expression with above-mentioned general formula (1-a) in identical implication.)
Among the Z of above-mentioned general formula (1-a-2), as halogen atom, preferred group can be enumerated chlorine atom, bromine atoms etc., and as lower alkoxy, it is 1～4 alkoxy etc. that preferred group can be enumerated carbon numbers such as methoxyl, ethoxy.
On the other hand; Said phenol is meant the aromatics that in a molecule, has 1 phenol property hydroxyl; As its concrete example, can enumerate with phenol, cresols, ethyl-phenol, n-pro-pyl phenol, isobutyl phenol, tert-butyl phenol, octyl phenol, xylenols, methyl butyl phenol, DI-tert-butylphenol compounds etc. be the alkylphenol of typical example various neighbours-,-, right-isomeride; With cyclopentyl phenol, cyclohexylphenol, cyclohexyl cresols etc. is the naphthenic base phenol of typical example; Or phenylphenol etc. has with as the R in the above-mentioned general formula (1-a) 41The group of being enumerated is substituent phenol.These phenol can be used combination use more than a kind or 2 kinds separately.
When carrying out above-mentioned condensation reaction, with respect to 1 mole compound of general formula (1-a-2) expression, the consumption of phenol is preferably 0.5～20 mole, is preferably 2～15 moles especially.
The preferred acid catalyst that uses can use various acid catalysts in the above-mentioned condensation reaction, but preferred hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous Aluminum chloride, zinc chloride etc., preferred especially p-toluenesulfonic acid, sulfuric acid, hydrochloric acid.Consumption for these acid catalysts does not have special qualification, but the compound that preferred use is represented with respect to general formula (1-a-2) is the acid catalyst of 0.1～30 weight %.
Above-mentioned condensation reaction can be carried out under condition of no solvent or in the presence of organic solvent.Concrete example as with an organic solvent the time can be enumerated toluene, xylene, methyl isobutyl ketone etc.The consumption of organic solvent is preferably 50～300 weight % of the general assembly (TW) of the raw material that is added, and is preferably 100～250 weight % especially.Temperature of reaction is preferably 40～180 ℃ of scopes, and the reaction time is preferably 1～8 hour.
After reaction finishes, carry out neutralisation treatment or wash the pH value of handling product being adjusted to 3～7, be preferably 5～7.Washing under the situation of processing, various alkaline matters such as organic amines such as alkaline earth metal hydroxides such as alkali metal hydroxide, calcium hydroxide, magnesium hydroxide, ammonia, sodium dihydrogen phosphate and diethylene triamine, trien, aniline, phenylenediamine such as use NaOH, potassium hydroxide etc. are handled as neutralizing agent and are got final product.In addition, washing is handled and is got final product according to conventional method.For example can be employed in the reaction mixture and to add the water that is dissolved with above-mentioned neutralizing agent, repeat the method for extracting operation.
After carrying out above-mentioned neutralisation treatment or washing processing, unreacted dihydroxy benzenes class and solvent are removed in distillation under the decompression heating, and product is concentrated, and obtain the compound of above-mentioned general formula (1-a-1) expression thus.
Obtain the method for the epoxy resin of the present invention (a) of above-mentioned general formula (1-a) expression as compound, can adopt known method from above-mentioned general formula (1-a-1) expression.For example; In the dissolving mixt of the compound of general formula (1-a-1) expression and excessive epihalohydrin (such as chloropropylene oxide, epibromohydrin etc.), adding alkali metal hydroxide (such as NaOH, potassium hydroxide etc.) in advance reacted their 1～10 hour in 20～120 ℃ temperature; Perhaps the temperature in 20～120 ℃ makes their reactions 1～10 hour when adding alkali metal hydroxide, can access the epoxy resin (a) of general formula (1-a) expression thus.
In the reaction of above-mentioned acquisition epoxy resin (a), alkali metal hydroxide can use its WS, in this case; Can be following method: the WS of this alkali metal hydroxide is added continuously in the reaction system; Meanwhile, under reduced pressure or water and epihalohydrin are distilled, carry out separatory again; Remove and anhydrate, epihalohydrin is turned back in the reaction system continuously.
In addition; Also can utilize following method to make epoxy resin (a): in the dissolving mixt of the compound of above-mentioned general formula (1-a-1) expression and epihalohydrin, to add quaternary ammonium salts such as tetramethyl ammonium chloride, tetramethylammonium bromide, Variquat B 200 as catalyzer; Make their reactions 1～5 hour in 50～150 ℃ temperature; The solid or the WS that in the halohydrin etherate of the compound of representing with general formula (1-a-1) that obtains, add alkali metal hydroxide; Again in 20～120 ℃ thermotonus 1～10 hour, with dehydrohalogenation (closed loop).
With respect to 1 equivalent hydroxyl of the compound of representing with general formula (1-a-1), the amount of the epihalohydrin that in such reaction, uses is generally 1～20 mole, is preferably 2～10 moles.And with respect to 1 equivalent hydroxyl of the compound of general formula (1-a-1) expression, the consumption of alkali metal hydroxide is generally 0.8～15 mole, is preferably 0.9～11 mole.
And then, carry out smoothly in order to make reaction, can add alcohols such as methyl alcohol, ethanol, can add aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide in addition and wait and react.When using pure time-like, the consumption of alcohols is 2～20 weight % with respect to the amount of epihalohydrin, is preferably 4～15 weight %.In addition, when using the aprotic polar solvent, the consumption of aprotic polar solvent is 5～100 weight % with respect to the amount of epihalohydrin, is preferably 10～90 weight %.
After the reaction product of above-mentioned epoxidation reaction washed; Or do not wash; Under the condition of heating decompression; For example under 110～250 ℃ temperature, condition below the pressure 1.3kPa (10mmHg), remove epihalohydrin and other solvent that is added etc., obtain epoxy resin (a) thus as target.
In addition; In order further to process the few epoxy resin of water-disintegrable halogen; Can resulting epoxy resin be dissolved in toluene, the methyl isobutyl ketone equal solvent once more, the WS that adds alkali metal hydroxides such as NaOH, potassium hydroxide reacts, and carries out closed loop reliably.At this moment, with respect to 1 equivalent hydroxyl of the compound of the general formula that in epoxidation, uses (1-a-1) expression, the consumption of alkali metal hydroxide is preferably 0.01～0.3 mole, is preferably 0.05～0.2 mole especially.Temperature of reaction is 50～120 ℃, and the reaction time is generally 0.5～2 hour.
Reaction is filtered after finishing, washing etc. removed the salt that is generated, and then toluene, methyl isobutyl ketone equal solvent are removed in distillation under the condition of heating decompression, can access thus to use the epoxy resin (a) of stating general formula (1-a) expression.
(2) contain the carboxylic acid (b) of unsaturated group
As the carboxylic acid that contains unsaturated group (b); Can enumerate unsaturated carboxylic acid with ethylenic unsaturated double-bond; As concrete example, can enumerate (methyl) acrylic acid, butenoic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, to monocarboxylic acids such as vinyl benzoic acid, (methyl) acrylic acid alpha-position alkylhalide group substituent, alkoxy substituent, halogen substituent, nitro substituent, cyanic acid substituent, 2-(methyl) acrylyl oxy-ethyl succinic acid, 2-acrylyl oxy-ethyl hexane diacid, 2-(methyl) acrylyl oxy-ethyl phthalic acid, 2-(methyl) acrylyl oxy-ethyl hexahydro-phthalic acid, 2-(methyl) acrylyl oxy-ethyl maleic acid, 2-(methyl) acryloyl-oxy propyl group succinic acid, 2-(methyl) acryloyl-oxy propyl group hexane diacid, 2-(methyl) acryloyl-oxy propyl group tetrahydrophthalic acid, 2-(methyl) acryloyl-oxy propyl group phthalic acid, 2-(methyl) acryloyl-oxy propyl group maleic acid, 2-(methyl) acryloyl-oxy butyl succinic acid, 2-(methyl) acryloyl-oxy butyl hexane diacid, 2-(methyl) acryloyl-oxy butyl hydrogenation phthalic acid, 2-(methyl) acryloyl-oxy butyl phthalic acid, 2-(methyl) acryloyl-oxy butyl maleic acid, in lactone such as addition 6-caprolactone, beta-propiolactone, gamma-butyrolacton, δ-Wu Neizhis on (methyl) acrylic acid and the monomer that obtains or addition succinic acid (acid anhydride), phthalic acid (acid anhydride), maleic acid acid such as (acid anhydrides) (acid anhydride) and the monomer that obtains, (methyl) acrylic acid dimer etc. on (methyl) acrylic acid hydroxyalkyl acrylate, pentaerythrite three (methyl) acrylic ester.
In the above-mentioned unsaturated carboxylic acid, consider preferred especially (methyl) acrylic acid from the sensitivity aspect.These unsaturated carboxylic acids can use a kind of separately, also can share two or more.
(3) epoxy resin (a) and the reaction that contains the carboxylic acid (b) of unsaturated group
As the epoxy radicals and the method that the carboxylic acid (b) that contains unsaturated group reacts that make in the epoxy resin (a), can use known method.For example; With quaternary ammonium salt, pyridine, triphenylphosphines etc. such as tertiary amines such as triethylamine, benzyl methyl amine, chlorination dodecyl trimethyl ammonium, tetramethyl ammonium chloride, etamon chloride, benzyltriethylammonium chlorides is catalyzer; Make epoxy resin (a) and the carboxylic acid (b) that contains unsaturated group in organic solvent 50～150 ℃ temperature of reaction stoichiometric number hour～tens of hours, thus can be on epoxy resin the addition carboxylic acid.
With respect to reacting material mixture (epoxy resin (a) with contain the total of the carboxylic acid (b) of unsaturated group), this catalyst consumption is preferably 0.01～10 weight %, is preferably 0.3～5 weight % especially.
And; For the polymerization in preventing to react; The preferred polymerization inhibitor (for example MEHQ (metoquinone), quinhydrones, methylnaphthohydroquinone, p methoxy phenol, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, phenothiazine etc.) that uses; The consumption of polymerization inhibitor is preferably 0.01～10 weight % with respect to reacting material mixture, is preferably 0.1～5 weight % especially.
Addition contain the carboxylic acid (b) of unsaturated group the ratio of epoxy radicals of epoxy resin (a) be generally 90～100 moles of %.Remaining epoxy radicals can produce harmful effect to storage stability, and therefore with respect to 1 equivalent epoxy radicals of epoxy resin (a), the carboxylic acid (b) that preferably contains unsaturated group reacts with common 0.8～1.5 equivalent, the particularly ratio of 0.9～1.1 equivalent.
(4) polyprotonic acid and/or its acid anhydrides (c)
As polyprotonic acid and/or its acid anhydrides (c) of addition on the hydroxyl of reaction product of epoxy resin (a) and the carboxylic acid (b) that contains unsaturated group; Can use known polyprotonic acid and/or its acid anhydrides; Can enumerate methylene tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, 5-ENB-2 in maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, the methyl; 3-dicarboxylic acid, methyl-5-ENB-2, dicarboxylic acids or its acid anhydrides such as 3-dicarboxylic acid; Polybasic carboxylic acids such as trimellitic acid, PMA, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid or its acid anhydrides etc.Wherein, preferably enumerate tetrabydrophthalic anhydride or succinic anhydride.These materials can use a kind of separately, also can share two or more.
The markup percentage of polyprotonic acid and/or its acid anhydrides (c) is generally 10～100 moles of % with respect to the hydroxyl that when the last addition of epoxy resin (a) contains the carboxylic acid (b) of unsaturated group, generates, and is preferably 20～100 moles of %, more preferably 30～100 moles of %.If this markup percentage is too much, the residual film ratio when then developing reduces sometimes, if this markup percentage is very few, then dissolubility is not enough sometimes, and perhaps the adaptation with substrate is not enough sometimes.
As containing carboxylic acid (b) the back addition polyprotonic acid of unsaturated group and/or the method for its acid anhydrides (c), can use known method in the last addition of above-mentioned epoxy resin (a).
In addition, in the present invention, like this behind addition polyprotonic acid and/or its acid anhydrides (c), can be on the part carboxyl that is generated addition contain the compound (d) of epoxy radicals.At this moment; In order to improve photo sensitivity; As the compound that contains epoxy radicals (d) can addition (methyl) glycidyl acrylate, (methyl) acrylic acid-3,4-epoxycyclohexyl ester, the glycidyl ether compound etc. with polymerism unsaturated group contain the unsaturated compound of epoxy radicals, perhaps in order to improve development property; Can addition do not have the glycidyl ether compound of polymerism unsaturated group as the compound that contains epoxy radicals (d), can share the two.As the concrete example of the glycidyl ether compound that does not have the polymerism unsaturated group, comprise have phenyl, the glycidyl ether compound of alkyl (it is by name that NAGASE changes into the commodity that industry (strain) makes: for that Cauer (DENACOL) EX-111, for that Cauer EX-121, for that Cauer EX-141, for that Cauer EX-145, for that Cauer EX-146, for that Cauer EX-171, for that Cauer EX-192) etc.
Alkali soluble resins of the present invention (A) can be to make above-mentioned epoxy resin (a) and containing the such compound that contains epoxy radicals (d) of addition on a part of carboxyl of the resin that the reaction product of the carboxylic acid (b) of unsaturated group further obtains with the reaction of polyprotonic acid and/or its acid anhydrides (c) and the resin that obtains.
(5) rerum natura of alkali soluble resins (A) etc.
The weight-average molecular weight (Mw) that is obtained by the polystyrene conversion alkali soluble resins (A) that the present invention is used, that utilize GPC (gel permeation chromatography) to measure is generally more than 3300; Be preferably more than 3500; And be generally below 50000, be preferably below 30000, more preferably below 10000.If the weight-average molecular weight of this alkali soluble resins (A) is too small, then poor sensitivity is if the weight-average molecular weight of this alkali soluble resins (A) is excessive, then to the dissolubility deficiency of developer solution, therefore not preferred.
Like this, among the present invention, compare, can significantly improve the sensitivity of the photosensitive color resin combination that contains this resin through using the bigger alkali soluble resins (A) of molecular weight with known in the past resin with identical skeleton.The unclear detailed mechanism that improves sensitivity, but infer as follows:
(1) usually, the part that the macromolecule through photopolymerization is quantized, in advance (before the photopolymerization) carry out some macromolecules and quantize, improved photopolymerisable efficient thus substantively, and
Therefore (2), the patience of developer solution is uprised etc. because basic framework has higher molecular weight.
In addition, the acid number (mgKOH/g) of the alkali soluble resins (A) that the present invention is used is generally more than 10, is preferably more than 50, and is generally below 200, is preferably below 150.If the acid number of alkali soluble resins (A) is low excessively, then can not get sufficient dissolubility sometimes, if the acid number of alkali soluble resins (A) is too high, then curable is not enough, and the superficiality of coated film is aggravated.
< other resin glue (F) >
In photosensitive color resin combination of the present invention, can use other resin glue (F) replacement part alkali soluble resins (A).That is, can share alkali soluble resins (A) and other resin glue.
Only otherwise damage performance of the present invention, for can with the not special restriction of other resin glue (F) that alkali soluble resins (A) share, from the normally used resin of photosensitive color resin composition for color institute, select to get final product.For example can enumerate the resin glue of record in TOHKEMY 2007-271727 communique, TOHKEMY 2007-316620 communique, the TOHKEMY 2007-334290 communique etc. etc., preferred especially below alkali soluble resins (A '), alkali soluble resins (A ") and the alkali soluble resins (A1 ") of narration.
In addition, other resin glue (F) can use a kind of separately, also can make up two or more uses.
(1) alkali soluble resins (A '): the epoxy compound (a ') and the α that make formula (1-a ') expression; β-unsaturated monocarboxylic and/or have the α of carboxyl at ester moiety, the reaction product of β-unsaturated monocarboxylic ester (b ') and polyprotonic acid and/or its acid anhydrides (c ') reaction and the alkali soluble resins that obtains (A ')
Figure G2008800010167D00151
[above-mentioned general formula (1-a ') in, p and q represent 0～4 integer, R independently of one another 31And R 32Represent alkyl or halogen atom independently of one another.R 33And R 34Represent alkylidene independently of one another.X and y represent the integer more than 0 independently of one another.]
(1-1) epoxy compound of general formula (1-a ') expression (a ')
At first, describe about the epoxy compound of above-mentioned general formula (1-a ') expression (a ') (below be sometimes referred to as " (a ') composition ").
