CN104977808A - Black photosensitive resin composite and black matrix made from the black photosensitive resin composite - Google Patents

Black photosensitive resin composite and black matrix made from the black photosensitive resin composite Download PDF

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Publication number
CN104977808A
CN104977808A CN201510158131.7A CN201510158131A CN104977808A CN 104977808 A CN104977808 A CN 104977808A CN 201510158131 A CN201510158131 A CN 201510158131A CN 104977808 A CN104977808 A CN 104977808A
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Prior art keywords
black
methyl
photosensitive resin
compound
acid
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柳廷昊
陆成熏
李在乙
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • 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
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)

Abstract

The invention discloses a black photosensitive resin composite and a black matrix made from the black photosensitive resin composite. The black photosensitive resin composite includes: (A) colorant, (B) alkali soluble resin, (C) photopolymerized compound, (D) photopolymerization initiator, and (E) solvent, wherein the colorant (A) includes carbon black with a primary particle diameter 20 nm to 60 nm; when the OD value is 1.5, the I-beam light transmittance of the carbon black is 0.3 or greater; the (B) alkali soluble resin is prepared through polymerization of monomer in the formula 1, thus reducing the difference of the optical density of the position and realizing the excellent pattern straightness.

Description

Black-colored photosensitive resin composition and the black matrix" manufactured with it
Technical field
The present invention relates to black-colored photosensitive resin composition and by its manufacture black matrix" and colored filter, the invention particularly relates to can be formed have improve linearity pattern black-colored photosensitive resin composition and by its manufacture black matrix" and colored filter.
Background technology
For in the colored filter of liquid crystal display, black matrix" has to block outside transparent small electrode and sends and the function of uncontrolled light, thus improves optical contrast ratio.Described black matrix" can be that raw material obtains with chromium or resin.When using chromium, film shading performance and pattern lines degree are fabulous, but, due to the processing cost etc. of environmental problem, high reflectance, great number, therefore preferably use resin type black matrix.
But for the photosensitive polymer combination for the manufacture of resin type black matrix, owing to suppressing the black pigment of photosensitive property significantly, therefore photo-crosslinking can not occur effectively.In addition, exist such as be called as being corroded by crossing of causing of developer of " undercutting (undercut) ", stable developing is not enough and the problem such as light sensitivity reduction.1995-7002313 korean patent application discloses to improve sensitivity, in for the photosensitive polymer combination of black matrix", use caldo (caldo) resin.But described caldo resin has huge molecular structure and makes cohesive reduce.Specifically, for black matrix", in order to obtain required optical density (OD), the content of black pigment increases, and therefore significantly reduces cohesive.Therefore, 2000-0055255 KR published patent discloses and comprises the caldo resin and silane coupling agent that different monomers obtains through copolymerization.But foregoing invention relates to poor storage stability, during rear baking, when forming fine pattern by hot-fluid, causes the problem producing and depend on the difference of the optical density (OD) of position.
Meanwhile, because pattern is formed more subtly, therefore the linearity of the shape of pattern, particularly pattern becomes more important.In this respect, if reduce the thermal fluidity of the resin being used as photosensitive polymer combination in order to the difference reducing the optical density (OD) depending on position, then this can cause the problem of the linearity reducing pattern.
Side by side can improve the linearity of pattern and the technology reducing the difference of the optical density (OD) of pattern formed also is not disclosed.
Summary of the invention
The object of this invention is to provide black-colored photosensitive resin composition, described black-colored photosensitive resin composition has excellent pattern lines degree while the difference of the optical density (OD) of position is depended in reduction.
Meanwhile, another object of the present invention be to provide can form fine pattern and there is excellent storage stability and the black-colored photosensitive resin composition of sensitivity.
Above-mentioned purpose of the present invention will be realized by following characteristics:
(1) black-colored photosensitive resin composition, it comprises: (A) colorant, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater, and (E) solvent,
Wherein, described colorant (A) comprises and has the carbon black that primary partical diameter is 20nm to 60nm, and when OD value is 1.5, the i-light beam transmittance of described carbon black is 0.3 or larger, and
Described alkali soluble resin (B) is obtained through polymerization by the monomer comprising the monomer represented as shown in the formula 1:
[formula 1]
(wherein, n is the integer of 2 to 4).
(2) composition according to above-mentioned (1), wherein, the primary partical diameter range of described carbon black is from 30nm to 45nm.
(3) composition according to above-mentioned (1), wherein, with whole monomer by 100 parts by weight, the consumption of the described monomer represented by formula 1 is 10 weight portion to 40 weight portions.
(4) composition according to above-mentioned (1), wherein, described alkali soluble resin (B) is obtained through polymerization by the monomer also comprising the monomer represented as shown in the formula 2:
[formula 2]
(wherein, m is the integer of 0 to 2).
(5) composition according to above-mentioned (4), wherein, with whole monomer by 100 parts by weight, the consumption of the described monomer represented by formula 2 is 10 weight portion to 40 weight portions.
(6) with the black matrix" that the black-colored photosensitive resin composition according to any one of above-mentioned (1) to (5) is obtained.
(7) colored filter of the black matrix" according to above-mentioned (6) is comprised.
(8) image display device of the colored filter according to above-mentioned (7) is comprised.
Black-colored photosensitive resin composition of the present invention comprises the polymer resin containing specific monomer, to realize the performance of very excellent formation fine pattern while having low thermal fluidity, thus reduces the difference depending on the optical density (OD) of position.Therefore, the black matrix" that evenly can block strong backlight can be prepared.
In addition, black-colored photosensitive resin composition of the present invention comprises special carbon black, to solve the problem of the reduction pattern lines degree that may be caused by low thermal fluidity, thus, while the difference of the optical density (OD) of position is depended in reduction, guarantee excellent pattern lines degree.
In addition, black-colored photosensitive resin composition of the present invention has excellent storage stability, between the storage life, therefore do not relate to the change of physical property, demonstrates excellent sensitivity on the contrary.
Embodiment
The invention discloses black-colored photosensitive resin composition, it comprises: (A) colorant, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater, (E) solvent, wherein, described colorant (A) comprises and has the carbon black that primary partical diameter is 20nm to 60nm, and when OD value is 1.5, the i-light beam transmittance of described carbon black is 0.3 or larger, described alkali soluble resin (B) is obtained through polymerization by the monomer comprising the monomer represented such as formula 1, thus reduce the difference of the optical density (OD) depending on position, and realize excellent pattern lines degree.
Hereinafter, the present invention will describe in further detail.
< black-colored photosensitive resin composition >
Black-colored photosensitive resin composition of the present invention can comprise: (A) colorant, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater, and (E) solvent.Certainly, any additional component conventional in association area can also be comprised, such as adjuvant, and it is had no particular limits.
< (A) colorant >
Colorant of the present invention can comprise the carbon black as element, wherein, it is 20nm to 60nm that described carbon black has primary partical diameter, and when optical density (OD) value (optical concentration) is 1.5, the i light transmittance of described carbon black is 0.3 or larger.When using above-mentioned carbon black, uniform OD value and excellent sensitivity can be realized simultaneously.Specifically, by improving the thermal fluidity of described resin, the linearity of pattern can be increased significantly, and this will more specifically describe hereinafter.
Usually, ultraviolet to described black-colored photosensitive resin composition radiation can comprise, such as, the different radiative combinations such as such as g-light beam (436nm), h-light beam (405nm), i-light beam (365nm), j-light beam (330nm), k-light beam (310nm) (with regard to the different wave length of light launched from exposure device), are associated with the polymerization initiation efficiency of Photoepolymerizationinitiater initiater simultaneously.In other words, the sensitivity of described black-colored photosensitive resin composition and the transmittance significant correlation of different emission of light (g-light beam, h-light beam, i-light beam, j-light beam and k-light beam) relative to described black-colored photosensitive resin composition.
But the OD value scope of normally used black matrix" is 2 to 5.Therefore, in order to accurately measure transmittance, the OD value in visible wavelength (400nm to 780nm) scope is set to 1.5, when UV transparent rate is used, can obtain more accurate transmittance values.
Therefore, in order to realize enough sensitivity at above-mentioned wavelength, when the OD value of described black-colored photosensitive resin composition is controlled in 1.5, the i-light beam transmittance that described black-colored photosensitive resin composition can have is 0.3 or larger, be preferably 0.4 or larger, be more preferably 0.5 or larger.If above-mentioned i-light beam transmittance is less than above-mentioned numerical value, then described sensitivity can reduce.In addition, j-light beam is also correlated with in the initiation of the polyreaction of described Photoepolymerizationinitiater initiater, and its transmittance can be 0.15 or larger, is preferably 0.3 or larger.Similarly, k-light beam is also relevant to the initiation of the photopolymerization reaction of described Photoepolymerizationinitiater initiater, and its transmittance can be 0.05 or larger, is preferably 0.1 or larger.
