WO2003081298A1 - Pigment-dispersed resist composition for color filters - Google Patents

Pigment-dispersed resist composition for color filters Download PDF

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Publication number
WO2003081298A1
WO2003081298A1 PCT/JP2003/003781 JP0303781W WO03081298A1 WO 2003081298 A1 WO2003081298 A1 WO 2003081298A1 JP 0303781 W JP0303781 W JP 0303781W WO 03081298 A1 WO03081298 A1 WO 03081298A1
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WO
WIPO (PCT)
Prior art keywords
pigment
orifice
resist composition
dispersion
color filter
Prior art date
Application number
PCT/JP2003/003781
Other languages
French (fr)
Japanese (ja)
Inventor
Kazunori Itoh
Masanori Kano
Original Assignee
Sakata Inx Corp.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sakata Inx Corp. filed Critical Sakata Inx Corp.
Priority to JP2003578977A priority Critical patent/JPWO2003081298A1/en
Priority to KR10-2004-7015120A priority patent/KR20050006135A/en
Publication of WO2003081298A1 publication Critical patent/WO2003081298A1/en

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Classifications

    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/20—Jet mixers, i.e. mixers using high-speed fluid streams
    • B01F25/25—Mixing by jets impinging against collision plates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F2025/91—Direction of flow or arrangement of feed and discharge openings
    • B01F2025/915—Reverse flow, i.e. flow changing substantially 180° in direction

Definitions

  • the present invention relates to a pigment dispersion resist composition for a color filter, and more particularly, to a color filter having extremely excellent pigment dispersibility and pigment dispersion stability, and excellent in hue (transparency, contrast) and coating film smoothness.
  • the present invention relates to a pigment dispersion resist composition for use. Background art
  • a color filter consists of two or more types of fine bands (stripe) of different hues arranged in parallel on the surface of a transparent substrate such as glass, or one in which fine pixels are arranged in a constant vertical and horizontal direction. ing.
  • the pixel size has a fine shape of several 100 to several 100 / im, and is arranged in a predetermined order for each hue. For this reason, various methods have been proposed for producing color filters.
  • color filters require high transparency and uniformity of film thickness with high precision, so conventionally, a photosensitive solution such as dichromic acid was used in aqueous solutions of dyeable natural polymers such as gelatin and casein.
  • a photo-lithography method is used to form a pixel pattern, and the above-described process of dyeing the pixel pattern into a desired color to obtain a color pattern is repeated three times to obtain a transparent colored fine pattern of three colors. It was manufactured by using a so-called dyeing method.
  • a resist composition using the active energy ray-curable resin described above has been used.
  • a coloring material used in such a resist composition for forming a color filter instead of a dye having excellent color characteristics but having limited heat and light resistance, a pigment having excellent light and heat resistance is used. Used in a dispersing machine such as a ball mill, an attritor, and a sand mill. More recently, pigments called high-grade organic pigments have come to be used, for example, because they require a clear hue and high fastness.
  • pigment dispersibility an initial fine dispersion stability and dispersion stability over time (hereinafter collectively referred to as pigment dispersibility), and a fluidity (very similar to Newtonian flow). Fluidity is required), so it is difficult to obtain the original clear hue, sedimentation due to agglomeration and decrease in fluidity occur, and the coating film smoothness also deteriorates. There are many problems.
  • the resist composition is applied to a transparent substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance and dried.
  • the pixels of each color are obtained by exposing and developing the coating film in a desired pattern.
  • it has been required to have a particularly sharp hue and to have a more precise coating smoothness.
  • These fine organic pigments have been further finely dispersed to satisfy this requirement. To achieve this, the above problems of dispersion stability and liquidity are important research issues that must be resolved.
  • JP-A-07-198933 discloses a microfluidizer.
  • a method using a high-pressure dispersing machine such as (Microfriedix), Nanomizer-1 (Nanomizer-1), and Ultimatemizer-1 (Sugino Machine) is disclosed.
  • the obtained pigment dispersions are all sufficiently improved in pigment dispersibility and fluidity as described above.
  • the pigment-dispersed resist composition for a color filter using the composition has a problem that a clear hue cannot be obtained and the coating film has poor smoothness.
  • the present invention has been made in view of the problems of such a pigment-dispersed resist composition for a color filter, and makes the pigment into fine particles (under a narrow particle size distribution) under the condition that the generation of an overdispersed substance is extremely reduced.
  • a color filter having a clear hue (transparency and contrast) and excellent coating smoothness can be obtained.
  • An object of the present invention is to provide a pigment-dispersed resist composition that can be obtained.
  • a linear orifice having no curved portion or bent portion and a linear orifice connected to the orifice have a large diameter.
  • a high-pressure emulsifier equipped with a hollow member of the formula (1) a mixture containing at least a pigment, an organic solvent, and a pigment dispersant as essential components at a flow rate of 100 to 100 Om / sec under pressure.
  • the pigment is further dispersed by a high-pressure emulsifier that discharges the mixture from the orifice into the mixed liquid that has flowed out and stays in the hollow member.
  • the inventors have found that the problem can be easily solved, and have reached the present invention.
  • the present invention provides (1) a pigment-dispersed resist composition for a color filter, which contains at least a pigment dispersion, a photopolymerizable compound, and a photopolymerization initiator.
  • a high-pressure emulsifier equipped with a linear orifice having no or bent portion and a linear hollow member having a diameter larger than the diameter of the orifice connected to the orifice. Selected from the group consisting of ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents, and nitrogen-containing organic solvents at 100 to 220 ° C.
  • a mixture containing at least one organic solvent and a pigment dispersant is passed through the orifice under pressure at a flow rate of 100 to 100 Om / sec. Further, the mixture is removed from the orifice. Staying in the hollow member, by ejecting the mixed solution that flows out above relates to an pigment dispersing composition for a color filter in which a pigment is dispersed.
  • the photopolymerizable compound and the photopolymerization initiator constituting the pigment dispersion resist composition for a color filter of (1) may be contained before or after the pigment dispersion treatment.
  • a component other than the photopolymerizable compound and the photopolymerization initiator constituting the pigment dispersion resist composition for a filter may be contained before or after the pigment dispersion treatment. That is, for example, the mixed solution of the pigment, the organic solvent, and the pigment dispersant further contains a photopolymerizable compound and a photopolymerization initiator, and after the pigment is dispersed, the photopolymerizable compound and the photopolymerization initiator are mixed.
  • the pigment for a color filter which is obtained without addition, may be a dispersion resist composition (or one of which is contained before the dispersion treatment and the other is contained after the dispersion treatment).
  • the present invention also relates to (2) a pigment dispersion resist composition for a color filter, wherein the pigment dispersant according to the above (1) is a pigment dispersant having a basic group.
  • the present invention also provides (3) a pigment dispersion resist composition for a color filter as described in (1) or (2) above, wherein the mixed liquid is a mixed liquid obtained by performing a premittastic treatment in a non-media type mixing apparatus.
  • the present invention provides an orifice having a fine diameter and a diameter larger than the orifice diameter.
  • the most characteristic feature is that the pigment is dispersed using a high-pressure emulsifier in which the hollow member is connected.
  • the pigment dispersion in the pigment-dispersed resist yarn for the color filter is firstly retained in a hollow member having a diameter larger than the diameter of the orifice due to the shearing action when the mixture passes through the orifice.
  • this pigment dispersion is very small compared to the tube diameter of a conventional high-pressure emulsifier, a sufficient stress for dispersing the pigment can be generated even in a non-collision type method.
  • the stress required to disperse the pigment can be easily controlled.
  • the pigment dispersing method of the present invention provides the optimal dispersing force (The cohesive force between the primary particles ⁇ dispersion force ⁇ the crushing strength of the primary particles) can be applied uniformly, and even with high-grade organic pigments, without excessively pulverized particles or undispersed particles This makes it possible to uniformly disperse the pigment down to the primary particles.
  • the pigment dispersant is immediately adsorbed on the hydrophobic surface of the uniformly dispersed pigment, and is thermodynamically stabilized. Good fluidity and dispersion stability can be obtained.
  • the present inventors have found that by using a pigment dispersion obtained by this pigment dispersion method in a pigment dispersion resist composition for one color filter, pigment dispersibility and fluidity are improved, and coating film smoothness is improved. It has been found that the hue is sharp. Further, the pigment-dispersed resist composition for a color filter of the present invention will be described in detail.
  • Pigments that can be used in the present invention (pigments suitable for coloring images such as red, green, blue, and black) ) has clear hue and high fastness, C. IP gement Red 19, 38, 43, 88, 122.123, 144, 149, 166, 168, 177, 178, 1 79, 188. 190, 207, 208, 209, 216, 224, 226, 242, 254 264 red pigments; C. I. Pigment Blue 15: 1, 15 3, 15 : 4, 15: Blue color of 6, 16, 22, 29, 60, 64; C. IPigment Li reen 1
  • a single pigment in order to obtain a red color image, a green color pigment, and a blue color pigment, a single pigment may be used, or other pigments may be mixed and used.
  • a red color image a single red pigment may be used, or a red pigment mixed with a yellow pigment, an orange pigment, or the like may be used, and a green color image may be used.
  • a blue colored image a single green pigment may be used, or a green pigment mixed with a yellow pigment may be used.
  • a blue pigment may be used, or a blue pigment mixed with a violet pigment or the like and toned may be used.
  • pigment dispersant that can be used in the present invention, a pigment dispersant conventionally used for dispersing a pigment that does not hinder photosensitivity can be used.
  • pigment-dispersing agents that are soluble in pigment and have a pigment dispersing property are also included in the present invention.
  • polyester polymer pigment dispersants Specifically, polyester polymer pigment dispersants, ataryl polymer pigment dispersants, polyurethane polymer pigment dispersants, pigment derivatives, cationic surfactants, nonionic surfactants, anionic surfactants And the like.
  • These pigment dispersants are They may be used alone or in combination of two or more.
  • a pigment dispersant containing a basic group is preferable as the pigment dispersant, since good pigment dispersibility can be obtained.
  • pigment dispersant containing a basic group As the pigment dispersant containing a basic group,
  • Amino groups of polyamine compounds for example, poly (lower alkyleneamine) such as polyallylamine, polybulamine, and polyethylenimine;
  • Alcohols such as methoxypolyethylene glycol and polyesters having one hydroxyl group such as hydraprotatonone polyester, and 2-3 isocyanate group-reactive functional groups in the isocyanate group of the polyisocyanate compound.
  • reaction product obtained by adding a polyether chain to a low-molecular-weight amino compound a reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group.
  • Meta At least one selected from acrylates and acrylates; and basics such as atarylamide, metharylamide, N-methylolamide, bulimidazole, bulpyridine, a monomer having an amino group and a polyproprolactone skeleton.
  • Copolymers of at least one of the group-containing polymerizable monomers with at least one of styrene, a styrene derivative, and other polymerizable monomers are exemplified. Among them, the above (1) to (6) are preferable.
  • the amount of the pigment dispersant used in the present invention is usually 1 to 200 parts by mass, preferably 1 to 60 parts by mass, based on 100 parts by mass of the pigment.
  • the amount of the pigment dispersant used is less than 1 part by mass, the pigment dispersibility decreases, while when it exceeds 200 parts by mass, the developability may decrease.
  • organic solvent examples include ester-based organic solvents and ether-based organic solvents having a boiling point of 100 to 220 ° C. at normal pressure (1.013 ⁇ 10 2 kPa). And at least one selected from ether ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents and nitrogen-containing organic solvents, and preferably contains these mainly. .
  • ethylene glycol monomethinolate ether ethylene glycol monoethylenolate ether, ethylene glycol monoisopropinole ether, ethylene glycol monomonotinole ether, dimethylene glycol / lemonomethinole ether, Diethylene glycol monoethyl ether ether, pyrene glycol monomethyl ether ether, propylene glycol resin monoethyl ether, propylene glycol monobutyl ether, diethylene glycol ethyl ether, diethylene glycol ethyl dimethyl ether, diethylene glycol ethanol Ether-based organic solvents such as ethyl ethyl ether; ethylene glycol monomethyl ether oleate acetate; ethylene glycol monomethyl ether enoate acetate; Ether ester organic solvents such as styrene glycol monobutyl ether acetate, propylene dalicol monomethinoleate eno
  • organic solvents can be used alone or in combination of two or more. Further, as the organic solvent, an organic solvent capable of dissolving or dispersing the pigment dispersant, for example, alcohol or the like can be used as long as the performance of the pigment-dispersed resist composition for a color filter is not deteriorated.
  • the organic solvent in the pigment dispersion resist composition for a color filter may be an ether organic solvent having a boiling point of 100 to 220 ° C or an ester in terms of solubility, pigment dispersibility, coatability, etc. At least one selected from the group consisting of organic solvents, ether ester organic solvents, ketone organic solvents, nitrogen-containing organic solvents, etc., in an organic solvent at 50% by mass or more, particularly 70% by mass / 0 %. What contains above is preferable.
  • ether organic solvents examples include diethylene glycol dimethyl ether, diethylene glycol methinoleetinooleate, ethylene glycolone monomethinoleate teracetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl etherate / reacetate, cycloate Hexanone, 2-heptanone, 2-ethylhydroxypropionate, 3-methyl-3-methoxybutylpropionate, pionate, 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate are preferred. More preferably, propylene glyco Makes the chromophore at the distal end Roh methyl ether acetate.
  • the organic solvent does not sufficiently evaporate and remains in the dried coating film, and The heat resistance of the dried coating film may decrease. Further, in a system containing a large amount of an organic solvent having a boiling point of less than 100 ° C., it is difficult to apply the coating uniformly without unevenness, and a coating film having excellent surface smoothness may not be obtained.
  • the photopolymerizable compound usable in the present invention include monomers and oligomers having one or more photopolymerizable unsaturated bonds in the molecule, and monomers having one photopolymerizable unsaturated bond in the molecule.
  • alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethynolehexynole methacrylate, methyl acrylate, butyl acrylate, 2-ethynolehexyl acrylate; Aralkyl methacrylates or acrylates such as methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyshethyl methacrylate and ptoxyshethyl acrylate; N, N-dimethylaminoethyl methacrylate; N, N-dimethylaminoethyl acrylate Methacrylates or acrylates of polyalkylene glycol alkyl ethers, such as diaminoglycol methacrylate or acrylate; diethylene glycol monoethylenoleate, triethylene glycol monoleptinoleate or dipropylene glycol methyl ether
  • photopolymerizable compounds can be used alone or in combination of two or more.
  • the photopolymerization initiator that can be used in the present invention is not particularly limited, and examples thereof include benzophenone, N, ⁇ ′-tetraethyl_4, A ′ diaminobenzozophenone, 4-methoxydimethylaminobenzobenzophenone, benzyl, 2, 2-Jetoxyacetophenone, benzoin, benzoinmethinoleatenore, benzoinsobutinoreatenore, penzinoresimetinoleketanore, ⁇ -hydroxyisobutinolephenone, tioxanthon, 2-clothoxyxanthone, 1-hydroxycyclohexylphenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-1- 2-methylanthraquinone, 2-
  • the pigment-dispersed resist composition for a color filter of the present invention usually contains a resin for improving the developability, and is preferably a developer used in the developing step of the color filter, particularly preferably an alcohol.
  • a resin for improving the developability is preferably a developer used in the developing step of the color filter, particularly preferably an alcohol.
  • An alcohol-soluble resin having solubility in an aqueous developer can be used, in particular, an alcohol-soluble resin having an epoxy group.
  • alkali-soluble resin having a carboxyl group examples include unsaturated monomers containing a carboxyl group such as acrylic acid and methacrylic acid, styrene, 2-hydroxyshetyl acrylate, 2-hydroxymetharyl acrylate, and arinorea acrylate.
  • unsaturated monomers containing a carboxyl group such as acrylic acid and methacrylic acid, styrene, 2-hydroxyshetyl acrylate, 2-hydroxymetharyl acrylate, and arinorea acrylate.
  • Aryl methacrylate, benzyl acrylate, benzyl methacrylate, glycerono remeth acrylate, glycerono remeth acrylate, ⁇ -fe-norema remide, polystyrene mac mouth monomer and polymethinole methacrylate macromo Copolymers with at least one member selected from the group of nomers can be used.
