CN108700685A - Colour spacer photosensitive coloring composition, solidfied material, coloring spacer, image display device - Google Patents

Colour spacer photosensitive coloring composition, solidfied material, coloring spacer, image display device Download PDF

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Publication number
CN108700685A
CN108700685A CN201780010607.XA CN201780010607A CN108700685A CN 108700685 A CN108700685 A CN 108700685A CN 201780010607 A CN201780010607 A CN 201780010607A CN 108700685 A CN108700685 A CN 108700685A
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CN
China
Prior art keywords
pigment
methyl
acid
coloring composition
mass
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Pending
Application number
CN201780010607.XA
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Chinese (zh)
Inventor
岩田训志
伊藤敦哉
小川善秀
裴丽华
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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Priority to CN202210140197.3A priority Critical patent/CN114545737A/en
Publication of CN108700685A publication Critical patent/CN108700685A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Liquid Crystal (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

High, primary divider that the issue of the present invention is to provide a kind of light-proofness and the difference in height of secondary spacer are controlled, and the coloring spacer formation photosensitive coloring composition that the light leakage in the full scope as wavelength 450nm~700nm of visible light region is also inhibited.The coloring spacer formation photosensitive coloring composition of the present invention contains (a) colorant, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, (a) colorant includes (a-1) organic pigment and (a-2) carbon black, (a-2) carbon black relative to the content ratio of (a) colorant is 20 mass % hereinafter, and highest transmissivity of the photosensitive coloring composition in 300~370nm of wavelength is 0.010% or more.

Description

Colour spacer photosensitive coloring composition, solidfied material, coloring spacer, image Display device
Technical field
The present invention relates to coloring spacer formation photosensitive coloring compositions etc..Specifically, it is related in such as liquid crystal The photosensitive coloring composition of coloring spacer etc. is preferably used to form in the optical filter of display etc., by the photosensitive color group The image display device for closing coloring spacer obtained from object solidification, having the coloring spacer.
Background technology
Liquid crystal display (LCD) is utilized under the action of the ON/OFF of the voltage applied to liquid crystal, the arrangement of liquid crystal molecule The property that mode changes.On the other hand, each component for constituting the unit of LCD is by using photoetching process as the profit of representative mostly It is formed with the method for photosensitive composite.For the photosensitive composite, since it is easy to form fine structure, appearance Easily carry out the such reason of the processing for large-area substrates, it is contemplated that arrive application of the photosensitive composite in wide scope from now on.
Recently, in order to cope with further fine, the high brightness of color LCD, in active-matrix (active Matrix) in type LCD, it is proposed that optical filter is set to TFT (thin film transistor (TFT), Thin Film Transistor) element base The optical filter of plate side is with integrated (the Color-filter on Array) mode (COA modes) of array substrate and only by black square Battle array is set to the black matrix" of TFT device substrates side and array substrate integrates (Black-matrix on Array) mode (BOA Mode).According to which, compared with the case where forming black matrix" in optical filter side, due to that need not take and activeleg The contraposition machine of side, therefore aperture opening ratio can be improved, as a result, high brightness can be sought.In the knot of such black matrix" In structure, it is desirable that high light-proofness and strongly inhibit light leakage (referring to patent document 1) in visible light region.
In addition, along with panel construction and the easy of manufacturing process, also developed for by 2 bases in liquid crystal display panel The interval holding of plate is constant, by so-called column spacer, light spacer it is integrated with black matrix" made of colour spacer. Method as structure as formation, it is proposed that the side of the different coloring spacer of height is disposably formed using photoetching process Method.For example, Patent Document 2 discloses the following contents:The specific pigment kind different by combining a variety of optical absorption characteristics, can be with Ensure the balance of the light absorption of ultraviolet region and visible light region, keeps the voltage retention of light-proofness and liquid crystal, and controllable The shape of spacer processed, the difference in height of primary divider and secondary spacer, while the high adhesion with substrate may be implemented.Patent text The following contents is disclosed in offering 3:By using specific black pigment and specific dispersant package, light-proofness is excellent, point It is also excellent to dissipate property, plate-making property, and shows sufficiently low capacitivity.The following contents is disclosed in patent document 4:By with spy Fixed compounding ratio use inorganic black colorant, organic black colorant and blue colorant, can meet simultaneously spacer and The characteristic of black matrix".
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2009-069822 bulletins
Patent document 2:International Publication No. 2013/115268
Patent document 3:International Publication No. 2015/046178
Patent document 4:Japanese Unexamined Patent Publication 2014-146029 bulletins
Invention content
The subject that the invention solves
In recent years, along with the variation of panel construction, coloring spacer is also required to show with black matrix" on an equal basis Function does not play shading unevenly in particular for the full scope in the wavelength 450nm to 700nm as visible light region Property.
The inventors of the present invention it has been investigated that, the photosensitive coloring composition as recorded in patent document 2, inhaled by light It is a variety of etc. come when making coloring spacer to receive the different specific pigment kind combination of characteristic, although light-proofness is high and can control master The difference in height of spacer and secondary spacer, but in the part wave-length coverage of visible light region, light-proofness is simultaneously insufficient, can not It is adequately suppressed the light leakage in the full scope of wavelength 450nm~700nm.
In addition, it is found that the photosensitive coloring composition recorded in patent document 3 can not realize the leakage of visible light region simultaneously The inhibition of light and the control of primary divider and the difference in height of secondary spacer.
In addition, it is found that the photosensitive coloring composition recorded in patent document 4 can not form primary divider and secondary spacer Difference in height.
Present invention is made in view of the above circumstances, is formed and is used the purpose of the present invention is to provide a kind of coloring spacer Photosensitive coloring composition, the difference in height of light-proofness high, controllable primary divider and secondary spacer, while can also inhibit The light leakage of the full scope of wavelength 450nm to 700nm as visible light region.
The method to solve the problem
It is that the inventors of the present invention have made intensive studies in order to solve the above problems as a result, it has been found that, by coloring spacer shape It will be applied in combination as the organic pigment of colorant and carbon black at using in photosensitive coloring composition, and make the content ratio of carbon black For particular range, and the highest transmissivity in 300~370nm of wavelength is set as particular range, the above subject can be solved, So as to complete the present invention.
That is, the present invention has Yi Xia [1]~[11]Composition.
[1]A kind of coloring spacer formation photosensitive coloring composition, contains:(a) colorant, (b) alkali-soluble Resin, (c) Photoepolymerizationinitiater initiater, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, wherein
(a) colorant includes (a-1) organic pigment and (a-2) carbon black,
(a-2) carbon black relative to (a) colorant content ratio be 20 mass % hereinafter, also,
The photosensitive coloring composition is 0.010% or more in the highest transmissivity of 300~370nm of wavelength.
[2]Shang Shu [1]The coloring spacer formation photosensitive coloring composition, wherein (a-1) organic face Material is containing selected from least one of red pigment, orange pigment, blue pigment and violet pigment.
[3]Shang Shu [1]Huo [2]The coloring spacer formation photosensitive coloring composition, wherein (a-1) Organic pigment contains selected from least one of red pigment and orange pigment and in blue pigment and violet pigment It is at least one.
[4]Shang Shu [1]Huo [2]The coloring spacer formation photosensitive coloring composition, wherein (a-1) Organic pigment contains blue pigment and violet pigment.
[5]Shang Shu [1]~[4]Any one of described in coloring spacer formation photosensitive coloring composition, wherein institute It states (a-1) organic pigment and contains organic black pigments.
[6]Shang Shu [5]The coloring spacer formation photosensitive coloring composition, wherein organic black face Expect for the geometry of following formula (1) compound represented, the geometric isomer of the compound, the salt of the compound or the compound The salt of isomers,
[Chemical formula 1]
(in above-mentioned formula (1), R1And R6Independently of one another hydrogen atom, CH3,CF3, fluorine atom or chlorine atom;
R2,R3,R4,R5,R7,R8,R9And R10It is independently of one another hydrogen atom, halogen atom, R to each other11,COOH,COOR11, COO-,CONH2,CONHR11,CONR11R12,CN,OH,OR11,COCR11,OOCNH2,OOCNHR11,OOCNR11R12,NO2,NH2, NHR11,NR11R12,NHCOR12,NR11COR12, N=CH2, N=CHR11, N=CR11R12,SH,SR11,SOR11,SO2R11,SO3R11, SO3H,SO3 -,SO2NH2,SO2NHR11Or SO2NR11R12;
Also, it is selected from R2With R3,R3With R4,R4With R5,R7With R8,R8With R9And R9With R10At least one of combination it is optional Mutual Direct Bonding or pass through oxygen atom, sulphur atom, NH or NR11Bridging and be mutually bonded;
R11And R12The independently of one another alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number The alkynyl of 2~12 alkenyl, the cycloalkenyl group of carbon atom number 3~12 or carbon atom number 2~12.)
[7]Shang Shu [1]~[6]Any one of described in coloring spacer formation photosensitive coloring composition, solidification The optical density of average every 1 μm of 1 μm of film thickness of film afterwards is 1.0 or more.
[8]Shang Shu [1]~[7]Any one of described in coloring spacer formation photosensitive coloring composition, be used for The different coloring spacer of height is disposably formed by photoetching process.
[9]A kind of solidfied material is by Shang Shu [1]~[8]Any one of described in coloring spacer formation photonasty Obtained from coloured composition solidification.
[10]A kind of coloring spacer, by Shang Shu [9]The solidfied material is formed.
[11]A kind of image display device has Shang Shu [10]The coloring spacer.
The effect of invention
According to the present invention it is possible to provide a kind of coloring spacer formation photosensitive coloring composition, light-proofness is high, can Control the difference in height of primary divider and secondary spacer, at the same can also inhibit the wavelength 450nm as visible light region extremely The light leakage of the full scope of 700nm.Furthermore it is possible to provide a kind of solidfied material and coloring spacer, light-proofness are excellent, controllable The difference in height of primary divider and secondary spacer, while the leakage of the full scope of the wavelength 450nm to 700nm as visible light region Light is also inhibited, it may, furthermore, provide having the image display device of such coloring spacer.
Specific implementation mode
Hereinafter, embodiments of the present invention are specifically described, but the present invention is not limited to the following embodiments and the accompanying drawings, and it can To implement after being made various changes in the range of its main points.
It should be noted that in the present invention, " (methyl) acrylic " refers to " acrylic and/or methylpropenyl ", " (methyl) acrylate ", " (methyl) acryloyl group " also illustrate that same meaning.
The meaning of " (co) polymer " include homopolymer (homopolymer) and copolymer (copolymer) this two The meaning of person, " sour (acid anhydrides) ", " ... sour (acid anhydride) " include both acid and its acid anhydrides.In addition, in the present invention, it is described " acrylic resin " refers to the (co) polymer comprising (methyl) acrylic acid, comprising (methyl) acrylate with carboxyl (co) polymer.
In addition, in the present invention, " monomer " is the term opposite with so-called polymer substance (polymer), in addition to Further include the meanings such as dimer, trimer, oligomer other than the monomer (monomer) of narrow sense.
In the present invention, described " total solid content " refers to institute in the ink described in photosensitive coloring composition or below Whole components other than the solvent contained.
In the present invention, " weight average molecular weight " refers to being measured using GPC (gel permeation chromatography) and being converted into polyphenyl second The weight average molecular weight (Mw) of alkene.
In addition, in the present invention, unless otherwise specified, " amine value " indicates the amine for being converted into effective solid constituent Value, is with the value for the alkali number that the KOH quality representations of equivalent are the every 1g solid constituents for being equivalent to dispersant.It should be noted that About its assay method, it is described below.On the other hand, unless otherwise specified, described " acid value " expression is converted into effectively The acid value of solid constituent, is calculated by acid-base titration.
In addition, in the present specification, the percentage indicated with the percentage of " quality " expression and part and with " weight " and part Indicate identical meanings.
[Spacer is coloured to be formed with Gan Guangxingzhesezuhewu ]
The coloring spacer formation of the present invention uses photosensitive coloring composition to contain following component as essential component:
(a) colorant
(b) alkali soluble resin
(c) Photoepolymerizationinitiater initiater
(d) olefinic unsaturated compound
(e) solvent
(f) dispersant,
Further contain the adaptations enhancers such as silane coupling agent, coating enhancer, development modifying agent, purple as needed Other gradation compositions such as ultraviolet absorbers, antioxidant, surfactant, pigment derivative, each gradation composition usually with dissolving or The state being scattered in solvent uses.
< (a) colorants >
The coloring spacer formation of the present invention contains (a-1) with (a) colorant used in photosensitive coloring composition to be had Machine pigment and (a-2) carbon black.So, it is easy to carry out shape, height by using the few organic pigment of ultraviolet radiation absorption High light-proofness may be implemented in addition, by also using carbon black other than using organic pigment in the control of difference.
The chemical constitution of these (a-1) organic pigments is not particularly limited, in addition to azo, phthalocyanines, quinoline azone class, benzene And imidazolone, isoindoline ketone, twoOther than the organic pigments such as piperazine class, indanthrone kinds, class, it can also utilize various Inorganic pigment etc..Hereinafter, the concrete example for the pigment for showing to be used in the present invention with pigment serial number.It is exemplified below Terms such as " C.I. paratoneres 2 " refer to pigment call number (C.I.).
As red pigment, can enumerate C.I. paratoneres 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 4s 8 can preferably be enumerated:1,122,149,168,177,179,194,202,206,207,209,224,242, 254,272, more preferably enumerate C.I. pigment red 149s, 177,179,194,209,224,254.It should be noted that from dispersion , it is preferable to use C.I. paratoneres 177,254,272, make photosensitive color combine using ultraviolet light from the aspect of property, light-proofness In the case of object is cured, as red pigment, it is preferable to use the low red pigment of absorption of UV, considers, more from the viewpoint It is preferable to use C.I. paratoneres 254,272.
As orange (orange) pigment, can enumerate C.I. pigment oranges 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.Its In, it can preferably enumerate C.I. pigment oranges 38,43,64,71,72.It should be noted that from the aspect of dispersibility, light-proofness, It is preferable to use C.I. pigment oranges 43,64,72, keep photosensitive coloring composition cured using ultraviolet light, as orange Color pigment considers, it is preferable to use the low orange pigment of absorption of UV from the viewpoint, more preferably using C.I. pigment oranges 64, 72。
As blue pigment, C.I. pigment blue 1s, 1 can be enumerated: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 it is possible to it is preferred that enumerate C.I. pigment blue 15s, 15:1,15:2,15:3,15:4,15:6,16,60, More preferably enumerate C.I. pigment blue 15s:6.
It should be noted that, it is preferable to use C.I. pigment blue 15s from the aspect of dispersibility, light-proofness:6,16,60, In the case of keeping photosensitive coloring composition cured using ultraviolet light, as blue pigment, it is preferable to use absorption of UV is low Blue pigment, from the viewpoint consider, more preferably use C.I. pigment blue 60s.
As violet pigment, C.I. pigment violet 1s, 1 can be enumerated: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 it is possible to it is preferred that enumerate C.I. pigment violet 1s 9,23, 29, more preferably enumerate C.I. pigment Violet 23s.
It should be noted that, it is preferable to use C.I. pigment Violet 23s, 29, are utilizing purple from the aspect of dispersibility, light-proofness In the case of outside line keeps photosensitive coloring composition cured, as violet pigment, it is preferable to use the low purple of absorption of UV Pigment considers from the viewpoint, more preferably uses C.I. pigment violets 29.
As the organic coloring face that can be used other than red pigment, orange pigment, blue pigment, violet pigment Material, it can be cited for example that viridine green, yellow uitramarine etc..
As viridine green, can enumerate C.I. naphthol greens 1,2,4,7,8,10,13,14,15,17,18,19,26,36, 45,48,50,51,54,55.Wherein it is possible to it is preferred that enumerate C.I. pigment Green 7s, 36.
As yellow uitramarine, C.I. pigment yellows 1,1 can be enumerated: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 it is possible to it is preferred that enumerate C.I. pigment yellow 83s, 117,129, 138,139,150,154,155,180,185, more preferably enumerate C.I. pigment yellow 83s, 138,139,150,180.
In these, from the viewpoint of adaptation, preferably comprise selected from red pigment, orange pigment, blue pigment and At least one of violet pigment.In particular, from the viewpoint of the control of light-proofness, shape and difference in height, preferably comprise with It is more than at least one of lower pigment.
Red pigment:C.I. paratonere 177,254,272
Orange pigment:C.I. pigment orange 43,64,72
Blue pigment:C.I. pigment blue 15:6,60
Violet pigment:C.I. pigment Violet 23,29
It should be noted that the combination for color is not particularly limited, from the viewpoint of light-proofness, choosing is preferably comprised From at least one of red pigment and orange pigment and it is selected from least one of blue pigment and violet pigment, it can be with It enumerates for example:The combination of red pigment and blue pigment, the combination of blue pigment and orange pigment, blue pigment and orange pigment With the combination of violet pigment etc..
In these, it is preferable to use blue from the viewpoint of the especially light-proofness of long wavelength region of visible light region Color pigment and/or violet pigment.In particular, the absorption spectrum of carbon black due to declining from short wavelength to long wavelength side its absorbance, And the dulling luminosity ratio organic pigment of ultraviolet region increases, therefore from the viewpoint of realizing light-proofness and plate-making property simultaneously, excellent Blue pigment and/or violet pigment are applied in combination with carbon black for choosing, more preferably combine blue pigment and violet pigment with carbon black It uses.
In addition, from the viewpoint of light-proofness, organic pigment preferably comprises organic black pigments.It is examined from the viewpoint of light-proofness Consider, it is preferable to use organic black pigments, the organic black pigments are the geometry of following formula (1) compound represented, the compound The salt of the geometric isomer of isomers, the salt of the compound or the compound.
&#91;Chemical formula 2&#93;
In formula (1), R1And R6Independently of one another hydrogen atom, CH3,CF3, fluorine atom or chlorine atom;
R2,R3,R4,R5,R7,R8,R9And R10It is independently of one another hydrogen atom, halogen atom, R to each other11,COOH,COOR11, COO-,CONH2,CONHR11,CONR11R12,CN,OH,OR11,COCR11,OOCNH2,OOCNHR11,OOCNR11R12,NO2,NH2, NHR11,NR11R12,NHCOR12,NR11COR12, N=CH2, N=CHR11, N=CR11R12,SH,SR11,SOR11,SO2R11,SO3R11, SO3H,SO3 -,SO2NH2,SO2NHR11Or SO2NR11R12;
Also, it is selected from R2With R3,R3With R4,R4With R5,R7With R8,R8With R9And R9With R10At least one of combination it is optional Mutual Direct Bonding or pass through oxygen atom, sulphur atom, NH or NR11Bridging and be mutually bonded;
R11And R12The independently of one another alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number The alkynyl of 2~12 alkenyl, the cycloalkenyl group of carbon atom number 3~12 or carbon atom number 2~12.
There is the geometric isomer of general formula (1) compound represented nuclear structure below (wherein, to be omitted in structural formula Substituent group), trans- trans isomer may be most stable of.
&#91;Chemical formula 3&#93;
In the case that the compound that general formula (1) indicates is anionic property, preferably utilize any known suitable sun from Son, such as metal, organic and inorganic or metal organic cation, be specially alkali metal, alkaline-earth metal, transition metal, primary amine, secondary Obtained from the quaternary ammoniums such as the tertiary amines such as amine, trialkylamine, tetra-allkylammonium or Organometallic complexes compensate its charge Salt.In addition, in the case that the geometric isomer for the compound that general formula (1) indicates is anionic property, preferably same salt.
In the substituent group of general formula (1) and their definition, consider from the tendency for improving screening rate, it is preferably below Substituent group.This is because, it is believed that substituent group below is without absorption, on the form and aspect of pigment without influence.
R2,R4,R5,R7,R9And R10It is preferably hydrogen atom, fluorine atom or chlorine atom independently of each other, more preferably hydrogen is former Son.
R3And R8It is preferably hydrogen atom, NO independently of each other2,OCH3,OC2H5, bromine atom, chlorine atom, CH3,C2H5,N (CH3)2,N(CH3)(C2H5),N(C2H5)2, Alpha-Naphthyl, betanaphthyl, SO3H or SO3 -, more preferably hydrogen atom or SO3H。
R1And R6It is preferably hydrogen atom, CH independently of each other3Or CF3, more preferably hydrogen atom.
It is preferably selected from R1With R6,R2With R7,R3With R8,R4With R9And R5With R10At least one of combination it is identical, more preferably R1With R6Identical, R2With R7Identical, R3With R8Identical, R4With R9Identical and R5With R10It is identical.
