WO2010110338A1 - 感光性着色組成物及びカラーフィルタ - Google Patents
感光性着色組成物及びカラーフィルタ Download PDFInfo
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- WO2010110338A1 WO2010110338A1 PCT/JP2010/055119 JP2010055119W WO2010110338A1 WO 2010110338 A1 WO2010110338 A1 WO 2010110338A1 JP 2010055119 W JP2010055119 W JP 2010055119W WO 2010110338 A1 WO2010110338 A1 WO 2010110338A1
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- acrylate
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- resin
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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
- G03F7/0005—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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- 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
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a photosensitive coloring composition, for example, a photosensitive coloring composition useful for forming a color filter used in a liquid crystal display device or a solid-state imaging device. Moreover, this invention relates to the color filter formed using this photosensitive coloring composition.
- the twisted nematic (TN) mode is a typical display mode adopted by the liquid crystal display device.
- a transmissive liquid crystal display device adopting a TN mode has a structure in which a liquid crystal layer is sandwiched between first and second polarizing plates.
- the liquid crystal layer allows the first linearly polarized light that has passed through the first polarizing plate to enter the second polarizing plate as it is, or converts it into circularly polarized light or elliptically polarized light and enters the second polarizing plate.
- the light is converted into a second linear change whose polarization plane is 90 ° different from that of the first linearly polarized light and is incident on the second polarizing plate. In this way, the amount of light transmitted by the second polarizing plate is controlled.
- Liquid crystal display devices usually display color images using color filters.
- the color filter is formed by arranging two or more kinds of fine band (striped) filter segments having different hues on a transparent substrate such as a glass substrate in parallel with each other or crossing each other. Two or more kinds of fine filter segments having different values are arranged so as to be sequentially arranged in each of the vertical direction and the horizontal direction.
- the filter segments have fine dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
- a transparent electrode for driving liquid crystal molecules is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal molecules in a certain direction is further formed thereon.
- Forming In order to sufficiently bring out the performance of the transparent electrode and the alignment film, the formation thereof is generally performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having not only light resistance but also excellent heat resistance as a colorant is mainly used.
- a colored layer such as a filter segment constituting the color filter is formed by the following method, for example.
- a pigment is dispersed in a resin such as an acrylic resin using a dispersant and a solvent to prepare a colored composition.
- a photopolymerizable monomer and a polymerization initiator are added to the colored composition to obtain a photosensitive colored composition.
- this photosensitive coloring composition is apply
- the colored layer is completed as described above.
- a photosensitive coloring composition is used as the coloring composition for the color filter. Therefore, part of the energy rays used for the photoreaction, for example, ultraviolet rays, are absorbed by the pigment. Therefore, when the pigment content of the coloring composition is high, even if the exposure amount in the surface side region is sufficient in the exposed portion of the coating film made of the photosensitive coloring composition, the exposure amount in the substrate side region May be insufficient. In this case, in the exposed part of the coating film obtained from the negative photosensitive coloring composition, the photocrosslinking is insufficient in the region on the substrate side, and the colored layer obtained through the subsequent development step is overhang ( Or undercut). For example, in this case, a colored layer having a reverse tapered shape, that is, a shape whose width increases as the distance from the substrate side increases is obtained.
- the cross section of the colored layer has a forward taper shape, that is, when the transparent electrode material is deposited on the colored layer by vapor deposition or sputtering when the width becomes narrower as the distance from the substrate side increases,
- This transparent electrode material covers not only the upper surface of the colored layer but also the inclined end surface thereof. Therefore, in this case, it is difficult to cause an electrical connection failure due to the discontinuous portion occurring in the transparent electrode.
- the transparent electrode material when the transparent electrode material is deposited on the colored layer having an overhang by vapor deposition or sputtering, the transparent electrode material is difficult to deposit below the overhang. It is likely to occur. That is, in this case, an electrical connection failure is likely to occur at a position below the overhang.
- JP 2007-114604 A in order to prevent overhang, at least one of acrylic acid ester and methacrylic acid ester, at least one of acrylic acid and methacrylic acid, hydroxyethyl acrylate and methacrylic acid are disclosed. It is described that a copolymer having a structure in which 2-isocyanate trimethylolethane triacrylate is added to a copolymer containing at least one kind of hydroxyethyl acid is used.
- Japanese Patent Application Laid-Open No. 2003-167115 describes that a colored layer having an overhang is heat-treated and deformed so that its cross section has a forward tapered shape.
- the photosensitive coloring composition is required to be capable of forming a colored layer having a forward tapered shape in cross section even when the pigment content is increased.
- the photosensitive coloring composition is also required to have excellent long-term storage stability.
- Japanese Unexamined Patent Application Publication No. 2004-101728 describes a photosensitive coloring composition containing a copolymer resin.
- This copolymer resin has a phenoxy group in which an unsubstituted or para hydrogen atom is substituted with an alkyl group at the side chain or the terminal.
- This copolymer resin is easily adsorbed on the pigment surface by the effect of ⁇ electrons on the benzene ring.
- the affinity of the pigment to the solvent is improved by adsorbing the copolymer resin. Therefore, this photosensitive coloring composition is excellent in long-term storage stability.
- a method of peeling a colored layer after post-baking from a glass substrate using a peeling liquid called a reworking liquid and returning the glass substrate to a state before applying the photosensitive coloring composition There is.
- the colored layer after post-baking has high heat resistance and high solvent resistance. Therefore, generally, a high-temperature and high-concentration strong alkaline solution is used as the rework liquid. In general, it is assumed that the rework liquid is recovered and reused. In this case, it is necessary to remove the peeling pieces from the used rework liquid using, for example, a filter.
- the present inventors investigated the reworkability when using the photosensitive coloring composition described in JP-A No. 2004-101728, and as a result, found the following facts. That is, the colored layer obtained from this photosensitive resin does not peel even if it is subjected to a treatment using a rework liquid after post-baking, or a peeled piece when it is subjected to a treatment using a rework liquid after post-baking. Can occur in the form of relatively large lumps. If the peeling piece is present in the rework liquid in the form of a relatively large lump, the filter is likely to be clogged.
- the present invention provides a photosensitive coloring composition that is excellent in pigment dispersion stability, can form a colored layer with a good cross-sectional shape, and can achieve good reworkability, and a color filter using the same.
- the purpose is to provide.
- the resin (A) contains a vinyl resin (F) in a proportion of 50% by weight or more based on the resin (A), and the vinyl resin (F) is a structural unit having a carboxyl group ( a) in a proportion of 2 to 50% by weight based on the vinyl resin (F), an aromatic ring group represented by the following general formula (1), an aromatic ring represented by the following general formula (2),
- the structural unit (b) having one or more kinds of cyclic structures selected from the group consisting of an aliphatic cyclic group represented by the formula (3) and an aliphatic cyclic group represented by the following general formula (4) is converted into the vinyl resin (F ) In a proportion of 2 to 50% by weight, and the other structural unit (c) is added to the vinyl resin (F Photosensitive coloring composition characterized by containing in
- R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring.
- one or more structural units selected from the group consisting of the structural units (a), (b) and (c) have an ethylene bond.
- a photosensitive coloring composition according to one aspect is provided.
- the precursor (a1) of the structural unit (a) is one or more monomers selected from the group consisting of acrylic acid and methacrylic acid.
- a photosensitive coloring composition according to the second aspect is provided.
- the carboxyl group contained in the structural unit (a) has an epoxy group by adding a polybasic acid anhydride to the structural unit having a hydroxyl group.
- the photosensitive coloring composition according to the first or second aspect, wherein the photosensitive coloring composition is introduced by adding a polybasic acid anhydride to a hydroxyl group formed by addition of a structural unit and an unsaturated monobasic acid. is provided.
- the precursor (b1) of the structural unit (b) is styrene, ⁇ -methylstyrene, indene, benzyl acrylate, benzyl methacrylate, a monomer represented by the following general formula (5), 1st thru
- a photosensitive coloring composition according to any one of the above is provided.
- the precursor (c1) of the structural unit (c) includes one or more monomers selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.
- a color filter comprising at least one of a filter segment and a black matrix formed from the photosensitive coloring composition according to any one of the first to sixth aspects. Provided.
- the above-mentioned photosensitive coloring composition is excellent in pigment dispersion stability.
- the photosensitive coloring composition has sufficient shape retention and relatively high thermoplasticity until it is completely cured. Therefore, even if the colored layer obtained from the photosensitive coloring composition has an overhang, the cross section thereof is a forward tapered shape by heat treatment at a high temperature of, for example, 150 ° C. or higher, typically 200 ° C. or higher. It can be made to be deformed. That is, a colored layer having a good cross-sectional shape can be formed.
- this photosensitive coloring composition is used, it is possible to achieve good reworkability.
- the photosensitive coloring composition according to one embodiment of the present invention is used for manufacturing a color filter included in a display device such as a liquid crystal display device and a solid-state imaging device or an electronic device, for example.
- This photosensitive coloring composition comprises a resin (A), a pigment (B), an active energy ray polymerization initiator (C), an active energy ray curable monomer (D), and a solvent (E). Contains.
- A a resin
- B a pigment
- C active energy ray polymerization initiator
- D active energy ray curable monomer
- E solvent
- the resin (A) contains the vinyl resin (F) in a proportion of 50% by weight or more with respect to the resin (A), preferably in a proportion of 60 to 100% by weight. .
- the vinyl resin (F) will be described in detail later.
- the transmittance of the resin (A) in the entire wavelength region of 400 to 700 nm is preferably 80% or more, more preferably 95% or more.
- the resin (A) is preferably used in a proportion of 30 to 700% by weight, more preferably 60 to 450% by weight, based on the weight of the pigment (B), from the viewpoint of dispersibility of the pigment.
- the resin (A) may not contain any resin other than the vinyl resin (F), but may further contain other resins in addition to the vinyl resin (F).
- a resin other than the vinyl resin (F) that the resin (A) can contain will be described.
- Examples of the resin other than the vinyl resin (F) that can be contained in the resin (A) include a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin. These can be used alone or in admixture of two or more.
- thermoplastic resin examples include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylenes such as high density polyethylene and low density polyethylene, polybutadienes and polyimide resins.
- thermosetting resin examples include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
- the active energy ray-curable resin for example, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group and an amino group has a reactive substituent such as an isocyanate group, an aldehyde group and an epoxy group (A resin in which a photocrosslinkable group such as a (meth) acryloyl group and a styryl group is introduced into the linear polymer by reacting with a (meth) acrylic compound or cinnamic acid is used.
- a photocrosslinkable group such as a (meth) acryloyl group and a styryl group is introduced into the linear polymer by reacting with a (meth) acrylic compound or cinnamic acid is used.
- the active energy ray-curable resin examples include linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and ⁇ -olefin-maleic anhydride copolymer, hydroxyalkyl (meth) Those half-esterified with a (meth) acrylic compound having a hydroxyl group such as acrylate are also used.