  • the pigment dispersion resist composition for a color filter of the present invention may contain, if necessary, a thermal polymerization inhibitor such as hydroquinone, pyrogallol, or t-butyl catechol, a pigment derivative, or a pigment dispersion for controlling a dark reaction.
  • a thermal polymerization inhibitor such as hydroquinone, pyrogallol, or
  • a pigment dispersion is produced from a mixed liquid containing a pigment, a pigment dispersant and an organic solvent as essential components (hereinafter, also simply referred to as a mixed liquid) using a high-pressure emulsifier having a specific structure described later.
  • a mixed liquid containing a pigment, a pigment dispersant and an organic solvent as essential components
  • a high-pressure emulsifier having a specific structure described later.
  • pigment dispersion is referred to as “dispersion obtained by subjecting a mixture containing at least a pigment, a pigment dispersant and an organic solvent as essential components to a pigment dispersion treatment using a high-pressure emulsifier”.
  • a pigment dispersion obtained by subjecting a mixture containing only essential components of a pigment, a pigment dispersant and an organic solvent to a pigment dispersion treatment using a high-pressure emulsifier is further added to a pigment for a color filter.
  • a pigment-dispersed resist composition for a color filter obtained by adding a material necessary for obtaining a dispersed resist composition will be described.
  • the present invention is not limited to this. That is, in addition to the essential components for constituting the above-mentioned mixed solution, a mixed solution obtained by arbitrarily adding and mixing other materials constituting the pigment-dispersed resist composition for a color filter using a high-pressure emulsifier.
  • the pigment-dispersed resist composition for a color filter obtained by adding a material necessary for obtaining a pigment-dispersed resist composition for a color filter, if necessary, to the pigment dispersion obtained by the It is a pigment dispersion resist composition for color filters of the present invention.
  • the color filter pigment-dispersed resist composition includes, for example, a photopolymerizable compound and a photopolymerization initiator, which are essential components for constituting the color filter-pigmented resist composition, in the mixture.
  • a photopolymerizable compound and a photopolymerization initiator which are essential components for constituting the color filter-pigmented resist composition, in the mixture.
  • the pigment After dispersing the pigment May be obtained without adding the photopolymerizable compound and the photopolymerization initiator, or the pigment may be dispersed by containing either the photopolymerizable compound or the photopolymerization initiator in the above-mentioned mixed solution. Alternatively, it may be obtained by dispersing the pigment and then adding one of the other.
  • Examples of the pigment dispersing machine used for finely dispersing the pigment of the pigment dispersion of the present invention include, as shown in FIGS. 1 and 2, a high-pressure unit having a pressure unit, an orifice, and a hollow member arranged in parallel.
  • An emulsifier can be used.
  • the high-pressure emulsifier having the configuration shown in FIGS. 1 and 2 illustrates a preferred embodiment of the present invention, and the present invention is not limited to this.
  • the mixed liquid to be subjected to the dispersion treatment stored in the mixed liquid tank 1 is pressurized by the high-pressure pump 2 and guided to the dispersion chamber 13, and the processed dispersion is guided to the storage tank 4. .
  • the distributed champers 13 those having the structure shown in FIG.
  • the dispersion chamber of the high-pressure milking machine in FIG. 2 has three essential components for dispersing the pigment: the mixture inlet 7, the orifice 8, and the hollow member 9; the back pressure valve 10; It has exit 1 1.
  • a high pressure pump 2 (not shown) is used to pass a mixture introduced into a mixture inlet 7 at high speed through an orifice 8 under pressure.
  • a high-speed jet stream of the mixed liquid generated by the orifice 8 is jetted into the hollow member 9, and is mixed by shearing stress generated by a speed difference between the mixed liquid staying in the hollow member 9 and jetting first. The liquid will be dispersed.
  • the orifice 8 In this high-pressure emulsifier, a fine orifice is used as the orifice 8 because it is necessary to generate a high-speed jet stream.
  • the orifice diameter is 0.01 from the viewpoint of productivity and equipment efficiency. It has a diameter of about 1.5 mm, and its shape is preferably a straight line having no curved or bent portions and hardly worn.
  • the material forming the orifice include diamond such as sintered diamond and single-crystal diamond, ceramic materials such as alumina, zirconium and carporundum, and metals such as stainless steel, iron and titanium. However, among them, materials of high hardness which are hard to wear are preferable.
  • the inside of the orifice and the inside of the hollow member It is necessary to adjust the speed of the mixture passing through the orifice so that the optimum stress applied to the mixture is obtained at Adjustment is possible depending on the conditions.
  • the mixture is a 5 X 1 0 3 ⁇ 3. 2 X 1 0 5 pressure conditions k P a, the mixture rate of 1 00 to: LO 0 Om / sec, more preferably 400 to 70 Om / sec.
  • the hollow member for injecting the high-speed jet flow of the mixed liquid generated by the orifice is preferably cylindrical so that the high-speed jet flow can flow linearly.
  • the hollow member can be configured by combining a plurality of cells with seals.
  • the ratio of the orifice to the hollow member tube diameter is set to 1: 2 to 50, so that a uniform flow can be generated in the hollow member and an appropriate speed difference occurs for the shearing stress to act between the mixed liquids.
  • the ratio is about 1: 5 to 10 and, in addition, it is desirable to have a sufficient volume so that the high-speed jet stream does not collide with the opposite surface of the hollow member with a strong force.
  • the material of the hollow member is also preferably hard to wear.
  • ceramic materials such as alumina, zirconium and carborundum, and metals such as stainless steel, iron and titanium can be used.
  • a discharge port may be provided at any part of the hollow member in order to discharge the treated dispersion.
  • a method in which the discharge port is provided on a wall facing the orifice of the hollow member can be used.
  • the structure must be such that the injected mixed liquid is not discharged without being dispersed.
  • a back pressure valve on the hollow member.
  • Back pressure By providing a valve to apply the pressure of the hollow member (called back pressure), it is possible to control the flow rate of the mixture in the hollow member and to prevent the dispersion force from decreasing due to the generation of microbubbles.
  • Back pressure will vary according to the boiling point or the like of the dispersion conditions and organic solvents, 1 X 1 0 3 k P a following effect is low, the change effect can be as high as 1 X 1 0 4 k P a more Disappears.
  • the number of times of dispersion (the number of times of passage through the orifice) in the high-pressure emulsifier according to the present invention is one or more times (in FIG. 1, the dispersion discharged from the dispersion discharge port is stored in the storage tank 4, but is again stored in the storage tank 4). It may be returned to the mixed liquid tank 1 or may have a structure that circulates it) .It should be appropriately selected according to the pigment to be used, the dispersion conditions, and the required particle size and particle size distribution of the pigment particles of the pigment dispersion. Can be.
  • a premix treatment is performed using a non-media type disperser such as a high-speed mixer or a high-speed homogenizer. That is, it is preferable to use, as the above-mentioned mixed liquid, a mixed liquid that has been subjected to a premixing process using a non-media type mixing device. It is preferable that the mixed liquid is adjusted to have an appropriate viscosity, for example, less than 1 Pa ⁇ s.
  • the pressure of the mixed solution is increased by using a high-pressure pump, and the mixed solution is passed through a high-speed jet stream 5 at a speed of 400 to 700 m / sec 5 through a straight orifice without a curved portion or a confluent portion.
  • the back pressure of the jet stream is 1 ⁇ 10 3 to 1 ⁇ 10 4 kPa (preferably, the speed at which the high-speed jet stream collides with the wall facing the orifice becomes 0). It is preferable to inject into the hollow member.
  • the production of the pigment dispersion is preferably performed at 40 to 70 ° C.
  • the temperature is preferably increased from the viewpoint of the wettability between the pigment and the organic solvent.
  • an organic solvent having a boiling point of 100 to 220 ° C. is used and there is a risk of ignition during production, it is preferable to carry out the reaction at 70 ° C. or lower.
  • the pigment is finely dispersed in a short period of time.
  • the fine dispersion of the pigment is averaged from the clear hue of the pigment dispersion. It is prepared so as to have a particle size of less than 150 nm.
  • the pigment dispersion that has been completely dispersed is guided to the tank from the dispersion outlet.
  • the pigment dispersion obtained by dispersing the pigment by such a production method may be further subjected to post-treatment such as centrifugal separation treatment or filter treatment of the pigment dispersion to remove coarse particles.
  • a photopolymerizable compound, a photopolymerization initiator, and, if necessary, an organic solvent, a modifying resin, and various additives are added to the pigment dispersion that has been completely dispersed by the above-mentioned production method, followed by stirring and mixing.
  • the pigment dispersion obtained by the mixed liquid composition and the production method described above disperses the pigment by a uniform and controlled shear force, and makes the pigment finer without generating excessive pulverized particles or undispersed particles. Excellent dispersion stability and fluidity because it enables uniform dispersion of primary particles or its vicinity and also prevents finely dispersed pigment particles from aggregating over time. It is.
  • the pigment dispersion resist composition for a color filter of the present invention As described above, the pigment dispersion resist composition for a color filter of the present invention,
  • particles having a narrow particle size distribution (preferably having an average particle size of less than 150 nm), in which the amount of the superdispersion is small and the pigment dispersant containing a basic group is adsorbed on a fine pigment
  • the obtained color filter has good transparency, contrast, and colorability, has a clear hue, and has good coating smoothness.
  • FIG. 1 is a schematic view of an example of a high-pressure emulsifier used in the production of the dispersion of the present invention.
  • FIG. 2 is a schematic view of one example of dispersion of a high-pressure emulsifier used in the production of the dispersion of the present invention. Explanation of reference numerals
  • a pigment dispersant containing a basic group is added to an organic solvent and mixed to obtain the composition shown in Table 1, the varnish is adjusted, and further the pigment is added and predispersed with a high-speed stirrer.
  • the pigment dispersants A to F containing a basic group, the ataryl resin, and the organic solvent shown in Table 1 are as follows.
  • the materials used and the dispersion conditions are as follows.
  • Poly (lower alkylene imine) derivative Solsperse 2 4 0 0 GR (trade name, Ab ecia)
  • Polyester having an amino group at the end Solsperse 17000 (trade name, manufactured by Abecia)
  • Polyurethane resin D i s p e r b y k-161 (trade name, manufactured by BYK Chemie)
  • a polyester having one hydroxyl group in the isocyanate group of the polyisocyanate compound a compound having two to three isocyanate group-reactive groups, an aliphatic group having an isocyanate group-reactive functional group and a tertiary amino group Or a reaction product obtained by sequentially reacting a heterocyclic hydrocarbon compound
  • Acrylic resin containing basic group EFKA-46 (trade name, manufactured by EFKA Chemica 1 B.V.)
  • Polyether chain adduct of low molecular weight amino compound Solsperse 20000 (trade name, manufactured by Abecia)
  • Disperkyk-2001 (trade name, manufactured by Big Chemie Japan Ltd.)
  • Ataryl resin benzyl methacrylate 'methacrylic acid copolymer (weight average molecule Amount: 20000, acid value 100)
  • Organic solvent benzyl methacrylate 'methacrylic acid copolymer (weight average molecule Amount: 20000, acid value 100)
  • Predispersed dispersion flow rate 60 Om / sec
  • Example 2 was obtained.
  • Comparative example 3 of pigment dispersion for color filter To 1 part of PMAC 77, 62 parts of a pigment dispersant A containing a basic group and 12 parts of acryl resin are added and mixed to prepare a varnish. Further, C.I. After pre-dispersing with a stirrer, use a Nanomizer-1 (manufactured by Nanomizer-1) as a high-pressure disperser, disperse under the following conditions, and then filter through a S / xpp pleated filter to remove coarse particles. Comparative Example 3 of a pigment dispersion for a color filter was obtained.
  • a Nanomizer-1 manufactured by Nanomizer-1
  • the dispersion conditions are as follows.
  • the dispersion conditions are as follows.
  • Pigment dispersion resist composition for color filter Examples 1 to 6 Comparative examples 1 to 4 Pigment dispersions for color filters of Examples 1 to 6 and Comparative examples 1 to 4 43.8 parts of acrylic resin 6 2.8 parts of dipentaerythritol hexatalylate, 0.9 part of photopolymerization initiator and 46.5 parts of PMAC were mixed and stirred, and the color filters of Examples 1 to 6 and Comparative Examples 1 to 4 were mixed. A pigment-dispersed resist composition was obtained. 3. Pigment dispersion (Example 7), pigment dispersion resist composition for color filter (Example 7)
  • Predispersed dispersion flow rate 60 Om / sec
  • the viscosity at 25 ° C. of the pigment dispersions for color filters of Examples 1 to 6 and Comparative Examples 1 to 4 and the pigment dispersion resist composition for color filters of Example 7 and Comparative Example 5 was measured using an R-type viscometer. Was measured and evaluated.
  • the viscosity at 25 ° C. of the pigment dispersions for color filters of Examples 1 to 6 and Comparative Examples 1 to 4 and the pigment dispersion resist compositions for color filters of Example 7 and Comparative Example 5 was used. After storage at 40 ° C for 7 days, the viscosity at 25 ° C was measured, and the increase was evaluated.
  • the pigment-dispersed resist composition for each color filter of Examples 1 to 7 and Comparative Examples 1 to 5 was applied on a glass substrate for a color filter by a spin coater and dried at 100 ° C. for 3 minutes to obtain a red coating. A membrane was obtained. Next, each unexposed coating film was exposed at a UV light exposure of 30 O mj Z cm 2 through a photomask using a high-pressure mercury lamp, and then exposed at 230 ° C. Boss beta was performed for 0 minutes to obtain a coating film. In this way, the substrate on which the coating film is formed is placed between the two deflection plates, and the brightness when the deflection axes of the deflection plates are parallel is set.
  • luminance ratio parallel luminance Z vertical luminance
  • the pigment-dispersed resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 5 were applied on a glass substrate for a color filter by a spin coater, and the state of the coating film surface was observed and evaluated with a microscope.
  • Example 1 Example 3 ⁇ 4 Example 3 ⁇ Example / j ui Example r no 'j 4 t7
  • Pigment dispersant D (EF A-46) 3.9
  • the pigment dispersion for a color filter of the present invention is made into fine particles (narrow particle size distribution) with very little overdispersion, the pigment dispersion and the fluidity are improved.
  • the pigment dispersion resist composition for a color filter using the pigment dispersion for a color filter, a colored image having a clear hue (transparency and contrast) and excellent in coating film smoothness is formed.

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Abstract

A pigment-dispersed resist composition capable of giving color filters which exhibit clear hue (excellent transmission and contrast) and are excellent in the smoothness of coating. The pigment dispersion of the pigment-dispersed resist composition of the present invention is produced by a process which comprises using a high-pressure emulsifier provided with a straight orifice free from crook and inflection and a straight hollow section which is connected to the orifice and has a diameter larger than that of the orifice, passing a mixed fluid comprising a pigment, an organic solvent containing at least one member selected from among ester solvents having boiling points of 100 to 220°C, ether solvents, ether-ester solvents, ketone solvents, aromatic hydrocarbon solvents, and nitrogenous organic solvents, and a pigment dispersant through the orifice under pressure at a flow rate of 100 to 1000 m/sec, and ejecting the resulting mixed fluid into the precedently discharged mixed fluid retained in the straight hollow section to disperse the pigment.

Description

明細書  Specification
カラーフィルタ一用顔料分散レジス ト組成物  Pigment dispersion resist composition for color filter
技術分野 Technical field
本発明は、 カラーフィルター用顔料分散レジス ト組成物に関し、 より詳しくは、 顔料分散性及び顔料分散安定性が非常に優れ、 且つ色相 （透明性、 コントラスト ) 及ぴ塗膜平滑性に優れるカラーフィルター用顔料分散レジスト組成物に関する。 背景技術  The present invention relates to a pigment dispersion resist composition for a color filter, and more particularly, to a color filter having extremely excellent pigment dispersibility and pigment dispersion stability, and excellent in hue (transparency, contrast) and coating film smoothness. The present invention relates to a pigment dispersion resist composition for use. Background art
カラーフィルタ一は、 ガラス等の透明な基板の表面に 2種類以上の異なる色相 の微細な帯 （ストライプ） を平行に配置したもの、 又は、 微細な画素を縦横一定 の配列に配置したものからなっている。 画素サイズは、 数 1 0〜数 1 0 0 /i mと いう微細な形状であり、 しかも色相毎に所定の順序で整然と配列される。 このた めカラーフィルターの製造法については、 種々の方法が提案されている。  A color filter consists of two or more types of fine bands (stripe) of different hues arranged in parallel on the surface of a transparent substrate such as glass, or one in which fine pixels are arranged in a constant vertical and horizontal direction. ing. The pixel size has a fine shape of several 100 to several 100 / im, and is arranged in a predetermined order for each hue. For this reason, various methods have been proposed for producing color filters.