The alkyl of carbon atom number 1~12 is, for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl Base, tertiary butyl, 2- methyl butyls, n-pentyl, 2- amyls, 3- amyls, 2,2- dimethyl propyls, n-hexyl, heptyl, n-octyl, 1,1,3,3- tetramethyl butyls, 2- ethylhexyls, nonyl, decyl, undecyl or dodecyl.
The naphthenic base of carbon atom number 3~12 is, for example, cyclopropyl, Cvclopropvlmethvl, cyclobutyl, cyclopenta, cyclohexyl, ring Hexyl methyl, trimethylcyclohexyl, thujyl (thujyl), norbornene, bornyl, norcarane alkyl, caryl,Alkyl, Norpinane base, pinane base, 1- adamantyls or 2- adamantyls.
The alkenyl of carbon atom number 2~12 is, for example, vinyl, allyl, 2- propylene -2- bases, 2- butene-1s-base, 3- fourths Alkene -1- bases, 1,3- butadiene -2- bases, 2- amylene -1- bases, 3- 2-pentenyls, 2-Base -1- butylene -3- bases, 2- methyl -3- Butene-2-base, 3- methyl-2-butene-1- bases, 1,4- pentadiene-3- bases, hexenyl, octenyl, nonenyl, decene base or ten Dialkylene.
The cycloalkenyl group of carbon atom number 3~12 be, for example, 2- cyclobutane -1- bases, 2- cyclopentene -1- bases, 2- cyclohexene -1- bases, 3- cyclohexene -1- bases, 2,4- cyclohexadiene -1- bases, 1- pairsAlkene -8- bases, 4 (10)-limonene -10- bases, 2- norbornene -1- Base, 2,5- norbornadiene -1- bases, 7,7- dimethyl -2,4- norcaranes diene -3- bases or camphyl.
The alkynyl of carbon atom number 2~12 is, for example, 1- propine -3- bases, 1- butine -4- bases, 1- pentyne -5- bases, 2- methyl - 3- crotonylenes-base, 1,4- pentadiine -3- bases, 1,3- pentadiine -5- bases, 1- hexin -6- bases, cis- 3- methyl -2- amylenes -4- Alkynes -1- bases, trans- 3- methyl -2- amylenes -4- alkynes -1- bases, 1,3- hexadiine -5- bases, 1- octyne -8- bases, 1- n-heptylacetylene -9- bases, 1- Decine -10- bases or 1- dodecyne -12- bases.
Halogen atom is, for example, fluorine atom, chlorine atom, bromine atom or iodine atom.
Organic black pigments shown in above-mentioned general formula (1) are preferably the following general formula (2) compound represented.
&#91;Chemical formula 4&#93;
As the concrete example of such organic black pigments, trade name Irgaphor (registered trademark) can be enumerated The organic black pigments of Black S 0100CF (BASF AG's manufacture).
The organic black pigments are preferably dispersed in dispersant, solvent by aftermentioned method and are used.In addition, if dividing There are the sulfonic acids of above-mentioned general formula (2) when scattered, then dispersibility, keeping quality improve sometimes.
In addition, as other organic black pigments, it is peaceful black, black etc. that nigrosine, match can also be enumerated.
Also include (a-2) carbon black other than above-mentioned (a-1) organic pigment as (a) colorant in the present invention.(a- 2) carbon black in whole wavelength of visible light region due to comprehensively having absorption spectrum, it can thus be assumed that by using (a-2) Carbon black can also inhibit the light leakage in the full scope as the wavelength 450nm to 700nm of visible light region.As carbon black Example can enumerate following such carbon black.
Mitsubishi chemical Co., Ltd's system:MA7,MA8,MA11,MA77,MA100,MA100R,MA100S,MA220,MA230, MA600,MCF88,#5,#10,#20,#25,#30,#32,#33,#40,#44,#45,#47,#50,#52,#55,#650,# 750,#850,#900,#950,#960,#970,#980,#990,#1000,#2200,#2300,#2350,#2400,#2600,# 2650,#3030,#3050,#3150,#3250,#3400,#3600,#3750,#3950,#4000,#4010,OIL7B,OIL9B, OIL11B,OIL30B,OIL31B
Degussa corporations:Printex (registered trademark, same as below) 3, Printex3OP, Printex30, Printex30OP,Printex40,Printex45,Printex55,Printex60,Printex75,Printex80, Printex85,Printex90,Printex A,Printex L,Printex G,Printex P,Printex U,Printex V,PrintexG,SpecialBlack550,SpecialBlack350,SpecialBlack250,SpecialBlack100, SpecialBlack6,SpecialBlack5,SpecialBlack4,Color Black FW1,Color Black FW2, Color Black FW2V,Color Black FW18,Color Black FW18,Color Black FW200,Color Black S160,Color Black S170
Cabot corporations:Monarch (registered trademark, same as below) 120, Monarch280, Monarch460, Monarch800,Monarch880,Monarch900,Monarch1000,Monarch1100,Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, same as below) 99, REGAL99R, REGAL415, REGAL415R,REGAL250,REGAL250R,REGAL330,REGAL400R,REGAL55R0,REGAL660R,BLACK PEARLS480, PEARLS130, VULCAN (registered trademark) XC72R, ELFTEX (registered trademark) -8
Columbian Carbon corporations:RAVEN (registered trademark, same as below) 11, RAVEN14, RAVEN15, RAVEN16,RAVEN22RAVEN30,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
Carbon black can also use the carbon black obtained from resin cladding.Use the carbon black obtained from resin cladding When, have the effect of improving adaptation to glass substrate, volumetric resistivity value.As using resin cladding obtained from carbon black, It can it is preferable to use the carbon blacks etc. described in such as Japanese Unexamined Patent Publication 09-71733 bulletins.From volume resistance, dielectric constant side Face considers, it is preferable to use resin coats carbon black.
As the carbon black for the cladding processing carried out using resin, the total content of preferably Na and Ca are 100ppm or less. Carbon black usually contains the ash content of a few percent, and the composition of the ash content is whole from feedstock oil when manufacture, fuel oil (or gas), reaction The mixed Na and Ca, K, Mg, Al, Fe etc. such as sealing and the stove material of granulation water and reacting furnace.Wherein, Na and Ca are usual Contain hundreds of ppm or more respectively, by reducing Na and Ca, can inhibit being impregnated with to transparent electrode (ITO) and other electrodes, exist It can prevent the tendency of electric short circuit.
As the method for the content for reducing the ash content that these contain Na, Ca, the content pole of stringent selection Na, Ca may be used Few substance as manufacture carbon black when feedstock oil, fuel oil (or gas) and reaction terminating water and strongly reduce for adjust knot The method of the additive amount of the alkaloid substance of structure.As other methods, can enumerate with water, hydrochloric acid etc. to the carbon black made from stove into Row washs and dissolves the method for removing Na, Ca.
Specifically, carbon black mixing is made to be scattered in water, hydrochloric acid or aquae hydrogenii dioxidi, then addition is insoluble in the solvent of water, At this point, carbon black is transferred to solvent side, while being completely separated from the water, the nearly all Na and Ca that are present in carbon black are dissolved in water Or it is removed in acid.In order to which although the total amount of Na and Ca are reduced to 100ppm hereinafter, also having only through individually stringent choosing It has selected the carbon black manufacturing process of raw material or has individually been dissolved in the case where mode that water or acid dissolve can be realized as, but is logical Crossing two ways being applied in combination is easier to make the total amount of Na and Ca for 100ppm or less.
In addition, resin coats the preferred pH6 of carbon black so-called acidic blacks below.Due to dispersion diameter (agglomerate in water Size, agglomerate size) become smaller, or even the cladding under fine unit can be carried out, therefore it is preferred that.More preferable average grain diameter 40nm or less, dibatyl phithalate (DBP) uptake 140ml/100g carbon blacks below.By in above range, to exist Obtain the tendency of the good film of light-proofness.Average grain diameter refers to number average bead diameter, refer to by particle picture parsing find out etc. Circular diameter is imitated, the particle picture parsing is shot with tens thousand of times using electron microscope observation, and what is shot is several The photo in the visual field measures the particle of 2000~3000 or so these photos by image processing apparatus.
The method of the carbon black of spare resin cladding processed is not particularly limited, such as the use level of carbon black and resin is suitable After adjustment, following method can be used:
1. resin and cyclohexanone, toluene, dimethylbenzene equal solvent are mixed and heated dissolving and resin solution is made, by carbon black And water mixes and suspension is made, and above-mentioned resin solution and above-mentioned suspension are mixed, and after so that carbon black is separated from water, removes Water simultaneously carries out heating mixing, obtains composition, is sheet by obtained composition molding, is made it dry after crushing;
2. the resin solution prepared as described above and suspension are mixed, it, will after carbon black and resin spheroidizing Obtained shot-like particle separation, heating, removes the solvent and water of remaining;
3. making the carboxylic acids such as maleic acid, fumaric acid in the solvent of above-mentioned example, adding carbon black and being mixed, make it Solvent is removed after drying, having obtained addition attachment (adding) has the carbon black of carboxylic acid, then adds resin wherein and carries out dry-mixed;
4. the monomer component containing reactive group for constituting resin to be covered is carried out high-speed stirred with water and is prepared Suspension is cooled down after polymerization, and the resin containing reactive group is obtained from polymer suspension, is then added thereto Carbon black is simultaneously kneaded, and makes carbon black and reaction-ity group reaction (carbon black is made to be grafted), then cooled down and crushed;Etc..
The type for carrying out the resin of cladding processing is also not particularly limited, usually synthetic resin, from dispersibility and dispersion From the aspect of stability, preferably further there is the resin of benzene nucleus in the structure, this is because it is as amphoteric surfactant It is with better function.
As specific synthetic resin, phenolic resin, melmac, xylene resin, phthalic acid can be used The thermosetting resins such as diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin and polystyrene, makrolon, Polyethylene terephthalate, polybutylene terephthalate (PBT), Noryl, polysulfones, poly- paraphenylene terephthalamide are to benzene two The heat such as amine, polyamidoimide, polyimides, polyaminobismaleimide, polyether sulfone polyphenylsulfone, polyarylate, polyether-ether-ketone Plastic resin.Resin is 1~30 mass % preferably with respect to the total amount of carbon black and resin to the covering amount of carbon black, by making it be More than above-mentioned lower limiting value, there is the tendency that can form the carbon black fully coated.On the other hand, by making packet of the resin to carbon black The amount of covering is for above-mentioned upper limit value hereinafter, in the presence of the tendency that can prevent the adhesion of resin to each other from making favorable dispersibility.
Coloring interval can be made in the carbon black for carrying out cladding processing using resin in this wise and being formed according to usual way The light screening material of object uses, and can be made by usual way using the coloring spacer as the colour filter of inscape.If Using such carbon black, then existing can be to be realized with a low cost inclining for high shading rate and the low coloring spacer of surface reflectivity To.In addition, by being coated to carbon blacksurface with resin, thus it is speculated that also have the function of Ca, Na being sealing into carbon black.
In addition, other than above-mentioned (a-1) organic pigment, (a-2) carbon black, dyestuff can also be used.As can make For the dyestuff that color material uses, azo dyes, anthraquinone dyes, phthalocyanines dye, quinone imides dyestuff, quinolines can be enumerated Dyestuff, nitro class dyestuff, carbonyl class dyestuff, methchlorenes dyes etc..
As azo dyes, it can be cited for example that:C.I. acid yellow 11, C.I. acid orange 7s, C.I. acid reds 37, C.I. acid red 18 0, C.I. acid blues 29, C.I. directly red 28, C.I. directly red 83, C.I. directly Huang 12, C.I. direct oranges 26, C.I. direct greens 28, C.I. direct greens 59, C.I. active yellows 2, C.I. active reds 17, C.I. active reds 120, C.I. activity Black 5, C.I. disperse oranges 5, C.I. disperse reds 58, C.I. disperse blues 165, C.I. alkali blues 41, C.I. Basic Red 18s, C.I. media Red 7, C.I. media Huang 5, C.I. Mordant Blacks 7 etc..
As anthraquinone dyes, it can be cited for example that:C.I. Vat blue 4, C.I. Acid Blue 40s, C.I. ACID GREEN 25s, C.I. active blue 19, C.I. reactive blue 4s 9, C.I. disperse red 60s, C.I. Disperse Blue-56s, C.I. disperse blue 60s etc..
In addition, as phthalocyanines dye, it can be cited for example that C.I. vat blues 5 etc., as quinone imides dyestuff, Ke Yiju Go out such as C.I. alkali blue 3s, C.I. alkali blues 9, as quinolines dyestuff, it can be cited for example that C.I. solvent yellow 33s, C.I. Quinoline yellow, C.I. dispersion yellow 64s etc., as nitro class dyestuff, it can be cited for example that C.I. Indian yellows 1, C.I. acid oranges 3, C.I. Disperse Yellow 42 etc..
It is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μ that these pigment, which are preferably dispersed into average grain diameter, M or less and use.Here, the benchmark of average grain diameter is the number of pigment particles.
It should be noted that in photosensitive coloring composition, the average grain diameter of pigment is by dynamic light scattering (DLS) The value for measuring and being found out by pigment particle size.Particle size determination (is usually carried out dilute to the photosensitive coloring composition after fully diluting Release and 0.005~0.2 mass % of pigment concentration is made or so, but according to determining instrument and when there is the concentration recommended, it is dense by this Degree) it carries out, and measured at 25 DEG C.
< (b) alkali soluble resins >
(b) used in the present invention alkali soluble resin, without spy as long as the resin comprising carboxyl or hydroxyl It does not limit, it can be cited for example that:Epoxy (methyl) acrylic resin, carboxylic epoxy resin, contains acrylic resin Carbamate resins, novolaks resinoid, polyvinylphenol resinoid of carboxyl etc., wherein preferred epoxy (methyl) Acrylic ester resin, acrylic resin.These can be used alone, or a variety of uses of mixing.
(b) used in the present invention alkali soluble resin particularly preferably uses following from the viewpoint of plate-making property Alkali soluble resin (b1) and/or alkali soluble resin (b2) (hereinafter sometimes referred to " epoxy (methyl) acrylic acid containing carboxyl Ester resin ").
< alkali soluble resins (b1) >
Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, then makes it With alkali soluble resin obtained from polyacid and/or its anhydride reaction.
< alkali soluble resins (b2) >
Make α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester and epoxy resin addition, then makes it With alkali soluble resin obtained from polyalcohol and polyacid and/or its anhydride reaction.
Here, so-called epoxy resin refers to, also including the raw material compound before heat cure forms resin Substance can be used suitable for selection from well known epoxy resin as the epoxy resin.In addition, epoxy resin can make Compound obtained from being reacted with epichlorohydrin with phenolic compounds.As phenolic compounds, the change with phenolic hydroxyl group preferably more than divalent It can also be polymer that conjunction object, which can be monomer,.
As the type of raw material epoxy resin, it is preferable to use cresol novolak type epoxy resin, phenol novolac are clear Paint shaped epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, triphenol methylmethane type epoxy resin, biphenyl phenolic aldehyde are clear Paint shaped epoxy resin, naphthol novolak type epoxy resin, as the sudden reaction object of bicyclopentadiene and phenol or cresols into one Epoxy resin, the epoxy resin containing adamantyl, the fluorenes type epoxy resin of reaction product etc. reacted with epichlorohydrin is walked, it can With suitable for using in this wise in epoxy resin of the main chain with aromatic rings.
In addition, as the concrete example of epoxy resin, it is preferable to use such as bisphenol A type epoxy resin (such as Mitsubishis Learn " Epikote (registered trademark, same as below) 828 ", " Epikote 1001 ", " Epikote of Co., Ltd.'s manufacture 1002 ", " Epikote 1004 " etc.), reacted with epichlorohydrin as the alcoholic extract hydroxyl group of bisphenol A type epoxy resin obtained from epoxidation Object (such as " NER-1302 " (76 DEG C of epoxide equivalent 323, softening point) of Nippon Kayaku K. K's manufacture), bisphenol F type resin It is (such as " Epikote 807 ", " EP-4001 ", " EP-4002 ", " EP-4004 etc. " of Mitsubishi chemical Co., Ltd's manufacture), logical Cross bisphenol f type epoxy resin alcoholic extract hydroxyl group reacted with epichlorohydrin obtained from epoxy resin (such as Nippon Kayaku K. K's system " NER-7406 " (66 DEG C of epoxide equivalent 350, the softening point) made), bisphenol-s epoxy resin, biphenyl glycidol ether (such as three " YX-4000 " of water chestnut Chemical Co., Ltd. manufacture), phenol novolak type epoxy resin (such as Nippon Kayaku K. K's system " EP-152 " of the manufacture of " EPPN-201 " that makes, Mitsubishi chemical Co., Ltd, " EP-154 ", the manufacture of Dow chemical companies " DEN-438 "), (o-, m-, p-) cresol novolak type epoxy resin (such as Nippon Kayaku K. K manufacture " EOCN (registered trademark, same as below) -102S ", " EOCN-1020 ", " EOCN-104S "), isocyanuric acid three-glycidyl ester (such as " TEPIC (registered trademark) " of Misao Kusano's manufacture), (such as the Japanese chemical drug strain of triphenol methylmethane type epoxy resin Formula commercial firm manufacture " EPPN (registered trademark, same as below) -501 ", " EPN-502 ", " EPPN-503 "), ester ring type asphalt mixtures modified by epoxy resin Fat (" Celloxide 2021P ", " Celloxide (registered trademark, the following phase of Daisel chemical industry Co., Ltd's manufacture EHPE " together)), the phenolic resin that generates bicyclopentadiene and reacting for phenol carry out it is glycidated obtained from epoxy Resin (such as " NC-7300 " of " EXA-7200 " of the manufacture of DIC companies, Nippon Kayaku K. K's manufacture), the following general formula (B1)~(B4) epoxy resin etc. indicated.Specifically, the day as epoxy resin shown in the following general formula (B1) can be enumerated " XD-1000 ", the Japanese chemical drug strain formula meeting shown in the following general formula (B2) as epoxy resin of this chemical drug Co., Ltd. manufacture " NC-3000 " of society's manufacture, shown in the following general formula (B4) as the manufacture of Nippon Steel & Sumitomo Metal Corporation of epoxy resin " ESF-300 " etc..
&#91;Chemical formula 5&#93;
In above-mentioned general formula (B1), a indicates average value, indicates 0~10 number, R111Indicate hydrogen atom, halogen atom, carbon atom Arbitrary group in the alkyl of number 1~8, the naphthenic base of carbon atom number 3~10, phenyl, naphthalene or xenyl.It needs to illustrate It is multiple R present in 1 molecule111It can be the same or different.
&#91;Chemical formula 6&#93;
In above-mentioned general formula (B2), b indicates average value, indicates 0~10 number, R121Indicate hydrogen atom, halogen atom, carbon atom Arbitrary group in the alkyl of number 1~8, the naphthenic base of carbon atom number 3~10, phenyl, naphthalene or xenyl.It needs to illustrate It is multiple R present in 1 molecule121It can be the same or different.
&#91;Chemical formula 7&#93;
In above-mentioned general formula (B3), X indicates to link group shown in the following general formula (B3-1) or (B3-2), wherein molecule knot Include 1 or more adamantane structure in structure, c indicates 2 or 3 integer.
&#91;Chemical formula 8&#93;
&#91;Chemical formula 9&#93;
In above-mentioned general formula (B3-1) and (B3-2), R131~R134And R135~R137Separately indicate that optionally there is substitution Adamantyl, hydrogen atom, the optionally alkyl of the carbon atom number 1~12 with substituent group or the optional benzene with substituent group of base Base, * indicate bonding position.
&#91;Chemical formula 10&#93;
In above-mentioned general formula (B4), p and q separately indicate 0~4 integer, R141And R142Separately indicate carbon The alkyl or halogen atom of atomicity 1~4, R143And R144Separately indicate the alkylidene of carbon atom number 1~4, x and y difference Independently indicate 0 or more integer.
, it is preferable to use epoxy resin represented by any of general formula (B1)~(B4) in these.