Above-mentioned general formula (1-a ') in, as R 31And R 32Alkyl, preferred carbon number is 1～10 alkyl, as halogen atom, can enumerate Cl, Br, F etc.As R 31And R 32Independent separately, preferred especially carbon number is 1～5 alkyl.
Though do not know R 31And R 32Alkyl, the detailed mechanism of action of halogen atom, but infer it is owing to influenced the three-dimensional structure of molecule, thereby controlled easy the to be deliquescent cause in developer solution.
Therefore, from above viewpoint, p and q in the above-mentioned general formula (1-a ') represent 0～4 integer independently of one another, but are preferably 1 or 2.
For R 31And R 32Have no particular limits with the bonding position of phenyl ring, but relatively preferred
Figure G2008800010167D00161
Perhaps
Be the ortho position.
Wherein, R 31And R 32Can be that identical group also can be a group inequality, but consider, be preferably identical group from the manufacturing cost aspect.
As R 33And R 34Alkylidene, can enumerate carbon number and be 1～10 alkylidene, especially preferably be ethylidene or propylidene independently of one another.
X and y represent the integer more than 0 independently of one another, are generally about 0～6, are preferably about 0～3.In general, the big more dissolubility of x and y is just high more, but x and y be when excessive, and sensitivity might reduce.
Wherein, R 33And R 34Can be that identical group also can be different group, but consider, be preferably identical group from the manufacturing cost aspect.
In the weight-average molecular weight (Mw) that is obtained by polystyrene conversion of utilizing that gel permeation chromatography (GPC) measures, the molecular weight of these (a ') compositions is generally 200～200, and 000, be preferably 300～100,000.If the not enough above-mentioned scope of molecular weight is then mostly having problems aspect tunicle formation property, opposite; If molecular weight surpasses the resin of above-mentioned scope; Then after the α that states, cause gelation easily during the addition reaction of β-unsaturated monocarboxylic etc., thereby might be difficult to make.
(1-2) α, β-unsaturated monocarboxylic and/or have the α of carboxyl at ester moiety, β-unsaturated monocarboxylic ester (b ')
At α, β-unsaturated monocarboxylic and/or have the α of carboxyl at ester moiety is among the β-unsaturated monocarboxylic ester (b ') (below be sometimes referred to as " (b ') composition "); As α; β-unsaturated monocarboxylic can be enumerated itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid etc., is preferably acrylic acid and methacrylic acid; Acrylic acid is rich reactive, so be preferably acrylic acid especially.
As the α that has carboxyl at ester moiety; β-unsaturated monocarboxylic ester; Can enumerate acrylic acid-2-amber acyloxy ethyl ester, acrylic acid-2-Malaysia acyloxy ethyl ester, acrylic acid-2-phthalyl 2-ethoxyethyl acetate, acrylic acid-2-hexahydro phthalyl 2-ethoxyethyl acetate, methacrylic acid-2-succinyl 2-ethoxyethyl acetate, methacrylic acid-2-Malaysia acyl-oxygen ethyl ester, methacrylic acid-2-phthalyl 2-ethoxyethyl acetate, methacrylic acid-2-hexahydro phthalyl 2-ethoxyethyl acetate, crotonic acid-2-succinyl 2-ethoxyethyl acetate etc.; Preferred acrylic acid-2-Malaysia acyl-oxygen ethyl ester and acrylic acid-2-phthalyl 2-ethoxyethyl acetate, preferred especially acrylic acid-2-Malaysia acyl-oxygen ethyl ester.
For the addition reaction of (b ') composition and above-mentioned (a ') composition, can use known method.For example, in the presence of esterification catalyst, make (b ') composition and (a ') composition reaction in 50～150 ℃ temperature.As the esterification catalyst that uses, can enumerate quaternary ammonium salts such as tertiary amines such as triethylamine, trimethylamine, benzyl methyl amine, benzyl diethylamide, tetramethyl ammonium chloride, etamon chloride, chlorination dodecyl trimethyl ammonium etc. here.
Wherein, (a ') composition, (b ') composition and esterification catalyst can use a kind of separately, also can share two or more.
With respect to the 1 equivalent epoxy radicals of (a ') composition, the consumption of (b ') composition is preferably 0.5～1.2 equivalent, more preferably 0.7～1.1 equivalent.
If the consumption of (b ') composition is few, then can make the import volume of unsaturated group not enough, make the reaction of and then carrying out also insufficient with polyprotonic acid and/or its acid anhydrides (c ').And residual a large amount of epoxy radicals also is disadvantageous.On the other hand, if consumption that should (b ') composition is too much, then (b ') composition gets off as unreacted reactant is remaining.Think that curing characteristics all aggravates under above-mentioned any situation.
(1-3) polyprotonic acid and/or its acid anhydrides (c ')
The further polyprotonic acid of addition and/or its acid anhydrides (c ') (below be sometimes referred to as " (c ') composition ") on (a ') composition of (b ') composition as in addition can be enumerated in the acid anhydrides that is selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, PMA, trimellitic acid, benzophenone tetrabasic carboxylic acid, methylhexahydrophthalic acid, interior methylene tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyltetracarboxyacid acid and these polyprotonic acids etc. one or more.
Be preferably the acid anhydrides of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, PMA, trimellitic acid, biphenyltetracarboxyacid acid or these polyprotonic acids.Be preferably tetrahydrophthalic acid, biphenyltetracarboxyacid acid, tetrabydrophthalic anhydride or biphenyl tetracarboxylic dianhydride especially.
The addition reaction of relevant (c ') composition also can be used known method, with to the reacting phase of (a ') composition addition (b ') composition with condition under, continue to react with (c ') composition, obtain alkali soluble resins thus.
The addition amount of (c ') composition is preferably the acid number that makes the alkali soluble resins that generated (the A ') degree in 10～150mgKOH/g scope, more preferably makes the degree of the acid number of alkali soluble resins (A ') in 20～140mgKOH/g scope.If the not enough above-mentioned scope of resinous acid value then has the tendency that lacks alkali-developable, on the contrary,, think that then curing performance is tending towards variation if resinous acid value surpasses above-mentioned scope.
In addition, when being somebody's turn to do the addition reaction of (c ') composition, can add polyfunctional alcohols such as trimethylolpropane, pentaerythrite, dipentaerythritol (d '), import multiple-branching construction.As polyvalent alcohol (d '), for example can enumerate with after the identical compound of compound enumerated of the example stated as polyvalent alcohol (d ").
The weight-average molecular weight (Mw) of the alkali soluble resins of measuring through gel permeation chromatography (GPC) that is obtained by polystyrene conversion (A ') is generally more than 1,000, is preferably 1; More than 500, and be generally below 30,000; Be preferably below 20,000 more preferably 10; Below 000, be preferably below 8,000 especially.If weight-average molecular weight is excessive, then development property might worsen, and on the contrary, if weight-average molecular weight is too small, then alkali resistance might variation.
(2) alkali soluble resins (A "): the reaction product of the epoxy compound (a ") that makes formula (1-a ") expression and the carboxylic acid that contains unsaturated group (b ") and polyprotonic acid and/or its acid anhydrides (c ") react and the alkali soluble resins that obtains (A "), and
Alkali soluble resins (A1 "): this potpourri and polyprotonic acid and/or its acid anhydrides (c ") are reacted and the alkali soluble resins that obtains (A1 ")
Figure G2008800010167D00191
[above-mentioned general formula (1-a ") in, X representes the linking group of formula (2a), (2b) or (3) expression.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
Figure G2008800010167D00192
(at above-mentioned general formula (2a) with (2b), R 1～R 4And R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
In above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure.
In above-mentioned general formula (2a), (2b) and (3), * represent with general formula (1-a ") in the position of glycidoxypropyl bonding.)]
(2-1) epoxy compound of general formula (1-a ") expression (a ")
At first, to the epoxy compound of above-mentioned general formula (1-a ") expression (a ") (below be sometimes referred to as " (a ") composition ") in radicals X describe.
When above-mentioned radicals X is an above-mentioned general formula (2a) or (2b) during the structure of expression, above-mentioned general formula (2a) and (2b) preferably all has 2～4 adamantane structures.If adamantane structure is 1, have then that anti-development fluidity reduces and the tendency that makes the resolving power variation.
When above-mentioned radicals X is the structure of above-mentioned general formula (3) expression; Y in the above-mentioned general formula (3) is so long as " having or do not have the substituent divalent linking group that comprises adamantane structure "; In addition just not special restriction, but be preferably the linking group of formula (4) for example or (5) expression.
Figure G2008800010167D00201
(any in above-mentioned general formula (4) and (5) can have substituting group, * represent with above-mentioned general formula (3) in the position of phenyl ring bonding.)
The epoxy compound of above-mentioned general formula (1-a ") expression (a ") is preferably the compound of formula (6) or (7) expression especially.
Figure G2008800010167D00202
[adamantyl of general formula (6), (7) expression can have substituting group.
In general formula (6), R 16～R 23Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.
In general formula (7), R 24And R 25It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.]
As the R in above-mentioned general formula (2a), (2b), (3), (6) and (7) 1～R 25Carbon number be 1～12 alkyl, can preferably enumerate carbon number and be 1～10 alkyl.
And,, can enumerate halogen atom, hydroxyl, carbon number and be 1～10 alkoxy, carbon number and be 2～10 alkenyl, phenyl, carboxyl, sulfenyl, phosphino-, amino and nitro etc. as the substituting group that these alkyl can have.
In addition, as the R in above-mentioned general formula (2a), (2b), (3), (6), (7) 1～R 25The phenyl substituting group that can have, can enumerate halogen atom, hydroxyl, carbon number and be 1～10 alkoxy, carbon number and be 2～10 alkenyl, phenyl, carboxyl, sulfenyl, phosphino-, amino and nitro etc.
In addition, as the R among above-mentioned general formula (2a), (2b) 1～R 4And R 13～R 15The diamantane ring that Y contained, the diamantane ring in the general formula (6), the adamantyl in the general formula (7), the R in the general formula (7) of adamantyl, general formula (3) 24, R 25The diamantane ring of adamantyl and general formula (4) and (5) substituting group that can have, can enumerate halogen atom, hydroxyl, carbon number and be 1～10 alkoxy, carbon number and be 2～10 alkenyl, phenyl, carboxyl, sulfenyl, phosphino-, amino and nitro etc.
In the above-mentioned general formula (6), R 16～R 23Be preferably alkyl, halogen atom, alkoxy, alkenyl or phenyl especially.
In addition, in the above-mentioned general formula (7), R 24And R 25Be preferably alkyl, halogen atom, alkoxy, alkenyl or phenyl especially.
The molecular weight of the X of general formula (1-a ") expression is preferably 200～1000.If the molecular weight of X less than 200, then has the tendency of chemical proofing difference, when the molecular weight of X greater than 1000, then sensitivity might reduce.
In addition, be preferably more than 210 with the epoxide equivalent of the epoxy compound of general formula (1-a ") expression (a "), more preferably more than 230.And this epoxide equivalent is preferably below 450, more preferably below 400.The epoxide equivalent of epoxy compound (a ") is less than under 210 the situation, and alkali resistance can be not enough sometimes, and the epoxide equivalent of epoxy compound (a ") is greater than under 450 the situation, and the sensitivity of the organic bond of generation has the tendency of reduction.
Epoxy compound (a ") can use a kind of separately, also can make up two or more the use.
Epoxy compound (a ") both can use commercially available article, also can use through the synthetic back of known method by the oxybenzene compound of following that kind.
Figure G2008800010167D00221
(the R among above-mentioned general formula (9a), (9b) and (10) 1～R 15Respectively with general formula (2a), (2b) and (3) in implication identical.)
For example; At general formula (9a) or (9b) add alkali metal hydroxide (such as NaOH, potassium hydroxide etc.) in the dissolving mixt of compound and the excessive epihalohydrin (such as chloropropylene oxide, epibromohydrin etc.) of expression in advance in 20～120 ℃ thermotonus 1～10 hour; Perhaps when adding alkali metal hydroxide in 20～120 ℃ thermotonus 1～10 hour, can access X in the general formula (1-a ") thus and be above-mentioned general formula (2a) or (2b) epoxy compound of the linking group of expression (a ").
In addition; In the dissolving mixt of the compound of general formula (10) expression and excessive epihalohydrin (such as chloropropylene oxide, epibromohydrin etc.), add alkali metal hydroxide (such as NaOH, potassium hydroxide etc.) in advance in 20～120 ℃ thermotonus 1～10 hour; Perhaps when adding alkali metal hydroxide in 20～120 ℃ thermotonus 1～10 hour, can access X in the general formula (1-a ") thus and be the epoxy compound (a ") of the linking group of above-mentioned general formula (3) expression.
In the reaction of above-mentioned acquisition epoxy compound (a "), can use its WS as alkali metal hydroxide.At this moment, can be following method: the WS of this alkali metal hydroxide is added continuously in the reaction system, meanwhile; Under reduced pressure or water and epihalohydrin are distilled; Carry out separatory again, remove and anhydrate, epihalohydrin is turned back in the reaction system continuously.
In addition; Also can utilize following method manufacturing with the epoxy compound of general formula (1-a ") expression (a "): perhaps to add quaternary ammonium salts such as tetramethyl ammonium chloride, tetramethylammonium bromide, Variquat B 200 as catalyzer in the dissolving mixt of compound and the epihalohydrin of (10) expression at above-mentioned general formula (9a), (9b); 50～150 ℃ of reactions 1～5 hour; Perhaps add the solid or the WS of alkali metal hydroxide what obtain in the halohydrin etherate of compound of (10) expression with general formula (9a), (9b); Again in 20～120 ℃ thermotonus 1～10 hour, with dehydrohalogenation (closed loop).
With respect to 1 equivalent hydroxyl of the compound of representing with general formula (9a), (9b) or (10), the amount of the epihalohydrin that in such reaction, uses is generally 1～20 mole, is preferably 2～10 moles.And with respect to 1 equivalent hydroxyl of the compound of general formula (9a), (9b) or (10) expression, the consumption of alkali metal hydroxide is generally 0.8～15 mole, is preferably 0.9～11 mole.
And then, carry out smoothly in order to make reaction, in above-mentioned reaction, can add alcohols such as methyl alcohol, ethanol, can add aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide in addition and wait and react.When using pure time-like, the consumption of alcohols is 2～20 weight % with respect to the amount of epihalohydrin, is preferably 4～15 weight %.In addition, when using the aprotic polar solvent, the consumption of aprotic polar solvent is 5～100 weight % with respect to the amount of epihalohydrin, is preferably 10～90 weight %.
(2-2) contain the carboxylic acid (b ") of unsaturated group
As the carboxylic acid that contains unsaturated group (b ") (below be sometimes referred to as " (b ") composition "); Can enumerate unsaturated carboxylic acid with ethylenic unsaturated group; As concrete example, can enumerate (methyl) acrylic acid, butenoic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, vinyl benzoic acid, cinnamic acid, alpha-position had monocarboxylic acids such as alkylhalide group, alkoxy, halogen atom, nitro or cyanic acid substituent (methyl) acrylic acid; 2-(methyl) acrylyl oxy-ethyl succinic acid; 2-(methyl) acrylyl oxy-ethyl hexane diacid; 2-(methyl) acrylyl oxy-ethyl phthalic acid; 2-(methyl) acrylyl oxy-ethyl hexahydro-phthalic acid; 2-(methyl) acrylyl oxy-ethyl maleic acid; 2-(methyl) acryloyl-oxy propyl group succinic acid; 2-(methyl) acryloyl-oxy propyl group hexane diacid; 2-(methyl) acryloyl-oxy propyl group tetrahydrophthalic acid; 2-(methyl) acryloyl-oxy propyl group phthalic acid; 2-(methyl) acryloyl-oxy propyl group maleic acid; 2-(methyl) acryloyl-oxy butyl succinic acid; 2-(methyl) acryloyl-oxy butyl hexane diacid; 2-(methyl) acryloyl-oxy butyl hydrogenation phthalic acid; 2-(methyl) acryloyl-oxy butyl phthalic acid; (methyl) acryloyloxyalkyl of dibasic acid such as 2-(methyl) acryloyl-oxy butyl maleic acid; Lactone such as addition 6-caprolactone, beta-propiolactone, gamma-butyrolacton, δ-Wu Neizhi on (methyl) acrylic acid and the monomer that obtains; (methyl) acrylic acid dimer etc.