カラーフィルタ一は、 高い透明性及び高い精度での皮膜の厚さの均一性が必要 とされるため、 従来、 ゼラチン、 カゼイン等の染色可能な天然高分子の水溶液に、 重クロム酸等の感光剤を加えて感光化し、 フォトリソグラフィ一法を用いて画素 パターンを形成し、 上記画素パターンを所望の色に染色して色パターンを得るェ 程を 3回繰り返して 3色の透明着色微細パターンを形成する、 いわゆる染色法を 用いることにより製造されていた。  Conventionally, color filters require high transparency and uniformity of film thickness with high precision, so conventionally, a photosensitive solution such as dichromic acid was used in aqueous solutions of dyeable natural polymers such as gelatin and casein. A photo-lithography method is used to form a pixel pattern, and the above-described process of dyeing the pixel pattern into a desired color to obtain a color pattern is repeated three times to obtain a transparent colored fine pattern of three colors. It was manufactured by using a so-called dyeing method.
近年、 カラー液晶ディスプレイパネルの大型化、 用途の多様化に伴い耐熱性、 耐光性といった信頼性の向上が要求されるようになり、 この要求に対して、 前記 の天然高分子の代わりに紫外線等の活性エネルギー線硬化型樹脂を用いたレジス ト組成物が使用されるようになっている。 そして、 この様なカラーフィルタ一形 成用のレジスト組成物に使用する色材としては、 色特性に優れるものの耐熱性や 耐光性に限界がある染料のかわりに、 耐光性及び耐熱性が優れる顔料をボールミ ル、 アトライター、 サンドミル等の分散機装置を使用して分散させたものが使用 されていた。 更に最近では、 鮮明な色相と高い堅牢度が要求される等の理由によ り、 高級有機顔料と呼ばれる顔料が使用されるようになってきている。 しかしながら、 これら高級有機顔料は他の顔料と比較して、 初期の微細分散安 定个生及び経時の分散安定性 （以下、 併せて顔料分散性という） 、 及び、 流動性 （ ニュートン流動に極めて近い流動性が要求される） が乏しいために、 本来、 有し ている鮮明な色相を得るのが困難な上に、 凝集による沈降や流動性の低下が起こ り、 塗膜平滑性も悪化する等の多くの問題がある。 In recent years, with the increase in the size of color liquid crystal display panels and the diversification of applications, improvements in reliability such as heat resistance and light resistance have been required. A resist composition using the active energy ray-curable resin described above has been used. As a coloring material used in such a resist composition for forming a color filter, instead of a dye having excellent color characteristics but having limited heat and light resistance, a pigment having excellent light and heat resistance is used. Used in a dispersing machine such as a ball mill, an attritor, and a sand mill. More recently, pigments called high-grade organic pigments have come to be used, for example, because they require a clear hue and high fastness. However, compared to other pigments, these higher organic pigments have an initial fine dispersion stability and dispersion stability over time (hereinafter collectively referred to as pigment dispersibility), and a fluidity (very similar to Newtonian flow). Fluidity is required), so it is difficult to obtain the original clear hue, sedimentation due to agglomeration and decrease in fluidity occur, and the coating film smoothness also deteriorates. There are many problems.
上記の顔料分散レジスト組成物を使用してカラーフィルターを製造するに当た つては、 透明基板上に又は予め所望のパターンの遮光層を形成した基板上にレジ スト組成物を塗布、 乾燥した後、 塗膜を所望のパターンで露光、 現像することに より、 各色の画素を得ている。 近年、 特に鮮明な色相を有すること、 及ぴ、 より 精度の高い塗膜平滑性を有することが要求されるようになってきており、 これら 高級有機顔料を更に微細に分散させてこの要求を満足するには、 上記の分散安定 性と流動性の問題は是非解決しなければならない重要な研究課題である。  In producing a color filter using the above-described pigment-dispersed resist composition, the resist composition is applied to a transparent substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance and dried. The pixels of each color are obtained by exposing and developing the coating film in a desired pattern. In recent years, it has been required to have a particularly sharp hue and to have a more precise coating smoothness. These fine organic pigments have been further finely dispersed to satisfy this requirement. To achieve this, the above problems of dispersion stability and liquidity are important research issues that must be resolved.
そこで、 これらの問題を解決する手段として、 顔料を分散させるために利用す る樹脂の改良が行われているが、 顔料分散効果は多少改善されるものの、 上述し た問題を完全に解決するまでには至っていない。  To solve these problems, the resin used to disperse the pigment has been improved.However, although the effect of dispersing the pigment is slightly improved, it is not until the above-mentioned problem is completely solved. Has not been reached.
また、 これらの問題を解決する別の手段として、 分散機の見直しによる分散性 の改良が行われている。  In addition, as another means to solve these problems, dispersibility has been improved by reviewing dispersers.
上述のポールミル、 アトライター、 サンドミル等の従来の分散機は、 分散槽内 にメディアを入れて攪拌し、 メディァ同士の衝突エネルギー又は摩擦エネルギー により顔料等を分散するものであるが、 得られる分散物には、 メディア等の破片 が混入している上に、 微小で粒径分布の狭い分散物を得ることが難しく、 また、 顔料に分散用樹脂を均一に吸着させようとした場合、 その能力も低いものであつ た。  Conventional dispersers such as the above-mentioned pole mills, attritors and sand mills disperse pigments and the like by means of collision energy or frictional energy between media, with media being stirred in a dispersion tank. In addition, it is difficult to obtain a fine dispersion with a narrow particle size distribution in addition to the inclusion of debris such as media, and the ability to uniformly adsorb the dispersing resin to the pigment also increases the ability. It was low.
そこで、 これらの問題を解決することを目的として、 カラーフィルター用途の レジスト組成物で顔料を微分散する装置として、 例えば、 特開平 0 7— 1 9 8 9 3 3号公報では、 マイクロフルイタィザー （マイクロフライディックス社製） 、 ナノマイザ一 (ナノマイザ一社製) 、 アルティマイザ一 (スギノマシン社製) 等 の高圧分散機を使用する方法が開示されている。  Therefore, in order to solve these problems, as a device for finely dispersing a pigment in a resist composition for a color filter, for example, JP-A-07-198933 discloses a microfluidizer. A method using a high-pressure dispersing machine such as (Microfriedix), Nanomizer-1 (Nanomizer-1), and Ultimatemizer-1 (Sugino Machine) is disclosed.
し力 しながら、 これらの高圧分散機による顔料分散は、 顔料分散液と分散機の 壁との衝突 （液一壁衝突） 、 顔料分散液同士の衝突 （液一液衝突） 等を利用し衝 撃力により、 粉碎'分散が進行するものであり、 顔料粒子に均一な分散力を与え ることができないという問題を有している。 その結果として、 分散力の強くかか る部分では過剰粉砕粒子が生じ、 また、 分散力の弱い部分では未分散粒子が生じ、 広い粒度分布を持つ顔料分散物となる。 さらに、 微細な粒子を得ようと分散力を 強くすると過剰粉砕粒子が増加し、 顔料粒子に均一に顔料分散用樹脂を吸着させ ることも難しくなることから、 結局、 顔料分散性及び流動性が低いままで問題の 解決には至っていない。 While dispersing the pigment by these high-pressure dispersers, the pigment dispersion and the disperser Crushing / dispersion is promoted by impact force using collisions with walls (liquid-wall collision), collisions between pigment dispersions (liquid-liquid collision), etc. There is a problem that it cannot be given. As a result, excessively pulverized particles are generated in a portion where the dispersing force is strong, and undispersed particles are generated in a portion where the dispersing force is weak, resulting in a pigment dispersion having a wide particle size distribution. Further, if the dispersing power is increased to obtain fine particles, excessively pulverized particles increase, and it becomes difficult to uniformly adsorb the pigment dispersing resin to the pigment particles. The problem has not been resolved at low levels.
以上のように、 顔料分散機として従来から知られている高圧分散機を使用して も、 得られる顔料分散物は、 いずれも上述したように顔料分散性及び流動性が充 分に改善されるとは言えず、 これを使用したカラーフィルター用顔料分散レジス ト組成物では、 鮮明な色相が得られず、 塗膜平滑性が悪い等の問題を有したまま である。 発明の要約  As described above, even when a high-pressure disperser conventionally known as a pigment disperser is used, the obtained pigment dispersions are all sufficiently improved in pigment dispersibility and fluidity as described above. However, it cannot be said that the pigment-dispersed resist composition for a color filter using the composition has a problem that a clear hue cannot be obtained and the coating film has poor smoothness. Summary of the Invention
本発明は、 このようなカラーフィルター用顔料分散レジスト組成物の問題点に 鑑みて成されたものであり、 過分散物の発生が非常に少なくなる条件で顔料を微 粒子化 （粒度分布も狭い） し、 且つ、 得られた顔料分散レジスト組成物の顔料分 散性及ぴ流動性を良好とすることにより、 色相 （透明性、 コントラスト） が鮮明 で、 塗膜平滑性が良好なカラーフィルターを得ることができる顔料分散レジスト 組成物を提供することを課題とするものである。  The present invention has been made in view of the problems of such a pigment-dispersed resist composition for a color filter, and makes the pigment into fine particles (under a narrow particle size distribution) under the condition that the generation of an overdispersed substance is extremely reduced. In addition, by improving the pigment dispersibility and fluidity of the obtained pigment-dispersed resist composition, a color filter having a clear hue (transparency and contrast) and excellent coating smoothness can be obtained. An object of the present invention is to provide a pigment-dispersed resist composition that can be obtained.
本発明者らは、 上記課題を解決するために研究を重ねた結果、 湾曲部や屈曲部 のない直線状のオリフィスと、 該オリフィスに連結されたオリフィスの径ょりも 大きい径を有する直線状の中空部材とを備えた高圧乳化機を用い、 少なくとも顔 料、 有機溶剤、 顔料分散剤を必須成分として含有する混合液を加圧下、 1 0 0〜 1 0 0 O m/ s e cの流速で該オリフィスを通過させた後、 更に該混合物を該ォ リフィスから該中空部材の中で滞留している、 先に流出した混合液中に吐出させ る高圧乳化機で顔料を分散させることにより、 上記の課題を容易に解決できるこ とを見出し、 本発明に到達したものである。 すなわち、 本発明は、 （1 ) 顔料分散物と光重合性化合物と光重合開始剤とを少 なくとも含有するカラーフィルター用顔料分散レジスト組成物であって、 当該顔 料分散物は、 湾曲部や屈曲部のない直線状のオリフィスと、 該オリフィスに連結 されたオリフィスの径ょりも大きい径を有する直線状の中空部材とを備えた高圧 乳化機を用い、 顔料と、 常圧における沸点が 1 0 0〜2 2 0 °Cであるエステル系 有機溶剤、 エーテル系有機溶剤、 エーテルエステル系有機溶剤、 ケトン系有機溶 剤、 芳香族炭化水素溶剤及び含窒素系有機溶剤からなる群より選択される少なく とも 1種を含有してなる有機溶剤と、 顔料分散剤とを含有する混合液を、 加圧下、 1 0 0〜1 0 0 O m/ s e cの流速で該オリフィスを通過させた後、 更に該混合 物を該オリフィスから該中空部材の中で滞留している、 先に流出した混合液中に 吐出させて、 顔料を分散させたものであるカラーフィルタ一用顔料分散組成物に 関する。 As a result of repeated studies to solve the above problems, the present inventors have found that a linear orifice having no curved portion or bent portion and a linear orifice connected to the orifice have a large diameter. Using a high-pressure emulsifier equipped with a hollow member of the formula (1), a mixture containing at least a pigment, an organic solvent, and a pigment dispersant as essential components at a flow rate of 100 to 100 Om / sec under pressure. After passing through the orifice, the pigment is further dispersed by a high-pressure emulsifier that discharges the mixture from the orifice into the mixed liquid that has flowed out and stays in the hollow member. The inventors have found that the problem can be easily solved, and have reached the present invention. That is, the present invention provides (1) a pigment-dispersed resist composition for a color filter, which contains at least a pigment dispersion, a photopolymerizable compound, and a photopolymerization initiator. Using a high-pressure emulsifier equipped with a linear orifice having no or bent portion and a linear hollow member having a diameter larger than the diameter of the orifice connected to the orifice. Selected from the group consisting of ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents, and nitrogen-containing organic solvents at 100 to 220 ° C. A mixture containing at least one organic solvent and a pigment dispersant is passed through the orifice under pressure at a flow rate of 100 to 100 Om / sec. Further, the mixture is removed from the orifice. Staying in the hollow member, by ejecting the mixed solution that flows out above relates to an pigment dispersing composition for a color filter in which a pigment is dispersed.
なお、 （1 ) のカラーフィルター用顔料分散レジスト組成物を構成する光重合 性化合物と光重合開始剤については、 顔料の分散処理前後のどちらに含ませても よく、 必要に応じて添加するカラーフィルター用顔料分散レジスト組成物を構成 する光重合性化合物及び光重合開始剤以外のものを顔料の分散処理前後のどちら に含ませてもよい。 すなわち、 例えば、 上記の顔料、 有機溶剤及び顔料分散剤の 混合液中に、 更に光重合性化合物と光重合開始剤とを含み、 顔料を分散した後に は光重合性化合物と光重合開始剤を加えないで得られるカラーフィルタ一用顔料 分散レジス ト組成物（あるいは、 どちらか一方を分散処理前に含ませて、 他の一 方を分散処理後に含ませたもの）でもよい。  The photopolymerizable compound and the photopolymerization initiator constituting the pigment dispersion resist composition for a color filter of (1) may be contained before or after the pigment dispersion treatment. A component other than the photopolymerizable compound and the photopolymerization initiator constituting the pigment dispersion resist composition for a filter may be contained before or after the pigment dispersion treatment. That is, for example, the mixed solution of the pigment, the organic solvent, and the pigment dispersant further contains a photopolymerizable compound and a photopolymerization initiator, and after the pigment is dispersed, the photopolymerizable compound and the photopolymerization initiator are mixed. The pigment for a color filter, which is obtained without addition, may be a dispersion resist composition (or one of which is contained before the dispersion treatment and the other is contained after the dispersion treatment).
また、 本発明は、 （2 ) 上記 （1 ) 項記載の顔料分散剤として、.塩基性基を含 有する顔料分散剤を用いるカラーフィルタ一用顔料分散レジス ト組成物に関する。 また、 本発明は、 （3 ) 上記混合液として、 非メディア型混合装置でプレミツ タス処理してなる混合液を使用する上記 （1 ) 又は （2 ) 記載のカラーフィルタ 一用顔料分散レジス ト組成物に関する。 発明の詳細な開示  The present invention also relates to (2) a pigment dispersion resist composition for a color filter, wherein the pigment dispersant according to the above (1) is a pigment dispersant having a basic group. The present invention also provides (3) a pigment dispersion resist composition for a color filter as described in (1) or (2) above, wherein the mixed liquid is a mixed liquid obtained by performing a premittastic treatment in a non-media type mixing apparatus. About things. Detailed Disclosure of the Invention
本発明は、 微細な径を有するオリフィスと、 そのオリフィス径より大きな径を 有する中空部材とを連結させた高圧乳化機を用いて顔料分散を行うことを最も大 きな特徴とするものである。、そして、 カラーフィルター用顔料分散レジスト糸且成 物中の顔料分散は、 まず、 混合液がオリフィスを通過する際のせん断作用及びォ リフィスの径より大きい径を有する中空部材内の中で滞留している、 先に流出し た混合液中に混合液をオリフィスから高速ジェット流のまま吐出することにより、 滞留している混合液との間 （速度差） で発生するせん断力によって行われるが、 混合液は低粘度の非圧縮流体であるため、 発生した応力はすぐに混合液全体に伝 わり、 顔料粒子には広い範囲にわたって均一のせん断作用が働くため、 過分散物 が少ない非常に均一な分散が短時間で効率的に行われることになる。 The present invention provides an orifice having a fine diameter and a diameter larger than the orifice diameter. The most characteristic feature is that the pigment is dispersed using a high-pressure emulsifier in which the hollow member is connected. The pigment dispersion in the pigment-dispersed resist yarn for the color filter is firstly retained in a hollow member having a diameter larger than the diameter of the orifice due to the shearing action when the mixture passes through the orifice. By discharging the mixed liquid from the orifice as a high-speed jet stream into the mixed liquid that has flowed out earlier, this is performed by the shear force generated between the retained mixed liquid (velocity difference), Since the liquid mixture is a low-viscosity, incompressible fluid, the generated stress is immediately transmitted to the entire liquid mixture, and the pigment particles undergo a uniform shearing action over a wide range. Dispersion is performed efficiently in a short time.