As α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester can enumerate (methyl) propylene The positions α halogenated alkyl, alkoxy, halogen atom, the nitre of acid, butenoic acid, o-, m- or p- vinyl benzoic acid, (methyl) acrylic acid The monocarboxylic acids such as base, cyano substituent, 2- (methyl) acrylyl oxy-ethyls succinic acid, 2- (methyl) acrylyl oxy-ethyls adipic acid, 2- (methyl) acrylyl oxy-ethyls phthalic acid, 2- (methyl) acrylyl oxy-ethyl hexahydro phthalic acid, 2- (methyl) acryloyl Oxygen ethyl maleic acid, 2- (methyl) acryloxypropyls succinic acid, 2- (methyl) acryloxypropyls adipic acid, 2- (methyl) third Four hydrogen phthalate of alkene monomethacryloxypropyl, 2- (methyl) acryloxypropyls phthalic acid, 2- (methyl) acryloxypropyls Malaysia Acid, 2- (methyl) acryloyl-oxy butyl succinic acid, 2- (methyl) acryloyl-oxy butyl adipic acid, 2- (methyl) acryloyl-oxy butyl Four hydrogen phthalates, 2- (methyl) acryloyl-oxy butyl phthalic acid, 2- (methyl) acryloyl-oxy butyl maleic acid, at (methyl) On acrylic acid monomer obtained from the lactones such as addition 6-caprolactone, beta-propiolactone, gamma-butyrolacton, δ-valerolactone or Addition succinic acid (acid anhydride) on (methyl) hydroxyalkyl acrylates, pentaerythrite three (methyl) acrylate, phthalic acid (acid anhydride), Monomer, (methyl) acrylic acid dimer etc. obtained from the acid such as maleic acid (acid anhydride) (acid anhydrides).
In these, from the aspect of sensitivity, particularly preferably (methyl) acrylic acid.
As the addition α on epoxy resin, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester Method can use well known method.For example, can in the presence of esterification catalyst, at 50~150 DEG C at a temperature of make α, β- Unsaturated monocarboxylic or α with carboxyl, β-unsaturated monocarboxylic ester are reacted with epoxy resin.It is urged as esterification used herein Agent can use tertiary amines, tetramethyl ammonium chloride, the tetrems such as triethylamine, trimethylamine, benzyldimethylamine, 2,4, benzyldiethylamine Quaternary ammonium salts such as ammonium chloride, dodecyl trimethyl ammonium chloride etc..
It should be noted that epoxy resin, α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester, And esterification catalyst may be used alone, can also be used in combination of two or more kinds.
The usage amount of α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester are as follows:Relative to epoxy 1 equivalent of epoxy group of resin, the preferably range of 0.5~1.2 equivalent, the more preferably range of 0.7~1.1 equivalent.α, β-are no When the usage amount of saturation monocarboxylic acid or the α with carboxyl, β-unsaturated monocarboxylic ester is few, the import volume of unsaturated group is insufficient, connects That gets off also becomes inadequate with polyacid and/or reacting for its acid anhydrides.In addition, remaining a large amount of epoxy group nor advantageous 's.On the other hand, when the usage amount is more, α, β-unsaturated monocarboxylic or the α with carboxyl, β-unsaturated monocarboxylic ester be not as Reactant and left behind.The tendency of curing characteristics deterioration is all confirmed in the case of any type.
As polyacid and/or its acid anhydrides, can enumerate selected from maleic acid, succinic acid, itaconic acid, phthalic acid, four Hydrogen phthalic acid, hexahydrophthalic acid, Pyromellitic Acid, trimellitic acid, benzophenone tetrabasic carboxylic acid, hexahydrophthalic acid Methyl esters, endo-methylene group tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, biphenyltetracarboxyacid acid, with And more than one kind or two kinds of acid anhydrides of these acid etc..
It is preferred that maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, The acid anhydrides of benzene tetracarboxylic acid, trimellitic acid, biphenyltetracarboxyacid acid or these acid.Particularly preferred tetrahydrophthalic acid, biphenyltetracarboxyacid acid, Tetrabydrophthalic anhydride or biphenyltetracarboxylic dianhydride.
About the addition reaction of polyacid and/or its acid anhydrides, well known method can be used, can with α, β-unsaturation Monocarboxylic acid or α with carboxyl are continued under the conditions of β-unsaturated monocarboxylic ester is same to the addition reaction of epoxy resin It reacts and obtains object.The addition amount of polyacid and/or its acid anhydrides ingredient preferably makes the carboxylic epoxy (methyl) of generation The acid value of acrylate is degree, further preferably 20~140mgKOH/g as the range of 10~150mgKOH/g Range as degree addition amount.By making the addition amount of polyacid and/or its acid anhydrides ingredient be above-mentioned lower limiting value or more, There are alkali-developables to become good tendency, in addition, by making the addition amount of polyacid and/or its acid anhydrides ingredient be the above-mentioned upper limit Value is hereinafter, there are curing performances to become good tendency.
It should be noted that in the addition reaction of the polyacid and/or its acid anhydrides, can add trimethylolpropane, The polyfunctional alcohols such as pentaerythrite, dipentaerythritol import multiple-branching construction.
Carboxylic epoxy (methyl) acrylate is generally as follows acquisition:To epoxy resin and α, β-unsaturation is single Carboxylic acid or α with carboxyl, in the reactant of β-unsaturated monocarboxylic ester after mixing polyacid and/or its acid anhydrides or To epoxy resin and α, β-unsaturated monocarboxylic or the α with carboxyl are mixed in the reactant of β-unsaturated monocarboxylic ester polynary Acid and/or its acid anhydrides and polyfunctional alcohol heat later.In this case, polyacid and/or its acid anhydrides and polyfunctional alcohol's is mixed Conjunction sequence is not particularly limited.By heating, polyacid and/or its acid anhydrides and it is present in epoxy resin and α, β-unsaturation list carboxylic Arbitrary hydroxyl in acid or the α with carboxyl, β-reactant of unsaturated monocarboxylic ester and the mixture of polyfunctional alcohol carries out Addition reaction.
As carboxylic epoxy (methyl) acrylate South Korea can also be enumerated other than above-mentioned enumerate Carboxylic epoxy (methyl) acrylate described in publication 10-2013-0022955 bulletins.
The polystyrene of carboxylic epoxy (methyl) acrylate measured by gel permeation chromatography (GPC) The weight average molecular weight (Mw) of conversion is usually 1,000 or more, is preferably 1,500 or more, is more preferably 2,000 or more, further Preferably 3,000 or more, still more preferably be 4,000 or more, particularly preferably 5,000 or more, and usually 10,000 with Under, preferably 8,000 or less, more preferably 6,000 or less.If the weight average molecular weight is small, there is the dissolving to developer solution Property the tendency that increases there is the tendency reduced to the dissolubility of developer solution if the weight average molecular weight is big.
The acid value of carboxylic epoxy (methyl) acrylate is not particularly limited, preferably 10mgKOH/g or more, More preferably 20mgKOH/g or more, further preferably 40mgKOH/g or more, still more preferably be 60mgKOH/g or more, Particularly preferably 80mgKOH/g or more, additionally, it is preferred that for 200mgKOH/g or less, more preferably 150mgKOH/g or less, into one Step is preferably 120mgKOH/g or less, particularly preferably 100mgKOH/g or less.By being set as above-mentioned lower limiting value or more, existing can Obtain the deliquescent tendency of suitable development, in addition, by be set as above-mentioned upper limit value hereinafter, in the presence of will not excessively develop so as to With the tendency for inhibiting film to dissolve.
Carboxylic epoxy (methyl) acrylate can be used alone, and can also mix tree of more than two kinds Fat uses.
Alternatively, it is also possible to which a part for foregoing carboxylic epoxy (methyl) acrylate is substituted for it Its adhesive resin and use.That is, can also be by carboxylic epoxy (methyl) acrylate and other adhesive resins It is applied in combination.In this case, it is preferred that by the ratio of carboxylic epoxy (methyl) acrylate in (b) alkali soluble resin Example is set as 50 mass % or more, is more preferably set as 60 mass % or more, is further preferably set as 70 mass % or more, is particularly preferred It is set as 80 mass % or more.
There is no limit for the other adhesive resins that can be applied in combination with carboxylic epoxy (methyl) acrylate, As long as being selected from commonly used resin in photosensitive coloring composition.It can be cited for example that Japanese Unexamined Patent Publication 2007- It is viscous described in No. 271727 bulletins, Japanese Unexamined Patent Publication 2007-316620 bulletins, Japanese Unexamined Patent Publication 2007-334290 bulletins etc. Mixture resin etc..It should be noted that other adhesive resins can be used alone any type, it can also be by two or more group It closes and uses.
In addition, as (b) alkali soluble resin, from from the viewpoint of the compatibility of pigment, dispersant etc., it is preferable to use Acrylic resin of the acrylic resin described in it is preferable to use Japanese Unexamined Patent Publication 2014-137466 bulletins.
As acrylic resin, it can be cited for example that the ethylenically unsaturated monomer with 1 or more carboxyl is (hereinafter, claim For " unsaturated monomer (b1) ") and other ethylenically unsaturated monomers (hereinafter referred to as " unsaturated monomer (b2) ") that can be copolymerized Copolymer.
As unsaturated monomer (b1), it can be cited for example that:(methyl) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid Such unsaturated monocarboxylic;Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, in Unsaturated dicarboxylic as health acid or its acid anhydrides;Hu Posuandan &#91;2- (methyl) Bing Xixianyangjiyizhis &#93;, edicarboxylic acid list &#91;2- (methyl) Bing Xixianyangjiyizhis &#93;The Dan &#91 of such 2 yuan or more of polybasic carboxylic acid;(methyl) Bing Xixianyangjiwanji &#93;Ester; Two ends as ω-carboxy-polycaprolactone list (methyl) acrylate have the list (methyl) third of the polymer of carboxyl and hydroxyl Olefin(e) acid ester;To vinyl benzoic acid etc..
These unsaturated monomers (b1) may be used singly or as a mixture of two or more.
In addition, as unsaturated monomer (b2), it can be cited for example that:
N- substituted maleimide amine as N-phenylmaleimide, N- N-cyclohexylmaleimides;Styrene, α-first Base styrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, to as vinylbenzyl glycidyl base ether, acenaphthylene Aromatic ethenyl compound;
(methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) propylene Sour 2- hydroxy methacrylates, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (methyl) acrylate, polyethylene glycol (degree of polymerization 2~ 10) single (methyl) acrylate of single (methyl) acrylate, polypropylene glycol (degree of polymerization 2~10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, San Huan &#91;5.2.1.02,6&#93;Decane -8- bases (methyl) acrylate, two ring of (methyl) acrylic acid Amylene ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 4- hydroxylphenyl esters, p-Cumenylphenol ethylene oxide change Property (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4- epoxycyclohexanecarboxylates, 3-&#91;(first Base) Bing Xixianyangjijiaji &#93;Oxetanes, 3-&#91;(methyl) Bing Xixianyangjijiaji &#93;As -3- Ethyloxetanes (methyl) acrylate;
Cyclohexyl vinyl ether, isobornyl vinyl ethers, San Huan &#91;5.2.1.02,6&#93;Decane -8- bases vinyl ethers, five rings Vinyl ethers as pentadecyl vinyl ethers, 3- (ethyleneoxy methyl) -3- Ethyloxetanes;Polystyrene, Poly- (methyl) methyl acrylate, poly- (methyl) n-butyl acrylate, polymer molecular chain as polysiloxanes end have The polymeric monomer etc. of single (methyl) acryloyl group.
These unsaturated monomers (b2) may be used singly or as a mixture of two or more.
In the copolymer of unsaturated monomer (b1) and unsaturated monomer (b2), the unsaturated monomer (b1) in the copolymer Copolymerization ratios be preferably 5~50 mass %, more preferably 10~40 mass %.By making unsaturated monomer with such range (b1) it is copolymerized, there is the tendency for the photosensitive coloring composition that can obtain alkali-developable and excellent storage stability.
As the concrete example of unsaturated monomer (b1) and the copolymer of unsaturated monomer (b2), it can be cited for example that Japan is special Open flat 7-140654 bulletins, Japanese Unexamined Patent Publication 8-259876 bulletins, Japanese Unexamined Patent Publication 10-31308 bulletins, Japanese Unexamined Patent Publication Flat 10-300922 bulletins, Japanese Unexamined Patent Publication 11-174224 bulletins, Japanese Unexamined Patent Publication 11-258415 bulletins, Japan are special Open copolymer disclosed in 2000-56118 bulletins, Japanese Unexamined Patent Publication 2004-101728 bulletins etc..
The copolymer of unsaturated monomer (b1) and unsaturated monomer (b2) can be manufactured by well known method, such as Japanese Unexamined Patent Publication 2003-222717 bulletins, Japanese Unexamined Patent Publication 2006-259680 bulletins, International Publication No. 2007/ can be passed through No. 029871 it is equal disclosed in method control its structure, Mw, Mw/Mn.
< (c) Photoepolymerizationinitiater initiaters >
(c) Photoepolymerizationinitiater initiater is directly to absorb light and cause decomposition reaction or hydrogen abstraction reaction, to polymerize with generation The ingredient of the function of living radical.It is additional that polymerization accelerant (chain-transferring agent), sensitizing dyestuff etc. can also be added as needed on Agent uses.
As Photoepolymerizationinitiater initiater, it can be cited for example that Japanese Unexamined Patent Application 59-152396 bulletins, Japanese Unexamined Patent Application 61- The Metallocenic compound for including cyclopentadiene titanium compound described in No. 151197 bulletins;Remember in Japanese Unexamined Patent Publication 2000-56118 bulletins The Hexaarylbiimidazole derivative of load;Halomethylation described in Japanese Unexamined Patent Publication 10-39503 bulletinsOxadiazole derivative, The N- such as halogen methyl Striazine derivative, N- phenylglycines aryl-alpha-amido acids, N- aryl-a-amino acid salt, N- virtues The free radicals activators such as base-a-amino acid esters, alpha-aminoalkyl benzophenone derivatives;Japanese Unexamined Patent Publication 2000-80068 bulletins, Oxime ester derivative etc. described in Japanese Unexamined Patent Publication 2006-36750 bulletins etc..
Specifically, it for example, as luxuriant titanium derivative class, can enumerate:Titanocene dichloride, bicyclopentadiene Base diphenyl titanium, dicyclopentadienyl two (2,3,4,5,6- phenyl-pentafluoride -1- bases) titanium, (2,3,5,6- tetra- of dicyclopentadienyl two Fluorobenzene -1- bases) titanium, dicyclopentadienyl two (2,4,6- trifluoro-benzene -1- bases) titanium, (2,6- difluorobenzenes-the 1- of dicyclopentadienyl two Base) titanium, dicyclopentadienyl two (2,4 difluorobenzene -1- bases) titanium, two (methyl cyclopentadienyl) two (five fluorine of 2,3,4,5,6- Benzene -1- bases) titanium, two (methyl cyclopentadienyl) two (2,6- difluorobenzene -1- bases) titanium, Er Huanwuerxiji &#91;Bis- fluoro- 3- of 2,6- (propyl- 1- yls)-benzene -1- Jis &#93;Titanium etc..
In addition, as diimidazole derivative species, can enumerate:2 aggressiveness of 2- (2 '-chlorphenyl) -4,5- diphenyl-imidazoles, 2- 2 aggressiveness of (2 '-chlorphenyl) -4,5- two (3 '-methoxyphenyl) imidazoles, 2 aggressiveness of 2- (2 '-fluorophenyl) -4,5- diphenyl-imidazoles, 2 aggressiveness of 2- (2 '-methoxyphenyl) -4,5- diphenyl-imidazoles, 2 aggressiveness of (4 '-methoxyphenyl) -4,5- diphenyl-imidazoles etc..
In addition, as halomethylationOxadiazole derivative can be enumerated:2- trichloromethyls -5- (2 '-benzofuranyl) - 1,3,4-Diazole, 2- trichloromethyls -5-&#91;β-(2 '-benzofuranyl) Yi Xiji &#93;-1,3,4-Diazole, 2- trichloromethyls- 5-&#91;β-(2 '-(6 "-benzofuranyl) vinyl) &#93;-1,3,4-Diazole, 2- trichloromethyl -5- furyls -1,3,4-Two Azoles etc..
In addition, as halogen methyl Striazine derivative class, can enumerate:Bis- (three chloromethanes of 2- (4- methoxyphenyls) -4,6- Base) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- methoxyl groups naphthalene) -4,6-, 2- (4- ethoxynaphthyls) -4,6- bis- (three Chloromethyl) s-triazine, bis- (trichloromethyl) s-triazine of 2- (4- carbethoxyl groups naphthalene) -4,6- etc..
In addition, as alpha-aminoalkyl benzophenone derivatives class, can enumerate:2- methyl-1s-&#91;4- (methyl mercapto) Ben Jis &#93;-2- Morpholinopropane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butanone -1,2- benzyl -2- dimethylaminos Base -1- (4- morpholino phenyls) butane -1- ketone, 4- dimethyl aminoethyls benzoic ether, 4- dimethylamino isoamyl benzene first Acid esters, 4- diethyl aminos benzoylformaldoxime, 4- dimethylaminos propiophenone, 2- ethylhexyl -1,4- dimethyl aminobenzoates, Bis- (the 4- diethylaminos benzal) cyclohexanone of 2,5-, 7- diethylaminos -3- (4- diethylaminos benzoyl) cumarin, 4- (diethylamino) chalcone etc..
As Photoepolymerizationinitiater initiater, especially from sensitivity, plate-making property this point from the point of view of, oxime ester compound be it is effective, The case where using alkali soluble resin comprising phenolic hydroxyl group etc., is unfavorable in terms of sensitivity, and therefore, such sensitivity is excellent Oxime ester compound is particularly useful.
As oxime ester compound, it can be cited for example that the oxime esters described in International Publication No. 2008/075564 In oxime ester compound, Japanese Unexamined Patent Publication 2011-132215 bulletins described in conjunction object, International Publication No. 2009/131189 Oxime ester compound, Japan's spy's table described in the oxime ester compound of record, International Publication No. 2008/078678 Oxime ester compound etc. described in 2014-500852 bulletins.
Photoepolymerizationinitiater initiater may be used alone, can also be used in combination of two or more kinds.
In order to improve induction sensitivity, it can coordinate in Photoepolymerizationinitiater initiater as needed and correspond to image exposure light source Wavelength sensitizing dyestuff, polymerization accelerant.As sensitizing dyestuff, can enumerate:Japanese Unexamined Patent Publication 4-221958 bulletins, day Xanthene pigment, Japanese Unexamined Patent Publication 3-239703 bulletins, Japanese Unexamined Patent Publication 5- described in this Unexamined Patent 4-219756 bulletins The cumarin pigment with heterocycle, Japanese Unexamined Patent Publication 3-239703 bulletins described in No. 289335 bulletins, Japanese Unexamined Patent Publication The methylene described in 3- oxos coumarin compound, Japanese Unexamined Patent Publication 6-19240 bulletins described in 5-289335 bulletins Lanaurin and Japanese Unexamined Patent Application 47-2528 bulletins, Japanese Unexamined Patent Application 54-155292 bulletins, Japanese Patent Publication 45- No. 37377 bulletins, Japanese Unexamined Patent Application 48-84183 bulletins, Japanese Unexamined Patent Application 52-112681 bulletins, Japanese Unexamined Patent Application 58- No. 15503 bulletins, Japanese Unexamined Patent Application 60-88005 bulletins, Japanese Unexamined Patent Application 59-56403 bulletins, Japanese Unexamined Patent Publication 2-69 Number bulletin, Japanese Unexamined Patent Application 57-168088 bulletins, Japanese Unexamined Patent Publication 5-107761 bulletins, Japanese Unexamined Patent Publication 5-210240 The pigment etc. with dialkyl amido benzene skeleton described in number bulletin, Japanese Unexamined Patent Publication 4-288818 bulletins.
In these sensitizing dyestufves, preferably amino-containing sensitizing dyestuff more preferably has ammonia in same intramolecular The compound of base and phenyl.Particularly preferred such as 4,4 '-dimethylamino benzophenones, 4,4 '-diethylamino benzophenone, 2- aminobenzophenones, 4- aminobenzophenones, 4,4 '-diaminobenzophenones, 3,3 '-diaminobenzophenones, 3,4- bis- The benzophenone compounds such as aminobenzophenone;2- (to dimethylaminophenyl) benzoAzoles, 2- are (to diethylamino benzene Base) benzoAzoles, 2- (p- dimethylaminophenyls) Ben Bing &#91;4,5&#93;BenzoAzoles, 2- (to dimethylaminophenyl) benzo &#91;6,7&#93;BenzoBis- (to diethylamino the phenyl) -1,3,4- of azoles, 2,5-Azoles, 2- (to dimethylaminophenyl) benzo thiophene Azoles, 2- (to diethylamino phenyl) benzothiazole, 2- (to dimethylaminophenyl) benzimidazole, 2- are (to diethylamino Phenyl) benzimidazole, bis- (p- diethylamino the phenyl) -1,3,4- thiadiazoles of 2,5-, (to dimethylaminophenyl) pyridine, (to diethylamino phenyl) pyridine, (to dimethylaminophenyl) quinoline, (to diethylamino phenyl) quinoline, (to diformazan Base aminophenyl) pyrimidine, (to diethylamino phenyl) pyrimidine etc. contain the compound etc. to dialkylaminophenyl.Wherein, Most preferably 4,4 '-dialkyl amido benzophenone.