For black-colored photosensitive resin composition of the present invention, the scope of the primary partical diameter that described colorant (A) (namely, carbon black) can have is 20nm to 60nm, to have desirable UV transparent rate.In addition, the lower limit of the primary partical diameter of described carbon black can be 30nm or larger, and the higher limit of the primary partical diameter of described carbon black can be 45nm or less.
For black-colored photosensitive resin composition of the present invention, if the primary partical diameter of described carbon black is less than 20nm, then the ultraviolet of radiation has low transmittance and can not provide enough sensitivity.In addition, be difficult to disperse described carbon black equably in described black-colored photosensitive resin composition, therefore can not obtain uniform OD value.On the other hand, when the primary partical diameter of described carbon black is 20nm or larger, enough UV transparent rates can be obtained, thus required sensitivity is provided, and improve dispersibility simultaneously.Result can obtain the black-colored photosensitive resin composition that can provide uniform OD value.In addition, use has the carbon black that primary partical diameter is 30nm or larger and can realize higher UV transparent rate, therefore strengthens photonasty, improves dispersibility further.Therefore, can obtain can provide evenly the black-colored photosensitive resin composition of OD value.
In addition, for black-colored photosensitive resin composition of the present invention, when the primary partical diameter of described carbon black is more than 60nm, although achieve enough UV transparent rates, but described carbon deposition is in described black-colored photosensitive resin composition, this causes carbon black to be difficult to disperse equably in black-colored photosensitive resin composition.In addition, because roughness increases, therefore above-mentioned black-colored photosensitive resin composition is used also to be difficult to form the black matrix" with good form.On the other hand, when described carbon black has the primary partical diameter of 60nm or less, enough UV transparent rates can be realized, therefore obtain required sensitivity, improve dispersibility further.In addition, when described carbon black has the primary partical diameter of 45nm or less, enough UV transparent rates can be realized, therefore can obtain required sensitivity, improve dispersibility further, thus can be easy to process in a manufacturing process.
Usually, in order to keep contrast image in the black matrix" that formed of the described black-colored photosensitive resin composition of application, needing to have the shading rate being expressed as 1.5 or larger with OD value, being preferably 3.0 or more greatly, being more preferably 4.0 or larger.
Simultaneously, after described black light sensitive resin composition solidification and development, the interface of pattern is normally uneven, described pattern has structure as described below: the bottom (side with substrate contacts) of described pattern is more etched than the top of pattern more, namely, the structure in back taper.The thermal fluidity of interface resin described in operating in rear baking subsequently on pattern top can become even, so described taperer can have pyramidal structure forward, thus guarantees the linearity of pattern.
Therefore, when the alkali soluble resin being used to photosensitive resin combination has low thermal fluidity, this can cause the problem reducing pattern lines degree.The present invention's alkali soluble resin hereinafter described also demonstrates low thermal fluidity, and when it is used alone, the linearity of described pattern can reduce.
But, when using the carbon black according to the primary partical diameter with particular range of the present invention, can thermal fluidity be improved, thus strengthen the linearity of described pattern.When described primary partical diameter exceeds above-mentioned scope, the effect improving pattern lines degree can not be implemented.
Colorant of the present invention, except carbon black mentioned above, not departing from the scope of the object of the invention, may further include the typical pigment for association area and fuel.
(a1) pigment
Additionally pigment used in this invention can comprise organic pigment and inorganic pigment.
This organic pigment can comprise various for the pigment such as printing-ink, ink for inking, such as, phthalocyanine aluminum chloride (water-soluble azo pigment, insoluble azo colour), phthalocyanine color, quinacridone pigment, isoindolenone pigments, isoindoline pigment, perylene dye, Perynone pigment, dioxazines pigment, anthraquinone pigment, DIANTHRAQUINONE base pigment, anthracene pyrimidine pigment, anthanthrone pigment, yellow anthrone pigment, pyranthrone pigments or diketo-pyrrolo pyrrole pigments etc.
Described inorganic pigment has no particular limits, the metallic compound of such as metal oxide or metal complex can be comprised, more specifically, the oxide of at least one metal in chosen from Fe, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black etc. is comprised.
Specifically, described organic pigment and inorganic pigment can comprise, and such as, are put under the compound of pigment according to colour index (dyeing man and colorist association publish).More specifically, the pigment with following colour index (C.I.) number can be illustrated by citing, but has no particular limits it.
The pigment being used to pigment dispensing composition according to the present invention can comprise the typical organic pigment or inorganic pigment that are used to association area, and described pigment can be used alone or wherein two or more be combinationally used.
If necessary, above-mentioned pigment can through plastic resin treatment, utilize there is the acidic-group of introducing or the pigment derivative of basic group surface treatment, utilize the migration process of the surface of pigments of polymkeric substance, utilize the atomizing micronizing effect of sulfuric acid, with an organic solvent or the carrying out washing treatment of water removal of impurity, to remove the ionic impurity etc. produced by ion-exchange.
The object lesson of above-mentioned pigment can comprise: C.I. pigment yellow 20,24,31,53,83,86,93,94,109,110,117,125,129,137,138,139,147,148,153,154,166,173,180 and 185;
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242,254,255 and 264;
C.I. pigment violet 14,19,23,32,33,36 and 38;
C.I. pigment blue 15 (15:3,15:4,15:6 etc.), 21,28,64 and 76;
C.I. pigment Green 7,10,15,25,36,47 and 58;
C.I. pigment brown 28; Deng.
Above-mentioned pigment is preferably used as the dispersible pigment dispersion with equally distributed particle diameter.The process adding pigment dispersing agent and make it disperse in pigment can be comprised for disperseing the example of the method for the particle diameter of described pigment equably.According to above-mentioned method, described pigment is evenly dispersed in solution, to form dispersible pigment dispersion.
For black-colored photosensitive resin composition of the present invention, described pigment (a1) can be involved with the form of dispersible pigment dispersion composition.
Described dispersible pigment dispersion composition can comprise (a1) pigment, (a2) spreading agent, (a3) disperse replenishers and (a4) dispersion solvent, in order to easily realize storage stability and dispersiveness, (a5) dispersion resin can be added further.
In addition, described pigment (a1) can be 20 % by weight to 90 % by weight involved with range of solid content relative to the total weight of dispersible pigment dispersion composition, is preferably 30 % by weight to 70 % by weight.If the content of described pigment is not comprised in above-mentioned scope, because viscosity increases, described storage stability is deteriorated, dispersion efficiency step-down, thus causes the adverse effect to contrast.
(a2) spreading agent
Spreading agent is added into the anti-agglomeration effect allowing described pigment and dyestuff, keeps the stability of described pigment and dyestuff, and described spreading agent can comprise any one spreading agent conventional in association area, does not limit it.Preferably, described spreading agent comprises acrylate-based spreading agent (hereinafter, being called as acrylate dispersant), such as butyl methacrylate (BMA) or methacrylic acid N, N-diformazan ammonia ethyl ester (DMAEMA).The product of the commercial acrylate dispersant bought can comprise, such as, and DISPERBYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 etc.These acrylate dispersant can be used alone, or wherein two or more are combinationally used.
According to spreading agent of the present invention, except above-mentioned acrylate dispersant, the pigment dispersing agent of different resins type can also be comprised.This kind of different resins type pigment dispersing agent can comprise any known resin-bonded pigment spreading agent.Specifically, water soluble resin or water-soluble polymers, such as, it comprises polyurethane, polycarboxylate (such as the polyacrylate of its representative), unsaturated polyester acid amides, poly carboxylic acid, the amine salt of poly carboxylic acid, the ammonium salt of poly carboxylic acid, the alkylamine salt of poly carboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, the polycarboxylate that hydroxyl replaces and modified outcome thereof, the acid amides formed by the reaction of the polyester and poly-(low-molecular-weight acid imide) with carboxyl freely or its salt, (methyl) acrylic-styrene copolymer, (methyl) acrylic acid-acrylic acid (first) ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), polyvinyl pyrrolidone etc., polyester, the polyacrylate of modification, such as oxirane/addition product such as propylene oxide, phosphate can be used.
The commercial product for spreading agent of the present invention bought can comprise, as resin cation spreading agent, such as: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPERBYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPERBYK-182, and DISPER BYK-184 (trade name of Bi Ke chemistry); EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, and EFKA-4800 (trade name of BASF AG); SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 (trade name of Lubrizol Corp.); HINOACT T-6000, HINOACT T-7000, HINOACT T-8000 (trade name of Chuan Yan Fine Chemicals); AJISPURPB-821, AJISPUR PB-822, AJUSPUR PB-823 (trade name of aginomoto company); FLORENEDOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENEDOPA-44 (trade name of Kyoaisha chemicals) etc.
Be 100 parts by weight with the pigment in colorant, the consumption of described spreading agent can be 5 weight portion to 60 weight portions, be preferably 15 weight portion to 50 weight portions.When described spreading agent is more than 60 weight portion, viscosity can increase.If the consumption of described spreading agent is lower than 5 weight portions, be then difficult to the gelatification problem after guiding the micronizing effect of described pigment maybe can cause peptizaiton.