- the compound when the expression “(meth) acryl” is used for a certain compound, the compound is a compound obtained by replacing “(meth) acryl” with “acryl”, and “(meth) acryl”. "Is replaced with” methacryl ", which means that any of the compounds may be used. Further, in this specification, when the expression “(meth) acrylo” is used for a certain functional group, the functional group is a functional group obtained by replacing “(meth) acrylo” with “acrylo”, and “( It means that any of the functional groups obtained by replacing “meth) acrylo” with “methacrylo” may be used.
- the compound is a compound in which “(meth) acrylate” is replaced with “acrylate”, and “(meth) acrylate” "Is replaced with” methacrylate "which means any compound.
- Said photosensitive coloring composition contains vinyl resin (F) in the predetermined ratio with respect to resin (A).
- Such a photosensitive coloring composition has the following characteristics (1) to (4).
- the colored layer after post-baking can be removed with a rework solution such as a strong alkaline rework solution. Moreover, the peeling piece of the colored layer does not become coarse.
- the vinyl resin (F) includes the following structural units (a) to (c).
- structural unit is synonymous with a repeating unit and a monomer unit.
- the structural unit (a) contributes to the feature (3). That is, the structural unit (a) has a carboxyl group and functions as an alkali-soluble site during development.
- the structural unit (a) also contributes to the feature (4).
- the term “carboxyl group” means a —COOH group and does not include an ester bond (—COOR) or an ion bond (—COOM) formed with an ion other than a hydrogen ion.
- the structural unit (a) further contains an atom or atomic group other than the carboxyl group.
- the structural unit (a) further includes a carbon atom constituting a part of the carbon chain of the vinyl resin (F).
- the carboxyl group may be directly bonded to the carbon atom constituting a part of the carbon chain of the vinyl resin (F), or may be bonded indirectly. In the latter case, the carboxyl group may be bonded to the carbon atom constituting part of the carbon chain, for example via an ester bond and optionally other atoms or atomic groups.
- the structural unit (a) can further include a functional group other than a carboxyl group, which is directly or indirectly bonded to a carbon atom constituting a part of the carbon chain of the vinyl resin (F).
- the structural unit (a) may contain an ethylene bond.
- ethylene bond means an olefinic double bond and does not imply an aromatic double bond.
- the structural unit (a) can be obtained by subjecting the following precursor (a1) to polymerization, particularly radical polymerization such as vinyl polymerization.
- the precursor (a1) of the structural unit (a) is a compound having an ethylene bond, and can become the structural unit (a) by radical polymerization such as polymerization, particularly vinyl polymerization.
- the precursor (a1) of the structural unit (a) for example, a compound containing a carboxyl group and having an ethylene bond can be used.
- unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and ⁇ -chloroacrylic acid, or unsaturated dicarboxylic acids such as maleic acid and fumaric acid can be used.
- an unsaturated dicarboxylic acid anhydride such as maleic anhydride, which is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate, may be used.
- (meth) acrylic acid is preferable and methacrylic acid is more preferable from the viewpoint of polymerizability, for example, ease of control of molecular weight. These may be used alone or in combination of two or more.
- the proportion of the structural unit (a) in the vinyl resin (F) is in the range of 2 to 50% by weight, preferably in the range of 10 to 40% by weight, from the viewpoint of developability. When this ratio is small, the removal of the unexposed portion with an alkali developer may be insufficient. If this ratio is large, the exposed portion may be dissolved in the alkaline developer.
- the structural unit (b) functions as an affinity site for the pigment (B) or the pigment composition containing the pigment (B) and a dispersant.
- the structural unit (b) includes an aromatic ring represented by the following general formula (1), an aromatic ring represented by the following general formula (2), an aliphatic ring represented by the following general formula (3), and the following general formula (4). 1 or more kinds of cyclic structures selected from the group consisting of aliphatic rings shown in FIG.
- R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring.
- the line segment in the para position with respect to R does not mean that the methyl group is bonded to the benzene ring, but the benzene ring is bonded to other structures in the para position. Represents what to do.
- the line segment at the meta position and the para position with respect to R does not mean that a methyl group is bonded to the benzene ring. Represents coupling with other structures in position.
- the line extending from the leftmost five-membered ring does not indicate that a methyl group is bonded to the five-membered ring. This means that any carbon atom present is bonded to another structure.
- the line segment extending from the leftmost five-membered ring does not indicate that a methyl group is bonded to the five-membered ring. This means that any of the carbon atoms present is bonded to another structure.
- the structural unit (b) further includes other atoms or atomic groups in addition to the cyclic structure represented by the general formulas (1) to (4).
- the structural unit (b) further includes a carbon atom constituting a part of the carbon chain of the vinyl resin (F).
- the cyclic structures represented by the general formulas (1) to (4) may be directly bonded to this carbon atom or may be bonded indirectly.
- the structural unit (b) is a cyclic structure represented by the general formulas (1) to (4) bonded directly or indirectly to a carbon atom constituting a part of the carbon chain of the vinyl resin (F).
- Other functional groups can be further included.
- the structural unit (b) may have an ethylene bond.
- the structural unit (b) can be obtained by subjecting the following precursor (b1) to polymerization, particularly radical polymerization such as vinyl polymerization.
- Examples of the precursor (b1) include styrene, ⁇ -methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, a monomer represented by the following general formula (5), and the following general formula (6). Or a monomer represented by the following general formula (7) can be used.
- R 1 is a hydrogen atom or a methyl group
- R 2 is an alkylene group having 2 or 3 carbon atoms
- R 3 may have a benzene ring.
- a good carbon number is an alkyl group having 1 to 20
- n is an integer of 1 to 15
- m is an integer of 0 to 2.
- Examples of the monomer represented by the general formula (5) include New Frontier CEA [EO (ethylene oxide) -modified cresol acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- the monomer represented by the general formula (5) for example, Aronix M-101A [phenol EO modified (n ⁇ 2) acrylate, manufactured by Toagosei Co., Ltd., R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n ⁇ 2], M-102 [phenol EO modified (n ⁇ 4) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n ⁇ 4], M-110 [Paracumylphenol EO modified (n ⁇ 1) acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : paracumyl, n ⁇ 1], M-111 [n-nonylphenol EO modified (n ⁇ 1) acrylate , R 1 : hydrogen atom, R 2 : ethylene group, R 3 : n-nonyl group, n ⁇ 1], M-113 [n-nonylphenol EO modified (n ⁇ 4) acrylate
- Bremer ANE-300 manufactured by NOF Corporation [nonylphenoxypolyethylene glycol acrylate, R 1 : hydrogen atom, R 2 : ethylene group, R 3 : n- Nonyl group, n ⁇ 5], ANP-300 [nonylphenoxypolypropylene glycol acrylate, R 1 : hydrogen atom, R 2 : propylene group, R 3 : n-nonyl group, n ⁇ 5], 43ANEP-500 [nonylphenoxy- Polyethylene glycol-polypropylene glycol-acrylate, R 1 : hydrogen atom, R 2 : ethylene group and propylene group, R 3 : n-nonyl group, n ⁇ 5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate] , R 1 : hydrogen atom, R 2 : ethylene group And prop
- NK ESTER AMP-10G manufactured by Shin-Nakamura Chemical Co., Ltd.
- phenoxyethylene glycol acrylate (EO 1 mol), R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n 1]
- AMP-20G phenoxyethylene glycol acrylate (EO 2 mol), R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n ⁇ 2]
- AMP-60G Phenoxyethylene glycol acrylate (EO 6 mol), R 1 : hydrogen atom, R 2 : ethylene group, R 3 : hydrogen atom, n ⁇ 6], or PHE-1G
- the precursor (b1) of the structural unit (b) includes styrene, ⁇ -methylstyrene, benzyl acrylate, benzyl methacrylate, a general formula from the viewpoint of copolymerization with other precursors and the dispersibility of the pigment (B).
- the monomer represented by (5), the monomer represented by the general formula (6), or the monomer represented by the general formula (7) is preferable.
- styrene, ⁇ -methylstyrene, benzyl acrylate, benzyl methacrylate, and the monomer represented by the general formula (5) are particularly preferable because a benzene ring can be introduced into the side chain of the vinyl resin (F).
- the benzene ring introduced into the side chain can be oriented so that the plane containing the ring faces the surface of the pigment (B). Therefore, by introducing a benzene ring into the side chain of the vinyl resin (F), adsorption of the resin to the pigment (B) can be promoted and aggregation of the pigment (B) can be suppressed. Furthermore, the monomer represented by the general formula (5) is most preferable because a polyethylene oxide or polypropylene oxide portion having an appropriate length effectively functions as a site having affinity for the solvent.
- R 3 is an alkyl group having 1 to 20 carbon atoms.
- the alkyl group preferably has 1 to 10 carbon atoms.
- This alkyl group may be a straight-chain alkyl group or a branched alkyl group. Further, this alkyl group may have a substituent that substitutes one or more of its hydrogen atoms and contains a benzene ring.
- this alkyl group is a vinyl resin (F).
- this alkyl group is a vinyl resin (F).
- the carbon number of the alkyl group exceeds 10
- the effect of steric hindrance due to the alkyl group is increased, and the adsorption of the vinyl resin (F) to the pigment (B) or the vinyl resin (F) to the pigment (B).
- the carbon number exceeds 20 the previous adsorption or orientation is greatly hindered.
- Examples of the alkyl group having a benzene ring in R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
- Increasing the number of benzene rings introduced into the side chain of the vinyl resin (F) increases the affinity for the solvent and the ability to orient the pigment (B). As a result, not only the dispersibility of the pigment (B) but also the developability of the photosensitive coloring composition and the thermal fluidity of the colored layer obtained using the same are improved.
- n is an integer of 1 to 15.
- n is preferably an integer of 1 to 4.
- the viscosity of the vinyl resin (F) increases. Therefore, the viscosity of the photosensitive coloring composition containing the same can be increased, and the thermal fluidity of the colored layer can be lowered.
- the proportion of the structural unit (b) in the vinyl resin (F) is in the range of 2 to 50% by weight, preferably 4 to 50% by weight, from the viewpoint of the dispersibility of the pigment (B) and the thermal fluidity of the colored layer. Within the range of%. When this ratio is small, it is difficult to uniformly disperse the pigment (B), and the dispersion stability of the pigment (B) may be insufficient. When this ratio is large, the thermal fluidity of the colored layer may be insufficient.
- the structural unit (c) is a structural unit of the vinyl resin (F) other than the structural units (a) and (b).
- the structural unit (c) mainly contributes to the above-described feature (1), that is, excellent thermal fluidity of the colored layer.
- the structural unit (c) may or may not have an ethylene bond.
- the side chain is preferably smaller than the relatively large cyclic structure contained in the structural unit (b).
- the thermal fluidity of the colored layer is improved with respect to the structural unit (b) having an affinity for the pigment (B) and having a relatively large side chain, and the affinity for the solvent (E). This is considered to be due to a synergistic effect with the structural unit (c) having a relatively small structure.
- the structural unit (c) is obtained, for example, by polymerizing the following precursor (c1), particularly by radical polymerization such as vinyl polymerization.
- the precursor (c1) may be any monomer having an ethylene bond other than the precursors (a1) and (a2).