また、 この顔料分散は、 オリフィス径が従来の高圧乳化機の管径と比較して非 常に細いため、 非衝突型の方式であっても顔料を分散させるための充分な応力を 発生させることができ、 更に混合液をオリフィスに通過させるために付加する圧 力を調整することによって、 顔料を分散させるための応力を簡単に制御できるも のである。  In addition, since the orifice diameter of this pigment dispersion is very small compared to the tube diameter of a conventional high-pressure emulsifier, a sufficient stress for dispersing the pigment can be generated even in a non-collision type method. By controlling the pressure applied to pass the mixture through the orifice, the stress required to disperse the pigment can be easily controlled.
従って、 顔料の一次粒子同士の凝集力及び一次粒子の破碎強度が、 各種顔料ご とに固有のものであっても、 本発明における顔料分散方法ではその固有の強度に 応じて最適な分散力 （一次粒子同士の凝集力 <分散力 <一次粒子の破砕強度） を 均一にかけることができ、 このような特徴から、 高級有機顔料であっても、 過剰 粉砕粒子や未分散粒子を発生させることなく、 顔料を一次粒子まで均一に分散さ せることを可能にする。  Therefore, even if the cohesive force between the primary particles of the pigment and the crushing strength of the primary particles are unique to each pigment, the pigment dispersing method of the present invention provides the optimal dispersing force ( The cohesive force between the primary particles <dispersion force <the crushing strength of the primary particles) can be applied uniformly, and even with high-grade organic pigments, without excessively pulverized particles or undispersed particles This makes it possible to uniformly disperse the pigment down to the primary particles.
更に、 本発明においては、 均一に分散された顔料の疎水性表面にすぐに顔料分 散剤が吸着し、 熱力学的に安定化するため、 経時において凝集をおこすことがな く、 再溶解性、 流動性、 分散安定性に優れたものが得られることになる。  Furthermore, in the present invention, the pigment dispersant is immediately adsorbed on the hydrophobic surface of the uniformly dispersed pigment, and is thermodynamically stabilized. Good fluidity and dispersion stability can be obtained.
本発明者らは、 この顔料分散方法により得られる顔料分散物をカラーフィルタ 一用顔料分散レジスト組成物に使用することにより、 顔料分散性及び流動性が良 好となり、 塗布膜平滑性が優れ、 色相が鮮明となる事実を見出したものである。 さらに、 本発明のカラーフィルター用顔料分散レジスト組成物について詳細に 説明する。  The present inventors have found that by using a pigment dispersion obtained by this pigment dispersion method in a pigment dispersion resist composition for one color filter, pigment dispersibility and fluidity are improved, and coating film smoothness is improved. It has been found that the hue is sharp. Further, the pigment-dispersed resist composition for a color filter of the present invention will be described in detail.
本発明で利用可能な顔料 （赤色、 緑色、 青色、 黒色等の着色画像に適した顔料 ) としては、 鮮明な色相と高い堅牢度を有する、 C. I P i gme n t R e d 1 9、 38、 43、 88、 122. 123、 144、 149、 166、 1 68、 177、 1 78、 1 79、 1 88. 190、 207、 208、 209、 2 16、 224、 226、 242、 254 264の赤色系顔料； C. I . P i gme n t B l u e 1 5 : 1、 1 5 3、 1 5 : 4、 1 5 : 6、 16、 22、 29、 60、 64の青色系顏料； C. I P i gme n t Li r e e n 1Pigments that can be used in the present invention (pigments suitable for coloring images such as red, green, blue, and black) ) Has clear hue and high fastness, C. IP gement Red 19, 38, 43, 88, 122.123, 144, 149, 166, 168, 177, 178, 1 79, 188. 190, 207, 208, 209, 216, 224, 226, 242, 254 264 red pigments; C. I. Pigment Blue 15: 1, 15 3, 15 : 4, 15: Blue color of 6, 16, 22, 29, 60, 64; C. IPigment Li reen 1
10、 36の緑色系顔料； C. I. P i gme n t Ye l l ow 24、 8 1、 83、 93、 95、 97、 108、 109、 1 10、 1 1 7、 1 23、 1 2 8、 137、 1 38、 1 39、 150、 1 53、 1 54、 166、 1 68、 18 0、 185の黄色系顔料； C. I. P i gme n t V i o l e t 19、 2 3、 29、 30、 31、 37、 88の紫色系顔料； C. I . P i gme n t O r a n g e 3 1、 38、 40、 43、 6 1、 71の橙色系顔料；カーボンブラ ック等の黒色系顔料等が使用できる。 Green pigments of 10, 36; CI Pigment Yellow 24, 81, 83, 93, 95, 97, 108, 109, 110, 1 117, 123, 128, 137, 1 38, 1 39, 150, 153, 154, 166, 168, 180, 185 yellow pigment; CI Pigment Violet 19, 23, 29, 30, 31, 37, 88 purple Pigment: CI Pigment O range 31, 38, 40, 43, 61, 71 orange pigments; black pigments such as carbon black, etc. can be used.
本発明において、 赤色系着色画像、 緑色系着色顔料、 青色系着色顔料を得るに は、 単一の顔料をもちいてもよいし、 他の顔料を混合して用いてもよい。 例えば、 赤色系着色画像を得るには、 単一の赤色顔料を用いてもよいし、 赤色顔料に黄色 顔料、 橙色顔料等を混合して調色したものを用いてもよく、 緑色系着色画像を得 るには、 単一の緑色顔料を用いてもよいし、 緑色顔料に黄色顔料等を混合して調 色したものを用いてもよく、 青色系着色画像を得るには、 単一の青色顔料を用い てもよいし、 青色顔料に紫色顔料等を混合して調色したものを用いてもよい。 尚、 より鮮明な色相を得るには、 顔料を後述する高圧乳化機で分散する前に、 従来公知の方法でプレミックス処理やソルトミリング処理をすることが好ましい。 また、 本発明で利用可能な顔料分散剤としては、 顔料を分散させるために従来 より使用されている顔料分散剤で、 感光性を妨げないものが使用できる。 尚、 本 発明では、 アル力リ可溶性樹脂で顔料分散性を有するものも顔料分散剤に含まれ るものとする。  In the present invention, in order to obtain a red color image, a green color pigment, and a blue color pigment, a single pigment may be used, or other pigments may be mixed and used. For example, to obtain a red color image, a single red pigment may be used, or a red pigment mixed with a yellow pigment, an orange pigment, or the like may be used, and a green color image may be used. In order to obtain a blue colored image, a single green pigment may be used, or a green pigment mixed with a yellow pigment may be used. A blue pigment may be used, or a blue pigment mixed with a violet pigment or the like and toned may be used. In order to obtain a clearer hue, it is preferable to perform a premixing treatment or a salt milling treatment by a conventionally known method before dispersing the pigment in a high-pressure emulsifier described below. As the pigment dispersant that can be used in the present invention, a pigment dispersant conventionally used for dispersing a pigment that does not hinder photosensitivity can be used. In the present invention, pigment-dispersing agents that are soluble in pigment and have a pigment dispersing property are also included in the present invention.
具体的には、 ポリエステル系高分子顔料分散剤、 アタリル系高分子顔料分散剤、 ポリウレタン系高分子顔料分散剤、 顔料誘導体、 カチオン系界面活性剤、 ノニォ ン系界面活性剤、 ァニオン系界面活性剤等が挙げられる。 これらの顔料分散剤は、 単独で用いてもよく、 また、 2種類以上組み合わせて用いてもよい。 中でも、 良 好な顔料分散性が得られる点から、 顔料分散剤としては、 塩基性基を含有する顔 料分散剤が好適である。 Specifically, polyester polymer pigment dispersants, ataryl polymer pigment dispersants, polyurethane polymer pigment dispersants, pigment derivatives, cationic surfactants, nonionic surfactants, anionic surfactants And the like. These pigment dispersants are They may be used alone or in combination of two or more. Among these, a pigment dispersant containing a basic group is preferable as the pigment dispersant, since good pigment dispersibility can be obtained.
上記塩基性基を含有する顔料分散剤としては、  As the pigment dispersant containing a basic group,
( 1 ) ポリアミン化合物 （例えば、 ポリアリルァミン、 ポリビュルァミン、 ポ リエチレンポリイミン等のポリ (低級アルキレンァミン) 等） のァミノ基及び (1) Amino groups of polyamine compounds (for example, poly (lower alkyleneamine) such as polyallylamine, polybulamine, and polyethylenimine);
Z又はイミノ基と、 遊離のカルボキシル基を有するポリエステル、 ポリアミド 及びポリエステルアミ ドからなる群より選択される少なくとも 1種との反応生 成物、 A reaction product of Z or an imino group with at least one selected from the group consisting of a polyester having a free carboxyl group, a polyamide, and a polyesteramide;
( 2 ) N , N7 ージメチルァミノプロピルアミン等の低分子アミノ化合物と遊離 のカルボキシル基を有するポリエステルとの反応生成物、 (2) N, reaction products of a polyester with N 7 over-dimethyl § amino propyl low molecular amino compounds with the free carboxyl groups such as amines,
( 3 ) ポリイソシァネート化合物のィソシァネート基に、 メ トキシポリエチレン グリコール等のアルコール類や力プロラタトンポリエステル等の水酸基を 1個有 するポリエステル類、 2〜 3個のイソシァネート基反応性官能基を有する化合物、 イソシァネート基反応性官能基と第 3級ァミノ基とを有する脂肪族又は複素環式 炭化水素化合物を順次反応させてなる反応生成物、  (3) Alcohols such as methoxypolyethylene glycol and polyesters having one hydroxyl group such as hydraprotatonone polyester, and 2-3 isocyanate group-reactive functional groups in the isocyanate group of the polyisocyanate compound. A compound, a reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having an isocyanate group-reactive functional group and a tertiary amino group,
( 4 ) アルコール性水酸基を有するァクリレートの重合物にポリイソシァネート 化合物とアミノ基を有する炭化水素化合物とを反応させた反応生成物、  (4) a reaction product obtained by reacting a polymer of an acrylate having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group,
( 5 ) 低分子アミノ化合物にポリエーテル鎖を付加させてなる反応生成物、 ( 6 ) イソシァネート基を有する化合物にアミノ基を有する化合物を反応させて なる反応生成物  (5) a reaction product obtained by adding a polyether chain to a low-molecular-weight amino compound; and (6) a reaction product obtained by reacting a compound having an isocyanate group with a compound having an amino group.
( 7 ) ポリェポキシ化合物に遊離の力ルポキシル基を有する線状ポリマー及ぴ 2 級アミノ基を 1個有する有機アミン化合物を反応させた反応生成物、  (7) a reaction product obtained by reacting a linear polymer having a free hydroxyl group and an organic amine compound having one secondary amino group with a polyepoxy compound,
( 8 ) 片末端にァミノ基と反応し得る官能基を有するポリカーボネート化合物と ポリアミン化合物との反応生成物、  (8) a reaction product of a polycarbonate compound having a functional group capable of reacting with an amino group at one end and a polyamine compound,
( 9 ) メチノレメタタリ レート、 ェチノレメタク リ レート、 プロピルメタクリ レー ト、 プチルメタタリ レート、 ステアリルメタタリ レート、 ベンジルメタク リ レ ート、 メチルァクリ レート、 ェチルァクリ レート、 プロピルァクリ レート、 プ チルアタリ レート、 ステアリルァクリ レート、 ベンジルァクリ レート等のメタ クリル酸エステル又はァクリル酸エステルから選択される少なく とも 1種と、 アタリルァミ ド、 メタタリルァミ ド、 N—メチロールァミ ド、 ビュルィミダゾ ール、 ビュルピリジン、 ァミノ基とポリ力プロラタ トン骨格を有するモノマー 等の塩基性基含有重合性モノマーの少なくとも 1種と、 スチレン、 スチレン誘 導体、 その他の重合性モノマーの少なくとも 1種との共重合体等が挙げられる。 これらの中でも、 上記 （1 ) 〜 （6 ) が好適である。 (9) Methynomethacrylate, etinomethacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate, etc. Meta At least one selected from acrylates and acrylates; and basics such as atarylamide, metharylamide, N-methylolamide, bulimidazole, bulpyridine, a monomer having an amino group and a polyproprolactone skeleton. Copolymers of at least one of the group-containing polymerizable monomers with at least one of styrene, a styrene derivative, and other polymerizable monomers are exemplified. Among them, the above (1) to (6) are preferable.
本発明における顔料分散剤の使用量は、 顔料 1 0 0質量部に対して、 通常 1〜 2 0 0質量部、 好ましくは 1〜6 0質量部である。 顔料分散剤の使用量が 1質量 部未満では、 顔料分散性が低下し、 一方、 2 0 0質量部を超える場合は、 現像性 が低下するおそれがある。  The amount of the pigment dispersant used in the present invention is usually 1 to 200 parts by mass, preferably 1 to 60 parts by mass, based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is less than 1 part by mass, the pigment dispersibility decreases, while when it exceeds 200 parts by mass, the developability may decrease.