One kind can also be used alone in sensitizing dyestuff, or combines two or more use.
As polymerization accelerant, such as ESCAROL 507 ethyl, benzoic acid 2- dimethylaminoethyls can be used The aliphatic amines such as the aromatic amines such as ester, n-butylamine, N methyldiethanol amine, the sulfhydryl compound described below etc..Polymerization promotes Agent may be used alone, can also be used in combination of two or more kinds.
< (d) olefinic unsaturated compounds >
The photosensitive coloring composition of the present invention includes (d) olefinic unsaturated compound.By including (d) olefinic unsaturation Compound, sensitivity improve.
The olefinic unsaturated compound used in the present invention is the chemical combination that intramolecular has at least one ethylenically unsaturated group Object.Specifically, it can be cited for example that (methyl) acrylic acid, (methyl) alkyl acrylate, acrylonitrile, styrene and have 1 The monoesters etc. that the carboxylic acid of ethylenic unsaturated bond is formed with polyalcohol or monohydric alcohol.
In the present invention, particularly preferably using the multifunctional olefinic with 2 or more ethylenically unsaturated groups in 1 molecule Monomer.The number of ethylenically unsaturated group possessed by multifunctional olefinic type monomers is not particularly limited, usually 2 or more, excellent It is selected as 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less.Under being set as above-mentioned More than limit value, exist with highly sensitive tendency, by being set as above-mentioned upper limit value hereinafter, being carried in the presence of dissolubility in a solvent High tendency.
As the example of multifunctional olefinic type monomers, it can be cited for example that:Aliphatic polyhydroxy compound and unsaturated carboxylic acid The ester of formation;The ester that aromatic polyhydroxy compounds are formed with unsaturated carboxylic acid;Pass through aliphatic polyhydroxy compound, aromatic series The polyols such as polyol and ester obtained from the esterification of unsaturated carboxylic acid and polybasic carboxylic acid etc..
As the ester that above-mentioned aliphatic polyhydroxy compound and unsaturated carboxylic acid are formed, ethylene glycol diacrylate can be enumerated Ester, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, methylolethane triacrylate, pentaerythrite Diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, two seasons penta The acrylic acid of the aliphatic polyhydroxy compounds such as five acrylate of tetrol, dipentaerythritol hexaacrylate, glyceryl acrylate The acrylate of these example compounds is replaced with methacrylate obtained from methacrylate, similarly replaced by ester It is changed to itaconate obtained from itaconate, replace with butenoate obtained from butenoate or replaces with maleate Obtained from maleate etc..
As the ester that aromatic polyhydroxy compounds and unsaturated carboxylic acid are formed, hydroquinone diacrylate can be enumerated Ester, hydroquinone dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate, 1,2,3- benzene Acrylate and methacrylate of the aromatic polyhydroxy compounds such as triphenol triacrylate etc..
As the ester as obtained from the esterification of polybasic carboxylic acid and unsaturated carboxylic acid and polyol, it is not necessary to be Single substance can enumerate the condensation of acrylic acid, phthalic acid and ethylene glycol if enumerating its representative specific example Object;The condensation product of acrylic acid, maleic acid and diethylene glycol;The condensation product of methacrylic acid, terephthalic acid (TPA) and pentaerythrite;Third The condensation product etc. of olefin(e) acid, adipic acid, butanediol and glycerine.
In addition, the example of multifunctional olefinic type monomers used in the present invention, polyisocyanate compound and hydroxyl (methyl) acrylate or (methyl) acrylate reactions of polyisocyanate compound and polyalcohol and hydroxyl and obtain Carbamate (methyl) esters of acrylic acid arrived;Polynary epoxide and hydroxyl (methyl) acrylate or (methyl) propylene Epoxy Acrylates as the addition reaction of acid;The acrylic amides such as ethylenebisacrylamide;Phthalic acid two The allyls esters such as allyl ester;The compound etc. containing vinyl such as phthalic acid divinyl base ester.
As above-mentioned carbamate (methyl) esters of acrylic acid, it can be cited for example that:DPHA-40H,UX-5000,UX- 5002D-P20, UX-5003D, UX-5005 (Nippon Kayaku K. K's manufacture), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong), UA-306H, UA-510H, UF-8001G (the Chemical Co., Ltd. manufacture of Xie Rong societies), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (Japan's synthesis Chemical Co., Ltd. manufactures) etc..
In these, from the viewpoint of curability, as (d) olefinic unsaturated compound, it is preferable to use (methyl) third Olefin(e) acid Arrcostab more preferably uses dipentaerythritol hexaacrylate.
They may be used alone, can also be used in combination of two or more kinds.
< (e) solvents >
The photosensitive coloring composition of the present invention includes (e) solvent.By the way that comprising (e) solvent, pigment can be scattered in In solvent, and it is coated with and becomes easy.
The photosensitive coloring composition of the present invention is usually to draw (a) colorant, (b) alkali soluble resin, (c) photopolymerization Hair agent, (d) olefinic unsaturated compound, (f) dispersant and various other materials used as needed are dissolved or dispersed in molten State in agent uses.In solvent, from the viewpoint of dispersibility, coating, preferable organic solvent.
In organic solvent, from the viewpoint of coating, the solvent that boiling point is 100~300 DEG C of ranges is preferably selected, More preferably select boiling point for the solvent of 120~280 DEG C of ranges.It should be noted that boiling point mentioned here refers in pressure Boiling point under 1013.25hPa.
As such organic solvent, for example, solvent below.
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, the third two Alcohol list ether, propylene glycol mono-n-butyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list N-butyl ether, methoxy amylalcohol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3- methyl -3- methoxybutanols, three second Glycol monomethyl ether, Triethylene glycol ethyl ether, glycol monoalkyl ethers as tripropylene glycol methyl ether;
Glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, dibutyl ethylene glycol ether, glycol dialkyl ether class as dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol mono-n-butyl ether acetic acid esters, propylene glycol list first Ether acetic acid ester, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, propylene glycol monobutyl ether acetic acid esters, methoxybutyl Acetic acid esters, 3- methoxybutyls acetic acid esters, methoxypentyl acetic acid esters, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol list second Ether acetic acid ester, diethylene glycol mono-n-butyl ether acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, triethylene glycol monomethyl ether acetic acid esters, three Glycol alkyl ether acetate esters as ethylene glycol monoethylether acetate, 3- methyl -3- methoxybutyl acetic acid esters;
The glycol diacetates classes such as ethylene acetate, 1,3 butylene glycol diacetate esters, 1,6-HD diacetate esters;
The alkyl acetates class such as cyclohexyl acetate;
Amyl ether, ether, dipropyl ether, Di Iso Propyl Ether, dibutyl ethers, diamyl ether, ethyl isobutyl ether, hexyl ether Such ethers;
Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl Ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, ethylpentyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy Ketone as pentanone;
Ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, three Ethylene glycol, methoxy amylalcohol, glycerine, monohydric alcohol or polyalcohols as benzylalcohol;
Pentane, normal octane, diisobutylene, n-hexane, hexene, isoprene, cinene, aliphatic as dodecane Hydro carbons;
Hexamethylene, hexahydrotoluene, methylcyclohexene, ester ring type hydro carbons as bicyclohexyl;
It is aromatic hydrocarbon as benzene,toluene,xylene, isopropylbenzene;
Amyl formate, Ethyl formate, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, second two Alcohol acetic ester, ethyl propionate, propyl propionate, butyl butyrate, isobutyl isobutyrate (IBIB), methyl isobutyrate, ethyl caprate, stearic acid fourth Ester, ethyl benzoate, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates, 3- methoxypropionic acids Ethyl ester, 3- methoxy propyls propyl propionate, 3- methoxy propyls acid butyl ester, chain as gamma-butyrolacton or cyclic annular esters;
Alkoxy carboxylic acids as 3- methoxypropionic acids, 3- ethoxy-propionic acids;
Halogenated hydrocarbon as chlorobutane, chloropentane;
Ether ketone as methoxy pentanone;
Nitrile etc. as acetonitrile, benzonitrile.
As above-mentioned commercially available organic solvent is equivalent to, can enumerate:Mineral spirits (Mineral spirit), Varsol#2, Apco#18solvent, Apco thinner, Socal solvent No.1 and No.2, Solvesso #150, Shell TS28solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (" cellosolve (cellosolve) " be registered trademark, it is same as below), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetic acid Ester, diethylene glycol dimethyl ether (diglyme) (above-mentioned is trade name) etc..
These organic solvents may be used alone or in combination of two or more kinds.
In the case of forming coloring spacer with photoetching process, as organic solvent, it is 100~200 DEG C to preferably select boiling point The organic solvent of (under the conditions of pressure 1013.25hPa, hereinafter, about boiling point all same) range.More preferably there are 120~170 DEG C Boiling point organic solvent.
In above-mentioned organic solvent, constituent good from the harmony of coating, surface tension etc., in composition it is molten From the aspect of Xie Du higher, preferred diol alkylether acetates class.
In addition, glycol alkyl ether acetate esters can be used alone, can also be used with other organic solvent combinations.As The organic solvent being applied in combination, particularly preferably glycol monoalkyl ethers.Wherein, from the dissolving of the constituent in composition Property consider, particularly preferred propylene glycol monomethyl ether.It should be noted that the polarity of glycol monoalkyl ethers is high, if its additive amount Excessively, then there is pigment to be easy cohesion and the viscosity of the colored resin composition obtained thereafter is made the storage stabilities decline such as to rise Tendency, therefore, the ratio of the glycol monoalkyl ethers in solvent is preferably the 5 mass % of mass %~30, more preferably 5 matter Measure the mass of %~20 %.
It is also preferable to organic solvent (hereinafter, sometimes referred to as " high boiling solvent ") group with 150 DEG C or more boiling points It closes and uses.By being applied in combination with such high boiling solvent, although photosensitive coloring composition becomes difficult to drying, have The effect for preventing the uniform dispersity of the pigment in the case where drastically drying in composition to be destroyed.That is, with for example Prevent from generating the effect of foreign matter defect because of the precipitation of color material etc., solidification in slit spray nozzle front end.In terms of such effect is high Consider, in above-mentioned various solvents, particularly preferred diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetic acid esters and diethyl 2-ethoxyethanol acetic acid esters.
The content ratio of high boiling solvent is preferably the 3 mass % of mass %~50, more preferably 5 mass % in organic solvent ~40 mass %, particularly preferably 5 mass of mass %~30 %.More than for above-mentioned lower limiting value, existing can inhibit for example The tendency of foreign matter defect is generated because of the precipitation of color material etc., solidification in slit spray nozzle front end, in addition, by for above-mentioned upper limit value with Under, it can be slack-off with the drying temperature of composite inhibiting, to which presence can inhibit the productive temp for being dried under reduced pressure technique bad, pre- Bake the tendency of the pin hole this problem of (pre-bake).
It should be noted that the high boiling solvent of 150 DEG C of boiling point or more can be glycol alkyl ether acetate esters, in addition Can be glycol alkyl ether class, in this case, high boiling solvent that can not also be in addition containing 150 DEG C of boiling point or more.
As preferred high boiling solvent, it can be cited for example that the diethylene glycol mono-n-butyl ether acetic acid in above-mentioned various solvents Ester, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1,3 butylene glycol diacetate esters, 1,6-HD two Acetic acid esters, glycerol triacetate etc..
< (f) dispersants >
In the photosensitive coloring composition of the present invention, due to making (a) colorant imperceptibly disperse and making its dispersity It stabilizes for ensuring that quality stability is important, therefore contains (f) dispersant.
As (f) dispersant, preferably there is the macromolecule dispersing agent of functional group, in addition, from the aspect of dispersion stabilization, It is preferred that having carboxyl;Phosphate;Sulfonic group;Or their alkali;Primary amino group, secondary amino group or tertiary amino;Quaternary ammonium salt base;From pyrrole The macromolecule dispersing agent of the functional groups such as the nitrogenous heterocyclic group such as pyridine, pyrimidine, pyrazine.Wherein, especially from when disperseing pigment From the viewpoint of capable of being disperseed with a small amount of dispersant, particularly preferably there is primary amino group, secondary amino group or tertiary amino;Quaternary ammonium salt Base;From the macromolecule dispersing agent of the basic functionalities such as the nitrogenous heterocyclic group such as pyridine, pyrimidine, pyrazine.
In addition, as macromolecule dispersing agent, it can be cited for example that:Carbamates dispersant, acrylic dispersants, Dispersant, the polyoxy that polyethyleneimine amine dispersant, polyallyl amine dispersant, the monomer with amino are formed with polymeric monomer Vinyl alkyl ethers dispersant, two esters dispersant of polyoxyethylene, polyethers phosphoric acid class dispersant, polyester phosphoric acid class dispersant, mountain Pears sugar alcohol acid anhydride aliphatic ester dispersant, aliphatic modified polyesters dispersant etc..
As the specific example of such dispersant, trade name EFKA (registered trademark, BASF AG's system can be enumerated Make), DISPERBYK (registered trademark, BYK-Chemie companies manufacture), Disparlon (registered trademark, nanmu this chemical conversion strain formula meeting Society manufactures), SOLSPERSE (registered trademark, Lubrizol companies manufacture), KP (Shin-Etsu Chemial Co., Ltd's manufacture), Polyflow (Kyoeisha Chemical Co., Ltd.'s manufacture), Ajisper (registered trademark, Ajincomoto Co., Inc's manufacture) etc..
These macromolecule dispersing agents can be used alone, or combine two or more use.
The weight average molecular weight (Mw) of macromolecule dispersing agent is usually 700 or more, preferably 1000 or more, and is usually 100,000 hereinafter, preferably 50, and 000 or less.
In these, from the viewpoint of pigment-dispersing, (f) dispersant preferably comprises the carbamic acid with functional group Esters macromolecule dispersing agent and/or acrylic polymer dispersant particularly preferably include acrylic polymer dispersant.
In addition, from the aspect of dispersibility, keeping quality, preferably with basic functionality and with polyester key and/or polyethers The macromolecule dispersing agent of key.
As carbamates and acrylic polymer dispersant, it can be cited for example that DISPERBYK 160~ 166,182 serial (they being carbamates), DISPERBYK2000,2001, LPN21116 etc. (being acrylic compounds) (with On be BYK-Chemie companies manufacture).
If specifically preferred chemical constitution of the example as carbamates macromolecule dispersing agent, can enumerate example Chemical combination such as by making the number-average molecular weight 300~10,000 of polyisocyanate compound, intramolecular with 1 or 2 hydroxyl Object and same intramolecular have weight average molecular weight 1,000~200,000 obtained from the reaction of the compound of active hydrogen and tertiary amino Dispersion resin etc..By being handled above-mentioned dispersion resin with the level Four such as benzyl chloride agent, the whole of tertiary amino can be made Or a part is changed into quaternary ammonium salt base.
As the example of above-mentioned polyisocyanate compound, can enumerate:Paraphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- bis- are different Cyanate, Toluene-2,4-diisocyanate, 6- diisocyanate, 4,4 '-methyl diphenylene diisocyanates, naphthalene -1,5- diisocyanate, ditolyl The aromatic diisocyanates such as amine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4- The aliphatic diisocyanates such as trimethyl hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate Ester, 4,4 '-di-2-ethylhexylphosphine oxides (cyclohexyl isocyanate), ω, alicyclic two isocyanide such as ω '-diisocyanate dimethyl cyclohexanes Acid esters, xylylene diisocyanate, α, α, α ', α '-tetramethyl xylylene diisocyanates etc. have the fat of aromatic rings (cyclo) aliphatic diisocyanates, lysine ester triisocyanate, hendecane -1,6,11- triisocyanates, 1,8- diisocyanate -4- Isocyanatomethyl octane, hexa-methylene -1,3,6- triisocyanates, bicycloheptane triisocyanate, triphenyl methane three are different The triisocyanates such as cyanate, D2EHDTPA triphenyl triisocyanate and their tripolymer, hydride and they Polyalcohol addition product etc..As polyisocyanates, the preferably tripolymer of organic diisocyanate, most preferably toluene The tripolymer of diisocyanate and the tripolymer of isophorone diisocyanate.They can be used alone, and can also combine Two or more is used.
The manufacturing method of tripolymer as isocyanates can enumerate following method:Use trimerization catalyst appropriate Agent carries out isocyanide such as tertiary amines, phosphine, alkoxide species, metal oxide, metal carboxylate to above-mentioned polyisocyanates The trimerizing of the part of perester radical makes trimerizing terminate, is then removed with solvent extraction, thin-film distillation by adding catalyst poison Unreacted polyisocyanates is removed, to obtain the polyisocyanates containing cyamelide ester group of target.
It, can be with as the compound of the number-average molecular weight 300~10,000 in same intramolecular with 1 or 2 hydroxyl Enumerate polyether Glycols, polyester diol, polycarbonate glycol, polyolefin dihydric alcohol etc. and the side of these compounds Substance and the mixture of more than two kinds in them obtained from alkyl alkoxide of the terminal hydroxyl by carbon atom number 1~25.
As polyether Glycols, polyetherdiol, polyethers esterdiol and their mixture of more than two kinds can be enumerated. As polyetherdiol, can enumerate will substance obtained from oxidation polyamino alkenyl or copolymerization, such as it is polyethylene glycol, polypropylene glycol, poly- Ethylene glycol propylene glycol, polyoxy butylen glycol, polyoxy hexylidene glycol, polyoxy octamethylene glycol and the of more than two kinds of theirs mix Close object.
As polyethers esterdiol, can enumerate by make the glycol containing ether or with the mixture and dicarboxyl of other glycol Acid or their anhydride reaction or substance obtained from making oxyalkylene be reacted with polyester-diol, such as poly- (polyoxy butylidene) Adipate ester etc..As polyetherdiol, most preferably polyethylene glycol, polypropylene glycol, polyoxy butylen glycol or these chemical combination Compound made of alkyl alkoxide of the side end hydroxyl of object by carbon atom number 1~25.
As polyester-diol, can enumerate:Dicarboxylic acids (succinic acid, glutaric acid, adipic acid, decanedioic acid, fumaric acid, Malaysia Acid, phthalic acid etc.) or their acid anhydrides and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, three Propylene glycol, 1,2- butanediols, 1,3 butylene glycol, 1,4- butanediols, 2,3- butanediols, 3- methyl-1s, 5- pentanediols, new penta 2 Alcohol, 2- methyl-1,3-propanediols, 2- methyl-2-propyl -1,3- propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,5- penta Glycol, 1,6-HD, 2- methyl -2,4-PD, 2,2,4- trimethyl -1,3- pentanediols, 2- ethyl -1,3- hexylene glycols, 2,5- dimethyl -2,5-HD, 1,8- ethohexadiols, 2- methyl-1s, it is the aliphatic diols such as 8- ethohexadiols, 1,9- nonanediols, double Aromatic diols, the N- methyl diethanols such as the alicyclic diols such as (methylol) hexamethylene, benzene dimethanol, bis- (hydroxyl-oxethyl) benzene N- alkyl dialkanol amines such as amine etc.) substance obtained from polycondensation, such as polyethylene glycol adipate, poly adipate succinic acid ester, Polyadipate 1,6- hexylene glycols ester, polyadipate ethylene glycol propylene glycol ester etc., or using above-mentioned glycols or carbon atom number 1~ 25 monohydric alcohol is as polylactone diol obtained from initiator or polylactone monohydric alcohol, such as polycaprolactone glycol, poly- methyl Valerolactone and their mixture of more than two kinds.As polyester-diol, most preferably polycaprolactone glycol or with carbon atom number 1~25 alcohol is the polycaprolactone that initiator obtains.
As polycarbonate glycol, poly- carbonic acid (1,6- hexylene glycol) ester, poly- carbonic acid (3- methyl-1s, 5- penta 2 can be enumerated Alcohol) ester etc. can enumerate the poly- isoamyl of polybutadiene diol, hydrogenation type polybutadiene diol, hydrogenation type two as polyolefin diols Enediol etc..
They may be used alone, can also be used in combination of two or more kinds.
It is usually 300~10,000 that same intramolecular, which has the number-average molecular weight of the compound of 1 or 2 hydroxyl, preferably It is 500~6,000, more preferably 1,000~4,000.
In same intramolecular there is the compound of active hydrogen and tertiary amino to illustrate to being used in the present invention.
As hydrogen atom of active hydrogen, the i.e. Direct Bonding on oxygen atom, nitrogen-atoms or sulphur atom, can enumerate hydroxyl, Hydrogen atom in the functional groups such as amino, sulfydryl, wherein the hydrogen atom of preferred amino, particularly primary amino group.
