WO2009116442A1 - 顔料分散組成物、着色感光性組成物、光硬化性組成物、カラーフィルタ、液晶表示素子、及び固体撮像素子 - Google Patents
顔料分散組成物、着色感光性組成物、光硬化性組成物、カラーフィルタ、液晶表示素子、及び固体撮像素子 Download PDFInfo
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- WO2009116442A1 WO2009116442A1 PCT/JP2009/054710 JP2009054710W WO2009116442A1 WO 2009116442 A1 WO2009116442 A1 WO 2009116442A1 JP 2009054710 W JP2009054710 W JP 2009054710W WO 2009116442 A1 WO2009116442 A1 WO 2009116442A1
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- 0 CC(C(NC)=O)O** Chemical compound CC(C(NC)=O)O** 0.000 description 8
- HBFVZLNCMLGDCL-UHFFFAOYSA-N C=Cc1ccc(CSc2nc(cccc3)c3[o]2)cc1 Chemical compound C=Cc1ccc(CSc2nc(cccc3)c3[o]2)cc1 HBFVZLNCMLGDCL-UHFFFAOYSA-N 0.000 description 1
- NFBHOUVLBYFANF-UHFFFAOYSA-N C=Cc1ccc(CSc2nc3ccccc3[nH]2)cc1 Chemical compound C=Cc1ccc(CSc2nc3ccccc3[nH]2)cc1 NFBHOUVLBYFANF-UHFFFAOYSA-N 0.000 description 1
- WFFSOPZRIXZCMT-UHFFFAOYSA-N C=Cc1ccc(CSc2nc3ccccc3[s]2)cc1 Chemical compound C=Cc1ccc(CSc2nc3ccccc3[s]2)cc1 WFFSOPZRIXZCMT-UHFFFAOYSA-N 0.000 description 1
- JGLIMUZWVDNAOX-UHFFFAOYSA-N C=Cc1cccc(CCN(c2ccccc22)c(cccc3)c3C2=O)c1 Chemical compound C=Cc1cccc(CCN(c2ccccc22)c(cccc3)c3C2=O)c1 JGLIMUZWVDNAOX-UHFFFAOYSA-N 0.000 description 1
- LCROTTIRNWHTLU-UHFFFAOYSA-N CC(c1ccc(C=C)cc1)N(C(c1ccccc11)=O)C1=O Chemical compound CC(c1ccc(C=C)cc1)N(C(c1ccccc11)=O)C1=O LCROTTIRNWHTLU-UHFFFAOYSA-N 0.000 description 1
- QYKVIDSQOQKHNQ-LCLSSZJLSA-N CCN(C(/C(/O1)=C\c(cc2)ccc2N(c2ccccc2)c2ccccc2)=O)/C1=N/c(cccc1)c1C(c1ccccc1)=O Chemical compound CCN(C(/C(/O1)=C\c(cc2)ccc2N(c2ccccc2)c2ccccc2)=O)/C1=N/c(cccc1)c1C(c1ccccc1)=O QYKVIDSQOQKHNQ-LCLSSZJLSA-N 0.000 description 1
- ZKFIJQZXKQGIDZ-UHFFFAOYSA-N CCN(C(c1cc2ccccc2cc11)=O)/C1=[O]\c1cc(C=C)ccc1 Chemical compound CCN(C(c1cc2ccccc2cc11)=O)/C1=[O]\c1cc(C=C)ccc1 ZKFIJQZXKQGIDZ-UHFFFAOYSA-N 0.000 description 1
- KXAVGZAQRJOSQO-UHFFFAOYSA-N CCN(C(c1cccc2cccc3c12)=O)/C3=[O]\c1cc(C=C)ccc1 Chemical compound CCN(C(c1cccc2cccc3c12)=O)/C3=[O]\c1cc(C=C)ccc1 KXAVGZAQRJOSQO-UHFFFAOYSA-N 0.000 description 1
- OHGORHLBIORZED-YVCQSLJMSA-N CCOC(c(cccc1)c1/N=C(/N(CCc(cc1)ccc1OC)C1=O)\O/C1=C/c(cc1)ccc1N(c1ccccc1)c1ccccc1)=O Chemical compound CCOC(c(cccc1)c1/N=C(/N(CCc(cc1)ccc1OC)C1=O)\O/C1=C/c(cc1)ccc1N(c1ccccc1)c1ccccc1)=O OHGORHLBIORZED-YVCQSLJMSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0061—Preparation of organic pigments by grinding a dyed resin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0069—Non aqueous dispersions of pigments containing only a solvent and a dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/002—Pigment pastes, e.g. for mixing in paints in organic medium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
Definitions
- the present invention relates to a pigment dispersion composition, a colored photosensitive composition containing the pigment dispersion composition, a color filter having a colored region formed by the colored photosensitive composition, and a liquid crystal display using the color filter
- the present invention relates to an element and a solid-state imaging element.
- the present invention is also excellent in dispersibility of pigments, excellent in fluidity and coloring power of pigment dispersion compositions and photocurable compositions, and can be suitably used in a wide range of paints, printing inks, color display plates and the like.
- the present invention relates to a pigment dispersion composition, a photocurable composition containing the same, and a color filter produced using the photocurable composition.
- the color filter contains a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components to form a colored photosensitive composition. It is manufactured by forming a colored pattern by a photolithography method, an ink jet method or the like.
- color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications.
- color filters are required to have high color characteristics in terms of chromaticity and contrast.
- color filters for use in image sensors are also required to have high color characteristics such as reduction in color unevenness and improvement in color resolution.
- the pigment contained in the colored photosensitive composition or the photocurable composition is dispersed in a finer state (good dispersibility), and is dispersed in a stable state ( Good dispersion stability) is demanded.
- good dispersibility When the dispersibility of the pigment is insufficient, fringes (jagged edges) and surface irregularities occur in the colored pixels formed by the photolithographic method, and there are many undeveloped residues (residues) on the substrate. There are problems that the chromaticity and dimensional accuracy of the color filter are lowered and the contrast is remarkably deteriorated.
- the film thickness uniformity in the coating process of the colored photosensitive composition or the photocurable composition may be reduced.
- the problem that the sensitivity in the exposure process decreases and the alkali solubility in the development process decreases tends to occur.
- the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened.
- a polymer-type pigment dispersant in which an organic dye structure and a polymer are combined has been proposed (see Japanese Patent Application Laid-Open No. 2008-009426).
- the primary particles of the pigment are made fine by a method of kneading a pigment, a water-soluble inorganic salt, or a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader (a salt milling method).
- a salt milling method a method of kneading a pigment, a water-soluble inorganic salt, or a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader.
- the obtained mixture of primary particles of fine pigment is put into water and stirred with a mixer or the like to form a slurry.
- the slurry is filtered, washed with water and dried to obtain a fine pigment as a secondary aggregate which is an aggregate of primary particles of the pigment.
- the dispersion step in a normal disperser such as a sand mill or a ball mill is a step of loosening the secondary aggregate that is an aggregate of primary particles of the pigment to obtain a
- the primary particles of the finely divided pigment can be obtained by the above-described method, etc.
- various pigment dispersants have been developed conventionally. Has been.
- Japanese Patent Application Laid-Open No. 2004-287409 proposes an ⁇ -carboxypolycaprolactone monomethacrylate copolymer for the purpose of obtaining high-definition pixels having good alkali developability. .
- JP-A-2003-238837 for the purpose of improving dispersibility and alkali developability, it has a polymer structure of a vinyl compound such as styrene and alkyl (meth) acrylate as a graft chain, and Polymer compounds having a heterocyclic structure in the side chain have been proposed.
- a vinyl compound such as styrene and alkyl (meth) acrylate
- Polymer compounds having a heterocyclic structure in the side chain have been proposed.
- the photocurable composition is applied and dried on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance. After that, the dried coating film is irradiated with radiation in a desired pattern (hereinafter referred to as “exposure”) and developed to obtain pixels of each color.
- the color filter manufactured in this manner is likely to cause residue and background contamination on the unexposed substrate or the light shielding layer in the development process, and the post-baked pixels after development have poor surface smoothness.
- the physical properties of the coating film were inferior.
- the degree of deterioration of residues, background stains and surface smoothness on the substrate or the light-shielding layer tends to become more prominent as the concentration of the pigment contained in the photocurable composition increases. With a photocurable composition, it was difficult to achieve a sufficient color density.
- a pigment dispersion composition using a block type, random type or linear polymer compound into which acrylic acid is introduced as an alkali-soluble resin is known (Japanese Patent No. 3094403). JP, 2004-287409, A), and it was still insufficient to achieve both the dispersibility of the pigment and the developability when applied to a curable composition for pattern formation such as a color filter.
- Slit coating has the advantages of superior coating film thickness uniformity and less waste of coating liquid compared to conventional spin coating.
- the coating liquid is exposed to the outside air at the slit opening at the head tip, the coating liquid (photocurable composition) is liable to dry and solidify at the head tip. This may cause clogging of the slit nozzles and vertical stripe unevenness of the coating film applied on the transparent substrate (vertical application stripes in the application direction).
- a dispersant such as a surfactant or a resin-type dispersant
- a dispersant such as a surfactant or a resin-type dispersant
- problems such as reduced coating strength, developability, adhesion to substrates such as glass, and durability, and dispersion stability of the photocurable composition.
- it is difficult to achieve both the excellent resolubility of the coating solution in dry film and the provision of strong adhesion between the coating film and a substrate such as glass.
- a pigment dispersion composition using a linear polymer compound such as a block type or a random type into which an acid is introduced is also known (see Japanese Patent Application Laid-Open No. 2004-287409).
- a linear polymer compound such as a block type or a random type into which an acid is introduced
- an extremely fine pigment has sufficient dispersibility. I haven't got it.
- the first object of the present invention is that the finely divided pigment can be dispersed in the form of primary particles, and the primary particles of the dispersed pigment can be stably maintained, and the contrast can be maintained.
- Another object of the present invention is to provide a pigment dispersion composition capable of forming a colored film excellent in the above.
- a second object of the present invention is to provide a colored photosensitive composition that includes the pigment dispersion composition and that can form a colored cured film having excellent coating properties and excellent contrast.
- a third object of the present invention is to provide a color filter formed using the colored photosensitive composition, having a high contrast, a color area with small color density unevenness and excellent color characteristics, and the color filter.
- An object of the present invention is to provide a liquid crystal display device and a solid-state imaging device.
- a fourth object of the present invention is a pigment dispersion excellent in dispersion stability, and self-dissolution (dry film) when aggregated or solidified at the tip of the coating liquid discharge port of the slit coating apparatus using the same.
- An object of the present invention is to provide a photocurable composition that is excellent in re-solubility), excellent in solubility in a developer, and excellent in developability in which generation of a development residue is suppressed.
- the fifth object of the present invention is to provide a high-quality color filter having a colored pattern formed using the photocurable composition, and further to provide the color filter with excellent color reproducibility and high
- a contrast liquid crystal display device and a solid-state imaging device with small color unevenness and high resolution are provided.
- the pigment dispersion composition according to the first aspect of the present invention includes (a) at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II). It contains a polymer compound, (b) a pigment, and (c) an organic solvent.
- R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group
- X 1 and X 2 each independently represent —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group
- L 1 and L 2 each independently represent a single bond or a divalent organic linking group.
- a 1 and A 2 each independently represents a monovalent organic group
- m and n each independently represents an integer of 2 to 8
- p and q each independently represents 1 to 100 Represents an integer.
- the polymer compound has an acid group in the side chain in the range of 50 mgKOH / g to 200 mgKOH / g.
- a high molecular compound has a heterocyclic group in a side chain.
- the pigment dispersion composition of the first aspect is preferably used for forming a colored region in a color filter.
- the colored photosensitive composition of the first aspect contains the pigment dispersion composition of the first aspect, a photopolymerizable compound, and a photopolymerization initiator. Moreover, the color filter of a 1st viewpoint has a colored area
- the polymer compound (a) functioning as a pigment dispersant contains a repeating unit represented by the general formula (I) or (II) and has a specific graft chain structure.
- This graft chain structure has low affinity with the pigment, but (c) the affinity with the organic solvent coexisting in the pigment dispersion composition is high, so that this graft chain portion does not adsorb to the pigment surface (b)
- the graft chain portion can have a structure extending to the organic solvent side.
- the (a) polymer compound in the first aspect has a graft chain structure that has a high affinity with the solvent, and thus has an extended structure when coexisting with the (b) pigment and (c) the organic solvent, It is considered that the adsorption to the pigment surface is efficiently performed, and as a result, it is considered that a stable dispersion state of the pigment can be maintained in the organic solvent.
- the graft chain structure having high affinity with the pigment and low affinity with the solvent the graft chain portion is adsorbed on the pigment surface, and the graft chain portion may be extended to the organic solvent side. Can not.
- a polymer compound having such a graft chain has a contracted structure when coexisting with a pigment and an organic solvent, and the adsorption to the pigment surface is not performed efficiently, resulting in aggregation of the pigment. It is thought that it will end.
- the graft chain end group is a highly interactive carboxyl group. Since the structure of the molecular compound is in a contracted state, the effect of pigment dispersibility cannot be sufficiently exhibited.
- the (a) polymer compound in the first aspect has a heterocyclic group in the side chain, which is a preferred embodiment, so that the heterocyclic structure and (b) the pigment have a strong electrostatic interaction.
- the polymer compound is strongly adsorbed on the pigment surface, and the secondary aggregates can be effectively loosened to maintain a stable dispersion state.
- the color filter using the pigment dispersion composition (a) dispersed with the pigment (b) by the polymer compound becomes turbid in the color area (pixel portion) at high temperature and high humidity.
- the problem that the pixel portion becomes cloudy can also be solved.
- a colored photosensitive composition using a pigment dispersion composition dispersed with (b) a pigment by (a) a polymer compound is excellent in coating properties (no coating unevenness occurs).
- this is because (a) the graft chain structure of the polymer compound has a high affinity with (c) the organic solvent, and thus the polymer compound is stretched to improve the film-forming property. This is probably because of this.
- the graft chain end group is a highly interactive carboxyl group, and the vinyl compound heavy compound of Japanese Patent Application Laid-Open No. 2003-238837 is also used.
- the present invention contains (A) a graft polymer compound having acrylic acid in the main chain, (B) a pigment, and (C) an organic solvent.
- the present inventors have found that the above problems can be solved by using a pigment dispersion composition, and have reached the present invention.
- the pigment dispersion composition according to the second aspect of the present invention comprises (A) a graft polymer having 5 to 30% by mass of acrylic acid copolymerized in the main chain, (B) a pigment, and (C) an organic solvent. To do.
- the photocurable composition of the second aspect contains the pigment dispersion composition of the second aspect, (F) a polymerizable compound, and (G) a photopolymerization initiator.
- the color filter of a 2nd viewpoint is a color filter formed using the photocurable composition of a 2nd viewpoint.
- the liquid crystal display device according to the second aspect is a liquid crystal display device using the color filter according to the second aspect.
- the solid-state image sensor according to the second aspect is a solid-state image sensor using the color filter according to the second aspect.
- the operation of the second viewpoint is not clear, it is considered as follows.
- the polymer compound has acrylic acid in the main chain, and the graft type Therefore, the main chain acrylic acid is more polar than methacrylic acid, and the main chain is flexible, so that when the acrylic acid acts on the pigment to the highly polar pigment, the pigment is effectively coated.
- the graft chain functions as a steric repulsion chain, it is considered that reaggregation of the pigments is suppressed.
- the secondary aggregates which are aggregates of primary particles of the pigment, can be effectively loosened, and the primary particles can be effectively prevented from reaggregating into secondary aggregates. . Therefore, it is considered that a dispersion in a state close to that of primary particles being dispersed can be obtained in the dispersion step. Therefore, it is considered that a color filter with a high contrast and a color filter with a small color density unevenness could be obtained by providing a coloring pattern made of a photocurable composition containing such a pigment dispersion composition. .
- the re-dissolvability of the dry film is good. This is because the pigment dispersed in the primary particles is covered with the graft polymer compound, and the graft polymer on the outer wall becomes the solvent. It is presumed that the affinity is high, and even if it becomes a dry film, it is easily dissolved in the solvent.
- the pigment dispersion composition dispersed with the polymer compound according to the second aspect is effective in coping with the problem that a part of the dispersant is precipitated when the pigment dispersion composition is stored at a low temperature. is there.
- This problem occurs particularly in a graft polymer compound having polycaprolactone as a graft chain. Since polycaprolactone is a highly crystalline polymer, the dispersion stability at low temperatures becomes poor.
- the high molecular compound (A) of the viewpoint is such that acrylic acid is copolymerized in the main chain, the flexibility of the polymer main chain is improved, and a carboxylic acid that is not easily solvated is used in the pigment dispersion composition.
- the polycaprolactone chain which easily aggregates with the solvent, is solvated with an organic solvent instead of being regularly arranged, so it becomes easily soluble in the solvent and can be stored stably at low temperatures.
- the finely divided pigment can be dispersed in the state of primary particles, and the dispersed primary particles of the pigment can be stably maintained, and the contrast is excellent.
- a pigment dispersion composition capable of forming a colored film can be provided.
- paintability and excellent in contrast including the said pigment dispersion composition can be provided.
- the color filter is formed using the colored photosensitive composition, has a high contrast, has a color density unevenness and excellent color characteristics, and includes the color filter.
- a liquid crystal display element and a solid-state image sensor can be provided.
- the pigment dispersion excellent in dispersion stability, and the self-dissolving property (recycled dry film) at the time of aggregation or solidification in the coating liquid discharge port tip of the slit coating apparatus using the pigment dispersion It is possible to provide a photocurable composition that is excellent in solubility, excellent in solubility in a developing solution, and excellent in developability in which generation of a development residue is suppressed. Furthermore, the present invention provides a high-quality color filter having a coloring pattern using the photocurable composition, and further, an excellent color reproducibility and high-contrast liquid crystal display device including the color filter, and It is possible to provide a high-resolution solid-state imaging device with small color unevenness.
- the pigment dispersion composition the colored photosensitive composition, the photocurable composition, the color filter, the liquid crystal display device, and the solid-state imaging device of the present invention will be described in detail.
- the pigment dispersion composition of the first embodiment of the present invention is (a) a high-strength composition containing at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II).
- a molecular compound, (b) a pigment, and (c) an organic solvent are contained.
- the polymer compound, (b) the pigment, and (c) the organic solvent constituting the pigment dispersion composition of the first embodiment will be described.
- the pigment dispersion composition of the first embodiment is a polymer compound (hereinafter referred to as “a compound compound”) containing at least one repeating unit selected from repeating units represented by any one of the following general formulas (I) and (II). It may be referred to as a “specific polymer”).
- R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group
- X 1 and X 2 each independently represent —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group
- L 1 and L 2 each independently represent a single bond or a divalent organic linking group.
- a 1 and A 2 each independently represents a monovalent organic group
- m and n each independently represents an integer of 2 to 8
- p and q each independently represents 1 to 100 Represents an integer.
- R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group.
- a substituted or unsubstituted alkyl group is preferable.
- the alkyl group an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
- the alkyl group has a substituent
- examples of the substituent include a hydroxy group and an alkoxy group (preferably having a carbon number of 1 to 5, more preferably 1 to 3 carbon atoms), a methoxy group, an ethoxy group, Examples include a cyclohexyloxy group.
- alkyl groups include methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, Examples include 3-hydroxypropyl group, 2-hydroxypropyl group, and 2-methoxyethyl group.
- R 1 , R 2 , R 4 , and R 5 are preferably hydrogen atoms
- R 3 and R 6 are most preferably hydrogen atoms or methyl groups from the viewpoint of adsorption efficiency on the pigment surface.
- X 1 and X 2 each independently represents —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group.
- —C ( ⁇ O) O—, —CONH—, and a phenylene group are preferable from the viewpoint of adsorptivity to the pigment, and —C ( ⁇ O) O— is most preferable.
- L 1 and L 2 each independently represents a single bond or a divalent organic linking group.
- the divalent organic linking group is preferably a substituted or unsubstituted alkylene group or a divalent organic linking group comprising the alkylene group and a hetero atom or a partial structure containing a hetero atom.
- the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
- hetero atom in the partial structure containing a hetero atom an oxygen atom, a nitrogen atom, and a sulfur atom are mentioned, for example, Among these, an oxygen atom and a nitrogen atom are preferable.
- preferable alkylene groups include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
- examples of the substituent include a hydroxy group.
- the divalent organic linking group includes a hetero atom or a hetero atom selected from —C ( ⁇ O) —, —OC ( ⁇ O) —, and —NHC ( ⁇ O) — at the end of the above alkylene group.
- a compound having a partial structure and linked to an adjacent oxygen atom via the heteroatom or a partial structure containing a heteroatom is preferable from the viewpoint of adsorptivity to the pigment.
- the adjacent oxygen atom means an oxygen atom that is bonded to L 1 in the general formula (I) and L 2 in the general formula (II) on the side chain end side.
- a 1 and A 2 each independently represents a monovalent organic group.
- a monovalent organic group a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is preferable.
- preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms.
- Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.
- a monovalent non-metallic atomic group other than hydrogen is used as the substituent of the substituted alkyl group.
- Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups.
- aryloxy group mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ure
- alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.
- substituents include alkoxy group, aryloxy group, alkylthio group, arylthio group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, aryl group, hetero
- An aryl group, an alkenyl group, an alkynyl group, and a silyl group are preferable from the viewpoint of dispersion stability.
- aryl group examples include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxy Phenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, Ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophen
- a 1 and A 2 from the viewpoints of dispersion stability and developability, a straight chain having 1 to 20 carbon atoms, a branched structure having 3 to 20 carbon atoms, and a number having 5 to 20 carbon atoms Cyclic alkyl groups are preferable, linear alkyl groups having 4 to 15 carbon atoms, branched alkyl groups having 4 to 15 carbon atoms, and cyclic alkyl groups having 6 to 10 carbon atoms are more preferable. Even more preferred are linear alkyl groups of 6 to 10 and branched alkyl groups of 6 to 12 carbon atoms.
- M and n each independently represents an integer of 2 to 8. From the viewpoint of dispersion stability and developability, 4 to 6 is preferable, and 5 is most preferable.
- P and q each independently represents an integer of 1 to 100. Two or more different p and different q may be mixed. p and q are preferably 5 to 60, more preferably 5 to 40, and still more preferably 5 to 20 from the viewpoints of dispersion stability and developability.
- the repeating unit represented by the general formula (I) is more preferably a repeating unit represented by the following general formula (I) -2.
- R 1 to R 3 each independently represents a hydrogen atom or a monovalent organic group
- La represents an alkylene group having 2 to 10 carbon atoms
- Lb represents —C ( ⁇ O) — or —NHC ( ⁇ O) —
- a 1 represents a monovalent organic group
- m represents an integer of 2 to 8
- p represents an integer of 1 to 100 Represents.
- the repeating unit represented by the general formula (I), (II), or (I) -2 is a simple unit represented by the following general formula (i), (ii), or (i) -2, respectively.
- the polymer is introduced as a repeating unit of the polymer compound by polymerization or copolymerization.
- R 1 to R 6 each independently represent a hydrogen atom or a monovalent organic group
- X 1 and X 2 are each Independently represents —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group
- L 1 and L 2 each independently represent a single bond or 2
- a valent organic linking group La represents an alkylene group having 2 to 10 carbon atoms
- Lb represents —C ( ⁇ O) —, or —NHC ( ⁇ O) —
- a 1 and A 2 represent Each independently represents a monovalent organic group
- m and n each independently represents an integer of 2 to 8
- p and q each independently represents an integer of 1 to 100.
- the specific polymer in 1st Embodiment should just contain the at least 1 sort (s) of repeating unit selected from the repeating unit represented by either of general formula (I) and (II), and contains only 1 type. It may be a thing and may contain 2 or more types.
- the content of the repeating unit represented by any one of the general formulas (I) and (II) is not particularly limited, but the total repeating unit contained in the polymer is 100% by mass.
- the repeating unit represented by any one of the general formulas (I) and (II) is preferably contained in an amount of 5% by mass or more, more preferably 50% by mass, and 50% by mass to 80% by mass. It is more preferable to contain.
- the specific polymer in the first embodiment includes a monomer having a functional group that can be adsorbed to the pigment, and the aforementioned general formulas (i), (ii), (i) — It is preferably a polymer compound obtained by copolymerizing the monomer represented by 2.
- Specific examples of the monomer having a functional group capable of adsorbing to the pigment include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, a monomer having a basic nitrogen atom, and an ionic group. A monomer etc. can be mentioned. Among these, a monomer having an organic dye structure or a heterocyclic structure is preferable from the viewpoint of the adsorptive power to the pigment.
- the monomer having an organic dye structure or a heterocyclic structure is preferably one selected from the group consisting of a monomer represented by the following general formula (1), a maleimide, and a maleimide derivative. Among these, a monomer represented by the following general formula (1) is particularly preferable.
- R 1 represents a hydrogen atom or an alkyl group.
- R 2 represents a single bond or a divalent linking group.
- Y represents —CO—, —C ( ⁇ O) O—, —CONH—, —OC ( ⁇ O) —, or a phenylene group.
- Z represents a group having a nitrogen-containing heterocyclic group.
- an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
- the alkyl group represented by R 1 has a substituent, the substituent is preferably, for example, an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, or a cyclohexyloxy group.
- an alkoxy group such as a hydroxy group, a methoxy group, an ethoxy group, or a cyclohexyloxy group.
- alkoxy group those having 1 to 5 carbon atoms are preferable, and those having 1 to 3 carbon atoms are preferable.
- preferable alkyl group represented by R 1 in the general formula (1) include, for example, methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n- Examples thereof include a hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.
- R 1 is most preferably a hydrogen atom or a methyl group.
- the divalent linking group represented by R 2 in the general formula (1) is preferably an alkylene group or a divalent group containing an alkylene group.
- the alkylene group may be a substituted alkylene group or an unsubstituted alkylene group.
- the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
- examples of the substituent include a hydroxy group.
- Specific examples of the preferable alkylene group represented by R 2 include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
- the divalent group containing an alkylene group represented by R 2 in the general formula (1) is a group in which two or more of the above alkylene groups are linked via a hetero atom (for example, an oxygen atom, a nitrogen atom, or a sulfur atom). It may be.
- the divalent group containing an alkylene group represented by R 2 includes —O—, —S—, —C ( ⁇ O) O—, — at the terminal of the alkylene group bonded to Z.
- a hetero atom selected from or a partial structure containing a hetero atom may be bonded.
- Tetrazole ring indole ring, quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure
- benzimidazole structure benztriazole structure
- benzthiazole structure cyclic amide structure
- cyclic urea structure cyclic imide structure
- the nitrogen-containing heterocyclic structure may be phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavan.
- thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, Thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzo Complex selected from azole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, pyrazine, tetrazol
- These nitrogen-containing heterocyclic structures may have a substituent.
- substituents include an alkyl group, an alkoxy group, a halogen atom, an aliphatic ester group, an aromatic ester group, and an alkoxycarbonyl group. Is mentioned.
- the nitrogen-containing heterocyclic group represented by Z is more preferably a group having a nitrogen-containing heterocyclic structure having 6 or more carbon atoms, and a nitrogen-containing heterocyclic structure having 6 to 12 carbon atoms. Particularly preferred is a group having Specific examples of the nitrogen-containing heterocyclic structure having 6 or more carbon atoms include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea A structure and a cyclic imide structure are preferable, and a structure represented by the following general formula (2), (3), or (4) is particularly preferable.
- X represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR A —, and One selected from the group consisting of —C ( ⁇ O) —.
- R A represents a hydrogen atom or an alkyl group.
- the alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group.
- X in the general formula (2) is preferably a single bond, a methylene group, —O— or —C ( ⁇ O) —, particularly preferably —C ( ⁇ O) —.
- Y and Z each independently represent —N ⁇ , —NH—, —N (R B ) —, —S—, or —O—.
- R B represents an alkyl group, which is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, t-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
- Y and Z in the general formula (4) —N ⁇ , —NH—, and —N (R B ) — are particularly preferable.
- a preferred combination of Y and Z is a combination (imidazolyl group) in which one of Y and Z is —N ⁇ and the other is —NH—.
- ring A, ring B, ring C, and ring D each independently represent an aromatic ring.
- the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, among others, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, phenoxazine ring,
- examples of the ring A and ring B in the general formula (2) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.
- examples of the ring C in the general formula (3) include a benzene ring, a naphthalene ring, a pyridine ring, and a pyrazine ring.
- Examples of the ring D in the general formula (4) include a benzene ring, a naphthalene ring, a pyridine ring, a pyrazine ring, and the like.
- a benzene ring and a naphthalene ring are more preferable from the viewpoint of dispersibility and dispersion stability over time, and the general formula (2)
- a benzene ring is more preferable
- a naphthalene ring is more preferable.
- the maleimide derivative in the first embodiment means a maleimide in which the N position is substituted with a substituent such as an alkyl group or an aryl group.
- the specific polymer in the first embodiment includes a repeating unit derived from one monomer selected from the group consisting of a monomer represented by the general formula (1), a maleimide, and a maleimide derivative. Only the seed may be included, or two or more kinds may be included.
- the content of the repeating unit derived from one monomer selected from the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives Is preferably 5% by mass or more, more preferably 10% by mass to 50% by mass, based on 100% by mass of all repeating units contained in the polymer. That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, it is represented by the general formula (1).
- the content of polymerized units derived from one monomer selected from the group consisting of monomers, maleimides, and maleimide derivatives is preferably 5% by mass or more.
- the group consisting of the monomer represented by the general formula (1), maleimide, and maleimide derivatives The content of polymerized units derived from one more selected monomer is preferably 50% by mass or less.
- Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
- Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
- an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylates can also be used.
- a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylates
- anhydride containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.
- (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.
- Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.
- the specific polymer in the first embodiment preferably includes a repeating unit derived from a monomer having an acidic group as described above. By including such a repeating unit, when the pigment dispersion composition of the first embodiment is applied to the colored photosensitive composition, the development removability of the unexposed area is excellent.
- the specific polymer in the first embodiment may include only one type of repeating unit derived from a monomer having an acidic group, or may include two or more types.
- the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mgKOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more.
- secondary aggregates which are aggregates of primary particles of pigment, or to effectively weaken the cohesive force of secondary aggregates, repeating units derived from monomers having acidic groups
- the content of is preferably 50 mgKOH / g to 200 mgKOH / g.
- Examples of the monomer having a basic nitrogen atom include (meth) acrylic acid ester, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, (meth) acrylic acid 1 -(N, N-dimethylamino) -1,1-dimethyl, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N (meth) acrylic acid -Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) Piperidinoethyl acrylate, 1-pyrrolidino
- a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group include monomers having the following structure.
- Examples of the monomer having an ionic group include vinyl monomers having an ionic group (anionic vinyl monomers and cationic vinyl monomers).
- Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having an acidic group, salts with organic amines (eg, tertiary amines such as triethylamine and dimethylaminoethanol), and the like.
- the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride or benzyl bromide; Alkylsulfonic acid esters such as acids (alkyl groups: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl groups: C1-18); dialkyl sulfates (alkyl groups: C1-4), etc. Quaternized with dialkyldiallylane Such as salt, and the like.
- alkyl halide alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom
- benzyl halide such as benzyl chloride or benzyl bromide
- Alkylsulfonic acid esters
- the monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of the pigment to be dispersed, and these may be used alone or in combination of two or more.
- the specific polymer in the first embodiment may further contain a repeating unit derived from a copolymerizable vinyl monomer as long as the effect is not impaired.
- vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".
- Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth)
- Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
- Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
- Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
- Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
- Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.
- Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
- Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl
- Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and ⁇ -methyls
- a preferable aspect of the specific polymer in the first embodiment is a monomer having at least a monomer represented by the general formula (i), (ii), or (i) -2 and an organic dye structure or a heterocyclic structure. More preferably, at least the monomer represented by the general formula (i) -2, the monomer represented by the general formula (1), and an acid group And a monomer having a copolymer. According to this embodiment, it is possible to provide a pigment dispersion composition having excellent pigment adsorption and excellent developability.
- the preferred molecular weight of the specific polymer in the first embodiment is preferably in the range of 5000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2500 to 50000 in terms of number average molecular weight (Mn). More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5000 to 30,000. In particular, the weight average molecular weight (Mw) is most preferably in the range of 10,000 to 30,000, and the number average molecular weight (Mn) is preferably in the range of 5,000 to 15,000.
- the weight average molecular weight (Mw) of the specific polymer is 1000 or more from the viewpoint of effectively loosening the secondary aggregate, which is an aggregate of primary particles of the pigment, or effectively weakening the reaggregation. It is preferable that Further, from the viewpoint of developability when producing a color filter from a colored photosensitive composition containing a pigment dispersion composition, the weight average molecular weight (Mw) of the specific polymer is preferably 30000 or less.
- the specific polymer in the first embodiment includes, for example, a monomer represented by the general formula (i), (ii), or (i) -2 and another radical polymerizable compound ( And various monomers as described above, and can be produced by an ordinary radical polymerization method.
- a suspension polymerization method or a solution polymerization method is used.
- the solvent used in the synthesis of such a specific polymer include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy.
- Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.
- a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.
- the range which does not impair the effect of 1st Embodiment you may use another high molecular compound simultaneously with the above-mentioned specific polymer as needed.
- natural resins modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like are used.
- the natural resin is typically rosin
- the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof.
- the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, and polyurethane resin.
- Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenol resins.
- Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.
- the second embodiment will be described in detail.
- (A) a graft type polymer compound in which 5 to 30% by mass of acrylic acid is copolymerized in the main chain hereinafter sometimes referred to as a specific graft polymer
- the specific graft polymer used in the second embodiment has acrylic acid in the main chain, and the acrylic acid content is 5-30.
- the graft type polymer compound is not particularly limited as long as it is mass% and has a weight average molecular weight in the range of 1,000 to 100,000.
- the acrylic acid group of 2nd Embodiment should just be included in the principal chain. Further, an acrylic acid group may be further included in the branch part.
- a method for synthesizing a specific graft polymer as described in New Polymer Experiments Vol. 2 (Kyoritsu Shuppan, 1995), etc., as a general method, (1) a method of polymerizing a branch monomer from a main chain polymer, ( 2) A method of bonding a branched polymer to a main chain polymer (3) A method of copolymerizing a main chain monomer with a branched polymer can be used.
- the specific graft polymer that can be used in the second embodiment is obtained by copolymerizing acrylic acid, a polymerizable oligomer (hereinafter referred to as a macromonomer) and another copolymerizable monomer.
- the amount of acrylic acid introduced is preferably 5 to 30% by mass from the viewpoint of dispersibility. If it exceeds 30% by mass, the amount of macromonomer to be copolymerized becomes relatively small, so that the effect of steric repulsion is reduced and sufficient dispersion stability cannot be obtained. On the other hand, if it is less than 5% by mass, sufficient flexibility as the whole polymer compound cannot be obtained, and it is difficult to obtain the effect of improving the dispersion stability and developability. Furthermore, the amount of acrylic acid introduced is preferably 10 to 30% by mass, and most preferably 10 to 25% by mass, although it depends on the type and molecular weight of the macromonomer.
- a preferred structure of the macromonomer is one or more of the repeating unit represented by the general formula (I), the repeating unit represented by the general formula (II), and the repeating unit represented by the following general formula (3). Of these, the repeating unit represented by formula (I) is most preferred.
- the repeating unit represented by the formula (I) is preferable, and the repeating unit represented by the formula (I) -2 is more preferable.
- the definition and preferred range of the formula (I) -2 are the same as those in the first embodiment, including the definition and preferred range of each symbol in the formula.
- the repeating units represented by the formulas (1), (2), and (1-2) are polymerized or copolymerized with the monomers represented by the formulas (i), (ii), and (i) -2, respectively. By polymerization, it is introduced as a repeating unit of the polymer compound.
- the definitions and preferred ranges of the formulas (i), (ii), and (i) -2 in the formula are the same as those in the first embodiment, including the definitions and preferred ranges of the symbols in the formula.
- R 7 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- W is a single bond or alkylene, alkenylene, cycloalkylene, phenylene, ether, thioether, ester, carbonyl, amino ,
- a 3 represents a repeating unit composed of a radical polymerizable monomer such as (meth) acrylic acid ester, (meth) acrylonitrile, styrene derivative, (meth) acrylamides and the like.
- macromonomer represented by the general formula (3) include the following.
- A has the same meaning as A 3 in formula (3), and preferred compounds of A include polymethyl methacrylate, polybutyl methacrylate, polystyrene, methyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-styrene copolymer. , Etc.
- the weight average molecular weight of the specific graft polymer of the second embodiment is not particularly limited as long as it is 1,000 to 100,000, but preferably in the range of 3,000 to 100,000.
- the range of 000 to 50,000 is more preferable, and the range of 10,000 to 30,000 is more preferable.
- the weight average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.
- the weight average molecular weight of the branch is preferably 300 to 10,000. Preferably it is 500 to 5,000, more preferably 1,000 to 3,000. When the molecular weight of the branch is in the above range, the developability is particularly good and the development latitude is wide.
- the specific graft polymer of the second embodiment may contain only one type of repeating unit composed of a macromonomer, or may contain two or more types.
- the content of the repeating unit composed of the macromonomer is not particularly limited, but when the total structural unit contained in the specific graft compound is 100% by mass, the content is preferably 5% by mass or more. More preferably, the content is 40 to 90% by mass, and further preferably 50 to 80% by mass.
- Other monomers copolymerizable with the specific graft polymer of the second embodiment include (1) a monomer having an organic dye structure or a heterocyclic structure, (2) a monomer having an acidic group, and (3) basic nitrogen.
- the monomer having an organic dye structure or a heterocyclic structure is preferably a monomer represented by the above general formula (1), a maleimide, or a maleimide derivative.
- the monomer represented by the general formula (1) is particularly preferable.
- the definition and preferred range of general formula (1) are the same as in the first embodiment, including the definition and preferred range of each symbol in the formula.
- the specific graft polymer of the second embodiment may contain only one type of copolymer unit derived from the monomer represented by the general formula (1), maleimide, and maleimide derivative, or 2 It may contain more than seeds.
- the content of the copolymer unit derived from the monomer represented by the general formula (1), maleimide, and maleimide derivative is not particularly limited, but is contained in the polymer.
- the total structural unit is 100% by mass, it is preferable to contain 5% by mass or more of copolymer units derived from the monomer represented by the general formula (1), maleimide, and maleimide derivatives. It is more preferable to contain 50 mass%.
- the monomer represented by the general formula (1) has high adsorptivity to the pigment. preferable. That is, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is represented by the general formula (1).
- the content of the copolymer unit derived from the monomer, maleimide, and maleimide derivative is preferably 5% by mass or more. From the viewpoint of developability when producing a color filter from a photocurable composition containing a pigment dispersion composition, the content of copolymer units derived from the monomer represented by the general formula (1) Is preferably 30% by mass or less.
- the specific graft polymer uses, for example, a normal radical polymerization method using a monomer represented by the general formula (i), a polymerizable oligomer (macromonomer), and another radical polymerizable compound as a copolymerization component. Can be manufactured by. In general, a suspension polymerization method or a solution polymerization method is used. Examples of the solvent used when synthesizing such a specific polymer include those listed as solvents that can be used when synthesizing the specific polymer of the first embodiment. These solvents may be used alone or in combination of two or more.
- the content of the specific graft polymer (A) is preferably 10 to 40% by mass in the total solid content.
- the pigment concentration is high, but the second embodiment has a high pigment concentration.
- Particularly effective in pigment dispersion compositions More specifically, the value obtained by dividing the total mass of the polymer compound contained in the pigment dispersion composition by the total mass of (B) pigment and (E) pigment derivative described later is 0.2 to 0.55. However, it is preferably in the range of 0.3 to 0.4. Even when the amount of the polymer compound is small, the dispersibility of the pigment is good, the dispersion stability is good, and the re-solubility of the dry film in the solvent is good when it is made into a photocurable composition. Thus, it is possible to provide a pigment dispersion composition with little residue during development.
- the pigment dispersion composition of the second embodiment preferably further contains (D) a basic graft polymer compound.
- (D) is a polymer compound having a structure other than the structure included in the range of the (A) polymer.
- a basic graft polymer is a polymer having a structure in which a branch polymer is graft-bonded to a trunk polymer portion having a plurality of basic groups, and an organic pigment and an acidic derivative using the basic group of the trunk polymer portion as an anchor Because of the multi-point adsorption to the surface, the steric repulsion effect of the branched polymer part acts effectively and expresses the function of promoting fine dispersion.
- the basic group of the trunk polymer part is preferably an amino group from the viewpoint of excellent adsorption characteristics
- the branch polymer part is preferably organic solvent-soluble from the viewpoint of excellent steric repulsion. Further, it preferably has a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer.
- Such a polymer can be represented, for example, by the following formula.
- the backbone polymer represented by EE ... EE is preferably one having an amino group, and specific examples thereof include polyethyleneimine, polyethylenepolyamine, polyxylylenepoly (hydroxypropylene) polyamine, Examples thereof include poly (aminomethylated) epoxy resins, amine-added glycidyl (meth) acrylate- (meth) acrylic acid esterified glycidyl (meth) acrylate copolymers, and the like. These synthesis methods are as follows, for example.
- Polyethyleneimine is obtained by ring-opening polymerization of ethyleneimine in the presence of an acid catalyst.
- Polyethylene polyamine can be obtained by polycondensation of ethylene dichloride and ammonia in the presence of an alkali catalyst.
- Poly (aminomethylated) epoxy resin is aminated after chloromethylation of aromatic rings such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, etc. And is also called Mannich base.
- Specific examples of the amine used in the amination include monomethylamine, monoethylamine, monomethanolamine, monoethanolamine, dimethylamine, diethylamine, dimethanolamine, diethanolamine and the like.
- the amine-added glycidyl (meth) acrylate- (meth) acrylic esterified glycidyl (meth) acrylate copolymer is polymerized by radical polymerization of glycidyl (meth) acrylate, and then a part of the epoxy group in the polymer. After adding the same amine as above to obtain poly [amine-added glycidyl (meth) acrylate], the remaining epoxy group is obtained by esterification reaction with carboxylic acid of (meth) acrylic acid.
- the branched polymer represented by FF... FF is preferably soluble in an organic solvent, and specific examples thereof include a carboxylic acid at the polymer terminal and an amino group in the trunk polymer as described above.
- examples thereof include ring-opening polymers such as poly (12-hydroxystearic acid), polyricinoleic acid, and ⁇ -caprolactone, which are polymers capable of forming a graft bond by amidation reaction with a group.
- the backbone polymer has a vinyl group such as the above-mentioned amine-added glycidyl (meth) acrylate- (meth) acrylic esterified glycidyl (meth) acrylate copolymer
- a polymer that can be graft-polymerized to the vinyl group is used.
- [Methyl (meth) acrylate], poly [(meth) ethyl acrylate] and the like can be exemplified as the branched polymer portion.
- Poly (12-hydroxystearic acid) is obtained by a dehydration polycondensation polyesterification reaction of 12-hydroxystearic acid.
- Polyricinoleic acid is similarly obtained by a dehydration polycondensation polyesterification reaction of ricinoleic acid.
- a ring-opening polymer of ⁇ -caprolactone is obtained by ring-opening polymerization by adding n-caproic acid, which is an aliphatic monocarboxylic acid, to ⁇ -caprolactone.
- the (b) pigment in the first embodiment conventionally known various inorganic pigments or organic pigments can be appropriately selected and used.
- the pigment considering that the pigment dispersion composition of the present invention is used in the colored region of the color filter and preferably having a high transmittance, an organic pigment is preferable, and the particle size is as small as possible. It is preferable to use one.
- the average primary particle size of the pigment is preferably 100 nm or less, more preferably 30 nm or less, and most preferably 5 nm to 25 nm.
- the average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
- the pigment dispersion composition of the second embodiment contains a pigment.
- the pigment used here has a higher contrast as a color filter as its particle size is smaller.
- a pigment having a particle size of 10 to 25 nm is dispersed using the specific graft polymer of the second embodiment, it can be dispersed well and the contrast is improved.
- the pigment of this size is fine, there is a problem that the pigment aggregates and the viscosity is improved when the pigment dispersion is stored for a long time under high temperature and high humidity. This problem can be solved by using the introduced graft type dispersant.
- the average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.
- the pigment concentration of the photocurable composition is usually 30% by weight or less, but in recent years, a higher pigment concentration has been demanded.
- the pigment concentration is increased, components that contribute to image forming properties, such as an additive resin that imparts solubility in an alkaline developer, are relatively reduced, resulting in a problem that the image forming performance originally possessed is lost. .
- the specific graft polymer of the second embodiment When the specific graft polymer of the second embodiment is used as a dispersant, it can be sufficiently solubilized in the developer without adding another resin in order to dissolve in the alkaline developer, so even in the high pigment concentration region. Can be used. Further, the specific graft polymer of the second embodiment has a characteristic that a fine pigment can be used at a high pigment concentration because it has dispersion stability.
- the pigment concentration can be used in the range of 10 to 55% by mass, but the effect is particularly prominent in the high pigment concentration region in the range of 35 to 55% by mass and in the range of 40 to 55% by mass.
- the pigment dispersion composition of the second embodiment contains at least one (B) pigment in an organic solvent.
- the pigment that can be used in the pigment dispersion composition of the second embodiment various conventionally known inorganic pigments or organic pigments can be used.
- the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, and considering handling properties.
- a pigment having an average primary particle diameter in the range of 10 to 25 nm is preferable.
- the pigment is a description common to the present invention including the pigment (b) and the pigment (B) of the first and second embodiments unless otherwise specified.
- the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.
- Examples of the organic pigment include: C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, C.
- the pigments that can be preferably used include the following.
- organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations of organic pigments are shown below.
- a red pigment an anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment
- a perylene red pigment, an anthraquinone red pigment, or a diketopyrrolopyrrole red pigment can be mixed and used.
- an anthraquinone pigment C.I. I. Pigment Red 177
- perylene pigments include C.I. I. Pigment red 155, C.I. I.
- Pigment red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred.
- the mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80 from the viewpoint of light transmittance from 400 nm to 500 nm and color purity. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.
- a halogenated phthalocyanine pigment is used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment.
- a disazo yellow pigment a quinophthalone yellow pigment
- an azomethine yellow pigment an isoindoline yellow pigment.
- an isoindoline yellow pigment be able to.
- C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83 C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
- the mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200 from the viewpoint of light transmittance of 400 nm to 450 nm and color purity. The mass ratio is particularly preferably in the range of
- a blue pigment a phthalocyanine pigment can be used alone or in combination with a dioxazine purple pigment.
- C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
- the mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.
- carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
- the mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. When this amount exceeds 100: 60 and the amount of titanium black is large, the dispersion stability may be lowered.
- a pigment obtained by finely pulverizing the above pigment may be used.
- a method including a step of preparing a liquid composition having a high viscosity together with a water-soluble organic solvent and a water-soluble inorganic salt, and grinding the pigment it is more preferable to use the following method for refining the pigment.
- a mixture liquid composition
- a single A pigment in the mixture is ground by applying a strong shearing force using a kneader such as a screw or twin screw extruder, and then the mixture is put into water and made into a slurry with a stirrer or the like.
- the slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a finer pigment.
- water-soluble organic solvent used for the above-mentioned miniaturization examples include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. , Propylene glycol, propylene glycolic monomethyl ether acetate and the like.
- the amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the pigment.
- sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate or the like is used as the water-soluble inorganic salt.
- the amount of water-soluble inorganic salt used is preferably 1 to 50 times the mass of the organic pigment, and a larger amount has a grinding effect, but from the viewpoint of productivity, a more preferred amount is 1 to 10 times the mass. is there.
- the water content in the liquid composition to be ground is preferably 1% by mass or less.
- a wet grinding device such as the kneader described above may be used.
- the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with the pulverizing media (water-soluble inorganic salt).
- the number is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large.
- the operation time is preferably 1 to 8 hours together with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 ° C.
- the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 ⁇ m to 50 ⁇ m, a sharp particle size distribution, and a spherical shape.
- the mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, and finely ground. A pigment can be obtained.
- the above-described organic pigment when the above-described organic pigment is refined, by using a resin that is at least partially soluble in a water-soluble organic solvent in the liquid composition, the surface is coated with the resin. A processed pigment with little aggregation of the pigment at the time can be obtained.
- the resin that is used when obtaining the processed pigment and is at least partially soluble in the water-soluble organic solvent a known resin that is used as a pigment dispersant can be used.
- the content of the pigment (b) in the pigment dispersion composition of the first embodiment is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, and more preferably 10% by mass to 20% by mass. Further preferred.
- the pigment of the second embodiment it is preferable to use a pigment that has been subjected to a refinement treatment in advance.
- the finer pigment primary particles are well known by mechanically kneading with i) a pigment, ii) a water-soluble inorganic salt, and iii) a water-soluble organic solvent that does not substantially dissolve the inorganic salt, using a kneader or the like. (Salt milling method).
- a pigment-coated polymer compound, v) a pigment derivative, etc. may be used simultaneously.
- the pigment examples include the same pigments as described above.
- the water-soluble inorganic salt is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like can be used. Sodium is preferably used.
- the amount of the inorganic salt used in the salt milling is preferably 1 to 30 times the mass of the organic pigment, particularly 5 to 25 times the mass of the organic pigment, and the water content is preferably 1% or less from the viewpoint of both the processing efficiency and the production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the organic pigment is larger, but the processing amount of one pigment is reduced.
- a small amount of a water-soluble organic solvent that does not substantially dissolve the inorganic salt serves to wet the organic pigment and the inorganic salt, dissolves (mixes) in water, and substantially uses the inorganic salt used. If it does not melt
- a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent easily evaporates.
- water-soluble organic solvent examples include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether.
- the addition amount of the water-soluble organic solvent is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the inorganic salt. More preferably, it is 10 to 40 parts by weight, and optimally 15 to 35 parts by weight.
- the addition amount is less than 5 parts by weight, uniform kneading becomes difficult and the particle size may become uneven.
- the addition amount is 50 parts by weight or more, the kneaded composition becomes too soft, and it becomes difficult to apply shear to the kneaded composition, so that a sufficient refinement effect may not be obtained.
- the water-soluble organic solvent may be added all at the beginning of salt milling, or may be added in divided portions.
- a water-soluble organic solvent may be used independently and can also use 2 or more types together.
- the operating conditions when the apparatus is a kneader are the rotational speed of the blade in the apparatus. 10 to 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large.
- the operation time is preferably 1 to 8 hours together with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C.
- the water-soluble inorganic salt as a grinding medium preferably has a grinding particle size of 5 to 50 ⁇ m, a sharp particle size distribution, and a spherical shape.
- the pigment-coated polymer compound is preferably a solid at room temperature, water-insoluble, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling, a natural resin, a modified natural resin, a synthetic resin, A synthetic resin modified with a natural resin or a graft type polymer obtained by copolymerizing (A) acrylic acid of the second embodiment can be used, and in particular, the (A) specific graft of the second embodiment. It is preferable to use a polymer.
- the compound used is preferably solid at room temperature.
- the natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof.
- the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and the like.
- synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
- Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.
- A As the specific graft polymer, the above-described polymer compounds can be used. The timing of adding these resins may be added all at the beginning of salt milling, or may be added in divided portions.
- As a pigment derivative in 2nd Embodiment the thing similar to the below-mentioned (E) pigment derivative is mentioned.
- the pigment dispersion composition of the first embodiment contains at least one (c) organic solvent.
- the organic solvent used in the pigment dispersion composition of the first embodiment include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, Examples thereof include ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene and xylene.
- the amount of the organic solvent added is appropriately selected according to the use of the pigment dispersion composition, etc., but when used for the preparation of the colored photosensitive composition described later, from the viewpoint of handleability, the pigment is included. It can be added so that the solid content concentration is 5 mass% to 50 mass%.
- a pigment derivative is preferably used for the pigment dispersion composition of the first embodiment.
- a portion having an affinity for the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the treated pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is finely divided.
- the particles can be dispersed in the pigment dispersion composition, and reaggregation can be prevented. That is, the pigment derivative has an effect of promoting adsorption of a polymer dispersant such as a specific polymer by modifying the pigment surface.
- the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent.
- organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic acids. Examples include imidazolone pigments.
- the host skeleton also includes light yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not generally called pigments.
- JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810. JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, etc. can be used.
- the amount used is preferably in the range of 1% by mass to 80% by mass with respect to the pigment, and 3% by mass to It is more preferably in the range of 65% by mass, and particularly preferably in the range of 5% by mass to 50% by mass.
- the content is within this range, the pigment can be favorably dispersed while keeping the viscosity low, and the dispersion stability after dispersion can be improved.
- a dispersant such as a surfactant can be used.
- the pigment dispersion composition of the first embodiment can be prepared by going through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
- the mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.
- the pigment dispersion composition of the first embodiment includes, for example, (a) a specific polymer, (b) a pigment, and (c) an organic solvent, a vertical or horizontal sand grinder, a pin mill, and a slit mill. It can be obtained by carrying out fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 mm to 1 mm using an ultrasonic disperser or the like. In addition, before carrying out fine dispersion with beads, use a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to carry out the kneading and dispersing process while giving.