Except above-mentioned spreading agent, the surfactant of cationic, negative ion, non-ionic, both sexes, polyester-type and/or polyamine type can be used as spreading agent.These surfactants can be used alone or wherein two or more be combinationally used.
The object lesson of above-mentioned surfactant can comprise polyoxyethylene alkyl ether class, polyxyethylated benzyl ethers, polyethylene glycol di class, Span class, fatty acid modified polyesters, tertiary amine groups modified polyurethane, polyethyleneimine etc.Except surfactant mentioned above, the commercial surfactant product bought can comprise, such as, KP (being produced by chemical industry company limited of SHIN-ETSU HANTOTAI), POLYFLOW (being produced by common prosperity chemical industry company limited), EFTOP (being produced by Tochem Products company), MEGFAC (being produced by large Japanese ink chemical industry company limited), Flourad (being produced by 3M company limited of Sumitomo), Asahi guard and Surflon (company limited produces by Asahi Glass), SOLSPERSE (being produced by Noveon Inc.), EFKA (being produced by EFKA chemical company), PB 821 (company limited produces by aginomoto) etc.
(a3) replenishers are disperseed
Described dispersion replenishers are used to described pigment to be dispersed into the form of particulate and the reagent preventing them from again reuniting.This dispersion replenishers are effective for forming the colorant with high-contrast and excellent light transmittance.
The present invention can dispersion replenishers can comprise, such as: 1, 8-diamido-4, 5-dihydroxy anthraquinone, 1, 5-two { [2-(lignocaine) ethyl] is amino } anthracene-9, 10-quinone, 1, two (this formamido) anthraquinone of 8-, 1, 4-two { [2-(4-hydroxyphenyl) ethyl] is amino } anthracene-9, 10-quinone, 1, two { [2-(dimethylamino) ethyl] is amino }-5 of 4-, 8-dihydroxy-anthracene-9, 10-quinone, 1, 8-dihydroxy-4-[4-(2-hydroxyethyl) benzamido group]-5-nitroanthracene-9, 10-quinone, 1, 4-dihydroxy anthraquinone, 1, two (the 4-butyl benzylamine base)-5 of 4-, 8-dihydroxy anthraquinone, 4'-(4-hydroxyl-1-anthraquinonyl is amino)-antifebrin, 1, 4-two [(2, 6-diethyl-4-aminomethyl phenyl) amino] anthraquinone, 1, two (butyl is amino)-9 of 4-, 10-amerantrone, 1, two (the 4-butyl benzylamine base)-5 of 4-, 8-dihydroxy anthraquinone, 1, two [(the 3-aminomethyl phenyl) amino-9 of 5-, 10-amerantrone, 1, 5-dicyclohexyl amino anthraquinones, 1, two (isopropylamino) anthraquinone of 4-, 1, two (methylamino) anthraquinone of 4-, 1, 4-two (2, 6-diethyl-4-methylbenzylamine base) anthraquinone, 2, 2'-(9, 10-dioxoanthracene-1, 4-diyldimino) two (5-metilsulfate), 1-benzamido group-4-hydroxy-anthraquione, 1-hydroxyl-4-[(4-aminomethyl phenyl) is amino]-9, 10-amerantrone, 1, two (para-totuidine base) anthraquinone of 4-, 1-amino-4-phenyl amino anthraquinones, N-[4-[(4-hydroxy-anthraquinone base-1-nyl) is amino] phenyl] acetamide, 1-(methyl amido)-4-(4-methylbenzylamine base)-9, 10-amerantrone and 1, 4, 5, 8-tetra hydroxyanthraquinone etc.
Except above-mentioned dispersion replenishers, selectively, the commercial dispersion replenishers product bought can be included further.Such as, SOLSPERSE-5000, SOLSPERSE-12000, with SOLSPERSE-22000 (Lubrizol Corp.), BYK-SYNERGIST 2100, with BYK-SINERGIST2105 (Bi Ke company), EFKA-6745, and EFKA-6750 (BASF AG) etc. can be used.
With the pigment in colorant by 100 parts by weight, the consumption of described dispersion replenishers can be 1 weight portion to 30 weight portion.When the consumption of described dispersion replenishers is more than 30 weight portion, there is the rotten and hard baking operation be colored further in layer preparation and fade in the intrinsic color of described colorant (A).
(a4) dispersion solvent
Described dispersion solvent can comprise any organic solvent being generally used for association area, and has no particular limits.
The object lesson of above-mentioned solvent can comprise: ethylene glycol monoalkyl ether (such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether etc.); Diethylene glycol alkyl ether (such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether etc.); Ethylene glycol alkylether acetates (such as methyl glycol acetate, ethoxyethyl acetate(EA) etc.); Alkylene glycols alkylether acetates (such as propylene glycol monoethyl ether acetic acid esters, ethoxy propyl acetate, propylene glycol one propyl ether acetic acid esters etc.); Aromatic hydrocarbon (such as benzene,toluene,xylene, 1,3,5-trimethylbenzene etc.); Ketone (such as MEK, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone etc.); Alcohols (such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.); Ester class (such as 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate, gamma-butyrolacton etc.).Preferably, use alkylene glycol alkyl ether acetic acid esters, ketone, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc., more preferably, propylene glycol monoethyl ether acetic acid esters, ethoxy propyl acetate, cyclohexanone, 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate etc. are used.
Described dispersion solvent can be used alone, or wherein two or more is combinationally used.
The content of described dispersion solvent has no particular limits, and such as, in the scope of 60-90 weight portion %, can be preferably 70-85 weight portion % relative to the general assembly (TW) of described pigment dispensing composition.If the content of described dispersion solvent exceeds above-mentioned scope, the storage stability of described pigment dispensing composition can be deteriorated.
(a5) dispersion resin
Described dispersion resin plays a role as the dispersion solvent of described colorant (A), can optionally be added into.Be used alone compared with spreading agent (a2), combine with dispersion resin (a5) the dispersible pigment dispersion composition making it possible to prepare and have excellent properties more.Described dispersion resin can comprise any one, has no particular limits it, as long as it can play a role as dispersion solvent.But consider the development of the black-colored photosensitive resin composition prepared by the form of dispersible pigment dispersion composition, the resin with acid number can be used, to realize the solubility to alkaline developer.
Here, described acid number be in and the measured value of total amount (mg) of potassium hydroxide needed for propenyl polymer, usually can be calculated by using the method for potassium hydroxide aqueous solution titration.
The described dispersion resin with acid number can by the carboxyl compound (b1) with unsaturated link with there is the compound (b2) that with compound (b1) unsaturated link of copolymerization can occur copolyreaction occur prepare.
The object lesson of above-mentioned dyestuff can comprise, described in there is unsaturated link carboxyl compound (b1) can comprise, such as: monocarboxylic acid (such as acrylic acid, methacrylic acid, butenoic acid etc.); Dicarboxylic acids (fumaric acid, methyl itaconic, methylene-succinic acid etc.) and their acid anhydrides; There is at its two ends unitary acrylic acid (first) ester polymer (such as ω-carboxyl polycaprolactone unitary acrylic acid (first) ester etc.) of carboxyl and hydroxyl, be preferably acrylic acid and methacrylic acid.In the present invention, described acrylic acid (first) ester refers to acrylate and methyl acrylate.
Can be used alone by the compound as compound (b1) enumerated, or wherein two or more are combinationally used respectively.There is the compound (b2) that can carry out the unsaturated link of copolymerization with compound (b1) can comprise, such as, aromatic ethenyl compound (such as styrene, vinyltoluene, α-methyl styrene, to chlorostyrene, o-methoxystyrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether etc.) etc., alkyl (methyl) acrylate (such as methyl (methyl) acrylate, ethyl (methyl) acrylate, n-pro-pyl (methyl) acrylate, isopropyl (methyl) acrylate, normal-butyl (methyl) acrylate, isobutyl (methyl) acrylate, sec-butyl (methyl) acrylate, the tert-butyl group (methyl) acrylate etc.), alicyclic (methyl) acrylate (such as cyclopentyl (methyl) acrylate, cyclohexyl (methyl) acrylate, 2-methylcyclohexyl (methyl) acrylate, thricyclohexyl [5,2,1,0,2,6] decane-8-base (methyl) acrylate, 2-bicyclopentyl oxygen ethyl (methyl) acrylate, isobornyl (methyl) acrylate etc.), aryl (methyl) acrylate (such as phenyl (methyl) acrylate, benzyl (methyl) acrylate etc.), hydroxyalkyl (methyl) acrylate (such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate etc.), N-replaces maleic amide compound (such as N-cyclohexyl maleic amide, N-benzyl maleic amide, N-phenyl maleimide, N-salicyl maleic amide, N-resorcyl maleic amide, N-is to hydroxyphenyl maleic amide, N-o-tolyl maleic amide, tolyl maleic amide between N-, N-p-methylphenyl maleic amide, N-o-methoxyphenyl maleic amide, N-m-methoxyphenyl maleic amide, N-p-methoxyphenyl maleic amide etc.), unsaturated acyl amines (such as (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide etc.), unsaturated oxetane compound (such as 3-(methacryl oxygen methyl) oxetanes, 3-(methacryl oxygen methyl)-3-Ethyloxetane, 3-(methacryl oxygen methyl)-2-trifluoromethyl oxetanes, 3-(methacryl oxygen methyl)-2-benzyl oxetanes, 2-(methacryl oxygen methyl) oxetanes, 2-(methacryl oxygen methyl)-4-trifluoromethyl oxetanes etc.), they can be used alone, or wherein two or more are combinationally used.