- the precursor (c1) is, for example, a compound having an ethylene bond, and can be the structural unit (c) by polymerization, particularly radical polymerization such as vinyl polymerization.
- precursor (c1) for example, alkyl (meth) acrylate or alkenyl (meth) acrylate can be used.
- alkyl (meth) acrylate or alkenyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( (Meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) Acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth)
- the side chain of the structural unit (c) is preferably short.
- 50% by weight or more of the structural unit (c) is obtained using methyl (meth) acrylate or ethyl (meth) acrylate as a precursor.
- Other monomers may be used as the precursor (c1).
- examples of other monomers include (meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate and 3-methyloxetanyl (meth) acrylate; methoxypolypropylene glycol (meth) acrylate and ethoxy Alkoxy polyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate; or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide, diacetone (meth) acrylamide, and (meth) acrylamides such as acryloylmorpholine.
- Still other monomers may be used as the precursor (c1). Still other monomers include, for example, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; or fatty acid vinyls such as vinyl acetate and vinyl propionate. It is done.
- vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether
- fatty acid vinyls such as vinyl acetate and vinyl propionate. It is done.
- a monomer having an epoxy group or a monomer having a hydroxyl group may be used as the precursor (c1).
- some of these monomers may not be used as the structural unit (c) depending on the modification. Therefore, when such a monomer is used, it is necessary to consider the influence of reaction conditions on the weight ratio of the structural units (a) to (c).
- the proportion of the structural unit (c) in the vinyl resin (F) is in the range of 10 to 80% by weight, preferably in the range of 25 to 80% by weight, from the viewpoint of the dispersibility of the pigment and the thermal fluidity of the colored layer. Within. When this ratio is small, the thermal fluidity of the colored layer may be insufficient. When this ratio is large, it may be difficult to uniformly disperse the pigment (B).
- the vinyl resin (F) can be obtained by subjecting the above-described monomer to radical copolymerization. Usually, bulk polymerization or solution polymerization using a radical polymerization initiator is performed.
- the radical polymerization initiator is preferably used in an amount of 0.001 to 5 parts by weight when the total amount of monomers is 100 parts by weight.
- the reaction temperature for radical copolymerization is preferably 40 to 150 ° C, more preferably 50 to 110 ° C.
- the reaction time for radical copolymerization is preferably 3 to 30 hours, more preferably 5 to 20 hours.
- an azo compound or an organic peroxide can be used as the radical polymerization initiator.
- azo compounds examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), and 2,2′-azobis [2- (2-imidazolin-2-yl) ) Propane].
- organic peroxides examples include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy
- examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.
- These polymerization initiators can be used alone or in combination of two or more.
- the radical polymerization can be carried out without a solvent or using a solvent.
- the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate can be used.
- These solvents can be used alone or in admixture of two or more.
- the amount of the solvent is preferably in the range of 0 to 300 parts by weight, and more preferably in the range of 0 to 100 parts by weight when the total amount of monomers is 100 parts by weight.
- the used solvent may be removed by an operation such as distillation after the completion of the reaction, or may be used as it is as a part of the product.
- ⁇ Introduction of ethylene bond to structural unit (a)> As a method for introducing an ethylene bond into the structural unit (a), for example, a copolymer obtained by copolymerizing a precursor (b1), a precursor (c1), and a monomer having an epoxy group is used. There is a method in which a carboxyl group of an unsaturated monobasic acid is added to a side chain epoxy group and, if necessary, a polybasic acid anhydride is reacted with a generated hydroxyl group. In this case, a structural unit having an ethylene monomer having an epoxy group as a precursor is a structural unit (a) containing an ethylene bond.
- Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, and 3,4 An epoxy cyclohexyl (meth) acrylate is mentioned. These may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.
- unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and (meth) acrylic acid ⁇ -position haloalkyl, alkoxyl, halogen, nitro or cyano substitution And monocarboxylic acids such as the body. These may be used alone or in combination of two or more.
- polybasic acid anhydride examples include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more.
- a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride.
- An anhydride group that has not been used for the reaction with a hydroxyl group may be hydrolyzed.
- polybasic acid anhydride having one or more ethylene bonds such as tetrahydrophthalic anhydride or maleic anhydride
- more ethylene bonds are formed in the structural unit (a). Can be introduced.
- ⁇ Introduction of ethylene bond to structural unit (b)> As a method for introducing an ethylene bond into the structural unit (b), for example, the monomer shown in the general formula (7) or the formula (5) except that R 3 has an ethylene bond is shown. There is a method of performing copolymerization using a monomer having the same structure as that of the precursor (b1) of the structural unit (b). However, any ethylene bond contained in the precursor (b1) may be used for polymerization. Since the ethylene bond in the cyclic structure has a relatively low reactivity, when the ethylene bond is introduced into the structural unit (b), the cyclic structure as a monomer represented by the general formula (7) is used as the precursor (b1). It is preferable to use a monomer having an ethylene bond therein.
- ⁇ Introduction of ethylene bond to structural unit (c)> As one method for introducing an ethylene bond into the structural unit (c), for example, copolymerization is performed using a monomer having a hydroxyl group as a part of the precursor (c1) of the structural unit (c). There is a method in which the isocyanate group of a monomer having an isocyanate group is reacted with the hydroxyl group of the side chain of the copolymer. As another method for introducing an ethylene bond into the structural unit (c), copolymerization is performed by using the monomer having an epoxy group as a part of the precursor (c1) of the structural unit (c).
- Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol (meta ) Acrylates and hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate. These may be used alone or in combination of two or more.
- polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, or (poly) ⁇ -valerolactone, (poly) ⁇ - Caprolactone and / or (poly) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid and the like can also be used.
- 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.
- Examples of the monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like.
- Other monomers may be used as the monomer having an isocyanate group. Moreover, these may be used independently and may use 2 or more types together.
- 2-hydroxyethyl methacrylate or glycerol methacrylate is used as a part of the precursor (c1) of the structural unit (c) for copolymerization, and 2- (meth) acryloyloxyethyl is bonded to the side chain hydroxyl group of the copolymer.
- a vinyl resin (F) obtained by reacting isocyanate is also preferable from the viewpoints of dispersibility of the pigment and thermal fluidity of the colored layer.
- the vinyl resin (F) is a product in which a carboxyl group is introduced using a polybasic acid anhydride.
- Polybasic acid anhydrides may be used alone or in combination of two or more.
- a carboxyl group into the structural unit (a) using a polybasic acid anhydride is described above in connection with introducing an ethylene bond into the structural unit (a).
- a saturated monobasic acid may be used instead of the unsaturated monobasic acid.
- a carboxyl group into the structural unit (a) using a polybasic acid anhydride can be adopted. That is, first, for example, a carboxyl group of an unsaturated monobasic acid is added to a monomer having an epoxy group, and if necessary, a polybasic acid anhydride is added to the generated hydroxyl group. Alternatively, for example, a polybasic acid anhydride is added to a monomer having a hydroxyl group. Thereby, it can also be set as the structural unit (a) containing the carboxyl group.
- the addition reaction between the carboxyl group of the unsaturated monobasic acid and the epoxy group is such that the epoxy group remains in the vinyl resin (F) in order to suppress gelation when the polybasic acid anhydride is reacted with the hydroxyl group. It adds so that a rate may be 20% or less, for example.
- the residual ratio of epoxy groups is preferably small, and most preferably the entire amount of epoxy groups is consumed in the reaction.
- the addition reaction between the polybasic acid anhydride and the hydroxyl group is preferably 10 to 100%, more preferably 20 to 100% of the hydroxyl group contained in the copolymer reacts with the polybasic acid anhydride.
- the ratio of the hydroxyl group causing the addition reaction is small, it may be difficult to achieve excellent developability and good reworkability.
- the addition of an excessive amount of polybasic acid anhydride is not preferable because the polybasic acid anhydride remains in the vinyl resin (F).
- Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, and 3,4 An epoxy cyclohexyl (meth) acrylate is mentioned. These may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.
- unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and (meth) acrylic acid ⁇ -position haloalkyl, alkoxyl, halogen, nitro or cyano substitution And monocarboxylic acids such as the body. These may be used alone or in combination of two or more. (Meth) acrylic acid is preferred.
- polybasic acid anhydride examples include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more.
- a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride.
- An anhydride group that has not been used for the reaction with a hydroxyl group may be hydrolyzed. Tetrahydrophthalic anhydride is preferred.
- the carboxyl group introduced by the addition reaction between the hydroxyl group and the polybasic acid anhydride has a distance from the main chain of the vinyl resin (F) as compared with, for example, a carboxyl group derived from a precursor such as (meth) acrylic acid. Long and therefore less susceptible to steric hindrance. And the carboxyl group is excellent in affinity with rework liquids, such as strong alkaline aqueous solution. Accordingly, the penetration of the rework liquid into the coating film having a high crosslinking density by exposure proceeds rapidly, and the swelling, reaction and dissolution of the coating film also proceed quickly.
- the functional group when a functional group that reacts with a carboxyl group is present in the photosensitive coloring composition, the functional group is part of the carboxyl group introduced using a polybasic acid anhydride during post-baking. Even if the resin is crosslinked, the distance between the crosslinked part and the main chain of the vinyl resin (F) is long, so that the penetration of the rework liquid into the coating film is not hindered. Therefore, also in this case, the removal of the coating proceeds promptly.
- the weight average molecular weight Mw of the vinyl resin (F) is preferably in the range of 2000 to 20000 from the viewpoint of achieving both excellent developability of the coating film and excellent thermal fluidity of the colored layer. More preferably, it is within the range.
- the optimal development time may be too short, or the adhesion of the pattern to the substrate may be insufficient.
- the weight average molecular weight Mw is large, the optimum development time may be too long, or the thermal fluidity of the colored layer may be insufficient.
- the pigment (B) may be an organic pigment that is an organic material, an inorganic pigment that is an inorganic material, or a mixture thereof.
- organic pigments and inorganic pigments those generally called dyes may be used, or natural pigments may be used. Among these, organic pigments are preferably used because of their excellent heat resistance and color developability.
- Organic pigment ⁇ Organic pigment> Below, the specific example of an organic pigment is shown by a color index number.
- red coloring composition for forming the red filter segment examples include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, Red pigments such as H.264 and 272 can be used.
- Red pigments such as H.264 and 272 can be used.
- a yellow pigment and an orange pigment can be used in combination with the red coloring composition.
- orange pigment examples include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61 and 71 can be mentioned.
- green coloring composition for forming the green filter segment examples include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37 and 58 can be used. In addition to the green pigment, a yellow pigment can be used in combination with the green coloring composition.
- Green pigments such as Pigment Green 7, 10, 36, 37 and 58 can be used.
- a yellow pigment can be used in combination with the green coloring composition.
- Examples of yellow pigments that can be used in combination with green pigments in the green coloring composition include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, It may be mentioned 75,176,
- the blue coloring composition for forming the blue filter segment includes, for example, C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 and 64 can be used.
- C.I. I. Purple pigments such as Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 and 50 can be used in combination.