And, can also enumerate acid anhydrides such as addition succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride on the such unsaturated compound that contains hydroxyl of the methacrylic acid addition product of acrylic acid addition product at pentaerythrite three (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, trimethylolpropane diacrylate, GMA, GMA and the compound that obtains.
The carboxylic acid (b ") that especially preferably contains unsaturated group is (methyl) acrylic acid.
These unsaturated carboxylic acids can use a kind of separately, also can mix two or more the use.
As the method that makes epoxy radicals and (b ") composition reaction in (a ") composition, can use known method.For example; With quaternary ammonium salt, pyridine, triphenylphosphines etc. such as tertiary amines such as triethylamine, benzyl methyl amine, chlorination dodecyl trimethyl ammonium, tetramethyl ammonium chloride, etamon chloride, benzyltriethylammonium chlorides is catalyzer; Make above-mentioned (a ") composition and (b ") composition in organic solvent 50～150 ℃ of stoichiometric numbers of temperature of reaction hour～tens of hours, thus can be on epoxy compound the addition carboxylic acid.
With respect to the total of reacting material mixture ((a ") composition with (b ") composition), this catalyst consumption is preferably 0.01～10 weight %, is preferably 0.3～5 weight % especially.And; For the polymerization in preventing to react; The preferred polymerization inhibitor (for example MEHQ, quinhydrones, methylnaphthohydroquinone, p methoxy phenol, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, phenothiazine etc.) that uses; The consumption of polymerization inhibitor is preferably 0.01～10 weight % with respect to reacting material mixture, is preferably 0.03～5 weight % especially.
The ratio of the epoxy radicals of (a ") composition of addition (b ") composition is generally 90～100 moles of %.Have during remaining epoxy radicals storage stability is produced harmful effect ground tendency, therefore with respect to the 1 equivalent epoxy radicals of (a ") composition, preferred (b ") composition reacts with common 0.8～1.5 equivalent, the particularly ratio of 0.9～1.1 equivalent.
(2-3) polyprotonic acid and/or its acid anhydrides (c ")
As polyprotonic acid and/or its acid anhydrides (c ") (below be sometimes referred to as " (c ") composition " or " polyprotonic acid (acid anhydride) "), dibasic acid and/or its acid anhydrides (below be called " dibasic acid (acid anhydride) "), ternary acid and/or its acid anhydrides (below be called " ternary acid (acid anhydride) "), tetra-atomic acid and/or its acid anhydrides (below be called " tetra-atomic acid (acid anhydride) ") etc. can be used.
As tetra-atomic acid (acid anhydride) (tetrabasic carboxylic acid and/or its dianhydride), can use known material, for example can enumerate tetrabasic carboxylic acid such as PMA, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid, diphenyl ether tetrabasic carboxylic acid or these sour dianhydrides etc.These tetra-atomic acids (acid anhydride) can use a kind of separately, also can make up two or more uses.
As tetra-atomic acid (acid anhydride), among above-mentioned exemplary compounds, preferred especially biphenyltetracarboxyacid acid or its acid anhydrides.
Reaction product that makes (a ") composition and (b ") composition and tetra-atomic acid (acid anhydride) reaction as (c ") composition increase molecular weight through cross-linking reaction thus.Therefore, have the effects such as adaptation, adjusting dissolubility, raising sensitivity and alkali resistance that improve with substrate, so be preferred.
As dibasic acid (acid anhydride) (dicarboxylic acid and/or its acid anhydrides), can enumerate for example maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydro-phthalic acid, the interior methylene tetrahydrophthalic acid of methyl, chlorendic acid, methyl tetrahydrophthalic acid or their acid anhydrides etc.Wherein, preferred tetrahydrophthalic acid, succinic acid or their acid anhydrides.These dibasic acid (acid anhydride) can use a kind of separately, also can make up two or more uses.
Reaction product that makes (a ") composition and (b ") composition and dibasic acid (acid anhydride) reaction as (c ") composition are regulated dissolubility thus easily, and have improved the adaptation with substrate, so be preferred.
As ternary acid (acid anhydride) (tricarboxylic acids and/or its acid anhydrides), can enumerate trimellitic acid, hexahydro trimellitic acid or their acid anhydrides etc.Preferred especially trimellitic anhydride, hexahydro trimellitic anhydride.These ternary acids (acid anhydride) can use a kind of separately, also can make up two or more uses.
Through using ternary acid (acid anhydride) as (c ") composition, can increase the molecular weight of alkali soluble resins (A "), in molecule, import branch, can realize the balance of molecular weight and viscosity.And, can increase the import volume of acidic group in molecule, can be accomplished the resin of balance of sensitivity and adaptation etc.
As (c ") composition, especially preferably use tetra-atomic acid (acid anhydride).In this case, the hydroxyl that generates during with respect to addition on (a ") composition (b ") composition, the markup percentage of tetra-atomic acid (acid anhydride) is generally 10～100 moles of %, is preferably 20～100 moles of %, more preferably 30～100 moles of %.If the markup percentage as the tetra-atomic acid (acid anhydride) of (c ") composition is very few, then the dissolubility of alkali soluble resins (A ") is not enough sometimes, and perhaps the adaptation with substrate is not enough sometimes.
In addition, consider, preferably use the part of the above-mentioned tetra-atomic acid (acid anhydride) of dibasic acid (acid anhydride) replacement from the aspect that viscosity is regulated and dissolubility is regulated of photosensitive color resin combination.
As (c ") composition, when share tetra-atomic acid (acid anhydride) and dibasic acid (acid anhydride), its mol ratio is preferably dibasic acid (acid anhydride): tetra-atomic acid (acid anhydride)=99: 1～20: 80, more preferably 80: 20～30: 70.When tetra-atomic acid (acid anhydride) was very few with respect to this scope, resulting film rerum natura of filming might reduce, and when dibasic acid (acid anhydride) was very few, the viscosity of resulting resin solution can increase sometimes, handled to become difficult.
In addition; In order to improve with the adaptation of substrate, regulate dissolubility easily, to improve the various balances that obtain molecular weight and viscosity, sensitivity, adaptation etc. on the basis of effects such as sensitivity and alkali resistance, preferably tetra-atomic acid (acid anhydride) and/or dibasic acid (acid anhydride) and ternary acid (acid anhydride) are share.
When tetra-atomic acid (acid anhydride) and/or dibasic acid (acid anhydride) and ternary acid (acid anhydride) being share as (c ") composition; if the consumption of ternary acid (acid anhydride) is very few; DeGrain then, alkali resistance might reduce, so the hydroxyl that generates during with respect to addition on (a ") composition (b ") composition; the consumption of ternary acid (acid anhydride) is generally 5～70 moles of %, is preferably the degree of 10～40 moles of %.
The hydroxyl that generates during with respect to addition on (a ") composition (b ") composition, total markup percentage of (c ") composition is generally 10～100 moles of %, is preferably 20～100 moles of %, more preferably 30～100 moles of %.If the markup percentage of (c ") composition is very few, the dissolubility of alkali soluble resins (A ") is not enough sometimes, and perhaps the adaptation with substrate is not enough sometimes.
In addition; The hydroxyl reaction that (c ") composition generates except with addition on (a ") composition (b ") composition the time; when the polyvalent alcohol of after wherein mixing, stating behind addition on (a ") composition (the b ") composition (d "), (c ") composition can also with arbitrary hydroxyl reaction of existing in this potpourri.
Behind addition on (a ") composition (b ") composition, or behind the polyvalent alcohol of after wherein mixing, stating (d "), addition (c ") composition can use known method as the method for addition (c ").
Its temperature of reaction is generally 80～130 ℃, is preferably 90～125 ℃.If temperature of reaction is greater than 130 ℃, then polymerization can take place in the part unsaturated group in (b ") composition, might cause the rapid increase of molecular weight.And, if temperature of reaction less than 80 ℃, then reaction can't be carried out smoothly, might be remaining (c ") composition.
(2-4) polyvalent alcohol (d ")
In photosensitive color resin combination of the present invention; With other resin glue (F) that alkali soluble resins (A) share can be the following alkali soluble resins that obtains (A1 "): addition on above-mentioned (a ") composition (b ") becomes further polyols blend in the reaction product that branch generates (d ") (below be sometimes referred to as " (d ") composition "); make the arbitrary hydroxyl generation addition reaction in above-mentioned (c ") composition and these potpourris, obtain alkali soluble resins (A1 ") thus.
As (d ") composition, be preferably selected from trimethylolpropane, two (trihydroxy methyl) propane, pentaerythrite, dipentaerythritol, trimethylolethane, 1,2, the polyvalent alcohol of one or more among the 3-propane triol.
Through using (d ") composition, the molecular weight of alkali soluble resins (A1 ") is increased, and can in molecule, import branch, can realize the balance of molecular weight and viscosity.And, can increase the importing rate of acidic group in molecule, can be accomplished the organic bond of balance of sensitivity and adaptation etc.
If the consumption of (d ") composition is very few; DeGrain then; if the consumption of (d ") composition is too much; Then exist viscosity to increase or the possibility of gelation, therefore with respect to the reaction product of (a ") composition with (b ") composition, (d ") consumption of composition be generally 0.01 times of weight～0.5 times of weight degree, be preferably the degree of 0.02 times of weight～0.2 times of weight.
(2-5) acid number and the molecular weight of alkali soluble resins (A ") and (A1 ")
The acid number of the alkali soluble resins that obtains like this (A ") and (A1 ") is generally more than the 10mgKOH/g, is preferably more than the 50mgKOH/g.If this acid number is less than 10mgKOH/g, development property deficiency sometimes then.And,, then aspect the alkali resistance of photosensitive color resin combination, have problems sometimes and (that is, under the effect of alkaline-based developer, cause the asperitiesization of patterned surfaces sometimes or cause film to reduce if acid number is too high.), so acid number is preferably below the 200mgKOH/g, more preferably below the 150mgKOH/g.
The weight-average molecular weight (Mw) that is obtained by polystyrene conversion of utilizing gel permeation chromatography (GPC) to measure of alkali soluble resins (A ") and (A1 ") is preferably more than 1,500, more preferably more than 2,000.And, be preferably below 20,000, more preferably below 10,000.If weight-average molecular weight is too small, then might have problems aspect sensitivity, coating strength, the alkali resistance, if weight-average molecular weight is excessive, then sometimes in development property or have problems aspect the dissolubility again.
< Photoepolymerizationinitiater initiater (B) >
Usually with the form use Photoepolymerizationinitiater initiater (B) of the promoter and the potpourri (Photoepolymerizationinitiater initiater system) of the adjuvants such as sensitizing coloring matter that add as required.Photoepolymerizationinitiater initiater system has direct absorbing light or under photosensitization, causes decomposition reaction or hydrogen abstraction reaction and produce the composition of the function of polymerization activity free radical.
As Photoepolymerizationinitiater initiater, can enumerate the metallocene compound that comprises the cyclopentadiene titanium compound that for example japanese kokai publication sho 59-152396 communique, japanese kokai publication sho 61-151197 number each communique are put down in writing; The hexa-aryl bi-imidazole derivant that TOHKEMY 2000-56118 communique is put down in writing; The halogen first base oxadiazole derivant of japanese kokai publication hei 10-39503 communique record, halomethyl Striazine derivative, be derivant such as N-such as N-phenylglycine aryl-alpha-amido acids, N-aryl-a-amino acid salt, N-aryl-free radical activity agent, alpha-aminoalkyl benzophenones such as α-An Jisuanzhi class; The oxime ester derivative that TOHKEMY 2000-80068 communique, TOHKEMY 2006-36750 communique etc. are put down in writing etc.
Specifically, for example,, can enumerate dichloride dicyclopentadienyltitanium, diphenyl dicyclopentadienyltitanium, two (2 as the cyclopentadienyltitanium derivatives class; 3,4,5,6-phenyl-pentafluoride-1-yl) dicyclopentadienyltitanium, two (2; 3,5,6-phenyl tetrafluoride-1-yl) dicyclopentadienyltitanium, two (2,4; 6-trifluoro-benzene-1-yl) dicyclopentadienyltitanium, two (2,6-two fluorobenzene-1-yl) dicyclopentadienyltitanium, two (2,4-two fluorobenzene-1-yl) dicyclopentadienyltitanium, two (2; 3,4,5; 6-phenyl-pentafluoride-1-yl) two (methyl cyclopentadienyl) titanium, two (2,6-two fluorobenzene-1-yl), two (methyl cyclopentadienyl) titanium, [2,6-two fluoro-3-(pyrroles-1-yl)-benzene-1-yl] dicyclopentadienyltitanium etc.
In addition; As the double imidazole derivative class, can enumerate 2-(2 '-chlorphenyl)-4,5-diphenyl-imidazole dimer, 2-(2 '-chlorphenyl)-4; Two (3 '-methoxyphenyl) imidazoles dimers of 5-, 2-(2 '-fluorophenyl)-4; 5-diphenyl-imidazole dimer, 2-(2 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer, (4 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer etc.
In addition, as halogen Jia Jiization oxadiazole derivatives class, can enumerate 2-trichloromethyl-5-(2 '-benzofuranyl)-1; 3,4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-benzofuranyl) vinyl]-1,3; 4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-(6 "-benzofuranyl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1; 3,4-oxadiazole etc.
In addition; As halomethyl Striazine derivative class; Can enumerate 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-methoxyl naphthyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-ethoxy naphthyl)-4; Two (trichloromethyl) s-triazine of 6-, 2-(4-carbethoxyl group naphthyl)-4, two (trichloromethyl) s-triazine of 6-etc.
In addition; As alpha-aminoalkyl benzophenone derivatives class; Can enumerate 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, 4-dimethylaminobenzoic acid-2-Octyl Nitrite (2-エ チ Le ヘ キ シ Le-1; 4-ジ メ チ Le ア ミ ノ Block Application ゾ エ one ト), 2, two (the 4-lignocaine benzylidene) cyclohexanone of 5-, 7-lignocaine-3-(4-lignocaine benzoyl) cumarin, 4-(lignocaine) chalcone etc.
In addition, as the oxime ester derivative class, can enumerate for example following compound etc.
Figure G2008800010167D00301
Figure G2008800010167D00311
Figure G2008800010167D00321
Figure G2008800010167D00331
Figure G2008800010167D00341
In addition, also can enumerate benzoin alkylether classes such as benzoin methylether, benzoin phenylate, benzoin isobutyl ether, benzoin iso-propylether; Anthraquinone derivative classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; Benzophenone derivates classes such as benzophenone, Michler's keton (Michler ' s ketone), 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone; 2; 2-dimethoxy-2-phenyl acetophenone, 2; 2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-(4 '-methyl mercapto phenyl)-2-morpholino-1-acetone, 1; 1,1-trichloromethyl-acetophenone derivs classes such as (to butyl phenyl) ketone; Thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, thioxanthone derivates classes such as 4-diisopropyl thioxanthones; (dimethylamino)-ethyl benzoate, to benzoate derivatives classes such as lignocaine ethyl benzoates; Acridine derivatives classes such as 9-phenylacridine, 9-(p-methoxyphenyl) acridine; 9, azophenlyene derivatives class such as 10-dimethylbiphenyl azophenlyene; Anthracyclinone derivatives classes such as benzanthrone etc.
Consider from the aspect of sensitivity, among these Photoepolymerizationinitiater initiaters, preferred especially oxime ester derivative class.
As the promoter that constitutes the Photoepolymerizationinitiater initiater set member, can use for example N, N such as N-dimethylaminobenzoic acid ethyl ester, N-dialkyl amido benzoic acid alkyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle; Or the multifunctional sulfhydryl compound of aliphatics etc.
These Photoepolymerizationinitiater initiaters and promoter can be used separately separately, also can share.
As concrete Photoepolymerizationinitiater initiater set member; For example can enumerate " FineChemicals " (1991; March 1 day number; Vol.20, the dialkyl benzene ethyl ketone system of record, benzoin, thioxanthone derivates etc. in No.4) the 16th～26 page, can also enumerate in addition records such as japanese kokai publication sho 58-403023 communique, the special public clear 45-37377 communique of Japan, hexa-aryl bi-imidazole system, trihalomethyl s-triazine system; But in japanese kokai publication hei 4-221958 communique, the japanese kokai publication hei 4-219756 communique etc. record with cyclopentadienyltitanium and xanthene pigment, have the system that the compound of the ethylenic unsaturated double-bond that contains addition polymerization of amino or carbamate groups combines; Or the like.