Can be used alone by the compound as compound (b2) enumerated, or wherein two or more are combinationally used respectively.
With the pigment in colorant by 100 parts by weight, the consumption of described dispersion resin can be 5 weight portion to 60 weight portions in solid content, is preferably 10 weight portion to 50 weight portions.When the consumption of described dispersion resin is more than 60 weight portion, described dispersion resin causes viscosity to increase.If the consumption of described dispersion resin is lower than 5 weight portions, then the consumption of described dispersion type resin is not enough, therefore, can not obtain the dispersible pigment dispersion composition of micronizing.
(a6) dyestuff
Described dyestuff can comprise any one, and has no particular limits it, as long as it has dissolubility in organic solvent.Specifically, preferably use following dyestuff, this dyestuff has the dissolubility to organic solvent, guarantees the reliability of the such as dissolubility to alkaline developer, thermotolerance and solvent resistant simultaneously.
Described dyestuff can comprise, and such as, is selected from the acid pigment with acidic-group (such as sulfonic acid or carboxylic acid); There is the salt of the acid dyes of nitrogen-containing compound; Any one in the sulfonamides compound of acid dyes and their derivant.Except above-mentioned substance, also can select azo group, oxa-anthryl or phthalocyanine base acid dyes and their derivant.
Specifically, above-mentioned dyestuff can comprise, and such as, is put under the compound of dyestuff or other are known to the dyestuff disclosed in printing and dyeing handbook (colour printing and dyeing company) according to colour index (dyeing man and colorist association publish).
The object lesson of above-mentioned dyestuff can comprise C.I. solvent dye:
C.I. solvent yellow 4,14,15,21,23,24,38,62,63,68,82,94,98,99 and 162;
C.I. solvent red 8,45,49,12,21,25 and 130;
C.I. solvent orange 2,7,11,15,26 and 56;
C.I. solvent blue 35,37,59 and 67;
C.I. solvent green 1,3,4,5,7,28,29,32,33,34 and 35 etc.;
Described dyestuff can comprise C.I. acid dyes, such as:
C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112,113,114,116,119,123,128,134,135,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243 and 251;
C.I. azogeramine, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422 and 426,
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169 and 173;
C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335 and 340;
C.I. acid violet 6B, 7,9,17 and 19;
C.I. acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106 and 109 etc.
Described dyestuff can comprise C.I. direct dyes, such as:
C.I. direct Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138 and 141;
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246 and 250;
C.I. direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106 and 107;
C.I. direct indigo plant 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293,
C.I. direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103 and 104;
C.I. direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79 and 82 etc.
Described dyestuff can comprise C.I. mordant dye, such as
C.I. mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62 and 65;
C.I. mordant rouge 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94 and 95;
C.I. mordant dyeing orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47 and 48;
C.I. mordant dyeing indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43,44,48,49,53,61,74,77,83 and 84;
C.I. mordant dyeing purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53 and 58;
C.I. viridon 1,3,4,5,10,15,19,26,29,33,34,35,41,43 and 53 etc.
Relative to the general assembly (TW) of described black-colored photosensitive resin composition of the present invention, the amount of involved described colorant (A) can be 20 % by weight to 80 % by weight in solid content, is preferably 35 % by weight to 70 % by weight.
< (B) alkali soluble resin >
Described alkali soluble resin can have activity to light or heat and alkali-soluble, can react as the dispersion solvent for the individual components in composition of the present invention.
Alkali soluble resin of the present invention can be obtained by the monomer polymerization comprising the monomer represented as shown in the formula 1.
[formula 1]
(wherein, n is the integer of 2 to 4)
Can improve the degree of adhesion of resin combination of the present invention and substrate such as formula 1 monomer represented, the resin of described polymerization does not have reactivity, and has been enhanced storage stability, therefore can not show change in live width along with the storage time.Further, during rear baking, thermal fluidity is low, depends on that the difference of the optical density (OD) of position can be enhanced, therefore, it is possible to preparation can block the black matrix" of backlight equably.
The compound represented by above formula 1 can comprise, specifically, and propenyl ethoxy succinate etc.Preferably, be selected from and can be used alone by any one in 4-(2-(acryloxy) ethoxy)-4-oxy butyrate, 5-(2-(acryloxy) ethoxy)-5-oxy pentanoic acid and 6-(2-(acryloxy) ethoxy)-6-oxy hexanoic acid, or used as potpourri, but it is had no particular limits.
The monomer represented by above formula 1, can be involved with 10-40 weight portion relative to whole monomers of the polymerization for alkali soluble resin (B) be introduced into.If the monomer represented by formula 1 is involved with the consumption lower than 10 weight portions, during formation pattern, the impact of the thermal fluidity after reducing during baking can become insignificant.Further, due to the formation of residual layer between pattern Formation period, linearity can be deteriorated.On the other hand, when above-mentioned consumption is more than 40 weight portions, due to the depositional phenomenon between pattern Formation period, therefore required linearity and uniformity of film cannot be obtained.
In addition, can pass through according to alkali soluble resin of the present invention (B), the monomer polymerization selectively comprising the monomer represented as shown in the formula 2 obtains.
[formula 2]
(wherein m is the integer of 0 to 2)
Monomer as above formula 2 expression can be reduced in the thermal fluidity during rear baking further, thus is reduced in the difference depending on the optical density (OD) of position between fine pattern Formation period further.
Can comprise such as formula 2 monomers represented, specifically, isobornyl methacrylate.Preferably, be selected from 1,7,7-trimethyl two ring [2,2,1] heptane-2-methyl acrylate, 7,7-dimethyl-1-propyl group two ring [2,2,1] heptane-2-methyl acrylate, 1-ethyl-7,7-dimethyl two ring [2,2,1] heptane-2-methyl acrylate and 1-ethyl-7, any one in 7-dimethyl two ring [2,2,1] heptane-2-methyl acrylate can be used alone, or used with their potpourri, it is had no particular limits.
Be 100 parts by weight with whole monomer, the consumption of the compound represented by above formula 2 can be 10 weight portion to 40 weight portions.If described consumption is lower than 10 weight portions, then between pattern Formation period, degree of adhesion dies down.When described content is more than 40 weight portion, be lowered along with to the increase development effect of base plate bonding degree, therefore cause and be difficult to form fine pattern.
Can the monomer polymerization that the monomer that can represent with molecular formula 2 or molecular formula 2 carries out the monomer of the unsaturated link of copolyreaction be had obtain by comprise further according to alkali soluble resin of the present invention.
Specifically, be selected from acrylic acid (first) ester compounds (here, described acrylic acid (first) ester comprises methyl acrylate and acrylate), aromatic vinyl compound, vinyl esters of carboxylic acids compound, vinyl cyanide based compound, maleimide compound, vinyl carboxylic acid ester compounds, unsaturated oxetane compound, monocarboxylic acid compound, dicarboxylic acid compound and any one had in carboxyl and hydroxyl can be further used alone at its two ends, or to use as potpourri.
Described acrylic acid (first) ester compounds can comprise, specifically, the alkyl ester compound (such as methyl (methyl) acrylate, ethyl (methyl) acrylate, butyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, benzyl (methyl) acrylate, aminoethyl (methyl) acrylate etc.) not being substituted or being substituted of unsaturated fatty acid; Undersaturated glycidyl carbonate (such as glycidyl methacrylate); The monocarboxylic acid ester compounds (such as low ethylidene glycol one alkyl (methyl) acrylate) etc. of ethylene glycol, is not particularly limited it.
The object lesson of aromatic ethenyl compound can comprise styrene, α-methyl styrene, vinyltoluene etc., but has no particular limits it.
The object lesson of vinyl esters of carboxylic acids compound can comprise vinyl acetate or propionate, but has no particular limits it.
The object lesson of the vinyl compound of prussiate can comprise vinyl cyanide, methacrylonitrile or α-chloro-acrylonitrile, but has no particular limits it.
The object lesson of maleimide compound can comprise N-N-cyclohexylmaleimide or N-phenylmaleimide, but has no particular limits it.
The object lesson of vinyl carboxylic acid ester compounds can comprise vinyl acetate or propionate, but has no particular limits it.
The object lesson of unsaturated oxetanes carbonate can comprise 3-methyl-3-acryloyloxymethyl oxetanes, 3-methyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-methyl-3-acryloyl-oxyethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloyl-oxyethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes etc., but it is had no particular limits.