- yellow coloring compositions for forming yellow filter segments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, Can be used yellow pigments such 75,176,177,179,180,
- orange coloring composition for forming the orange filter segment examples include C.I. I. Orange pigments such as Pigment Orange ⁇ 36, 43, 51, 55, 59, 61 and 71 can be used.
- Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16 and 81 can be used.
- magenta color composition for forming the magenta color filter segment examples include C.I. I. Purple pigments such as Pigment Violet 1 and 19, and C.I. I. Red pigments such as Pigment Red 144, 146, 177, 169 and 81 can be used.
- the magenta colored composition can be used in combination with the same yellow pigment as described above for the yellow colored composition for forming the yellow filter segment.
- Inorganic pigments and dyes> In order to ensure good coatability, sensitivity, developability, and the like while balancing saturation and lightness, it is possible to use an inorganic pigment in combination with the organic pigment.
- inorganic pigments include, for example, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green and cobalt green, metal oxide powders, metal sulfide powders and metal powders. Can be mentioned.
- the above-mentioned photosensitive coloring composition can contain a dye within a range that does not reduce heat resistance for color matching.
- the light shielding layer generally called a black matrix can be formed from, for example, a photosensitive coloring composition containing a black pigment as the pigment (B).
- a black pigment examples include carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, manufactured by Mitsubishi Chemical Corporation.
- a pigment derivative may be used as at least a part of the pigment.
- the pigment derivative is obtained by introducing, for example, a substituent having affinity for a solvent into an organic pigment. This pigment derivative enhances its dispersibility when used in combination with ordinary pigments. That is, the pigment derivative can serve as a pigment dispersant.
- the pigment in order to uniformly disperse the pigment in the solvent, the pigment may be used in combination with a pigment dispersant such as a resin-type pigment dispersant and a surfactant.
- a pigment dispersant such as a resin-type pigment dispersant and a surfactant.
- the pigment dispersant is excellent in the ability to disperse the pigment and has a great effect of preventing reaggregation of the dispersed pigment. Therefore, when a pigment dispersant is used, a filter segment having excellent transparency can be obtained.
- the pigment dispersant is used at a ratio of, for example, 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.
- the pigment derivative is, for example, a compound represented by the following general formula (8).
- the pigment derivatives include those having a basic substituent and those having an acidic substituent.
- pigment derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, and JP-B-5-9469. You can use what you have. These can be used alone or in admixture of two or more.
- the pigment derivative When the pigment derivative is used in combination with a normal pigment, the pigment derivative is preferably used at a ratio of 0.5 to 25 parts by weight with respect to 100 parts by weight of the total of the pigment derivative and the normal pigment. When this ratio is small, the effect of increasing the dispersibility of the pigment is small. When this ratio is large, the heat resistance and light resistance of the colored layer may be insufficient.
- examples of the organic pigment constituting the organic pigment residue X include azo pigments such as diketopyrrolopyrrole, disazo and polyazo; phthalocyanines such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Pigments; anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, or metal complex pigments can be used.
- azo pigments such as diketopyrrolopyrrole, disazo and polyazo
- phthalocyanines such as copper phthal
- the resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier.
- the resin-type pigment dispersant functions to adsorb to the pigment and stabilize the dispersion of the pigment on the pigment carrier (dispersion medium).
- Resin type pigment dispersants can be classified into, for example, polyvinyl type, polyurethane type, polyester type, polyether type, formalin condensation type, silicone type, and composite type dispersants thereof.
- pigment affinity site examples include carboxyl groups, hydroxyl groups, phosphate groups, phosphate ester groups, sulfonate groups, hydroxyl groups, amino groups, quaternary ammonium bases, amide groups, and other polar groups, as well as polyethylene oxide and polypropylene.
- examples thereof include hydrophilic polymer chains such as oxides and complexes thereof.
- dye carrier a long-chain alkyl chain, a polyvinyl chain, a polyether chain, and a polyester chain are mentioned, for example.
- resin-type dispersant examples include styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly (meth) acrylate, styrene- (meth) acrylic acid copolymer, (meth) acrylic.
- Anionic resin-type pigment dispersants such as acrylic acid copolymer, carboxymethylcellulose, polyurethane having carboxyl groups, formalin condensate of naphthalene sulfonate, and sodium alginate; polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, and polymer starch Any nonionic resin-type pigment dispersant; or reaction of polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline, polyurethane having amino group, poly (lower alkyleneimine) and polyester having free carboxyl group And cationic resin type pigment dispersants such as Satokinsan.
- Examples of commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by BYK Chemie.
- pigment dispersant may be used as the pigment dispersant. Moreover, these can also be used individually or in mixture of 2 or more types.
- surfactant examples include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalene sulfonate, sodium alkyldiphenylether disulfonate, lauryl.
- Anionic surfactants polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene noni Nonionic surfactants such as phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants; alkylbetaines such as alkyldimethylaminoacetic acid betaines; or amphoteric surfactants such as alkylimidazolines can be used. These can be used alone or in admixture of two or more.
- the active energy ray polymerization initiator (C) for example, a photopolymerization initiator, gives the resin a property of curing when irradiated with active energy rays such as ultraviolet rays and electron beams.
- the active energy ray polymerization initiator (C) is preferably used in a ratio of 5 to 200% by weight with respect to the pigment (B). From the viewpoint of sensitivity to active energy rays and developability, the pigment (B) More preferably, it is used at a ratio of 10 to 150% by weight.
- Examples of the active energy ray polymerization initiator (C) include an acetophenone-based active energy ray polymerization initiator, a benzoin-based active energy ray polymerization initiator, a benzophenone-based active energy ray polymerization initiator, a thioxanthone-based active energy ray polymerization initiator, Use triazine active energy ray polymerization initiator, borate photoactive energy ray polymerization initiator, carbazole active energy ray polymerization initiator, imidazole active energy ray polymerization initiator, or oxime ester active energy ray polymerization initiator be able to.
- acetophenone-based active energy ray polymerization initiator examples include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-ylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and 2-methyl-1- [4- (methylthio) phenyl] There may be mentioned -2-morpholinopropan-1-one.
- benzoin-based active energy ray polymerization initiator examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal.
- benzophenone-based active energy ray polymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide. Can do.
- thioxanthone-based active energy ray polymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone.
- triazine-based active energy ray polymerization initiators examples include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (p-methoxyphenyl).
- a sensitizer can be used in combination with the active energy ray polymerization initiator (C).
- the sensitizer include ⁇ -acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethyliso Phthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, or 4,4′-diethylaminobenzophenone can be used.
- the sensitizer is preferably used at a ratio of 3 to 60% by weight with respect to the active energy ray polymerization initiator (C). From the viewpoint of sensitivity to active energy rays and developability, it is more preferable to use them at a ratio of 5 to 50% by weight with respect to the active energy ray polymerization initiator (C).
- the active energy ray-curable monomer (D) is a monomer (monomer) and / or oligomer that is cured by irradiation with active energy rays to form a resin.
- Examples of the active energy ray-curable monomer (D) include linear or branched alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, fluoroalkyl (meth) acrylates, (meth) acryloxy-modified polydimethyl Siloxane (silicone macromers), (meth) acrylates having a heterocyclic ring, (meth) acrylates having an aromatic ring, (poly) alkylene glycol monoalkyl ethers (meth) acrylates, (meth) acrylates having a carboxyl group , (Meth) acrylates having a hydroxyl group, (poly) alkylene glycol di (meth) acrylates, di (meth) acrylates, (meth) acrylates having a tertiary amino group, trifunctional or more polyfunctional ( (Meth) acrylates, Epoxy (Meth) acrylates, can be used (meth) acryloyl-modified
- linear or branched alkyl (meth) acrylates examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), Tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) Examples include acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, and isostearyl
- cyclic alkyl (meth) acrylates examples include cyclohexyl (meth) acrylate, tertiarybutylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyl. Mention may be made of (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and isobornyl (meth) acrylate.
- fluoroalkyl (meth) acrylates examples include trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate. .
- Examples of (meth) acrylates having a heterocyclic ring include tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate.
- Examples of (meth) acrylates having an aromatic ring include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, and paracumylphenoxypolyethylene glycol. Mention may be made of (meth) acrylates and nonylphenoxypolyethylene glycol (meth) acrylates.
- Examples of (poly) alkylene glycol monoalkyl ether (meth) acrylates include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl ( (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether ( (Meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meta) Acrylate, polyethylene glycol mono lauryl ether (meth) acrylate, and polyethylene glycol monostearyl ether (meth) acrylate.
- Examples of the (meth) acrylate having a carboxyl group include (meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) ) Acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide modified succinic acid (meth) acrylate, ⁇ -carboxyethyl (meth) acrylate, and ⁇ -carboxypolycaprolactone (meth) Mention may be made of acrylates.
- Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) phthalate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol Mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate Poly can be mentioned - - (tetramethylene glycol propylene glycol) mono (meth) acrylate, and glycerol (meth) acrylate (ethylene glycol tet
- Examples of (poly) alkylene glycol di (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol.
- di (meth) acrylates examples include dimethylol dicyclopentane di (meth) acrylate, neopentyl glycol hydroxy (pivalate) di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, and ethylene oxide-modified bisphenol A.
- Examples of (meth) acrylates having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. it can.
- trifunctional or higher polyfunctional (meth) acrylates examples include glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Mention may be made of penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
- Epoxy (meth) acrylates include, for example, glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct 1,6-butanediol diglycidyl ether, alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide (Meth) acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl -T
- Examples of (meth) acryloyl-modified resin oligomers include (meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, ( Mention may be made of (meth) acryloyl-modified polybutadiene and (meth) acryloyl-modified rosin.
- vinyls examples include styrene, ⁇ -methylstyrene, vinyl acetate, vinyl (meth) acrylate, and allyl (meth) acrylate.
- vinyl ethers examples include hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and pentaerythritol trivinyl ether.
- amides include (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and N-vinylformamide.
- active energy ray-curable monomer (D) Other compounds may be used as the active energy ray-curable monomer (D). Moreover, the compound mentioned above regarding the active energy ray hardening monomer (D) can be used individually or in mixture of 2 or more types.
- the solvent (E) serves to sufficiently disperse the pigment (B) in the pigment carrier.
- the solvent (E) makes it easy to apply a photosensitive resin on a substrate such as a transparent substrate, such as a glass substrate, so that the dry film thickness is in the range of 0.2 to 5 ⁇ m, for example. .
- solvent (E) examples include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and 2-heptanone.
- glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate
- ketones such as cyclohexanone
- solvent (E) may be used as the solvent (E).
- these can be used individually or in mixture of 2 or more types.
- the photosensitive coloring composition can be adjusted to an appropriate viscosity, and a desired colored layer having a uniform thickness can be formed.
- the solvent (E) is preferably used at a ratio of 800 to 4000% by weight with respect to the pigment (B).
- the photosensitive coloring composition preferably further contains a leveling agent so that a coating film excellent in flatness can be easily formed on the substrate.
- dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable.
- dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning and BYK-333 manufactured by BYK Chemie.
- dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie.
- Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination.
- the concentration of the leveling agent in the photosensitive coloring composition is usually set within a range of 0.003 to 0.5% by weight.