The sensitizing coloring matter that can in the Photoepolymerizationinitiater initiater set member, mix the wavelength that is fit to the image exposure light source as required is to improve induction sensitivity.As said sensitizing coloring matter, can enumerate the xanthene pigment that japanese kokai publication hei 4-221958 number, japanese kokai publication hei 4-219756 communique are put down in writing; The cumarin pigment that japanese kokai publication hei 3-239703 number, japanese kokai publication hei 5-289335 communique are put down in writing with heterocycle; The 3-ketone group coumarin compound (3-ketocoumarins) of japanese kokai publication hei 3-239703 number, japanese kokai publication hei 5-289335 number record; Pyrroles's methine pigment that japanese kokai publication hei 6-19240 communique is put down in writing can be enumerated the pigment with dialkyl amido benzene skeleton that japanese kokai publication sho 47-2528 number, japanese kokai publication sho 54-155292 number, special public clear 45-37377 number of Japan, japanese kokai publication sho 48-84183 number, japanese kokai publication sho 52-112681 number, japanese kokai publication sho 58-15503 number, japanese kokai publication sho 60-88005 number, japanese kokai publication sho 59-56403 number, japanese kokai publication hei 2-69 number, japanese kokai publication sho 57-168088 number, japanese kokai publication hei 5-107761 number, japanese kokai publication hei 5-210240 number, japanese kokai publication hei 4-288818 communique put down in writing etc. in addition.
Among these sensitizing coloring matters, preferably contain amino sensitizing coloring matter, more preferably in a part, have the compound of amino and phenyl.For example particularly preferably be 4; 4 '-dimethylamino benzophenone, 4,4 '-lignocaine benzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4 '-diaminobenzophenone, 3; 3 '-diaminobenzophenone, 3, benzophenone based compounds such as 4-diaminobenzophenone; 2-(to dimethylamino phenyl) benzoxazole, 2-(to the lignocaine phenyl) benzoxazole, 2-(to dimethylamino phenyl) benzo [4; 5] benzoxazoles, 2-(to dimethylamino phenyl) benzo [6; 7] benzoxazoles, 2; Two (to the lignocaine phenyl)-1 of 5-; 3,4-oxazole, 2-(to dimethylamino phenyl) benzothiazole, 2-(to the lignocaine phenyl) benzothiazole, 2-(to dimethylamino phenyl) benzimidazole, 2-(to the lignocaine phenyl) benzimidazole, 2, two (to the lignocaine phenyl)-1 of 5-; 3,4-thiadiazoles, (to dimethylamino phenyl) pyridine, (to the lignocaine phenyl) pyridine, (to dimethylamino phenyl) quinoline, (to the lignocaine phenyl) quinoline, (to dimethylamino phenyl) pyrimidine, (to the lignocaine phenyl) pyrimidine etc. contain compound of dialkyl amido phenyl etc.
Among these compounds most preferably 4,4 '-dialkyl amido benzophenone.
In addition, sensitizing coloring matter can use a kind of separately, also can be also with two or more.
< colorant (C) >
Colorant (C) is to instigate the painted material of photosensitive color resin combination of the present invention.As colorant, can use dyestuff, pigment, but consider preferred pigments from aspects such as thermotolerance, photostability.
As pigment, can use versicolor pigment such as blue pigment, viridine green, red pigment, yellow uitramarine, violet pigment, orange pigment, brown, black pigment.And as its structure, azo system, phthalocyanine system, quinacridone, benzimidazolone system, isoindolinone are that the 、 dioxazine is except that utilizing, indanthrene system, perylene system etc. are the organic pigment, can also utilize various inorganic pigments etc.
Below, with the concrete example of the spendable pigment of pigment numbering expression the present invention.In addition, terms such as " the C.I. paratoneres 2 " below enumerated is meant Colour index number (C.I.).
As red pigment, can enumerate C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276.Wherein, C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242,254 can be preferably enumerated, C.I. paratonere 177,209,224,254 can be more preferably enumerated.
As blue pigment, can enumerate C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79.Wherein, C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6 can be preferably enumerated, the C.I. pigment blue 15 can be more preferably enumerated: 6.
As viridine green, can enumerate C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54,55.Wherein, can preferably enumerate C.I. pigment Green 7,36.
As yellow uitramarine, can enumerate C.I. pigment yellow 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207,208.Wherein, C.I. pigment yellow 83,117,129,138,139,150,154,155,180,185 can be preferably enumerated, C.I. pigment yellow 83,138,139,150,180 can be more preferably enumerated.
As orange pigment, can enumerate C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79.Wherein, can preferably enumerate C.I. pigment orange 38,71.
As violet pigment, can enumerate C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50.Wherein, C.I. pigment violet 19,23 can be preferably enumerated, the C.I. pigment Violet 23 can be more preferably enumerated.
In addition, when at the bottom of the resin black that photosensitive color resin combination of the present invention is a color filter during,, can use black pigment as colorant (C) with the photosensitive color resin combination.For black pigment, can use black pigment separately, also can mix use with colorants such as redness, green, bluenesss.In addition, these colorants can be from suitable selection the among inorganic or organic pigment, the dyestuff.
Modulation black pigment, the pigment can be mixed as may be mentioned Victoria Pure Blue (Victoria? Pure? Blue) (42595), Auramine O (41000), Long bright yellow magnetic card (cathilonbrilliant? Yellow) ( Alkaline 13), rhodamine 6GCP (45160), Rhodamine B (45170), saffron OK70: 100 (50240), poppy red X (42080), No.120 / Roe Noel (Lionol) Yellow (21090), Roe Noel yellow GRO (21090), Secretary Tim La (symuler) Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Secretary Tim La Fast Red 4015 (12355), Roe Noel Red 7B4401 ( 15850), Fastogen? Blue? TGR-L (74160), Roe Noel Blue SM (26150), Roe Noel Blue ES (Pigment Blue 15:6), Justin Noel Red GD (Pigment Red 168), Justin Noel Green 2YS (Pigment Green 36), etc. (In addition, the figures in brackets refer to Colour Index (CI)).
In addition; To can further mixing other pigment of use; With the expression of C.I. numbering, can enumerate for example C.I. yellow uitramarine 20,24,86,93,109,110,117,125,137,138,147,148,153,154,166, C.I. orange pigment 36,43,51,55,59,61, C.I. red pigment 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240, C.I. violet pigment 19,23,29,30,37,40,50, C.I. blue pigment 15,15:1,15:4,22,60,64, C.I. viridine green 7, C.I. brown 23,25,26 etc.
In addition, as the black pigment that can use separately, it is black etc. to enumerate carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine, cyanine black (シ ア ニ Application Block ラ Star Network), titanium.
From the aspect of shading rate, picture characteristics, preferred carbon black among these black pigments.As the example of carbon black, can enumerate following carbon black.
Mitsubishi Chemical society makes: MA7; MA8; MA11; MA100; MA100R; MA220; MA230; MA600; #5; #10; #20; #25; #30; #32; #33; #40; #44; #45; #47; #50; #52; #55; #650; #750; #850; #950; #960; #970; #980; #990; #1000; #2200; #2300; #2350; #2400; #2600; #3050; #3150; #3250; #3600; #3750; #3950; #4000; #4010; OIL7B; OIL9B; OIL11B; OIL30B; OIL31B
Degussa society makes: Printex3; Printex3OP; Printex30; Printex30OP; Printex40; Printex45; Printex55; Printex60; Printex75; Printex80; Printex85; Printex90; Printex A; Printex L; Printex G; Printex P; Printex U; PrintexV; PrintexG; SpecialBlack550; SpecialBlack350; SpecialBlack250; SpecialBlack100; SpecialBlack6; SpecialBlack5; SpecialBlack4; Color BlackFW1; Color Black FW2; Color Black FW2V; Color Black FW18; ColorBlack FW18; Color Black FW200; Color Black S160; Color Black S170
Cabot society makes: Monarch120; Monarch280; Monarch460; Monarch800; Monarch880; Monarch900; Monarch1000; Monarch1100; Monarch1300; Monarch1400; Monarch4630; REGAL99; REGAL99R; REGAL415; REGAL415R; REGAL250; REGAL250R; REGAL330; REGAL400R; REGAL55R0; REGAL660R; BLACK PEARLS480; PEARLS130; VULCANXC72R; ELFTEX-8
Columbian Carbon society makes: RAVEN11; RAVEN14; RAVEN15; RAVEN16; RAVEN22; RAVEN30; RAVEN35; RAVEN40; RAVEN410; RAVEN420; RAVEN450; RAVEN500; RAVEN780; RAVEN850; RAVEN890H; RAVEN1000; RAVEN1020; RAVEN1040; RAVEN1060U; RAVEN1080U; RAVEN1170; RAVEN1190U; RAVEN1250; RAVEN1500; RAVEN2000; RAVEN2500U; RAVEN3500; RAVEN5000; RAVEN5250; RAVEN5750; RAVEN7000
As other black pigment, the black pigment that can use that titanium is black, the organic pigment of nigrosine, iron oxide black pigment and redness, green, blue three kinds of colors mixes.
In addition, as pigment, can use barium sulphate, lead sulfate, titanium dioxide, yellow lead, colcother, chromium oxide etc.
Above-mentioned various pigment also can share multiple.For example,, viridine green and yellow uitramarine can be share, also blue pigment and violet pigment can be share in order to regulate colourity.
Being dispersed into mean grain size when in addition, these pigment optimizations use is generally 1 μ m, is preferably below the 0.5 μ m, more preferably below the 0.25 μ m.
In addition, in the present invention, the mean grain size of pigment is the value of being obtained by the pigment particle size of measuring through dynamic light scattering DLS.In the particle size determination, the colored resin composition after the abundant dilution (through dilution, is modulated into the degree that pigment concentration is 0.005～0.2 weight % usually.If but the concentration that has determining instrument to recommend is then modulated by the concentration of recommending) measure, and in 25 ℃ of mensuration.
In addition, as enumerating azo based dye, anthraquinone based dye, phthalocyanine based dye, quinone imines based dye, quinoline based dye, nitro based dye, carbonyl based dye, methine based dye etc. as the dyestuff of colorant.
As the azo based dye, for example can enumerate that C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. are directly red 28, C.I. is directly red 83, C.I. is directly yellow 12, C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I. reactive yellow 2, C.I. reactive red 17, C.I. reactive red 120, C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 165, C.I. alkali blue 41, C.I. Basic Red 18, C.I. mordant rouge 7, C.I. mordant yellow 5, C.I. mordant dyeing black 7 etc.
As the anthraquinone based dye, for example can enumerate C.I. father-in-law's indigo plant 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60 etc.
In addition, as the phthalocyanine based dye, for example can enumerate C.I. father-in-law blue 5 etc.; As the quinone imines based dye; For example can enumerate C.I. alkali blue 3, C.I. alkali blue 9 etc.,, for example can enumerate C.I. solvent yellow 33, C.I. quinoline yellow, C.I. dispersion yellow 64 etc. as the quinoline based dye; As the nitro based dye, for example can enumerate C.I. Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42 etc.
< spreading agent (D) >
Among the present invention, making the fine dispersion of colorant (C) and making its disperse state stabilization is important to the stability of guaranteeing quality, therefore preferably contains spreading agent (D).
As spreading agent (D), preferably have the macromolecule dispersing agent of functional group, and then, consider preferably have carboxyl from the aspect of dispersion stabilization; Phosphate; Sulfonic group; Or their alkali; Primary amino radical, secondary amino group or uncle are amino; Quaternary ammonium salt base; The macromolecule dispersing agent of the functional groups such as group that nitrogen heterocyclic rings such as pyridine, pyrimidine, pyrazine are derived.Wherein, especially preferably has primary amino radical, secondary amino group or uncle's amino; Quaternary ammonium salt base; The macromolecule dispersing agent of the basic functionalities such as group that nitrogen heterocyclic rings such as pyridine, pyrimidine, pyrazine are derived.
In addition; As macromolecule dispersing agent, for example can enumerate carbamate and be spreading agent, acrylic acid series spreading agent, polyethyleneimine and be spreading agent, PAH and be spreading agent, be that spreading agent, polyoxyethylene diester-based spreading agent, polyethers phosphoric acid are that spreading agent, polyester phosphoric acid are that spreading agent, sorbitan aliphatic ester are that spreading agent, aliphatics modified poly ester are spreading agent etc. by having spreading agent, polyoxyethylene alkyl ether that amino monomer and macromonomer form.
As the concrete example of such spreading agent, its trade name can be enumerated EFKA (manufacturing of EFKAChemicals BV (EFKA) society), Disperbyk (manufacturing of BYK-Chemie society), Supreme Being Si Balong (DISPARLON) (nanmu originally changes into society and makes), SOLSPERSE (manufacturing of Lubrizol society), KP (manufacturing of chemical industry society of SHIN-ETSU HANTOTAI), Poly-Flow (chemistry society of common prosperity society makes), AJISPER (manufacturing of aginomoto society) etc.
These macromolecule dispersing agents can use a kind of separately, also can share two or more.
The weight-average molecular weight of macromolecule dispersing agent (Mw) is generally more than 700, is preferably more than 1000, and is generally below 100,000, is preferably below 50,000.
In these spreading agents, consider that from adaptation and rectilinearity aspect it is macromolecule dispersing agent and/or acrylic acid series macromolecule dispersing agent that spreading agent (D) especially preferably contains the carbamate with functional group.
As carbamate system and acrylic acid series macromolecule dispersing agent, for example can enumerate Disperbyk160～166,182 series (more than be carbamate system), Disperbyk2000,2001 etc. (more than be acrylic acid series) (above) all by the manufacturing of BYK-Chemie society.
As carbamate is macromolecule dispersing agent; If concrete example illustrates preferred chemical constitution; Then can enumerate for example to make and have 1 or 2 hydroxyls in polyisocyanate compound, the molecule and number-average molecular weight is 300～10; 000 compound and the weight-average molecular weight that obtains with having the amino compound reaction of reactive hydrogen and uncle in a part are 1,000～200,000 dispersion resin etc.
Example as above-mentioned polyisocyanate compound; Can enumerate PPDI, 2; 4-toluene diisocyanate, 2; 6-toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, naphthalene-1, aromatic diisocyanates such as 5-diisocyanate, tolidine diisocyanate; Hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, aliphatic diisocyanates such as 4-trimethyl hexamethylene diisocyanate, dimer acid diisocyanate; IPDI, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), ω, ω '-alicyclic diisocyanates such as diisocyanate based dimethyl cyclohexane; XDI, α, α, α ', α '-tetramethylxylylene diisocyanate etc. has the aliphatic diisocyanate of aromatic rings; Lysine ester triisocyanate, 1; 6; 11-undecane triisocyanate, 1; 8-is diisocyanate based-4-NCO methyloctane, 1,3, and triisocyanates such as 6-hexa-methylene triisocyanate, bicycloheptane triisocyanate, three (NCO phenylmethane), three (NCO phenyl) thiophosphate; And their tripolymer, water addition product and their polyvalent alcohol addition product etc.As polyisocyanates, the preferably tripolymer of organic diisocyanate, the most preferably tripolymer of toluene diisocyanate and Trimerization of Isophorone Diisocyanate body.These tripolymers can use a kind of separately, also can share two or more.
Trimerical manufacturing approach as isocyanates; Can enumerate following method: use suitable catalyst for trimerization (for example tertiary amines, phosphine class, pure salt, metal oxide, metal carboxylate etc.); Above-mentioned polyisocyanates is carried out the part trimerizing of NCO; Through after adding catalytic poison trimerizing being stopped, utilizing solvent extraction, thin-film distillation to remove unreacted polyisocyanates, thereby obtain the polyisocyanates that contains the isocyanuric acid ester group as target.
As being 300～10 with having 1 or 2 hydroxyls and number-average molecular weight in a part; 000 compound, a terminal hydroxyl can enumerating PTMEG, polyester-diol, PCDL, polyolefin diols etc. and these compounds are that 1～25 alkyl has carried out compound and the potpourri of two or more these compounds after the alkoxylate by carbon number.
As PTMEG, can enumerate the potpourri of PTMEG, polyether ester glycol and two or more these compounds.As PTMEG; Can enumerate the PTMEG that makes alkylene oxide homopolymerization or copolymerization and obtain, for example the potpourri of polyglycol, polypropylene glycol, polyglycol-propylene glycol, polyoxy tetramethylene glycol, polyoxy hexamethylene glycol, polyoxy eight methylene glycols and two or more these compounds.