The object lesson of monocarboxylic acid compound can comprise acrylic acid, methacrylic acid, butenoic acid etc., but has no particular limits it.
The object lesson of dicarboxylic acid compound can comprise fumaric acid, mesaconic acid or itaconic acid, but has no particular limits it.
The object lesson respectively at each compound two ends with the compound of carboxyl and hydroxyl can comprise ω-carboxyl polycaprolactone, unitary acrylic acid (first) ester etc.But it is had no particular limits.
If necessary, then alkali soluble resin of the present invention may further include various different known and usually carried out alkali soluble resin used in combination in association area by with resin of the present invention.
It is 3000 to 100000 that described alkali soluble resin can have weight-average molecular weight, preferably, is 5000 to 50000 for polystyrene.If the weight-average molecular weight of described alkali soluble resin exceeds above-mentioned scope, then during developing, do not prevent the minimizing of film, thus the appearance causing pattern part to lack.
The acid number of alkali soluble resin can in the scope of 20 to 200 (KOHmg/g), preferably at 60 to 140 (KOHmg/g), more preferably at 80 to 135 (KOHmg/g), most preferably at 80 to 130 (KOHmg/g).If the scope of described acid number is in the scope of 20 to 200 (KOHmg/g), the dissolubility of developer can be enhanced, and residual layer speed also can be increased.
In this regard, described acid number be meant to in and the consumption (mg) of potassium hydroxide needed for 1g acryl polymer, usually can be calculated by using the method for potassium hydroxide aqueous solution titration.
Relative to the general assembly (TW) of black-colored photosensitive resin composition of the present invention, the content of above-mentioned alkali soluble resin can be 10 % by weight to 80 % by weight in solid content, is preferably 10 % by weight to 70 % by weight.In above-mentioned scope, it is enough in the solubleness of developer, thus easily forms pattern, and can prevent the minimizing being positioned at the film of the pixel portion in exposure portion when developing, and therefore advantageously protects non-pixel portion without disappearance.
< (C) photopolymerizable compound >
The photopolymerizable compound that black-colored photosensitive resin composition of the present invention comprises refers to the compound that can be obtained by the active institute initiated polymerization of light and Photoepolymerizationinitiater initiater as mentioned below, and can comprise simple function group, difunctional and/or other multi-functional monomer.
The present invention's photopolymerizable compound used can comprise the photopolymerizable compound that two or more have different functional groups structure or number of functional groups, to improve development capability, sensitivity and cohesive, and overcome the cosmetic issue in black-colored photosensitive resin composition, but the scope of above-claimed cpd has no particular limits.The object lesson of Monofunctional monomers can comprise nonyl phenyl acrylate, 2-hydroxyl 3-benzene oxygen propyl acrylate, 2-ethylhexyl diglycol one ethyl ether acetate ester, 2-hydroxy-ethyl acrylate, NVP etc.Bifunctional monomer can comprise, such as, two (methyl) acrylate of 1,6-hexanediol, ethylene glycol bis (methyl) acrylate, two (methyl) acrylate of neopentyl glycol, triethylene glycol two (methyl) acrylate, two (acrylyl oxy-ethyl) Bisphenol A Ether, two (methyl) acrylate of 3-methyl pentanediol base etc.In addition, polyfunctional monomer can comprise, such as, trihydroxy methyl propyl group three (methyl) acrylate, ethoxy trihydroxy methyl propyl group three (methyl) acrylate, propoxyl group trihydroxy methyl propyl group three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, bipentaerythrite five (methyl) acrylate, ethoxy dipentaerythritol six (methyl) acrylate, propoxyl group dipentaerythritol six (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc.Wherein, polyfunctional monomer (such as difunctional or polyfunctional monomer) is more appropriately used.
Press 100 parts by weight relative to the general assembly (TW) of the alkali soluble resin in chromatic photosensitivity composition and photopolymerization compounds, the content of described photopolymerization compounds can be that 1 weight portion to 90 weight portion, preferably 10 weight portion to 80 weight portions use in solid content.
< (D) Photoepolymerizationinitiater initiater >
Photoepolymerizationinitiater initiater used herein can comprise any Photoepolymerizationinitiater initiater conventional in association area, has no particular limits it.
Such as, one or more compounds be selected from compound in triazine class, acetophenone compounds, bisglyoxaline compounds and oxime compound can be used, but are not limited to this.Described photosensitive polymer combination comprises and has highly sensitive Photoepolymerizationinitiater initiater.
Described compound in triazine class can comprise, such as 2, 4-bis-(trichloromethyl)-6-(4-methoxyphenyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(4-methoxyl naphthyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-3, 4-(methylenedioxy) benzyl-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-(4-methoxyethyl)-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-[2-(5-methylfuran-2-base) ethylidine]-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-[2-(furans-2-base) ethylidine]-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-[2-(4-dimethylamino-2-tolyl) ethylidine]-1, 3, 5-triazine, 2, 4-bis-(trichloromethyl)-6-[2-(3, 4-Dimethoxyphenyl) methine]-1, 3, 5-triazine etc.
Described acetophenone compounds can comprise, such as, resacetophenone, 2-hydroxy-2-methyl-1-phenylpropyl-1-ketone, pheiiyldimetliyl ketal, 1-hydroxyl-1-[4-(2-hydroxyethyl) phenyl]-2-methyl-propyl-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methylbenzene sulfydryl)-2-morphoinopropyl-1-ketone, 2-phenyl-2-dimethylamino-1-(4-morphlinophenyl) butyl-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propyl group-1-ketone etc.
Further, described acetophenone compounds can comprise, such as, by the compound shown in following formula 4.
[formula 4]
(wherein, R 1to R 4be independently of one another hydrogen atom, halogen atom, hydroxyl, can by the alkyl of carbon number 1-12 replace benzyl, can by the alkyl of carbon number 1-12 replace phenyl or can by the alkyl of carbon number 1-12 replace naphthyl).
Can be comprised by the compound shown in above formula 4, such as: 2-methyl-2-amino (4-morphlinophenyl) ethyl-1-ketone, 2-ethyl-2-amino (4-morphlinophenyl) ethyl-1-ketone, 2-propyl group-2-amino (4-morphlinophenyl) ethyl-1-ketone, 2-butyl-2-amino (4-morphlinophenyl) ethyl-1-ketone, 2-methyl-2-amino (4-morphlinophenyl) propyl group-1-ketone, 2-methyl-2-amino (4-morphlinophenyl) butyl-1-ketone, 2-ethyl-2-amino (4-morphlinophenyl) propyl group-1-ketone, 2-ethyl-2-amino (4-morphlinophenyl) butyl-1-ketone, 2-methyl-2-methylamino (4-morphlinophenyl) propyl group-1-ketone, 2-methyl-2-dimethylamino (4-morphlinophenyl) propyl group-1-ketone, 2-ethyl-2-diethylamino (4-morphlinophenyl) propyl group-1-ketone etc.
Described bisglyoxaline compounds can comprise, such as: 2, and 2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (alkyl phenyl) bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (trialkylphenyl) bisglyoxaline, 4,4 ', 5,5 ' position is replaced the glyoxaline compound etc. with phenyl substituent by alkoxy carbonyl group.In above-claimed cpd, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline or 2,2'-bis-(2,3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is more appropriately used.
Described oxime compound can comprise adjacent carbethoxyl group-α-oxyimino group-1-phenyl propyl-1-ketone, or the compound etc. represented by formula 5, formula 6 and formula 7.
[formula 5]
[formula 6]
[formula 7]
Further, other Photoepolymerizationinitiater initiater well-known can be added into and uses together with above-mentioned initiating agent, as long as they do not damage effect of the present invention in the related art.These additional Photoepolymerizationinitiater initiaters can comprise, such as, styrax compounds, benzophenone compound, thioxanthone compounds, anthracene compounds etc., these compounds above-mentioned can be used alone, or wherein two or more are combinationally used.
Described styrax compounds can comprise, such as, and styrax, styrax methyl ether, styrax ethylether, benzoin isobutyl propyl group ether, benzoin isobutyl butyl ether etc.
Described benzophenone compound can comprise; such as; benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenones etc.
Described thioxanthone compounds can comprise, such as, and 2-isopropyl thioxanthone, 2,4-diethyl thioxanthones, 2,4-bis-chlorothiaxanthenones, 1-chloro-4-propoxyl group thioxanthone etc.
Described anthracene compounds can comprise, such as, and 9,10-dimethoxy anthracene, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene etc.
In addition to the above compounds, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, 10-butyl-2-chloro acridone, 2-methylanthraquinone, benzyl, 9,10-phenanthrenequione, camphorquinone, methyl phenyl glyoxylate methyl esters, cyclopentadiene titanium compound etc. can be used as Photoepolymerizationinitiater initiater.
In addition, the substituting Photoepolymerizationinitiater initiater having the group that chain tra nsfer can occur also can be used.This Photoepolymerizationinitiater initiater can comprise, such as, and compound disclosed in 3002-544205 Japanese patent application.