また、 本発明で利用可能な有機溶剤としては、 常圧 （1 . 0 1 3 X 1 0 2 k P a ) における沸点 1 0 0〜2 2 0 °Cのエステル系有機溶剤、 エーテル系有機溶剤、 エーテルエステル系有機溶剤、 ケトン系有機溶剤、 芳香族炭化水素溶剤及び含窒 素系有機溶剤から選択される少なくとも 1種を含有するものであり、 これらを主 として含有するものであることが好ましい。 具体的には、 エチレングリコールモ ノメチノレエーテノレ、 エチレングリコーノレモノエチノレエーテノレ、 エチレングリコー ノレイソプロピノレエ一テル、 エチレングリコーノレモノプチノレエーテル、 ジェチレン グリ コー/レモノメチノレエーテル、 ジエチレングリ コーノレモノェチルエーテノレ、 プ 口ピレングリコーノレモノメチノレエーテノレ、 プロピレンダリコーノレモノエチノレエ一 テル、 プロピレングリコールモノブチルエーテル、 ジエチレングリコールジェチ ルエーテル、 ジエチレングリコーノレジメチルエーテル、 ジエチレングリコーノレメ チルェチルェ一テル等のエーテル系有機溶剤；エチレングリコールモノメチルェ ーテノレアセテート、 エチレングリ コーノレモノェチノレエーテノレアセテート、 ェチレ ングリコールモノプチルエーテルァセテ一ト、 プロピレンダリコールモノメチノレ エーテノレアセテート、 プロピレングリコーノレモノェチノレエーテノレアセテート等の エーテルエステル系有機溶剤；メチルイソブチルケトン、 シク口へキサノン、 2 一へプタノン、 δ一プチ口ラク トン等のケトン系有機溶剤； 2—ヒドロキシプロ ピオン酸メチル、 2—ヒドロキシプロピオン酸ェチル、 2—ヒドロキシ一 2—メ チルプロピオン酸ェチル、 3—メチルー 3—メ トキシブチルプロピオネート、 3 ーメ トキシプロピオン酸メチル、 3—メ トキシプロピオン酸ェチル、 3—ェトキ シプロピオン酸メチル、 3—ェトキシプロピオン酸ェチル、 エトキシ酢酸ェチル、 ヒ ドロキシ酢酸ェチル、 蟻酸 n—ァミル等のエステル系有機溶剤； トルエン、 キ シレン等の芳香族炭化水素溶剤； N—メチルピロリ ドン、 N , N—ジメチルホル ムアミド、 N， N—ジメチルァセトアミド等の含窒素系有機溶剤等を挙げること ができる。 これらの有機溶剤は、 単独で又は 2種以上を混合して使用することが できる。 また、 有機溶剤には、 カラーフィルター用顔料分散レジスト組成物の性 能を低下させない範囲で、 顔料分散剤を溶解又は分散させ得る有機溶剤、 例えば、 アルコール等を使用することも可能である。 Examples of the organic solvent that can be used in the present invention include ester-based organic solvents and ether-based organic solvents having a boiling point of 100 to 220 ° C. at normal pressure (1.013 × 10 2 kPa). And at least one selected from ether ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents and nitrogen-containing organic solvents, and preferably contains these mainly. . Specifically, ethylene glycol monomethinolate ether, ethylene glycol monoethylenolate ether, ethylene glycol monoisopropinole ether, ethylene glycol monomonotinole ether, dimethylene glycol / lemonomethinole ether, Diethylene glycol monoethyl ether ether, pyrene glycol monomethyl ether ether, propylene glycol resin monoethyl ether, propylene glycol monobutyl ether, diethylene glycol ethyl ether, diethylene glycol ethyl dimethyl ether, diethylene glycol ethanol Ether-based organic solvents such as ethyl ethyl ether; ethylene glycol monomethyl ether oleate acetate; ethylene glycol monomethyl ether enoate acetate; Ether ester organic solvents such as styrene glycol monobutyl ether acetate, propylene dalicol monomethinoleate enoleacetate, propylene glycolone monoethylenoate enorea acetate; methyl isobutyl ketone; cyclohexanone; Ketone-based organic solvents such as heptanone and δ-lactose lactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-12-methylpropionate, 3-methyl-3-methoxy Butyl propionate, 3 -Ethyl organic solvents such as methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl ethyl hydroxyacetate, and n-amyl formate Aromatic hydrocarbon solvents such as toluene and xylene; and nitrogen-containing organic solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide. These organic solvents can be used alone or in combination of two or more. Further, as the organic solvent, an organic solvent capable of dissolving or dispersing the pigment dispersant, for example, alcohol or the like can be used as long as the performance of the pigment-dispersed resist composition for a color filter is not deteriorated.
尚、 カラーフィルター用顔料分散レジス ト組成物中の有機溶剤は、 溶解性、 顔 料分散性、 塗布性等の点で、 沸点 1 0 0〜 2 2 0 °Cのエーテル系有機溶剤、 エス テル系有機溶剤、 エーテルエステル系有機溶剤、 ケトン系有機溶剤及び含窒素系 有機溶剤等からなる群より選択される少なくとも 1種を、 有機溶剤中 5 0質量％ 以上、 特には 7 0質量 °/0以上含有してなるものが好ましい。 The organic solvent in the pigment dispersion resist composition for a color filter may be an ether organic solvent having a boiling point of 100 to 220 ° C or an ester in terms of solubility, pigment dispersibility, coatability, etc. At least one selected from the group consisting of organic solvents, ether ester organic solvents, ketone organic solvents, nitrogen-containing organic solvents, etc., in an organic solvent at 50% by mass or more, particularly 70% by mass / 0 %. What contains above is preferable.
上記沸点 1 0 0〜 2 2 0 °Cのエーテル系有機溶剤、 エステル系有機溶剤、 エー テルエステル系有機溶剤、 ケトン系有機溶剤及び含窒素系有機溶剤の中でも、 溶 解性、 顔料分散性、 塗布性の点で、 ジエチレングリコールジメチルエーテル、 ジ エチレングリコースレメチノレエチノレエーテノレ、 エチレングリコーノレモノメチノレエー テルアセテート、 プロピレングリコールモノメチルエーテルアセテート、 プロピ レングリコーノレモノェチノレエーテ /レアセテート、 シクロへキサノン、 2—ヘプタ ノン、 2—ヒ ドロキシプロピオン酸ェチル、 3—メチルー 3—メ トキシブチルプ 口ピオネート、 3—メ トキシプロピオン酸ェチル、 3 _エトキシプロピオン酸メ チル、 蟻酸 n—ァミル等が好ましく、 更に好ましくは、 プロピレングリコールモ ノメチルエーテルアセテートである。  Among the above-mentioned ether organic solvents, ester organic solvents, ether ester organic solvents, ketone organic solvents and nitrogen-containing organic solvents having a boiling point of 100 to 220 ° C., the solubility, the pigment dispersibility, From the viewpoint of applicability, diethylene glycol dimethyl ether, diethylene glycol methinoleetinooleate, ethylene glycolone monomethinoleate teracetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl etherate / reacetate, cycloate Hexanone, 2-heptanone, 2-ethylhydroxypropionate, 3-methyl-3-methoxybutylpropionate, pionate, 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate are preferred. More preferably, propylene glyco Makes the chromophore at the distal end Roh methyl ether acetate.
尚、 沸点が 2 2 0 °C以上の有機溶剤を多く含有した系では、 塗布形成された塗 膜をプレベータする際に、 有機溶剤が充分に蒸発せずに乾燥塗膜内に残存し、 乾 燥塗膜の耐熱性が低下するおそれがある。 また、 沸点 1 0 0 °C未満の有機溶剤を 多く含有した系では、 ムラなく均一に塗布することが困難になり、 表面平滑性に 優れた塗膜が得られなくなるおそれがある。 また、 本発明で利用可能な光重合性化合物としては、 光重合性不飽和結合を分 子内に 1個以上有するモノマー、 オリゴマー等で、 光重合性不飽和結合を分子内 に 1個有するモノマーとしては、 メチルメタアタリレート、 プチルメタアタリレ ート、 2—ェチノレへキシノレメタクリレート、 メチルァクリレート、 ブチルアタリ レート、 2ーェチノレへキシルァクリレート等のアルキルメタクリレート又はァク リレート ；ベンジ/レメタクリレート、 ベンジルァクリレート等のァラルキルメタ クリレート又はァクリレート ；ブトキシェチルメタクリレート、 プトキシェチル ァクリレート等のアルコキシアルキルメタクリレート又はァクリレート ； N， N ージメチルアミノエチルメタクリレート、 N， N—ジメチルアミノエチルアタリ レート等のァミノアルキルメタクリレート又はァクリレート ；ジエチレングリコ ーノレエチノレエーテノレ、 ト リエチレングリコ一ノレプチノレエーテノレ、 ジプロピレンク" リコールメチルエーテル等のポリアルキレングリコールアルキルエーテルのメタ クリル酸エステル又はァクリル酸エステル；へキサエチレングリコールフエニル エーテル等のポリアルキレングリコールァリールエーテルのメタクリル酸エステ ル又はァクリル酸エステル；ィソボニルメタクリレート又はァクリレート ；グリ セロールメタクリレート又はァクリレート ； 2—ヒ ドロキシェチノレメタクリレー ト又はァクリ レート等が挙げられ、 光重合性不飽和結合を分子内に 2個以上有す るモノマーとしては、 ビスフエノール Aジメタクリレート、 1， 4一ブタンジォ 一ルジメタクリレート、 1， 3—プチレングリコー/レジメタクリレート、 ジェチ レングリコールジメタタリレート、 グリセロールジメタタリレート、 ネオペンチ ノレグリコーノレジメタクリレート、 ポリエチレングリコ一/レジメタクリレート、 ポ リプロピレングリコールジメタクリレート、 テトラエチレングリコールジメタク リレート、 トリメチロールプロパントリメタタリレート、 ペンタエリスルトール トリメタタリレート、 ペンタエリスリ トールテトラメタタリレート、 ジペンタエ リスリ トールテトラメタタリレート、 ジペンタエリスリ トールへキサメタクリレ 一卜、 ジペンタエリスリ トーノレペンタメタクリ レート、 ビスフエノ一ノレ Aジァク リレート、 1， 4一ブタンジォーノレジァクリレート、 1 , 3—ブチレングリコー ルジァクリレート、 ジェチレングリコ一/レジァタリレート、 グリセ口一ルジァク リレート、 ネオペンチノレグリコールジァクリレート、 ポリエチレングリコ一ルジ アタリ レート、 ポリプロピレングリコールジアタリ レート、 テトラエチレンダリ コールジァクリ レート、 トリメチローノレプロパントリアタリ レート、 ペンタエリ スルトールトリアタリ レート、 ペンタエリスリ トールテトラアタリレート、 ジぺ ンタエリスリ トールテトラアタリレート、 ジペンタエリスリ トールへキサァクリ レート、 ジペンタエリスリ トールペンタアタリレート等が挙げられる。 これらの 光重合性化合物は、 単独で又は 2種以上を組み合わせて用いることができる。 また、 本発明に利用可能な光重合開始剤としては、 特に制限なく、 例えば、 ベ ンゾフエノン、 N， Ν' ーテトラェチル _ 4 , A ' ージァミノべンゾフエノン、 4ーメ トキシー ージメチルァミノべンゾフエノン、 ベンジル、 2 , 2—ジェ トキシァセトフエノン、 ベンゾイン、 ベンゾインメチノレエーテノレ、 ベンゾインィ ソブチノレエーテノレ、 ペンジノレジメチノレケターノレ、 α—ヒ ドロキシイソプチノレフエ ノン、 チォキサントン、 2—クロ口チォキサントン、 1ーヒ ドロキシシクロへキ シルフェニルケトン、 tーブチルアントラキノン、 1—クロ口アントラキノン、 2， 3—ジクロロアントラキノン、 3—クロル一 2—メチルアントラキノン、 2 ーェチルアントラキノン、 1， 4一ナフトキノン、 1， 2—べンゾアントラキノ ン、 1， 4—ジメチルアントラキノン、 2—フエ二ルアントラキノン、 トリアジ ン系光重合開始剤等が挙げられる。 これらの光重合開始剤は単独で又は 2種以上 を組み合わせて用いられる。 ' In a system containing a large amount of an organic solvent having a boiling point of 220 ° C or more, when precoating a formed coating film, the organic solvent does not sufficiently evaporate and remains in the dried coating film, and The heat resistance of the dried coating film may decrease. Further, in a system containing a large amount of an organic solvent having a boiling point of less than 100 ° C., it is difficult to apply the coating uniformly without unevenness, and a coating film having excellent surface smoothness may not be obtained. Examples of the photopolymerizable compound usable in the present invention include monomers and oligomers having one or more photopolymerizable unsaturated bonds in the molecule, and monomers having one photopolymerizable unsaturated bond in the molecule. As alkyl methacrylates or acrylates such as methyl methacrylate, butyl methacrylate, 2-ethynolehexynole methacrylate, methyl acrylate, butyl acrylate, 2-ethynolehexyl acrylate; Aralkyl methacrylates or acrylates such as methacrylate and benzyl acrylate; alkoxyalkyl methacrylates or acrylates such as butoxyshethyl methacrylate and ptoxyshethyl acrylate; N, N-dimethylaminoethyl methacrylate; N, N-dimethylaminoethyl acrylate Methacrylates or acrylates of polyalkylene glycol alkyl ethers, such as diaminoglycol methacrylate or acrylate; diethylene glycol monoethylenoleate, triethylene glycol monoleptinoleate or dipropylene glycol methyl ether; Methacrylic acid ester or acrylic acid ester of polyalkylene glycol aryl ether such as oxaethylene glycol phenyl ether; isobonyl methacrylate or acrylate; glycerol methacrylate or acrylate; 2-hydroxyhexenolemethacrylate or acrylic acid Monomers having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate and 1,4-butanedioxide. 1-didimethacrylate, 1,3-butyleneglycol / resin methacrylate, butylene glycol dimethacrylate, glycerol dimethacrylate, neopentinole glycolone resin methacrylate, polyethylene glycol mono / resin methacrylate, polypropylene glycol dimethacrylate, tetraethylene Glycol dimethacrylate, trimethylolpropane trimetatalate, pentaerythritol trimetatalylate, pentaerythritol tetramethatalylate, dipentaerythritol tetrametaarylate, dipentaerythritol hexamethacrylate, dipentaerythry tonolepentamethacrylate, bispheno 1-butanediol acrylate, 1,4-butanedioloacrylate, 1,3-butylene Coat Rujiakurireto, Jechirenguriko one / Rejiatarireto, glycerin port one Rujiaku Relate, neopentyl Honoré glycol § chestnut, polyethylene glycolate one distearate Atalilate, polypropylene glycol diatalylate, tetraethylenedalichol diacrylate, trimethylonolepropane triatalylate, pentaerythritol triatalylate, pentaerythritol tetraatalylate, dipentaerythritol tetraatarylate, dipentaerythritol hexaacrylate, Dipentaerythritol pentaatalylate and the like. These photopolymerizable compounds can be used alone or in combination of two or more. The photopolymerization initiator that can be used in the present invention is not particularly limited, and examples thereof include benzophenone, N, Ν′-tetraethyl_4, A ′ diaminobenzozophenone, 4-methoxydimethylaminobenzobenzophenone, benzyl, 2, 2-Jetoxyacetophenone, benzoin, benzoinmethinoleatenore, benzoinsobutinoreatenore, penzinoresimetinoleketanore, α-hydroxyisobutinolephenone, tioxanthon, 2-clothoxyxanthone, 1-hydroxycyclohexylphenyl ketone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-1- 2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1 , 2—Venzoanthraquinone, 1, 4 Dimethyl anthraquinone, 2-phenylene Le anthraquinone include triazine emissions based photopolymerization initiator and the like. These photopolymerization initiators are used alone or in combination of two or more. '
また、 本発明のカラーフィルター用顔料分散レジスト組成物には、 通常、 現像 性改質のための樹脂を含み、 カラーフィルターを製造する際にその現像処理工程 において用いられる現像液、 特に好ましくはアル力リ現像液に対して可溶性を有 するアル力リ可溶性樹脂、 とりわけ、 力ルポキシル基を有するアル力リ可溶性樹 脂を使用することができる。  In addition, the pigment-dispersed resist composition for a color filter of the present invention usually contains a resin for improving the developability, and is preferably a developer used in the developing step of the color filter, particularly preferably an alcohol. An alcohol-soluble resin having solubility in an aqueous developer can be used, in particular, an alcohol-soluble resin having an epoxy group.
カルボキシル基を有するアルカリ可溶性樹脂としては、 例えば、 アクリル酸、 メタクリル酸等のカルボキシル基含有不飽和単量体と、 スチレン、 2—ヒ ドロキ シェチルアタリレート、 2—ヒ ドロキシェチ メタタリ レート、 ァリノレアクリレ ート、 ァリルメタタリレート、 ベンジルアタリレート、 ベンジルメタタリレート、 グリセローノレモノアタリレート、 グリセローノレメタタリレート、 Ν—フエ-ノレマ レイミ ド、 ポリスチレンマク口モノマー及びポリメチノレメタクリレートマクロモ ノマーの群から選ばれる少なくとも 1種との共重合体が使用できる。 Examples of the alkali-soluble resin having a carboxyl group include unsaturated monomers containing a carboxyl group such as acrylic acid and methacrylic acid, styrene, 2-hydroxyshetyl acrylate, 2-hydroxymetharyl acrylate, and arinorea acrylate. , Aryl methacrylate, benzyl acrylate, benzyl methacrylate, glycerono remeth acrylate, glycerono remeth acrylate, Ν-fe-norema remide, polystyrene mac mouth monomer and polymethinole methacrylate macromo Copolymers with at least one member selected from the group of nomers can be used.
また、 本発明のカラーフィルター用顔料分散レジス ト組成物には、 必要に応じ て、 暗反応を制御するためにハイドロキノン、 ピロガロール、 t—プチルカテコ ール等の熱重合禁止剤、 顔料誘導体、 顔料分散助剤、 基板との密着性を向上させ るためのシラン力ップリング剤やチタネートカツプリング剤、 紫外線吸収剤、 酸 化防止剤等の各種添加剤を適宜使用することもできる。  The pigment dispersion resist composition for a color filter of the present invention may contain, if necessary, a thermal polymerization inhibitor such as hydroquinone, pyrogallol, or t-butyl catechol, a pigment derivative, or a pigment dispersion for controlling a dark reaction. Auxiliaries and various additives such as a silane coupling agent, a titanate coupling agent, an ultraviolet absorber, and an antioxidant for improving the adhesion to the substrate can be used as appropriate.