Tertiary amino is not particularly limited, it can be cited for example that the amino or heterocycle of the alkyl with carbon atom number 1~4 Structure, more specifically imidazole ring or triazole ring etc..
If the such compound in same intramolecular with active hydrogen and tertiary amino of example, can enumerate N, N- bis- Methyl-1,3- propane diamine, N, N- diethyl -1,3- propane diamine, N, N- dipropyl -1,3- propane diamine, N, N- dibutyl -1,3- third Diamines, N, N- dimethyl-ethylenediamines, N, N- diethyl ethylenediamines, 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, the nitrogen heterocyclic ring in the case of being nitrogen heterocyclic ring structure as tertiary amino, can enumerate:Pyrazole ring, miaow Azoles ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoAzoles ring, benzo Nitrogenous 5 circle heterocyclic ring such as thiazole ring, diazosulfide ring, it is pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, different Nitrogenous 6 circle heterocyclic ring such as quinoline ring.In these nitrogen heterocyclic rings, preferably imidazole ring or triazole ring.
If these compounds with imidazole ring and amino of specific example can enumerate 1- (3- aminopropyls) miaow Azoles, histidine, 2- aminooimidazoles, 1- (2- amino-ethyls) imidazoles etc..In addition, if specific example these with triazole ring and ammonia The compound of base, then can enumerate 3- amino-1,2,4-triazoles, 5- (2- amino -5- chlorphenyls) -3- phenyl -1H-1, and 2,4- tri- Azoles, 4- amino -4H-1,2,4- triazole -3,5- glycol, 3- amino-5-phenyl -1H-1,3,4- triazoles, 5- amino -1,4- hexichol Base -1,2,3- triazoles, 3- amino -1- benzyl -1H-2,4- triazoles etc..Wherein, preferably N, N- dimethyl -1,3- propane diamine, N, N- Diethyl -1,3- propane diamine, 1- (3- aminopropyls) imidazoles, 3- amino -1,2,4- triazoles.
They can be used alone, or combine two or more use.
The optimizing mixing proporiton rate of raw material is as follows when manufacturing carbamates macromolecule dispersing agent:Relative to polyisocyanates 100 mass parts of compound in same intramolecular there is the compound of number-average molecular weight 300~10,000 of 1 or 2 hydroxyl to be 10~200 mass parts, preferably 20~190 mass parts, more preferably 30~180 mass parts have active in same intramolecular The compound of hydrogen and tertiary amino is 0.2~25 mass parts, preferably 0.3~24 mass parts.
Known method that the manufacture of carbamates macromolecule dispersing agent is manufactured according to polyurethane resin carries out.As Solvent when manufacture, usually using ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclohexanone, isophorones;Second The esters such as acetoacetic ester, butyl acetate, cellosolve acetate;The hydro carbons such as benzene,toluene,xylene, hexane;It is diacetone alcohol, isopropanol, secondary The chloro things such as the parts such as butanol, tert-butyl alcohol alcohols, dichloromethane, chloroform;The ethers such as tetrahydrofuran, ether;Dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide isopolarity aprotic solvent etc..They can be used alone, or combination 2 kinds with Upper use.
In above-mentioned manufacture, usually using urethane catalysts.As the catalyst, it can be cited for example that Tin system, the acetylacetone,2,4-pentanediones such as dibutyltin dilaurate, dioctyl tin dilaurate, dibutyl tin dicaprylate, tin octoate Tertiary amines such as the iron such as iron, iron chloride system, triethylamine, triethylenediamine etc..They can be used alone, or combination 2 kinds with Upper use.
It is preferably to control the amine value after reaction that same intramolecular, which has the import volume of the compound of active hydrogen and tertiary amino, In the amount of 1~100mgKOH/g ranges, more preferably amount of the control in 5~95mgKOH/g ranges.Amine value is with acid to basic amine group Carry out acid-base titration, the value corresponding with acid value indicated with the mg numbers of KOH.When amine value is less than above range, there are dispersion energy The tendency that power declines, in addition, if it exceeds above range, then developability is easily reduced.
It should be noted that in above reaction in macromolecule dispersing agent in the case of remaining isocyanate group, if Isocyanate group further is destroyed with alcohol, amino-compound, then the ageing stability of product is got higher, therefore preferably.
The weight average molecular weight (Mw) of carbamates macromolecule dispersing agent is usually 1,000~200,000, preferably 2, 000~100,000, more preferably 3,000~50,000 range.When the molecular weight is less than 1,000, dispersibility and stably dispersing Property is poor, if it exceeds 200,000, then decreased solubility, the control of bad dispersibility, simultaneous reactions becomes difficult.
As acrylic polymer dispersant, it is preferable to use (functional group mentioned here is as height with functional group The functional group that functional group contained in dispersal agent molecule describes in front) and monomer containing unsaturated group with do not have function Random copolymer, graft copolymer, the block copolymer that group but monomer containing unsaturated group are formed.These copolymers can be with It is manufactured with well known method.
As the monomer with functional group and containing unsaturated group, (methyl) acrylic acid, 2- (methyl) third can be enumerated Alkene acyloxyethyl succinic acid, 2- (methyl) acrylyl oxy-ethyls phthalic acid, 2- (methyl) acrylyl oxy-ethyl hexahydrobenzene diformazan Acid, acrylic acid dimer etc. have unsaturated monomer, dimethyl aminoethyl (methyl) acrylate, the diethylamino of carboxyl Ethyl (methyl) acrylate and their quaternaries etc. have tertiary amino, quaternary ammonium salt base unsaturated monomer as concrete example. They can be used alone, or combine two or more use.
As the monomer without functional group but containing unsaturated group, (methyl) methyl acrylate, (first can be enumerated Base) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, (methyl) tert-butyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid Cyclohexyl, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid phenoxy group methyl esters, (methyl) 2-EHA, (methyl) isobornyl acrylate, (methyl) acrylic acid tricyclodecyl, (methyl) tetrahydrofurfuryl acrylate, N- ethenyl pyrrolidones Ketone, Styrene and its derivatives, α-methylstyrene, N- N-cyclohexylmaleimides, N-phenylmaleimide, N- benzyl horses Come the N- substituted maleimides such as acid imide amine, acrylonitrile, vinyl acetate and poly- (methyl) methyl acrylate polymeric monomer, polyphenyl second Alkene polymeric monomer, polyethylene glycol polymeric monomer, polypropylene glycol polymeric monomer, gathers in oneself poly- (methyl) acrylic acid 2- hydroxy methacrylates polymeric monomer Polymeric monomers such as ester polymeric monomer etc..They can be used alone, or combine two or more use.
Acrylic polymer dispersant particularly preferably by with functional group A blocks with without functional group B block A-B the or B-A-B block copolymers of composition, at this point, above-mentioned comprising functional group and containing unsaturated group in addition to deriving from A blocks Other than the part-structure of the monomer of group, it can also contain and not include functional group but the monomer containing unsaturated group from above-mentioned Part-structure, these structures in the A blocks can by random copolymerization or block copolymerization it is arbitrary in the form of contain.In addition, Content of the part-structure without functional group in A blocks is usually 80 mass % hereinafter, preferably 50 mass % are hereinafter, more excellent It is selected as 30 mass % or less.
B block includes the part-structure without functional group but the monomer containing unsaturated group from above-mentioned, in 1 B Can contain the part-structure from two or more monomer in block, these structures in the B block can with random copolymerization or Any form of block copolymerization contains.
Living polymerization as shown below for example can be used to prepare in A-B the or B-A-B block copolymers.
Living polymerization includes living anion polymerization method, anion living polymerization method, radical living polymerization method, In, the polymerization activity kind of living anion polymerization method is anion, such as is indicated by following synthetic routes.
&#91;Chemical formula 11&#93;
In said synthesis route, Ar1For 1 valence organic group, Ar2To be different from Ar11 valence organic group, M is that metal is former Son, s and t are respectively 1 or more integer.
The polymerization activity kind of radical living polymerization method is free radical, such as is indicated by following synthetic routes.
&#91;Chemical formula 12&#93;
In said synthesis route, Ar1For 1 valence organic group, Ar2To be different from Ar11 valence organic group, j and k are respectively 1 or more integer, RaFor hydrogen atom or 1 valence organic group, RbWith RaDifference is hydrogen atom or 1 valence organic group.
When synthesizing the acrylic polymer dispersant, may be used Japanese Unexamined Patent Publication 9-62002 bulletins, 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 great Yi, field Tagayasu Den one of the right hand, Process Technology of Polymer, 36,366 (1987), East Village is quick to be prolonged, damp this light man, macromolecule Collection of thesis, 46,189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic, 109,4737 (1987), phase Tian Zhuosan, well Upper auspicious flat, Synthetic Organic Chemistry, 43,300 (1985), D.Y.Sogoh, W.R.Hertler et al, Macromolecules, Well known method described in 20,1473 (1987) etc..
The acrylic polymer dispersant that can be used in the present invention can be A-B block copolymers, or B-A-B block copolymers, constitute the A blocks of its copolymer/B block than preferably 1/99~80/20, particularly preferably 5/95~ 60/40 (mass ratio), by making it that can ensure that dispersibility and the balanced of storage stability are inclined within the scope of this, to exist To.
In addition, in A-B block copolymers that 1g can be used in the present invention, B-A-B block copolymers, quaternary ammonium salt base The amount of group is preferably generally 0.1~10mmol, by making it within the scope of this, inclining for good dispersibility can be ensured by existing To.
It should be noted that in such block copolymer, the ammonia generated in the fabrication process would generally be contained sometimes Base, amine value is 1~100mgKOH/g or so, from the viewpoint of dispersibility, preferably 10mgKOH/g or more, is more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, and preferably 90mgKOH/g or less, more preferably 80mgKOH/g or less, further preferably 75mgKOH/g or less.
Here, the amine value of the dispersant of these block copolymers etc. is with being equivalent in dispersant sample in addition to solvents The comparable KOH mass of alkali number of solid constituent 1g indicates, is measured by following method.
Accurate weighing dispersant 0.5~1.5g of sample in the beaker of 100mL, with the acetic acid of 50mL, using having The automatic titration device of pH electrodes, with the HClO of 0.1mol/L4Acetic acid solution carries out acid-base titration to the solution, and titration pH is bent The inflection point of line finds out amine value according to the following formula as titration end-point.
An Zhi &#91;mgKOH/g&#93;=(561 × V)/(W × S)
&#91;Wherein, W:Indicate the dispersant sample Liang of weighing &#91;g&#93;,V:Indicate the Di Dingliang &#91 in titration end-point;mL&#93;,S:It indicates to divide The Gu Tichengfennongdu &#91 of powder sample;Quality %&#93;.&#93;
In addition, the amine value of the block copolymer depends on the presence or absence of acidic-group as acid value basis and its type, Generally preferable acid value junior, usually 10mgKOH/g is hereinafter, its weight average molecular weight (Mw) is preferably 1000~100,000 Range.By making it be there is the tendency that can ensure good dispersibility in above range.
Concrete structure with quaternary ammonium salt group as the macromolecule dispersing agent of functional group is not particularly limited, but from From the viewpoint of dispersibility, the repetitive unit preferably with following formula (i) expression (hereinafter, sometimes referred to as " repetitive unit (i) ").
&#91;Chemical formula 13&#93;
In above-mentioned formula (i), R31~R33It is each independently hydrogen atom, optionally alkyl with substituent group, optional with taking The aryl of Dai Ji or the optionally aralkyl with substituent group, R31~R33In 2 or more can be mutually bonded and form cyclic annular knot Structure.R34For hydrogen atom or methyl, X is the connection group of divalent, Y-For counter anion.
The R of above-mentioned formula (i)31~R33In, the carbon atom number of the alkyl optionally in the alkyl with substituent group does not limit especially It is fixed, usually 1 or more, additionally, it is preferred that for 10 or less, more preferably 6 or less.As the concrete example of alkyl, can enumerate methyl, Ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc., in these, preferably methyl, ethyl, propyl, butyl, amyl Or hexyl, more preferably methyl, ethyl, propyl or butyl.Furthermore it is possible to for the arbitrary form in straight-chain, branched.Separately Outside, the cyclic structures such as cyclohexyl, cyclohexyl methyl can also be contained.
The R of above-mentioned formula (i)31~R33In, the carbon atom number of the aryl optionally in the aryl with substituent group does not limit especially It is fixed, usually 6 or more, and preferably 16 hereinafter, more preferably 12 or less.As the specific example of aryl, benzene can be enumerated Base, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, naphthalene, anthryl etc., in these, preferably phenyl, first Base phenyl, ethylphenyl, 3,5-dimethylphenyl or diethyl phenyl, more preferably phenyl, aminomethyl phenyl or ethylphenyl.
The R of above-mentioned formula (i)31~R33In, the carbon atom number of the aralkyl optionally in the aralkyl with substituent group is without spy It does not limit, usually 7 or more, and preferably 16 hereinafter, more preferably 12 or less.It, can be with as the specific example of aralkyl Phenylmethylene, phenyl-ethylene, phenylpropylene, phenyl butylidene, phenyl isopropylidene etc. are enumerated, in these, preferably Phenylmethylene, phenyl-ethylene, phenylpropylene or phenyl butylidene, more preferable phenylmethylene or phenyl-ethylene.
In these, from the viewpoint of dispersibility, preferably R31~R33It is each independently alkyl or aralkyl, specifically Ground, preferably R31And R33It is each independently methyl or ethyl and R32For phenylmethylene or phenyl-ethylene, more preferable R31And R33For methyl and R32For phenylmethylene.
In addition, above-mentioned macromolecule dispersing agent have tertiary amine as functional group in the case of, it is excellent from the viewpoint of dispersibility Select the repetitive unit that there is following formula (ii) to indicate (hereinafter, sometimes referred to as " repetitive unit (ii) ").
&#91;Chemical formula 14&#93;
In above-mentioned formula (ii), R35And R36It is each independently hydrogen atom, the alkyl optionally with substituent group, optionally has The aryl of substituent group or the optionally aralkyl with substituent group, R35And R36It can be mutually bonded and form cyclic structure, R37For hydrogen Atom or methyl, Z are the connection group of divalent.
In addition, the R as above-mentioned formula (ii)35And R36In optionally with substituent group alkyl, can preferably be employed as State the R of formula (i)31~R33And exemplary group.
Similarly, the R as above-mentioned formula (ii)35And R36In optionally with substituent group aryl, can preferably be employed as The R of above-mentioned formula (i)31~R33And exemplary group.In addition, the R as above-mentioned formula (ii)35And R36In optionally with substituent group Aralkyl can preferably be employed as the R of above-mentioned formula (i)31~R33And exemplary group.
In these, R35And R36It is preferred that being each independently the optionally alkyl with substituent group, more preferably methyl or second Base.
R as above-mentioned formula (i)31~R33And the R of above-mentioned formula (ii)35And R36In alkyl, aralkyl or aryl institute optionally The substituent group having can enumerate halogen atom, alkoxy, benzoyl, hydroxyl etc..
In above-mentioned formula (i) and (ii), as connection the group X and Z of divalent, it can be cited for example that:Carbon atom number 1~10 Alkylidene, carbon atom number 6~12 arlydene ,-CONH-R43Base ,-COOR44Ji &#91;Wherein, R43And R44It is former for singly-bound, carbon The alkylidene of subnumber 1~10 or ether (the alkyl oxyalkyl) &#93 of carbon atom number 2~10;Deng preferably-COO-R44Base.
In addition, in above-mentioned formula (i), the Y as counter anion-, Cl can be enumerated-,Br-,I-,ClO4 -,BF4 -, CH3COO-,PF6 -Deng.
The content ratio for the repetitive unit that above-mentioned formula (i) indicates is not particularly limited, from the viewpoint of dispersibility, relatively In above-mentioned formula (i) indicate repetitive unit content ratio and above-mentioned formula (ii) indicate repetitive unit content ratio it is total Preferably 60 moles of % or less, more preferably 50 moles of % or less, meter is more preferably 40 moles of % or less, particularly preferred For 35 moles of % hereinafter, and preferably 5 moles of % or more, more preferably 10 moles of % or more, further preferably 20 rubbing You are % or more, particularly preferably 30 moles of % or more.
Contain in addition, the repetitive unit of above-mentioned formula (i) expression is shared in whole repetitive units of macromolecule dispersing agent Ratio is not particularly limited, from the viewpoint of dispersibility, preferably 1 mole of % or more, more preferably 5 moles of % or more, into One step is preferably 10 moles of % or more, and preferably 50 moles of % or less, preferably 30 moles of % or less, more preferably 20 is rubbed You are % or less, particularly preferably 15 moles of % or less.
Contain in addition, the repetitive unit of above-mentioned formula (ii) expression is shared in whole repetitive units of macromolecule dispersing agent Ratio is not particularly limited, from the viewpoint of dispersibility, preferably 5 moles of % or more, more preferably 10 moles of % or more, into One step be preferably 15 moles of % or more, particularly preferably 20 moles of % or more, and preferably 60 moles of % or less, more preferably 40 moles of % or less, further preferably 30 moles of % or less, particularly preferably 25 moles of % or less.
In addition, from improve with the compatibility of the adhesive ingredients such as solvent, so that dispersion stabilization is improved from the viewpoint of, high score The repetitive unit that sub- dispersant is preferably indicated with following formula (iii) (hereinafter, sometimes referred to as " repetitive unit (iii) ").
&#91;Chemical formula 15&#93;
In above-mentioned formula (iii), R40For ethylidene or propylidene, R41For the alkyl optionally with substituent group, R42For hydrogen atom Or methyl, the integer that n is 1~20.
The R of above-mentioned formula (iii)41In, the carbon atom number of the alkyl optionally in the alkyl with substituent group is not particularly limited, Usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less.It, can as the specific example of alkyl To enumerate methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc., in these, preferably methyl, ethyl, third Base, butyl, amyl or hexyl, more preferably methyl, ethyl, propyl or butyl.Furthermore it is possible to be in straight-chain, branched Any form.Alternatively, it is also possible to contain the cyclic structures such as cyclohexyl, cyclohexyl methyl.It, can be with as the substituent group that person has Enumerate halogen atom, alkoxy, benzoyl, hydroxyl etc..
In addition, from the viewpoint of the compatibility and dispersibility relative to adhesive ingredients such as solvents, in above-mentioned formula (iii) N be preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
Contain in addition, the repetitive unit of above-mentioned formula (iii) expression is shared in whole repetitive units of macromolecule dispersing agent It is proportional to be not particularly limited, preferably 1 mole of % or more, more preferably 2 moles of % or more, further preferably 4 moles of % More than, and preferably 30 moles of % or less, more preferably 20 moles of % or less, further preferably 10 moles of % or less. In the case of in above range, there is the compatibility and dispersion stabilization that can be achieved at the same time relative to adhesive ingredients such as solvents Tendency.
In addition, from improve dispersant relative to the adhesive ingredients such as solvent compatibility, make dispersion stabilization improve sight Point considers that repetitive unit of the macromolecule dispersing agent preferably with following formula (iv) expression is (hereinafter, sometimes referred to as " repetitive unit (iv)")。
&#91;Chemical formula 16&#93;
In above-mentioned formula (iv), R38Have for the alkyl optionally with substituent group, the aryl optionally with substituent group or optionally The aralkyl of substituent group.R39For hydrogen atom or methyl.
The R of above-mentioned formula (iv)38In, the carbon atom number of the alkyl optionally in the alkyl with substituent group is not particularly limited, Usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less.As alkyl Specific example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl etc. can be enumerated, in these, preferably Methyl, ethyl, propyl, butyl, amyl or hexyl, more preferably methyl, ethyl, propyl or butyl.Furthermore it is possible to be straight chain Any form in shape, branched.Alternatively, it is also possible to contain the cyclic structures such as cyclohexyl, cyclohexyl methyl.
The R of above-mentioned formula (iv)38In, the carbon atom number of the aryl optionally in the aryl with substituent group is not particularly limited, Usually 6 or more, and preferably 16 or less, more preferably 12 or less, further preferably 8 or less.As the specific of aryl Example can enumerate phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, naphthalene, anthryl etc., these are worked as In, preferably phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl or diethyl phenyl, more preferably phenyl, aminomethyl phenyl Or ethylphenyl.
The R of above-mentioned formula (iv)38In, the carbon atom number of the aralkyl optionally in the aralkyl with substituent group does not limit especially It is fixed, usually 7 or more, and preferably 16 or less, more preferably 12 or less, further preferably 10 or less.As aralkyl Specific example, phenylmethylene, phenyl-ethylene, phenylpropylene, phenyl butylidene, phenyl isopropylidene can be enumerated Deng in these, preferably phenylmethylene, phenyl-ethylene, phenylpropylene or phenyl butylidene, more preferably phenyl are sub- Methyl or phenyl ethylidene.