- the colored photosensitive composition of the first embodiment comprises the pigment dispersion composition of the first embodiment described above, a photopolymerizable compound, and a photopolymerization initiator, and further contains an alkali-soluble resin. It is preferable to include, and other components may be included as necessary. Hereinafter, each component contained in the colored photosensitive composition of 1st Embodiment is explained in full detail.
- the colored photosensitive composition of 1st Embodiment is comprised using at least 1 type of the pigment dispersion composition of above-described 1st Embodiment.
- the details of the pigment dispersion composition of the first embodiment constituting the colored photosensitive composition are as described above.
- the content of the pigment dispersion composition in the colored photosensitive composition of the first embodiment is such that the pigment content is 5% by mass to 70% by mass with respect to the total solid content (mass) of the colored photosensitive composition. % Is preferable, and an amount in the range of 15% by mass to 60% by mass is more preferable. When the content of the pigment dispersion composition is within this range, the color density is sufficient and effective in securing excellent color characteristics.
- the colored photosensitive composition of the first embodiment contains at least one photopolymerizable compound.
- the photopolymerizable compound that can be used in the first embodiment is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably two. It is selected from the compounds having the above. Such compound groups are widely known in the industrial field, and in the first embodiment, they can be used without any particular limitation.
- the photopolymerizable compound has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.
- Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
- unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
- esters and amides thereof examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof.
- an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
- ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol.
- Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (me
- Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc.
- crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
- isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
- maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
- esters examples include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.
- amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
- amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.
- urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
- a vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (a) to a polyisocyanate compound having two or more isocyanate groups.
- urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.
- polyester acrylates examples include polyester acrylates, epoxy resins and (meth) acrylic acid described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, and JP-B-1-40336, and vinyl phosphonic acid compounds described in JP-A-2-25493 can also be exemplified. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.
- the details of usage methods such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the performance design of the final colored photosensitive composition.
- it is selected from the following viewpoints. From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using these together.
- the selection of the addition polymerization compound with respect to the compatibility and dispersibility with other components in the colored photosensitive composition is an important factor.
- compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
- a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.
- the addition polymerizable compound is preferably used in the range of 5% by mass to 70% by mass, more preferably 10% by mass to 60% by mass with respect to the nonvolatile components in the colored photosensitive composition. These may be used alone or in combination of two or more.
- an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface tackiness, and the like.
- a pigment derivative is added to the pigment dispersion composition of the second embodiment as necessary.
- the pigment is introduced into the photocurable composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group introduced onto the pigment surface and using this as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective in constructing a color filter having high contrast and excellent transparency.
- the pigment derivative is a compound in which an organic pigment is used as a base skeleton and an acidic group, a basic group, or an aromatic group is introduced as a substituent in the side chain.
- organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned.
- light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.
- Examples of the dye derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP-A-2005-234478, JP-A-2003-240938, JP-A-2001-356210, etc. can be used.
- the content of the pigment derivative according to the second embodiment in the pigment dispersion composition is preferably 1 to 30 parts by weight and more preferably 3 to 20 parts by weight with respect to 100 parts by weight of the pigment.
- the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained.
- it can be configured to have high contrast with good color characteristics.
- the timing of adding the pigment derivative may be added during salt milling or may be added during dispersion. It may be added to both during salt milling and dispersion.
- the dispersion method is, for example, using a bead disperser using zirconia beads or the like (for example, a disperse mat made by GETZMANN Co., Ltd.) that has been previously mixed with a pigment and a dispersant and previously dispersed with a homogenizer or the like. This can be done by fine dispersion.
- the dispersion time is preferably about 3 to 6 hours.
- the pigment dispersion composition of the second embodiment contains at least one dispersant. With this dispersant, the dispersibility of the pigment can be improved. As the dispersant, it is necessary to use at least the above-mentioned (A) specific graft polymer. Thereby, the dispersion state of the pigment in the organic solvent becomes good, and for example, when the color filter is configured using the pigment dispersion composition of the second embodiment, it is high even when the pigment is contained at a high concentration. Developability and surface smoothness can be expressed. (A) When the specific graft polymer is used as a dispersant, the above-described polymer compound can be used.
- Known dispersants include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.
- the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.
- the ratio of the pigment-coated polymer compound and the dispersant is not particularly limited. However, when the dispersant is a polymer dispersant, 10/90 to 90/10 is preferable, and 20/80 to 80/20 is more preferable. preferable.
- the solvent in the pigment dispersion composition of the second embodiment is not particularly limited as long as it is an organic solvent, and can be appropriately selected from known solvents such as 1-methoxy-2-propyl acetate, 1- (Poly) alkylene glycol monoalkyl ethers such as methoxy-2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like Acetic acid esters; Acetic acid esters such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate and i-butyl acetate; Aromatic hydrocarbons such as benzene, toluene and xylene Methyl ethyl ketone, acetone,
- the content of the solvent in the pigment dispersion composition is appropriately selected according to the use of the pigment dispersion composition.
- the pigment dispersion composition is used for the preparation of a photocurable composition described later, it should be contained so that the solid content concentration including the pigment and the pigment dispersant is 5 to 50% by mass from the viewpoint of handleability. Can do.
- (C) It is preferable to have 10% by mass or more of 1-methoxy-2-propyl acetate as the organic solvent.
- a preferable aspect of the pigment dispersion composition of the second embodiment is that a processed pigment coated with a polymer compound having a weight average molecular weight of 1,000 or more, a pigment derivative, and a dispersant are dispersed in an organic solvent.
- This is a pigment dispersion composition.
- the specific graft polymer may be used as a pigment-coated polymer compound added at the time of pigment processing, or may be used as a dispersant, or both of the independent (A) specific graft polymers may be used. However, it is preferably used as a dispersant.
- the addition amount of the dispersant is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and more preferably 5 to 80% by mass with respect to the pigment. % Is particularly preferred.
- the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained.
- the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.
- the preparation mode of the pigment dispersion composition of the second embodiment is not particularly limited.
- a pigment, a pigment dispersant, and a solvent are mixed into a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, and the like.
- knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.
- the pigment dispersion composition of the second embodiment is suitably used for a photocurable composition used for producing a color filter.
- the photocurable composition of the second embodiment comprises the pigment dispersion composition of the second embodiment described above, (F) a polymerizable compound, and (G) a photopolymerization initiator.
- a photopolymerization initiator such as an alkali-soluble resin may be contained.
- the pigment concentration of the photocurable composition of the second embodiment is preferably 35% by mass or more, and more preferably 40% by mass or more.
- the second embodiment is particularly effective when the pigment concentration is high, and the dispersibility of the pigment is high.
- the photocurable composition is used, the dispersion stability that cannot be achieved by the conventional technique is exhibited. It is possible to provide a photocurable composition having a high solvent solubility in the film and a small amount of residue on the substrate when developed.
- (F) Polymerizable compound As the polymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable. Is more preferable.
- Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxy
- compounds described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof are compounds that are (meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol.
- dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable.
- These oligomer types can also be used.
- urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.
- urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 ”(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like. Further, ethylenically unsaturated compounds having an acid group are also suitable.
- TO-756 which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate.
- TO-1382 and the like can be mentioned.
- a polymeric compound can be used in combination of 2 or more types, in addition to being used alone.
- the content of the polymerizable compound in the photocurable composition is preferably 3 to 55% by mass, more preferably 10 to 50% by mass, based on the total solid content of the composition. When the content of the polymerizable compound is within the above range, the curing reaction can be sufficiently performed.
- Photopolymerization initiator The following description of the photopolymerization initiator is a description common to the present invention including the first and second embodiments.
- Examples of the photopolymerization initiator in the present invention include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-oxa described in JP-B-59-1281, JP-A-53-133428, and the like.
- Active halogen compounds such as s-triazine, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent Application No. 88050, US Pat. No.
- Aromatic ketone compounds such as benzophenones described in the description, (thio) xanthones or acridine compounds described in French Patent No. 2456741, coumarins or lophine dimers described in JP-A-10-62986 And the like, sulfos such as JP-A-8-015521 Umm organic boron complex, etc., etc. can be mentioned.
- active halogen compounds triazine, oxadiazole, coumarin
- acridine biimidazole
- An oxime ester type is preferable.
- acetophenone photopolymerization initiator examples include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Preferable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.
- ketal photopolymerization initiator examples include benzyldimethyl ketal and benzyl- ⁇ -methoxyethyl acetal.
- benzophenone photopolymerization initiator examples include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. it can.
- benzoin-based or benzoyl-based photopolymerization initiator examples include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.
- Preferred examples of the xanthone photopolymerization initiator include diethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chlorothioxanthone and the like.
- Examples of the active halogen compounds include, for example, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl).
- Preferred examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.
- biimidazole photopolymerization initiator examples include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.
- 2-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.
- the content of the photopolymerization initiator in the colored photosensitive composition is preferably 0.1% by mass to 10.0% by mass with respect to the total solid content of the composition, and more The content is preferably 0.5% by mass to 5.0% by mass.
- the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well to form a film with good strength.
- the content of the photopolymerization initiator in the photocurable composition is preferably 0.1 to 10.0% by mass, more preferably 0.8%, based on the total solid content of the composition. 5 to 5.0% by mass.
- the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.
- the colored photosensitive composition of the first embodiment preferably contains an alkali-soluble resin.
- the pattern forming property can be further improved when the colored photosensitive composition is applied to pattern formation by a photolithography method.
- the photocurable composition of the second embodiment may also contain an alkali-soluble resin. The following description regarding the alkali-soluble resin is a description common to the present invention including the first and second embodiments.
- the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
- a known radical polymerization method can be applied.
- Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
- a polymer having a carboxylic acid in the side chain is preferable.
- side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.
- benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
- those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.
- the polymer can be used by mixing in an arbitrary amount.
- 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.
- the alkali-soluble resin in the present invention include a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith.
- (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid
- (meth) acrylate is also a general term for acrylate and methacrylate.
- Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
- the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
- alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.
- copolymerizable monomers can be used singly or in combination of two or more.
- Other preferred copolymerizable monomers are selected from CH 2 ⁇ CR 1 R 2 , CH 2 ⁇ C (R 1 ) (COOR 3 ), phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. At least one selected from the group consisting of CH 2 ⁇ CR 1 R 2 and / or CH 2 ⁇ C (R 1 ) (COOR 3 ).
- the content of the alkali-soluble resin in the colored photosensitive composition in the first embodiment is preferably 1% by mass to 30% by mass, more preferably 1% by mass with respect to the total solid content of the composition. -25% by mass, particularly preferably 2% by mass to 20% by mass.
- the content of the alkali-soluble resin in the photocurable composition is preferably 0 to 15% by mass, more preferably 1 to 12% by mass in the total solid content of the composition. It is particularly preferably 1 to 10% by mass.
- the colored photosensitive composition of the first embodiment can be suitably prepared by using a solvent together with the aforementioned components.
- Solvents used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, lactic acid Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl esters of 3-oxypropionic acid such as ethy
- methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, propylene glycol methyl ether acetate, etc. is preferred. You may use a solvent in combination of 2 or more types besides using independently.
- the colored photosensitive composition of the first embodiment includes, as necessary, a sensitizing dye, an epoxy resin, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a filler, and the alkali.
- a sensitizing dye such as an epoxy resin, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, a filler, and the alkali.
- Various additives such as a polymer compound other than the soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.
- sensitizing dye may be added to the colored photosensitive composition of the first embodiment as necessary. Also in the second embodiment, it is preferable to add a sensitizing dye as necessary.
- the following description regarding the sensitizing dye includes the first embodiment and the second embodiment, and is a description common to the present invention.
- the sensitizing dye can accelerate the radical generating reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.
- Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal).
- Cyanines eg thiacarbocyanine, oxacarbocyanine
- merocyanines eg merocyanine, carbomerocyanine
- thiazines eg thionine, methylene blue, toluidine blue
- acridines eg acridine orange, chloroflavin
- Acriflavine phthalocyanines
- phthalocyanines eg, phthalocyanine, metal phthalocyanine
- porphyrins eg, tetraphenylporphyrin, central metal-substituted porphyrin
- chlorophylls eg, chlorophyll
- Chlorophyllin center metal-substituted chlorophyll
- metal complexes for example, the following compound
- anthraquinones e.g., anthraquinone
- squaryliums e.g., squarylium
- sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 nm to 450 nm.
- polynuclear aromatics eg, pyrene, perylene, triphenylene
- xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
- cyanines eg, thiacarbocyanine, oxacarbocyanine
- merocyanine Eg, merocyanine, carbomerocyanine
- thiazines eg, thionine, methylene blue, toluidine blue
- acridines eg, acridine orange, chloroflavin, acriflavine
- anthraquinones eg, anthraquinone
- squalium eg
- sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).
- a 1 represents a sulfur atom or —NR 60 —
- R 60 represents an alkyl group or an aryl group
- L 01 represents the basicity of the dye in combination with the adjacent A 1 and carbon atom.
- R 61 and R 62 each independently represent a hydrogen atom or a monovalent non-metallic atomic group
- R 61 and R 62 are bonded to each other to form an acidic nucleus of the dye
- W may represent an oxygen atom or a sulfur atom.
- Preferable specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.
- Ar 1 and Ar 2 each independently represent an aryl group, -L 02 - are connected via a bond by wherein -L 02 -. Is -O- or -S- In addition, W is synonymous with that shown in the general formula (XIV).
- Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].
- a 2 represents a sulfur atom or —NR 69 —
- L 03 represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A 2 and a carbon atom
- R 63 , R 64 , R 65 , R 66 , R 67 , and R 68 each independently represent a monovalent nonmetallic atomic group
- R 69 represents an alkyl group or an aryl group.
- a 3 and A 4 each independently represent —S— or —NR 73 —, and R 73 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
- L 04 and L 05 each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A 3 , A 4 and a carbon atom, and R 71 and R 72 are each independently These are monovalent non-metallic atomic groups and can be bonded to each other to form an aliphatic or aromatic ring.
- Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].
- sensitizing dyes used in the present invention include those represented by the following formula (XVIII).
- a 5 represents an aromatic ring or a hetero ring which may have a substituent
- X represents an oxygen atom, a sulfur atom, or —N (R 74 ) —
- Y represents An oxygen atom, a sulfur atom, or ⁇ N (R 74 )
- each of R 74 , R 75 , and R 76 independently represents a hydrogen atom or a monovalent non-metallic atomic group, and A 5 and R 74 , R 75 and R 76 can be bonded to each other to form an aliphatic or aromatic ring.
- R 74 , R 75 , and R 76 represent a monovalent non-metallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
- R 74 , R 75 and R 76 will be specifically described.
- preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms.
- a monovalent non-metallic atomic group other than hydrogen is used as the substituent of the substituted alkyl group.
- Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups.
- aryloxy group mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ure
- a phosphonooxy group (—OPO 3 H 2 ) and its conjugate base group hereinafter referred to as phosphonatooxy group
- a dialkylphosphonooxy group —OPO 3 (alkyl) 2
- a diarylphosphonooxy group —OPO 3 (—OPO 3 ( aryl) 2)
- alkylaryl phosphono group -OPO 3 (alkyl) (aryl )
- Monoarukiruho Honookishi group (-OPO 3 H (alkyl)) and its conjugated base group
- alkylphosphonato group monoarylphosphono group
- -OPO 3 H (aryl) monoarylphosphono group
- cyano group nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
- Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have
- aryl group examples include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group.
- heteroaryl group a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, Is
- alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc.
- alkynyl examples include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
- G 1 in the acyl group examples include hydrogen and the above alkyl groups and aryl groups.
- halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N-alkylsulfam
- examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms.
- R 74 , R 75 , or R 76 obtained by combining the above substituents with an alkylene group
- substituents with an alkylene group include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropy
- preferred aryl groups as R 74 , R 75 , or R 76 include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
- Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.
- R 74 , R 75 , or R 76 include a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group. What has is used.
- preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group.
- Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group.
- R 75 and R 76 include a substituted or unsubstituted alkyl group.
- R 74 includes a substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.
- a 5 represents an aromatic ring or a heterocyclic ring which may have a substituent
- specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R 74 in formula (XVIII).
- R 75 , or R 76 may be the same as those exemplified in the above description.
- preferable A 5 includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A 5 includes an aryl group having an amino group.
- Y in the general formula (XVIII) will be described.
- X in the general formula (XVIII) represents an oxygen atom, a sulfur atom, or —N (R 74 ) —.
- a 5 represents an aromatic ring or a hetero ring which may have a substituent
- X represents an oxygen atom, a sulfur atom, or —N (R 74 ) —.
- R 74 , R 77 , and R 78 are each independently a hydrogen atom or a monovalent nonmetallic atomic group
- a 5 and R 74 , R 77 , or R 78 are each aliphatic or aromatic. They can be joined to form a family ring.
- Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituents on the Ar skeleton need to have a sum of Hammett values greater than zero.
- the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents.
- the sum of Hammett values at may be greater than zero.
- a 5 and R 74 have the same meanings as in general formula (XVIII), R 77 is R 75 in general formula (XVIII), and R 78 is R in general formula (XVIII).
- 76 synonymous.
- Ar represents an aromatic ring or a hetero ring having a substituent, and has the same meaning as A 5 in formula (XVIII).
- the substituent that can be introduced into Ar in the general formula (XVIII-1) must have a sum of Hammett values of 0 or more.
- Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group.
- the Hammett values of these substituents are shown below.
- Trifluoromethyl group (—CF 3 , m: 0.43, p: 0.54), carbonyl group (for example, —COHm: 0.36, p: 0.43), ester group (—COOCH 3 , m: 0 37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (For example, —SOCH 3 , m: 0.52, p: 0.45), an amide group (for example, —NHCOCH 3 , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0.
- the parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position.
- m: 0.50 is the Hammett value of 0.50 when the substituent is introduced at the meta position.
- preferred examples of Ar include a phenyl group having a substituent
- preferred substituents on the Ar skeleton include an ester group and a cyano group.
- the substitution position is particularly preferably located at the ortho position on the Ar skeleton.
- the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep curability.
- the above sensitizing dyes can be subjected to various chemical modifications as described below for the purpose of improving the characteristics of the colored photosensitive composition of the present invention.
- a sensitizing dye and an addition polymerizable compound structure for example, an acryloyl group or a methacryloyl group
- a method such as a covalent bond, an ionic bond, or a hydrogen bond
- the content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.01% by mass to 10% by mass, and still more preferably based on the total solid content of the colored photosensitive composition. Is 0.1% by mass to 5% by mass.
- the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.
- the colored photosensitive composition of the first embodiment can use an epoxy resin as a thermal polymerization component in order to increase the strength of the formed coating film.
- the epoxy resin is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
- the cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above Toto Kasei), Denacol EM-125, etc.
- alicyclic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl
- Epiclon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned.
- 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin, and the like can also be used.
- “molecular weight / number of epoxy rings” is preferably 100 or more, more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage during curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is poor.
- Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ′, 5′-tetramethyl. -4,4 'diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, and the like.
- the colored photosensitive composition of the first embodiment or the photocurable composition of the second embodiment has a liquid characteristic (particularly fluidity) when it is used as a coating liquid by containing a fluorine-based organic compound.
- the uniformity of coating thickness and the liquid-saving property can be improved. That is, a colored photosensitive composition or a photocurable composition containing a fluorine-based organic compound reduces the interfacial tension between the coated surface and the coating liquid, and improves the wettability to the coated surface. Therefore, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it can form a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorine-based organic compound is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
- the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.
- fluorinated organic compound for example, Megafac F171, F172, F173, F177, F141, F142, F143, F144, R30, F437 (or larger) Nippon Ink Chemical Co., Ltd.), FLORAD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.
- the fluorine-based organic compound is effective in preventing coating unevenness and thickness unevenness when forming a thin coating film using the colored photosensitive composition of the first embodiment. Furthermore, it is also effective when the colored photosensitive composition of the first embodiment is applied to slit coating that tends to cause liquid breakage.
- the addition amount of the fluorine-based organic compound is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored photosensitive composition. is there.
- a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
- Specific commercially available products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass Co., Ltd.), Ftop EF351, 352, 801,
- the fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.
- the addition amount of the fluorinated organic compound is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable composition.
- thermal polymerization initiator It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the first embodiment or the photocurable composition of the second embodiment.
- thermal polymerization initiator include various azo compounds and peroxide compounds.
- the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, and peroxide. Examples thereof include oxydicarbonate.
- surfactant Various surfactants may be added to the colored photosensitive composition of the first embodiment from the viewpoint of improving coatability.
- various nonionic, cationic, and anionic surfactants can be used in addition to the above-mentioned fluorine-based surfactant.
- the above-described nonionic surfactants are preferably fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants.
- Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.
- cationic surfactants include phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
- nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate.
- Stearate, sorbitan fatty acid ester plural L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.
- Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
- additives in the first embodiment include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, and hydroxyl group
- An acid anhydride added to a polymer an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, Polymer dispersing agents such as EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Industrial Co., Ltd.), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by Sannopco);
- the colored photosensitive composition of the first embodiment is added with an organic carboxylic acid, preferably It is preferable to add a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less.
- aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid
- a thermal polymerization inhibitor may be added to the colored photosensitive composition of the first embodiment.
- the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.
- the colored photosensitive composition of the first embodiment is a photopolymerizable compound, a photopolymerization initiator, and, if necessary, alkali-soluble with respect to the pigment dispersion composition of the first embodiment described above. It can prepare by adding additives, such as resin, a solvent, and surfactant.
- the colored photosensitive composition of the first embodiment includes a pigment dispersion composition containing the treated pigment of the present invention
- the treated pigment is excellent in dispersibility and color characteristics. Therefore, it is preferably used to form a colored region of a color filter that requires good color characteristics.
- the color filter of the first embodiment has a colored region formed on the substrate by the colored photosensitive composition of the first embodiment described above.
- the coloring region includes both a three-color or four-color coloring pattern (pixel portion) and a black matrix.
- the color filter of the first embodiment will be described in detail through its manufacturing method.
- a method for manufacturing the color filter of the first embodiment will be described.
- the colored photosensitive composition of the first embodiment is applied to a substrate directly or via another layer by a coating method such as spin coating, slit coating, casting coating, roll coating, or bar coating.
- a coating film made of a colored photosensitive composition is formed (coating step).
- the coating film is exposed through a predetermined mask pattern (exposure process).
- the uncured portion of the coating film is developed and removed with a developer (development process).
- a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
- a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
- each step will be described in detail.
- a substrate used for the color filter of the first embodiment for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like, which are used for liquid crystal display elements, and a transparent conductive film are attached to these.
- a photoelectric conversion element substrate used for a solid-state imaging device for example, a silicone substrate or a plastic substrate.
- a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
- the plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.
- a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used.
- TFT type liquid crystal driving substrate a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed.
- TFT type liquid crystal driving substrate examples include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
- These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
- a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.
- the method for applying the colored photosensitive composition of the first embodiment to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method. (Hereinafter referred to as slit nozzle coating method) is preferred.
- a slit nozzle coating method the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm ⁇ 1250 mm) is coated by the spinless coating method.
- the discharge amount of the colored photosensitive composition from the slit nozzle is usually 500 microliters / second to 2000 microliters / second, preferably 800 microliters / second to 1500 microliters / second.
- the speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
- the solid content of the colored photosensitive composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.
- the thickness of the coating film is generally 0.3 ⁇ m to 5.0 ⁇ m, preferably 0. It is 5 ⁇ m to 4.0 ⁇ m, most preferably 0.5 ⁇ m to 3.0 ⁇ m.
- the thickness of the coating film is preferably in the range of 0.5 ⁇ m to 5.0 ⁇ m.
- a pre-bake treatment is performed after coating.
- vacuum treatment can be performed before pre-baking.
- the vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
- the pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C., using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds.
- high-frequency treatment or the like may be used in combination with the pre-bake treatment.
- the high frequency treatment can be used alone.
- the coating film made of the colored photosensitive composition formed as described above is exposed through a predetermined mask pattern.
- the radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
- exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
- the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.
- the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
- the development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds. Any developer can be used as long as it dissolves the coating film of the colored photosensitive composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
- Examples of the organic solvent used for development include the solvents described above that can be used when preparing the colored photosensitive composition of the first embodiment.
- Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide.
- alkaline compound such as 1,8-diazabicyclo- [5.4.0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0
- alkaline aqueous solution dissolved so as to be 0.01% by mass to 1% by mass can be mentioned.
- An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.
- the development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like.
- the surface to be developed can be previously moistened with water or the like to prevent uneven development. It is also possible to develop with the substrate tilted. Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.
- a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
- the rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.
- the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.
- the color filter of the first embodiment has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.
- the black matrix on the substrate is a colored photosensitive composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.
- liquid crystal display element and the solid-state imaging device of the first embodiment are provided with the color filter of the first embodiment. More specifically, for example, a liquid crystal display element panel according to the first embodiment is formed by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling and sealing the liquid crystal in the gap portion. Is obtained.
- the solid-state image sensor of 1st Embodiment is obtained by forming a color filter on a light receiving element.
- the photocurable composition of the second embodiment includes a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, and the alkali-soluble resin as necessary.
- Various additives such as a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.
- Chain transfer agent examples include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzo Examples thereof include mercapto compounds having a heterocyclic ring such as thiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
- a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
- Thermal polymerization component It is also effective to include a thermal polymerization component in the photocurable composition of the second embodiment.
- an epoxy compound can be added to increase the strength of the coating film.
- the epoxy compound include compounds having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound.
- bisphenol A types include Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc.
- the bisphenol F type and bisphenol S type can also be mentioned.
- Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used.
- the cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above Toto Kasei), Denacol EM-125, etc.
- cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl
- 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester
- glycidyl esters such as Epototo YH-434 and YH-434L, which are amine type epoxy resins, and glycidyl esters in which dimer acid is modified in the skeleton of bisphenol A type epoxy resin can also be used.
- the photocurable composition of the second embodiment preferably contains various surfactants from the viewpoint of improving coating properties, and in addition to the above-mentioned fluorosurfactants, nonionic, cationic, and anionic Various surfactants can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.
- nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred.
- polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether
- Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene
- Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co.
- additives can be added to the photocurable composition.
- additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate.
- Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers
- alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.
- the pigment dispersion composition may be an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Can be added. Specific examples thereof include those exemplified as the low molecular weight organic carboxylic acid having a molecular weight of 1000 or less added in the first embodiment.