As the polyether ester glycol; Can enumerate through making the glycol that contains ether or containing potpourri and dicarboxylic acid or the material that its acid anhydrides reacts and obtains of glycol and other glycol of ether; The material that perhaps obtains through polyester-diol and alkylene oxide are reacted for example gathers (PolyTHF) adipate etc.As PTMEG, most preferably to use carbon number be 1～25 alkyl carries out the compound that alkoxylate obtains with a terminal hydroxyl of polyglycol, polypropylene glycol, polyoxy tetramethylene glycol or these compounds.
As polyester-diol, can enumerate and make dicarboxylic acid (succinic acid, glutaric acid, hexane diacid, decanedioic acid, fumaric acid, maleic acid, phthalic acid etc.) or their acid anhydrides and glycol (monoethylene glycol, diglycol, triethylene glycol, propylene glycol, DPG, tripropylene glycol, 1,2-butylene glycol, 1,3 butylene glycol, 1; 4-butylene glycol, 2,3-butylene glycol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 2-methyl isophthalic acid, ammediol, 2-methyl-2-propyl group-1; Ammediol, 2-butyl-2-ethyl-1, ammediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2; 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1; 3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1; 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, aliphatic diols such as 9-nonanediol; Alicyclic diols such as dihydroxy methylcyclohexane; Aromatic diols such as xylyleneglycol, two hydroxyl-oxethyl benzene; N-alkyl dioxane hydramine such as N methyldiethanol amine etc.) polycondensation and the polyester-diol that obtains (for example polyethyleneglycol adipate, polytetramethylene glycol adipate, gather the hexanediol adipate, gather (ethylene glycol and 1,2-propylene glycol) adipate etc.); Or the polylactone glycol that to use said glycols or carbon number be 1～25 monohydroxy alcohol obtains as initiating agent or polylactone monohydroxy alcohol (for example polycaprolactone glycol, gather methylpent lactone (polymethylvalerolactone)), and the two or more potpourri of these polymkeric substance.As polyester-diol, polycaprolactone glycol or be the polycaprolactone that 1～25 alcohol obtains as initiating agent with carbon number most preferably.
As PCDL, can enumerate and gather (1, the 6-hexanediol) carbonic ester, gather (3-methyl isophthalic acid, 5-pentanediol) carbonic ester etc., as polyolefin diols, can enumerate polybutadiene diol, hydrogenated butadiene polymer glycol, hydrogenated polyisoprene glycol etc.
These can use a kind of separately, also can share two or more.
Number-average molecular weight with the compound that has 1 or 2 hydroxyl in a part is generally 300～10, and 000, be preferably 500～6,000, further be preferably 1,000～4,000.
Describe being used for the compound that in a part, has reactive hydrogen and uncle's amino of the present invention.As reactive hydrogen (that is) with the hydrogen atom of oxygen atom, nitrogen-atoms or sulphur atom Direct Bonding, can enumerate the hydrogen atom in the functional groups such as hydroxyl, amino, thiol, wherein, preferred amino hydrogen atom, the hydrogen atom of preferred especially primary amino radical.
To amino not special qualification of uncle, for example can enumerate and have the amino or heterocycle structure that carbon number is 1～4 alkyl, more particularly, can enumerate imidazole ring or triazole ring etc.
If illustration goes out to have in so same a part reactive hydrogen and the amino compound of uncle, then can enumerate N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1; 3-propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N; N-dimethyl-ethylenediamine, N, N-diethyl ethylenediamine, N, N-dipropyl ethylenediamine, N, N-dibutyl ethylenediamine, N; N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N; N-dipropyl-1 ,-4-butanediamine, N, N-dibutyl-1,4-butanediamine etc.
In addition; This nitrogen heterocyclic ring when being the nitrogen heterocyclic ring structure as uncle is amino can be enumerated nitrogenous five-ring heterocycles such as pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, diazosulfide ring; Nitrogenous hexa-member heterocycles such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring.In these nitrogen heterocyclic rings, preferably imidazole ring or triazole ring.
Have imidazole ring and amino compound if concrete example illustrates these, then can enumerate 1-(3-aminopropyl) imidazoles, histidine, 2-aminooimidazole, 1-(2-amino-ethyl) imidazoles etc.And, if illustrating, concrete example has triazole ring and amino compound, then can enumerate 3-amino-1,2; 4-triazole, 5-(2-amino-5-chlorphenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2; 4-triazole-3,5-glycol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1; 4-diphenyl-1,2,3-triazoles, 3-amino-1-benzyl-1H-2,4-triazole etc.Wherein, preferred N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1-(3-aminopropyl) imidazoles, 3-amino-1,2,4-triazole.
These compounds can use a kind of separately, also can share two or more.
The preferred blending ratio of raw material when being macromolecule dispersing agent about making carbamate; With respect to 100 weight portion polyisocyanate compounds, the number-average molecular weight that in a part, has 1 or 2 hydroxyl is that 300～10,000 compound is 10～200 weight portions; Be preferably 20～190 weight portions; Further being preferably 30～180 weight portions, is 0.2～25 weight portion with having the amino compound of reactive hydrogen and uncle in a part, is preferably 0.3～24 weight portion.
Can carry out the manufacturing that carbamate is a macromolecule dispersing agent according to the manufacturing approach of known urethane resin.Solvent during as manufacturing can use ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone usually; Ester classes such as ethyl acetate, butyl acetate, cellosolve acetate; Hydro carbons such as benzene,toluene,xylene, hexane; Part alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol; Chloride such as methylene chloride, methenyl choloride; Ethers such as tetrahydrofuran, ether; Aprotic polar solvents such as dimethyl formamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc.These solvents can use a kind of separately, also can share two or more.
And, in above-mentioned manufacturing, use the urethane catalysts usually.As this catalyzer, for example can enumerate tin systems such as dibutyl tin laurate, two lauric acid dioctyl tins, two sad dibutyl tins, stannous octoate; Iron such as acetyl acetone iron, iron chloride system; One or more of tertiary amine such as triethylamine, triethylenediamine system etc.
In reacted amine value, preferably will be controlled at the scope of 1～100mgKOH/g with the import volume that has the amino compound of reactive hydrogen and uncle in a part.The scope of 5～95mg KOH/g more preferably.This amine value is with acid alkaline amino to be carried out acid-base titration, and value that with the mg numerical table of KOH show corresponding with acid number.When if the amine value is lower than above-mentioned scope, the tendency that then has dispersibility to reduce, and if the amine value exceed above-mentioned scope, then development property is prone to reduce.
In addition; Be reflected in the macromolecule dispersing agent under the remaining situation that NCO arranged through above; When further using alcohol, amino-compound and isocyanates radical reaction, the ageing stability of product improves, so preferably further use alcohol, amino-compound and isocyanates radical reaction.
Carbamate is that the weight-average molecular weight (Mw) of macromolecule dispersing agent is generally 1,000～200,000, is preferably 2,000～100,000, more preferably 3,000～50,000.If this molecular weight is less than 1,000, then dispersed and dispersion stabilization deterioration, if this molecular weight greater than 200,000, then dissolubility reduces, dispersed deterioration is difficult to control simultaneously and reacts.
As the acrylic acid series macromolecule dispersing agent, preferred the have functional group monomer that contains unsaturated group and the random copolymers, graft copolymer, the segmented copolymer that do not have the monomer that contains unsaturated group of functional group of (said here functional group is that the functional group contained as macromolecule dispersing agent is in functional group mentioned above) of using.These multipolymers can pass through the known method manufacturing.
As the monomer that contains unsaturated group with functional group, the season thing etc. that its concrete example can be enumerated unsaturated monomer that (methyl) acrylic acid, 2-(methyl) acryloxy ethyl succinic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl hexahydro-phthalic acid, acrylic acid dimer etc. have carboxyl, (methyl) dimethylaminoethyl acrylate, (methyl) acrylic acid lignocaine ethyl ester and they has the unsaturated monomer of uncle's amino, quaternary ammonium salt base.These monomers can use a kind of separately, also can share two or more.
As the monomer that contains unsaturated group that does not have functional group, can enumerate N-substituted maleimide amine, vinyl cyanide, vinyl acetates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid phenoxy group methyl esters, (methyl) acrylic acid-2-ethyl caproite, (methyl) IBOA, tristane (methyl) acrylic ester, tetrahydrofurfuryl (methyl) acrylic ester, N-vinylpyrrolidone, styrene and derivant thereof, AMS, N-cyclohexyl maleimide, N-phenylmaleimide, N-benzyl maleimide and gather (methyl) methyl acrylate macromonomer, polystyrene macromolecular monomer, gather (methyl) acrylic acid-2-hydroxyl ethyl ester macromonomer, macromonomer such as polyglycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer etc.These monomers can use a kind of separately, also can share two or more.
The acrylic acid series macromolecule dispersing agent is preferably by the A block with functional group especially and does not have A-B or the B-A-B segmented copolymer that the B block of functional group constitutes; But this moment; In the A block; Except containing the above-mentioned monomer that contains unsaturated group with functional group, also can contain the above-mentioned monomer that contains unsaturated group that does not have functional group, these monomers can be contained in any state in random copolymerization or the block copolymerization in this A block.And the content of structure in the A block that does not have functional moieties is generally below the 80 weight %, is preferably below the 50 weight %, more preferably below the 30 weight %.
The B block is made up of the above-mentioned monomer that contains unsaturated group that does not have functional group, can contain the monomer more than 2 kinds in 1 B block, and these monomers can be contained in any state in random copolymerization or the block copolymerization in this B block.
Living polymerization method shown in below this A-B or B-A-B segmented copolymer are for example capable of using is modulated.
Living anion polymerization method, cation activity polymerization, radical living polymerization method are arranged in the living polymerization method, and wherein, in the living anion polymerization method, the polymerization activity kind is a negative ion, shown in the for example following sketch.
(living anion polymerization method)
Monomer ①:?
Figure G2008800010167D00471
Monomer ②:?
Figure G2008800010167D00472
in the case
Polymerization activity kind in the radical living polymerization method is a free radical, shown in the for example following sketch.
(radical living polymerization method)
(nitroxyl method)
Monomer ①:?
Figure G2008800010167D00481
Monomer ②:? in the case
Figure G2008800010167D00483
(ATRP method)
Monomer ①:?
Figure G2008800010167D00484
Monomer ②:?
Figure G2008800010167D00485
in the case
Figure G2008800010167D00486
When synthetic this acrylic acid series macromolecule dispersing agent, can adopt the known method of being put down in writing in the following document etc.: japanese kokai publication hei 9-62002 communique, P.Lutz, P.Masson et al, Polym. Bull.12,79 (1984); B.C.Anderson, G.D.Andrews et al, Macromolecules, 14,1601 (1981); K.Hatada, K.Ute, et al, Polym.J.17,977 (1985); 18,1037 (1986), the right hand is great one, dry land ploughs one, Process Technology of Polymer, 36,366 (1987), and East Village is quick to be prolonged, pool this light man, macromolecule collection of thesis, 46; 189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic; 109,4737 (1987), phase Tian Zhuosan, aboveground auspicious flat, Synthetic Organic Chemistry, 43,300 (1985), D.Y.Sogoh; W.R.Hertler et al, Macromolecules, 20,1473 (1987) etc.
Being used for acrylic acid series macromolecule dispersing agent of the present invention can be the A-B segmented copolymer; It also can be the B-A-B segmented copolymer; A block/B block the ratio that constitutes this multipolymer is preferably 1/99～80/20, is preferably 5/95～60/40 (weight ratio) especially; If A block/B block then can not have both good thermotolerance and dispersiveness sometimes than outside above-mentioned scope.
In addition, the amount of the quaternary ammonium salt base in 1g A-B segmented copolymer of the present invention, B-A-B segmented copolymer is preferably 0.1～10mmol usually, if outside this scope, then can not have both good thermotolerance and dispersiveness sometimes.
In addition, possibly contain the amino that in manufacture process, generates usually in such segmented copolymer, its amine value is the degree of 1～100mgKOH/g.
Here, the amine value of spreading agent such as these segmented copolymers with the spreading agent sample in the KOH weight of alkali number a great deal of of per 1 gram solid constituent (having removed solvent) represent that this amine value is measured through following method.
Accurate weighing 0.5～1.5g spreading agent sample dissolves with 50mL acetate in the beaker of 100mL.Use is equipped with the automatic titration device of pH electrode, with the HClO of 0.1mol/L 4Acetum carries out acid-base titration to this solution.With titration pH point of inflexion on a curve is titration end-point, obtains the amine value by following formula.
Amine value [mgKOH/g]=(561 * V)/(W * S)
(wherein, W representes the spreading agent sample amount of weighing [g], and V is shown in the titer [mL] of titration end-point, and S representes the solid component concentration [weight %] of spreading agent sample.)
In addition; The acid number of this segmented copolymer is according to having or not as the kind of the acidic-group of the origin of this acid number and acidic-group and different; But in general, the acid number of preferred block copolymer is low, is generally below the 10mgKOH/g; Its weight-average molecular weight (Mw) is preferably 1000～100,000 scope.If the weight-average molecular weight of segmented copolymer, then has the tendency that reduces dispersion stabilization less than 1000, if the weight-average molecular weight of segmented copolymer, then has the tendency that reduces development property, resolution greater than 100,000.
And, consider from the aspect that improves dispersion stabilization, spreading agent (D) preferably with after the pigment derivative stated share.
< photopolymerization monomer (E) >
In the present invention, consider the preferred photopolymerization monomer (E) (optical polymerism compound) that further uses from aspects such as sensitivity.
As the photopolymerization monomer that uses among the present invention (E), can enumerate the compound that has at least one ethylenic unsaturated group in the molecule (below be sometimes referred to as " ethylenic monomer ").Specifically, for example can enumerate (methyl) acrylic acid, (methyl) alkyl acrylate, vinyl cyanide, styrene and have the carboxylic acid of 1 ethylenic unsaturated link and the monoesters of polyvalent alcohol or monohydroxy alcohol etc.
In the present invention, especially preferably use the multifunctional ethylenic monomer that has 2 above ethylenic unsaturated groups in 1 molecule.
As the example of so multifunctional ethylenic monomer, for example can enumerate the ester of aliphatic polyhydroxy compound and unsaturated carboxylic acid; The ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid; Ester that esterification through multi-hydroxy compounds such as aliphatic polyhydroxy compound, aromatic polyhydroxy compounds and unsaturated carboxylic acid and polybasic carboxylic acid obtains etc.
As the ester of above-mentioned aliphatic polyhydroxy compound and unsaturated carboxylic acid, can enumerate aliphatic polyhydroxy compounds such as glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane trimethacrylate acrylic ester, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, glycerine acrylic ester acrylic ester, the acrylic ester of these exemplary compounds is replaced with methacrylate behind the methacrylate, likewise replaces with itaconate behind the itaconate, maleate etc. after replacing with the butenoate behind the butenoate or replacing with maleate.
As the ester of aromatic polyhydroxy compounds and unsaturated carboxylic acid, can enumerate acrylic ester and the methacrylate etc. of the aromatic polyhydroxy compounds of quinhydrones diacrylate, quinhydrones dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate, 1,2,3,-thrihydroxy-benzene triacrylate etc.
As the ester that the esterification through polybasic carboxylic acid and unsaturated carboxylic acid and polyol obtains, might not be one matter, as representational concrete example, can enumerate the condensation product of acrylic acid, phthalic acid and monoethylene glycol; The condensation product of acrylic acid, maleic acid and diglycol; The condensation product of methacrylic acid, terephthalic acid (TPA) and pentaerythrite; The condensation product of acrylic acid, hexane diacid, butylene glycol and glycerine etc.
In addition; The example of the multifunctional ethylenic monomer that uses as the present invention can be enumerated through (methyl) acrylate reactions that makes polyisocyanate compound and hydroxyl, carbamate (methyl) esters of acrylic acid that perhaps obtains through (methyl) acrylate reactions that makes polyisocyanate compound and polyvalent alcohol and hydroxyl; The epoxy acrylate class that the acrylic acid addition reaction product of polynary epoxy compound and hydroxyl (methyl) acrylic ester or (methyl) is such; Acrylic amides such as ethylenebis acrylic amide; Allyl ester classes such as phthalic acid allyl ester; Phthalic acid divinyl ester etc. contains the compound of vinyl etc.
These monomers can use a kind of separately, also can share two or more.
< other blending constituent of photosensitive color resin combination >
Except mentioned component, mixed organic solvents, adaptation improving agent, coating improving agent, development modifying agent, ultraviolet light absorber, anti-oxidant, silane coupling agent, surfactant, pigment derivative etc. can suit in photosensitive color resin combination of the present invention.