In these, from the viewpoint of solvent intermiscibility and dispersion stabilization, R38Preferably alkyl or aralkyl, it is more excellent It is selected as methyl, ethyl or phenylmethylene.
As R38In the substituent group that optionally has of alkyl, halogen atom, alkoxy etc. can be enumerated.In addition, as virtue The substituent group that base or aralkyl optionally have can enumerate alkyl, halogen atom, alkoxy of chain etc..In addition, R38Shown in The alkyl of chain includes any one of straight-chain and branched.
In addition, from the viewpoint of dispersibility, the whole of repetitive unit that above-mentioned formula (iv) indicates in macromolecule dispersing agent Shared content ratio is preferably 30 moles of % or more, more preferably 40 moles of % or more, is more preferably in repetitive unit 50 moles of % or more, and preferably 80 moles of % or less, more preferably 70 moles of % or less.
Macromolecule dispersing agent can also have repetitive unit (i), repetitive unit (ii), repetitive unit (iii) and repeat single Repetitive unit other than first (iv).As the example of such repetitive unit, can enumerate from styrene, Alpha-Methyl benzene second The styrene monomers such as alkene;(methyl) acryloyl chloride etc. (methyl) acryloyl chloride class monomer;(methyl) acrylamide, N- methylols Acrylamide etc. (methyl) acrylamide monomers;Vinyl acetate;Acrylonitrile;Allyl glycidyl ether, butenoic acid contracting Water glycerin ether;The repetitive unit of the monomers such as N- metering system morpholides.
From the viewpoint of further increasing dispersibility, macromolecule dispersing agent is preferably the block with A blocks and B block Copolymer, the A blocks have repetitive unit (i) and repetitive unit (ii), and the B block is without repetitive unit (i) and again Multiple unit (ii).The block copolymer is preferably A-B block copolymers or B-A-B block copolymers.By being imported in A blocks Quaternary ammonium salt group and tertiary amino unexpectedly have the tendency for the dispersibility for significantly improving dispersant.In addition, B block preferably has There is repetitive unit (iii), in addition, more preferably having repetitive unit (iv).
In A blocks, repetitive unit (i) and repetitive unit can be contained with any form of random copolymerization, block copolymerization (ii).Furthermore it is possible to contain two or more repetitive unit (i) and repetitive unit (ii) respectively in 1 A block, in this case, Each repetitive unit can be contained with any form of random copolymerization, block copolymerization in the A blocks.
Furthermore it is also possible to contain the repetitive unit other than repetitive unit (i) and repetitive unit (ii) in A blocks, as The example of such repetitive unit can enumerate the repetitive unit etc. from above-mentioned (methyl) acrylic ester monomer.Weight Content of the repetitive unit in A blocks other than multiple unit (i) and repetitive unit (ii) is preferably 0~50 mole of %, more preferably For 0~20 mole of %, the repetitive unit is free of most preferably in A blocks.
The repetitive unit other than repetitive unit (iii) and (iv) can be contained in B block, as such repetitive unit Example, can enumerate from styrene monomers such as styrene, α-methylstyrenes;(methyl) such as (methyl) acryloyl chlorides Acryloyl chloride class monomer;(methyl) acrylamide, N hydroxymethyl acrylamide etc. (methyl) acrylamide monomers;Vinyl acetate Ester;Acrylonitrile;Allyl glycidyl ether, butenoic acid glycidol ether;The repetition list of the monomers such as N- metering system morpholides Member.Content of the repetitive unit in B block other than repetitive unit (iii) and repetitive unit (iv) is preferably 0~50 mole of %, More preferably 0~20 mole of % is free of the repetitive unit most preferably in B block.
In addition, from the aspect of improving dispersion stabilization, preferably (f) dispersant is combined with the pigment derivative described below It uses.
Other gradation composition > of < photosensitive coloring compositions
It, can be suitable for cooperation silane coupling agent etc. other than mentioned component in the photosensitive coloring composition of the present invention Closely sealed enhancer, coating enhancer, development modifying agent, ultra-violet absorber, antioxidant, surfactant, pigment derivative, Photoacid generator, crosslinking agent etc..
(1) closely sealed enhancer
In order to improve the adaptation with substrate, closely sealed raising can be contained in the photosensitive coloring composition of the present invention Agent.As closely sealed enhancer, the preferably compound etc. of silane coupling agent, phosphorous acidic group.
It, can be various silane coupled by epoxies, (methyl) acrylic compounds, amino etc. as the type of silane coupling agent 1 kind of exclusive use in agent, or two or more is used in mixed way.
As preferred silane coupling agent, it can be cited for example that:3- methacryloxypropyls methyl dimethoxysilane, (methyl) acryloxy silane such as 3- methyl allyl acyloxypropyl trimethoxysilanes class, 2- (3,4- epoxycyclohexyls) ethyl Trimethoxy silane, 3- glycidoxy-propyltrimethoxy silanes, 3- glycidoxypropyls diethoxy silane, 3- epoxies Ureido silanes class, the 3- isocyanic acids third such as the epoxy silanes classes such as the third oxygen propyl group triethoxysilane, 3- urea propyl-triethoxysilicanes The isocynate silanes class such as ethyl triethoxy silicane alkane, the particularly preferably silane coupling agent of epoxy silane class.
As the compound of phosphorous acidic group, the phosphoric acid ester of (methyl) acryloyl group, more preferable the following general formula are preferably comprised (g1), the compound that (g2) or (g3) is indicated.
&#91;Chemical formula 17&#93;
In above-mentioned general formula (g1), (g2) and (g3), R51The integer that expression hydrogen atom or methyl, l and l ' they are 1~10, m 1, 2 or 3.
The compound of these phosphorous acidic groups may be used alone, can also be used in combination of two or more kinds.
(2) surfactant
In order to improve coating, surfactant can also be contained in the photosensitive coloring composition of the present invention.
As surfactant, can use for example anionic surfactant, cationic surface active agent, it is non-from The various surfactants such as subtype surfactant, amphoteric surfactant.Wherein, dysgenic from being brought to various characteristics The low this respect of possibility considers, it is preferable to use nonionic surface active agent, wherein from the aspect of coating, fluorine class, silicon class Surfactant is effective.
As such surfactant, it can be cited for example that:TSF4460 (manufacture of organosilicon Co., Ltd. of GE Toshiba), DFX-18 (manufacture of NEOS companies), BYK-300, BYK-325, BYK-330 (manufacture of BYK Chemie companies), (SHIN-ETSU HANTOTAI has KP340 Ji Gui Co., Ltd. manufactures), F-470, F-475, F-478, F-559 (manufacture of DIC companies), SH7PA (Toray Silicone public affairs Department manufacture), DS-401 (Daikin Co., Ltd's manufacture), L-77 (Nippon Unicar Co. Ltd.'s manufacture), FC4430 (Sumitomo 3M public affairs Department's manufacture) etc..
It should be noted that surfactant can use one kind, can also in any combination with 2 kinds of ratio combine with Upper use.
(3) pigment derivative
In order to improve dispersibility, keeping quality, it can also contain in photosensitive coloring composition of the invention and be helped as dispersion The pigment derivative of agent.
As pigment derivative, can enumerate azo, phthalocyanines, quinoline azone class, benzimidazole ketone, quinophthalone class, Isoindoline ketone, twoPiperazine class, Anthraquinones, indanthrone kinds, perylene kinds, pyrene ketone, diketopyrrolo-pyrrole class, twoThe derivative of piperazine class etc., wherein preferred phthalocyanines, quinophthalone class.
As the substituent group of pigment derivative, sulfonic group, sulfoamido and its quaternary salt, phthalimide first can be enumerated Base, dialkyl aminoalkyl, hydroxyl, carboxyl, amide groups etc., they can be bonded in directly or across alkyl, aryl, heterocycle etc. On pigment skeleton, in the substituent group of above-mentioned pigment derivative, preferred sulfonic group.In addition, can replace on a pigment skeleton These multiple substituent groups.
As the concrete example of pigment derivative, the sulfonic acid of phthalocyanine, the sulfonic acid of quinophthalone, anthraquinone can be enumerated Sulfonic acid, the sulfonic acid of quinoline azone, the sulfonic acid of diketopyrrolo-pyrrole, twoThe sulfonic acid of piperazine Deng.These pigment derivatives can be used alone, or combine two or more use.
(4) photoacid generator
The photoacid generator is the compound for referring to generate acid by ultraviolet light, by being produced when being exposed The effect of raw acid, enables cross-linking reaction to carry out in the presence of the crosslinking agents such as such as melamine compound.Such In photoacid generator, dissolubility preferably in a solvent, particularly molten in the solvent for photosensitive coloring composition The high substance of solution property, such as can enumerate:Diphenyl iodine, xylyl iodine, phenyl (to methoxybenzyl) iodine, it is double (m-nitro base) iodine, bis- (to tert-butyl-phenyl) iodine, bis- (rubigan) iodine, bis- (dodecyl) iodine, To isobutyl phenenyl (p-methylphenyl) iodine, p-isopropyl phenyl (p-methylphenyl) iodineEtc. Diaryl iodoniumsOr triphenyl Chloride, bromide or the boron fluoride salt of the triaryl mattes such as sulfonium, hexafluorophosphate, hexafluoro arsenite, aromatic sulphonate, four The sulfoniums Organic Bor Complex classes such as (pentafluorophenyl group) borate etc., diphenyl phenacyl sulfonium (normal-butyl) triph-enylborate or The triazines chemical combination such as bis- (trichloromethyl) triazines of person's 2- methyl -4,6-, bis- (trichloromethyl) triazines of 2- (4- methoxyphenyls) -4,6- Object etc., but not limited to this.
(5) crosslinking agent
The present invention photosensitive coloring composition in crosslinking agent can further be added, for example, can be used melamine or Guanamines compound.As these crosslinking agents, it can be mentioned, for example melamine or the chemical combination of guanamines shown in the following general formula (6) Object.
&#91;Chemical formula 18&#93;
In formula (6), R61Expression-NR66R67The aryl of base or carbon atom number 6~12, R61For-NR66R67In the case of base, R62,R63,R64,R65,R66And R67In an expression-CH2OR68Base, R61In the case of aryl for carbon atom number 6~12, R62,R63,R64And R65In an expression-CH2OR68Base, remaining R62,R63,R64,R65,R66And R67Table independently from each other Show hydrogen or-CH2OR68Base, wherein R68Indicate hydrogen atom or the alkyl of carbon atom number 1~4.
Here, the aryl of typical carbon atom number 6~12 is phenyl, 1- naphthalenes or 2- naphthalenes, is gone back on these phenyl, naphthalene The substituent groups such as alkyl, alkoxy, halogen atom can be bonded.The carbon atom number of alkyl and alkoxy is respectively 1~6 or so.It is above-mentioned In, R68The alkyl of expression is methyl or ethyl, is particularly preferably methyl.
Melamine class compound corresponding with general formula (6), the i.e. compound of the following general formula (6-1) include:Six hydroxyl first Base melamine, pentamethylol melamine, tetra methylol melamine, hexamethoxymethyl melamine, pentamethoxyl first Base melamine, tetramethoxymethyl melamine, six ethoxyl methyl melamines etc..
&#91;Chemical formula 19&#93;
In formula (6-1), R62,R63,R64,R65,R66And R67In one in the case of aryl, R62,R63,R64And R65In An expression-CH2OR68Base, remaining R62,R63,R64,R65,R66And R67Hydrogen atom or-CH are indicated independently of one another2OR68 Base, here, R68Indicate hydrogen atom or alkyl.
In addition, guanamines compound corresponding with general formula (6), the R i.e. in general formula (6)61Include for the compound of aryl: Tetra methylol benzoguanamine, tetramethoxymethyl benzoguanamine, trimethoxy methyl benzoguanamine, tetraethoxy methyl benzocarbamidine Amine etc..
Furthermore it is also possible to use the crosslinking agent with methylol or hydroxymethyl alkyl ether.It is exemplified below the example.
Bis- (hydroxymethyl) phenol of bis- (the hydroxymethyl) -4- methylphenols of 2,6-, 4- tertiary butyls -2,6-, 5- ethyls -1,3- Bis- (hydroxymethyl) perhydro -1,3,5- triazine -2- ketone (common name N- ethyl dihydroxymethyls triazinone) or its dimethyl ether body, dihydroxy Methyl trimethylene urea or bis- (hydroxymethyl) perhydro -1,3,5- of its dimethyl ether body, 3,5-(the common name two of diazine -4- ketone Hydroxymethylfurfural) or its dimethyl ether body, two urea of tetra methylol glyoxal (tetramethyrol glyoxal diureine) Or its tetramethyl ether body.
It should be noted that these crosslinking agents can be used alone, can also be applied in combination two or more.Use friendship Join agent when, amount relative to all solids ingredient of photosensitive coloring composition be preferably 0.1~15 weight %, particularly preferably 0.5~10 weight %.
(6) sulfhydryl compound
In addition, in order to improve the adaptation to substrate, the sulfhydryl compound as polymerization accelerant can also be added.
As the type of sulfhydryl compound, 2-mercaptobenzothiazole, 2- sulfydryl benzos can be enumeratedAzoles, 2- sulfydryl benzos Imidazoles, ethanthiol, two mercaptan of the last of the ten Heavenly stems, 1,4- dimethyl sulfydryls benzene, dimercapto propionic acid butanediol ester, dimercapto acetic acid butanediol Ester, glycol dimercaptosuccinate, trimethylolpropane tris mercaptoacetate, dimercapto propionic acid butanediol ester, trihydroxy methyl third Alkane tri-thiol propionic ester, trimethylolpropane tris mercaptoacetate, four mercaptopropionic acid ester of pentaerythrite, four sulfydryl second of pentaerythrite Acid esters, tri-thiol propionic acid trihydroxy ethyl ester, ethylene glycol bis- (3- mercaptobutylates), butanediol bis- (3- mercaptobutylates), 1,4- Bis- (3- sulfydryls butyryl acyloxy) butane, trimethylolpropane tris (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), Pentaerythrite three (3- mercaptobutylates), ethylene glycol bis- (3- mercaptoisobutanoics acid esters), butanediol bis- (3- mercaptoisobutanoics acid esters), three Hydroxymethyl-propane three (3- mercaptoisobutanoics acid esters), 1,3,5- tri- (3- sulfydryls butoxyethyl group) -1,3,5- triazines -2,4,6 (1H, 3H, 5H) sulfhydryl compound or the multifunctional sulfhydryl compound of aliphatic etc. with heterocycle such as-triketone.These sulfhydryl compounds can One kind is used alone, or two or more can also be used in mixed way.
Components matching amount > in < photosensitive coloring compositions
In the photosensitive coloring composition of the present invention, relative to all solids ingredient in photosensitive coloring composition The content ratio of amount, (a) colorant is usually 10 mass % or more, preferably 20 mass % or more, more preferably 30 mass % Above, be more preferably 35 mass % or more, and preferably generally 70 mass % or less, more preferably 60 mass % with Under, further preferably 50 mass % or less, particularly preferably 45 mass % or less.By by the content ratio of (a) colorant Be set as above-mentioned lower limiting value or more, exist to obtain the tendency of enough optical density (OD), in addition, by be set as above-mentioned upper limit value with Under, there is the tendency for being easy to control difference in height formative.
In addition, (a-1) organic pigment relative to the content ratio of (a) colorant be preferably 70 mass % or more, more preferably For 80 mass % or more, further preferably 85 mass % or more, particularly preferably 90 mass % or more, and preferably 99 matter Measure % or less, more preferably 97 mass % or less, further preferably 95 mass % or less, particularly preferably 93 mass % with Under.By being set as above-mentioned lower limiting value or more, there is the tendency that can control difference in height formation.In addition, by being set as the above-mentioned upper limit Value is hereinafter, in the presence of the tendency for being easy to control difference in height formative.
In addition, being selected from content ratio of at least one of red pigment and the orange pigment pigment relative to (a) colorant Preferably 1 mass % or more, more preferably 2 mass % or more, further preferably 3 mass % or more, and preferably 30 matter Measure % or less, more preferably 20 mass % or less, further preferably 15 mass % or less, particularly preferably 10 mass % with Under.By being set as above-mentioned lower limiting value or more, there is the tendency that enough optical density (OD) can be obtained, by being set as above-mentioned upper limit value Hereinafter, in the presence of the tendency for being easy to control difference in height formative.
In addition, being selected from content ratio of at least one of blue pigment and the violet pigment pigment relative to (a) colorant Preferably 20 mass % or more, more preferably 40 mass % or more, further preferably 60 mass % or more, still more preferably For 80 mass % or more, it is particularly preferably 85 mass % or more, and preferably 99 mass % or less, more preferably 97 mass % Below, it is more preferably 95 mass % or less, particularly preferably 93 mass % or less, is most preferably 90 mass % or less.It is logical It crosses and is set as above-mentioned lower limiting value or more, there is the tendency that can ensure light-proofness, be easy by being set as above-mentioned upper limit value hereinafter, existing Control the tendency of difference in height formative.
In addition, (a-2) carbon black is preferably 1 mass % or more, more preferably 2 matter relative to the content ratio of (a) colorant It measures % or more, further preferably 5 mass % or more, be still more preferably 7 mass % or more, particularly preferably 8 mass % More than, and usually 20 mass % or less, preferably 18 mass % or less, more preferably 15 mass % or less, further it is excellent It is selected as 13 mass % or less.By being set as above-mentioned lower limiting value or more, exist it is easy to ensure that in the wavelength as visible light region The tendency of light-proofness in the full scope of 450nm to 700nm, by being set as above-mentioned upper limit value hereinafter, in the presence of height is easy to control The tendency of the poor formative of degree.
(a) in the case that colorant contains organic black pigments, organic black pigments relative to (a) colorant containing than Example is preferably 5 mass % or more, more preferably 10 mass % or more, further preferably 20 mass % or more, and is preferably 50 mass % or less, more preferably 40 mass % or less, further preferably 30 mass % or less, particularly preferably 20 mass % Below.By being set as above-mentioned lower limiting value or more, there is the tendency that enough optical density (OD) can be obtained, by being set as the above-mentioned upper limit Value is hereinafter, in the presence of the tendency for being easy to control difference in height formative.
Relative to the present invention photosensitive coloring composition all solids ingredient, (b) alkali soluble resin containing than Example is usually 5 mass % or more, preferably 10 mass % or more, more preferably 20 mass % or more, further preferably 30 matter Measure % or more, and usually 80 mass % or less, preferably 60 mass % or less, more preferably 50 mass % or less, further Preferably 40 mass % or less.Content ratio by making (b) alkali soluble resin is above-mentioned lower limiting value or more, and existing can press down Unexposed portion processed deliquescent reduction in developer solution, so as to inhibit the tendency of poor visualization.In addition, by being set as Above-mentioned upper limit value is hereinafter, in the presence of that can inhibit developer solution to improve the impregnability of exposure portion, so as to inhibit the sharp of pixel (sharp) tendency that property, adaptation decline.
Relative to the present invention photosensitive coloring composition all solids ingredient, (c) Photoepolymerizationinitiater initiater containing than Example is usually 0.1 mass % or more, preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 matter Measure % or more, particularly preferably 3 mass % or more, and usually 15 mass % or less, preferably 10 mass % or less, more preferably For 8 mass % or less.Content ratio by making (c) Photoepolymerizationinitiater initiater is above-mentioned lower limiting value or more, and spirit can be inhibited by existing The tendency that sensitivity declines, by being set as above-mentioned upper limit value hereinafter, in the presence of can inhibit unexposed portion dissolubility in developer solution Decline, so as to inhibit the tendency of poor visualization.
In the case of using (c) Photoepolymerizationinitiater initiater and polymerization accelerant at the same time, the photonasty relative to the present invention The all solids ingredient of color composition, the content ratio of polymerization accelerant are preferably 0.05 mass % or more, and usually 10 matter % or less, preferably 5 mass % are measured hereinafter, polymerization accelerant relative to 100 mass parts of (c) Photoepolymerizationinitiater initiater is usually 0.1 ~50 mass parts are particularly preferably used with the ratio of 0.1~20 mass parts.By making the content ratio of polymerization accelerant be above-mentioned More than lower limiting value, there is the tendency that the sensitivity for exposure light can be inhibited to decline, by being set as above-mentioned upper limit value hereinafter, In the presence of can inhibit unexposed portion decreased solubility in developer solution, so as to inhibit the tendency of poor visualization.
In addition, for mixing ratio shared in photosensitive coloring composition of the sensitizing dyestuff in the present invention, from spirit It is usually 20 mass % or less, preferably 15 from the viewpoint of sensitivity, in the total solid content in photosensitive coloring composition Quality % or less, more preferably 10 mass % or less.