- thermopolymerization inhibitor for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol. Pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzo Imidazole and the like are useful.
- a thermal polymerization inhibitor for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol.
- Pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzo Imidazole and the like are useful.
- An exemplary configuration of the second embodiment will be described below.
- a pigment dispersion composition comprising (A) a graft polymer having 5 to 30% by mass of acrylic acid copolymerized in the main chain, (B) a pigment, and (C) an organic solvent.
- the graft polymer (A) in which 5 to 30% by mass of acrylic acid is copolymerized in the main chain further contains a heterocyclic structure in the side chain and has a weight average molecular weight of 1,000 to 100,000.
- the pigment dispersion composition according to ⁇ 1> which is 000.
- a photocurable composition comprising the pigment dispersion composition according to any one of ⁇ 1> to ⁇ 5>, (F) a polymerizable compound, and (G) a photopolymerization initiator.
- ⁇ 10> A solid-state imaging device using the color filter according to ⁇ 8>.
- the obtained monomer (A-5) is mentioned as a preferred specific example of the monomer represented by the aforementioned general formula (i), (ii) or (i) -2.
- Monomers (A-1) to (A-4) and (A-6) to (A-23) were synthesized by the same method as described above.
- V-65 2,2-azobis (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.
- Specific polymers (P-1) to (P-4), (P-6) to (P-30), and comparative polymers (C-1) to (C-4) have specific weights. Synthesis was performed in the same manner except that the monomers used in the synthesis of the union (P-5) and the amounts thereof were replaced with the monomers and amounts described in Tables 1 and 2 below. Tables 1 and 2 below show the single polymers used in the synthesis of the specific polymers (P-1) to (P-30) and the comparative polymers (C-1) to (C-4). It shows about a body and its preparation amount, the weight average molecular weight of the synthesized polymer, and an acid value.
- the monomers M-11, M-1, M-6, M-14, M-31, and M-33 in Tables 1 and 2 are each a single monomer represented by the general formula (1).
- Maleimides, and maleimide derivatives are those mentioned as preferred specific examples.
- the monomers B-1 to B-3 in Table 2 are as follows.
- composition (1) ⁇ C. I. Pigment Red 254 (average primary particle size: 26 nm) 90 parts. 10 parts of pigment derivative A having the following structure. Specific polymer or comparative polymer described in Table 3 below. 600 parts of methoxy-2-propyl acetate
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat made by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 ⁇ m. This sample was placed between two polarizing plates, the amount of transmitted light was measured when the polarization axis was parallel and when the polarization axis was parallel, and the ratio was taken as contrast.
- a high contrast indicates that the pigment is uniformly dispersed in a highly refined state, and thus the transmittance, that is, the coloring power is high.
- the pigment dispersion composition obtained on a 100 mm ⁇ 100 mm glass substrate (trade name: manufactured by Corning) was applied so that the film thickness after drying was 2.0 ⁇ m, and 90 ° C. For 60 seconds. Thereafter, the coating film was subjected to a heat treatment (post-bake) for 30 minutes in an oven at 230 ° C., and the presence or absence of precipitates (pigments) on the colored film was confirmed with an optical microscope (manufactured by Olympus Corporation) at a magnification of 100. In addition, the same post-baking process was repeated and the presence or absence of the deposit on a colored film was confirmed each time.
- the evaluation index is as follows. Here, it shows that it is hard to precipitate and the transparency of a colored film is so favorable that the number of an index
- -Evaluation index- 4 Precipitate is generated at the fourth post-bake 3: Precipitate is generated at the third post-bake 2: Precipitate is generated at the second post-bake 1: Precipitate is generated at the first post-bake
- the pigment dispersion composition of the example containing the specific polymer has a higher contrast than the comparative example, suppresses the precipitation of the pigment due to post-baking, and further increases the viscosity over time. I understand that it is small
- composition (2) ⁇ C. I. Pigment Green 36 (average primary particle size: 16 nm) 100 parts Specific polymer or comparative polymer listed in Table 4 below (30% by mass solution) 120 parts 1-methoxy-2-propyl acetate 750 parts
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat manufactured by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the pigment dispersion composition of the example containing the specific polymer has a higher contrast than the comparative example, suppresses the precipitation of the pigment due to post-baking, and further increases the viscosity over time. I understand that it is small.
- composition (3) ⁇ C. I. Pigment Red 254 (average primary particle size: 26 nm) 110 parts • Specific polymer or comparative polymer described in Table 5 below (260 mass% solution) 260 parts • 1-methoxy-2-propyl acetate 750 parts
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat manufactured by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the prepared colored photosensitive composition (color resist solution) was applied on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the coated film after the exposure was treated with a 1% aqueous solution of an alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). And rested for 60 seconds.
- Contrast A polarizing plate is placed on the coloring pattern of the color filter, the coloring pattern is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using a BM-5 manufactured by Topcon Corporation.
- a value obtained by dividing the luminance of the above by the luminance at the time of orthogonality was used as an index for evaluating the contrast. Larger values indicate higher contrast.
- the measurement sample is dipped in the developer prepared as described above and the up-and-down operation of drawing it out is repeated 20 times, and the solubility of the coating film after pre-baking and the presence or absence of the suspension in the developer are visually observed. It was judged.
- the immersion time in the developer was 1 second to 2 seconds per time.
- the evaluation index is as follows. Here, the larger the index number, the better the developability of the coating film.
- -Evaluation index- 5 The coating film is completely dissolved in the vertical movement 1 to 10 times, and there is no suspension in the alkaline developer 4: The coating film is completely dissolved in the vertical movement 11 to 20 times, and in the alkaline developer No suspension 3: The coating film is completely dissolved in 1 to 10 movements up and down, but there is a suspension in the alkaline developer 2: The coating film is completely dissolved in 11 to 20 movements up and down, but the alkali There is a suspension in the developer 1: The coating film is insoluble even after 20 vertical movements
- the coating film subjected to the exposure and development treatment is subjected to a heat treatment (post-bake) for 30 minutes in an oven at 230 ° C., and the precipitate on the colored cured film is subjected to an optical microscope (manufactured by Olympus). The presence or absence of (pigment) was confirmed. Then, the same post-baking process was repeated 3 times, and the presence or absence of the deposit on a colored cured film was confirmed each time.
- the evaluation index is as follows. Here, it shows that it is hard to precipitate and the transparency of a colored cured film is so favorable that the number of a parameter
- index is large.
- the colored photosensitive compositions of the examples have better solubility in the alkaline developer of the coating film than the comparative examples, and the precipitation of the pigment after post-baking is suppressed. I understand. Moreover, it turns out that the color filter of an Example has high contrast compared with a comparative example.
- composition (4) ⁇ C. I. Pigment red 254 (average primary particle size: 26 nm) 120 parts C.I. I. Pigment Red 177 (average primary particle size: 22 nm) 20 parts. Specific polymer or comparative polymer described in Table 6 below (250 mass solution) 250 parts. Pigment derivative B having the following structure 25 parts. 1- 750 parts of methoxy-2-propyl acetate
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat made by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the obtained colored photosensitive composition (color resist solution) was applied on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the coated film after the exposure was treated with a 1% aqueous solution of an alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). And rested for 60 seconds.
- the thickness of the colored photosensitive composition obtained by the above-described method after drying is 2.0 ⁇ m. It was applied and dried (prebaked) in an oven at 90 ° C. for 60 seconds. Thereafter, exposure is performed at 100 mJ / cm 2 without using a mask (illuminance is 20 mW / cm 2 ), and a 1% aqueous solution of an alkali developer (trade name: CDK-1, manufactured by FUJIFILM Electronics Materials Co., Ltd.) is used. The coating film was developed at 25 ° C. and subjected to heat treatment (post-baking) for 30 minutes in an oven at 230 ° C.
- the glass substrate in which the colored cured film was formed was obtained.
- the glass substrate on which this colored cured film is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 ⁇ m glass beads, and then manufactured by Merck & Co., Inc.
- Liquid crystal MJ9711189 (trade name) was injected to produce a liquid crystal cell.
- the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica Co., Ltd.
- the voltage holding ratio is a value of a voltage applied at a liquid crystal cell potential difference after 16.7 milliseconds / 0 milliseconds.
- the conditions for measuring this voltage holding ratio are as follows.
- the evaluation index is as follows. Here, it can be seen that the larger the index number, the higher the voltage holding ratio and the better the electrical characteristics.
- -Evaluation index- 5 90% or more 4: 85% or more and less than 90% 3: 80% or more and less than 85% 2: 75% or more and less than 80% 1: less than 75%
- the colored photosensitive compositions of the examples have better solubility in the alkaline developer of the coating film than the comparative examples, and the voltage holding ratio of the colored cured film after post-baking is high. I understand that. Moreover, it turns out that the color filter of an Example has high contrast compared with a comparative example.
- composition (5) ⁇ C. I. Pigment Blue 15: 6 (average primary particle size: 20 nm) 80 parts C.I. I. Pigment Violet 23 (average primary particle size: 26 nm) 20 parts • 15 parts of pigment derivative B having the above structure • Specific polymer or comparative polymer described in Table 7 below (30 mass% solution) 260 parts 750 parts of methoxy-2-propyl acetate
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat manufactured by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the obtained colored photosensitive composition (color resist solution) was applied on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the coated film after the exposure was treated with a 1% aqueous solution of an alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). And rested for 60 seconds.
- the coating film thickness after drying is 2 ⁇ m between the slit and the substrate.
- the coating solution of the colored photosensitive composition was applied onto a rectangular glass substrate having a width of 230 mm, a length of 300 mm, and a thickness of 0.7 mm at an application speed of 50 mm / sec. A coated surface having a length of 260 mm was obtained. After the application, the film was pre-baked at 90 ° C. for 60 seconds with a hot plate, and then visually observed to count the number of stripe-shaped unevenness on the coated surface.
- the evaluation index is as follows. A: No streaky unevenness on the coated surface B: One to five streaky unevenness on the coated surface C: Six or more streaky unevenness on the coated surface
- composition (6) ⁇ C. I. Pigment Green 36 (average primary particle size: 16 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size: 26 nm) 45 parts • Specific polymer or comparative polymer listed in Table 8 below (280% by mass solution) 280 parts • 1-methoxy-2-propyl acetate 750 parts
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat manufactured by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the obtained colored photosensitive composition (color resist solution) was applied on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the coated film after exposure was 1% aqueous solution of alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer.
- CDK-1 manufactured by FUJIFILM Electronics Materials Co., Ltd.
- the coating film that has been exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored region) for the color filter on the glass substrate.
- a filter substrate color filter was produced.
- the colored photosensitive compositions of the examples can form a good coated surface without coating unevenness, and the solubility of the coated film in an alkaline developer is better than that of the comparative example. It turns out that it is. Moreover, it turns out that the color filter of an Example has high contrast compared with a comparative example.
- Example 48 to 50 and Comparative Examples 17 and 18 ⁇ Miniaturization of pigment> C.
- I. Pigment Red 254 50 g, 400 g of sodium chloride, 40 g of a specific polymer or a comparative polymer solution (30% by mass solution) shown in Table 9 below, and 100 g of diethylene glycol are charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel. And kneading for 6 hours.
- this mixture is poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to obtain a specific polymer or a comparative polymer.
- a coated processed pigment was obtained.
- the average primary particle diameter of the obtained processed pigment was 24 nm.
- the ingredients of the following composition (7) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
- composition (7) 100 parts of the above processed pigment-150 parts by "Solsperse 24000" (30% by weight solution) manufactured by Lubrizol Corporation-600 parts of 1-methoxy-2-propyl acetate
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.2 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat made by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- the pigment dispersion composition of the example containing the specific polymer has a higher contrast than the comparative example, suppresses the precipitation of the pigment due to post-baking, and further increases the viscosity over time. I understand that it is small.
- Examples 51 to 53, Comparative Examples 19 and 20 Using the pigment dispersion compositions obtained in Examples 48 to 50 and Comparative Examples 17 and 18, the following colored photosensitive compositions were prepared.
- Example 43 Using the obtained colored photosensitive composition (color resist solution), a colored pattern (colored region) for a color filter is formed on a glass substrate in the same manner as in Example 43, and a colored filter substrate (color filter) is formed. Produced. Moreover, about the produced colored photosensitive composition and colored filter substrate (color filter), in the same manner as in Example 43, (1) contrast and (2) solubility in alkaline developer, and in alkaline developer The suspension and (5) coating unevenness were evaluated. The results are summarized in Table 10 below.
- the colored photosensitive compositions of the examples can form a good coating surface without coating unevenness, and the solubility of the coating film in an alkaline developer is better than that of the comparative example. It turns out that it is. Moreover, it turns out that the color filter of an Example has high contrast compared with a comparative example.
- ⁇ Preparation of silicon wafer with undercoat layer> A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 ⁇ m, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.
- ⁇ Preparation of pigment dispersion composition Components of the following composition (8) were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
- composition (8) 100 parts of the pigment described in Table 11 200 parts of the specific polymer or comparative polymer described in Table 11 (30% by mass solution) 750 parts of 1-methoxy-2-propyl acetate
- the mixed solution obtained above was further subjected to a dispersion treatment for 3 hours by a bead disperser disperse mat (manufactured by GETZMANN) using 0.8 mm ⁇ zirconia beads, and then further a high pressure disperser NANO with a pressure reducing mechanism.
- a bead disperser disperse mat manufactured by GETZMANN
- NANO a high pressure disperser NANO with a pressure reducing mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 5 times to obtain a pigment dispersion composition.
- the silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the center of rotation to the shower nozzle to perform a rinsing treatment, and then spray-dried.
- the minimum exposure amount in which the film thickness after development in the region irradiated with light in the exposure process was 95% or more with respect to the film thickness 100% before exposure was evaluated as the exposure sensitivity.
- a smaller exposure sensitivity value indicates higher sensitivity.
- the evaluation results are shown in Table 11.
- the luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the ratio of pixels with a deviation from the average within ⁇ 5% to the total number of pixels.
- the evaluation criteria are as follows. First, the colored photosensitive composition prepared as described above was applied onto the undercoat layer of the silicon wafer with an undercoat layer obtained by the above-described method, thereby forming a coating film. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 ⁇ m.
- the colored cured film surface was irradiated with light from the optical microscope side, and the reflection state was observed with an optical microscope provided with a digital camera with a magnification of 1000 times.
- the digital camera installed in the optical microscope is equipped with a CCD with 1.28 million pixels and photographed the surface of the colored cured film in a reflective state.
- the photographed image was stored as digitally converted data (digital image) in an 8-bit bitmap format.
- the colored cured film surface was photographed for 20 arbitrarily selected regions.
- the digitally converted data was digitized and stored as a density distribution of 256 gradations in which the luminance of each of the three primary colors RGB was 0 to 255.
- the stored digital image was divided into a lattice shape so that one lattice size corresponds to 2 ⁇ m square on the actual substrate, and the luminance in one partition was averaged.
- 2 ⁇ m on the actual substrate was 2 mm on the captured image
- the image size on the display was 452 mm ⁇ 352 mm.
- the total number of sections in one area was 39976.
- the evaluation criteria are as follows. The evaluation results are shown in Table 11. -Evaluation criteria- A: Deviation from the average is less than 2% B: Deviation from the average is 2% or more and less than 5% C: Deviation from the average is 5% or more
- the colored photosensitive compositions of the examples have higher sensitivity than the comparative examples, and color unevenness occurs in the colored cured films obtained from the colored photosensitive compositions of the examples. I understand that there is no.
- the obtained liquid crystal display device had excellent contrast, no color unevenness, and good image display performance. I understood.
- the obtained solid-state imaging device had no color unevenness and had excellent color separation. It was found to have performance.
- the polymers 1 to 6 obtained above are (A) specific graft polymers of the present invention, and each of the polymers 1 to 6 is composed of at least macromonomers AA-6, Plaxel FM5, and A-5. It is a polymer obtained by copolymerizing any of them with acrylic acid.
- ⁇ Preparation of pigment dispersion composition The components having the composition shown in Table 12 below were mixed, and the mixture was stirred for 3 hours at 3,000 rpm using a homogenizer and mixed to prepare a mixed solution containing a pigment. Subsequently, the obtained mixed solution was further subjected to a dispersion treatment for 6 hours using a bead disperser disperse mat (made by GETZMANN) using 0.2 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO-3000 with a decompression mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using -10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
- a high contrast indicates that the pigment is uniformly dispersed in a highly refined state.
- Pigment R1 C.I. I. Pigment Red 254 Average primary particle size 30 nm
- Pigment R2 C.I. I. Pigment Red 254 Average primary particle size 23 nm
- Basic graft type polymer Polymer obtained by amidation reaction of polyester obtained by ring-opening polymerization of ⁇ -caprolactone with dodecanoic acid and polyethyleneimine Weight average molecular weight: 20000
- PGMEA 1-methoxy-2-propyl acetate
- Examples 57 to 70 using the specific graft polymer of the present invention have a small increase in viscosity over time, good dispersion stability, high contrast, pigment particles, as compared with Comparative Examples. It can be seen that is finely dispersed.
- composition (11) Components of the following compositions (11) to (14) were mixed and mixed by stirring for 3 hours at a rotational speed of 3,000 rpm using a homogenizer to prepare a mixed solution containing a pigment.
- Composition (11) ⁇ C. I. Pigment Red 254 Average primary particle size 25 ⁇ m 110 parts Polymer 1 as a dispersant (30% by weight solution) 200 parts 1-methoxy-2-propyl acetate 750 parts
- composition (12) ⁇ C. I. Pigment Red 254 Average primary particle size 25 ⁇ m 110 parts ⁇ Polymer 3 (30% by mass solution) as a dispersant 200 parts ⁇ 1-methoxy-2-propyl acetate 750 parts
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat made by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions (11) to (15).
- ⁇ Preparation of color filter using photocurable composition The obtained photocurable composition (color resist solution) was applied on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the x value serving as an index of color density was 0.650. It was dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the coated film after exposure was 1% aqueous solution of alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). Covered with and rested for a certain time.
- CDK-1 manufactured by FUJIFILM Electronics Materials Co., Ltd.
- Polymerizable compound dipentaerythritol pentahexaacrylate photopolymerization initiator: 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine
- Solvent 1-methoxy-2-propyl acetate
- ⁇ Preparation of pigment dispersion composition The components of the following compositions (16) to (19) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
- composition (16) ⁇ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Polymer 1 (30% by weight solution) as a dispersant 180 parts 1-methoxy-2-propyl acetate 750 parts
- Composition (17) ⁇ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts
- Polymer 3 as a dispersing agent (30% by mass solution) 180 parts 1-methoxy-2-propyl acetate 750 parts
- composition (18) ⁇ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Polymer 3 (30% by weight solution) as a dispersant 60 parts Basic graft type dispersant (same as that used in Example 65) 36 parts / 1 -Methoxy-2-propyl acetate 820 parts
- composition (20) ⁇ C. I. Pigment Green 36 (average primary particle size 20 nm) 55 parts C.I. I. Pigment Yellow 150 (average primary particle size 24 nm) 45 parts Polymer 3 (30% by mass solution) as a dispersant 40 parts Basic graft type dispersant (same as used in Example 65) 36 parts / 1 -Methoxy-2-propyl acetate 750 parts
- the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism.
- a bead disperser disperse mat made by GETZMANN
- NANO high-pressure disperser NANO with a decompression mechanism.
- -3000-10 manufactured by Nippon BEE Co., Ltd.
- This dispersion treatment was repeated 10 times to obtain pigment dispersion compositions (16) to (19).
- ⁇ Preparation of photocurable composition> Using the obtained pigment dispersion composition, photocurable compositions having a pigment concentration of 35 mass% and 42 mass% were prepared. ⁇ Preparation of color filter using photocuring composition> The obtained photocurable composition (color resist solution) was applied on a 100 mm ⁇ 100 mm glass substrate (1737, manufactured by Corning) so that the y value serving as an index of color density was 0.650, It was dried in an oven at 90 ° C. for 60 seconds (pre-baking).
- the entire surface of the coating film was exposed at 200 mJ / cm 2 (illuminance 20 mW / cm 2 ), and the coated film after exposure was 1% aqueous solution of alkali developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). Covered with and rested for a certain time. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.
- CDK-1 manufactured by FUJIFILM Electronics Materials Co., Ltd.
- ⁇ Preparation of resist solution> Components of the following composition were mixed and dissolved to prepare a resist solution.
- Composition of resist solution 1-methoxy-2-propyl acetate 19.20 parts ethyl lactate 36.67 parts benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (molar ratio 60/22/18) 40% of polymer 1-methoxy-2-propyl acetate (PGMEA) solution 30.51 parts • dipentaerythritol hexaacrylate 12.20 parts • polymerization inhibitor (p-methoxyphenol) 0.0061 parts • fluorinated surfactant 0.83 parts (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) ⁇ Photopolymerization initiator (manufactured by Midori Chemical Co., Ltd. TAZ-107) 0.586 parts
- ⁇ Preparation of pigment dispersion composition The components of the following compositions (21) and (22) are mixed, and using a homogenizer, the rotational speed is 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution containing the pigment.
- composition 21 ⁇ Pigment (pigment described in Table 15) 100 parts ⁇ Polymer 1 (30% by weight solution) 200 parts as a dispersant ⁇ 750 parts of 1-methoxy-2-propyl acetate
- composition 22 Pigment described in Table 15-100 parts-Comparative polymer 1 (30% by weight solution) as a dispersant-200 parts-1-methoxy-2-propyl acetate 750 parts
- each mixed solution obtained above was further subjected to a dispersion treatment for 3 hours by a bead disperser disperse mat (manufactured by GETZMANN) using 0.8 mm ⁇ zirconia beads, and then further a high pressure disperser with a pressure reducing mechanism.
- Dispersion treatment was performed using NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) at a flow rate of 500 g / min under a pressure of 2,000 kg / cm 3 . This dispersion treatment was repeated 5 times to obtain the pigment dispersion compositions shown in Table 15.
- composition> 1000 parts of the above pigment dispersion-Photopolymerization initiator (CGI-124 manufactured by Ciba Specialty Chemicals) 20 parts-polymerizable compound dipentaerythritol hexaacrylate 20 parts-polymerizable compound (TO-756, manufactured by Toagosei Co., Ltd.) 35 parts- 1-methoxy-2-propyl acetate 20 parts
- CGI-124 manufactured by Ciba Specialty Chemicals
- TO-756 manufactured by Toagosei Co., Ltd.
- the photocurable composition prepared as described above was applied on the undercoat layer of the silicon wafer with the undercoat layer described above to form a colored layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 ⁇ m. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), various exposure doses in the range of 50 to 1200 mJ / cm 2 through an Island pattern mask having a pattern of 1.5 ⁇ m square at a wavelength of 365 nm And exposed.
- FPA-3000i5 + manufactured by Canon Inc.
- the silicon wafer substrate on which the coating film after exposure is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film Electronics Material). Paddle development was performed at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer.
- DW-30 type manufactured by Chemitronics Co., Ltd.
- CD-2000 Fluji Film Electronics Material
- a silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is supplied from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device.
- a rinsing process was performed by supplying a shower from a jet nozzle, followed by spray drying.
- ⁇ Evaluation of uneven color> In the same manner as the preparation of the silicon wafer with the undercoat layer described above, a resist solution is applied onto the glass plate to create a glass substrate with the undercoat layer, and the photocurable composition is applied onto the glass with the undercoat layer and colored. A layer (coating film) was formed. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 ⁇ m. The luminance distribution of the coated glass plate was analyzed from images taken with a microscope MX-50 (Olympus). The luminance distribution was analyzed, and the color unevenness was evaluated based on the ratio of the pixels whose deviation from the average is within ⁇ 5% to the total number of pixels. The evaluation criteria are as follows.