The described Photoepolymerizationinitiater initiater with the group that chain tra nsfer can occur can comprise, such as, by the compound shown in following formula 8-13.
[formula 8]
[formula 9]
[formula 10]
[formula 11]
[formula 12]
[formula 13]
In addition, according to the present invention, described Photoepolymerizationinitiater initiater can cause reagents recombination with photopolymerization and use.When using Photoepolymerizationinitiater initiater, the photopolymerization matched with it is coordinated to cause reinforcing agent, comprise above-mentioned Photoepolymerizationinitiater initiater and the photosensitive polymer combination of reinforcing agent that matches can have higher sensitivity, therefore form the pattern with the green coating layer of superior sensitivity.
Cause reinforcing agent as photopolymerization, preferably use aminated compounds or carboxylic acid compound.
Photopolymerization causes in the middle of reinforcing agent, and the object lesson of aminated compounds can comprise, such as: aliphatic amine compound (such as triethanolamine, methylethanolamine, triisopropanolamine etc.); Aromatic amine compound (4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethyl-p-toluidine, 4, (the common name: michaelis ketone (Michler ' s ketone), 4,4 '-bis-(lignocaine) benzophenone etc. of 4 '-bis-(dimethylamino) benzophenone.Wherein, aromatic amine compound is more appropriately used by as aminated compounds.
Photopolymerization causes in reinforcing agent, and the object lesson of carboxylic acid compound can comprise the assorted substituted acetic acid (such as phenyl acetic acid, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenylthio acetic acid, dimethoxyphenylthio acetic acid, chlorophenylthio acetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.) of fragrance.
The content of described Photoepolymerizationinitiater initiater in the scope of 0.1-40 weight portion, can be preferably 1-30 weight portion relative to the solid content of the general assembly (TW) of the alkali soluble resin in black-colored photosensitive resin composition and photopolymerizable compound.Further, described photopolymerization causes the content of reinforcing agent with reference to standard same as described above, in the scope of 0.1-50 weight portion, can be preferably 1-40 weight portion.If the content of described Photoepolymerizationinitiater initiater is in above-mentioned scope, described photosensitive polymer combination can become has high sensitivity, and the film layer using above-mentioned composition to be formed also can have excellent sensitivity and cut without the need to pattern.In addition, if described photopolymerization causes reinforcing agent in above-mentioned scope, the sensitivity of described Photosensitve resin composition will be raised, and the film layer using this composition to be formed can have the advantage in the stability of pattern.
< (E) solvent >
Solvent used herein can be any one be usually used in association area, has no particular limits.
The object lesson of described solvent can comprise ethylene glycol monoalkyl ether class (such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether etc.), diethylene glycol dialkyl ether class (such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether etc.), ethylene glycol alkylether acetates class (such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.), alkylene glycols alkylether acetates (such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic acid esters, methoxyacetic acid butyl ester, methoxyacetic acid pentyl ester etc.), propylene-glycol monoalky lether class (such as propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether etc.), propylene glycol dialkyl ether (such as Propylene Glycol Dimethyl Ether, propylene glycol diethyl ether, propylene glycol methyl ether, propylene glycol dipropyl ether, propylene glycol methyl propyl ether, propylene glycol ethyl propyl ether etc.), propylene glycol alkyl ether propionic acid ester (such as methyl proxitol propionic ester, propylene glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.), butylene glycol monoalky lether comprises methoxybutanol, ethoxybutanol, propoxyl group butanols, butoxy butanols etc., butylene glycol monoalkyl acetic acid esters (such as methoxybutyl acetic acid esters, ethoxybutyl acetic acid esters, propyloxybutyl acetic acid esters, butoxybutyl acetic acid esters etc.), butylene glycol monoalkyl propionic acid ester (such as methoxybutyl propionic ester, ethoxybutyl propionic ester, propyloxybutyl propionic ester, butoxybutyl propionic ester etc.), dipropylene glycol dialkyl ether (such as dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether etc.), compound fragrant hydrocarbon (such as benzene,toluene,xylene, trimethylbenzene etc.), ketone (such as MEK, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone etc.), alcohols (such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.), ester class (such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxyethyl propyl ester, 2-hydroxy-methyl methyl propyl ester, 2-hydroxy-methylethyl propyl ester, hydroxymethyl ethyl ester, hydroxyethyl ethyl ester, hydroxybutyl ethyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxymethyl propyl ester, 3-hydroxyethyl propyl ester, 3-hydroxypropyl propyl ester, 3-hydroxybutyl propyl ester, 2-hydroxy-3-methyl methylbutyl butenoate, methoxy ethyl ester, , methoxy ethyl ethyl ester, methoxy-propyl ethyl ester, methoxybutyl ethyl ester, ethoxyl methyl ethyl ester, ethoxyethyl group ethyl ester, ethoxycarbonyl propyl ethyl ester, ethoxybutyl ethyl ester, propoxy methyl ethyl ester, Among ethyl ester, propoxypropyl ethyl ester, propyloxybutyl ethyl ester, butoxymethyl ethyl ester, butoxyethyl group ethyl ester, butoxypropyl ethyl ester, butoxybutyl ethyl ester, 2-methoxy propyl ester, 2-methoxy ethyl propyl ester, 2-methoxy-propyl propyl ester, 2-methoxybutyl propyl ester, 2-ethoxyl methyl propyl ester, 2-ethoxyethyl group propyl ester, 2-ethoxycarbonyl propyl propyl ester, 2-ethoxybutyl propyl ester, 2-butoxymethyl propyl ester, 2-butoxyethyl group propyl ester, 2-butoxypropyl propyl ester, 2-butoxybutyl propyl ester, 3-methoxy propyl ester, 3-methoxy ethyl propyl ester, 3-methoxy-propyl propyl ester, 3-methoxybutyl propyl ester, 3-ethoxyl methyl propyl ester, 3-ethoxyethyl group propyl ester, 3-ethoxycarbonyl propyl propyl ester, 3-ethoxybutyl propyl ester, 3-propoxy methyl propyl ester, 3-Among propyl ester, 3-propoxypropyl propyl ester, 3-propyloxybutyl propyl ester, 3-butoxymethyl propyl ester, 3-butoxyethyl group propyl ester, 3-butoxypropyl propyl ester, 3-butoxybutyl propyl ester etc.), cyclic ethers class (such as tetrahydrofuran, pyrans etc.), cyclic esters (such as gamma-butyrolacton etc.).The above-mentioned compound enumerated can be used alone or will wherein at least two or more combinationally use.
Consider the character of application and dyestuff, here solvent used can be ester class, such as, it comprises alkylene glycol alkyl ether acetic acid ester, ketone, butylene glycol alkylether acetates, butylene glycol monoalkyl ethers, 3-ethoxyethyl propionic ester, 3-methoxyl methyl propionic ester etc.More preferably, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, cyclohexanone, methoxyacetic acid butyl ester, methoxybutanol, 3-ethoxyethyl propionic ester, 3-methoxyl methyl propionic ester etc. can be used.
Relative to the general assembly (TW) of photosensitive polymer combination comprising this solvent, the content of described solvent in the scope of 50 % by weight to 90 % by weight, can be preferably 60 % by weight to 85 % by weight.If described solvent is in above-mentioned scope, due to when described solvent is by using rotary coating machine, the rotary coating machine of slit &, slit type coater (being sometimes called slot-die-coating head or Curtain flow coater), ink-jet etc. applied, good Painting effect can be obtained, because of but favourable.
< (F) adjuvant >
Photosensitive polymer combination according to the present invention may further include the polymerizable compound, hardening agent, levelling agent, adhesion inhibitors, antioxidant, ultraviolet light absorber, anti-coagulants, chain-transferring agent etc. that such as filling agent, confession substitute.
The object lesson of filling agent can comprise glass, silicon dioxide, aluminium oxide etc.
Object lesson for the polymerizable compound substituted can comprise curable resin (such as epoxy resin, maleimide resin etc.), thermoplastic resin (such as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-Fluoroalkyl acrylate, polyester, polyurethane etc.).
Described hardening agent is a kind of for deep solidification and the component improving physical strength, and the object lesson of hardening agent can comprise epoxy compound, polyfunctional isocyanate compound, melamine compound, oxetane compound etc.
The object lesson of the epoxy compound in described hardening agent can comprise the brominated derivative of bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, novalac epoxy, other aromatic epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, epihydric alcohol amine resin or epoxy resin; Except the epoxide of the aliphatic series of epoxy resin, alicyclic or aromatic epoxy compound and brominated derivative thereof, butadiene (being total to) polymkeric substance; The epoxide of isoprene (being total to) polymkeric substance; Glycidyl (methyl) acrylate (being total to) polymkeric substance; Triglycidyl group isocyanuric acid ester etc.