(1) organic solvent
In the photosensitive color resin combination of the present invention, alkali soluble resins (A), Photoepolymerizationinitiater initiater (B), colorant (C) and employed as required various materials use with the state that dissolves or be dispersed in the organic solvent usually.
As organic solvent, preferred boiling point is the solvent of 100～300 ℃ scope.The solvent that more preferably has 120～280 ℃ boiling point.
As such organic solvent, for example can enumerate following solvent.
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-butyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary n-butyl ether, methoxy amylalcohol, DPG list ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol list ether, the such glycol monoalkyl ethers of tripropylene glycol methyl ether;
Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol dipropyl ether, diethylene glycol dibutyl ether, the such glycol dialkyl ether of DPG dimethyl ether;
Ethylene glycol monomethyl ether acetate; Ethylene glycol monoethyl ether acetate; The ethylene glycol mono-n-butyl ether acetic acid esters; Propylene glycol methyl ether acetate; Propylene glycol monoethyl ether acetate; The propylene glycol monopropyl ether acetic acid esters; The propylene glycol monobutyl ether acetic acid esters; Methoxy butyl acetate; Acetate-3-methoxyl butyl ester; Acetate methoxyl pentyl ester; The diethylene glycol monomethyl ether acetic acid esters; The diethylene glycol monoethyl ether acetic acid esters; Diglycol monotertiary n-butyl ether acetic acid esters; The dipropylene glycol monomethyl ether acetic acid esters; The triethylene glycol monomethyl ether acetic acid esters; The triethylene glycol monoethyl ether acetate; Acetate-such glycol alkyl ether the acetate esters of 3-methyl-3-methoxyl butyl ester;
Ethylene acetate, 1,3 butylene glycol diacetate esters, 1, glycol diacetate classes such as 6-hexanediol diacetate esters;
Alkyl acetate classes such as adnoral acetate;
Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, diamyl ether, ethyl isobutyl ether, the such ethers of two hexyl ethers;
Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, DIBK, methyl isobutyl ketone, cyclohexanone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, the such ketone of methoxy pentanone;
Ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, propylene glycol, butylene glycol, diglycol, DPG, triethylene glycol, methoxy amylalcohol, glycerine, such monohydroxy alcohol or the polyalcohols of phenmethylol;
N-pentane, normal octane, diisobutylene, normal hexane, hexene, isoprene, cinene, the such aliphatic hydrocarbon of dodecane;
Cyclohexane, methylcyclohexane, methylcyclohexene, the such ester ring type hydro carbons of bis cyclohexane;
Such aromatic hydrocarbon based of benzene,toluene,xylene, cumene;
Amyl formate; Ethyl formate; Ethyl acetate; Butyl acetate; Propyl acetate; Pentyl acetate; Methyl isobutyrate; The ethylene glycol ethyl ethers acid esters; Ethyl propionate; Propyl propionate; Butyl butyrate; Isobutyl isobutyrate (IBIB); Methyl isobutyrate; Ethyl caprilate; Butyl stearate; Ethyl benzoate; 3-ethoxy-propionic acid methyl esters; The 3-ethoxyl ethyl propionate; 3-methoxypropionic acid methyl esters; 3-methoxy propyl acetoacetic ester; 3-methoxy propyl propyl propionate; 3-methoxy propyl acid butyl ester; Chain ester that gamma-butyrolacton is such or cyclic ester class;
3-methoxypropionic acid, the such alkoxy carboxylic acids of 3-ethoxy-propionic acid;
Chlorobutane, the such halogenated hydrocarbon of chloropentane;
The ether ketone that the methoxy pentanone is such;
Nitrile that acetonitrile, benzonitrile are such etc.
As with above-mentioned suitable commercially available solvent; Can enumerate Mineral Spirit (a kind of solvent oil, about 150-200 ℃ cut), valsol (バ Le ソ Le) #2, Apco (ア プ コ) #18 Solvent, Apco thinning agent, Socal solvent No.1 and No.2, SOLVESO#150, Shell TS28 Solvent, carbitol, ethyl carbitol, BC, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methylcellosolve acetate, diethylene glycol dimethyl ether (more than be trade name) etc.
These organic solvents can use separately, also can share two or more.
Organic solvent when (1-1) forming pixel or the black matrix of color filter with photoetching process
When utilizing photoetching process to form pixel or the black matrix of color filter, as organic solvent, preferentially select boiling point be 100～200 ℃ (under pressure 1013.25 [hPa] condition.Hereinafter, relevant with boiling point pressure condition is all like this) the solvent of scope.The solvent that more preferably has 120～170 ℃ boiling point.
Preferred diol alkyl ether acetate esters in the above-mentioned organic solvent is considered in the higher aspect of solubleness of the constituent, the composition good from the balance of coating, surface tension etc.
In addition, the glycol alkyl ether acetate esters can use separately, but also can share other organic solvents.As the organic solvent that share, particularly preferably be the glycol monoalkyl ethers.Wherein, the deliquescent angle of the constituent from composition, preferred especially propylene glycol monomethyl ether.In addition; The polarity of glycol monoalkyl ethers is high; If addition is too much, then pigment is prone to aggegation, the tendency that the storage stabilities such as viscosity rising of the colored resin composition that obtains after existing reduce; Therefore the ratio of the glycol monoalkyl ethers in the solvent is preferably 5 weight %～30 weight %, more preferably 5 weight %～20 weight %.
In addition, also preferably share organic solvent (hereinafter being sometimes referred to as " high boiling solvent ") with boiling point more than 150 ℃.Through share such high boiling solvent, colored resin composition is difficult for doing, and has the effect that the homogeneously dispersed state that prevents pigment in the composition is destroyed by rapid draing.That is, have and for example prevent the effect of separating out, solidifying the foreign matter defective that causes that occurs colorant etc. at slit spray nozzle front end.Consider from the aspect that such effect is high, among above-mentioned all kinds of solvents, preferred especially diglycol monotertiary n-butyl ether, diglycol monotertiary n-butyl ether acetic acid esters and diethylene glycol monoethyl ether acetic acid esters.
High boiling solvent in the organic solvent contain the proportional 3 weight %～50 weight % that are preferably, more preferably 5 weight %～40 weight % are preferably 5 weight %～30 weight % especially.If the amount of high boiling solvent is very few; Then for example colorant etc. might separate out, solidify and cause the foreign matter defective at slit spray nozzle front end; And if the amount of high boiling solvent is too much; Then the rate of drying of composition is slack-off, after in the color filter manufacturing process that states, might cause the such problem of enforcement pin hole bad or prebake that drying under reduced pressure is handled.
In addition, the high boiling solvent of boiling point more than 150 ℃ can be the glycol alkyl ether acetate esters, and can be the glycol alkyl ether class, in this case, can not contain the high boiling solvent of boiling point more than 150 ℃ in addition.
As preferred high boiling solvent; Among for example above-mentioned all kinds of solvents; Can enumerate diglycol monotertiary n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1,3 butylene glycol diacetate esters, 1,6-hexanediol diacetate esters, glycerol triacetate etc.
Organic solvent when (1-2) utilizing ink-jet method to form the pixel of color filter
When utilizing ink-jet method to form the pixel of color filter, the organic solvent that as organic solvent, boiling point is generally 130 ℃～300 ℃, be preferably 150 ℃～280 ℃ is suitable.If the boiling point of organic solvent is low excessively, then there is the bad tendency of resulting homogeneity of filming.On the contrary; If the boiling point of solvent is too high; Then as the back was said, it is better that the drying of colored resin composition suppresses effect, but also have a large amount of residual solvents in after heat is fired, filming sometimes; Produce the bad problem on the quality, prolong, increased problems such as processing time the drying time that has perhaps produced vacuum drying etc.
And,, use that vapor pressure is generally below the 10mmHg, is preferably below the 5mmHg, the organic solvent below the 1mmHg more preferably from resulting inhomogeneity viewpoint of filming.
In addition, in the color filter that utilizes ink-jet method is made, very fine by the printing ink of nozzle ejection; Be number skin liter～tens of skin liters; Therefore before in being splashed to jet hole periphery or pixel storehouse (picture element バ Application Network), concentrated, dried solid tendency that organic solvent evaporation, printing ink have.For fear of this problem, the boiling point of the organic solvent that preferred colored resin composition is contained is higher, and specifically, it is the solvent more than 180 ℃ that colored resin composition preferably contains boiling point.It is the organic solvent more than 200 ℃ that colored resin composition more preferably contains boiling point, and especially preferably containing boiling point is the organic solvent more than 220 ℃.And, after the printing ink stated and/or color filter with whole organic solvents that colored resin composition contained in, boiling point is that the high boiling solvent more than 180 ℃ is preferably more than the 50 weight %, more preferably more than the 70 weight %, most preferably is more than the 90 weight %.At whole organic solvent mid-boiling points is under the situation of ratio less than 50 weight % of the high boiling solvent more than 180 ℃, can't give full play to preventing the effect of solvent from droplet evaporation sometimes.
Preferred example as the high boiling solvent of boiling point more than 180 ℃; For example among above-mentioned all kinds of solvents; Can enumerate diglycol monotertiary n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1; 3-butylene glycol diacetate esters, 1,6-hexanediol diacetate esters, glycerol triacetate etc.
And then, for after viscosity adjustment and the solubleness adjustment of solid constituent of printing ink, the colored resin composition stated, it also is effective containing the organic solvent that some boiling point is lower than 180 ℃.As such organic solvent, preferred viscosities is low and dissolubility is high, the low such solvent of surface tension, preferred ethers, ester class or ketone etc.Wherein, preferred especially cyclohexanone, DPG dimethyl ether, adnoral acetate etc.
On the other hand, if organic solvent contains alcohols, the deterioration sometimes of the discharge stability in the ink-jet method then.Therefore, preferably alcohols is set at below the 20 weight % that account for whole organic solvents, more preferably below the 10 weight %, below the preferred especially 5 weight %.
(2) silane coupling agent
In order to improve the adaptation with substrate, can add silane coupling agent.As the silane coupling agent kind, can use the independent a kind of of various silane coupling agents such as epoxy system, metha crylic, amino system or mix two or more uses, the silane coupling agent that preferred especially epoxy is.
(3) surfactant
As surfactant; Can use one or more of various surfactants such as negative ion system, kation system, nonionic system, amphoteric surfactant; From the low aspect of the dysgenic possibility of all characteristics is considered that preferred nonionic is a surfactant.
As such surfactant, for example can use the surfactant of putting down in writing in the TOHKEMY 2003-322716 communique well.
(4) pigment derivative
As pigment derivative; The derivant that can enumerate azo system, phthalocyanine system, quinacridone, Benzimidazolinone system, quinophthalone, isoindolinone and be that the 、 dioxazine is, anthraquinone system, indanthrene system, perylene system, perilla ketone system, diketopyrrolo-pyrrole is 、 dioxazine system etc., wherein preferred quinophthalone.
Substituting group as pigment derivative; Can enumerate sulfonic group, sulfoamido and quaternary salt thereof, phthalimide methyl, dialkyl aminoalkyl, hydroxyl, carboxyl, amide group etc. can be directly or be bonded to the group of pigment skeleton, wherein preferred sulfonic group through alkyl, aryl, heterocyclic radical etc.And, in a pigment skeleton, can have a plurality of these substituting groups.As the concrete example of pigment derivative, can enumerate the sulfonic acid etc. of sulfonic acid 、 dioxazine of sulfonic acid, the diketopyrrolo-pyrrole of sulfonic acid, the quinacridone of sulfonic acid, the anthraquinone of sulfonic acid, the quinophthalone of phthalocyanine.These materials can use a kind of separately, also can share two or more.
< combined amount of the composition in the photosensitive color resin combination >
With respect to all solids composition of photosensitive color resin combination of the present invention, the content of alkali soluble resins (A) is generally more than the 5 weight %, is preferably more than the 10 weight %, and is generally below the 85 weight %, is preferably below the 80 weight %.If the content of alkali soluble resins (A) is obviously few, then the dissolubility of unexposed portion in developer solution reduces, and causes poor visualization easily.On the contrary, if the content of alkali soluble resins (A) is too much, then developer solution improves to the perviousness of exposure portion, makes the sharpening property and the adaptation variation of pixel.
As stated, in the present invention, can the part of alkali soluble resins (A) be replaced with other resin glue (F).
At this moment; In photosensitive color resin combination of the present invention; Preferably: below the 90 weight % in the alkali soluble resins (A) that contains with above-mentioned ratio with other resin glue (F) replacement, for example 10～90 weight %, preferred 20～80 weight %, more preferably 30～70 weight %; Promptly with alkali soluble resins (A) and with other resin glue (F); So that with respect to the total of alkali soluble resins (A) and other resin glue (F), the ratio of other resin glue (F) is below the 90 weight %, for example 10～90 weight %, be preferably 20～80% weight %, 30～70 weight % more preferably.
That is, for example through and as other resin glue (F), can obtain following effect with above-mentioned alkali soluble resins (A '): the rectilinearity raising of resulting pattern, it is easy that the adjustment of development time and coning angle becomes; And as other resin glue (F), can obtain following effect through using alkali soluble resins (A "), alkali soluble resins (A1 "): the rectilinearity of resulting pattern improves, and it is easy that the adjustment of development time and coning angle becomes.But; If the content of these materials is very few; Then can't fully obtain the effect of the present invention of using these other resin glues (F) to be brought; If the content of these materials is too much, the ratio of alkali soluble resins then of the present invention (A) reduces, and damages the effect that this alkali soluble resins (A) brings thus.
Therefore, when share alkali soluble resins (A) and other resin glue (F), it share ratio and is preferably set to above-mentioned scope.
The content of Photoepolymerizationinitiater initiater (B) is generally more than the 0.1 weight % with respect to all solids composition of photosensitive color resin combination of the present invention; Be preferably more than the 0.5 weight %; More preferably more than the 0.7 weight %, and be generally below the 30 weight %, be preferably below the 20 weight %.If the content of Photoepolymerizationinitiater initiater (B) is very few, cause sometimes that then sensitivity reduces, on the contrary, if the content of Photoepolymerizationinitiater initiater (B) is too much, then the dissolubility of unexposed portion in developer solution reduces, and causes poor visualization easily.
When with Photoepolymerizationinitiater initiater (B) when using promoter simultaneously; The content of promoter is generally more than the 0 weight % with respect to all solids composition of photosensitive color resin combination of the present invention; Be preferably more than the 0.02 weight %, and be generally more than the 10 weight %, be preferably below the 5 weight %; Employed promoter is preferably 0.1～50 weight % with respect to the ratio of Photoepolymerizationinitiater initiater (B), is preferably 0.1～10 weight % especially.
If the blending ratio of the Photoepolymerizationinitiater initiater set member of being made up of Photoepolymerizationinitiater initiater (B) and promoter etc. is low excessively; Then cause sometimes the sensitivity of exposure light is reduced; On the contrary; If the blending ratio of this Photoepolymerizationinitiater initiater set member is too high, then the dissolubility of unexposed portion in developer solution reduces, and causes poor visualization sometimes.
In addition, the shared blending ratio of sensitizing coloring matter is generally 0～20 weight % in all solids composition in the photosensitive color resin combination in photosensitive color resin combination of the present invention, is preferably 0～15 weight %, more preferably 0～10 weight %.
The content of colorant (C) can be selected in the scope that becomes component to be generally 1～70 weight % with respect to all solids in the photosensitive color resin combination.In this scope, more preferably 10～70 weight %, wherein preferred especially 20～60 weight %.If colorant (C) content is very few, then corresponding to colour saturation, it is excessive that thickness becomes, and the clearance control during sometimes to liquid crystal cell etc. is brought harmful effect.On the contrary, if colorant (C) content is too much, then can't obtain sufficient imaging sometimes.
And in the photosensitive color resin combination, alkali soluble resins (A) is generally 20～500 weight % with respect to the content of colorant (C), is preferably 30～300 weight %, more preferably the scope of 50～200 weight %.If the content with respect to the alkali soluble resins (A) of colorant (C) is low excessively, then the dissolubility of unexposed portion in developer solution reduces, and causes poor visualization easily, if this too high levels then is difficult to obtain desirable pixel thickness.