Abstract
Description
一般に、顔料の1次粒子の微細化は、顔料、水溶性の無機塩、該無機塩を実質的に溶解しない水溶性有機溶剤をニーダー等で機械的に混練する方法(ソルトミリング法)がよく知られている。得られた微細顔料の1次粒子の混合物を水中に投入し、ミキサー等で撹拌しスラリー状とする。次に、このスラリーをろ過、水洗して乾燥することにより、顔料の1次粒子の凝集体である2次凝集体として微細顔料が得られる。サンドミル、ボールミル等の通常の分散機での分散工程は、顔料の1次粒子の凝集体である2次凝集体をほぐして1次粒子に近い状態の分散体を得る工程である。
これらの顔料分散剤の中でも、例えば、特開2004-287409号公報では、アルカリ現像性が良好で、高精細の画素を得る目的として、ω-カルボキシポリカプロラクトンモノメタクリレート共重合体が提案されている。
また、例えば、特開2003-238837号公報では、分散性、アルカリ現像性を向上させることを目的として、スチレン、アルキル(メタ)アクリレートといったビニル系化合物の重合体構造をグラフト鎖として有し、且つ複素環構造を側鎖に有する高分子化合物が提案されている。
しかしながら、これらの方法によっても、更に高くなる市場からのコントラストの要求に応じることはできず、微細な顔料における更に高度な分散性、分散安定性が望まれていた。
即ち、本発明の第1の目的は、微細化された顔料を1次粒子の状態で分散させることができ、且つ、分散させた顔料の1次粒子を安定的に維持することができ、コントラストに優れた着色被膜を形成し得る顔料分散組成物を提供することにある。
また、本発明の第2の目的は、前記顔料分散組成物を含み、塗布性に優れ、且つ、コントラストに優れた着色硬化膜を形成し得る着色感光性組成物を提供することにある。
更に、本発明の第3の目的は、前記着色感光性組成物を用いて形成され、コントラストが高く、また、色濃度ムラが小さく色特性に優れた着色領域を有するカラーフィルタ、該カラーフィルタを備えた液晶表示素子、及び固体撮像素子を提供することにある。
本発明の第4の目的は、分散安定性に優れた顔料分散液、及び、それを用いた、スリット塗布装置の塗布液吐出口先端部において、凝集あるいは固化した際の自己溶解性(乾燥膜再溶解性)に優れ、また現像液に対する溶解性が良好で、現像残渣の発生が抑制された現像性に優れた光硬化性組成物を提供することにある。
本発明の第5の目的は、該光硬化性組成物を用いてなる着色パターンを有する高品質なカラーフィルタを提供すること、さらには、該カラーフィルタを備えた、色再現性に優れ、高コントラストの液晶表示装置、及び、色むらが小さく、高解像度の固体撮像素子を提供することにある。
即ち、本発明の第1の観点の顔料分散組成物は、(a)下記一般式(I)及び(II)のいずれかで表される繰り返し単位から選択される少なくとも1種の繰り返し単位を含む高分子化合物、(b)顔料、及び(c)有機溶剤を含有する。
また、(a)高分子化合物が、側鎖に複素環基を有することも好ましい態様の一つである。
更に、第1の観点の顔料分散組成物は、カラーフィルタにおける着色領域の形成に用いられることが好ましい。
また、第1の観点のカラーフィルタは、基板上に、第1の観点の着色感光性組成物により形成された着色領域を有する。
更に、第1の観点の液晶表示素子、及び固体撮像素子は、いずれも、第1の観点のカラーフィルタを備える。
即ち、顔料分散剤として機能する(a)高分子化合物は、一般式(I)又は(II)で表される繰り返し単位を含んでおり、特定のグラフト鎖構造を有していることが分かる。このグラフト鎖構造は顔料との親和性は低いが、顔料分散組成物において共存する(c)有機溶剤との親和性が高いことから、このグラフト鎖部分が(b)顔料表面に吸着することなく、グラフト鎖部分が有機溶剤側に伸張した構造をとることができる。つまり、第1の観点における(a)高分子化合物は、グラフト鎖構造が溶媒との親和性が高いことから、(b)顔料及び(c)有機溶剤と共存させた際、伸張した構造となり、顔料表面への吸着が効率よく行われると考えられ、その結果として、有機溶剤中で顔料の安定した分散状態を保つことできると考えられる。
逆に、顔料との親和性が高く、溶媒との親和性が低いグラフト鎖構造では、グラフト鎖部分が顔料表面に吸着してしまい、グラフト鎖部分が有機溶剤側に伸張した構造をとることができない。そのため、このようなグラフト鎖を有する高分子化合物は、顔料及び有機溶剤と共存させた場合に、収縮した構造となり、顔料表面への吸着が効率よく行われず、結果として、顔料の凝集が生じてしまうと考えられる。
特開2004-287409号公報のω-カルボキシポリカプロラクトンモノメタクリレート共重合体では、グラフト鎖末端基が相互作用性の強いカルボキシル基のため、また、特開2003-238837号公報のビニル系化合物の重合体におけるグラフト鎖では、有機溶剤との親和性が低い構造のため、どちらも高分子化合物の構造として収縮した状態になるために、被膜形成性は低く、その結果として、塗布性を高めることが困難であると思われる。
前記第4と第5の課題に関しては、本発明者が鋭意検討した結果、(A)主鎖にアクリル酸を有するグラフト型高分子化合物、(B)顔料、および(C)有機溶剤を含有する顔料分散組成物を用いることで上記課題を解決しうることを見出し、本発明に至った。
第2の観点のカラーフィルタは、第2の観点の光硬化性組成物を用いてなるカラーフィルタである。
第2の観点の液晶表示装置は、第2の観点のカラーフィルタを用いた液晶表示装置である。
第2の観点の固体撮像素子は、第2の観点のカラーフィルタを用いた固体撮像素子である。
第2の観点の顔料分散組成物に含まれる(A)主鎖にアクリル酸を有するグラフト型高分子化合物を分散剤として使用すると、高分子化合物が主鎖にアクリル酸を有し、かつグラフト型であることから、主鎖のアクリル酸がメタクリル酸よりも極性が高く、かつ主鎖が柔軟なため、高極性の顔料に対してアクリル酸が顔料に作用する際に効果的に顔料を被覆し、かつグラフト鎖が立体反発鎖として機能するために顔料同士の再凝集を抑制したものと考えられる。従って、顔料の1次粒子の凝集体である2次凝集体を効果的にほぐし、また、1次粒子が、2次凝集体へ再凝集するのを効果的に抑制することができると考えられる。そのため分散工程において、1次粒子が分散したのに近い状態の分散体を得ることができるものと考えられる。
従って、このような顔料分散組成物を含有する光硬化性組成物からなる着色パターンを備えることで、コントラストの高いカラーフィルタ、および色濃度ムラの小さいカラーフィルタを得ることができたものと考えられる。
また、第1の観点によれば、前記顔料分散組成物を含み、塗布性に優れ、且つ、コントラストに優れた着色硬化膜を形成し得る着色感光性組成物を提供することができる。
更に、第1の観点によれば、前記着色感光性組成物を用いて形成され、コントラストが高く、また、色濃度ムラが小さく色特性に優れた着色領域を有するカラーフィルタ、該カラーフィルタを備えた液晶表示素子、及び固体撮像素子を提供することができる。
さらに、該光硬化性組成物を用いてなる着色パターンを有する高品質なカラーフィルタを提供し、さらには、該カラーフィルタを備えた、色再現性に優れ、高コントラストの液晶表示装置、及び、色むらが小さく、高解像度の固体撮像素子を提供することができる。
本発明の第1の実施形態の顔料分散組成物は、(a)下記一般式(I)及び(II)のいずれかで表される繰り返し単位から選択される少なくとも1種の繰り返し単位を含む高分子化合物、(b)顔料、及び(c)有機溶剤を含有する。
以下、第1の実施形態の顔料分散組成物を構成する(a)高分子化合物、(b)顔料、及び(c)有機溶剤について説明する。
第1の実施形態の顔料分散組成物は、下記一般式(I)及び(II)のいずれかで表される繰り返し単位から選択される少なくとも1種の繰り返し単位を含む高分子化合物(以下、「特定重合体」と称する場合がある。)を含有する。
アルキル基が置換基を有する場合、該置換基としては、例えば、ヒドロキシ基、アルコキシ基(好ましくは炭素数1~5、より好ましくは炭素数1~3がより好ましい。)メトキシ基、エトキシ基、シクロヘキシロキシ基等が挙げられる。
好ましいアルキル基として、具体的には、例えば、メチル基、エチル基、プロピル基、n-ブチル基、i-ブチル基、t-ブチル基、n-ヘキシル基、シクロヘキシル基、2-ヒドロキシエチル基、3-ヒドロキシプロピル基、2-ヒドロキシプロピル基、2-メトキシエチル基が挙げられる。
R1、R2、R4、及びR5としては、水素原子が好ましく、R3及びR6としては、水素原子又はメチル基が、顔料表面への吸着効率の点からも最も好ましい。
好ましいアルキレン基として、具体的には、例えば、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基が挙げられる。
アルキレン基が置換基を有する場合、該置換基としては、例えば、ヒドロキシ基等が挙げられる。
2価の有機連結基としては、上記のアルキレン基の末端に、-C(=O)-、-OC(=O)-、-NHC(=O)-から選ばれるヘテロ原子又はヘテロ原子を含む部分構造を有し、該ヘテロ原子又はヘテロ原子を含む部分構造を介して、隣接した酸素原子と連結したものが、顔料への吸着性の点から好ましい。ここで、隣接した酸素原子とは、一般式(I)におけるL1、及び一般式(II)におけるL2に対し、側鎖末端側で結合する酸素原子を意味する。
好ましいアルキル基の例としては、炭素原子数が1から20までの直鎖状、分岐状、及び環状のアルキル基を挙げることができ、その具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、s-ブチル基、t-ブチル基、イソペンチル基、ネオペンチル基、1-メチルブチル基、イソヘキシル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロヘキシル基、シクロペンチル基、2-ノルボルニル基を挙げることができる。
これらの置換基における、アルキル基の具体例としては、前述のアルキル基が挙げられ、これらは更に置換基を有していてもよい。
置換基としては、アルコキシ基、アリーロキシ基、アルキルチオ基、アリールチオ基、N,N-ジアルキルアミノ基、N,N-ジアリールアミノ基、N-アルキル-N-アリールアミノ基、アシルオキシ基、アリール基、ヘテロアリール基、アルケニル基、アルキニル基、シリル基が、分散安定性の点から好ましい。
顔料に吸着し得る官能基を有する単量体としては、具体的には、有機色素構造或いは複素環構造を有するモノマー、酸性基を有するモノマー、塩基性窒素原子を有するモノマー、イオン性基を有するモノマーなどを挙げることができる。中でも、顔料への吸着力の点で、有機色素構造或いは複素環構造を有するモノマーが好ましい。
R1で表されるアルキル基が置換基を有する場合、該置換基としては、例えば、ヒドロキシ基や、メトキシ基、エトキシ基、シクロヘキシロキシ基等のアルコキシ基が好ましい。該アルコキシ基としては、炭素数1~5であるものが好ましく、炭素数1~3のものが好ましい。
中でも、R1としては、水素原子又はメチル基が最も好ましい。
また、このアルキレン基が置換基を有する場合、該置換基としては、例えば、ヒドロキシ基等が挙げられる。
R2で表される好ましいアルキレン基として、具体的には、例えば、メチレン基、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基が挙げられる。
また、R2で表されるアルキレン基を含む2価の基としては、上記アルキレン基におけるZに結合する方の末端に、-O-、-S-、-C(=O)O-、-CONH-、-C(=O)S-、-NHCONH-、-NHC(=O)O-、-NHC(=O)S-、-OC(=O)-、-OCONH-、及び-NHCO-から選ばれるヘテロ原子又はヘテロ原子を含む部分構造が結合したものであってもよい。
これらの含窒素複素環構造は、置換基を有していてもよく、該置換基としては、例えば、アルキル基、アルコキシ基、ハロゲン原子、脂肪族エステル基、芳香族エステル基、アルコキシカルボニル基等が挙げられる。
炭素数が6以上である含窒素複素環構造として、具体的には、フェノチアジン環、フェノキサジン環、アクリドン環、アントラキノン環、ベンズイミダゾール構造、ベンズトリアゾール構造、ベンズチアゾール構造、環状アミド構造、環状ウレア構造、及び環状イミド構造が好ましく、下記一般式(2)、(3)、又は(4)で表される構造であることが特に好ましい。
上記した中でも、一般式(2)におけるXとしては、単結合、メチレン基、-O-、又は-C(=O)-が好ましく、-C(=O)-が特に好ましい。
上記した中でも、一般式(4)における、Y及びZとしては、-N=、-NH-、及び-N(RB)-が特に好ましい。Y及びZの組み合わせとしては、Y及びZのいずれか一方が-N=であり他方が-NH-である組み合わせ(イミダゾリル基)が好ましいものとして挙げられる。
一般式(3)における環Cとしては、例えば、ベンゼン環、ナフタレン環、ピリジン環、ピラジン環、等が挙げられる。
一般式(4)における環Dとしては、例えば、ベンゼン環、ナフタレン環、ピリジン環、ピラジン環、等が挙げられる。
即ち、顔料の1次粒子の凝集体である2次凝集体の生成を効果的に抑制、或いは、2次凝集体の凝集力を効果的に弱めるためには、一般式(1)で表される単量体、マレイミド、及びマレイミド誘導体からなる群より選択された1種の単量体に由来する重合単位の含有量は5質量%以上であることが好ましい。また、顔料分散組成物を含有する着色感光性組成物によりカラーフィルタを製造する際の現像性の観点からは、一般式(1)で表される単量体、マレイミド、及びマレイミド誘導体からなる群より選択された1種の単量体に由来する重合単位の含有量は50質量%以下であることが好ましい。
カルボキシル基を有するビニルモノマーとして、(メタ)アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、2-ヒドロキシエチル(メタ)アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートなども利用できる。また、カルボキシル基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。なおこれらの内では、共重合性やコスト、溶解性などの観点から(メタ)アクリル酸が特に好ましい。
特定重合体において、酸性基を有するモノマーに由来する繰り返し単位の含有量は、好ましくは50mgKOH/g以上であり、特に好ましくは50mgKOH/g~200mgKOH/gである。即ち、現像液中での析出物の生成抑制という点では、酸性基を有するモノマーに由来する繰り返し単位の含有量は50mgKOH/g以上であることが好ましい。顔料の1次粒子の凝集体である2次凝集体の生成を効果的に抑制、或いは、2次凝集体の凝集力を効果的に弱めるためには、酸性基を有するモノマーに由来する繰り返し単位の含有量は50mgKOH/g~200mgKOH/gであることが好ましい。
ビニルエステル類の例としては、ビニルアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート、及び安息香酸ビニルなどが挙げられる。
マレイン酸ジエステル類の例としては、マレイン酸ジメチル、マレイン酸ジエチル、及びマレイン酸ジブチルなどが挙げられる。
フマル酸ジエステル類の例としては、フマル酸ジメチル、フマル酸ジエチル、及びフマル酸ジブチルなどが挙げられる。
イタコン酸ジエステル類の例としては、イタコン酸ジメチル、イタコン酸ジエチル、及びイタコン酸ジブチルなどが挙げられる。
スチレン類の例としては、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、ヒドロキシスチレン、メトキシスチレン、ブトキシスチレン、アセトキシスチレン、クロロスチレン、ジクロロスチレン、ブロモスチレン、クロロメチルスチレン、酸性物質により脱保護可能な基(例えばt-Bocなど)で保護されたヒドロキシスチレン、ビニル安息香酸メチル、及びα-メチルスチレンなどが挙げられる。
この態様により、顔料吸着に優れ、且つ、現像性に優れた顔料分散組成物を与えることができる。
特に、重量平均分子量(Mw)で10000~30000の範囲、数平均分子量(Mn)で5000~15000の範囲であることが最も好ましい。
即ち、顔料の1次粒子の凝集体である2次凝集体を効果的にほぐし、或いは、再凝集を効果的に弱めるための観点からは、特定重合体の重量平均分子量(Mw)は1000以上であることが好ましい。また、顔料分散組成物を含有する着色感光性組成物によりカラーフィルタを製造する際の現像性の観点からは、特定重合体の重量平均分子量(Mw)は30000以下であることが好ましい。
一般的には、懸濁重合法或いは溶液重合法などを用いる。このような特定重合体を合成する際に用いられる溶媒としては、例えば、エチレンジクロリド、シクロヘキサノン、メチルエチルケトン、アセトン、メタノール、エタノール、プロパノール、ブタノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、2-メトキシエチルアセテート、1-メトキシ-2-プロパノール、1-メトキシ-2-プロピルアセテート、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、トルエン、酢酸エチル、乳酸メチル、乳酸エチルなどが挙げられる。これらの溶媒は単独或いは2種以上混合してもよい。
なお、ラジカル重合の際、ラジカル重合開始剤を使用することができ、また、更に連鎖移動剤(例、2-メルカプトエタノール及びドデシルメルカプタン)を使用することができる。
他の高分子化合物としては、天然樹脂、変性天然樹脂、合成樹脂、天然樹脂で変性された合成樹脂等が用いられる。
天然樹脂としてはロジンが代表的であり、変性天然樹脂としては、ロジン誘導体、繊維素誘導体、ゴム誘導体、タンパク誘導体及びそれらのオリゴマーが挙げられる。合成樹脂としては、エポキシ樹脂、アクリル樹脂、マレイン酸樹脂、ブチラール樹脂、ポリエステル樹脂、メラミン樹脂、フェノール樹脂、ポリウレタン樹脂等が挙げられる。天然樹脂で変性された合成樹脂としては、ロジン変性マレイン酸樹脂、ロジン変性フェノール樹脂等が挙げられる。
合成樹脂としては、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、ポリウレタン、ポリエステル、ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物が挙げられる。
第2の実施形態の顔料分散組成物は、(A)主鎖にアクリル酸を5~30質量%共重合したグラフト型高分子化合物(以下、特定グラフト重合体と称することがある。)、(B)顔料、および(C)有機溶剤を含んでなる顔料分散組成物であり、必要によって前記(A)主鎖にアクリル酸を共重合したグラフト型高分子化合物がさらに、側鎖に複素環を含んでいてもよい。
第2の実施形態で使用される特定グラフト重合体は、アクリル酸を主鎖に有し、アクリル酸の含有量は5~30質量%であり、重量平均分子量1,000~100、000の範囲のグラフト型高分子化合物であれば、特に制限されない。
特定グラフト重合体の合成方法は、新高分子実験学第2巻(共立出版、1995年)などにあるように、一般的な方法として(1)主鎖高分子から枝モノマーを重合させる方法、(2)主鎖高分子に枝高分子を結合させる方法(3)主鎖モノマーを枝高分子と共重合させる方法などが使用可能である。
即ち、第2の実施形態で使用できる特定グラフト重合体は、アクリル酸と重合性オリゴマー(以下、マクロモノマーと称する)と他の共重合可能なモノマーとを共重合させて得られるものである。
マクロモノマーの好ましい構造は、前記一般式(I)で表される繰り返し単位、前記一般式(II)で表される繰り返し単位、下記一般式(3)で表される繰返し単位のうち一つ以上を有するものであり、このうち、一般式(I)で表される繰り返し単位が最も好ましい。
式(i)、(ii)、(i-2)で表される単量体の好ましい具体例は第1の実施形態の場合と同様であるが、第2の実施形態はこれらに制限されるものではない。
特に枝部の重量平均分子量は、300~10,000が好ましい。好ましくは500~5,000、より好ましくは1,000~3,000である。枝部の分子量が上記範囲中にあると、現像性が特に良好であり、現像ラチチュードが広い。
第2の実施形態の特定グラフト重合体において、一般式(1)で表される単量体、マレイミド、マレイミド誘導体に由来する共重合単位の含有量は、特に制限はないが、重合体に含有される全構造単位を100質量%とした場合に、一般式(1)で表される単量体、マレイミド、マレイミド誘導体に由来する共重合単位を5質量%以上含有することが好ましく、10~50質量%含有することがより好ましい。
即ち、顔料の1次粒子の凝集体である2次凝集体の生成を効果的に抑制、あるいは、2次凝集体の凝集力を効果的に弱めるためには、一般式(1)で表される単量体、マレイミド、マレイミド誘導体に由来する共重合単位の含有量は5質量%以上であることが好ましい。また、顔料分散組成物を含有する光硬化性組成物によりカラーフィルタを製造する際の現像性の観点からは、一般式(1)で表される単量体に由来する共重合単位の含有量は30質量%以下であることが好ましい。
第2の実施形態の顔料分散組成物中、特定グラフト重合体の含有量としては質量比で、顔料:特定グラフト重合体=1:0.1~1:2が好ましく、より好ましくは、1:0.2~1:1であり、さらに好ましくは、1:0.4~1:0.7である。第2の実施形態のアクリル酸の効果が顕著に現れるのは、顔料:特定グラフト重合体=1:0.4~1:0.55のときである。
また、第2の実施形態において(A)特定グラフト重合体の含有量は、全固形分のうち、10~40質量%が好ましい。
高分子化合物の量が少ない状態であっても、顔料の分散性が良好で、分散安定性も良く、且つ、光硬化性組成物にしたときに、乾燥膜の溶剤への再溶解性が良好で、現像での残渣が少ない顔料分散組成物を提供することができる。
(D)塩基性グラフト型高分子化合物は、複数の塩基性基を有する幹ポリマー部に枝ポリマーがグラフト結合した構造のポリマーであり、幹ポリマー部の塩基性基をアンカーとして有機顔料および酸性誘導体の表面に多点吸着するため、枝ポリマー部の立体反発効果が有効に作用し、微細分散化促進機能を発現する。幹ポリマー部の塩基性基は、吸着特性に優れる点でアミノ基が好ましく、また、枝ポリマー部は立体反発鎖に優れる点で有機溶媒可溶性を有するものであるのが好ましい。さらに、幹ポリマー1分子に2分子以上の枝ポリマーがグラフト結合した分子構造を有していることが好ましい。このようなポリマーは、例えば下記式のように表すことができる。
第1の実施形態における(b)顔料としては、従来公知の種々の無機顔料又は有機顔料を適宜選択して用いることができる。
顔料としては、本発明の顔料分散組成物がカラーフィルタの着色領域に用いられ、その際に高透過率であることが好ましいこと等を考慮すると、有機顔料が好ましく、また、なるべく粒子サイズの小さいものを使用することが好ましい。
顔料分散組成物及びこれを含有する着色感光性組成物のハンドリング性を考慮すると、顔料の平均1次粒子径としては、100nm以下が好ましく、30nm以下がより好ましく、5nm~25nmが最も好ましい。該粒子径が前記範囲内であると、透過率が高く、色特性が良好であると共に、高いコントラストのカラーフィルタを形成するのに有効である。
平均1次粒子径は、SEM或いはTEMで観察し、粒子が凝集していない部分で粒子サイズを100個計測し、平均値を算出することによって求める。
第2の実施形態の顔料分散組成物は顔料を含有する。ここで用いられる顔料はその粒子径が小さいほどカラーフィルタとしてのコントラストが向上する。特に粒子径が10~25nmの顔料を第2の実施形態の特定グラフト重合体を用いて分散すると、良好に分散でき、コントラストが向上する。また、このサイズの顔料は、微細であるために、顔料分散液を高温高湿度下にて長期保管すると、顔料が凝集して粘度が向上するという問題があったが、本発明のアクリル酸を導入したグラフト型分散剤を使用すると、この問題が解決できる。
顔料の粒子径が前記範囲内であると、透過率が高く、色特性が良好であると共に、高いコントラストのカラーフィルタを形成するのに有効である。
平均一次粒子径は、SEMあるいはTEMで観察し、粒子が凝集していない部分で粒子サイズを100個計測し、平均値を算出することによって求める。
顔料濃度は、10~55質量%の範囲で使用可能だが、特に35~55質量%の範囲、40~55質量%の範囲の高顔料濃度領域で効果が顕著に現れる。
第2の実施形態の顔料分散組成物に用いることができる顔料としては、従来公知の種々の無機顔料又は有機顔料を用いることができる。また、顔料は、無機顔料または有機顔料を問わず、高透過率であることが好ましいことを考慮すると、できるだけ粒子径が小さく微少な粒子サイズの顔料を使用することが好ましく、ハンドリング性をも考慮すると、好ましくは平均一次粒子径10~25nmの範囲の顔料である。
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279、
C.I.Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214、
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73、
C.I.Pigment Green 7,10,36,37、
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,79のCl置換基をOHに変更したもの,80、
C.I.Pigment Violet 1,19,23,27,32,37,42、
C.I.Pigment Brown 25,28、
C.I.Pigment Black 1,7等を挙げることができる。
但し、本発明においてはこれらに限定されるものではない。
C.I.Pigment Yellow 11,24,108,109,110,138,139,150,151,154,167,180,185、
C.I.Pigment Orange 36,71、
C.I.Pigment Red 122,150,171,175,177,209,224,242,254,255,264、
C.I.Pigment Violet 19,23,32、
C.I.Pigment Blue 15:1,15:3,15:6,16,22,60,66、
C.I.Pigment Green 7,36,37、
C.I.Pigment Black 1,7
例えば、赤の顔料としては、アントラキノン系顔料、ペリレン系顔料、ジケトピロロピロール系顔料を単独で、又は、それらの少なくとも1種と、ジスアゾ系黄色顔料、イソインドリン系黄色顔料、キノフタロン系黄色顔料又はペリレン系赤色顔料、アントラキノン系赤色顔料、ジケトピロロピロール系赤色顔料と、を混合して用いることができる。
例えば、アントラキノン系顔料としては、C.I.ピグメント・レッド177が挙げられ、ペリレン系顔料としては、C.I.ピグメント・レッド155、C.I.ピグメント・レッド224が挙げられ、ジケトピロロピロール系顔料としては、C.I.ピグメント・レッド254が挙げられ、色再現性の点でC.I.ピグメント・イエロー83、C.I.ピグメント・イエロー139又はC.I.ピグメント・レッド177との混合が好ましい。また、赤色顔料と他顔料との質量比は、400nmから500nmの光透過率と色純度の点から、100:5~100:80が好ましい。特に、上記質量比としては、100:10~100:65の範囲が最適である。なお、赤色顔料同士の組み合わせの場合は、色度に併せて調整することができる。
例えば、このような例としては、C.I.ピグメント・グリーン7、36、37とC.I.ピグメント・イエロー83、C.I.ピグメント・イエロー138、C.I.ピグメント・イエロー139、C.I.ピグメント・イエロー150、C.I.ピグメント・イエロー180又はC.I.ピグメント・イエロー185との混合が好ましい。緑顔料と黄色顔料との質量比は、400nm~450nmの光透過率と色純度の点から、100:5~100:200が好ましい。上記質量比としては100:20~100:150の範囲が特に好ましい。
特に好適な例として、C.I.ピグメント・ブルー15:6とC.I.ピグメント・バイオレット23との混合を挙げることができる。
青色顔料と紫色顔料との質量比は、100:0~100:100が好ましく、より好ましくは100:70以下である。
また、カーボンブラックとチタンブラックとの質量比は、100:0~100:60の範囲が好ましい。この100:60を超えてチタンブラックの量が多い場合、分散安定性が低下する場合がある。
第1の実施形態においては、必要に応じて、上記のような顔料を、微細で、かつ、整粒化してなる顔料を用いてもよい。
この顔料の微細化には、顔料を、水溶性有機溶剤及び水溶性無機塩類と共に高粘度な液状組成物を調製し、これを摩砕する工程を含む方法を用いることが好ましい。
第1の実施形態においては、顔料の微細化には、以下の方法を用いることがより好ましい。
即ち、まず、有機顔料、水溶性有機溶剤、及び水溶性無機塩類の混合物(液状組成物)に対し、二本ロール、三本ロール、ボールミル、トロンミル、ディスパー、ニーダー、コニーダー、ホモジナイザー、ブレンダー、単軸若しくは2軸の押出機等の混練機を用いて、強い剪断力を与えることで、混合物中の顔料を摩砕した後、この混合物を水中に投入し、攪拌機等でスラリー状とする。次いで、このスラリーをろ過、水洗し、水溶性有機溶剤及び水溶性無機塩を除去した後、乾燥することで、微細化された顔料を得る方法である。
また、少量用いることで顔料に吸着して、廃水中に流失しないならば、ベンゼン、トルエン、キシレン、エチルベンゼン、クロロベンゼン、ニトロベンゼン、アニリン、ピリジン、キノリン、テトラヒドロフラン、ジオキサン、酢酸エチル、酢酸イソプロピル、酢酸ブチル、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、シクロヘキサン、メチルシクロヘササン、ハロゲン化炭化水素、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、ジメチルホルムアミド、ジメチルスルホキシド、N-メチルピロリドン等を用いてもよい。また、必要に応じて2種類以上の溶剤を混合して使用してもよい。
これら水溶性有機溶剤の使用量は、顔料に対して、50質量%~300質量%の範囲が好ましく、より好ましくは100質量%~200質量%の範囲である。