The all solids ingredient of photosensitive coloring composition relative to the present invention, (d) olefinic unsaturated compound contain Proportional is usually 30 mass % or less, preferably 20 mass % or less.By make (d) olefinic unsaturated compound containing than Example is above-mentioned upper limit value hereinafter, increasing to the impregnability of exposure portion in the presence of can inhibit developer solution, to be easy to get good figure The tendency of picture.It should be noted that (d) lower limiting value of the content ratio of olefinic unsaturated compound be usually 5 mass % or more, Preferably 10 mass % or more.
It should be noted that the photosensitive coloring composition of the present invention is adjusted by using (e) solvent so that it is solid Body constituent concentration is usually 5~50 mass %, preferably 10~30 mass %.
In the solid constituent of photosensitive coloring composition, (f) content ratio of dispersant be usually 1 mass % or more, Preferably 3 mass % or more, more preferably 5 mass % or more, and usually 30 mass % or less, preferably 20 mass % with Under, more preferably 15 mass % or less, further preferably 10 mass % or less.In addition, (f) dispersant is coloured relative to (a) The content ratio of 100 mass parts of agent is usually 5 mass parts or more, is more preferably 10 mass parts or more, and usually 50 mass Part or less, it is particularly preferably 30 below mass part.Content ratio by making (f) dispersant is above-mentioned lower limiting value or more, is existed Be easy to get the tendency of enough dispersibilities, by be set as above-mentioned upper limit value hereinafter, in the presence of can by relative to reduce it is other at Point ratio and inhibit sensitivity, plate-making property etc. declines tendency.
Using closely sealed enhancer, content ratio is relative to all solids in photosensitive coloring composition Ingredient is usually 0.1 mass % or more, preferably 0.2 mass % or more, more preferably 0.4 mass % or more, and usually 5 Quality % or less, preferably 3 mass % or less, more preferably 2 mass % or less.Content ratio by making closely sealed enhancer is More than above-mentioned lower limiting value, there is the tendency for the improvement effect that can fully obtain adaptation, by be set as above-mentioned upper limit value with Under, existing can inhibit sensitivity to decline, remain residue after development and the tendency as defect.
In addition, using surfactant, content ratio is relative to complete in photosensitive coloring composition Portion's solid constituent be usually 0.001 mass % or more, preferably 0.005 mass % or more, more preferably 0.01 mass % or more, Further preferably 0.03 mass % or more, and usually 10 mass % or less, preferably 1 mass % or less, more preferably 0.5 mass % or less, further preferably 0.3 mass % or less.By make surfactant content be above-mentioned lower limiting value with On, there is the tendency of the flatness, uniformity that are easy to show film, table is easy hereinafter, existing by being set as above-mentioned upper limit value Reveal flatness, the uniformity of film, and the tendency of the deterioration of other characteristics can be inhibited.
< colours the physical property > of spacer formation photosensitive coloring composition
Highest transmissivity of the coloring spacer formation photosensitive coloring composition of the present invention in 300~370nm of wavelength It is 0.010% or more.When forming the solidfied materials such as spacer using photosensitive coloring composition, usually has and carried out using ultraviolet lamp The process of exposure.The luminescent spectrum of ultraviolet lamp is bright-line spectrum, has multiple glow peaks in the range of 300~370nm of wavelength.Cause This, forms the spacer of Desired Height difference to use photosensitive coloring composition, preferably makes the photosensitive coloring composition It is sufficiently high in the transmissivity of 300~370nm of wavelength.
Highest transmissivity of the coloring spacer formation photosensitive coloring composition of the present invention in 300~370nm of wavelength Usually 0.010% or more, preferably 0.020% or more, more preferably 0.030% or more, further preferably 0.040% with Above, still more preferably it is 0.045% or more, particularly preferably 0.050% or more, most preferably 0.055% or more, and usually It is 5% or less.By being set as above-mentioned lower limiting value or more, exists and be easy to be formed inclining for primary divider and the difference in height of secondary spacer To.
If front describes, coloring spacer formation photosensitive coloring composition of the invention is in 300~370nm of wavelength Highest transmissivity be 0.010% or more, but can also replace the highest transmissivity of 300~370nm of wavelength will be in wavelength The highest transmissivity of 300~450nm is as index.The coloring spacer formation photosensitive coloring composition of the present invention is in wavelength The highest transmissivity of 300~450nm is preferably 0.1% or more, more preferably 0.15% or more, further preferably 0.2% with Above, still more preferably it is 0.25% or more, be especially preferably 0.3% or more, is particularly preferably 0.4% or more, is most preferably 0.5% or more, and usually 10% or less.By being set as above-mentioned lower limiting value or more, exists and be easy to be formed between primary divider and pair The tendency of the difference in height of parting.
Highest transmissivity of the photosensitive coloring composition in wavelength 300~370nm and 300~450nm can determine as follows: It is 3 μm of cured film to form film thickness using the photosensitive coloring composition, using spectrophotometric determination wavelength 300~ The transmissivity of the range of 370nm and 300~450nm.Detailed determination condition etc. is not particularly limited, such as can utilize following Method measure.
First, it is coated with photosensitive coloring composition on glass substrate (AGC corporations " AN100 ") using spinner, connect It, at 90 DEG C in heat drying on hot plate 90 seconds, forms coated film.Obtained coated film is carried out under air ultraviolet Line irradiates, and the use of the intensity at wavelength 365nm is 32mW/cm2Ultraviolet light, light exposure be set as 70mJ/cm2.Then, it uses By the nonionic surface active agent (KAO. Corp. SA's system " A-60 ") of the potassium hydroxide containing 0.05 mass % and 0.08 mass % The developer solution that constitutes of aqueous solution, implement the spray development of hydraulic pressure 0.15MPa at 25 DEG C, then stop developing with pure water, It is cleaned using washing spray.Spray developing time adjusts between 10~120 seconds, and it is molten to be set as unexposed film Solve 1.5 times of the time removed.By the full coat film obtained by aforesaid operations (solid film) substrate in an oven, in 230 DEG C heating 20 minutes, so that pattern is cured, obtain film thickness be 3 μm full coat film pattern substrate.Then, it with uncoated photonasty The glass substrate of color composition as a contrast, using Shimadzu Scisakusho Ltd spectrophotometer UV-3150 in wavelength 300 The range of~370nm and 300nm~450nm is measured the light transmittance of the substrate, measures spacing and is set as 2nm.Then, it calculates Go out the highest light transmittance in the range of wavelength 300~370nm and 300nm~450nm.
By photosensitive coloring composition in the case where the highest transmissivity of 300~370nm of wavelength, 300~450nm are set as above-mentioned Specific method more than limit value is not particularly limited, it is preferable to use the highest in 300~370nm of wavelength, 300~450nm transmits Pigment, particularly (a-1) organic pigment of the sufficiently high pigment of rate as the main light absorption ingredient contained in the composition, Particularly preferably use the sufficiently high pigment of the transmissivity of the 365nm of common maximum luminous wavelength in as exposure process.
Specifically, the pigment content ratio preferably in using all solids ingredient is the photosensitive color of 30 mass % Transmissivity when composition forms film, forms the cured film of 1.0 μm of film thickness after firing at wavelength 365nm reach 2% with On organic pigment, more preferable transmissivity reaches 5% or more organic pigment, further preferred transmissivity reaches 10% or more Organic pigment, particularly preferred transmissivity reach 15% or more organic pigment, and usually 60% or less.Under above-mentioned Organic pigment more than limit value, there is the highest transmissivity being easy to get in 300~370nm of wavelength, 300~450nm of wavelength is Photosensitive coloring composition more than above-mentioned lower limiting value.Table 1 shows that representative organic pigment forms film after firing Transmission when thick 1.0 μm of cured film (the pigment content ratio in all solids ingredient is 30 mass %) at wavelength 365nm Rate (%).
&#91;Table 1&#93;
Pigment kind In the transmissivity (%) of wavelength 365nm
C.I. pigment orange 64 18
C.I. paratonere 177 30
C.I. paratonere 254 39
C.I. paratonere 272 16
C.I. pigment Violet 23 8
C.I. pigment violet 29 27
C.I. pigment blue 15:6 1
C.I. pigment blue 60 24
C.I. pigment yellow 13 9 14
Irgaphor Black S0100CF (BASF AG's system) 6
Additionally, it is preferred that whole organic pigments contained by (a-1) organic pigment form the solidification of 1.0 μm of film thickness after firing The average value of transmissivity when film at wavelength 365nm be 1% or more, more preferably 3% or more, further preferably 5% with It is upper, be still more preferably 10% or more, particularly preferably 15% or more, and usually 60% or less.Under being set as above-mentioned More than limit value, there is the tendency for being able to easily form primary divider and the difference in height of secondary spacer.Above-mentioned transmissivity is averaged Value can be based on each organic pigment compounding ratio (mass ratio) contained in whole organic pigments to the value of their transmissivity into Row averagely calculates.
On the other hand, coloring spacer formation photosensitive coloring composition of the invention can be preferred for coloring interval Object forms purposes, and from the viewpoint of as coloring spacer, black is preferably presented.In addition, average every 1 μm of film thickness of its film Optical density (OD) be preferably 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, particularly preferably 1.8 with On, and usually 4.0 or less, more preferably 3.0 or less.
< colours the manufacturing method > of spacer formation photosensitive coloring composition
Coloring spacer the is formationed photosensitive coloring composition (hereinafter, be sometimes referred to as " resist ") of the present invention can be according to It is prepared by usual way.
In general, (a) colorant preferably uses paint shaker, sand mill, ball mill, roller mill, burrstone mill, air-flow in advance Mill, homogenizer etc. carry out decentralized processing.By decentralized processing, (a) colorant is by micronized, therefore, the coating characteristics of resist It is improved.
Decentralized processing is generally preferably with by (a) colorant, (e) solvent, (f) dispersant and (b) alkali soluble resin Part or all of system being applied in combination carries out (hereinafter, will supply the mixture of decentralized processing sometimes and in the processing In obtained composition be known as " ink " or " dispersible pigment dispersion ").In particular, if being divided using macromolecule dispersing agent as (f) Powder, then obtained ink and resist through when thickening be inhibited (dispersion stabilization is excellent), therefore preferably.
Therefore, preferably fabricated at least to contain (a) colorant, (e) solvent and (f) disperse in the process of manufacture resist The dispersible pigment dispersion of agent.As (a) colorant, (e) organic solvent and (f) dispersant that can be used in dispersible pigment dispersion, Those of can preferably be employed as capable of using in photosensitive coloring composition respectively.
It should be noted that being carried out at dispersion for the liquid containing the whole components coordinated in colored resin composition In the case of reason, generated heat release when due to decentralized processing, high response ingredient is likely to occur modification.It is therefore preferable that with System containing macromolecule dispersing agent carries out decentralized processing.
, it is preferable to use the bead or oxygen of 0.1~8mm of grain size or so in the case of making (a) colorant disperse with sand mill Change zirconium pearl.For decentralized processing condition, temperature is usually 0 DEG C to 100 DEG C, is preferably room temperature to 80 DEG C of range, according to The difference of the composition of liquid and the size of decentralized processing device etc., the suitable time of jitter time simultaneously differ, therefore can be appropriate It adjusts.Dispersion rough standard be:The gloss of ink is controlled so that 20 degree of mirror surface luster (JIS of resist Z8741) reach 50~300 range.In the case of the glossiness of resist is lower, decentralized processing is insufficient, remaining coarse Pigment (color material) particle it is more, developability, adaptation, distinguishing etc. may become inadequate.In addition, if carrying out decentralized processing It is more than above range to gloss value, then pigment is crushed and generates a large amount of ultramicrons, therefore it is impaired to there is dispersion stabilization instead Tendency.
In addition, the dispersion particle diameter for the pigment being dispersed in ink is usually 0.03~0.3 μm, dynamic light scattering method can be passed through Etc. measuring.
Then, the ink obtained by above-mentioned decentralized processing is mixed with above-mentioned other ingredients included in resist, Uniform solution is made.In the manufacturing process of resist, since to be mixed into the situation in liquid more for fine dust, because This, obtained resist wishes to be filtered processing by filter etc..
&#91;Gu Huawu &#93;
It can be by making the photosensitive coloring composition solidification of the present invention obtain solidfied material.Photosensitive coloring composition is solid Solidfied material obtained from change can be preferably used as coloring spacer.
&#91;Colour Jian Gewu &#93;
Then, spacer is coloured obtained from the photosensitive coloring composition for having used the present invention, according to its manufacture Method illustrates.
(1) supporter
As the supporter for being used to form coloring spacer, as long as the intensity with appropriateness, to its material without spy It does not limit.Transparent substrate is mainly used, as its material, it can be cited for example that the polyesters tree such as polyethylene terephthalate The thermoplastic resins film-making such as the polyolefin resins such as fat, polypropylene, polyethylene, makrolon, polymethyl methacrylate, polysulfones The thermosetting resins pieces or various glass etc. such as material, epoxy resin, unsaturated polyester resin, poly- (methyl) acrylic resin.Its In, from the viewpoint of heat resistance, preferably glass, heat-resistant resin.In addition, also having in substrate surface film forming ITO, IZO etc. The case where transparent electrode.Other than transparent substrate, it can also be formed on tft array.
In order to improve the surface physical properties such as cementability, can also Corona discharge Treatment, ozone be carried out to supporter as needed Film formation processing of the various resins such as processing, silane coupling agent, urethane based resin etc..
The thickness of transparent substrate is usually the range of 0.05~10mm, preferably 0.1~7mm.In addition, carrying out various trees In the case of the film formation processing of fat, film thickness is usually 0.01~10 μm, preferably 0.05~5 μm of range.
(2) spacer is coloured
The photosensitive coloring composition of the present invention is used for same as well known colour filter photosensitive coloring composition Purposes.Hereinafter, the case where for being used as coloring spacer (black light spacer), according to the photonasty for having used the present invention The specific example of the forming method of the black light spacer of coloured composition illustrates.
In general, on the substrate of black light spacer to be arranged, by the methods of coating with the supply sense of membranaceous or pattern-like Photosensitiveness coloured composition, and make solvent seasoning.Then, pattern is carried out by the methods of the photoetching process for being exposed-developing to be formed. Then, additional exposure, heat cure processing are carried out as needed, thus form black light spacer on the substrate.
(3) formation of spacer is coloured
&#91;1&#93;To the supply method of substrate
The photosensitive coloring composition of the present invention is usually supplied with the state being dissolved or dispersed in solvent on substrate.Make For its supply method, can by known method, for example spin-coating method, bar (Wirebar) method, flow coat method, die coating method, Rolling method, spray coating method etc. carry out.Furthermore it is possible to by ink-jet method, print process etc. for giving to form pattern-like.
When wherein, using die coating method, the usage amount of coating fluid can be substantially cut down, and completely without using spin-coating method when institute The influence of the smog of attachment etc. can inhibit foreign matter generation etc., be preferred from the viewpoint of synthesis.
Coating weight is different according to purposes, such as in the case of black light spacer, is usually in terms of dry film thickness 0.5 μm~10 μm, preferably 1 μm~9 μm, particularly preferably 1 μm~7 μm of range.In addition, it is important that dry film thickness or most End form at spacer height on entire substrate uniformly.In the case of uneven big, it will produce striped in liquid crystal display panel and lack It falls into.
Wherein, the different black of height is disposably formed by photoetching process using the photosensitive coloring composition of the present invention In the case of light spacer, the height of finally formed black light spacer is different, the height of primary divider and secondary spacer it Difference becomes difference in height.
It should be noted that as substrate, substrate well known to glass substrate etc. can be used.In addition, substrate surface is preferred For plane.
&#91;2&#93;Drying means
To on substrate supply photosensitive coloring composition after film drying preferably by using hot plate, IR baking ovens, The seasoning of convection oven carries out.It is dry alternatively, it is also possible to combine the decompression for not improving temperature and being dried in pressure-reducing chamber Dry method.
Dry condition according to the type of solvent composition, the performance of drying machine to be used etc. come suitable for selection.It is dry Time according to the type of solvent composition, the performance of drying machine to be used etc. usually 40 DEG C~130 DEG C temperature, 15 seconds ~5 minutes ranges are selected, and are preferably selected in 50 DEG C~110 DEG C of temperature, 30 seconds~3 minutes ranges.
&#91;3&#93;Exposure method
Exposure is the mask pattern of minus to be overlapped on the film of photosensitive coloring composition, and shine across the mask pattern The light source of ultraviolet light or luminous ray is penetrated to carry out.In the case of being exposed using exposed mask, may be used makes exposure Method of the mask close to the film of photosensitive coloring composition;It can be by the way that exposed mask be disposed substantially away from photosensitive color group The position of the film of object is closed, and is carried out across the method for the exposed mask projection exposure light.Alternatively, it is also possible to by not using Mask pattern is carried out in the way of the scan exposure of laser.At this point, as needed, light is poly- caused by oxygen in order to prevent The sensitivity of conjunction property layer declines, and can be exposed under deoxidizing atmosphere or form polyvinyl alcohol layer on optical polymerism layer It is exposed after equal oxygen barrier layers.
As the preferred embodiment of the present invention, the case where different black light spacers of height are formed simultaneously by photoetching process Under, for example, using with light shielding part (light transmittance 0%) and as the average transmittance of multiple opening portions relative to average transmittance The exposed mask of the highest opening portion opening portion small (completely through opening portion) (centre penetrates opening portion).In this way, By centre through opening portion and completely through opening portion average transmittance difference, i.e. the difference of light exposure by generate residual film ratio Difference.
It is known that intermediate transmission is for example made by the rectangular light-shielding pattern of the lightproof unit with small polygon The method etc. of opening portion.Additionally, it is known that being controlled by being used as the film of the materials such as the chromium system of absorber, molybdenum system, tungsten system, silicon systems Light rate and the method etc. made.
In order to obtain the different coloring spacer of the height that is made of primary divider and secondary spacer, preferably such as Japanese Unexamined Patent Publication Recorded in 2015-127748 bulletins like that, by the light exposure of secondary spacer relative to the light exposure of primary divider be set as compared with Low, the preferably intermediate transmissivity through opening portion relative to the transmissivity completely through opening portion is 20% or less, more preferably 15% or less, it is more preferably 10% or less.
Light source is not particularly limited used in above-mentioned exposure.As light source, it can be mentioned, for example:Xenon lamp, halogen lamp, tungsten The lamps such as lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, metal halide lamp, middle medium pressure mercury lamp, Cooper-Hewitt lamp, carbon arc, fluorescent lamp Light source;Argon laser, YAG laser, excimer laser, N_2 laser, helium cadmium laser, green violet semiconductor laser, near-infrared half Laser light sources such as conductor Laser etc..When being irradiated using the light of specific wavelength, optical filter can also be utilized.
Can be the type for the light transmittance that exposure wavelength can be for example controlled with film, as this as optical filter In the case of material, it can be cited for example that Cr compounds (oxide, nitride, oxynitride, fluoride of Cr etc.), MoSi, Si, W, Al etc..
As light exposure, usually 1mJ/cm2Above, it is preferably 5mJ/cm2Above, it is more preferably 10mJ/cm2More than, and Usually 300mJ/cm2Below, it is preferably 200mJ/cm2Below, it is more preferably 150mJ/cm2Below.
In addition, close in the case of Exposure mode, as exposure object at a distance from mask pattern, usually 10 μm with It is upper, preferably 50 μm or more, more preferably 75 μm or more, in addition, usually 500 μm or less, be preferably 400 μm or less, more excellent It is selected as 300 μm or less.
&#91;4&#93;Developing method
After having carried out above-mentioned exposure, by using the development of the aqueous solution or organic solvent of alkali compounds, Ke Yi Picture pattern is formed on substrate.In the aqueous solution, surfactant, organic solvent, buffer, complexing can further be contained Agent, dyestuff or pigment.
As alkali compounds, can enumerate:Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, carbonic acid Hydrogen sodium, saleratus, sodium metasilicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, biphosphate The inorganic alkaline compounds such as sodium, potassium dihydrogen phosphate, ammonium hydroxide or monoethanolamine, diethanol amine or triethanolamine, monomethyl Amine, dimethyl amine or Trimethylamine, monoethylamine, diethylamide or triethylamine, single isopropylamine or diisopropylamine, positive fourth Base amine, monoisopropanolamine, diisopropanolamine (DIPA) or triisopropanolamine, aziridine, ethylene diimine, tetramethylammonium hydroxide (TMAH), the organic basic compounds such as choline.These alkali compounds can be mixture of more than two kinds.
As above-mentioned surfactant, it can be mentioned, for example:Polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, The nonionic surface active agent such as polyxyethylated ester class, sorbitan alkyl esters, monoglyceride alkyl esters;Alkyl The anion such as benzenesulfonates, alkyl naphthalene sulfonic acid salt, alkylsurfuric acid salt, alkyl sulfonates, sulfosuccinate ester salt class Type surfactant;The amphoteric surfactantes such as alkyl betaines bases, amino acids.