次に、 上記カラーフィルター用顔料分散レジスト組成物を構成する材料を用い て、 本発明のカラーフィルター用顔料分散レジスト組成物を得るための製造方法 について説明する。  Next, a method for producing the pigment-dispersed resist composition for a color filter of the present invention using the materials constituting the pigment-dispersed resist composition for a color filter will be described.
本発明では、 後述する特定の構造からなる高圧乳化機を用いて、 顔料、 顔料分 散剤及び有機溶剤を必須成分として含有する混合液 （以下、 単に混合液とも記載 する） から顔料分散物を製造するが、 まず、 その方法について説明する。  In the present invention, a pigment dispersion is produced from a mixed liquid containing a pigment, a pigment dispersant and an organic solvent as essential components (hereinafter, also simply referred to as a mixed liquid) using a high-pressure emulsifier having a specific structure described later. First, the method will be described.
尚、 上記の 「顔料分散物」 とは、 「顔料、 顔料分散剤及び有機溶剤を必須成分 として少なくとも含有する混合液を、 高圧乳化機を用いて顔料分散処理すること により得られる分散物」 という条件を満足すればよい。 従って、 ここでは、 顔料、 顔料分散剤及び有機溶剤の必須成分だけを含有する混合液を、 高圧乳化機を用い て顔料分散処理することにより得られた顔料分散物に、 更に、 カラーフィルター 用顔料分散レジスト組成物を得るために必要である材料を加えて得られるカラー フィルター用顔料分散レジスト組成物について説明するが、 これは、 本発明でよ り好ましい実施形態の一例であり、 本発明はこれに限定されるものではない。 す なわち、 上記混合液を構成するための必須成分の他にもカラーフィルター用顔料 分散レジスト組成物を構成するその他の材料を任意に添加混合して得られる混合 液を、 高圧乳化機を用いて顔料分散処理することにより得られた顔料分散物に、 更に必要ならばカラーフィルタ一用顔料分散レジスト組成物得るために必要な材 料を加えて得られるカラーフィルター用顔料分レジスト組成物も本発明のカラー フィルター用顔料分散レジスト組成物である。  The above-mentioned “pigment dispersion” is referred to as “dispersion obtained by subjecting a mixture containing at least a pigment, a pigment dispersant and an organic solvent as essential components to a pigment dispersion treatment using a high-pressure emulsifier”. The condition should be satisfied. Therefore, here, a pigment dispersion obtained by subjecting a mixture containing only essential components of a pigment, a pigment dispersant and an organic solvent to a pigment dispersion treatment using a high-pressure emulsifier is further added to a pigment for a color filter. A pigment-dispersed resist composition for a color filter obtained by adding a material necessary for obtaining a dispersed resist composition will be described. However, this is an example of a more preferred embodiment of the present invention. However, the present invention is not limited to this. That is, in addition to the essential components for constituting the above-mentioned mixed solution, a mixed solution obtained by arbitrarily adding and mixing other materials constituting the pigment-dispersed resist composition for a color filter using a high-pressure emulsifier. The pigment-dispersed resist composition for a color filter obtained by adding a material necessary for obtaining a pigment-dispersed resist composition for a color filter, if necessary, to the pigment dispersion obtained by the It is a pigment dispersion resist composition for color filters of the present invention.
上記カラーフィルター用顔料分散レジスト組成物は、 例えば、 カラ一フィルタ 一用顔料分散レジスト組成物を構成するための必須成分である光重合性化合物と 光重合開始剤とを上記混合液中に含有させて顔料を分散し、 顔料を分散した後に は光重合性化合物と光重合開始剤とを添加しないで得られるものであってもよい し、 光重合性化合物と光重合開始剤のどちらか一方を上記混合液中に含有させて 顔料を分散し、 顔料を分散した後に更にどちらか他方を添カ卩して得られるもので あってもよレヽ。 The color filter pigment-dispersed resist composition includes, for example, a photopolymerizable compound and a photopolymerization initiator, which are essential components for constituting the color filter-pigmented resist composition, in the mixture. After dispersing the pigment May be obtained without adding the photopolymerizable compound and the photopolymerization initiator, or the pigment may be dispersed by containing either the photopolymerizable compound or the photopolymerization initiator in the above-mentioned mixed solution. Alternatively, it may be obtained by dispersing the pigment and then adding one of the other.
本発明の顔料分散物の顔料を微分散するために用いる顔料分散機としては、 例 えば、 図 1、 図 2に示すように、 加圧部、 オリフィス、 中空部材を並列的に構成 させた高圧乳化機が使用できる。 図 1及び図 2に示した構成を有する高圧乳化機 は、 本発明における好ましい実施形態を例示したものであり、 本発明はこれに限 定されるものではない。  Examples of the pigment dispersing machine used for finely dispersing the pigment of the pigment dispersion of the present invention include, as shown in FIGS. 1 and 2, a high-pressure unit having a pressure unit, an orifice, and a hollow member arranged in parallel. An emulsifier can be used. The high-pressure emulsifier having the configuration shown in FIGS. 1 and 2 illustrates a preferred embodiment of the present invention, and the present invention is not limited to this.
図 1において、 混合液タンク 1に貯蔵されている分散処理の対象となる混合液 を、 高圧ポンプ 2により加圧して分散チャンバ一 3に導き、 処理された分散物は、 保存タンク 4に導かれる。 上記分散チャンパ一 3の例としては、 図 2に示す構造 のもの等が挙げられる。  In FIG. 1, the mixed liquid to be subjected to the dispersion treatment stored in the mixed liquid tank 1 is pressurized by the high-pressure pump 2 and guided to the dispersion chamber 13, and the processed dispersion is guided to the storage tank 4. . As an example of the distributed champers 13, those having the structure shown in FIG.
図 2における高圧乳ィヒ機の分散チャンバ一は、 混合液注入口 7、 オリフィス 8 及び中空部材 9の、 顔料分散のための 3つの必須の構成と、 背圧バルブ 1 0、 分 散物排出口 1 1を備えたものである。 この装置では、 高圧ポンプ 2 (図示せず） を用いて混合液注入口 7に導入された混合液を、 加圧下で、 オリフィス 8を高速 で通過させる。 更に、 オリフィス 8により発生した混合液の高速ジェット流を中 空部材 9中に噴射させ、 先に噴射させて中空部材 9中に滞留している混合液との 速度差によって発生するせん断応力により混合液を分散させることになる。  The dispersion chamber of the high-pressure milking machine in FIG. 2 has three essential components for dispersing the pigment: the mixture inlet 7, the orifice 8, and the hollow member 9; the back pressure valve 10; It has exit 1 1. In this device, a high pressure pump 2 (not shown) is used to pass a mixture introduced into a mixture inlet 7 at high speed through an orifice 8 under pressure. Furthermore, a high-speed jet stream of the mixed liquid generated by the orifice 8 is jetted into the hollow member 9, and is mixed by shearing stress generated by a speed difference between the mixed liquid staying in the hollow member 9 and jetting first. The liquid will be dispersed.
本高圧乳化機では、 高速ジェット流を発生させる必要があることから、 上記ォ リフィス 8として微細なオリフィスを利用するが、 そのオリフィス径としては、 生産性や装置の効率の面から 0 . 0 1〜1 . 5 mm程度の径を有するものであり、 その形状は湾曲部や屈曲部のない摩耗し難い直線状であることが好ましい。 更に、 オリフィスを形成する材料としては、 例えば、 焼結ダイャモンド及び単結晶ダイ ャモンド等のダイヤモンド、 アルミナ、 ジルコ二ァ及ぴカーポランダム等のセラ ミック材料及びステンレス、 鉄及びチタン等の金属が挙げられるが、 その中でも 摩耗し難い高硬度の材質のものが好ましい。  In this high-pressure emulsifier, a fine orifice is used as the orifice 8 because it is necessary to generate a high-speed jet stream. However, the orifice diameter is 0.01 from the viewpoint of productivity and equipment efficiency. It has a diameter of about 1.5 mm, and its shape is preferably a straight line having no curved or bent portions and hardly worn. Further, examples of the material forming the orifice include diamond such as sintered diamond and single-crystal diamond, ceramic materials such as alumina, zirconium and carporundum, and metals such as stainless steel, iron and titanium. However, among them, materials of high hardness which are hard to wear are preferable.
また、 均一で微細な顔料分散物を得るためには、 オリフィス内及ぴ中空部材内 で混合液にかかる最適な応力が得られるように、 オリフィスを通過させる混合液 の速度を調整することが必要となるが、 この混合液の通過速度は、 オリフィス径、 混合液の粘度及び加圧条件によって調整が可能である。 通常、 混合液を湾曲部及 ぴ屈曲部のない直線状のオリフィスを通過させる場合は、 5 X 1 0 3〜 3 . 2 X 1 0 5 k P aの加圧条件で、 混合液速度を 1 0 0〜： L O 0 O m/ s e c , より好 適には 4 0 0〜 7 0 O m/ s e cにすることが好ましい。 In order to obtain a uniform and fine pigment dispersion, the inside of the orifice and the inside of the hollow member It is necessary to adjust the speed of the mixture passing through the orifice so that the optimum stress applied to the mixture is obtained at Adjustment is possible depending on the conditions. Usually, when passing a straight orifice with no curved portion及Pi bent portion the mixture is a 5 X 1 0 3 ~ 3. 2 X 1 0 5 pressure conditions k P a, the mixture rate of 1 00 to: LO 0 Om / sec, more preferably 400 to 70 Om / sec.
更に、 オリフィスによって発生した混合液の高速ジエツト流を噴射させる中空 部材としては、 高速ジエツト流が直線的に流動できるように円筒形状が好ましい。 尚、 本発明では、 中空部材は、 シールが付いたセルを複数個組み合わせ構成でき るようになっている。  Further, the hollow member for injecting the high-speed jet flow of the mixed liquid generated by the orifice is preferably cylindrical so that the high-speed jet flow can flow linearly. In the present invention, the hollow member can be configured by combining a plurality of cells with seals.
また、 中空部材内に均一な流れができて、 混合液同士でせん断応力が働くため の適度な速度差が生じる様に、 オリフィス：中空部材の管径の比を 1 ： 2〜5 0、 より好適には 1 ： 5〜1 0程度とし、 加えて、 高速ジェット流が中空部材の対面 に強い力で衝突しないために充分な容積を有することが望ましい。  Also, the ratio of the orifice to the hollow member tube diameter is set to 1: 2 to 50, so that a uniform flow can be generated in the hollow member and an appropriate speed difference occurs for the shearing stress to act between the mixed liquids. Preferably, the ratio is about 1: 5 to 10 and, in addition, it is desirable to have a sufficient volume so that the high-speed jet stream does not collide with the opposite surface of the hollow member with a strong force.
尚、 中空部材の材料もまた、 摩耗し難いものが好ましく、 例えば、 アルミナ、 ジルコ二ァ及ぴカーボランダム等のセラミック材料や、 ステンレス、 鉄及びチタ ン等の金属が利用できる。  The material of the hollow member is also preferably hard to wear. For example, ceramic materials such as alumina, zirconium and carborundum, and metals such as stainless steel, iron and titanium can be used.
本宪明で利用する高圧乳化機では、 処理された分散物を排出するために、 中空 部材のどの部分に排出口を設けてもよく、 例えば、 中空部材のオリフィスと対面 する壁に設ける方法 （図示せず） 、 中空部材のオリフィス側近傍に設ける方法 （ 図 2 ) の両方ともが利用可能である。  In the high-pressure emulsifier used in the present invention, a discharge port may be provided at any part of the hollow member in order to discharge the treated dispersion. For example, a method in which the discharge port is provided on a wall facing the orifice of the hollow member ( Both methods (not shown) and the method of providing the hollow member near the orifice side (FIG. 2) can be used.
図 2に示したように、 混合液をオリフィス 8側の分散物排出口 1 1より排出す る構造にした場合は、 中空部材の中心部を流れる高速ジェット流の方向と、 分散 物排出口 1 1に向かう混合液の流れの方向とが対向するようになるので、 せん断 の効果が高くなるために、 本発明において用い得るより強固な一次粒子の凝集力 を有する高級有機顔料を分散させるのに有利となる。  As shown in Fig. 2, when the mixed liquid is discharged from the dispersion outlet 11 on the orifice 8 side, the direction of the high-speed jet flow flowing through the center of the hollow member and the dispersion outlet 1 Since the direction of the flow of the mixture toward 1 becomes opposite, the effect of shearing is increased, so that higher organic pigments having a stronger cohesive force of primary particles that can be used in the present invention are dispersed. This is advantageous.
尚、 混合液をオリフィス 8側の分散物排出口 1 1より排出する構造にした場合 は、 注入した混合液が分散されないままに排出されないような構造にする必要が ある。 例えば、 中空部材に背圧バルブを設けることが好ましい。 中空部材に背圧 バルブを設けて中空部材の圧力 （背圧という） をかけることにより、 中空部材中 の混合物の流速の制御や微小泡の発生による分散力低下の防止等もできる。 背圧 は、 分散の条件や有機溶剤の沸点等により変化するが、 1 X 1 0 3 k P a以下で は効果は低く、 1 X 1 0 4 k P a以上と高くしても効果は変わらなくなる。 本発明の高圧乳化機における分散回数 （オリフィス通過回数） は、 1回又はそ れ以上であり （図 1では、 分散物排出口から排出された分散物は保存タンク 4に 貯留されるが、 再び混合液タンク 1に戻してもよく、 循環させるような構造であ つてもよい） 、 使用する顔料、 分散条件及び要求される顔料分散物の顔料粒子の 粒子径、 粒度分布等によって適宜選択することができる。 If the mixed liquid is discharged from the dispersion outlet 11 on the orifice 8 side, the structure must be such that the injected mixed liquid is not discharged without being dispersed. For example, it is preferable to provide a back pressure valve on the hollow member. Back pressure on hollow members By providing a valve to apply the pressure of the hollow member (called back pressure), it is possible to control the flow rate of the mixture in the hollow member and to prevent the dispersion force from decreasing due to the generation of microbubbles. Back pressure will vary according to the boiling point or the like of the dispersion conditions and organic solvents, 1 X 1 0 3 k P a following effect is low, the change effect can be as high as 1 X 1 0 4 k P a more Disappears. The number of times of dispersion (the number of times of passage through the orifice) in the high-pressure emulsifier according to the present invention is one or more times (in FIG. 1, the dispersion discharged from the dispersion discharge port is stored in the storage tank 4, but is again stored in the storage tank 4). It may be returned to the mixed liquid tank 1 or may have a structure that circulates it) .It should be appropriately selected according to the pigment to be used, the dispersion conditions, and the required particle size and particle size distribution of the pigment particles of the pigment dispersion. Can be.
さらに、 上記混合液と上記高圧乳化機 （分散チャンバ一 3として図 2の構造の ものを使用） を用いて、 カラーフィルター用顔料分散レジスト組成物を得るため の好適な製造方法の一例について説明する。  Further, an example of a preferred production method for obtaining a pigment-dispersed resist composition for a color filter using the above-mentioned mixed solution and the above-mentioned high-pressure emulsifier (the one having the structure shown in FIG. 2 as the dispersion chamber 13) will be described. .
まず、 顔料、 有機溶剤及び顔料分散剤を含有する混合液を、 高圧乳化機により 分散する前に、 高速ミキサーや高速ホモジナイザー等の非メディア型分散機を利 用してプレミックス処理する。 すなわち上記混合液としては、 非メディア型混合 装置でプレミックス処理してなる混合液を使用することが好ましい。 尚、 混合液 • は、 適度な粘度、 例えば 1 P a · s未満に調整するのがよい。  First, before dispersing a mixture containing a pigment, an organic solvent, and a pigment dispersant by a high-pressure emulsifier, a premix treatment is performed using a non-media type disperser such as a high-speed mixer or a high-speed homogenizer. That is, it is preferable to use, as the above-mentioned mixed liquid, a mixed liquid that has been subjected to a premixing process using a non-media type mixing device. It is preferable that the mixed liquid is adjusted to have an appropriate viscosity, for example, less than 1 Pa · s.