The object lesson of the oxetane compound in described hardening agent has no particular limits, can comprise, such as, carbonic acid dioxygen azetidine, dimethylbenzene dioxygen azetidine, hexane diacid dioxygen azetidine, terephthalic acid (TPA) dioxygen azetidine, cyclohexane dicarboxylic acid dioxygen azetidine etc.
Described hardening agent can have auxiliary curing agent compound, and described auxiliary curing agent compound makes the epoxy radicals of epoxy compound together with hardening agent or the oxetanes scaffolds open polymerization of oxetane compound.Described auxiliary curing agent compound can comprise, such as, and polyvalent carboxylic acid, polyvalent carboxylic acid's acid anhydride, acid agent etc.
Described carboxylic acid anhydrides can comprise any commercially available epoxy curing agent arrived.Described epoxy curing agent commercially can comprise, such as, Adekahadona EH-700 (trade name, manufactured by Adeka Engineering Co., Ltd), Likashitdo HH (trade name, manufactured by new Japanese Chemical Co., Ltd.), MH-700 (trade name is manufactured by new Japanese Chemical Company) etc.Above-mentionedly can be used alone or wherein two or more be combinationally used by the hardening agent enumerated.
Described levelling agent can comprise any commercially commercially available surfactant, such as silicones, fluorine, ester, the surfactant etc. of cationic, negative ion, non-ionic or both sexes, it can be used separately or wherein two or more be combinationally used.
Described surfactant can comprise, such as, and polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol di, fatty acid esters of sorbitan, fatty acid modified polyester, tertiary-amine modified polyurethane, polyethyleneimine etc.
Commercially commercially available surfactant can comprise, such as, KP (manufacture of chemical industrial company of SHIN-ETSU HANTOTAI), POLYFLOW (manufacture of common prosperity chemical company), EFTOP (being produced by Tochem Products Co., Ltd), MEGFAC (make and manufactured by Dainippon Ink. & Chemicals Inc), Flourad (being produced by 3M company limited of Sumitomo), Asahi guard and Surflon (being manufactured by Asahi Glass Co., Ltd), SOLSPERSE (being manufactured by company limited of Zeneca company), EFKA (being manufactured by EFKA chemical company), PB821 (being manufactured by Azinomoto company limited) etc.
Silane type constituents is more appropriately used as adhesion promotor, specifically, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycydoxy trimethoxy silane, 3-glycydoxy dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane etc. can be used.
Described antioxidant can comprise, specifically, and the 2-tert-butyl group-6-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-4-aminomethyl phenyl acrylate, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl acrylate, 6-[3-(3-tertiary butyl-4-hydroxy-5-methyl amyl) propoxyl group]-2,4,8,10-tetra-tert dibenzo [d, f] [1,3,2] dioxane phosphines, 3,9-bis-[2-{3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) oxopropoxy }-1,1-dimethyl ethyl]-2,4,8,10-tetra-oxa-spiral [5.5] undecanes, 2,2'-di-2-ethylhexylphosphine oxide (6-tert-butyl-4-methyl-Phenol), 4,4'-butylidene two (the 6-tert-butyl group-3-methylphenol), 4,4'-thiobis (the 2-tert-butyl group-5-methylphenol), 2,2'-thiobis (6-tert-butyl-4-methyl-Phenol), dodecane 3,3'-thiodipropionate, the tetradecane 3,3'-thiodipropionate, pentaerythrite four (3-dodecyl sulfo-) propionic ester, 1,3,5-tri-(3,5-di-tert-butyl-hydroxy phenyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, 3,3', 3 ", 5,5', 5 " and-six tert-butyl group-a, a', a "-(trimethylbenzene-2,4,6-tri-base) three paracresol, four [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, BHT etc.
Described ultraviolet light absorber can comprise, specifically, and 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.
Described chain-transferring agent can comprise, specifically, and lauryl mercaptan, 2,4-diphenyl-4-methyl-1-pentene etc.
< black matrix", colored filter and image display device >
The present invention also provides the black matrix" using described black-colored photosensitive resin composition to prepare, the colored filter comprising this black matrix" and comprises the image display device of above-mentioned colored filter.In addition, black-colored photosensitive resin composition of the present invention also can be used to manufacture black column spacer (column spacer).Therefore, colored filter of the present invention can comprise black column spacer further.
The image display device with above-mentioned colored filter can comprise, such as, and liquid crystal indicator, OLED, flexible display etc., but it is had no particular limits.On the contrary, can be exemplified at the known all types of applicable image display apparatus of correlative technology field.
Described black matrix" by being coated on substrate by black-colored photosensitive resin composition, then can carry out photocuring and development treatment to it, to form pattern to prepare.
First, described black-colored photosensitive resin composition is being coated on after on substrate, by heating and the substrate of drying coated cloth, is removing volatile components (such as solvent), thus level and smooth film is provided.
Coating process used herein can comprise, such as, and spin coating, soft painting, roller coat, slit & spin coating or slot coated etc.After coating, by heating and dry (freely toasting) or vacuum drying, then heated substrates thus volatile constituent (such as solvent) is volatilized.At this, normally, described heating carries out at the temperature of 70 DEG C-200 DEG C, is preferably 80 DEG C-130 DEG C.Heating and dried film thickness is generally 1 μm to 8 μm.Prepared film by the mask for the formation of pattern by ultraviolet radiation.At this, in order at whole expose portion with radiation parallel light beam equably, arrange described mask in the appropriate position relative to described substrate, the device as exposure machine or litho machine can be suitably used.When use ultraviolet carries out radiation to described film, solidified by the part of radiation.
Above-mentioned ultraviolet can comprise g-light beam (wavelength: 436nm), h-light beam, i-light beam (wavelength: 365nm) etc.The amount of ultraviolet radiation can be appropriately selected, but the present invention is not limited to this.After solidification the film that obtains can with developer contact, to dissolve and the unexposed portion that develop, thus the pattern needed for formation.
Developing method used herein can comprise the method that any one comprises liquid interpolation, dipping, spraying etc.In addition, described substrate can inclination at any angle in developing process.Described developer normally contains the water-soluble solution of alkali compounds and surfactant.Described alkali compounds can be selected from any one in inorganic and organo-alkali compound.Inorganic alkaline compound can comprise, such as, NaOH, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), potassium hydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium borate, potassium borate, ammonia etc.Described organic basic compound can comprise, such as, and Tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethyl amine, diethylamine, triethylamine, Mono Isopropylamine, diisopropylamine, monoethanolamine etc.
These mineral compounds and organic compound can be used alone or wherein two or more be combinationally used respectively.The concentration of the alkali compounds in alkaline developer can in the scope of 0.01 % by weight to 10 % by weight, preferably in the scope of 0.03 % by weight to 5 % by weight.
The surfactant of alkaline developer can for being selected from least one in the surfactant of non-ionic surfactant, anionic surfactant or both sexes.
Described non-ionic surfactant can comprise, such as, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkylaryl ether, other polyoxyethylene deriv, oxygen ethene/oxypropylene block multipolymer, sorbitan fatty ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine etc.
Described anionic surfactant can comprise, such as, higher alcohol sulfate salt (such as lauryl alcohol sodium sulfovinate or oleyl sulfate sodium), alkyl sulfate (such as lauryl sodium sulfate or ammonium lauryl sulfate), alkylaryl sulfomates (such as neopelex or dodecyl sodium naphthalene sulfonate) etc.
Described cationic surfactant can comprise, such as, and amine salt (such as stearyl amine hydrochloride) or DTAC, quaternary ammonium salt etc.These surfactants can be used alone, or wherein two or more are combinationally used respectively.
The concentration of the surfactant in developer can 0.01 % by weight to 10 % by weight, preferably change in the scope of 0.05 % by weight to 8 weight portion %, more preferably 0.1 % by weight to 5 weight portion %.After development treatment, after products obtained therefrom is cleaned, selectively carry out the rear baking process of 10 minutes to 50 minutes at 150 DEG C to 230 DEG C.
According to above-mentioned process, black matrix" or black column spacer can be manufactured.The technical configuration of colored filter and being known in association area for its method manufactured, therefore, will no longer specifically describe.
Hereinafter, be preferred embodiment suggested more specifically to describe the present invention.But following example is only used for the present invention is described, those those skilled in the art will understand within the spirit and scope of the present invention significantly, and various change and modification are possible.This change and modification are comprised in the appended claims fully.
the preparation of < preparation example > dispersible pigment dispersion (M-1)
Using 20.0g carbon black (primary partical diameter is 23 μm), 6g as Ajisper PB821 (being produced by aginomoto fine chemistry), the 74g of spreading agent as the propylene glycol monomethyl ether of solvent, in bead mill, mix dispersion 12 hours, prepare dispersible pigment dispersion (M-1).
In addition, change according to following table 1 except carbon black, dispersible pigment dispersion M-2 to M-5, be applicable to the preparation process identical with M-1.