- an anionic, cationic, nonionic or amphoteric surfactant may be added to the photosensitive coloring composition. Only 1 type of surfactant may be added to a photosensitive coloring composition, and 2 or more types may be mixed and added for it.
- Examples of the chaotic surfactant that assists the function of the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts.
- Nonionic surfactants that assist the function of the leveling agent include, for example, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan mono Examples include stearate and polyethylene glycol monolaurate.
- Fluorine-based surfactant or silicone-based surfactant may be used as a surfactant that assists the function of the leveling agent.
- Said photosensitive coloring composition may contain the other component further.
- the photosensitive coloring composition may contain a storage stabilizer in order to improve the viscosity stability with time.
- the photosensitive coloring composition may contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion between the colored layer and the substrate.
- the storage stabilizer examples include quaternary ammonium chlorides such as benzyltrimethylammonium chloride and diethylhydroxyamine; organic acids such as lactic acid and oxalic acid; methyl esters of the organic acids; catechols such as t-butylpyrocatechol Organic phosphines such as triphenylphosphine, tetraethylphosphine and tetraphenylphosphine; and phosphites.
- the storage stabilizer is used at a ratio of, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment (B).
- silane coupling agent examples include vinyl silanes such as vinyltris ( ⁇ -methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane; (meth) acrylsilanes such as ⁇ -methacryloxypropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) methyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane, ⁇ - (3,4 Epoxy silanes such as -epoxycyclohexyl) methyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxypropyltriethoxysilane; N- ⁇ (aminoethyl) ⁇ -a
- the silane coupling agent is used in a ratio of preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the pigment (B).
- Said photosensitive coloring composition is manufactured with the following method, for example. First, a pigment (B) is prepared. As the pigment (B), it is preferable to use a pigment that has been refined by a salt milling treatment.
- Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is heated with a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill while heating After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water.
- the water-soluble inorganic salt works as a crushing aid, and it is considered that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Therefore, during the kneading, the crushing of the pigment and the crystal growth occur at the same time. Therefore, pigments having different primary particle sizes depending on the kneading conditions can be obtained.
- the heating temperature is preferably in the range of 40 to 150 ° C.
- the heating temperature is less than 40 ° C.
- crystal growth does not occur sufficiently, and the shape of the pigment particles becomes close to amorphous, which is not preferable.
- the heating temperature exceeds 150 ° C.
- crystal growth proceeds excessively and the primary particle diameter of the pigment increases, which is not preferable as a colorant for the color filter coloring composition.
- the kneading time for the salt milling treatment is preferably 2 to 24 hours from the viewpoint of the balance between the particle size distribution of the primary particles of the salt milling treatment pigment and the cost required for the salt milling treatment.
- the average particle size of the primary particles is very small, and the width of the particle size distribution of the primary particles is narrow, that is, a pigment having a sharp particle size distribution. Obtainable.
- the primary particle diameter of the pigment (B) obtained by TEM is preferably in the range of 20 to 100 nm.
- the primary particle diameter is smaller than 20 nm, it is difficult to disperse the pigment (B) in the organic solvent. If the primary particle size is larger than 100 nm, it is difficult to obtain a sufficient contrast ratio.
- a particularly preferable primary particle diameter range is 25 to 85 nm.
- the water-soluble inorganic salt used in the salt milling treatment is, for example, sodium chloride, barium chloride, potassium chloride, or sodium sulfate. From the viewpoint of price, it is preferable to use sodium chloride (salt).
- the water-soluble inorganic salt is preferably used in a ratio of 50 to 2000% by weight with respect to the pigment and more preferably in a ratio of 300 to 1000% by weight with respect to the pigment from both aspects of processing efficiency and production efficiency. .
- the water-soluble organic solvent used in the salt milling process functions to wet the pigment and the water-soluble inorganic salt, and can be dissolved (mixed) in water and does not substantially dissolve the water-soluble inorganic salt.
- the boiling point of the water-soluble organic solvent is preferably 120 ° C. or more from the viewpoint of safety.
- water-soluble organic solvent examples include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol. , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, or liquid polypropylene glycol Is used.
- the water-soluble organic solvent is preferably used in a ratio of 5 to 1000 parts by weight with respect to 100 parts by weight of the pigment, and more preferably in a ratio of 50 to 500 parts by weight with respect to 100 parts by weight of the pigment.
- a resin When performing the salt milling treatment, a resin may be added as necessary.
- the kind of this resin is not particularly limited, and for example, a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used.
- the resin is preferably solid at room temperature and water-insoluble, and more preferably partially soluble in the organic solvent. This resin is preferably used in a ratio of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.
- the photosensitive coloring composition After preparing the pigment (B), the resin (A), the pigment (B), the solvent (E), and an optional pigment dispersant are mixed. Next, the pigment (B) is uniformly dispersed in the mixed liquid containing the resin (A) and the solvent (E) by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. Furthermore, an active energy ray polymerization initiator (C) and an active energy ray polymerizable monomer (D) are added to this dispersion. A photosensitive coloring composition is obtained as described above. In addition, when manufacturing the photosensitive coloring composition containing 2 or more types of pigments, first, the some dispersion liquid from which the kind of pigment differs may be prepared, and those may be mixed after that.
- various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attri
- a color filter according to an embodiment of the present invention includes a filter segment or a black matrix formed from the above-described photosensitive coloring composition on a substrate such as a transparent substrate and a reflective substrate.
- a typical color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment , And at least one yellow filter segment.
- the transparent substrate for example, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali aluminoborosilicate glass, or resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate are used.
- a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of a glass plate or a resin plate in order to drive liquid crystal molecules after forming a panel.
- the formation of the filter segment and the black matrix by the photolithography method is performed by the following method, for example.
- the above photosensitive coloring composition is applied on a transparent substrate.
- a coating method such as spin coating or die coating is used.
- a mask having a predetermined pattern is placed in contact with or away from the coating film, and the coating film is irradiated with light such as ultraviolet rays through the mask. .
- the coating film is hardened in the irradiation part irradiated with light or an electron beam.
- the coating film is subjected to development processing. Thereby, the unexposed part which is an unhardened part is removed from a coating film.
- a developer for example, an alkali aqueous solution such as a sodium carbonate aqueous solution and a sodium hydroxide aqueous solution, or an organic alkali such as dimethylbenzylamine and triethanolamine is used.
- the developer may further contain additives such as an antifoaming agent and a surfactant.
- a shower development method, a spray development method, a dip (immersion) development method, or a paddle (liquid accumulation) development method can be used.
- the pattern obtained by development is heated as necessary to accelerate the polymerization reaction.
- the black matrix is formed prior to the formation of the filter segment.
- a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied onto the previous coating film. This may be dried.
- a coating film made of a water-soluble or alkali-soluble resin prevents oxygen from inhibiting the polymerization reaction during exposure. Therefore, when this coating film is formed, the sensitivity of the coating film made of the photosensitive coloring composition to exposure light can be increased.
- each of the filter segment and the black matrix is directly formed on the substrate using photolithography.
- the black matrix is formed using the photosensitive coloring composition described above, but other materials may be used for the black matrix.
- a black matrix a layer made of an inorganic material such as a chromium layer, a multilayer film of a chromium layer and a chromium oxide layer, and a titanium nitride layer may be formed.
- a thin film transistor may be formed on the substrate.
- TFT thin film transistor
- an active matrix liquid crystal display device when a color filter is formed on a TFT substrate, a higher aperture ratio is achieved compared to a case where a color filter is formed on a counter substrate, and thus a higher luminance is achieved. Can be achieved.
- An overcoat layer or an electrode may be formed on the color filter layer.
- an overcoat layer and a plurality of pixel electrodes are sequentially formed on a color filter layer on a TFT substrate, a through-hole for electrically connecting the pixel electrode and the TFT is provided in the color filter layer and the overcoat layer. You may keep it.
- the colored layer is peeled from the substrate using a rework liquid, for example, a highly concentrated strong alkaline solution as a peeling liquid.
- the substrate may be regenerated, and the regenerated substrate may be reused for manufacturing the color filter. That is, the substrate may be reworked.
- the rework liquid has a high pH and contains, for example, at least one of KOH and NaOH, an organic alkali, a hydrophilic solvent, a surfactant, and water.
- the unlast cleaner 22 can be used.
- the colored layer formed by baking the coating film made of the photosensitive coloring composition at 230 ° C. for 60 minutes may exhibit a solubility of 30 to 120 mg with respect to 100 g of the rework liquid at 65 ° C. desirable. If this solubility is low, the colored layer cannot be peeled from the substrate using the rework liquid, or the peeled pieces may be generated in the form of relatively large lumps. If the peeling piece is present in the rework liquid in the form of a relatively large lump, the filter for purifying the used rework liquid is likely to be clogged.
- the above-mentioned solubility can be set to 30 to 120 mg due to the synergistic effect of the structural unit (a) and the structural unit (b) and / or the structural unit (c). Moreover, a peeling piece can be produced with a sufficiently small dimension. Therefore, excellent reworkability can be achieved.
- the color filter described above can be used in, for example, a liquid crystal display device or a solid-state image sensor.
- a liquid crystal display device including a color filter will be described below.
- the color liquid crystal display device includes a liquid crystal display panel and, optionally, a backlight or a front light that illuminates the liquid crystal display panel.
- a liquid crystal display panel displays a color image using a color filter
- the twisted nematic (TN) mode the super twisted nematic (STN) mode
- the in-plane switching (IPS) mode the vertical Any display mode such as an aligned (VA) mode and an optically compensated bend (OCB) mode may be employed.
- TN twisted nematic
- STN super twisted nematic
- IPS in-plane switching
- VA aligned
- OBC optically compensated bend
- the liquid crystal display panel includes first and second substrates and a liquid crystal layer.
- the first and second substrates face each other with a gap therebetween.
- the distance between the first and second substrates is kept constant by granular spacers interposed between them or columnar spacers formed on at least one of them.
- a seal material layer having a frame shape is provided between the first and second substrates.
- the sealing material layer is provided with a missing portion that serves as an inlet.
- a liquid crystal material is injected into the space surrounded by the first and second substrates and the sealing material layer through the previous injection port. The liquid crystal material filling this space forms a liquid crystal layer.
- the inlet is sealed with a sealing material.
- Each of the first and second substrates includes an insulating substrate. At least one of the first and second substrates further includes an electrode positioned between the insulating substrate and the liquid crystal layer. This electrode is covered with an alignment film as necessary.
- One of the first and second substrates further includes a color filter. The color filter is located between the insulating substrate of the first or second substrate including the color filter and the liquid crystal layer.
- the liquid crystal display panel further includes a polarizing plate attached to at least one of the first and second substrates.
- the liquid crystal display panel may further include a wave plate.
- the molecular weight of the resin described below is a polystyrene-equivalent number average molecular weight or weight average molecular weight measured under the following conditions. Specifically, in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation, four separation columns were connected in series. The packing materials of these separation columns include “TSK-GEL SUPER H2000”, “TSK-GEL SUPER H2000”, “TSK-GEL SUPER H3000” and “TSK-GEL SUPER H2000” manufactured by Tosoh Corporation in the order of connection of the columns. And tetrahydrofuran was used as the mobile phase.