The content of spreading agent (D) is below the 50 weight % in the solid constituent of photosensitive color resin combination, is preferably below the 30 weight %, and is generally more than the 1 weight %, is preferably more than the 3 weight %.And, with respect to colorant (C), the content of spreading agent (D) preferably: be generally more than the 5 weight %, particularly more than the 10 weight %, and be generally below the 200 weight %, particularly below the 80 weight %.If the content of spreading agent (D) is very few, then can't obtain sufficient dispersiveness sometimes, if the content of spreading agent (D) is too much, then other components in proportions reduces relatively, the tendency that has colour saturation, sensitivity, film forming etc. to reduce.
As spreading agent (D), especially preferably share macromolecule dispersing agent and pigment derivative.At this moment; With respect to all solids composition of photosensitive color resin combination of the present invention, the cooperation ratio of pigment derivative preferably: be generally more than the 0 weight %, be preferably more than the 1 weight %; And be generally below the 10 weight %, be preferably below the 5 weight %.
When using photopolymerization monomer (E), its content is generally below the 90 weight % with respect to all solids composition of photosensitive color resin combination, is preferably below the 80 weight %.If the content of photopolymerization monomer (E) is too much, then developer solution strengthens to the perviousness of exposure portion, is difficult to obtain preferable image sometimes.In addition, the lower limit of the content of photopolymerization monomer (E) is generally more than the 1 weight %, is preferably more than the 5 weight %.
When using surfactant, its content is generally 0.001～10 weight % with respect to all solids composition in the photosensitive color resin combination, is preferably 0.005～1 weight %, and more preferably 0.01～0.5 weight % most preferably is 0.03～0.3 weight %.If the content of surfactant is less than above-mentioned scope; Then might can't realize flatness, the homogeneity of coated film; If the content of surfactant is more than above-mentioned scope, except the flatness that can't realize coated film, the homogeneity, also can make other characteristic degradation sometimes.
In addition, for photosensitive color resin combination of the present invention, can use above-mentioned organic solvent to be modulated into the liquid that its solid component concentration is generally 5～50 weight %, is preferably 10～30 weight %.
< manufacturing approach of photosensitive color resin combination >
Colored resin composition of the present invention (hereinafter is sometimes referred to as " resist ".) can make according to common method.
Usually colorant (C) preferably uses paint regulator (Paint Conditioner), sand mill, bowl mill, edge runner, burrstone mill, airslide disintegrating mill, homogenizer etc. to carry out dispersion treatment in advance.Through dispersion treatment, colorant (C) is by micronize, so the coating characteristics of resist is improved.And, when using black pigment, help to improve light shielding ability as colorant (C).
Usually preferably carry out dispersion treatment with a part or the whole such system of share colorant (C), organic solvent and spreading agent in case of necessity (D) and alkali soluble resins (A) and/or other resin glue (F).(below, the composition that will be used for the potpourri of dispersion treatment sometimes and utilize this processing to obtain is called " printing ink ".) when particularly using macromolecule dispersing agent as spreading agent (D), the viscosity that can suppress resulting printing ink and resist increases (dispersion stabilization is excellent) in time, therefore preferred use macromolecule dispersing agent is as spreading agent (D).
In addition, when the liquid that contains the whole compositions that in colored resin composition, mix was carried out dispersion treatment, the heat release that produces during owing to dispersion treatment was so modification might take place in the composition of high response.Thereby, preferably carry out dispersion treatment with the system that contains above-mentioned composition.
When utilizing sand mill that colorant (C) is disperseed, preferably use the beaded glass or the zirconium oxide bead of particle diameter 0.1mm～8mm degree.About the dispersion treatment condition, temperature is generally 0 ℃～100 ℃, is preferably the scope of room temperature～80 ℃.Because the composition of liquid and dispersion treatment device size etc. is different, and makes suitable jitter time different, therefore to the jitter time adjusting that suits.The standard of disperseing is: the gloss of control printing ink, so that 20 degree mirror surface lusters (JIS Z8741) of resist are 100～200 scope.When the glossiness of resist was hanged down, dispersion treatment was insufficient, and thick pigment (colorant) particle is residual in a large number, and development property, adaptation, resolution etc. might be not enough.In addition, if dispersion treatment is proceeded to gloss number greater than above-mentioned scope, then pigment is damaged, produces a large amount of ultra microns, has the tendency of infringement dispersion stabilization on the contrary.
Next, above-mentioned other compositions that contained in the printing ink that will be obtained by above-mentioned dispersion treatment and the resist mix, and process uniform solution.Therefore in the manufacturing process of resist, fine impurity is often sneaked in the liquid, preferably utilizes filtrator etc. that resulting resist is carried out filtration treatment.
[color filter]
Next, the color filter that uses photosensitive color resin combination of the present invention is described according to its manufacturing approach.
(1) transparency carrier (support)
As the transparency carrier of color filter, so long as transparent and have the intensity of appropriateness, then to the not special restriction of its material.As material, for example can enumerate thermoplastic resin film-makings such as polyolefin-based resins such as polyester based resin, polypropylene, tygon, polycarbonate, polymethylmethacrylate, polysulfones, epoxy resin, unsaturated polyester resins such as polyethylene terephthalate, gather thermoset resin sheets such as (methyl) acrylic resin or various glass etc.Wherein, consider preferred glass, heat-resistant resin from stable on heating aspect.
In order to improve surface physical property such as cementability, transparency carrier and black matrix are formed substrate can carry out Corona discharge Treatment, ozone treatment as required, be the film forming processing of various resins such as resin etc. with silane coupling agent or carbamate.
The thickness of transparency carrier is generally 0.05～10mm, is preferably the scope of 0.1～7mm.And when carrying out film forming processing with various resins, its thickness is generally 0.01～10 μ m, is preferably the scope of 0.05～5 μ m.
(2) black matrix
Black matrix is set on transparency carrier; And form red, green, blue pixels image usually; Can make color filter of the present invention thus, coating fluid is used at least a resist formation that photosensitive color resin combination of the present invention can be used as in black, redness, green, the blueness.Relevant black resist is coated with on transparency carrier upper glass blank face, the various processing of heat drying, image exposure, development and heat curing; Relevant red, green, blue resist; On the formation face at the bottom of the resin black that forms on the transparency carrier or using chromium compound and other shading metal materials and be coated with on the formation face at the bottom of the metal black that forming, the various processing of heat drying, image exposure, development and heat curing, form versicolor pixel image thus.
Black matrix forms on transparency carrier with the photosensitive color resin combination at the bottom of utilizing shading metallic film or resin black.As the shading metal material, can use chromium compounds such as crome metal, chromium oxide, chromium nitride, nickel and tungalloy etc., also can be the multilayer shape material that these metal material laminations are formed.
These metal photomask general using sputtering methods form; Utilize positive light anti-etching agent on membranoid substance, to form desirable pattern; Then, use the mixed nitrate cerium ammonium and the etching solution of perchloric acid and/or nitric acid that chromium is carried out etching, carry out etching corresponding to the etching solution of material for other material use; Peel off positive light anti-etching agent with special-purpose remover at last, can form black matrix thus.
At this moment, at first utilize vapour deposition method or sputtering method etc. on transparency carrier, to form the film of these metals or metal-metallic oxide.Next, after forming the filming of photosensitive color resin combination on this film, use the photomask that has striped, inlays repeat patterns such as (mosaic), triangle to make public and develop, form the resist image thus filming.Then, to this enforcement etch processes of filming, thereby can form black matrix.
When utilizing at the bottom of the resin black, use the photosensitive color resin combination of the present invention that contains black pigment, thereby form black matrix with the photosensitive color resin combination.For example; Can use the photosensitive color resin combination of the black pigment that independent or two or more black pigments that contain that carbon black, graphite, iron oxide black, nigrosine, cyanine are black, titanium is black etc. or the redness of from inorganic or organic pigment, dyestuff, suitably selecting, green, blueness etc. mix, utilize the method formation black matrix red with following formation, green, that the blue pixel image is identical.
(3) formation of pixel
(3-1) coating of photosensitive color resin combination
On being provided with the transparency carrier of black matrix, be coated with the photosensitive color resin combination of the colorant that contains a kind of color in redness, green, the blueness and carry out drying; Stacked photomask on this is filmed then; Carry out image exposure across this photomask, and develop, carry out heat curing or photocuring as required; Thereby the formation pixel image is processed dyed layer thus.Through carrying out this operation respectively, can form the color filter image with red, green, blue this three color sensations photosensitiveness colored resin composition.
The coating of photosensitive color resin composition for color can be coated with method, rolling method or spray-on process etc. through spin-coating method, the excellent method that winds the line, curtain coating, mould.Wherein, when utilizing mould to be coated with method, can reduce the use amount of coating fluid significantly, and the influence of the mist that adheres to when not utilizing spin-coating method fully etc., can suppress foreign matter generation etc., therefore from comprehensive viewpoint, preferred mould is coated with method.
If the thickness of filming is blocked up, then pattern development becomes difficult, is difficult to simultaneously regulate the gap in the liquid crystal cell chemical industry preface, if the thickness of filming is thin excessively, then is difficult to improve pigment concentration, can not show desirable color sometimes.The thickness of filming is preferably the scope of 0.2～20 μ m usually with dried film thickness gauge, and the scope of 0.5～10 μ m more preferably further is preferably the scope of 0.8～5 μ m.
The drying of (3-2) filming
The drying of filming behind coating photosensitive color resin combination on the substrate is preferably based on uses the seasoning of heating plate, IR bake or convection oven to carry out.Drying condition can be according to the kind of above-mentioned solvent composition, the suitable selections such as performance of employed dryer.Usually be chosen as the drying of under 40～200 ℃ temperature carrying out 15 second～5 minute according to the kind of solvent composition, the performance of employed dryer etc. drying time, is preferably and under 50～130 ℃ of temperature, carries out 30 seconds～3 minutes dryings.
Baking temperature is high more then to improve the cementability of filming to transparency carrier more, and still, if baking temperature is too high, then resin glue decomposes, and brings out thermal polymerization sometimes and produces poor visualization.In addition, in the drying process that this is filmed, also can utilize the hypobaric drying method that does not improve temperature and in decompression chamber, carry out drying.
(3-3) exposure
Stacked minus mask pattern on the filming of photosensitive color resin combination across this mask pattern irradiation ultraviolet radiation or visible light source, carries out image exposure thus.At this moment, can on optical polymerism is filmed, form the sensitivity that makes public again behind the oxygen shielding layer such as polyvinyl alcohol layer with the optical polymerism layer that prevents to be caused by oxygen as required descends.The employed light source of above-mentioned image exposure there is not special qualification.As light source, for example can enumerate LASER Light Sources such as lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent light or Argon ion laser, YAG laser instrument, excimer laser, nitrogen laser, He-Cd laser device, semiconductor laser etc.Under situation about using behind the light of irradiation specific wavelength, also can utilize optical filter.
(3-4) develop
After utilizing above-mentioned light source that filming of being formed by the photosensitive color resin combination carried out image exposure; The WS that with an organic solvent perhaps contains surfactant and alkali compounds develops; On substrate, form image, can make color filter of the present invention thus.This WS can further contain organic solvent, buffering agent, complexing agent, dyestuff or pigment.
As alkali compounds, can enumerate inorganic alkaline compound (such as NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sal tartari, soda mint, saleratus, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide etc.) and organic basic compound (such as monoethanolamine, diethanolamine or triethanolamine, monomethyl amine, dimethylamine or trimethylamine, monoethyl amine, diethylamine or triethylamine, an isopropylamine or diisopropylamine, n-butylamine, an isopropanolamine, diisopropanolamine or triisopropanolamine, ethylene imine, second diimine, tetramethyl ammonium hydroxide (TMAH), choline etc.).These alkali compounds can be the potpourris of two or more compounds.
As surfactant, for example can enumerate nonionics such as polyethylene oxide alkyl ethers class, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, single glycerine alkyl esters is amphoteric surfactantes such as anionic surfactants such as surfactant, alkyl benzene sulfonate, alkyl naphthalene sulfonic acid salt, alkylsurfuric acid salt, alkyl sulfonates, sulfosuccinate ester salt class, alkyl betaine class, amino acids.
As organic solvent, for example can enumerate isopropyl alcohol, benzylalcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, propylene glycol, DAA etc.Organic solvent can use separately, also can share with the WS.
Condition to development treatment does not have special qualification; Development temperature is generally 10 ℃～50 ℃ scope; Be preferably 15 ℃～45 ℃; Be preferably 20 ℃～40 ℃ especially, can utilize any method in immersion development method, spray development method, brush development method, the ultrasound wave development method etc. to develop for developing method.
(3-5) heat curing is handled
On the filter substrate after the development, implementing heat curing handles.The heat curing treatment conditions of this moment are that temperature is selected from 100～280 ℃ of scopes, preferred 150～250 ℃ scope, and the time is selected from 5～60 minutes scope.After these a series of operations, accomplished the formation of monochromatic patterning image.Repeat this operation, carry out the patterning of black, redness, green, blueness, thereby form color filter.Wherein, the order of the patterning of 4 kinds of colors is not limited to said sequence.
(3-6) formation of transparency electrode
Keeping color filter is above-mentioned state; On image, form transparency electrodes such as ITO; Thereby the part as parts such as color monitor, liquid crystal indicators in order to improve surface smoothing property and permanance, also can be provided with surface coatings such as polyamide, polyimide as required on image.In addition, in the purposes of planar orientation type type of drive (IPS pattern) etc., part does not form transparency electrode sometimes.
[liquid crystal indicator]
Liquid crystal indicator of the present invention is to use above-mentioned color filter of the present invention to make.
Liquid crystal indicator is made with following method usually: on color filter, form alignment films; After making chock insulator matter (spacer) be dispersed on this alignment films, form liquid crystal cell, in the liquid crystal cell that forms, inject liquid crystal with the subtend baseplate-laminating; Be connected with counter electrode, thereby process liquid crystal indicator.As alignment films, resin moldings such as preferred polyimide.When forming alignment films, adopt woodburytype and/or aniline printing method usually, the thickness of alignment films is set to several 10nm.Through heat fire alignment films is cured processing after, the processing that the surface is implemented the ultraviolet ray irradiation or utilized friction cloth to carry out, thus be processed into the surface state that can regulate the liquid crystal degree of tilt.
As chock insulator matter, can use size to be suitable for the chock insulator matter with the space (gap) of subtend substrate, be preferably 2～8 μ m usually.Also can use photoetching process on filter substrate, to form the light chock insulator matter (PS) of transparent resin film, thereby utilize this light chock insulator matter (PS) to replace chock insulator matter.As the subtend substrate, use array base palte usually, TFT (thin film transistor (TFT)) substrate is specially suitable.
With the space of the applying of subtend substrate according to the different purposes of liquid crystal indicator and different, but select in the scope of 2～8 μ m usually.Behind the subtend baseplate-laminating, the part beyond the liquid crystal injecting port seals with encapsulants such as epoxy resin.Through UV irradiation and/or heating encapsulant is solidified, thereby with the sealing of liquid crystal cell periphery.
After the liquid crystal cell that periphery is sealed cuts into panel unit, in vacuum chamber, reduce pressure, above-mentioned liquid crystal injecting port impregnated in liquid crystal after, through seepage in chamber liquid crystal is injected in the liquid crystal cell.Decompression degree in the liquid crystal cell is generally 1 * 10 -2～1 * 10 -7Pa is preferably 1 * 10 -3～1 * 10 -6Pa.And, preferably when decompression, heating liquid crystal cell, heating-up temperature is generally 30 ℃～100 ℃, is preferably 50 ℃～90 ℃.Keep the time of heating to be set at 10 minutes usually during decompression～60 minutes, impregnated in the liquid crystal thereafter.For the liquid crystal cell that has injected liquid crystal, solidify through making the UV cured resin, with the liquid crystal injecting port sealing, thereby accomplished liquid crystal indicator (panel).
To the not restriction especially of kind of liquid crystal, for existing known liquid crystal such as fragrant family, fatty family, polycyclic compound, both can be lyotropic liquid crystal, also can be thermotropic liquid crystal etc.Thermotropic liquid crystal is known to have nematic crystal, smectic crystal and cholesteryl liquid crystal etc., and liquid crystal of the present invention can be any one in them.
[organic el panel]
Organic el panel of the present invention is to use color filter of the present invention to make.