次に、 この混合液を、 高圧ポンプを使用し昇圧し、 湾曲部、 合流部のない直線 状のォリフィス中を 4 0 0〜 7 0 0 m/ s e cの高速ジエツト流 5通過 せ、 こ の高速ジェット流を背圧が 1 X 1 0 3〜 1 X 1 0 4 k P a (好適には、 高速ジェ ット流がオリフィスと対面する壁に衝突する速度が 0となるように制御） である 中空部材に噴射させることが好ましい。 Next, the pressure of the mixed solution is increased by using a high-pressure pump, and the mixed solution is passed through a high-speed jet stream 5 at a speed of 400 to 700 m / sec 5 through a straight orifice without a curved portion or a confluent portion. The back pressure of the jet stream is 1 × 10 3 to 1 × 10 4 kPa (preferably, the speed at which the high-speed jet stream collides with the wall facing the orifice becomes 0). It is preferable to inject into the hollow member.
尚、 顔料分散物の製造は、 4 0〜 7 0 °Cで行うことが好ましい。 顔料と有機溶 剤の濡れ性の点から温度は高くして行うことが好ましい。 しかし、 沸点 1 0 0〜 2 2 0 °Cの有機溶剤を使用しており、 製造時引火するおそれがあるので 7 0 °C以 下で行うことが好ましい。  The production of the pigment dispersion is preferably performed at 40 to 70 ° C. The temperature is preferably increased from the viewpoint of the wettability between the pigment and the organic solvent. However, since an organic solvent having a boiling point of 100 to 220 ° C. is used and there is a risk of ignition during production, it is preferable to carry out the reaction at 70 ° C. or lower.
これにより、 短時間で、 顔料は微分散され、 分散槽、 メディア等の破片が混入 していない、 過分散の粒子が少ない、 粒度分布が狭い、 顔料分散剤が微細な顔料 に吸着した粒子となる。 尚、 顔料の微分散は、 顔料分散物の鮮明な色相から平均 粒子径 1 5 0 n m未満となるように調製される。 分散を完了した顔料分散物は、 分散物排出口からタンクに導かれる。 このような製造方法で顔料を分散させて得 られる顔料分散物は、 更に、 顔料分散物を遠心分離処理、 フィルター処理等の後 処理により粗大粒子の除去を行ってもよい。 As a result, the pigment is finely dispersed in a short period of time. Become. The fine dispersion of the pigment is averaged from the clear hue of the pigment dispersion. It is prepared so as to have a particle size of less than 150 nm. The pigment dispersion that has been completely dispersed is guided to the tank from the dispersion outlet. The pigment dispersion obtained by dispersing the pigment by such a production method may be further subjected to post-treatment such as centrifugal separation treatment or filter treatment of the pigment dispersion to remove coarse particles.
上記製造方法により分散を完了した顔料分散物に、 光重合性化合物、 光重合開 始剤、 必要に応じて有機溶剤、 改質用樹脂、 各種添加剤を添加し攪拌混合する。 以上で説明した混合液組成と製造方法で得られる顔料分散物は、 均一で制御さ れたせん断力によって、 顔料が分散され、 過剰粉砕粒子や未分散粒子を発生させ ることなく、 顔料を微細な一次粒子又はその近傍まで均一に分散させることを可 能にする上に、 微細分散した顔料粒子が経時においても凝集を起こすことがない ために、 分散安定性及ぴ流動性が極めて優れたものである。  A photopolymerizable compound, a photopolymerization initiator, and, if necessary, an organic solvent, a modifying resin, and various additives are added to the pigment dispersion that has been completely dispersed by the above-mentioned production method, followed by stirring and mixing. The pigment dispersion obtained by the mixed liquid composition and the production method described above disperses the pigment by a uniform and controlled shear force, and makes the pigment finer without generating excessive pulverized particles or undispersed particles. Excellent dispersion stability and fluidity because it enables uniform dispersion of primary particles or its vicinity and also prevents finely dispersed pigment particles from aggregating over time. It is.
以上、 本発明のカラーフィルター用顔料分散レジスト組成物は、  As described above, the pigment dispersion resist composition for a color filter of the present invention,
( 1 ) 分散槽、 メディア等の破片が混入しない、  (1) No debris such as dispersion tank and media is mixed.
( 2 ) 過分散物が少なく、 塩基性基を含有する顔料分散剤が微細な顔料に吸着し た粒度分布の狭い粒子 (好ましくは平均粒子径 1 5 0 n m未満) であり、  (2) particles having a narrow particle size distribution (preferably having an average particle size of less than 150 nm), in which the amount of the superdispersion is small and the pigment dispersant containing a basic group is adsorbed on a fine pigment,
( 3 ) 顔料分散性の向上により保存安定性が良好であり、  (3) Good storage stability due to improved pigment dispersibility;
( 4 ) 再溶解性、 顔料分散性、 流動性の向上により、 現像残渣がなくなり、 (4) Improvement in resolubility, pigment dispersibility, and fluidity eliminates development residues,
( 5 ) 得られるカラーフィルタ一は、 透明性、 コントラスト、 着色性が良好とな り、 鮮明な色相となり、 塗膜平滑性も良好となるものである。 図面の簡単な説明 (5) The obtained color filter has good transparency, contrast, and colorability, has a clear hue, and has good coating smoothness. BRIEF DESCRIPTION OF THE FIGURES
図 1は、 本発明の分散物の製造において用いられる高圧乳化機の一例の概略図 である。  FIG. 1 is a schematic view of an example of a high-pressure emulsifier used in the production of the dispersion of the present invention.
図 2は、 本発明の分散物の製造において用いられる高圧乳化機の分散： 一の一例の概略図である。 符号の説明  FIG. 2 is a schematic view of one example of dispersion of a high-pressure emulsifier used in the production of the dispersion of the present invention. Explanation of reference numerals
1 混合液タンク  1 Mix tank
2 高圧ポンプ 3 分散チャンバ一 2 High pressure pump 3 Dispersion chamber
4 保存タンク  4 Storage tank
5 混合液  5 Mixture
6 分散物  6 dispersion
7 混合液注入口  7 Mixed liquid inlet
8 オリフィス  8 orifice
9 中空部材  9 Hollow member
1 0 背圧バノレブ  1 0 Back pressure vanolev
1 1 分散物排出口 発明を実施するための最良の形態  1 1 Dispersion outlet Best mode for carrying out the invention
以下、 実施例に基づいて本発明をより具体的に説明するが、 本発明はこれら実 施例に限定されるものではない。 尚、 特に断りのない限り、 本実施例において、 「部」 及び 「％」 は、 それぞれ 「質量部」 及び 「質量％」 を表す。  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.
1 . カラーフィルター用顔料分散物の調整 1. Preparation of pigment dispersion for color filter
1 - 1 ) カラーフィルター用顔料分散物実施例 1〜6  1-1) Pigment dispersion for color filter Examples 1 to 6
表 1に記載した配合になるように、 有機溶剤に塩基性基を含有する顔料分散剤 を加え混合し、 ワニスを調整し、 更に顔料を加えて高速撹拌機でプレ分散し、 図 A pigment dispersant containing a basic group is added to an organic solvent and mixed to obtain the composition shown in Table 1, the varnish is adjusted, and further the pigment is added and predispersed with a high-speed stirrer.
2で表わされる高圧乳化機で下記の条件を用いて分散した後、 3 μ p ρのプリ一 ッフィルタ一で濾過して粗大粒子を除去しカラーフィルタ一用顔料分散物実施例 1〜 6を得た。 表 1で示す塩基性基を含有する顔料分散剤 A〜F、 アタリル樹脂、 有機溶剤は次に示すものである。 なお、 使用した材料、 分散条件は以下の通りである。 After dispersing using a high-pressure emulsifier represented by 2 under the following conditions, the mixture was filtered through a 3 μ p ρ pre-filter to remove coarse particles, and pigment dispersion examples for color filters 1 to 6 were obtained. Was. The pigment dispersants A to F containing a basic group, the ataryl resin, and the organic solvent shown in Table 1 are as follows. The materials used and the dispersion conditions are as follows.
<使用した材料 >  <Material used>
塩基性基を含有する顔料分散剤 Pigment dispersant containing basic group
( 1 ) 塩基性基を含有する顔料分散剤 A  (1) Pigment dispersant A containing a basic group
ポリ （低級アルキレンィミン） 誘導体：ソルスパース 2 4 0 0 0 G R (商品名、 Ab e c i a社製） Poly (lower alkylene imine) derivative: Solsperse 2 4 0 0 GR (trade name, Ab ecia)
(ポリ （低級アルキレンィミン） に遊離のカルボキシル基を有するポリエステル を反応させて得られる反応生成物）  (Reaction product obtained by reacting poly (lower alkylene imine) with polyester having free carboxyl group)
(2) 塩基性基を含有する顔料分散剤 B  (2) Pigment dispersant B containing a basic group
末端にアミノ基を有するポリエステル： ソルスパース 17000 (商品名、 Ab e c i a社製） Polyester having an amino group at the end: Solsperse 17000 (trade name, manufactured by Abecia)
(低分子ァミノ化合物に遊離のカルボキシル基を有するポリエステルを反応させ て得られる反応生成物）  (Reaction product obtained by reacting low molecular weight amino compound with polyester having free carboxyl group)
(3) 塩基性基を含有する顔料分散剤 C  (3) Pigment dispersant C containing a basic group
ポリウレタン樹脂： D i s p e r b y k- 161 (商品名、 BYK C h e m i e社製） Polyurethane resin: D i s p e r b y k-161 (trade name, manufactured by BYK Chemie)
(ポリイソシァネート化合物のイソシァネート基に、 水酸基を 1個有するポリエ ステル、 2〜 3個のイソシァネート基反応性基を有する化合物、 イソシァネート 基反応性官能基と第 3級ァミノ基とを有する脂肪族又は複素環式炭化水素化合物 を順次反応させてなる反応生成物)  (A polyester having one hydroxyl group in the isocyanate group of the polyisocyanate compound, a compound having two to three isocyanate group-reactive groups, an aliphatic group having an isocyanate group-reactive functional group and a tertiary amino group Or a reaction product obtained by sequentially reacting a heterocyclic hydrocarbon compound)
(4) 塩基性基を含有する顔料分散剤 D  (4) Pigment dispersant D containing a basic group
塩基性基含有アクリル樹脂： EFKA— 46 (商品名、 EFKA Ch em i c a 1 B. V. 社製） Acrylic resin containing basic group: EFKA-46 (trade name, manufactured by EFKA Chemica 1 B.V.)
(アルコール性水酸基を有するァクリレートの重合物にポリィソシァネート化合 物とアミノ基を有する炭化水素化合物を反応させてなる反応生成物)  (A reaction product obtained by reacting a polyisocyanate compound with a hydrocarbon compound having an amino group with a polymer of an acrylate having an alcoholic hydroxyl group)
(5) 塩基性基を含有する顔料分散剤 E  (5) Pigment dispersant E containing a basic group
低分子ァミノ化合物のポリエーテル鎖付加物： ソルスパース 20000 (商品名、 Ab e c i a社製） Polyether chain adduct of low molecular weight amino compound: Solsperse 20000 (trade name, manufactured by Abecia)
(6) 塩基性基を含有する顔料分散剤 F  (6) Pigment dispersant F containing a basic group
塩基性基含有ァクリル樹脂： D i s p e r b y k- 2001 (商品名、 ビック ケミー .ジャパン社製） アル力リ可溶性樹脂 Basic group-containing acrylyl resin: Disperkyk-2001 (trade name, manufactured by Big Chemie Japan Ltd.)
アタリル樹脂：ベンジルメタクリレート 'メタタリル酸共重合体 （重量平均分子 量： 20000、 酸価 100) 有機溶剤 Ataryl resin: benzyl methacrylate 'methacrylic acid copolymer (weight average molecule Amount: 20000, acid value 100) Organic solvent
プロピレンダリコールモノメチルエーテルァセテ一ト （PMAC) Propylene dalycol monomethyl ether acetate (PMAC)
<高圧乳化機の分散条件 > <Dispersion conditions of high-pressure emulsifier>
分散圧力： 2 X 1 05 k P a Distributed pressure: 2 X 1 0 5 k P a
プレ分散した分散物流速： 60 Om/ s e c Predispersed dispersion flow rate: 60 Om / sec
オリフィス径： 0. 1 5 mm Orifice diameter: 0.15 mm
中空部材形状 直径： 1 mm Hollow member shape Diameter: 1 mm
背圧： 7000 k P a Back pressure: 7000 kPa
製造温度： 50 °C Production temperature: 50 ° C
パス回数： 5回 1— 2) カラーフィルター用顔料分散物比較例 1 Number of passes: 5 1–2) Comparative example 1 of pigment dispersion for color filter
PMAC 771部に塩基性基を含有する顔料分散剤 A 62部、 アクリル樹 脂 12部を加え混合し、 ワニスを調製し、 更に C. I . ビグメントイエロー 15 0 1 55部を加えて高速撹拌機でプレ分散した後、 湿式サーキユレーションミ ルで 10時間練肉分散し、 その後、 3 μ p pのプリーツフィルターで濾過して粗 大粒子を除去し、 カラーフィルター用顔料分散物比較例 1を得た。  62 parts of a pigment dispersant A containing a basic group and 12 parts of an acrylic resin are added to 771 parts of PMAC and mixed to prepare a varnish. Further, C.I. After pre-dispersion with a machine, the mixture was kneaded and dispersed with a wet circulation mill for 10 hours, and then filtered with a 3 μpp pleated filter to remove coarse particles. Obtained.
1 -3) カラーフィルター用顔料分散物比較例 2 1-3) Comparative example 2 of pigment dispersion for color filter
PMAC 786部に塩基性基を含有する顔料分散剤 E 47部、 ァクリル樹 月旨 1 2部を加え混合し、 ワニスを調製し、 更に C. I . ビグメントレッド 25 4 1 55部を加えて高速撹拌機でプレ分散した後、 湿式サーキュレーションミ ルで 10時間練肉分散し、 その後、 3 μ p ρのプリーツフィルターで濾過して粗 大粒子を除去し、 カラーフィルタ一用顔料分散物比較例 2を得た。  To 786 parts of PMAC, 47 parts of pigment dispersant E containing a basic group and 12 parts of Acryl Tree are added and mixed to prepare a varnish. Further, C.I. After pre-dispersing with a high-speed stirrer, knead and disperse with a wet circulation mill for 10 hours, and then filter through a 3 μp ρ pleated filter to remove coarse particles. Example 2 was obtained.
1 -4) カラーフィルター用顔料分散物比較例 3 PMAC 77 1部に塩基性基を含有する顔料分散剤 A 62部、 ァクリル樹 脂 1 2部を加え混合し、 ワニスを調製し、 更に C. I . ビグメントイエロー 15 0 155部を加えて高速撹拌機でプレ分散した後、 高圧分散機としてナノマイ ザ一 （ナノマイザ一社製） を使用し下記の条件で分散し、 その後、 S /x p pのプ リーツフィルターで濾過して粗大粒子を除去し、 カラーフィルター用顔料分散物 比較例 3を得た。 1 -4) Comparative example 3 of pigment dispersion for color filter To 1 part of PMAC 77, 62 parts of a pigment dispersant A containing a basic group and 12 parts of acryl resin are added and mixed to prepare a varnish. Further, C.I. After pre-dispersing with a stirrer, use a Nanomizer-1 (manufactured by Nanomizer-1) as a high-pressure disperser, disperse under the following conditions, and then filter through a S / xpp pleated filter to remove coarse particles. Comparative Example 3 of a pigment dispersion for a color filter was obtained.
なお、 分散条件は以下の通りである。 The dispersion conditions are as follows.