水溶性無機塩の使用量は、有機顔料の1倍質量~50倍質量が好ましく、多い方が摩砕効果はあるが、生産性の点から、より好ましい量は1倍質量~10倍質量である。
また、水溶性無機塩の溶解を防ぐため、摩砕される液状組成物中の水分が1質量%以下であることが好ましい。
上記のような摩砕後の混合物を、80℃の温水と混合することで、水溶性有機溶剤と水溶性無機塩類とを溶解させ、その後、ろ過、水洗し、オーブンで乾燥して、微細な顔料を得ることができる。
ここで、加工顔料を得る際に用いられる、水溶性有機溶剤に少なくとも一部可溶な樹脂としては、顔料分散剤として用いられている公知の樹脂を用いることができるが、第1の実施形態においては、前述の(a)特定重合体を用いることが好ましい。
第2の実施形態の顔料は、予め微細化処理を施したものを使用することが好ましい。顔料1次粒子の微細化は、i)顔料、ii)水溶性の無機塩、iii)該無機塩を実質的に溶解しない水溶性有機溶剤をニーダー等で機械的に混練する方法がよく知られている(ソルトミリング法)。この工程において、必要に応じて、iv)顔料被覆高分子化合物、v)顔料誘導体等を同時に使用してもよい。
ii)水溶性の無機塩としては、水に溶解するものであれば特に限定されず、塩化ナトリウム、塩化バリウム、塩化カリウム、硫酸ナトリウム等を用いることができるが、価格の点から塩化ナトリウムまたは硫酸ナトリウムを用いるのが好ましい。ソルトミリングする際に用いる無機塩の量は、処理効率と生産効率の両面から、有機顔料の1~30倍質量、特に5~25倍質量で、さらに水分が1%以下であることが好ましい。有機顔料に対する無機塩の量比が大きいほど微細化効率が高いが、1回の顔料の処理量が少なくなるからである。
第2の実施形態における湿式粉砕装置の運転条件については特に制限はないが粉砕メディアによる磨砕を効果的に進行させるため、装置がニーダーの場合の運転条件は、装置内のブレードの回転数は、10~200rpmが好ましく、また2軸の回転比が相対的に大きい方が、摩砕効果が大きく好ましい。運転時間は乾式粉砕時間と併せて1時間~8時間が好ましく、装置の内温は50~150℃が好ましい。また粉砕メディアである水溶性無機塩は粉砕粒度が5~50μmであり、その粒子径の分布がシャープであり、且つ球形であることが好ましい。
合成樹脂としては、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、ポリウレタン、ポリエステル、ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物が挙げられる。
(A)特定グラフト重合体としては、既述の高分子化合物を使用できる。
これらの樹脂を加えるタイミングは、ソルトミリング初期にすべてを添加してもよく、分割して添加してもよい。
第2の実施形態における顔料誘導体としては、後述の(E)顔料誘導体と同様のものが挙げられる。
第1の実施形態の顔料分散組成物は、少なくとも1種の(c)有機溶剤を含有する。
第1の実施形態の顔料分散組成物に用いられる有機溶剤としては、1-メトキシ-2-プロピルアセテート、1-メトキシ-2-プロパノール、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、酢酸エチル、酢酸ブチル、乳酸エチル、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、n-プロパノール、2-プロパノール、n-ブタノール、シクロヘキサノール、エチレングリコール、ジエチレングリコール、トルエン、キシレンなどを挙げることができる。
また、有機溶剤の添加量は、顔料分散組成物の用途などに応じて適宜選択されるが、後述する着色感光性組成物の調製に用いる場合には、取り扱い性の観点から、顔料等を含む固形分濃度が5質量%~50質量%となるように添加することができる。
第1の実施形態の顔料分散組成物には、顔料誘導体が好適に用いられる。
第1の実施形態においては、分散剤と親和性のある部分、或いは、極性基を導入した顔料誘導体を処理顔料表面に吸着させ、これを分散剤の吸着点として用いることで、顔料を微細な粒子として顔料分散組成物中に分散させることができ、また、その再凝集をも防止することができる。つまり、顔料誘導体は顔料表面を改質することで、(a)特定重合体の如き高分子分散剤の吸着を促進させる効果を有する。
また、母体骨格としては、一般に、色素と呼ばれていないナフタレン系、アントラキノン系、トリアジン系、キノリン系等の淡黄色の芳香族多環化合物も含まれる。
この顔料分散組成物をカラーフィルタの製造に適用することで、透過率が高く、優れた色特性を有し、高いコントラストのカラーフィルタを得ることができる。
第1の実施形態の顔料分散組成物は、各種の混合機、分散機を使用して混合分散する混合分散工程を経ることによって、調製することができる。
なお、混合分散工程は、混練分散とそれに続けて行う微分散処理からなるのが好ましいが、混練分散を省略することも可能である。
なお、ビーズによる微分散を行なう前に、二本ロール、三本ロール、ボールミル、トロンミル、ディスパー、ニーダー、コニーダー、ホモジナイザー、ブレンダー、単軸若しくは2軸の押出機等を用いて、強い剪断力を与えながら混練分散処理を行なうことも可能である。
第1の実施形態の着色感光性組成物は、既述の第1の実施形態の顔料分散組成物と、光重合性化合物と、光重合開始剤とを含んでなり、更に、アルカリ可溶性樹脂を含むことが好ましく、必要に応じて、他の成分を含んでいてもよい。
以下、第1の実施形態の着色感光性組成物に含まれる各成分について詳述する。
第1の実施形態の着色感光性組成物は、前記した第1の実施形態の顔料分散組成物の少なくとも一種を用いて構成されるものである。着色感光性組成物を構成する第1の実施形態の顔料分散組成物の詳細については、既述の通りである。
第1の実施形態の着色感光性組成物中における顔料分散組成物の含有量としては、着色感光性組成物の全固形分(質量)に対して、顔料の含有量が5質量%~70質量%の範囲となる量が好ましく、15質量%~60質量%の範囲となる量がより好ましい。顔料分散組成物の含有量がこの範囲内であると、色濃度が充分で優れた色特性を確保するのに有効である。
第1の実施形態の着色感光性組成物は、少なくとも1種の光重合性化合物を含有する。
第1の実施形態に用いることができる光重合性化合物は、少なくとも一個のエチレン性不飽和二重結合を有する付加重合性化合物であり、末端エチレン性不飽和結合を少なくとも1個、好ましくは2個以上有する化合物から選ばれる。このような化合物群は当該産業分野において広く知られるものであり、第1の実施形態においてはこれらを特に限定無く用いることができる。光重合性化合物は、例えば、モノマー、プレポリマー、すなわち2量体、3量体及びオリゴマー、又はそれらの混合物並びにそれらの共重合体などの化学的形態をもつ。
クロトン酸エステルとしては、エチレングリコールジクロトネート、テトラメチレングリコールジクロトネート、ペンタエリスリトールジクロトネート、ソルビトールテトラジクロトネート等がある。イソクロトン酸エステルとしては、エチレングリコールジイソクロトネート、ペンタエリスリトールジイソクロトネート、ソルビトールテトライソクロトネート等がある。マレイン酸エステルとしては、エチレングリコールジマレート、トリエチレングリコールジマレート、ペンタエリスリトールジマレート、ソルビトールテトラマレート等がある。
CH2=C(R)COOCH2CH(R’)OH
(ただし、R及びR’は、それぞれ、H又はCH3を示す。)
例えば、次のような観点から選択される。感度の点では1分子あたりの不飽和基含量が多い構造が好ましく、多くの場合、2官能以上が好ましい。また、硬化膜の強度を高くするためには、3官能以上のものがよく、更に、異なる官能数・異なる重合性基(例えば、アクリル酸エステル、メタクリル酸エステル、スチレン系化合物、ビニルエーテル系化合物)のものを併用することで、感度と強度の両方を調節する方法も有効である。
また、基板等との密着性を向上せしめる目的で特定の構造を選択することもあり得る。付加重合性化合物は、着色感光性組成物中の不揮発性成分に対して、好ましくは5質量%~70質量%、更に好ましくは10質量%~60質量%の範囲で使用される。また、これらは単独で用いても2種以上併用してもよい。その他、付加重合性化合物の使用法は、酸素に対する重合阻害の大小、解像度、かぶり性、屈折率変化、表面粘着性等の観点から適切な構造、配合、添加量を任意に選択できる。
第2の実施形態の顔料分散組成物は、必要に応じて、顔料誘導体が添加される。分散剤と親和性のある部分、あるいは極性基を導入した顔料誘導体を顔料表面に吸着させ、これを分散剤の吸着点として用いることで、顔料を微細な粒子として光硬化性組成物中に分散させ、その再凝集を防止することができ、コントラストが高く、透明性に優れたカラーフィルタを構成するのに有効である。
第2の実施形態の顔料分散組成物は、分散剤の少なくとも一種を含有する。この分散剤により、顔料の分散性を向上させることができる。
分散剤としては、前述した(A)特定グラフト重合体を少なくとも用いることを要する。これにより、有機溶媒中の顔料の分散状態が良好になると共に、例えば第2の実施形態の顔料分散組成物を用いてカラーフィルタを構成したときには、顔料を高濃度で含む場合であっても高い現像性と表面平滑性を発現することができる。
(A)特定グラフト重合体を分散剤として用いる場合には、既述の高分子化合物を使用することができる。
高分子分散剤は、その構造からさらに直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。
第2の実施形態の顔料分散組成物における溶剤としては、有機溶剤であれば特に制限はなく、公知のものの中から適宜選択することができ、例えば、1-メトキシ-2-プロピルアセテート、1-メトキシ-2-プロパノール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等の(ポリ)アルキレングリコールモノアルキルエーテルおよびこれらの酢酸エステル類;酢酸エチル、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル等の酢酸エステル類;ベンゼン、トルエン、キシレンなどの芳香族炭化水素類;メチルエチルケトン、アセトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類;エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、ジエチレングリコール、グリセリン等のアルコール類、などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。これらの中でも、アルキレングリコールモノアルキルエーテル類、およびその酢酸エステル類、酢酸エステル類、メチルエチルケトン、などが好ましい。
(C)有機溶剤として、1-メトキシ-2-プロピルアセテートを10質量%以上有することが好ましい。
第2の実施形態の顔料分散組成物の調製態様は、特に制限されないが、例えば、顔料と顔料分散剤と溶剤とを、縦型もしくは横型のサンドグラインダー、ピンミル、スリットミル、超音波分散機等を用いて、0.01~1mmの粒径のガラス、ジルコニア等でできたビーズで微分散処理を行なうことにより得ることができる。
第2の実施形態の光硬化性組成物は、既述の第2の実施形態の顔料分散組成物と、(F)重合性化合物と、(G)光重合開始剤とを含んでなり、必要に応じてアルカリ可溶性樹脂などの他の成分を含んでいてもよい。以下、各成分を詳述する。
重合性化合物としては、少なくとも1個の付加重合可能なエチレン性不飽和基を有し、沸点が常圧で100℃以上である化合物が好ましく、中でも4官能以上のアクリレート化合物がより好ましい。
更に、日本接着協会誌Vol.20、No.7、300~308頁に光硬化性モノマー及びオリゴマーとして紹介されているものも使用できる。
中でも、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、及びこれらのアクリロイル基がエチレングリコール、プロピレングリコール残基を介している構造が好ましい。これらのオリゴマータイプも使用できる。
また、酸基を有するエチレン性不飽和化合物類も好適であり、市販品としては、例えば、東亞合成株式会社製のカルボキシル基含有3官能アクリレートであるTO-756、及びカルボキシル基含有5官能アクリレートであるTO-1382などが挙げられる。
重合性化合物の光硬化性組成物中における含有量としては、該組成物の全固形分中、3~55質量%が好ましく、より好ましくは10~50質量%である。重合性化合物の含有量が前記範囲内であると、硬化反応が充分に行なえる。
以下の光重合開始剤についての説明は、第1と第2の実施形態を含め本発明に共通する説明である。本発明における光重合開始剤としては、例えば、特開平57-6096号公報に記載のハロメチルオキサジアゾール、特公昭59-1281号公報、特開昭53-133428号公報等に記載のハロメチル-s-トリアジン等活性ハロゲン化合物、米国特許第4318791号、欧州特許出願公開第88050等の各明細書に記載のケタール、アセタール、又はベンゾインアルキルエーテル類等の芳香族カルボニル化合物、米国特許第4199420号明細書に記載のベンゾフェノン類等の芳香族ケトン化合物、仏国特許発明第2456741号明細書に記載の(チオ)キサントン類又はアクリジン類化合物、特開平10-62986号公報に記載のクマリン類又はロフィンダイマー類等の化合物、特開平8-015521号公報等のスルホニウム有機硼素錯体等、等を挙げることができる。
また、これらの光重合開始剤を併用することもできる。
第1の実施形態の着色感光性組成物は、アルカリ可溶性樹脂を含有することが好ましい。着色感光性組成物にアルカリ可溶性樹脂を含有することで、該着色感光性組成物をフォトリソ法によるパターン形成に適用した際において、パターン形成性をより向上させることができる。また第2の実施形態の光硬化性組成物もアルカリ可溶性樹脂を含有していてもよい。以下のアルカリ可溶性樹脂に関する説明は、第1と第2の実施形態を含め本発明に共通する説明である。
この他、2-ヒドロキシエチルメタクリレートを共重合したもの等も有用なものとして挙げられる。該ポリマーは任意の量で混合して用いることができる。
前記アルキル(メタ)アクリレート及びアリール(メタ)アクリレートの具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、オクチル(メタ)アクリレート、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、トリル(メタ)アクリレート、ナフチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等を挙げることができる。
好ましい共重合可能な他の単量体は、CH2=CR1R2、CH2=C(R1)(COOR3)、フェニル(メタ)アクリレート、ベンジル(メタ)アクリレート、及びスチレンから選択される少なくとも1種であり、特に好ましくは、CH2=CR1R2、及び/又は、CH2=C(R1)(COOR3)である。
第1の実施形態の着色感光性組成物は、一般に、前述の各成分と共に溶剤を用いることで、好適に調製することができる。
用いられる溶剤としては、エステル類、例えば、酢酸エチル、酢酸-n-ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、アルキルエステル類、乳酸メチル、乳酸エチル、オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル;3-オキシプロピオン酸メチル、3-オキシプロピオン酸エチルなどの3-オキシプロピオン酸アルキルエステル類;3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、2-オキシプロピオン酸メチル、2-オキシプロピオン酸エチル、2-オキシプロピオン酸プロピル、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル、2-オキシ-2-メチルプロピオン酸メチル、2-オキシ-2-メチルプロピオン酸エチル、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル等;エーテル類、例えばジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等;ケトン類、例えば、メチルエチルケトン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン等;芳香族炭化水素類、例えば、トルエン、キシレン;等が挙げられる。
溶剤は、単独で用いる以外に2種以上を組み合わせて用いてもよい。
第1の実施形態の着色感光性組成物には、必要に応じて、増感色素、エポキシ樹脂、フッ素系有機化合物、熱重合開始剤、熱重合成分、熱重合防止剤、充填剤、上記アルカリ可溶性樹脂以外の高分子化合物、界面活性剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤などの各種添加物を含有することができる。
第1の実施形態の着色感光性組成物は、必要に応じて増感色素を添加してもよい。また、第2の実施形態においても必要に応じて増感色素を添加することが好ましい。以降の増感色素に関する説明は第1の実施形態と第2の実施形態を含め、本発明に共通する説明である。増感色素は、この増感色素が吸収しうる波長の露光により上記光重合開始剤のラジカル発生反応等や、それによる前記光重合性化合物の重合反応が促進させることができる。
このような増感色素としては、公知の分光増感色素又は染料、又は光を吸収して光重合開始剤と相互作用する染料又は顔料が挙げられる。
本発明に用いられる増感色素として好ましい分光増感色素又は染料は、多核芳香族類(例えば、ピレン、ペリレン、トリフェニレン)、キサンテン類(例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンB、ローズベンガル)、シアニン類(例えば、チアカルボシアニン、オキサカルボシアニン)、メロシアニン類(例えば、メロシアニン、カルボメロシアニン)、チアジン類(例えば、チオニン、メチレンブルー、トルイジンブルー)、アクリジン類(例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン)、フタロシアニン類(例えば、フタロシアニン、メタルフタロシアニン)、ポルフィリン類(例えば、テトラフェニルポルフィリン、中心金属置換ポルフィリン)、クロロフィル類(例えば、クロロフィル、クロロフィリン、中心金属置換クロロフィル)、金属錯体(例えば、下記化合物)、アントラキノン類、(例えば、アントラキノン)、スクアリウム類(例えば、スクアリウム)、等が挙げられる。
特公平37-13034号公報に記載のスチリル系色素;特開昭62-143044号公報に記載の陽イオン染料;特公昭59-24147号公報記載のキノキサリニウム塩;特開昭64-33104号公報記載の新メチレンブルー化合物;特開昭64-56767号公報記載のアントラキノン類;特開平2-1714号公報記載のベンゾキサンテン染料;特開平2-226148号公報及び特開平2-226149号公報記載のアクリジン類;特公昭40-28499号公報記載のピリリウム塩類;特公昭46-42363号公報記載のシアニン類;特開平2-63053号記載のベンゾフラン色素;特開平2-85858号公報、特開平2-216154号公報の共役ケトン色素;特開昭57-10605号公報記載の色素;特公平2-30321号公報記載のアゾシンナミリデン誘導体;特開平1-287105号公報記載のシアニン系色素;特開昭62-31844号公報、特開昭62-31848号公報、特開昭62-143043号公報記載のキサンテン系色素;特公昭59-28325号公報記載のアミノスチリルケトン;特開平2-179643号公報記載の色素;特開平2-244050号公報記載のメロシアニン色素;特公昭59-28326号公報記載のメロシアニン色素;特開昭59-89303号公報記載のメロシアニン色素;特開平8-129257号公報記載のメロシアニン色素;特開平8-334897号公報記載のベンゾピラン系色素が挙げられる。
増感色素の他の好ましい態様として、以下の化合物群に属しており、且つ、350nm~450nmに極大吸収波長を有する色素が挙げられる。
例えば、多核芳香族類(例えば、ピレン、ペリレン、トリフェニレン)、キサンテン類(例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンB、ローズベンガル)、シアニン類(例えばチアカルボシアニン、オキサカルボシアニン)、メロシアニン類(例えば、メロシアニン、カルボメロシアニン)、チアジン類(例えば、チオニン、メチレンブルー、トルイジンブルー)、アクリジン類(例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン)、アントラキノン類(例えば、アントラキノン)、スクアリウム類(例えば、スクアリウム)が挙げられる。
以下に、一般式(XIV)で表される化合物の好ましい具体例〔(F-1)~(F-5)〕を示す。
一般式(XV)で表される化合物の好ましい例としては、以下のもの〔(F-6)~(F-8)〕が挙げられる。
一般式(XVI)で表される化合物の好ましい例としては、以下のもの〔(F-9)~(F-11)〕が挙げられる。
一般式(XVII)で表される化合物の好ましい例としては、以下のもの〔(F-12)~(F-15)〕が挙げられる。
次に、R74、R75、R76の好ましい例について具体的に述べる。好ましいアルキル基の例としては、炭素原子数が1から20までの直鎖状、分岐状、及び環状のアルキル基を挙げることができ、その具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、s-ブチル基、t-ブチル基、イソペンチル基、ネオペンチル基、1-メチルブチル基、イソヘキシル基、2-エチルヘキシル基、2-メチルヘキシル基、シクロヘキシル基、シクロペンチル基、2-ノルボルニル基を挙げることができる。これらの中では、炭素原子数1から12までの直鎖状、炭素原子数3から12までの分岐状、並びに炭素原子数5から10までの環状のアルキル基がより好ましい。
これらの置換基における、アルキル基の具体例としては、前述のアルキル基が挙げられ、これらは更に置換基を有していてもよい。
中でも、好ましいA5としては、アルコキシ基、チオアルキル基、アミノ基を有するアリール基が挙げられ、特に好ましいA5としてはアミノ基を有するアリール基が挙げられる。
また、一般式(XVIII)におけるXは、酸素原子、硫黄原子、又は-N(R74)-を表す。
ただし、一般式(XVIII-1)におけるArに導入可能な置換基としては、ハメット値の総和が0以上であることが必須であり、そのような置換基の例としては、トリフルオロメチル基、カルボニル基、エステル基、ハロゲン原子、ニトロ基、シアノ基、スルホキシド基、アミド基、カルボキシル基等を挙げることができる。これら置換基のハメット値を以下に示す。トリフルオロメチル基(-CF3、m:0.43、p:0.54)、カルボニル基(例えば-COHm:0.36、p:0.43)、エステル基(-COOCH3、m:0.37、p:0.45)、ハロゲン原子(例えばCl、m:0.37、p:0.23)、シアノ基(-CN、m:0.56、p:0.66)、スルホキシド基(例えば-SOCH3、m:0.52、p:0.45)、アミド基(例えば-NHCOCH3、m:0.21、p:0.00)、カルボキシル基(-COOH、m:0.37、p:0.45)等が挙げられる。かっこ内は、その置換基のアリール骨格における導入位置と、そのハメット値を表し、(m:0.50)とは、当該置換基がメタ位に導入された時のハメット値が0.50であることを示す。このうち、Arの好ましい例としては置換基を有するフェニル基を挙げることができ、Ar骨格上の好ましい置換基としてはエステル基、シアノ基が挙げられる。置換の位置としてはAr骨格上のオルト位に位置していることが特に好ましい。
増感色素の含有量がこの範囲であることで、超高圧水銀灯の露光波長に対して高感度であり、膜深部硬化性が得られると共に、現像マージン、パターン形成性の点で好ましい。
第1の実施形態の着色感光性組成物は、形成された塗布膜の強度を上げるために、熱重合成分として、エポキシ樹脂を用いることができる。
エポキシ樹脂としては、ビスフェノールA型、クレゾールノボラック型、ビフェニル型、脂環式エポキシ化合物などのエポキシ環を分子中に2個以上有する化合物である。
例えば、ビスフェノールA型としては、エポトートYD-115、YD-118T、YD-127、YD-128、YD-134、YD-8125、YD-7011R、ZX-1059、YDF-8170、YDF-170など(以上東都化成製)、デナコールEX-1101、EX-1102、EX-1103など(以上ナガセ化成製)、プラクセルGL-61、GL-62、G101、G102(以上ダイセル化学製)の他に、これらの類似のビスフェノールF型、ビスフェノールS型も挙げることができる。また、Ebecryl 3700、3701、600(以上ダイセルユーシービー製)などのエポキシアクリレートも使用可能である。
また、1,1,2,2-テトラキス(p-グリシジルオキシフェニル)エタン、トリス(p-グリシジルオキシフェニル)メタン、トリグリシジルトリス(ヒドロキシエチル)イソシアヌレート、o-フタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、他にアミン型エポキシ樹脂であるエポトートYH-434、YH-434L、ビスフェノールA型エポキシ樹脂の骨格中にダイマー酸を変性したグリシジルエステル等も使用できる。
具体的な好ましい化合物としては、エポトートYD-115、118T、127、YDF-170、YDPN-638、YDPN-701、プラクセルGL-61、GL-62、3,5,3’,5’-テトラメチル-4,4’ジグリシジルビフェニル、セロキサイド2021、2081、エポリードGT-302、GT-403、EHPE-3150などが挙げられる。
第1の実施形態の着色感光性組成物あるいは第2の実施形態の光硬化性組成物は、フッ素系有機化合物を含有することで、塗布液としたときの液特性(特に、流動性)を向上させ、塗布厚の均一性や省液性を改善することができる。
すなわち、フッ素系有機化合物を含有する着色感光性組成物あるいは光硬化性組成物は、被塗布面と塗布液との界面張力を低下させて被塗布面への濡れ性が改善され、被塗布面への塗布性が向上するため、少量の液量で数μm程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成が可能である点で有効である。
フッ素系有機化合物の添加量は、着色感光性組成物の全質量に対して、0.001質量%~2.0質量%が好ましく、より好ましくは0.005質量%~1.0質量%である。
フッ素系有機化合物の添加量は、光硬化性組成物の全質量に対して、0.001~2.0質量%が好ましく、より好ましくは0.005~1.0質量%である。
第1の実施形態の着色感光性組成物あるいは第2の実施形態の光硬化性組成物には、熱重合開始剤を含有させることも有効である。
熱重合開始剤としては、例えば、各種のアゾ系化合物、過酸化物系化合物が挙げられる。
前記アゾ系化合物としては、アゾビス系化合物を挙げることができ、前記過酸化物系化合物としては、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、パーオキシジカーボネートなどを挙げることができる。
第1の実施形態の着色感光性組成物には、塗布性を改良する観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、前述のフッ素系界面活性剤の他に、ノニオン系、カチオン系、アニオン系の各種界面活性剤を使用できる。
中でも、前記のノニオン系界面活性剤でパーフルオロアルキル基を有するフッ素系界面活性剤や、ノニオン系界面活性剤が好ましい。
フッ素系界面活性剤の具体例としては、大日本インキ化学工業(株)製のメガファック(登録商標)シリーズ、3M社製のフロラード(登録商標)シリーズなどが挙げられる。
ノニオン系界面活性剤として具体的には、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ステアリルエーテル、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オクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル(BASF社製のプルロニックL10、L31、L61、L62、10R5、17R2、25R2、テトロニック304、701、704、901、904、150R1等が挙げられる。
更に、アニオン系界面活性剤として具体的には、W004、W005、W017(裕商社製)等が挙げられる。
上記以外に、第1の実施形態の着色感光性組成物には各種の添加物を添加することができる。
添加物の具体例としては、ガラス、アルミナ等の充填剤;イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの、アルコール可溶性ナイロン、ビスフェノールAとエピクロルヒドリンとから形成されたフェノキシ樹脂などのアルカリ可溶の樹脂;EFKA-46、EFKA-47、EFKA-47EA、EFKAポリマー100、EFKAポリマー400、EFKAポリマー401、EFKAポリマー450(以上森下産業社製)、ディスパースエイド6、ディスパースエイド8、ディスパースエイド15、ディスパースエイド9100(サンノプコ社製)等の高分子分散剤;ソルスパース3000、5000、9000、12000、13240、13940、17000、24000、26000、28000などの各種ソルスパース分散剤(ゼネカ社製);アデカプルロニックL31,F38,L42,L44,L61,L64,F68,L72,P95,F77,P84,F87、P94,L101,P103,F108、L121、P-123(旭電化社製)及びイソネットS-20(三洋化成社製);2-(3-t-ブチル-5-メチル-2-ヒドロキシフェニル)-5-クロロベンゾトリアゾール、アルコキシベンゾフェノン等の紫外線吸収剤;及びポリアクリル酸ナトリウム等の凝集防止剤等がある。