- the liquid in the flask was charged with 20 parts of methacrylic acid, 30 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 19 parts of benzyl methacrylate, A mixture of 16 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 16000.
- Mw weight average molecular weight
- Resin solutions 2 to 15 and comparative resin solutions 1 to 6 were prepared by the same method as described for the resin solution 1 except that the ratios of the various components were changed as shown in Tables 1 to 3.
- Tables 1 to 3 show the measurement results of the weight average molecular weight.
- MAA Methacrylic acid AA: Acrylic acid
- GMA Glycidyl methacrylate
- THPA Tetrahydromaleic anhydride
- M110 Aronix M110 (paracumylphenol ethylene oxide modified acrylate) manufactured by Toa Gosei Co., Ltd.
- -FA-513M Funkrill FA-513M (dicyclopentanyl methacrylate) manufactured by Hitachi Chemical Co., Ltd.
- FA-512MT Hitachi Chemical's FANCLIL FA-512MT (dicyclopentenyloxyethyl methacrylate) ⁇ BzMA: benzyl methacrylate ⁇ 2MTA: 2-methoxyethyl acrylate ⁇ St: styrene ⁇ MMA: methyl methacrylate ⁇ EMA: ethyl methacrylate ⁇ BMA: n-butyl methacrylate ⁇ HEMA: 2-hydroxyethyl methacrylate ⁇ GLMA: glycerol methacrylate ⁇ MOI : Showen Denko Karenz MOI (2-methacryloyloxyethyl isocyanate) Mw: weight average molecular weight In addition, the annotations in Tables 1 to 3 are described below.
- the supply of nitrogen gas into the flask was stopped, and then the total amount of the obtained copolymer solution was stirred for 1 hour while supplying dry air into the flask. Thereafter, the copolymer solution was cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxylethyl isocyanate, 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added at 70 ° C. over 3 hours. It was dripped.
- the gas in the flask was replaced with air, and 32 parts of glycidyl methacrylate (66% of the carboxyl group), 32 parts of cyclohexanone, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were supplied into the flask. .
- the reaction was continued at 90 ° C. for 6 hours to obtain an acrylic resin solution.
- the reaction rate of glycidyl methacrylate was determined from the change in the acid value of the polymer before and after the reaction. As a result, the reaction rate was 99%.
- a pigment, a dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol), a dispersion resin solution, and a solvent (propylene glycol monomethyl ether acetate) were mixed, and the pigment was uniformly dispersed in this mixed solution.
- a planetary ball mill using zirconia beads as a grinding medium was used for this mixing and dispersion. In this manner, pigment dispersions according to Examples 1 to 18 and 20 to 26 and Comparative Examples 1 to 10 were obtained.
- a pigment dispersion according to Example 19 was prepared by the following method. First, a pigment, a dispersing agent (“Solsperse 20000” manufactured by Nippon Lubrizol), a resin solution 3 and a solvent (propylene glycol monomethyl ether acetate) were mixed, and the pigment was uniformly dispersed in this mixed solution. For this mixing and dispersion, a planetary ball mill using zirconia beads as a grinding medium was used. In this way, a pigment dispersion according to Example 19 was obtained.
- Tables 4 to 6 list the type and content of each component of the pigment dispersion and the color index number of the pigment.
- each of the pigment dispersions according to Examples 1 to 26 and Comparative Examples 1 to 6 and 8 to 10 was mixed with a resin solution, an active energy ray-curable monomer (dipentaerythritol hexaacrylate), and active energy ray polymerization.
- Initiator (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), sensitizer (2,4-diethylthioxanthone)
- a solvent propylene glycol monomethyl ether acetate
- each of the photosensitive coloring compositions according to Examples 1 to 26 and Comparative Examples 1 to 6 and 8 to 10 was prepared.
- the viscosity at 25 ° C. of the photosensitive coloring composition obtained by the above-described method was measured using an E-type viscometer (TUE-20L type manufactured by TOKI SANGYO). Specifically, the rotation speed was set to 20 rpm, and the viscosity was measured on the day when the photosensitive coloring composition was produced and after storage for 7 days in a constant temperature room at 40 ° C. And the viscosity on the day of producing the photosensitive coloring composition, that is, the initial viscosity ( ⁇ 0: mPa ⁇ s) and the viscosity after storage for 7 days in a constant temperature room at 40 ° C. ( ⁇ 7: mPa ⁇ s) are as follows: The storage stability of each photosensitive coloring composition was evaluated with reference to the above criteria. The results are summarized in Tables 10 to 12 below.
- Ratio ⁇ 7 / ⁇ 0 is less than 1.20, almost no increase in viscosity occurs, and dispersion stability is good.
- the ratio ⁇ 7 / ⁇ 0 is 1.20 or more and less than 1.50, a slight increase in viscosity is observed, and the dispersion stability is slightly inferior.
- Each of the red, green and blue photosensitive coloring compositions is spin-coated on a 10 cm ⁇ 10 cm transparent glass substrate, which is pre-baked at 70 ° C. for 20 minutes, resulting in a dry film thickness of about 2.0 ⁇ m. Coating film was obtained.
- this coating film was irradiated with ultraviolet rays through a mask.
- the exposure amount was 50 mJ / cm 2 .
- the mask a mask having a light shielding portion and a light transmitting portion provided in a stripe shape was used.
- the coating film was developed using an alkaline developer.
- T1 the elapsed time from the start of development required until the entire unexposed area is dissolved
- T1 the time 1.5 times the time T1.
- the black coloring pattern was obtained by the method similar to the above except having used the black photosensitive coloring composition and having changed the exposure amount to 100 mJ / cm ⁇ 2 >.
- Time T1 is less than 60 sec and there is no pattern peeling.
- X Time T1 is 60 sec or more or pattern peeling occurs.
- the glass substrate on which the colored pattern was formed by the method described above was cut into half dimensions (5 cm ⁇ 10 cm) to obtain two test pieces.
- test pieces Only one of these test pieces was post-baked for 20 minutes in a high-temperature oven set at 230 ° C. Next, each post-baked test piece was cut into 1 cm square, and Pt and Pd were vapor-deposited on the surface provided with the colored pattern using a sputtering apparatus (E-1030) manufactured by Hitachi, Ltd. Subsequently, using a scanning electron microscope (S-4300) manufactured by Hitachi, Ltd., the acceleration voltage was set to 15 kV and the observation magnification was set to 10,000 times, and the cross-sectional shape of the colored pattern was observed.
- a sputtering apparatus E-1030
- S-4300 scanning electron microscope
- the pattern shape was evaluated with reference to the following criteria with respect to the cross-sectional shape of the colored pattern, the angle ( ⁇ ) formed between the principal surface of the glass substrate and the edge portion of the cross-section of the colored pattern.
- the results are shown in the column labeled “After Post Bake” in Tables 10 to 12 below.
- A Forward tapered shape of ⁇ ⁇ 20.
- A A forward taper shape of 20 ⁇ ⁇ ⁇ 45.
- X Sharp forward taper shape with ⁇ > 80 or overhang.
- this measurement was performed as follows. That is, the distance from the central area of the filter paper and the central area is 1 cm, the two areas arranged in the horizontal direction with the central area in between, and the distance from the previous central area is 1 cm. Each of the two regions arranged in the vertical direction with the region interposed therebetween was observed at a magnification of 500 times. Next, 10 peel pieces in each visual field were selected in descending order of the maximum length, and the average of the maximum lengths was determined for a total of 50 peel pieces selected. Then, the reworkability was evaluated by referring to the average of the maximum lengths thus obtained, that is, the average maximum length, based on the following criteria. The results are summarized in Tables 10 to 12 below.
- ⁇ The average maximum length is less than 300 ⁇ m.
- ⁇ The average maximum length is 300 ⁇ m or more and less than 500 ⁇ m.
- X The average maximum length is 500 ⁇ m or more.
- the colored pattern before post-baking had an overhang. That is, in any of Examples 1 to 26 and Comparative Examples 1 to 10, the pattern shape before post-baking was poor. In Comparative Examples 1 to 10, the pattern shape remained defective even after post-baking.
- the colored pattern after post-baking had a forward tapered cross section. That is, thermal fluidity was recognized in the colored patterns according to Examples 1 to 26. Among these, the coloring patterns according to Examples 3, 16, 19 to 24, and 26 had the most excellent pattern shape.