[table 1]
the synthesis of < synthesis example 1-20> alkali soluble resin
In the 1000mL flask that stirrer, thermometer, reflux condenser, tap funnel and nitrogen conduit are housed, propylene glycol monomethyl ether (PGMA), AIBN, 2-acryloyloxyethyl succinate class (B-1), normal phenyl maleimide, styrene, methacrylic acid and isoborneol methyl acrylic ester (B-2) is dropped into respectively with the metering of following table 3 and table 4, pass into nitrogen, use nitrogen displaced air, (the numerical value unit in following table 3 and table 4 is g).Then, after raising reacting liquid temperature to 100 DEG C while stirring, the thermotonus raised 7 hours.For synthesis alkali soluble resin, use final solid content, this solid content acid number and by GPC, measure weight-average molecular weight.Its result is as shown in following table 3 and table 4.(B-1) and (B-2) that each synthesis example uses is as shown in table 2 below.
[table 2]
[table 3]
[table 4]
the preparation of < embodiment 1-13> black-colored photosensitive resin composition
Utilize the composition of the composition shown in following table 5 and table 6, prepare black-colored photosensitive resin composition.Numerical value unit in following table 5 and table 6 is g.
[table 5]
[table 6]
the preparation of < comparative example 1-7> black-colored photosensitive resin composition
The composition of the composition according to following table 7, prepares black-colored photosensitive resin composition.Numerical value unit in following table 7 is g.
[table 7]
< experimental example 1> is to the evaluation of thermal fluidity
Be applied to after on glass substrate by each black-colored photosensitive resin composition prepared by described embodiment 1-13 and comparative example 1-7, the substrate of described coating is placed on heating plate, and keeps 2 minutes at the temperature of 100 DEG C, to form film.Then, load test pieces photomask on the membrane, the distance irradiation ultraviolet radiation of 50 μm between test pieces photomask and film, described test pieces photomask has the pattern of transmittance stepped change within the scope of 1-100% and the live width/pitch pattern (line/space pattern) of 1 μm-50 μm.At this on the one hand, ultraviolet light source uses the 1kW high-pressure mercury-vapor lamp containing whole g-light beam, h-light beam, i-light beam, with 50mJ/cm 2irradiance irradiate.Do not use any special optical filter.To have irradiated ultraviolet film be soak in the water-soluble developer of KOH of 10.5 to develop for 2 minutes at pH by described.After being washed by the glass substrate distilled water being coated with this film, nitrogen blowing carries out drying, heats 20 minutes in the heating oven of 230 DEG C, thus obtained colored filter.The film thickness of above-mentioned obtained colored filter is 1.0 microns.The film thickness of 20 μm of patterns in residue exposure portion measure development before and after rear baking process after, mensuration thermal fluidity as described below, and by following standard, its result is evaluated, result is as shown in table 8 below.
*
More than zero: 97%; Δ: 95-97%; ×: less than 95%
[table 8]
As shown in table 8, can find out that the black-colored photosensitive resin composition of embodiment demonstrates thermal fluidity and reduces, the film thickness before and after rear baking process does not have large change.On the other hand, can find out that the black-colored photosensitive resin composition of comparative example demonstrates large thermal fluidity, thus cause the difference before and after rear baking process on generation film thickness.
< experimental example 2> is to the evaluation of storage stability
The shading black-colored photosensitive resin composition that above-described embodiment 1-13 and comparative example 1-7 is obtained places 5 days, 3 days, 1 day obtained sample respectively at 25 DEG C; Before carrying out utilizing standard model and the experiment of obtained sample evaluation pattern generating, be applied on glass substrate by obtained composition method of spin coating, then, the substrate of described coating is placed on heating plate, keep 2 minutes at 100 DEG C of temperature, to form film.And then, load test pieces photomask on the membrane, the distance irradiation ultraviolet radiation of 50 μm between test pieces photomask and film; Described test pieces photomask has the pattern of 20 μm.At this on the one hand, ultraviolet light source uses the 1kW high-pressure mercury-vapor lamp containing whole g-light beam, h-light beam, i-light beam, with 50mJ/cm 2irradiance irradiate, do not use special optical filter.To have irradiated ultraviolet film be soak in the water-soluble developer of KOH of 10.5 to develop for 2 minutes at pH by described.After being washed by the glass substrate distilled water being coated with this film, nitrogen blowing carries out drying, heats 20 minutes in the heating oven of 230 DEG C, obtained colored filter.In above-mentioned obtained colored filter, be determined at the wire spoke with the pattern that the photomask of 20 μm of wire spokes is formed respectively, measure the wire spoke variable quantity (Δ CD) of different standing time, its result is as shown in table 9 below.
Δ CD=carries out the pattern wire spoke evaluated with the resin combination after the resin combination obtained the same day carries out the pattern wire spoke evaluated-place with normal temperature
Less than zero: Δ CD=0.5 μm
Δ：ΔCD＝0.5-1.0μm
×: more than Δ CD=1.0 μm
[table 9]
As above, shown in table 9, the black-colored photosensitive resin composition of embodiment does not depend on that the pattern wire spoke of the time of composition placement is at normal temperatures poor.But the composition of comparative example starts the change demonstrating pattern wire spoke difference after placing 3 days.
< experimental example 3> is to the evaluation of fine property and susceptibility
Be applied to after on glass substrate by each black-colored photosensitive resin composition that described embodiment and comparative example obtain, the substrate of described coating is placed on heating plate, and keeps 2 minutes at the temperature of 100 DEG C, to form film.Then, load test pieces photomask on the membrane, the distance irradiation ultraviolet radiation of 50 μm between test pieces photomask and film, described test pieces photomask has according to 1 μm of unit, the pattern of the change from 2 μm to 20 μm.At this on the one hand, ultraviolet light source uses the 1kW high-pressure mercury-vapor lamp containing whole g-light beam, h-light beam, i-light beam, with 50mJ/cm 2irradiance irradiate.Do not use any special optical filter.To have irradiated ultraviolet film be soak in the water-soluble developer of KOH of 10.5 to develop for 2 minutes at pH by described.By be coated with this film the washing of glass substrate distilled water after, with observation by light microscope, to determine the size left on film of pattern (in μm), its result is as shown in table 10 below.
[table 10]
As shown in table 10, can find out that example composition is compared with the composition in comparative example, there is excellent fine patterns and sensitivity usually.
Specifically, embodiment achieves very excellent sensitivity, because described film has remain in the great majority on it lower than the pattern of 4 μm, the embodiment 4 except the monomer represented by formula 1 or formula 2 containing low content demonstrates fine patterns and sensitivity reduces slightly.
< experimental example 4> is to the evaluation of pattern lines degree
As described in experimental example 1 to 3, until after developing process carries out identical step, by described product distilled water, washed for 10 seconds by UHV (ultra-high voltage) washing methods (2MPa).After this, peeled off by observation by light microscope pattern, described linearity is evaluated by following standard.The result evaluated is as shown in table 11.
Zero: when measurement 10 μm of patterns, protruding or released part is of a size of 0.5 μm or larger, and its quantity is 1 or less
△: when measurement 10 μm of patterns, protruding or released part is of a size of 0.5 μm or larger, and their quantity is 2 or more, but is no more than 5
×: when measurement 10 μm of patterns, protruding or released part is of a size of 0.5 μm or larger, and their quantity is 5 or more
[table 11]
With reference to upper table 11, can find out, compared to those compositions in a comparative example, the composition in embodiment has more excellent pattern lines degree.

Claims (8)

1. a black-colored photosensitive resin composition, comprising: (A) colorant, (B) alkali soluble resin, (C) photopolymerizable compound, (D) Photoepolymerizationinitiater initiater, and (E) solvent,
Wherein, described colorant (A) comprises and has the carbon black that primary partical diameter is 20nm to 60nm, and when optical density OD value is 1.5, the i-light beam transmittance of described carbon black is 0.3 or larger, and
Described alkali soluble resin (B) is obtained through polymerization by the monomer comprising the monomer represented as shown in the formula 1:
[formula 1]
Wherein, n is the integer of 2 to 4.
2. composition according to claim 1, wherein, the primary partical diameter range of described carbon black is from 30nm to 45nm.
3. composition according to claim 1, wherein, with whole monomer by 100 parts by weight, the consumption of the described monomer represented by formula 1 is 10 weight portion to 40 weight portions.
4. composition according to claim 1, wherein, described alkali soluble resin (B) is obtained through polymerization by the monomer also comprising the monomer represented as shown in the formula 2:
[formula 2]
Wherein, m is the integer of 0 to 2.
5. composition according to claim 4, wherein, with whole monomer by 100 parts by weight, the consumption of the described monomer represented by formula 2 is 10 weight portion to 40 weight portions.
6. a black matrix", described black matrix" is made up of the black-colored photosensitive resin composition according to any one of claim 1-5.
7. a colored filter, comprises black matrix" according to claim 6.
8. an image display device, comprises colored filter according to claim 7.
CN201510158131.7A 2014-04-04 2015-04-03 Black photosensitive resin composite and black matrix made from the black photosensitive resin composite Pending CN104977808A (en)

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Application publication date: 20151014