具体的には、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸等の脂肪族モノカルボン酸;シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、テトラメチルコハク酸、シトラコン酸等の脂肪族ジカルボン酸;トリカルバリル酸、アコニット酸、カンホロン酸等の脂肪族トリカルボン酸;安息香酸、トルイル酸、クミン酸、ヘメリト酸、メシチレン酸等の芳香族モノカルボン酸;フタル酸、イソフタル酸、テレフタル酸、トリメリト酸、トリメシン酸、メロファン酸、ピロメリト酸等の芳香族ポリカルボン酸;フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸等のその他のカルボン酸が挙げられる。
熱重合防止剤としては、例えば、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、2-メルカプトベンゾイミダゾール等が有用である。
そのため、良好な色特性が求められるカラーフィルタの着色領域を形成するために用いられることが好ましい。
第1の実施形態のカラーフィルタは、基板上に、前述の第1の実施形態の着色感光性組成物により形成された着色領域を有する。
ここで、着色領域とは、3色或いは4色の着色パターン(画素部)と、ブラックマトリクスと、の両方を含むものである。
以下、第1の実施形態のカラーフィルタについて、その製造方法を通じて詳述する。
まず、第1の実施形態の着色感光性組成物を、直接又は他の層を介して基板上に、回転塗布、スリット塗布、流延塗布、ロール塗布、バー塗布等の塗布方法により塗布して、着色感光性組成物からなる塗布膜を形成する(塗布工程)。その後、塗布膜に対し、所定のマスクパターンを介して露光を行う(露光工程)。露光後、塗布膜の未硬化部を現像液で現像除去する(現像工程)。これらの工程を経ることで、各色(3色或いは4色)の画素からなる着色パターンが形成され、カラーフィルタを得ることができる。
このような方法により、液晶表示素子や固体撮像素子に用いられるカラーフィルタをプロセス上の困難性が少なく、高品質で、且つ、低コストに作製することができる。
以下、各工程について詳細に説明する。
まず、塗布工程で用いられる基板について説明する。
第1の実施形態のカラーフィルタに用いられる基板としては、例えば、液晶表示素子等に用いられる無アルカリガラス、ソーダガラス、パイレックス(登録商標)ガラス、石英ガラス、及びこれらに透明導電膜を付着させたものや、固体撮像素子等に用いられる光電変換素子基板、例えば、シリコーン基板や、プラスチック基板が挙げられる。
これらの基板上には、各画素を隔離するブラックマトリクスが形成されていたり、密着促進等のために透明樹脂層が設けられたりしていてもよい。
また、プラスチック基板は、その表面に、ガスバリヤー層及び/又は耐溶剤性層を有していることが好ましい。
TFT方式液晶駆動用基板における基板としては、例えば、ガラス、シリコーン、ポリカーボネート、ポリエステル、芳香族ポリアミド、ポリアミドイミド、ポリイミド等を挙げることができる。これらの基板には、所望により、シランカップリング剤等による薬品処理、プラズマ処理、イオンプレーティング、スパッタリング、気相反応法、真空蒸着等の適宜の前処理を施しておくこともできる。例えば、TFT方式液晶駆動用基板の表面に、窒化ケイ素膜等のパッシベーション膜を形成した基板を用いることができる。
スリットノズル塗布法において、スリット・アンド・スピン塗布法とスピンレス塗布法は、塗布基板の大きさによって条件は異なるが、例えば、スピンレス塗布法により第五世代のガラス基板(1100mm×1250mm)を塗布する場合、スリットノズルからの着色感光性組成物の吐出量は、通常、500マイクロリットル/秒~2000マイクロリットル/秒、好ましくは800マイクロリットル/秒~1500マイクロリットル/秒であり、また、塗工速度は、通常、50mm/秒~300mm/秒、好ましくは100mm/秒~200mm/秒である。
また、塗布工程で用いられる着色感光性組成物の固形分としては、通常、10%~20%、好ましくは13%~18%である。
また、固体撮像素子用のカラーフィルタの場合であれば、塗布膜の厚み(プリベーク処理後)は、0.5μm~5.0μmの範囲が好ましい。
真空乾燥の条件は、真空度が、通常、0.1torr~1.0torr、好ましくは0.2torr~0.5torr程度である。
また、プリベーク処理は、ホットプレート、オーブン等を用いて50℃~140℃の温度範囲で、好ましくは70℃~110℃程度であり、10秒~300秒の条件にて行うことができる。なお、プリベーク処理には、高周波処理などを併用してもよい。高周波処理は単独でも使用可能である。
露光工程では、前述のようにして形成された着色感光性組成物からなる塗布膜に対し、所定のマスクパターンを介して露光を行う。
露光の際に使用される放射線としては、特に、g線、h線、i線、j線等の紫外線が好ましい。
なお、液晶表示装置用のカラーフィルタを製造する際には、プロキシミテイ露光機、ミラープロジェクション露光機により、主として、h線、i線を使用した露光が好ましく用いられる。
また、固体撮像素子用のカラーフィルタを製造する際には、ステッパー露光機にて、主として、i線を使用することが好ましい。
なお、TFT方式液晶駆動用基板を用いてカラーフィルタを製造する際には、用いられるフォトマスクは、画素(着色パターン)を形成するためのパターンの他、スルーホール或いはコの字型の窪みを形成するためのパターンが設けられているものが使用される。
現像工程では、露光後の塗布膜の未硬化部を現像液に溶出させ、硬化分のみを基板上に残存させる。
現像温度としては、通常20℃~30℃であり、現像時間としては20秒~90秒である。
現像液としては、未硬化部における着色感光性組成物の塗布膜を溶解する一方、硬化部を溶解しないものであれば、いずれのものも用いることができる。
具体的には、種々の有機溶剤の組合せやアルカリ性の水溶液を用いることができる。
また、アルカリ性の水溶液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン等のアルカリ性化合物を、濃度が0.001質量%~10質量%、好ましくは0.01質量%~1質量%となるように溶解したアルカリ性水溶液が挙げられる。
アルカリ性水溶液には、例えば、メタノール、エタノール等の水溶性有機溶剤や界面活性剤等を適量添加することもできる。
また、固体撮像素子用のカラーフィルタを製造する場合にはパドル現像も用いられる。
リンス工処理は通常は純水で行うが、省液のために、最終洗浄で純水を用い、洗浄初期は使用済の純水を使用したり、また、基板を傾斜させて洗浄したり、超音波照射を併用したりする方法を用いてもよい。
この加熱処理(ポストベーク)は、現像後の塗布膜を、上記条件になるようにホットプレートやコンベクションオーブン(熱風循環式乾燥機)、高周波加熱機等の加熱手段を用いて、連続式或いはバッチ式で行うことができる。
第1の実施形態のカラーフィルタは、コントラストが高く、色濃度ムラの小さい、色特性の良好であることから、固体撮像素子又は液晶表示素子に好適に用いることができる。
基板上のブラックマトリックスは、カーボンブラック、チタンブラックなどの黒色顔料の加工顔料を含有する着色感光性組成物を用い、塗布、露光、及び現像の各工程を経て、その後、必要に応じて、ポストベークすることにより形成することができる。
第1の実施形態の液晶表示素子及び固体撮像素子は、第1の実施形態のカラーフィルタを備えてなるものである。より具体的には、例えば、カラーフィルタの内面側に配向膜を形成し、電極基板と対向させ、間隙部に液晶を満たして密封することにより、第1の実施形態の液晶表示素子であるパネルが得られる。また、例えば、受光素子上にカラーフィルタを形成することにより、第1の実施形態の固体撮像素子が得られる。
第2の実施形態の光硬化性組成物は、必要に応じて、連鎖移動剤、フッ素系有機化合物、熱重合開始剤、熱重合成分、熱重合防止剤、その他充填剤、上記のアルカリ可溶性樹脂以外の高分子化合物、界面活性剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤などの各種添加物を含有することができる。
第2の実施形態の光硬化性組成物に添加し得る連鎖移動剤としては、例えば、N,N-ジメチルアミノ安息香酸エチルエステルなどのN,N-ジアルキルアミノ安息香酸アルキルエステル、2-メルカプトベンゾチアゾール、2-メルカプトベンゾオキサゾール、2-メルカプトベンゾイミダゾールなどの複素環を有するメルカプト化合物、および脂肪族多官能メルカプト化合物などが挙げられる。
連鎖移動剤は、1種単独で用いてもよく、2種以上を併用してもよい。
第2の実施形態の光硬化性組成物には、熱重合成分を含有させることも有効である。必要によっては、塗膜の強度を上げるために、エポキシ化合物を添加することができる。エポキシ化合物としては、ビスフェノールA型、クレゾールノボラック型、ビフェニル型、脂環式エポキシ化合物などのエポキシ環を分子中に2個以上有する化合物などがある。例えばビスフェノールA型としては、エポトートYD-115、YD-118T、YD-127、YD-128、YD-134、YD-8125、YD-7011R、ZX-1059、YDF-8170、YDF-170など(以上東都化成製)、デナコールEX-1101、EX-1102、EX-1103など(以上ナガセ化成製)、プラクセルGL-61、GL-62、G101、G102(以上ダイセル化学製)の他に、これらの類似のビスフェノールF型、ビスフェノールS型も挙げることができる。またEbecryl 3700、3701、600(以上ダイセルユーシービー製)などのエポキシアクリレートも使用可能である。クレゾールノボラック型としては、エポトートYDPN-638、YDPN-701、YDPN-702、YDPN-703、YDPN-704など(以上東都化成製)、デナコールEM-125など(以上ナガセ化成製)、ビフェニル型としては3,5,3’,5’-テトラメチル-4,4’ジグリシジルビフェニルなど、脂環式エポキシ化合物としては、セロキサイド2021、2081、2083、2085、エポリードGT-301、GT-302、GT-401、GT-403、EHPE-3150(以上ダイセル化学製)、サントートST-3000、ST-4000、ST-5080、ST-5100など(以上東都化成製)などを挙げることができる。また1,1,2,2-テトラキス(p-グリシジルオキシフェニル)エタン、トリス(p-グリシジルオキシフェニル)メタン、トリグリシジルトリス(ヒドロキシエチル)イソシアヌレート、o-フタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、他にアミン型エポキシ樹脂であるエポトートYH-434、YH-434L、ビスフェノールA型エポキシ樹脂の骨格中にダイマー酸を変性したグリシジルエステル等も使用できる。
第2の実施形態の光硬化性組成物は、塗布性を改良する観点から、各種の界面活性剤を含むことが好ましく、前述のフッソ系界面活性剤の他にノニオン系、カチオン系、アニオン系の各種界面活性剤を使用できる。中でも、前記のフッ素系界面活性剤、ノニオン系界面活性剤が好ましい。
第2の実施形態の光硬化性組成物には、以上のほかに更に、熱重合防止剤を加えておくことが好ましく、例えば、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4′-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、2-メルカプトベンゾイミダゾール等が有用である。
以下に第2の実施形態の例示的な構成を記載する。
<1> (A)主鎖にアクリル酸を5~30質量%共重合したグラフト型高分子重合体、(B)顔料、および(C)有機溶剤を含有する顔料分散組成物。
<2> 前記(A)主鎖にアクリル酸を5~30質量%共重合したグラフト型高分子重合体が、さらに側鎖に複素環構造を含有し、且つ重量平均分子量1,000~100,000である<1>に記載の顔料分散組成物。
<3> 前記(B)顔料の平均1次粒子径が、10~25nmの範囲である<1>、または<2>に記載の顔料分散組成物。
<4> さらに、(D)塩基性グラフト型高分子化合物を含有する<1>~<3>のいずれか1項に記載の顔料分散組成物。
<5> 前記顔料分散組成物に含まれる高分子化合物の総質量を、前記(B)顔料と(E)顔料誘導体との総質量で除した値が、0.55以下である<1>~<4>のいずれか1項に記載の顔料分散組成物。
<7> 顔料濃度が35質量%以上である<6>記載の光硬化性組成物。
<8> <6>、または<7>に記載の光硬化性組成物を用いてなるカラーフィルタ。
<9> <8>に記載のカラーフィルタを用いた液晶表示装置。
<10> <8>に記載のカラーフィルタを用いた固体撮像素子。
日本出願2008-068337、2008-219785、2008-075656の開示はその全体が参照により本明細書に取り込まれる。
500mL三口フラスコに、ε-カプロラクトン160.0g、2-エチル-1-ヘキサノール18.3gを導入し、窒素を吹き込みながら、攪拌溶解した。モノブチル錫オキシド0.1gを加え、100℃に加熱した。8時間後、ガスクロマトグラフィーにて、原料が消失したのを確認後、80℃まで冷却した。2,6-ジt-ブチル-4-メチルフェノール0.1gを添加した後、2-メタクリロイロキシエチルイソシアネート22.2gを添加した。5時間後、1H-NMRにて原料が消失したのを確認後、室温まで冷却し、固体状の単量体(A-5)を200g得た。単量体(A-5)であることは、H NMR、IR、質量分析により確認した。
また、上記と同様の方法により、単量体(A-1)~(A-4)及び(A-6)~(A-23)を合成した。
単量体(A-5)37.5g、単量体M-115.0g、メタクリル酸7.5g、ドデシルメルカプタン1.3、及び1-メトキシ-2-プロパノール116.7gを、窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して75℃まで昇温した。これに、2,2-アゾビス(2,4-ジメチルバレロニトリル)(和光純薬(株)製の「V-65」)を0.3g加え、75℃にて2時間加熱攪拌を行った。2時間後、更にV-65を0.3g加え、3時加熱攪拌の後、特定重合体(P-5)の30%溶液を得た。
得られた特定重合体(P-5)の重量平均分子量をポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、1.8万であった。
下記表1及び表2には、特定重合体(P-1)~(P-30)、及び、比較用重合体(C-1)~(C-4)を合成する際に用いられる単量体とその仕込み量、合成された重合体の重量平均分子量、及び酸価について示す。
また、上記表2中の単量体B-1~B-3は、以下の通りである。
<顔料分散組成物の調製>
下記組成(1)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメント・レッド254(平均1次粒子径:26nm) 90部
・下記構造の顔料誘導体A 10部
・下記表3に記載の特定重合体又は比較用重合体(30質量%溶液) 150部
・1-メトキシ-2-プロピルアセテート 600部
得られた顔料分散組成物について、下記の(1)~(3)の評価を行った。結果を表3にまとめて示す。
得られた顔料分散組成物について、E型粘度計を用いて、分散直後の顔料分散組成物の粘度η1及び分散後室温にて1週間経過した後の顔料分散組成物の粘度η2を測定し、増粘の程度を評価した。ここで、粘度が低いことは、分散剤に起因する粘度の上昇が抑制されており、顔料の分散性及び分散安定性が良好であることを示す。
得られた顔料分散組成物を、ガラス基板上に塗布し、乾燥後の塗布膜の厚さが1μmになるようにサンプルを作製した。2枚の偏光板の間にこのサンプルを置き、偏光軸が平行のときと垂直のときとの透過光量を測定し、その比をコントラストとした(この評価法は、「1990年第7回 色彩光学コンファレンス、512色表示10.4“サイズTFT-LCD用カラーフィルター、植木、小関、福永、山中」を参考にした)。ここで、コントラストが高いことは、顔料が高度に微細化された状態で均一に分散されているため、透過率すなわち着色力が高いことを示す。
100mm×100mmのガラス基板(商品名:1737 コーニング社製)上に得られた顔料分散組成物を乾燥後の膜厚が2.0μmとなるように塗布し、90℃のオーブンで60秒乾燥した。
その後、塗布膜を230℃のオーブンで30分間加熱処理(ポストベーク)を施し、光学顕微鏡(オリンパス社製)にて、倍率100で着色被膜上の析出物(顔料)の有無を確認した。なお、同じポストベーク処理を繰り返して、その都度、着色被膜上の析出物の有無を確認した。
-評価指標-
4:ポストベーク4回目で析出物が発生
3:ポストベーク3回目で析出物が発生
2:ポストベーク2回目で析出物が発生
1:ポストベーク1回目で析出物が発生
<顔料分散組成物の調製>
下記組成(2)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメント・グリーン36(平均1次粒子径:16nm) 100部
・下記表4に記載の特定重合体又は比較用重合体(30質量%溶液) 120部
・1-メトキシ-2-プロピルアセテート 750部
得られた顔料分散組成物について、実施例1と同様にして、前記の(1)~(3)の評価を行った。結果を表4にまとめて示す。
<顔料分散組成物の調製>
下記組成(3)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメント・レッド254(平均1次粒子径:26nm) 110部
・下記表5に記載の特定重合体又は比較用重合体(30質量%溶液) 260部
・1-メトキシ-2-プロピルアセテート 750部
上記のようにして得られた顔料分散組成物を用いて、下記の着色感光性組成物を調製した。
・ジペンタエリスリトールヘキサアクリレート(光重合性化合物) 100部
・4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン(光重合開始剤) 30部
・メタクリル酸ベンジル/メタクリル酸(=75/25[質量比])共重合体(重量平均分子量:12,000)のプロピレングリコールモノメチルエーテルアセテート溶液(固形分30%)(アルカリ可溶性樹脂) 400部
・1-メトキシ-2-プロピルアセテート(溶剤) 390部
調製された着色感光性組成物(カラーレジスト液)を、100mm×100mmのガラス基板(1737、コーニング社製)上に、色濃度の指標となるx値が0.650となるように塗布し、90℃のオーブンで60秒間乾燥させた(プリベーク)。その後、塗布膜の全面に200mJ/cm2にて(照度20mW/cm2)露光し、露光後の塗布膜をアルカリ現像液CDK-1(富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液にて覆い、60秒間静止した。静止後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗布膜を220℃のオーブンで1時間加熱処理し(ポストベーク)、ガラス基板上にカラーフィルタ用の着色パターン(着色領域)を形成し、着色フィルタ基板(カラーフィルタ)を作製した。
作製された着色感光性組成物及び着色フィルタ基板(カラーフィルタ)について、以下のようにして評価を行った。結果を下記表5にまとめて示す。
カラーフィルタの着色パターン上に偏光板を置いて着色パターンを挟み込み、偏光板が平行時の輝度と直交時の輝度とをトプコン社製のBM-5を用いて測定し、平行時の輝度を直交時の輝度で除して得られる値(=平行時の輝度/直交時の輝度)を、コントラストを評価するための指標とした。値が大きいほど高コントラストであることを示す。
アルカリ現像液(商品名:CDK-1、富士フイルムエレクトロニクスマテリアルズ(株)製)の10%水溶液100gを150mlビーカーに計りとる。
一方、100mm×100mmのガラス基板(商品名:1737 コーニング社製)上に前記着色感光性組成物を膜厚2.5μmとなるように塗布し、90℃のオーブンで60秒乾燥(プリベーク)した試料を、25mm×100mmとなるようにガラスを切断し、うち2枚を塗布面が外側となるよう重ね合わせ、測定試料を作製した。
この測定試料を、上記のようにして準備した現像液中に浸漬しては抜き上げする上下動作を20回繰り返し、プリベーク後の塗布膜の溶解性と現像液中の懸濁物の有無を目視判断した。
なお、現像液中の浸漬時間は1回当たり1秒~2秒であった。
-評価指標-
5:上下動1回~10回で塗布膜が完溶、且つ、アルカリ現像液中の懸濁物なし
4:上下動11回~20回で塗布膜が完溶、且つ、アルカリ現像液中の懸濁物なし
3:上下動1回~10回で塗布膜が完溶するが、アルカリ現像液中に懸濁物あり
2:上下動11回~20回で塗布膜が完溶するが、アルカリ現像液中に懸濁物あり
1:上下動20回でも塗布膜が不溶
100mm×100mmのガラス基板(商品名:1737 コーニング社製)上に、前記着色感光性組成物を乾燥後の膜厚が2.0μmとなるように塗布し、90℃のオーブンで60秒乾燥(プリベーク)した。その後、20μmの線幅をもつマスクを用い、100mJ/cm2の露光(照度は20mW/cm2)を行ない、アルカリ現像液(商品名:CDK-1、富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液を用いて25℃で現像した。
以上のように、露光及び現像処理を施した塗布膜に対し、230℃のオーブンで30分間加熱処理(ポストベーク)を施し、光学顕微鏡(オリンパス社製)にて、着色硬化膜上の析出物(顔料)の有無を確認した。その後、同じポストベーク処理を3回繰り返して、その都度、着色硬化膜上の析出物の有無を確認した。
-評価指標-
4:ポストベーク4回目で析出物が発生
3:ポストベーク3回目で析出物が発生
2:ポストベーク2回目で析出物が発生
1:ポストベーク1回目で析出物が発生
<顔料分散組成物の調製>
下記組成(4)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメント・レッド254(平均1次粒子径:26nm) 120部
・C.I.ピグメント・レッド177(平均1次粒子径:22nm) 20部
・下記表6に記載の特定重合体又は比較用重合体(30質量%溶液) 250部
・下記構造の顔料誘導体B 25部
・1-メトキシ-2-プロピルアセテート 750部
上記のようにして得られた顔料分散組成物を用いて、下記の着色感光性組成物を調製した。
・ジペンタエリスリトールヘキサアクリレート(光重合性化合物) 80部
・4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン(光重合開始剤) 50部
・メタクリル酸ベンジル/メタクリル酸(=75/35[質量比])共重合体(重量平均分子量:10,000)のプロピレングリコールモノメチルエーテルアセテート溶液(固形分30%)(アルカリ可溶性樹脂) 300部
・1-メトキシ-2-プロピルアセテート(溶剤) 390部
得られた着色感光性組成物(カラーレジスト液)を、100mm×100mmのガラス基板(1737、コーニング社製)上に、色濃度の指標となるx値が0.650となるように塗布し、90℃のオーブンで60秒間乾燥させた(プリベーク)。その後、塗布膜の全面に200mJ/cm2にて(照度20mW/cm2)露光し、露光後の塗布膜をアルカリ現像液CDK-1(富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液にて覆い、60秒間静止した。静止後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗布膜を220℃のオーブンで1時間加熱処理し(ポストベーク)、ガラス基板上にカラーフィルタ用の着色パターン(着色領域)を形成し、着色フィルタ基板(カラーフィルタ)を作製した。
作製された着色感光性組成物及び着色フィルタ基板(カラーフィルタ)について、実施例20と同様に、(1)コントラスト、及び、(2)アルカリ現像液に対する溶解性、及びアルカリ現像液中の懸濁物の評価を行った。加えて、(4)電圧保持率についても以下のように評価した。結果を下記表6にまとめて示す。
ITO電極つきのガラス基板(商品名:1737、コーニング社製)上に、前述の方法で得られた着色感光性組成物を乾燥後の膜厚が2.0μmとなるように塗布し、90℃のオーブンで60秒乾燥(プリベーク)した。その後、マスクを介さずに100mJ/cm2の露光(照度は20mW/cm2)を行い、アルカリ現像液(商品名:CDK-1、富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液を用いて25℃で現像し、塗布膜を230℃のオーブンで30分間加熱処理(ポストベーク)を施した。これにより、着色硬化膜が形成されたガラス基板を得た。
次に、この着色硬化膜が形成されたガラス基板と、ITO電極を所定形状に蒸着しただけの基板と、を5μmのガラスビーズを混合したシール剤で貼り合わせた後、メルク(株)社製液晶MJ971189(商品名)を注入して、液晶セルを作製した。
なお、電圧保持率は、16.7ミリ秒後の液晶セル電位差/0ミリ秒で印加した電圧の値である。
また、この電圧保持率を測定する際の条件は以下の通りである。
・電極間距離:5μm
・印加電圧パルス振幅:5V
・印加電圧パルス周波数:60Hz
・印加電圧パルス幅:16.67msec
-評価指標-
5:90%以上
4:85%以上90%未満
3:80%以上85%未満
2:75%以上80%未満
1:75%未満
<顔料分散組成物の調製>
下記組成(5)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメント・ブルー15:6(平均1次粒子径:20nm) 80部
・C.I.ピグメント・バイオレット23(平均1次粒子径:26nm) 20部
・前記構造の顔料誘導体B 15部
・下記表7に記載の特定重合体又は比較用重合体(30質量%溶液) 260部
・1-メトキシ-2-プロピルアセテート 750部
上記のようにして得られた顔料分散組成物を用いて、下記の着色感光性組成物を調製した。
・ジペンタエリスリトールヘキサアクリレート(光重合性化合物) 100部
・4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン(光重合開始剤) 30部
・メタクリル酸ベンジル/メタクリル酸(=75/25[質量比])共重合体(重量平均分子量:12,000)のプロピレングリコールモノメチルエーテルアセテート溶液(固形分30%)(アルカリ可溶性樹脂) 400部
・1-メトキシ-2-プロピルアセテート(溶剤) 390部
得られた着色感光性組成物(カラーレジスト液)を、100mm×100mmのガラス基板(1737、コーニング社製)上に、色濃度の指標となるx値が0.650となるように塗布し、90℃のオーブンで60秒間乾燥させた(プリベーク)。その後、塗布膜の全面に200mJ/cm2にて(照度20mW/cm2)露光し、露光後の塗布膜をアルカリ現像液CDK-1(富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液にて覆い、60秒間静止した。静止後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗布膜を220℃のオーブンで1時間加熱処理し(ポストベーク)、ガラス基板上にカラーフィルタ用の着色パターン(着色領域)を形成し、着色フィルタ基板(カラーフィルタ)を作製した。
作製された着色フィルタ基板(カラーフィルタ)について、実施例20と同様に、(1)コントラストの評価を行った。加えて、作製された着色感光性組成物の(5)塗布ムラについても以下のように評価した。結果を下記表7にまとめて示す。
スリット間隙が50μmの塗布有効幅が20mmのスリットヘッドを備えたスリット塗布装置を用いて、乾燥後の塗布膜厚が2μmになるようにスリットと基板間の間隙を調節して、50mm/秒の塗布スピードで前記着色感光性組成物の塗布液を、幅230mm、長さ300mm、厚み0.7mmの矩形状ガラス基板上に塗布し、塗布幅21mm、長さ260mmの塗布面を得た。塗布後、ホットプレートで90℃、60秒間プリベークした後、目視にて観察して塗布面のスジ状ムラの本数をカウントした。
A:塗布面にスジ状のムラが全くないもの
B:塗布面のスジ状のムラが1本~5本のもの
C:塗布面のスジ状のムラが6本以上もの
<顔料分散組成物の調製>
下記組成(6)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメント・グリーン36(平均1次粒子径:16nm) 55部
・C.I.ピグメント・イエロー150(平均1次粒子径:26nm) 45部
・下記表8に記載の特定重合体又は比較用重合体(30質量%溶液) 280部
・1-メトキシ-2-プロピルアセテート 750部
上記のようにして得られた顔料分散組成物を用いて、下記の着色感光性組成物を調製した。
・ジペンタエリスリトールヘキサアクリレート(光重合性化合物) 100部
・4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン(光重合開始剤) 30部
・メタクリル酸ベンジル/メタクリル酸(=75/25[質量比])共重合体(重量平均分子量:12,000)のプロピレングリコールモノメチルエーテルアセテート溶液(固形分30%)(アルカリ可溶性樹脂) 400部
・1-メトキシ-2-プロピルアセテート(溶剤) 390部
得られた着色感光性組成物(カラーレジスト液)を、100mm×100mmのガラス基板(1737、コーニング社製)上に、色濃度の指標となるx値が0.650となるように塗布し、90℃のオーブンで60秒間乾燥させた(プリベーク)。その後、塗膜の全面に200mJ/cm2にて(照度20mW/cm2)露光し、露光後の塗膜をアルカリ現像液CDK-1(富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液にて覆い、60秒間静止した。静止後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗膜を220℃のオーブンで1時間加熱処理し(ポストベーク)、ガラス基板上にカラーフィルタ用の着色パターン(着色領域)を形成し、着色フィルタ基板(カラーフィルタ)を作製した。