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Abstract
Description
本発明の第6側面によると、前記構成単位(c)の前駆体(c1)は、メチルアクリレート、メチルメタクリレート、エチルアクリレート、及びエチルメタクリレートからなる群より選ばれる1種類以上の単量体を含んでいることを特徴とする第1乃至第5側面の何れか1つに係る感光性着色組成物が提供される。
上記の感光性着色組成物において、樹脂(A)は、ビニル樹脂(F)を、樹脂(A)に対して50重量%以上の割合で、好ましくは60乃至100重量%の割合で含んでいる。ビニル樹脂(F)については、後で詳しく説明する。
樹脂(A)は、ビニル樹脂(F)以外の樹脂を含んでいなくてもよいが、ビニル樹脂(F)に加えて、他の樹脂を更に含むことができる。ビニル樹脂(F)の説明に先立ち、樹脂(A)が含み得るビニル樹脂(F)以外の樹脂について説明する。
上記の感光性着色組成物は、ビニル樹脂(F)を、樹脂(A)に対して所定の割合で含んでいる。そのような感光性着色組成物は、下記特徴(1)乃至(4)を有している。
感光性着色組成物を基材に塗布し、この塗膜を露光及び現像することによって得られる着色層、例えばフィルタセグメントは、オーバーハングを有していたとしても、その後に行う加熱処理、例えば150℃以上のポストベークによって部分的に流動化する。その結果、着色層は、断面が順テーパ形状を有するように変形する。
ビニル樹脂(F)は顔料(B)に吸着され易く、顔料(B)がビニル樹脂(F)を吸着すると、その溶剤に対する親和性が高くなる。それ故、優れた分散状態が長期間に亘って維持され得る。
現像工程において未露光部のみを、現像液、例えばアルカリ現像液で容易に除去可能である。
ポストベーク後の着色層を、リワーク液、例えば強アルカリ性のリワーク液で除去可能である。また、着色層の剥離片が粗大になることはない。
構成単位(a)は、上記特徴(3)に寄与する。即ち、構成単位(a)は、カルボキシル基を有しているものであって、現像時に、アルカリ可溶性部位として機能する。また、構成単位(a)は、上記特徴(4)にも寄与する。なお、ここで、用語「カルボキシル基」は、-COOH基を意味し、エステル結合(-COOR)又は水素イオン以外のイオンとイオン結合(-COOM)を形成しているものは包含しない。
構成単位(b)は、顔料(B)又は顔料(B)と分散剤等とを含んだ顔料組成物に対して親和性の部位として機能する。
構成単位(c)は、構成単位(a)及び(b)以外のビニル樹脂(F)の構成単位である。構成単位(c)は、主に、上記の特徴(1)、即ち着色層の優れた熱流動性に寄与する。構成単位(c)は、エチレン結合を有していてもよく、有していなくてもよい。
ビニル樹脂(F)は、上述した単量体をラジカル共重合に供することによって得られる。通常、ラジカル重合開始剤を用いた塊状重合又は溶液重合を行う。
これらの重合開始剤は、単独で又は2種類以上を組み合わせて用いることができる。
溶剤としては、例えば、酢酸エチル、酢酸n-ブチル、酢酸イソブチル、トルエン、キシレン、アセトン、ヘキサン、メチルエチルケトン、シクロヘキサノン、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、又はジエチレングリコールモノブチルエーテルアセテートを使用することができる。これらの溶剤は、単独で又は2種類以上を混合して使用することができる。
構成単位(a)乃至(c)の1種以上にエチレン結合を導入すると、顔料の分散性、着色層の熱流動性、及びパターン形状を劣化させることなく、着色層における架橋密度を高めることができ、従って、カラーフィルタの耐性を向上させることができる。なお、以下の反応は、公知の触媒を使用して行なうことができる。
構成単位(a)にエチレン結合を導入する方法としては、例えば、前駆体(b1)と前駆体(c1)とエポキシ基を有する単量体とを共重合することによって得られた共重合体の側鎖エポキシ基に、不飽和一塩基酸のカルボキシル基を付加反応させ、必要に応じて、生成した水酸基に多塩基酸無水物を反応させる方法がある。この場合、エポキシ基を有するエチレン単量体を前駆体とする構成単位が、エチレン結合を含んだ構成単位(a)となる。
構成単位(b)にエチレン結合を導入する方法として、例えば、一般式(7)に示す単量体、又は、R3がエチレン結合を有していること以外は一般式(5)に示したのと同様の構造を有する単量体を構成単位(b)の前駆体(b1)として使用した共重合を行う方法がある。但し、前駆体(b1)が含んでいるエチレン結合は、何れも重合に使用される可能性がある。環状構造内のエチレン結合は反応性が比較的低いので、構成単位(b)にエチレン結合を導入する場合、前駆体(b1)として、一般式(7)に示す単量体のように環状構造内にエチレン結合を有している単量体を使用することが好ましい。
構成単位(c)にエチレン結合を導入する1つの方法として、例えば、水酸基を有している単量体を構成単位(c)の前駆体(c1)の一部として使用して共重合を行い、共重合体の側鎖の水酸基に、イソシアネート基を有する単量体のイソシアネート基を反応させる方法がある。構成単位(c)にエチレン結合を導入する他の方法として、上記エポキシ基を有する単量体を構成単位(c)の前駆体(c1)の一部として使用して共重合を行い、共重合体の側鎖のエポキシ基に、上記不飽和一塩基酸のカルボキシル基を付加反応させ、更に、生成した水酸基に、イソシアネート基を有する単量体のイソシアネート基を反応させる方法がある。
着色層の優れた熱流動性とガラス基板などの基板の良好なリワーク性とを両立する観点から、ビニル樹脂(F)は、多塩基酸無水物を用いてカルボキシル基を導入したものであることが好ましい。多塩基酸無水物は、単独で用いても、2種類以上を併用しても構わない。
ビニル樹脂(F)の重量平均分子量Mwは、塗膜の優れた現像性と着色層の優れた熱流動性とを両立する観点から、2000乃至20000の範囲にあることが好ましく、4000乃至19000の範囲内にあることがより好ましい。重量平均分子量Mwが小さい場合、最適な現像時間が短すぎるか、又は、パターンの基板に対する密着性が不十分となる可能性がある。重量平均分子量Mwが大きい場合には、最適な現像時間が長すぎるか、又は、着色層の熱流動性が不十分となる可能性がある。
顔料(B)は、有機物である有機顔料であってもよいし、無機物である無機顔料であってもよいし、それらの混合物であってもよい。有機顔料及び無機顔料として、一般に染料と呼ばれているものを使用してもよく、天然色素を使用してもよい。これら中でも、耐熱性及び発色性に優れていることから、有機顔料が好適に用いられる。
以下に、有機顔料の具体例を、カラーインデックス番号で示す。
彩度と明度とのバランスを取りつつ、良好な塗布性、感度及び現像性等を確保するために、上記有機顔料と組み合わせて、無機顔料を用いることも可能である。無機顔料としては、例えば、黄色鉛、亜鉛黄、べんがら(赤色酸化鉄(III))、カドミウム赤、群青、紺青、酸化クロム緑及びコバルト緑などの金属酸化物粉、金属硫化物粉並びに金属粉を挙げることができる。
一般にブラックマトリックスと呼ばれている遮光層は、例えば、顔料(B)として黒色顔料を含んだ感光性着色組成物から形成することができる。この黒色顔料としては、例えば、三菱化学社製のカーボンブラック #2400、#2350、#2300、#2200、#1000、#980、#970、#960、#950、#900、#850、MCF88、#650、MA600、MA7、MA8、MA11、MA100、MA220、IL30B、IL31B、IL7B、IL11B、IL52B、#4000、#4010、#55、#52、#50、#47、#45、#44、#40、#33、#32、#30、#20、#10、#5、CF9、#3050、#3150、#3250、#3750、#3950、ダイヤブラックA、ダイヤブラックN220M、ダイヤブラックN234、ダイヤブラックI、ダイヤブラックLI、ダイヤブラックII、ダイヤブラックN339、ダイヤブラックSH、ダイヤブラックSHA、ダイヤブラックLH、ダイヤブラックH、ダイヤブラックHA、ダイヤブラックSF、ダイヤブラックN550M、ダイヤブラックE、ダイヤブラックG、ダイヤブラックR、ダイヤブラックN760M、若しくはダイヤブラックLR;キャンカーブ社製のカーボンブラックサーマックス N990、N991、N907、N908、N990、N991若しくはN908;旭カーボン社製のカーボンブラック 旭#80、旭#70、旭#70L、旭F-200、旭#66、旭#66HN、旭#60H、旭#60U、旭#60、旭#55、旭#50H、旭#51、旭#50U、旭#50、旭#35、旭#15若しくはアサヒサーマル;又は、デグサ社製のカーボンブラックColorBlack Fw200、ColorBlack Fw2、ColorBlack Fw2V、ColorBlack Fw1、ColorBlack Fw18、ColorBlack S170、ColorBlack S160、SpecialBlack6、SpecialBlack5、SpecialBlack4、SpecialBlack4A、SpecialBlack250、SpecialBlack350、PrintexU、PrintexV、Printex140U若しくはPrintex140V(何れも商品名)を使用することができる。
顔料を溶剤中で均一に分散させるために、顔料の少なくとも一部として顔料誘導体を使用してもよい。なお、顔料誘導体は、例えば、溶剤に対して親和性の置換基を有機顔料に導入してなるものである。この顔料誘導体は、通常の顔料と併用した場合に、その分散性を高める。即ち、顔料誘導体は、顔料分散剤としての役割を果たし得る。
顔料誘導体は、例えば、下記一般式(8)で示される化合物である。顔料誘導体には、塩基性置換基を有するものと、酸性置換基を有するものとがある。
X-Y
なお、一般式(8)において、Xは有機顔料残基であり、Yは塩基性置換基であるか又は酸性置換基である。
樹脂型顔料分散剤は、顔料に吸着する性質を有する顔料親和性部位と、顔料担体と相溶性のある部位とを有している。樹脂方顔料分散剤は、顔料に吸着して、顔料の顔料担体(分散媒)への分散を安定化する働きをするものである。
界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム、スチレン-アクリル酸共重合体のアルカリ塩、ステアリン酸ナトリウム、アルキルナフタリンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、ラウリル硫酸モノエタノールアミン、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ステアリン酸モノエタノールアミン、ステアリン酸ナトリウム、ラウリル硫酸ナトリウム、スチレン-アクリル酸共重合体のモノエタノールアミン、及びポリオキシエチレンアルキルエーテルリン酸エステルなどのアニオン性界面活性剤;ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンソルビタンモノステアレート、及びポリエチレングリコールモノラウレートなどのノニオン性界面活性剤;アルキル4級アンモニウム塩及びそれらのエチレンオキサイド付加物などのカオチン性界面活性剤;アルキルジメチルアミノ酢酸ベタインなどのアルキルベタイン;又は、アルキルイミダゾリンなどの両性界面活性剤を使用することができる。これらは、単独で又は2種以上を混合して用いることができる。
活性エネルギー線重合開始剤(C)、例えば光重合開始剤は、紫外線及び電子線などの活性エネルギー線を照射することによって硬化する性質を樹脂に与える。活性エネルギー線重合開始剤(C)は、顔料(B)に対して5乃至200重量%の比率で使用することが好ましく、活性エネルギー線に対する感応性及び現像性の観点では、顔料(B)に対して10乃至150重量%の比率で使用することがより好ましい。
増感剤としては、例えば、α-アシロキシエステル、アシルフォスフィンオキサイド、メチルフェニルグリオキシレート、ベンジル、9,10-フェナンスレンキノン、カンファーキノン、エチルアンスラキノン、4,4’-ジエチルイソフタロフェノン、3,3’,4,4’-テトラ(t-ブチルパーオキシカルボニル)ベンゾフェノン、又は4,4’-ジエチルアミノベンゾフェノンを使用することができる。
活性エネルギー線硬化性単量体(D)は、活性エネルギー線照射により硬化して樹脂を生成する単量体(モノマー)及び/又はオリゴマーである。
溶剤(E)は、顔料(B)を顔料担体中に充分に分散させる役割を果たす。加えて、溶剤(E)は、透明基板などの基板、例えばガラス基板上に、感光性樹脂を、乾燥膜厚が例えば0.2乃至5μmの範囲内となるように塗布することを容易にする。
平坦性に優れた塗膜を基板上に容易に形成可能とするべく、上記の感光性着色組成物は、レベリング剤を更に含んでいることが好ましい。
上記の感光性着色組成物は、更に他の成分を含んでいてもよい。例えば、この感光性着色組成物には、その粘度の経時安定性を向上させるべく、貯蔵安定剤を含有させてもよい。また、この感光性着色組成物には、着色層と基板との密着性を高めるべく、シランカップリング剤などの密着向上剤を含有させてもよい。
上記の感光性着色組成物は、例えば、以下の方法により製造する。
まず、顔料(B)を準備する。顔料(B)としては、ソルトミリング処理を施して微細化したものを使用することが好ましい。