When using color filter of the present invention to make organic el panel; For example as shown in Figure 1; At first be produced on the transparent support substrate 10 and form figuratum color filter, this pattern by colored resin composition form (that is, pixel 20 and be arranged on the resin black between the adjacent pixels 20 at the bottom of (not shown)); On this color filter,, can produce organic EL 100 thus across organic protection layer 30 and inorganic oxide film 40 lamination organic luminorphors 500.In addition, at least one among at the bottom of pixel 20 and resin black is to use photosensitive color resin combination of the present invention to produce.As the lamination method of organic luminorphor 500, can enumerate: the method that on color filter, forms transparent anode 50, hole injection layer 51, hole transmission layer 52, luminescent layer 53, electron injecting layer 54 and negative electrode 55 successively; To be fitted in method on the inorganic oxide film 40 etc. at the organic luminorphor that forms on other substrates 500.Can use the organic EL of producing like this 100, utilize method that " organic el panel " (オ one system society, distribution on August 20th, 2004, former quiet scholar, Anda thousand wave vectors, village Tian Yingxing work) for example put down in writing etc. to produce organic el panel.
In addition, color filter of the present invention can either be applied to organic el panel of passive type of drive, also can be applied to organic el panel of active drive mode.
Embodiment
Below enumerate synthetic example, embodiment and comparative example the present invention is explained more specifically, but the present invention only otherwise exceed its main points, is not limited to following examples.
< synthetic example 1: alkali soluble resins (II) synthetic >
" NC3000 " (R in the above-mentioned general formula (1-a) with 400 weight portions Japan's chemical drugs (strain) manufacturing 41=H, weight-average molecular weight are 1900, epoxide equivalent is 288), 102 parts by weight of acrylic acid, 0.3 weight portion p methoxy phenol, 5 weight portion triphenylphosphines and the 264 weight portion propylene glycol methyl ether acetates reaction vessel of packing into, stirring until acid number in 95 ℃ is below the 3mgKOH/g.Acid number reaches desired value needs 9 hours (acid number is 2.2mgKOH/g).Next; Further add 151 weight portion tetrabydrophthalic anhydrides; Make their reactions 4 hours in 95 ℃, the weight-average molecular weight that is converted into polystyrene (Mw) that to obtain acid number thus be 102mgKOH/g, utilize GPC to measure is 3200 alkali soluble resins (II) solution.
< synthetic example 2: alkali soluble resins (III) synthetic >
" NC3000H " (R in the above-mentioned general formula (1-a) with 400 weight portions Japan's chemical drugs (strain) manufacturing 4169 ℃ of=H, epoxide equivalent 288, softening point), 102 parts by weight of acrylic acid, 0.3 weight portion p methoxy phenol, 5 weight portion triphenylphosphines and the 264 weight portion propylene glycol methyl ether acetates reaction vessel of packing into, being stirred to acid number in 95 ℃ is below the 3mgKOH/g.Acid number reaches desired value needs 9 hours (acid number is 2.2mgKOH/g).Next, further add 151 weight portion tetrabydrophthalic anhydrides, make their reactions 4 hours in 95 ℃, the polystyrene conversion weight-average molecular weight (Mw) that to obtain acid number thus be 102mgKOH/g, utilize GPC to measure is 3900 alkali soluble resins (III) solution.
< synthetic example 3: alkali soluble resins (IV) synthetic >
Use weight-average molecular weight be 3900 epoxy resin (in the above-mentioned general formula (1-a), R 41=H) replace " NC3000H ", utilizing synthetic method based on synthetic example 2 to obtain acid number is 6800 alkali soluble resins (IV) solution for 102mgKOH/g, GPC measure the polystyrene conversion weight-average molecular weight (Mw) that obtains.
< synthetic example 4: the preparation of printing ink >
Colored at 50 weight portions with carbon black (" MA-8 " that Mitsubishi Chemical society makes; Mean grain size 24 μ m; DBP oil absorption 58ml/100g) adding propylene glycol methyl ether acetate (PGMEA) and carbamate are macromolecule dispersing agent " Disperbyk-182 " (BYK-Chemie society system) in; This spreading agent is counted 10 weight portions with solid constituent, and the solid component concentration of dispersion liquid reaches 30 weight % after adding.The general assembly (TW) of dispersion liquid is 181g.
Fully stir this dispersion liquid with stirring machine, carry out premixed.Then, utilize the coating wobbler to carry out 6 hours dispersion treatment 25～45 ℃ scope.As bead, use the zirconium oxide bead of 0.5mm φ, add zirconium oxide bead with the dispersion liquid identical weight.Disperse to finish back (20 degree mirror surface lusters based on JIS Z8741 are 170), utilize filtrator that bead is separated with dispersion liquid, thereby prepare printing ink 1.
< synthetic example 5: alkali soluble resins (V) synthetic >
With 140 weight portions " NC3000H " and 260 weight portions " NC3000 " replacement " 400 weight portion NC3000H ", utilize synthetic method based on synthetic example 2 obtain acid number for 102mgKOH/g, to measure the polystyrene conversion weight-average molecular weight (Mw) that obtains by GPC be 3450 alkali soluble resins (V) solution.
< synthetic example 6: alkali soluble resins (VI) synthetic >
The weight-average molecular weight of using 160 weight portions in synthetic example 3, to use be 3900 epoxy resin (in the above-mentioned general formula (1-a), R 41=H) and 240 weight portions " NC3000H " replace 400 weight portions " NC3000H "; Utilization is based on the synthetic method of synthetic example 2, and the polystyrene conversion weight-average molecular weight (Mw) of obtain acid number and be 102mgKOH/g, measuring with GPC is 5100 alkali soluble resins (VI) solution.
< synthetic example 7: alkali soluble resins (VII) synthetic >
In the flask that thermometer, stirring machine, condenser pipe are installed, add epoxy compound (epoxide equivalent 231), 12.7g acrylic acid, 47.8g methoxy butyl acetate, 1.00g triphenylphosphine and 0.025g p methoxy phenol that 40g said structure formula is represented; Under agitation in 90 ℃ make their the reaction, be below the 5mgKOH/g up to acid number.Reaction needed 15 hours obtains the epoxy acrylic ester solution.
In the flask that thermometer, stirring machine, condenser pipe are installed, add 25 parts of above-mentioned epoxy acrylic ester solutions and 0.76 weight portion trimethylolpropane (TMP), 3.7 weight portion biphenyl tetracarboxylic dianhydrides (BPDA) and 3.9 weight portion tetrabydrophthalic anhydrides (THPA); Under agitation slowly be warmed up to 105 ℃, make their reactions.
When resin solution becomes when transparent, dilute with methoxy butyl acetate, adjusting to solid constituent is 50 weight %, thus obtaining acid number is 131mgKOH/g, the polystyrene conversion weight-average molecular weight (Mw) measured with GPC is 3000 alkali soluble resins (VII).
Wherein, this alkali soluble resins (VII) is equivalent to " alkali soluble resins (A ') " of the present invention.
< synthetic example 8: alkali soluble resins (VIII) synthetic >
Figure G2008800010167D00681
The epoxy compound (epoxide equivalent 264), 13.65g acrylic acid, 60.5g methoxy butyl acetate, 0.936g triphenylphosphine and the 0.032g p methoxy phenol that in the flask that thermometer, stirring machine, condenser pipe are installed, add the 50g said structure; Under agitation in 90 ℃ make their the reaction, be below the 5mgKOH/g up to acid number.Reaction needed 12 hours obtains the epoxy acrylic ester solution.
In the flask that thermometer, stirring machine, condenser pipe are installed, add above-mentioned epoxy acrylic ester solution of 25 weight portions and 0.76 weight portion trimethylolpropane (TMP), 3.3 weight portion biphenyl tetracarboxylic dianhydrides (BPDA), 3.5 weight portion tetrabydrophthalic anhydrides (THPA); Under agitation slowly be warmed up to 105 ℃, make their reactions.
When resin solution becomes when transparent; Dilute with methoxy butyl acetate; Adjusting to solid constituent is 50 weight %, thereby obtaining acid number is 131mgKOH/g, the polystyrene conversion weight-average molecular weight (Mw) measured with GPC is 2600 alkali soluble resins (VIII).
Wherein, this alkali soluble resins (VIII) is equivalent to " alkali soluble resins (A1 " of the present invention) ".
[embodiment 1～6 and comparative example 1～3]
(1) preparation of resist (photosensitive color resin combination)
Use the printing ink 1 of preparation in the synthetic example 4, add each composition, utilize stirrer to stir, make their dissolvings, thereby prepare the black resist with following proportioning.
< proportioning >
The printing ink 1 of preparation in the synthetic example 4:, be 50g with solid component meter
Each alkali soluble resins solution of preparation in synthetic example 1～3 and the synthetic example 5～8:, be 30g with solid component meter
Photopolymerization monomer (dipentaerythritol acrylate): 10g
The solution of pbz polymer spreading agent (" byk-182 " that BYK-Chemie society makes):, be 5g with solid component meter
Photoepolymerizationinitiater initiater (" CGI242 " that Ciba Specialty Chemicals society makes; Oxime ester based compound shown in the following structural formula): 5g
Figure G2008800010167D00691
Organic solvent (PGMEA): 300g
Surfactant (" FC-430 " fluorine class surfactant that 3M society in Sumitomo makes): the concentration in the resist reaches the amount of 100ppm
(2) evaluation of resist
Utilize spinner with black resist-coated of preparation in (1) on glass substrate (" 7059 " that Corning society makes), with heating plate in 80 ℃ of dryings 1 minute.With the thickness of the dried resist of contact pin type film thickness gauge (" α-STEP " that Tencor society makes) mensuration, thickness is 1 μ m as a result.Next, utilize high-pressure sodium lamp to change exposure and this sample is carried out image exposure through mask., in the aqueous sodium carbonate of temperature 25 ℃ working concentration 0.8 weight %s carry out spray development, obtain the resist pattern thus thereafter.
To the sensitivity of formed resist pattern evaluation, resolving power and light-proofness, the result lists in table-1 with following benchmark.
1. sensitivity
Can form the correct exposure amount (mJ/cm of the mask pattern that is of a size of 20 μ m with accurate dimension 2) expression sensitivity.That is, the resist that its exposure is few can form images with low exposure, so exposure is represented highly sensitive less.
2. resolving power
With 200 times multiplying powers under the exposure of the mask pattern that can faithful reappearance be of a size of 20 μ m, distinguishable resist minimum pattern size carries out microscopic examination, estimate with following benchmark.
Minimum pattern is of a size of below the 10 μ m: ◎
The minimum pattern size is greater than 10 μ m and be below the 15 μ m: zero
The minimum pattern size is greater than 15 μ m: *
3. light-proofness
Measure the optical concentration (OD) of setting-out portion with Macbeth reflection of the concentration (" TR927 " that コ Le モ Le グ Application society makes).In addition, the OD value is the numerical value of expression light shielding ability, and numerical value is big more, and the expression light-proofness is strong more.
4. rectilinearity
With 1000 times multiplying powers the shape of the fine rule black picture element under the exposure of the mask pattern that can faithful reappearance be of a size of 20 μ m is carried out microscopic examination.
The rectilinearity at edge is excellent: ◎
The rectilinearity at edge is comparatively good: zero
There is several projections or concavo-convex: △ at the edge
There are a large amount of projections or concavo-convex at the edge: *
[table 1]
Figure G2008800010167D00701
Can know by table 1,, photosensitive color resin combination highly sensitive, excellence aspect resolution, light-proofness can be provided according to the present invention.
Use ad hoc fashion that the present invention is specified, but those skilled in the art understand under the condition that does not break away from the intent of the present invention and scope and can carry out various distortion.
In addition, the application is the basis with the Japanese patent application that proposed on June 11st, 2007 (the special 2007-154159 of hope of Japan), quotes its full content by reference at this.

Claims (14)

1. photosensitive color resin composition for color; It is characterized in that; Said composition contains alkali soluble resins (A), Photoepolymerizationinitiater initiater (B) and colorant (C); Said alkali soluble resins (A) is further to react with polyacid and/or its acid anhydrides (c) by the product of epoxy resin (a) that makes formula (1-a) expression and the carboxylic acid (b) that contains unsaturated group to obtain; The weight average molecular weight of the alkali soluble resins of measuring by gel permeation chromatography GPC (A) that is obtained by polystyrene conversion is 3300～50000
Figure FSB00000517541700011
In the above-mentioned general formula (1-a), n representes mean value and representes 0～10 number; R 41Expression hydrogen atom, halogen atom, carbon number are that 1～8 alkyl, carbon number are any group in 3～10 naphthenic base, phenyl, naphthyl or the xenyl; And, be present in 2 above R in 1 molecule 41Can be mutually the same, also can be different; G representes glycidyl.
2. photosensitive color resin composition for color as claimed in claim 1, wherein, said composition also contains spreading agent (D).
3. according to claim 1 or claim 2 photosensitive color resin composition for color, wherein, said composition also contains photopolymerization monomer (E).
4. photosensitive color resin composition for color as claimed in claim 1; Wherein, Said composition also contains alkali soluble resins (A '), and said alkali soluble resins (A ') is through epoxy compound that makes formula (1-a ') expression (a ') and α, β-unsaturated monocarboxylic and/or have the α of carboxyl at ester moiety; The reaction product of β-unsaturated monocarboxylic ester (b ') and polyprotonic acid and/or its acid anhydrides (c ') reaction obtains
Figure FSB00000517541700021
Above-mentioned general formula (1-a ') in, p and q represent 0～4 integer, R independently of one another 31And R 32Represent alkyl or halogen atom independently of one another, R 33And R 34Represent alkylidene independently of one another, x and y represent the integer more than 0 independently of one another.
5. photosensitive color resin composition for color as claimed in claim 1; Wherein, Said composition also contains alkali soluble resins (A "); said alkali soluble resins (A ") is to react through the reaction product of the epoxy compound that makes formula (1-a ") expression (a ") and the carboxylic acid that contains unsaturated group (b ") and polyprotonic acid and/or its acid anhydrides (c ") to obtain
Figure FSB00000517541700022
Above-mentioned general formula (1-a ") in, X representes the linking group of formula (2a), (2b) or (3) expression; Wherein, in molecular structure, comprise more than one adamantane structure; L representes 2 or 3 integer,
Figure FSB00000517541700023
At above-mentioned general formula (2a) with (2b), R 1～R 4And R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl,
In above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl, Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure,
In above-mentioned general formula (2a), (2b) and (3), *The position of the glycidoxypropyl bonding in expression and the general formula (1-a ").
6. photosensitive color resin composition for color as claimed in claim 5, wherein, said polyprotonic acid and/or its acid anhydrides (c ") contain following (i) and (ii):
(i) acid anhydrides of the acid anhydrides of tetra-atomic acid and/or tetra-atomic acid and/or dibasic acid and/or dibasic acid;
(ii) ternary acid and/or its acid anhydrides.
7. photosensitive color resin composition for color as claimed in claim 1; Wherein, Said composition also contains alkali soluble resins (A1 "); said alkali soluble resins (A1 ") is to obtain through this potpourri and polyprotonic acid and/or its acid anhydrides (c ") are reacted
Figure FSB00000517541700031
Above-mentioned general formula (1-a ") in, X representes the linking group of formula (2a), (2b) or (3) expression; Wherein, in molecular structure, comprise more than one adamantane structure; L representes 2 or 3 integer,
Figure FSB00000517541700041
At above-mentioned general formula (2a) with (2b), R 1～R 4And R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl,
In above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl, Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure,
In above-mentioned general formula (2a), (2b) and (3), *The position of the glycidoxypropyl bonding in expression and the general formula (1-a ").
8. photosensitive color resin composition for color as claimed in claim 7, wherein, said polyprotonic acid and/or its acid anhydrides (c ") contain as follows (i) and (ii):
(i) acid anhydrides of the acid anhydrides of tetra-atomic acid and/or tetra-atomic acid and/or dibasic acid and/or dibasic acid;
(ii) ternary acid and/or its acid anhydrides.
9. photosensitive color resin composition for color as claimed in claim 1, wherein, said Photoepolymerizationinitiater initiater (B) comprises the oxime ester derivative class.
10. photosensitive color resin composition for color as claimed in claim 1, wherein, in all solids composition of photosensitive color resin combination, the content of said colorant (C) is 20 weight %～60 weight %.
11. photosensitive color resin composition for color as claimed in claim 1, wherein, said colorant (C) contains black pigment.
12. a color filter, this color filter have pixel or the black matrix of using each described photosensitive color resin combination of claim 1～11 to form on transparency carrier.
13. a liquid crystal indicator, this liquid crystal indicator are to use the described color filter of claim 12 to make.
14. an organic EL display panel, this organic EL display panel are to use the described color filter of claim 12 to make.
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