作製された着色感光性組成物及び着色フィルタ基板(カラーフィルタ)について、実施例20と同様に、(1)コントラスト、及び、(2)アルカリ現像液に対する溶解性、及びアルカリ現像液中の懸濁物の評価を行った。加えて、実施例37と同様に、作製された着色感光性組成物の(5)塗布ムラについても以下のように評価した。結果を下記表8にまとめて示す。
<顔料の微細化>
C.I.ピグメント・レッド254:50g、塩化ナトリウム400g、下記表9に記載の特定重合体又は比較用重合体溶液(30質量%溶液)40g、及びジエチレングリコール100gをステンレス製1ガロンニーダー(井上製作所製)に仕込み、6時間混練した。次に、この混合物を約3リットルの水中に投入し、ハイスピードミキサーで約1時間撹拌した後に、ろ過、水洗して塩化ナトリウム及び溶剤を除き、乾燥して特定重合体又は比較用重合体で被覆された加工顔料を得た。
得られた加工顔料の平均1次粒子径:24nmであった。
・上記加工顔料 100部
・ルーブリゾール社製「ソルスパース 24000」(30質量%溶液) 150部
・1-メトキシ-2-プロピルアセテート 600部
得られた顔料分散組成物について、実施例1と同様にして、(1)粘度、(2)コントラスト、及び(3)析出性について、評価を行った。結果を表9にまとめて示す。
実施例48~50、比較例17、18で得られた顔料分散組成物を用いて、下記の着色感光性組成物を調製した。
・ジペンタエリスリトールヘキサアクリレート(光重合性化合物) 100部
・4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン(光重合開始剤) 30部
・メタクリル酸ベンジル/メタクリル酸(=75/25[質量比])共重合体(重量平均分子量:12,000)のプロピレングリコールモノメチルエーテルアセテート溶液(固形分30%)(アルカリ可溶性樹脂) 400部
・1-メトキシ-2-プロピルアセテート(溶剤) 390部
また、作製された着色感光性組成物及び着色フィルタ基板(カラーフィルタ)について、実施例43と同様に、(1)コントラスト、及び、(2)アルカリ現像液に対する溶解性、及びアルカリ現像液中の懸濁物、並びに(5)塗布ムラについて評価した。結果を下記表10にまとめて示す。
<レジスト液の調製>
下記組成の成分を混合して溶解し、レジスト液を調製した。
・プロピレングリコールモノメチルエーテルアセテート 19.20部
・乳酸エチル 36.67部
・メタクリル酸ベンジル/メタクリル酸/メタクリル酸-2-ヒドロキシエチル(モル比=60/22/18)共重合体の40%プロピレングリコールモノメチルエーテルアセテート(PGMEA)溶液 30.51部
・ジペンタエリスリトールヘキサアクリレート 12.20部
・重合禁止剤(p-メトキシフェノール) 0.0061部
・フッ素系界面活性剤(F-475、大日本インキ化学工業(株)製) 0.83部
・TAZ-107(みどり化学社製) 0.586部
6inchシリコンウエハーを、オーブン中で200℃下で30分間、加熱処理した。次いで、このシリコンウエハー上に前記レジスト液を乾燥膜厚が1.5μmになるように塗布し、更に220℃のオーブン中で1時間加熱乾燥させて下塗り層を形成し、下塗り層付シリコンウエハー基板を得た。
下記組成(8)の成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・下記表11に記載の顔料 100部
・下記表11に記載の特定重合体又は比較用重合体(30質量%溶液) 200部
・1-メトキシ-2-プロピルアセテート 750部
上記で得られた顔料分散組成物を用い、下記組成となるように撹拌、混合を行なって着色感光性組成物の溶液を調製した。
・CGI-124 20部
(チバ・スペシャルティ・ケミカルズ社製;オキシム系光重合開始剤)
・ジペンタエリスリトールヘキサアクリレート(光重合性化合物) 20部
・TO-756(東亞合成社製、光重合性化合物) 35部
・プロピレングリコールモノメチルエーテルアセテート 20部
(感度の評価)
上記のように調製した着色感光性組成物を、前述の方法で得られた下塗り層付シリコンウエハーの下塗り層上に塗布し、塗布膜を形成した。そして、この塗布膜の乾燥膜厚が0.7μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行なった。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、365nmの波長でパターンが1.5μm四方のIslandパターンマスクを通して50~1200mJ/cm2の範囲で種々の露光量で露光した。
その後、露光後の塗布膜が形成されているシリコンウエハー基板をスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載せ、CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間、パドル現像を行ない、シリコンウエハー上に着色パターン(着色領域)を形成した。
輝度分布を下記方法で解析し、平均からのズレが±5%以内である画素が全画素数に占める割合をもとに色ムラを評価した。評価基準は以下の通りである。
まず、上記のように調製した着色感光性組成物を、前述の方法で得られた下塗り層付シリコンウエハーの下塗り層上に塗布し、塗布膜を形成した。そして、この塗布膜の乾燥膜厚が0.7μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行なった。
また、デジタル変換したデータは、撮影画像をRGBの3原色それぞれの輝度を0~255までの256階調の濃度分布として数値化して保存した。
本実施例においては、128万画素のデジタルカメラで光学1000倍の画像を撮影したため、実基板上の2μmは撮影画像上の2mmとなり、ディスプレイ上における画像サイズが452mm×352mmであったことから、一つの領域における総区画数は39776個であった。
-評価基準-
A:平均からのズレが2%未満
B:平均からのズレが2%以上5%未満
C:平均からのズレが5%以上
また、前記実施例54~56の着色感光性組成物から得られたカラーフィルタを備えた固体撮像素子を作製したところ、得られた固体撮像素子は、色ムラの発生もなく、優れた色分解性能を有することが分かった。
M-11(前述の例示化合物M-11) 14.0g、末端にメタクリロイル基を有するポリメチルメタクリレート(AA-6:東亜合成社製)105.0g、アクリル酸 21.0g、n-ドデシルメルカプタン5.6gおよびメトキシプロピレングリコール327gを、窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して75℃まで昇温する。これに2,2-アゾビス(2-メチルプロピオン酸ジメチル)(和光純薬(株)製、V-601)を1.1g加え、75℃にて2時間加熱攪拌を行った。その後、さらにV-601を1.1g加えて2時間過熱攪拌した後、90℃に昇温して2時加熱攪拌した後、重合体1の30%溶液を得た。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、1.9万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、117mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、20/65/15であった。
M-11 14.0g、ヒドロキシエチルメタクリレートのカプロラクトン5mol付加オリゴマー(プラクセルFM5、ダイセル化学工業(株)製)105.0g、アクリル酸 21.0g、n-ドデシルメルカプタン3.3gおよびメトキシプロピレングリコール327gを、窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して75℃まで昇温する。これに2,2-アゾビス(2-メチルプロピオン酸ジメチル)(和光純薬(株)製、V-601)を1.2g加え、75℃にて2時間加熱攪拌を行った。その後、さらにV-601を1.2g加えて2時間過熱攪拌した後、90℃に昇温して2時加熱攪拌した後、重合体2の30%溶液を得た。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、1.5万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、117mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、20/65/15であった。
合成例1と同様にして単量体A-5を合成した。
M-11 14.0g、上記で合成したA-5 105.0g、アクリル酸 21.0g、n-ドデシルメルカプタン3.1gおよびメトキシプロピレングリコール327gを、窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して75℃まで昇温した。これに2,2-アゾビス(2-メチルプロピオン酸ジメチル)(和光純薬(株)製、V-601)を1.2g加え、75℃にて2時間加熱攪拌を行った。その後、さらにV-601を1.2g加えて2時間過熱攪拌した後、90℃に昇温して2時加熱攪拌した後、重合体3の30%溶液を得た。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、2.3万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、117mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、20/65/15であった。
ベンジルメタクリレート 28.0g、上記で合成したA-5 91.0g、アクリル酸 21.0g、n-ドデシルメルカプタン4.2gおよびメトキシプロピレングリコール327gを、窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して75℃まで昇温する。これに2,2-アゾビス(2-メチルプロピオン酸ジメチル)(和光純薬(株)製、V-601)を1.0g加え、75℃にて2時間加熱攪拌を行った。その後、さらにV-601を1.0g加えて2時間過熱攪拌した後、90℃に昇温して2時加熱攪拌した後、重合体4の30%溶液を得た。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、2.1万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、117mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、20/65/15であった。
ベンジルメタクリレート 28.0g、上記で合成したA-5 105.0g、アクリル酸 7.0g、n-ドデシルメルカプタン3.8gに変更した以外は、重合体4と同様に合成した。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、2.3万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、39mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、20/65/5であった。
ベンジルメタクリレート 14.0g、上記で合成したA-5 84.0g、アクリル酸 42.0g、n-ドデシルメルカプタン4.5gに変更した以外は、重合体4と同様に合成した。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、1.8万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、234mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、10/60/30であった。
M-11 14.0g、末端にメタクリロイル基を有するポリメチルメタクリレート(AA-6:東亜合成社製)105.0g、メタクリル酸 21.0g、n-ドデシルメルカプタン5.6gおよびメトキシプロピレングリコール327gを、窒素置換した三口フラスコに導入し、攪拌機(新東科学(株):スリーワンモータ)にて攪拌し、窒素をフラスコ内に流しながら加熱して75℃まで昇温した。これに2,2-アゾビス(2-メチルプロピオン酸ジメチル)(和光純薬(株)製、V-601)を1.1g加え、75℃にて2時間加熱攪拌を行った。その後、さらにV-601を1.1g加えて2時間過熱攪拌した後、90℃に昇温して2時加熱攪拌し、比較重合体1の30%溶液を得た。
得られた高分子化合物の重量平均分子量を、ポリスチレンを標準物質としたゲルパーミエーションクロマトグラフィー法(GPC)により測定した結果、2.2万であった。
また、水酸化ナトリウムを用いた滴定から、固形分あたりの酸価は、98mgKOH/g、1H-NMRから求めた繰り返し単位組成比(質量比)は、20/65/15であった。
下記表12で表される組成の成分を混合し、ホモジナイザーを用いて回転数3,000rpmで3時間撹拌して混合し、顔料を含む混合溶液を調製した。
続いて、得られた混合溶液を、さらに0.2mmφジルコニアビーズを用いたビーズ分散機ディスパーマット(GETZMANN社製)にて6時間分散処理を行ない、その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、顔料分散組成物を得た。
得られた顔料分散組成物について下記の評価を行った。結果を表12に示す。
(1)粘度の測定、評価
得られた顔料分散組成物について、E型粘度計を用いて、分散直後の顔料分散組成物の粘度η1、および分散後(60℃にて)10日間経過した後の顔料分散組成物の粘度η2を測定し、増粘の程度を評価した。ここで、粘度が低いことは、分散剤に起因する粘度の上昇が抑制されており、顔料の分散性及び分散安定性が良好であることを示す。
得られた顔料分散組成物をガラス基板上に塗布し、乾燥後の塗布膜の厚さが1μmになるようにサンプルを作製した。2枚の偏光板の間に、このサンプルを置き、偏光板が平行時の輝度と直行時の輝度とを(トプコン社製 BM-5)にて測定し、コントラスト=平行時の輝度/直行時の輝度 を求めた。ここで、コントラストが高いことは、顔料が高度に微細化された状態で均一に分散されていることを示す。
顔料R1: C.I.ピグメントレッド254 平均1次粒子径30nm
顔料R2: C.I.ピグメントレッド254 平均1次粒子径23nm
塩基性グラフト型重合体: ドデカン酸でε-カプロラクトンを開環重合して得られたポリエステルとポリエチレンイミンをアミド化反応させて得た重合体
重量平均分子量:20000
PGMEA: 1-メトキシ-2-プロピルアセテート
下記組成(11)~(14)の各成分を混合し、ホモジナイザーを用いて回転数3,000rpmで3時間撹拌して混合し、顔料を含む混合溶液を調製した。
〔組成(11)〕
・C.I.ピグメントレッド254 平均1次粒径 25μm 110部
・分散剤として重合体1(30質量%溶液) 200部
・1-メトキシ-2-プロピルアセテート 750部
・C.I.ピグメントレッド254 平均1次粒径 25μm 110部
・分散剤として重合体3(30質量%溶液) 200部
・1-メトキシ-2-プロピルアセテート 750部
・C.I.ピグメントレッド254 平均1次粒径 25μm 110部
・分散剤として重合体1(30質量%溶液) 100部
・塩基性グラフト型分散剤(実施例65で用いたものと同一) 30部
・1-メトキシ-2-プロピルアセテート 820部
〔組成(14)〕
・C.I.ピグメントレッド254 平均1次粒径 25μm 110部
・分散剤として重合体3(30質量%溶液) 100部
・塩基性グラフト型分散剤(実施例65で用いたものと同一) 30部
・1-メトキシ-2-プロピルアセテート 820部
・C.I.ピグメントレッド254 平均1次粒径 25μm 110部
・分散剤として比較重合体1(30質量%溶液) 200部
・1-メトキシ-2-プロピルアセテート 750部
得られた顔料分散組成物を用いて、顔料濃度35質量%と42質量%の光硬化性組成物を作製した。
得られた光硬化性組成物(カラーレジスト液)を、100mm×100mmのガラス基板(1737、コーニング社製)上に、色濃度の指標となるx値が0.650となるように塗布し、90℃のオーブンで60秒間乾燥させた(プリベーク)。その後、塗膜の全面に200mJ/cm2にて(照度20mW/cm2)露光し、露光後の塗膜をアルカリ現像液CDK-1(富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液にて覆い、一定時間静止した。静止後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗膜を220℃のオーブンで1時間加熱処理し(ポストベーク)、ガラス基板上にカラーフィルタ用の着色パターン(着色樹脂被膜)を形成し、着色フィルタ基板(カラーフィルタ)を作製した。
作製した着色フィルタ基板(カラーフィルタ)について、以下のようにして評価を行なった。結果を下記表13に示す。
(1)コントラスト
着色フィルタ基板の着色樹脂被膜の上に偏光板を置いて着色樹脂被膜を挟み込み、偏光板が平行時の輝度と直交時の輝度とを、トプコン社製のBM-5を用いて測定し、平行時の輝度を直交時の輝度で除して得られる値(=平行時の輝度/直交時の輝度)を、コントラストを評価するための指標とした。値が大きいほど高コントラストであることを示す。
現像時間を20秒、30秒、50秒、70秒と変更した基板を光学顕微鏡にて、未露光部のガラス基板への残り具合を観察した。点数が高いほどよい。
現像時間20秒でも残渣が全くない:5
現像時間30秒以上では残渣が全くないが、現像時間20秒では、残渣がある:4
現像時間50秒以上では残渣が全くないが、現像時間30秒では、残渣がある:3
現像時間70秒以上では残渣が全くないが、現像時間50秒以下では、残渣がある:2
現像時間70秒でも、未露光部に残渣がある:1
スリット塗布における異物欠陥発生の有無を評価する代替法として以下の再溶解性の評価を行った。
各実施例及び比較例の光硬化性組成物をそれぞれ、50mm角のガラス基板にスピンコート法により乾燥後の膜厚が1μmとなるよう塗布し、60分風乾した。その後、該光硬化性組成物を形成する溶剤1-メトキシ-2-プロピルアセテート(以下、PGMEAともいう。)を1μLずつ滴下した。6滴以下で溶解したものをA、7~8滴で溶解したものをB、9滴以上滴下しても再溶解しないものをCとした。
尚、スリット塗布による異物欠陥発生率が0%となるのは、再溶解性試験におけるPGMEA 6滴以下で溶解する膜に相当した。
重合性化合物:ジペンタエリスリトールペンタヘキサアクリレート
光重合開始剤:4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン
アルカリ可溶性樹脂:メタクリル酸ベンジル/メタクリル酸(=75/25[質量比])共重合体(重量平均分子量:12,000)の1-メトキシ-2-プロピルアセテート溶液(固形分30%)
溶剤:1-メトキシ-2-プロピルアセテート
下記組成(16)~(19)の各成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・C.I.ピグメントグリーン36(平均1次粒子径 20nm) 55部
・C.I.ピグメントイエロー150(平均1次粒子径 24nm) 45部
・分散剤として重合体1(30質量%溶液) 180部
・1-メトキシ-2-プロピルアセテート 750部
〔組成(17)〕
・C.I.ピグメントグリーン36(平均1次粒子径 20nm) 55部
・C.I.ピグメントイエロー150(平均1次粒子径 24nm) 45部
・分散剤として重合体3(30質量%溶液) 180部
・1-メトキシ-2-プロピルアセテート 750部
・C.I.ピグメントグリーン36(平均1次粒子径 20nm) 55部
・C.I.ピグメントイエロー150(平均1次粒子径 24nm) 45部
・分散剤として重合体3(30質量%溶液) 60部
・塩基性グラフト型分散剤(実施例65で用いたものと同一) 36部
・1-メトキシ-2-プロピルアセテート 820部
・C.I.ピグメントグリーン36(平均1次粒子径 20nm) 55部
・C.I.ピグメントイエロー150(平均1次粒子径 24nm) 45部
・分散剤として比較重合体1(30質量%溶液) 180部
・1-メトキシ-2-プロピルアセテート 750部
・C.I.ピグメントグリーン36(平均1次粒子径 20nm) 55部
・C.I.ピグメントイエロー150(平均1次粒子径 24nm) 45部
・分散剤として重合体3(30質量%溶液) 40部
・塩基性グラフト型分散剤(実施例65で用いたものと同一) 36部
・1-メトキシ-2-プロピルアセテート 750部
得られた顔料分散組成物を用いて、顔料濃度35質量%と42質量%の光硬化性組成物を作製した。
<光硬化組成物を用いたカラーフィルタの調製>
得られた光硬化性組成物(カラーレジスト液)を、100mm×100mmのガラス基板(1737、コーニング社製)上に、色濃度の指標となるy値が0.650となるように塗布し、90℃のオーブンで60秒間乾燥させた(プリベーク)。その後、塗膜の全面に200mJ/cm2にて(照度20mW/cm2)露光し、露光後の塗膜をアルカリ現像液CDK-1(富士フイルムエレクトロニクスマテリアルズ(株)製)の1%水溶液にて覆い、一定時間静止した。静止後、純水をシャワー状に散布して現像液を洗い流した。そして、上記のように露光及び現像が施された塗膜を220℃のオーブンで1時間加熱処理し(ポストベーク)、ガラス基板上にカラーフィルタ用の着色パターン(着色樹脂被膜)を形成し、着色フィルタ基板(カラーフィルタ)を作製した。
作製した着色フィルタ基板(カラーフィルタ)について、実施例71と同様にして評価を行なった。結果を下記表14に示す。
重合性化合物:ジペンタエリスリトールペンタヘキサアクリレート
光重合開始剤:4-[o-ブロモ-p-N,N-ジ(エトキシカルボニル)アミノフェニル]-2,6-ジ(トリクロロメチル)-S-トリアジン
アルカリ可溶性樹脂:メタクリル酸ベンジル/メタクリル酸(=75/25[質量比])共重合体(重量平均分子量:12,000)の1-メトキシ-2-プロピルアセテート溶液(固形分30%)
溶剤:1-メトキシ-2-プロピルアセテート
下記組成の成分を混合して溶解し、レジスト液を調製した。
レジスト液の組成
・1-メトキシ-2-プロピルアセテート 19.20部
・乳酸エチル 36.67部
・メタクリル酸ベンジル/メタクリル酸/メタクリル酸-2-ヒドロキシエチル(モル比=60/22/18)共重合体の40% 1-メトキシ-2-プロピルアセテート(PGMEA)溶液 30.51部
・ジペンタエリスリトールヘキサアクリレート 12.20部
・重合禁止剤(p-メトキシフェノール) 0.0061部
・フッ素系界面活性剤 0.83部
(F-475、大日本インキ化学工業(株)製)
・光重合開始剤 (みどり化学社製 TAZ-107) 0.586部
6inchシリコンウエハを、オーブン中で200℃下で30分間、加熱処理した。次いで、このシリコンウエハ上に前記レジスト液を乾燥膜厚が1.5μmになるように塗布し、更に220℃のオーブン中で1時間加熱乾燥させて下塗り層を形成し、下塗り層付シリコンウエハ基板を得た。
下記組成(21)、及び(22)の各成分を混合し、ホモジナイザーを用いて回転数3,000r.p.m.で3時間撹拌して混合し、顔料を含む混合溶液を調製した。
・顔料(表15記載の顔料) 100部
・分散剤として重合体1(30質量%溶液) 200部
・1-メトキシ-2-プロピルアセテート 750部
・顔料(表15記載の顔料) 100部
・分散剤として比較重合体1(30質量%溶液) 200部
・1-メトキシ-2-プロピルアセテート 750部
上記で得られた各顔料分散液を用い、下記組成となるように撹拌、混合を行なって光硬化性組成物を調製した。
〈組成〉
・上記の顔料分散液 1000部
・光重合開始剤(チバ・スペシャルティ・ケミカルズ社製 CGI-124)
20部
・重合性化合物 ジペンタエリスリトールヘキサアクリレート 20部
・重合性化合物(東亞合成社製、TO-756) 35部
・1-メトキシ-2-プロピルアセテート 20部
上記のように調製した光硬化性組成物を、前述の下塗り層付シリコンウエハの下塗り層上に塗布し、着色層(塗布膜)を形成した。そして、この塗布膜の乾燥膜厚が0.7μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行なった。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、365nmの波長でパターンが1.5μm四方のIslandパターンマスクを通して50~1200mJ/cm2の範囲で種々の露光量で露光した。
前述の下塗り層付シリコンウエハの作成と同様にして、ガラス板上にレジスト液を塗布して下塗り層付ガラス基板を作成し、光硬化性組成物を、下塗り層付きガラス上に塗布し、着色層(塗布膜)を形成した。この塗布膜の乾燥膜厚が0.7μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行なった。この塗布済みガラス板の輝度分布を、顕微鏡MX-50(オリンパス社製)にて撮影した画像から解析した。
輝度分布を解析し、平均からのズレが±5%以内である画素が全画素数に占める割合をもとに色ムラを評価した。評価基準は以下の通りである。
A:平均からのズレが±5%以内である画素が全画素数中の99%以上
B:平均からのズレが±5%以内である画素が全画素数中の95%以上99%未満
C:平均からのズレが±5%以内である画素が全画素数中の95%未満
本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (18)
- 前記(a)高分子化合物が、側鎖に酸基を50mgKOH/g以上200mgKOH/g以下の範囲で有する請求項1に記載の顔料分散組成物。
- 前記(a)高分子化合物が、側鎖に複素環基を有する請求項1又は請求項2に記載の顔料分散組成物。
- カラーフィルタにおける着色領域の形成に用いられる請求項1~請求項3のいずれか1項に記載の顔料分散組成物。
- 請求項1~請求項3のいずれか1項に記載の顔料分散組成物、光重合性化合物、及び光重合開始剤を含有する着色感光性組成物。
- 基板上に、請求項5に記載の着色感光性組成物により形成された着色領域を有するカラーフィルタ。
- 請求項6に記載のカラーフィルタを備える液晶表示素子。
- 請求項6に記載のカラーフィルタを備える固体撮像素子。
- (A)主鎖にアクリル酸を5~30質量%共重合したグラフト型高分子重合体、(B)顔料、および(C)有機溶剤を含有する顔料分散組成物。
- 前記(A)主鎖にアクリル酸を5~30質量%共重合したグラフト型高分子重合体が、さらに側鎖に複素環構造を含有し、且つ、重量平均分子量1,000~100,000である請求項9に記載の顔料分散組成物。
- 前記(B)顔料の平均1次粒子径が、10~25nmの範囲である請求項9または請求項10に記載の顔料分散組成物。
- さらに、(D)塩基性グラフト型高分子化合物を含有する請求項9~請求項11のいずれか1項に記載の顔料分散組成物。
- 前記顔料分散組成物に含まれる高分子化合物の総質量を、前記(B)顔料と(E)顔料誘導体との総質量で除した値が、0.55以下である請求項9~請求項12のいずれか1項に記載の顔料分散組成物。
- 請求項9~請求項13のいずれか1項に記載の顔料分散組成物と、(F)重合性化合物と、(G)光重合開始剤と、を含有する光硬化性組成物。
- 顔料濃度が35質量%以上である請求項14記載の光硬化性組成物。
- 請求項14または請求項15に記載の光硬化性組成物を用いてなる着色パターンを有するカラーフィルタ。
- 請求項16に記載のカラーフィルタを備える液晶表示装置。
- 請求項16に記載のカラーフィルタを備える固体撮像素子。
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EP09722925.6A EP2270110B1 (en) | 2008-03-17 | 2009-03-12 | Pigment-dispersed composition, colored photosensitive composition, photocurable composition, color filter, liquid crystal display element, and solid image pickup element |
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US12/922,849 US8362140B2 (en) | 2008-03-17 | 2009-03-12 | Pigment-dispersed composition, colored photosensitive composition, photocurable composition, color filter, liquid crystal display device, and solid-state image pickup device |
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Also Published As
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TW201000569A (en) | 2010-01-01 |
US20110014401A1 (en) | 2011-01-20 |
KR101671249B1 (ko) | 2016-11-01 |
KR101654666B1 (ko) | 2016-09-06 |
KR20100124767A (ko) | 2010-11-29 |
CN101978004B (zh) | 2013-11-06 |
EP2270110B1 (en) | 2015-02-25 |
EP2270110A1 (en) | 2011-01-05 |
EP2270110A4 (en) | 2011-04-27 |
TWI460233B (zh) | 2014-11-11 |
KR20160014785A (ko) | 2016-02-11 |
US8362140B2 (en) | 2013-01-29 |
CN101978004A (zh) | 2011-02-16 |
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