次に、本発明の一形態に係るカラーフィルタについて説明する。
上述したカラーフィルタの製造工程において、フィルタセグメント及びブラックマトリクスなどの着色層に不具合が発見された場合、リワーク液、例えば高濃度の強アルカリ性溶液を剥離液として用いて基板から着色層を剥離して基板を再生し、この再生した基板をカラーフィルタの製造に再利用してもよい。即ち、基板のリワークを行ってもよい。
上述したカラーフィルタは、例えば、液晶表示装置又は固体撮像素子において使用することができる。以下に、カラーフィルタを含んだ液晶表示装置の一例を説明する。
第1及び第2基板は、間隙を隔てて互いに向き合っている。第1及び第2基板間の距離は、それらの間に介在した粒状スペーサ又はそれらの少なくとも一方に形成された柱状スペーサによって一定に保たれている。
下記実施例及び比較例において、「部」及び「%」は、それぞれ「重量部」及び「重量%」を意味している。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン233部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、メタクリル酸20部、パラクミルフェノールエチレンオキサイド変性アクリレート(東亜合成社製アロニックスM110)30部、ベンジルメタクリレート19部、メタクリル酸メチル16部、2-ヒドロキシエチルメタクリレート15部、及び2,2'-アゾビスイソブチロニトリル1.33部の混合物を2時間かけて滴下した。滴下終了後、反応を更に3時間継続し、重量平均分子量(Mw)が16000の樹脂溶液を得た。
各種成分の比率を表1乃至3に示すように変更したこと以外は樹脂溶液1について説明したのと同様の方法により、樹脂溶液2乃至15及び比較樹脂溶液1乃至6を調製した。重量平均分子量の測定結果を表1乃至3に示す。
・MAA:メタクリル酸
・AA:アクリル酸
・GMA:グリシジルメタクリレート
・THPA:テトラヒドロ無水マレイン酸
・M110:東亜合成社製アロニックスM110(パラクミルフェノールエチレンオキサイド変性アクリレート)
・FA-513M:日立化成社製ファンクリル FA-513M(ジシクロペンタニルメタクリレート)
・FA-512MT:日立化成社製ファンクリル FA-512MT(ジシクロペンテニルオキシエチルメタクリレート)
・BzMA:ベンジルメタクリレート
・2MTA:2-メトキシエチルアクリレート
・St:スチレン
・MMA:メチルメタクリレート
・EMA:エチルメタアクリレート
・BMA:n-ブチルメタクリレート
・HEMA:2-ヒドロキシエチルメタクリレート
・GLMA:グリセロールメタクリレート
・MOI:昭和電工社製カレンズMOI(2-メタクリロイルオキシエチルイソシアネート)
・Mw:重量平均分子量
また、表1乃至3の注釈を以下に記載する。
・注1: 共重合体中のGMAにAA及びTHPAを付加。
・注2: 共重合体中のGMAにMAA及びTHPAを付加。
・注3: 共重合体中のHEMAにTHPAを付加。
・注4: 共重合体中のGMAにMAAを付加。
・注5: 共重合体中のMAAにGMAを付加。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン207部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、メタクリル酸20部、パラクミルフェノールエチレンオキサイド変性アクリレート(東亜合成社製アロニックスM110)20部、メタクリル酸メチル45部、2-ヒドロキシエチルメタクリレート8.5部、及び2,2'-アゾビスイソブチロニトリル1.33部の混合物を2時間かけて滴下した。滴下終了後、反応を更に3時間継続し、共重合体溶液を得た。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン207部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、メタクリル酸20部、パラクミルフェノールエチレンオキサイド変性アクリレート(東亜合成社製アロニックスM110)20部、メタクリル酸メチル45部、グリセロールモノメタクリレート8.5部及び2,2'-アゾビスイソブチロニトリル1.33部の混合物を2時間かけて滴下した。滴下終了後、反応を更に3時間継続し、共重合体溶液を得た。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン370部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、パラクミルフェノールエチレンオキサイド変性アクリレート(東亜合成社製アロニックスM110)18部、ベンジルメタクリレート10部、グリシジルメタクリレート18.2部、メタクリル酸メチル25部、及び2,2'-アゾビスイソブチロニトリル2.0部の混合物を2時間かけて滴下した。滴下終了後、100℃で3時間に亘って更に反応させた。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン233部を注ぎ、これを110℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、スチレン4部、グリシジルメタクリレート27部、メタクリル酸メチル27部、2-メトキシエチルアクリレート8部、2-ヒドロキシエチルメタクリレート6部、及びジメチル2,2'-アゾビス(2-メチルプロピオネート)13部の混合物を2時間かけて滴下した。滴下終了後、110℃で3時間に亘って更に反応させて共重合体を得た。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン233部を注ぎ、これを110℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、メタクリル酸30部、ベンジルメタクリレート10部、メタクリル酸メチル16部、2-メトキシエチルアクリレート6部、2-ヒドロキシエチルメタクリレート6部、及びジメチル2,2'-アゾビス(2-メチルプロピオネート)13部の混合物を2時間かけて滴下した。滴下終了後、110℃で3時間に亘って更に反応させた。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコに、シクロヘキサノン233部、メタクリル酸20部、パラクミルフェノールエチレンオキサイド変性アクリレート30部、ベンジルメタクリレート19部、メタクリル酸メチル16部、2-ヒドロキシエチルメタクリレート15部、及びオクチルメルカプタン15部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、2,2'-アゾビスイソブチロニトリル1.33部を添加した。5時間に亘って反応を継続することにより、重量平均分子量(Mw)が1500の樹脂溶液を得た。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコに、シクロヘキサノン233部、メタクリル酸20部、パラクミルフェノールエチレンオキサイド変性アクリレート30部、ベンジルメタクリレート19部、メタクリル酸メチル16部、2-ヒドロキシエチルメタクリレート15部、及びオクチルメルカプタン11部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、2,2'-アゾビスイソブチロニトリル0.9部を添加した。5時間に亘って反応を継続することにより、重量平均分子量(Mw)が25000の樹脂溶液を得た。
温度計、冷却管、窒素ガス導入管、滴下管及び撹拌装置を備えたセパラブル4口フラスコにシクロヘキサノン233部を注ぎ、これを80℃に昇温した。フラスコ内のガスを窒素ガスで置換した後、フラスコ内の液に、滴下管より、メタクリル酸13部、メタクリル酸メチル10部、メタクリル酸ブチル77部、及び2,2'-アゾビスイソブチロニトリル1.33部の混合物を2時間かけて滴下した。滴下終了後、反応を更に3時間継続し、重量平均分子量(Mw)が25000の樹脂溶液を得た。
実施例1乃至18及び20乃至26並びに比較例1乃至10に係る顔料分散体の各々を、以下の方法により調製した。
まず、顔料、分散剤(日本ルーブリゾール社製「ソルスパース20000」)、樹脂溶液3、及び溶剤(プロピレングリコールモノメチルエーテルアセテート)を混合し、この混合液において顔料を均一に分散させた。この混合及び分散には、粉砕媒体としてジルコニアビーズを用いた遊星型ボールミルを利用した。このようにして、実施例19に係る顔料分散体を得た。
・P.R.254:C.I.Pigment Red 254(ジケトピロロピロール系赤色顔料)
・P.R.177:C.I.Pigment Red 177(アントラキノン系赤色顔料)
・P.Y.150:C.I.Pigment Yellow 150(アゾメチン系黄色顔料)
・P.G.36:C.I.Pigment Green 36(ハロゲン化銅フタロシアニン系緑色顔料)
・P.B.15:6:C.I.Pigment Blue 15:6(銅フタロシアニン系青色顔料)
・P.V.23:C.I.Pigment Violet 23(ジオキサジン系紫色顔料)
・CB:カーボンブラック(デグサ社製 Pritex75)
また、表4乃至6の注釈を以下に記載する。
・注6: 樹脂溶液3に変更。
上述した方法によって得られた感光性着色組成物の25℃における粘度を、E型粘度計(TOKI SANGYO社製TUE-20L型)を用いて測定した。具体的には、回転数を20rpmに設定して、感光性着色組成物を製造した当日と、これを40℃の恒温室内での7日間に亘る保存後とに粘度の測定を行った。そして、感光性着色組成物を製造した当日の粘度、即ち初期粘度(η0:mPa・s)と40℃の恒温室内での7日間に亘る保存後の粘度(η7:mPa・s)とを下記の基準に参照して、各感光性着色組成物の保存安定性を評価した。その結果を、下記表10乃至12に纏める。
△:比η7/η0が1.20以上1.50未満であり、僅かに粘度の上昇が見られ分散安定性が若干劣る。
赤色、緑色及び青色の感光性着色組成物の各々を、10cm×10cmの透明ガラス基板上にスピンコートし、これを70℃で20分間に亘ってプリベークして、乾燥膜厚が約2.0μmの塗膜を得た。
以上のようにして、赤色、緑色及び青色の各色の着色パターンを得た。
×:時間T1が60sec以上であるか又はパターンの剥離を生じている。
上述した方法によって着色パターンを形成したガラス基板を半分の寸法(5cm×10cm)に切断して、2つの試験片とした。
○:20≦θ≦45の順テーパ形状。
△:45<θ≦80の順テーパ形状。
×:θ>80のシャープな順テーパ形状又はオーバーハングあり。
上記の現像性評価に用いた試料、即ち着色パターンを形成した基板を、230℃で90分間に亘ってポストベークした。
Claims (7)
- 樹脂(A)と、顔料(B)と、活性エネルギー線重合開始剤(C)と、活性エネルギー線硬化性単量体(D)と、溶剤(E)とを含有し、
前記樹脂(A)は、ビニル樹脂(F)を50重量%以上の割合で含み、
前記ビニル樹脂(F)は、
カルボキシル基を有する構成単位(a)を2乃至50重量%の割合で含み、
下記一般式(1)に示す芳香族環、下記一般式(2)に示す芳香族環、下記一般式(3)に示す脂肪族環、及び下記一般式(4)に示す脂肪族環からなる群より選ばれる1種類以上の環状構造を有する構成単位(b)を2乃至50重量%の割合で含み、
その他の構成単位(c)を10乃至80重量%の割合で含んだ
ことを特徴とする感光性着色組成物。
- 前記構成単位(a)、(b)及び(c)からなる群から選ばれる1種以上の構成単位は、エチレン結合を有していることを特徴とする請求項1に記載の感光性着色組成物。
- 前記構成単位(a)の前駆体(a1)は、アクリル酸及びメタクリル酸からなる群から選ばれる1種以上の単量体であることを特徴とする請求項1又は2に記載の感光性着色組成物。
- 前記構成単位(a)が含んでいるカルボキシル基の少なくとも一部は、水酸基を有する構成単位に多塩基酸無水物を付加することにより、又は、エポキシ基を有する構成単位と不飽和一塩基酸との付加により形成される水酸基に多塩基酸無水物を付加することにより導入したものであることを特徴とする請求項1又は2に記載の感光性着色組成物。
- 前記構成単位(c)の前駆体(c1)は、メチルアクリレート、メチルメタクリレート、エチルアクリレート、及びエチルメタクリレートからなる群より選ばれる1種類以上の単量体を含んでいることを特徴とする請求項1乃至5の何れか1項に記載の感光性着色組成物。
- 請求項1乃至6の何れか1項に記載の感光性着色組成物から形成されるフィルタセグメント及びブラックマトリックスの少なくとも一方を具備したことを特徴とするカラーフィルタ。
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TW201039060A (en) | 2010-11-01 |
CN102365586A (zh) | 2012-02-29 |
JP2010230957A (ja) | 2010-10-14 |
JP5617177B2 (ja) | 2014-11-05 |
TWI443456B (zh) | 2014-07-01 |
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