As organic solvent, it can be mentioned, for example:Isopropanol, benzylalcohol, ethyl cellosolve, butyl cellosolve, ethylene glycol monophenyl ether, Propylene glycol, diacetone alcohol etc..Organic solvent can be used alone, and can also be applied in combination with aqueous solution.
The condition of development treatment is not particularly limited, the range, preferably that can be usually 10 DEG C~50 DEG C in development temperature At 15 DEG C~45 DEG C, particularly preferably at 20~40 DEG C using immersion development method, spray development method, fur brush development method, ultrasonic wave Any means in the developing methods such as development method carry out.
&#91;5&#93;Additional exposure and heat cure processing
For the substrate after development, additional exposure can be carried out according to method same as above-mentioned exposure method as needed Light, alternatively, it is also possible to carry out heat cure processing.Heat cure treatment conditions at this time are as follows:Model of the temperature at 100 DEG C~280 DEG C It encloses, the range preferably at 150 DEG C~250 DEG C selects, range selection of the time at 5 minutes~60 minutes.
It is suitable that size, shape of coloring spacer of the present invention etc. can be carried out according to specification for the colour filter for using it etc. Adjustment, photosensitive coloring composition of the invention are formed simultaneously primary divider and secondary spacer especially for by photoetching process Highly different black light spacers is useful, in this case, the height of primary divider is usually 2~7 μm or so, pair interval Object is usually with 0.2~1.5 μm lower than primary divider or so of height.
The shape of coloring spacer to be formed is not particularly limited, and can usually enumerate primary divider and secondary spacer shape As the form of column independently, in this case, can be by the difference of the height of primary divider and the height of secondary spacer As difference in height.On the other hand, it can also enumerate as recorded in Japanese Unexamined Patent Publication 2014-146029 bulletins, form The mode of shape made of black matrix" is integrated with intercolumniation parting, in this case, can be by the height and intercolumniation of black matrix" The difference of the height of parting is as difference in height.
In addition, from the viewpoint of light-proofness, the optical density (OD) for being equivalent to the coloring spacer of 1 μm of the present invention is preferred Be 1.0 or more, more preferably 1.2 or more, further preferably 1.5 or more, particularly preferably 1.8 or more, and usually 4.0 with Under, preferably 3.0 or less.Optical density (OD) mentioned here is the value measured by the method described below.
&#91;Lv Guangpian &#93;
The colour filter of the present invention has the coloring spacer of above-mentioned such present invention, such as can manufacture as follows:In conduct The glass substrate superimposed layer black matrix" of transparent substrate, pixel shader layer, the face coat of red, green, blue form coloring After spacer, alignment films are formed.
Such colour filter with coloring spacer of the invention and liquid crystal drive side group plate are bonded and form liquid crystal Box injects liquid crystal in being formed by liquid crystal cell, it is possible thereby to manufacture the liquid crystal display dress for having the coloring spacer of the present invention Set equal image display devices.
Embodiment
Then, Examples and Comparative Examples are enumerated more specifically the present invention will be described, but as long as without departing from the present invention's Purport, the present invention is not limited to embodiments below.
The constituent of the photosensitive coloring composition used in following Examples and Comparative Examples is as follows.
< organic black pigments >
BASF AG manufactures, and Irgaphor (registered trademark) Black S 0100CF (have chemistry shown in following formula (2) Structure)
&#91;Chemical formula 20&#93;
< alkali soluble resin-I >
145 mass parts of propylene glycol methyl ether acetate are stirred while carrying out nitrogen displacement, are warming up to 120 ℃.10 mass parts of styrene, 85.2 mass parts of glycidyl methacrylate are added dropwise thereto and there is tricyclodecane skeleton Monomethacrylates the FA-513M of manufacture (Hitachi Chemical Co., Ltd.) 66 mass parts, and with dropwise addition 2,2 '-in 3 hours Double 8.47 mass parts of -2- methylbutyronitriles of azo, then continue to have stirred 2 hours at 90 DEG C.Then, will become in reaction vessel Air is replaced, and three (dimethylaminomethyl) phenol, 0.7 mass parts and hydroquinone are put into 43.2 mass parts of acrylic acid 0.12 mass parts, the reaction was continued at 100 DEG C 12 hours.Then, be added tetrabydrophthalic anhydride (THPA) 56.2 mass parts, 0.7 mass parts of triethylamine are reacted 3.5 hours at 100 DEG C.Pass through the GPC alkali soluble resin-I's obtained above measured Weight average molecular weight Mw is about 8400, acid value 80mgKOH/g.
< alkali soluble resin-II >
" ZCR-1642H " (MW=6500, the acid value=98mg-KOH/g) of Nippon Kayaku K. K's manufacture
< alkali soluble resin-III >
&#91;Chemical formula 21&#93;
By epoxide (epoxide equivalent 264) 50g of above structure, methacrylic acid 16.21g, methoxybutyl second Acid esters 54.8g, triphenylphosphine 1.272g and p methoxy phenol 0.032g, which are added to, is equipped with thermometer, blender, cooling tube Flask in, so that it is reacted at 90 DEG C while stirring, until acid value reaches 5mgKOH/g or less.Reaction needs 12 hours, obtains Epoxy acrylic ester solution is arrived.
By above-mentioned 25 mass parts of epoxy acrylic ester solution, 0.25 mass parts of trimethylolpropane (TMP), bibenzene tetracarboxylic 2.52 mass parts of dianhydride (BPDA), 1.61 mass parts of tetrabydrophthalic anhydride (THPA), which are added to, is equipped with thermometer, stirring Machine, cooling tube flask in, be to slowly warm up to 105 DEG C while stirring, make its reaction.
It when resin solution becomes transparent, is diluted with methoxybutyl acetic acid esters, is prepared into 50 matter of solid constituent % is measured, has obtained that acid value be 105mgKOH/g, the weight average molecular weight (Mw) of polystyrene conversion that measures by GPC is 2480 Alkali soluble resin-III.
< dispersant-I >
" DISPERBYK-LPN21116 " of BYK-Chemie companies manufacture (has quaternary ammonium salt base and tertiary amino by side chain A blocks and the acrylic A-B block copolymer constituted without the B block of quaternary ammonium salt base and amino, amine value are 70mgKOH/g, acid value are 1mgKOH/g or less)
Include following formula (1a) and the repetitive unit of (2a) in the A blocks of dispersant-I, includes following formula (3a) in B block Repetitive unit.The repetitive unit of following formula (1a), (2a) and (3a) is shared in whole repetitive units of dispersant-I to be contained Proportional is respectively 11.1 moles of %, 22.2 moles of %, 6.7 moles of %.
&#91;Chemical formula 22&#93;
< dispersant-II >
" DISPERBYK-167 " (the carbamates macromolecule dispersing agent) of BYK-Chemie companies manufacture
< pigment derivatives >
" Solsperse12000 " of Lubrizol companies manufacture
< solvent-I >
PGMEA:Propylene glycol methyl ether acetate
< solvent-II >
MB:3- methoxybutanols
< Photoepolymerizationinitiater initiater-I >
&#91;Chemical formula 23&#93;
< Photoepolymerizationinitiater initiater-II >
&#91;Chemical formula 24&#93;
< photopolymerization monomers >
DPHA:The dipentaerythritol hexaacrylate of Nippon Kayaku K. K's manufacture
< additive-I >
Nippon Kayaku K. K's manufacture, KAYAMER PM-21 (phosphate containing methylacryloyl)
< additive-II >
The SH6040 (3- glycidoxy-propyltrimethoxy silanes) of DOW CORNING TORAY companies manufacture
< surfactants >
The Megafac F-559 of DIC companies manufacture
The evaluation > of < optical density (OD)
Tool described below is determined using transmission-type densimeter (" D200-II " of the manufacture of Gretag Macbeth companies) There is the optical density (OD) of the glass substrate of pattern 2.In addition, being also determined to the film thickness of measurement site, and calculate every list The optical density (unit OD) of position film thickness (1 μm).
The evaluation > of < differences in height
It measures and corresponds to completely through the height of the primary divider pattern of opening portion and corresponding to centre through opening portion The height of secondary spacer patterns calculates the difference (Δ H) of its height.Δ H is set as zero for 0.4 μm or more person, will be less than 0.4 μm person is set as ×.
The light transmittance > of < ultraviolet regions
As a contrast with the glass substrate of uncoated photosensitive coloring composition, using Shimadzu Scisakusho Ltd's system point Range light transmissions to described below glass substrate with pattern 2 of the light photometer UV-3150 in wavelength 300nm~450nm Rate is determined.It measures spacing and is set as 2nm.
Calculate the highest light transmittance in wavelength 300nm~450nm ranges.Similarly, calculate wavelength 300nm~ The highest light transmittance of 370nm.
Light transmittance >s of the < in wavelength 450nm to 700nm
As a contrast with the glass substrate of uncoated photosensitive coloring composition, using Shimadzu Scisakusho Ltd's system point Range light transmissions to described below glass substrate with pattern 2 of the light photometer UV-3150 in wavelength 450nm~700nm Rate is determined.It measures spacing and is set as 2nm.
Calculate the highest light transmittance in wavelength 450nm~700nm ranges.
The preparation > of < dispersible pigment dispersions 1,3~5
By pigment, dispersant, dispersing aid, alkali soluble resin and the solvent described in table 2 according to the matter recorded in table 2 Amount ratio is mixed.The solution has been carried out in 25~45 DEG C of range with paint shaker to 3 hours decentralized processings.As Pearl uses the zirconium oxide bead of 0.5mm φ, adds 2.5 times of quality of dispersion liquid.After dispersion, filter is utilized Pearl is detached with dispersion liquid, is prepared for dispersible pigment dispersion 1,3~5.
&#91;Table 2&#93;
< dispersible pigment dispersions 2 (cladding carbon black dispersion liquid) >
Carbon black is manufactured using common Audit For Process.Wherein, as feedstock oil, the poor ethylene of Na, Ca, S is used Residue oil, and coke oven gas has been used to be used for burning.In addition, as reaction terminating water, uses and use ion exchange The pure water that resin is handled.Using homogenizer with 5,000~6,000rpm to obtained carbon black 540g and pure water 14500g It is stirred together 30 minutes, has obtained slurry.The slurry is transferred in the container with screw type blender, on one side with big About 1,000rpm is mixed, and is marginally added to respectively on one side dissolved with epoxy resin " Epikote828 " (Mitsubishi Chemical's strain Formula commercial firm manufactures) the toluene 600g of 60g.About 15 minutes, the carbon black being dispersed in water was fully transferred to toluene side, forms about The particle of 1mm.
Then, it has been carried out removing moisture with the metal mesh of 60 mesh, be then placed in vacuum drier, dry 7 at 70 DEG C Hour, toluene and water are removed completely.
Obtained cladding carbon black, dispersant, pigment derivative and solvent are carried out according to the mass ratio recorded in table 2 Mixing.
It is sufficiently stirred, is pre-mixed using blender.Then, the model using paint shaker at 25~45 DEG C It encloses 6 hours decentralized processings of progress and uses the zirconium oxide bead of 0.5mm φ as pearl, and add matter identical with dispersion liquid Amount, after dispersion, is detached pearl with dispersion liquid using filter, to be prepared for dispersible pigment dispersion 2.
&#91;1~4&#93 of Examples 1 to 3 and comparative example;
Using the dispersible pigment dispersion 1~5 of above-mentioned preparation, each ingredient is added so that the ratio in solid constituent is matching for table 3 Composition and division in a proportion example, is further added PGMEA so that solid constituent is 22 mass %, and being stirred makes them dissolve, and is prepared for photonasty Coloured composition.It is evaluated using obtained photosensitive coloring composition, according to the method described below.
&#91;Table 3&#93;
The disposable forming method > of the different solidfied material of < height
Using spinner each coloring photosensitive combination is coated on glass substrate (" AN100 " of the manufacture of AGC companies).It connects , on hot plate at 90 DEG C heat drying 90 seconds, form film.
Using with 5~50 μm (5~20 μm of diameter:1 μm, 25 μm~50 μm of interval:Interval 5 μm) various diameters circle Shape pattern completely through 5~50 μm (5~20 μm of opening portion and diameter:1 μm, 25 μm~50 μm of interval:Interval 5 μm) it is various The centre of the circular pattern of diameter penetrates the exposed mask of opening portion, and exposure-processed has been carried out to obtained film.It is intermediate saturating Cross the film that opening portion is the Cr oxides that the light transmittance under wavelength 365nm is 14 ± 2%.Expose spacing (mask and coated face Between distance) be 200 μm.As irradiation light, it is 32mW/cm to use the intensity at wavelength 365nm2Ultraviolet light, expose Light quantity is 70mJ/cm2.In addition, ultraviolet light irradiation carries out in air.
Then, using the nonionic surface active agent by the potassium hydroxide containing 0.05 weight % and 0.08 weight % Developer solution made of the aqueous solution of (" A-60 " of Kao Corp's manufacture), implements the spray of hydraulic pressure 0.15MPa at 25 DEG C After development, is terminated and developed with pure water, spraying is washed with water and is cleaned.Spray developing time is adjusted between 10~120 seconds It is whole, it is set as 1.5 times that dissolving removes the time of unexposed film.
By aforesaid operations, the pattern for eliminating unnecessary portion has been obtained.The substrate of the pattern will be formed in baking oven In, heated 20 minutes at 230 DEG C and pattern made to cure, obtained generally cylindrical spacer patterns (pattern 1).In addition, Other than exposed mask is not used, the pattern (pattern 2) for the full coat film that film thickness is 3 μm has also been made according to same sequence.
Then, the optical density (OD) of the per unit film thickness (1 μm) of above-mentioned pattern 2 is determined using foregoing method. In addition, determining pattern 2 in the range of 300~450nm of wavelength, the range of 300~370nm of wavelength using foregoing method And the highest light transmittance of the range of wavelength 450nm~700nm.In addition, having carried out the height of pattern 1 using foregoing method Difference evaluation.These results are shown in table 3.
So, the photonasty for being 0.010% or more by using the highest transmissivity in 300~370nm of wavelength Color composition can form the difference in height of Desired Height in colouring spacer.In particular, as colorant in addition to organic pigment Also use carbon black, and make its content ratio be all coloring agent in 20 mass % hereinafter, light leakage can also be inhibited, and will not be damaged Evil difference in height.
On the other hand, in order to make the highest transmissivity in 300~370nm of wavelength be 0.010% or more and be hidden as high Light, including the method that combines a variety of organic pigments as the comparative example 1.But along with a variety of absorption light have been applied in combination Different organic pigments is composed, is partly increased in specific wave-length coverage transmissivity, that is, exist in specific wave-length coverage shading Property tendency that is partly insufficient and generating light leakage.For example, according to the difference of the combination of used pigment kind, in short wavelength region Transmissivity partly increases sometimes for domain, long wavelength region.
Therefore, as Examples 1 to 55, other than above-mentioned organic pigment, whole waves in visible light region are also used The comprehensively carbon black with absorption spectrum in length, even if to which transmission can be reduced if the described particular range of wavelengths in front Rate, especially by making the content ratio of carbon black be 20 mass % or less in all coloring agent, it is believed that front institute will not be damaged The formative for the difference in height stated, and the full scope in the wavelength 450nm to 700nm as visible light region can also be inhibited In light leakage.
On the other hand, it is known that be added specifically in the mixed system of organic black pigments and carbon black as comparative example 2 The method of blue pigment.But since the highest transmissivity in 300~370nm of wavelength is low, it is difficult to form desired difference in height.
In addition, it is also known that the method that organic black pigments and specific blue pigment are applied in combination like that for comparative example 3, but Due to being free of carbon black as the comparative example 1, partly increase in specific wave-length coverage transmissivity, as visible light region The inhibition of light leakage in the full scope of wavelength 450nm to 700nm is insufficient.In addition, since pigment concentration is low, The cure components such as alkali soluble resin, photopolymerization monomer are more, it is difficult to control difference in height.
As the content ratio of the high carbon black of ultraviolet-absorbing comparative example 4 in all coloring agent more than 20 mass % In the case of, it is believed that the highest transmissivity of 300~370nm of wavelength is low, solidification corresponding to the intermediate pattern through opening portion It becomes inadequate, in development, the pattern is removed.
Using specific mode, the present invention is described in detail, but those skilled in the art it should be clear that Without prejudice to the intent and scope of the present invention, various modifications may be made, deformation.It should be noted that the application Shen is proposed based on 2 12nd, 2016 Japanese patent applications (Patent 2016-024975) filed an application and September in 2016 within 2nd Japanese patent application (Patent 2016-172027) please and complete, entire contents are introduced in the application as reference.
Industrial applicibility
Coloring spacer formation photosensitive coloring composition according to the present invention can provide light-proofness height, master space The difference in height of object and secondary spacer is controlled, and in the full scope of the wavelength 450nm to 700nm as visible light region In the solidfied material that is also inhibited of light leakage and coloring spacer, it is furthermore possible to also provide having such coloring spacer Image display device.Therefore, the present invention is in coloring spacer formation photosensitive coloring composition, solidfied material, coloring spacer And industrial practicability is high in each field of image display device.

Claims (11)

1. a kind of coloring spacer formation photosensitive coloring composition, contains:(a) colorant, (b) alkali soluble resin, (c) Photoepolymerizationinitiater initiater, (d) olefinic unsaturated compound, (e) solvent and (f) dispersant, wherein
(a) colorant includes (a-1) organic pigment and (a-2) carbon black,
(a-2) carbon black relative to (a) colorant content ratio be 20 mass % hereinafter, also,
The photosensitive coloring composition is 0.010% or more in the highest transmissivity of 300~370nm of wavelength.
2. coloring spacer formation photosensitive coloring composition according to claim 1, wherein (a-1) is organic Pigment contains selected from least one of red pigment, orange pigment, blue pigment and violet pigment.
3. coloring spacer formation photosensitive coloring composition according to claim 1 or 2, wherein (a-1) has Machine pigment contain selected from least one of red pigment and orange pigment and in blue pigment and violet pigment extremely Few one kind.
4. coloring spacer formation photosensitive coloring composition according to claim 1 or 2, wherein (a-1) has Machine pigment contains blue pigment and violet pigment.
5. coloring spacer formation photosensitive coloring composition according to any one of claims 1 to 4, wherein institute It states (a-1) organic pigment and contains organic black pigments.
6. coloring spacer formation photosensitive coloring composition according to claim 5, wherein organic black face Expect for the geometry of following formula (1) compound represented, the geometric isomer of the compound, the salt of the compound or the compound The salt of isomers,
In above-mentioned formula (1), R1And R6Independently of one another hydrogen atom, CH3,CF3, fluorine atom or chlorine atom;
R2,R3,R4,R5,R7,R8,R9And R10It is independently of one another hydrogen atom, halogen atom, R to each other11,COOH,COOR11,COO-, CONH2,CONHR11,CONR11R12,CN,OH,OR11,COCR11,OOCNH2,OOCNHR11,OOCNR11R12,NO2,NH2,NHR11, NR11R12,NHCOR12,NR11COR12, N=CH2, N=CHR11, N=CR11R12,SH,SR11,SOR11,SO2R11,SO3R11,SO3H, SO3 -,SO2NH2,SO2NHR11Or SO2NR11R12;
Also, it is selected from R2With R3,R3With R4,R4With R5,R7With R8,R8With R9And R9With R10At least one of combination optionally mutually between Direct Bonding or pass through oxygen atom, sulphur atom, NH or NR11Bridging and be mutually bonded;
R11And R12The independently of one another alkyl of carbon atom number 1~12, the naphthenic base of carbon atom number 3~12, carbon atom number 2~12 Alkenyl, the cycloalkenyl group of carbon atom number 3~12 or the alkynyl of carbon atom number 2~12.
7. according to coloring spacer formation photosensitive coloring composition according to any one of claims 1 to 6, after solidification The optical density of average every 1 μm of film thickness of film be 1.0 or more.
8. coloring spacer formation photosensitive coloring composition according to any one of claims 1 to 7, is used to lead to It crosses photoetching process and disposably forms the different coloring spacer of height.
9. a kind of solidfied material is by coloring spacer formation photosensitive color group according to any one of claims 1 to 8 It closes obtained from object solidification.
10. a kind of coloring spacer is formed by the solidfied material described in claim 9.
11. a kind of image display device has coloring spacer according to any one of claims 10.
CN201780010607.XA 2016-02-12 2017-02-09 Colour spacer photosensitive coloring composition, solidfied material, coloring spacer, image display device Pending CN108700685A (en)

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