<分散条件 > <Dispersion condition>
処理圧力： 5 X 107P a Processing pressure: 5 X 10 7 Pa
処理回数： 5回 Processing times: 5 times
1- 5) カラーフィルター用顔料分散物比較例 4 1-5) Comparative example 4 of pigment dispersion for color filter
PMAC 786部に塩基性基を含有する顔料分散剤 E 47部、 アクリル樹 月旨 1 2部を加え混合し、 ワニスを調製し、 更に C. I . ビグメントレッド 254 1 55部を加えて高速撹拌機でプレ分散した後、 高圧分散機としてナノマイザ 一 （ナノマイザ一社製） を使用し下記の条件で分散し、 その後、 のプリ 一ッフィルタ一で濾過して粗大粒子を除去し、 カラーフィルタ一用顔料分散物比 較例 4を得た。  To 786 parts of PMAC, add 47 parts of a pigment dispersant E containing a basic group and 12 parts of an acrylic resin, mix and prepare a varnish, and further add 55 parts of C.I. After pre-dispersing with a stirrer, use a Nanomizer-1 (manufactured by Nanomizer-1) as a high-pressure disperser, disperse under the following conditions, and then filter through a prefilter to remove coarse particles. Comparative Example 4 was obtained.
なお、 分散条件は以下の通りである。 The dispersion conditions are as follows.
ぐ分散条件 >  Dispersion conditions>
処理圧力： 5 X 107 P a Processing pressure: 5 X 10 7 Pa
処理回数： 5回 Processing times: 5 times
2. カラーフィルター用顔料分散レジスト組成物実施例 1〜 6、 比較例 1〜 4 実施例 1〜6、 比較例 1〜4の各カラーフィルター用顔料分散物 43. 8·部に、 アクリル樹脂 6部、 ジペンタエリスリ トールへキサアタリレート 2. 8部、 光重 合開始剤 0. 9部、 PMAC 46. 5部を配合し攪捽し、 実施例 1〜 6、 比較 例 1〜4のカラーフィルタ一用顔料分散レジスト組成物を得た。 3. 顔料分散物 （実施例 7) 、 カラーフィルター用顔料分散レジスト組成物 （実 施例 7 ) 2. Pigment dispersion resist composition for color filter Examples 1 to 6, Comparative examples 1 to 4 Pigment dispersions for color filters of Examples 1 to 6 and Comparative examples 1 to 4 43.8 parts of acrylic resin 6 2.8 parts of dipentaerythritol hexatalylate, 0.9 part of photopolymerization initiator and 46.5 parts of PMAC were mixed and stirred, and the color filters of Examples 1 to 6 and Comparative Examples 1 to 4 were mixed. A pigment-dispersed resist composition was obtained. 3. Pigment dispersion (Example 7), pigment dispersion resist composition for color filter (Example 7)
(実施例 7の顔料分散物であると同時に実施例 7のカラーフィルタ一用顔料分散 レジス ト組成物である）  (It is a pigment dispersion resist composition for one color filter of Example 7 at the same time as the pigment dispersion of Example 7)
PMAC 786部に塩基性基を含有する顔料分散剤 E 47部、 アクリル樹 月旨 12部を加え混合し、 ヮ-スを調製し、 更に C. I . ビグメントレッド 254 To 786 parts of PMAC, 47 parts of pigment dispersant E containing a basic group and 12 parts of acrylic resin were added and mixed to prepare a base, and C.I.
155部を加えて高速撹拌機でプレ分散した。 次いで、 プレ分散物 438部に、 アクリル樹脂 60部、 ジペンタエリスリ トールへキサアタリレート 28部、 光重 合開始剤 9部、 PMAC 465部を配合し攪拌し、 図 2で表わされる高圧乳化 機で下記の条件を用いて分散した後、 3 / p pのプリーツフィルターで濾過して 粗大粒子を除去し実施例 7の顔料分散物を得ると同時に実施例 7のカラーフィル ター用顔料分散レジスト組成物を得た。 155 parts were added and predispersed with a high-speed stirrer. Then, 438 parts of the pre-dispersion, 60 parts of acrylic resin, 28 parts of dipentaerythritol hexatalylate, 9 parts of a photopolymerization initiator, and 465 parts of PMAC were mixed and stirred, and the mixture was stirred using a high-pressure emulsifier shown in FIG. After dispersing using the conditions described above, the mixture was filtered through a 3 / pp pleated filter to remove coarse particles, thereby obtaining the pigment dispersion of Example 7 and the pigment dispersion resist composition for a color filter of Example 7 at the same time. Was.
<高圧乳化機の分散条件 > <Dispersion conditions of high-pressure emulsifier>
分散圧力： 2 X 105 k P a Dispersion pressure: 2 X 10 5 kPa
プレ分散した分散物流速： 60 Om/ s e c Predispersed dispersion flow rate: 60 Om / sec
オリフィス径： 0. 1 5 mm Orifice diameter: 0.15 mm
中空部材形状 直径： 1mm  Hollow member shape Diameter: 1mm
背圧： 7000 k P a Back pressure: 7000 kPa
製造温度： 50°C Production temperature: 50 ° C
パス回数： 5回 Number of passes: 5
4. 比較例 5 4. Comparative Example 5
1 -3) カラーフィルタ一用顔料分散レジス ト組成物比較例 5  1-3) Comparative example 5 of pigment dispersion resist composition for color filter
カラーフィルター用顔料分散物比較例 2の調製と同様に、 PMAC 786部 に塩基性基を含有する顔料分散剤 E 47部、 アタリル樹脂 12部を加え混合 し、 ワニスを調製し、 更に C. I . ビグメントレッド 254 155部を加えて 高速撹拌機でプレ分散した後、 湿式サーキュレーションミルで 10時間練肉分散 した。 次いで、 該分散物 438部に、 アクリル樹脂 60部、 ジペンタエリスリ ト 一ルへキサァクリレート 28部、 光重合開始剤 9部、' PMAC 46 5部を配合 し攪拌し、 その後、 3 / p pのプリーツフィルターで濾過して粗大粒子を除去し、 カラーフィルタ一用顔料分散レジスト組成物比較例 5を得た。 5. 評価方法 In the same manner as in the preparation of Comparative Example 2 of the pigment dispersion for a color filter, 47 parts of a pigment dispersant E containing a basic group and 12 parts of ataryl resin were added to 786 parts of PMAC and mixed to prepare a varnish. After adding 254 parts of Pigment Red 254 and predispersing with a high-speed stirrer, the mixture was kneaded and dispersed with a wet circulation mill for 10 hours. Then, 438 parts of the dispersion, 60 parts of acrylic resin, dipentaerythritol 28 parts of hexyl acrylate, 9 parts of photopolymerization initiator and 5 parts of PMAC46 are mixed and stirred, and then filtered through a 3 / pp pleated filter to remove coarse particles. Composition Comparative Example 5 was obtained. 5. Evaluation method
顔料分散性は、 実施例 1~6、 比較例 1〜4については顔料分散物、 実施例 '7、 比較例 5についてはカラーフィルター用顔料分散レジスト組成物で評価した c 流動性 Pigment dispersibility, Examples 1-6, pigment dispersion for Comparative Examples 1-4, Example '7, c fluidity was evaluated by the color filter pigment dispersion resist composition for Comparative Example 5
実施例 1〜 6、 比較例 1〜4のカラーフィルタ一用顔料分散物及び実施例 7、 比較例 5のカラーフィルター用顔料分散レジスト組成物について、 R型粘度計を 用いて 25°Cにおける粘度を測定し、 評価した。  The viscosity at 25 ° C. of the pigment dispersions for color filters of Examples 1 to 6 and Comparative Examples 1 to 4 and the pigment dispersion resist composition for color filters of Example 7 and Comparative Example 5 was measured using an R-type viscometer. Was measured and evaluated.
A :粘度が 3. 0 X 10— 2P a · s以下のもの A: viscosity 3. 0 X 10- 2 P a · s or less of those
C :粘度が 3. 0 X 1 Cr2P a · sを超えるもの 経時安定性 C: viscosity exceeding 3.0 X 1 Cr 2 Pas
実施例 1 ~ 6、 比較例 1〜4のカラーフィルタ一用顔料分散物及び実施例 7、 比較例 5のカラーフィルター用顔料分散レジスト組成物について、 R型粘度計を 用いて 25°Cにおける粘度、 40°C7日間保存後の 25°Cにおける粘度を測定し、 その上昇率で評価した。  Using the R-type viscometer, the viscosity at 25 ° C. of the pigment dispersions for color filters of Examples 1 to 6 and Comparative Examples 1 to 4 and the pigment dispersion resist compositions for color filters of Example 7 and Comparative Example 5 was used. After storage at 40 ° C for 7 days, the viscosity at 25 ° C was measured, and the increase was evaluated.
A： 1. 5倍以内のもの  A: 1.5 times or less
B ： 1. 5〜 2倍のもの  B: 1.5 to 2 times
C ： 2倍を超えるもの 一濾過性  C: More than 2 times monofiltration
実施例 1〜 6、 比較例 1〜4のカラーフィルタ一用顔料分散物及ぴ実施例 7、 比較例 5のカラーフィルター用顔料分散レジスト組成物について、 3 p pのプ ルーッフィルタ一にて濾過した場合の圧力上昇があるかな 1/、かで評価した。 A：圧力上昇のないもの C ：圧力上昇のあるもの コントラス ト When the pigment dispersions for color filters of Examples 1 to 6 and Comparative Examples 1 to 4 and the pigment-dispersed resist compositions for color filters of Example 7 and Comparative Example 5 were filtered through a 3 pp blue filter. 1 /, there was a pressure rise of A: No pressure increase C: Pressure increase Contrast
実施例 1〜 7、 比較例 1〜 5の各力ラーフィルタ一用顔料分散レジスト組成物 をカラーフィルター用ガラス基板上にスピンコーターで塗布し 1 0 0 °Cで 3分間 乾燥させ、 赤色の塗膜を得た。 次いで、 未露光の各塗膜を、 高圧水銀ランプを用 い、 フォトマスクを介して、 3 0 O m j Z c m 2の紫外線の露光量で露光を行つ た後、 2 3 0 °Cで 2 0分間ボストベータを行い、 塗膜を得た。 こうして、 塗膜が 形成された基板を 2枚の偏向板の間に置き、 偏向板の偏向軸が平行のときの輝度The pigment-dispersed resist composition for each color filter of Examples 1 to 7 and Comparative Examples 1 to 5 was applied on a glass substrate for a color filter by a spin coater and dried at 100 ° C. for 3 minutes to obtain a red coating. A membrane was obtained. Next, each unexposed coating film was exposed at a UV light exposure of 30 O mj Z cm 2 through a photomask using a high-pressure mercury lamp, and then exposed at 230 ° C. Boss beta was performed for 0 minutes to obtain a coating film. In this way, the substrate on which the coating film is formed is placed between the two deflection plates, and the brightness when the deflection axes of the deflection plates are parallel is set.
(平行輝度） と偏向軸が垂直のときの輝度 （垂直輝度） との比 （輝度比 =平行輝 度 Z垂直輝度） を測定しコン小ラストとした。 塗膜平滑性 The ratio between the (parallel luminance) and the luminance when the deflection axis is vertical (vertical luminance) (luminance ratio = parallel luminance Z vertical luminance) was measured and set as the small last. Coating smoothness
実施例 1〜 7、 比較例 1〜5のカラーフィルタ一用顔料分散レジスト組成物を カラーフィルター用ガラス基板上にスピンコーターで塗布後、 塗膜表面の状態を 顕微鏡で観察し評価した。  The pigment-dispersed resist compositions for color filters of Examples 1 to 7 and Comparative Examples 1 to 5 were applied on a glass substrate for a color filter by a spin coater, and the state of the coating film surface was observed and evaluated with a microscope.
A：粗粒が確認されないもの A: No coarse particles are found
C ：粗粒が確認されるもの C: Coarse grains are confirmed
カラーフィルタ一用顔料分散物 Pigment dispersion for color filter
施例 1 施例ク ¾施例 3 ϋ施 /j ui例 rノ' j 4 t7 套施例 6 Example 1 Example ¾ Example 3 ϋExample / j ui Example r no 'j 4 t7
C Iビゲメ トイエロー 150 1 5 5 C I Bigemet Yellow 150 1 5 5
O Iドゲメソ フ し一 1 1 5 5  O I Dogemesofu 1 1 5 5
高級有機顔斜 G Iピゲメ レソト Ί 77 1  Luxury organic face slant G I Pigueme Lesotho Ί 77 1
·1. 。ゲ レ ゥ 54 * 1リ》リ 1  · 1.レ 54 * 1 li >> li
G.I.ヒ11ク■*メン卜レツ卜 *207 1 1 5 5GI HI 11 ku * mentlet * 207 1 1 5 5
A: (ソルス A—ス 24000GR) 6.2 A: (Sorce A-24000GR) 6.2
B: (ソルスハ。 -ス 17000) 3.9  B: (Sorusha. -S 17000) 3.9
塩基性基を C:(Disperbyk-161 ) 3.1  C: (Disperbyk-161) 3.1
含有する  contains
顔料分散剤 D:(EF A-46) 3.9  Pigment dispersant D: (EF A-46) 3.9
E: (ソルスハ '-ス 20000) 4.7  E: (Solsha'-S 20000) 4.7
F:(Disperbyk-2001) 3.9 溶剤 PMAC 77.1 79.4 80.2 79.4 78.6 79.4 アルカリ可溶性樹脂 アクリル樹脂 1.2 1.2 1.2 1.2 1.2 1.2 α 1 100.0 100.0 100.0 100.0 100.0 100.0 表 2 実施例 1比較例 1比較例 3実施例 2実施例 3実施例 4実施例 5比較例 2比較例 4実施例 6 流動性 A A A A A A A A A A 顔料 経時  F: (Disperbyk-2001) 3.9 Solvent PMAC 77.1 79.4 80.2 79.4 78.6 79.4 Alkali-soluble resin Acrylic resin 1.2 1.2 1.2 1.2 1.2 1.2 α1 100.0 100.0 100.0 100.0 100.0 100.0 Table 2 Example 1 Comparative Example 1 Comparative Example 3 Example 2 Example Example 3 Example 4 Example 5 Comparative Example 2 Comparative Example 4 Example 6 Flowability AAAAAAAAAA Pigment Aging
A  A
分散物 C B A A A A A A A 安定性 濾過性 A C C A A A A C C A コン卜ラスト 1400 1000 1100 420 900 873 850 720 775 760 レジス卜  Dispersion C B A A A A A A A A Stability Filtration A C C A A A A A C C A Contrast 1400 1000 1100 420 900 873 850 720 775 760 Registry
組成物  Composition
塗膜 A c c A A A A C C A 平滑性 表 3 Paint A cc AAAACCA Smoothness Table 3
Figure imgf000027_0001
産業上の利用可能性
Figure imgf000027_0001
Industrial applicability
以上、 本発明のカラーフィルター用顔料分散物は、 過分散物の発生が非常に少 ない状態で微粒子化 （粒度分布も狭い） されたものであるので、 顔料分散性及ぴ 流動性が良好となり、 その結果、 このカラーフィルター用顔料分散物を使用した カラーフィルター用顔料分散レジスト組成物を用いることにより、 色相 （透明性、 コントラスト） が鮮明で、 塗膜平滑性に優れた着色画像を形成することができる c As described above, since the pigment dispersion for a color filter of the present invention is made into fine particles (narrow particle size distribution) with very little overdispersion, the pigment dispersion and the fluidity are improved. As a result, by using the pigment dispersion resist composition for a color filter using the pigment dispersion for a color filter, a colored image having a clear hue (transparency and contrast) and excellent in coating film smoothness is formed. Can c

Claims

請求の範囲 The scope of the claims
1 . 顔料分散物と光重合性化合物と光重合開始剤とを少なくとも含有する力ラ 一フィルター用顔料分散レジス ト組成物であって、 1. A pigment dispersing resist composition for a filter containing at least a pigment dispersion, a photopolymerizable compound, and a photopolymerization initiator,
当該顔料分散物は、 湾曲部や屈曲部のない直線状のオリフィスと、 該オリフィス に連結されたオリフィスの径よりも大きい径を有する直線状の中空部材とを備え た高圧乳化機を用い、 顔料と、 常圧における沸点が 1 0 0〜2 2 0 °Cであるエス テル系有機溶剤、 エーテル系有機溶剤、 エーテルエステル系有機溶剤、 ケトン系 有機溶剤、 芳香族炭化水素溶剤及び含窒素系有機溶剤からなる群より選択される 少なくとも 1種を含有してなる有機溶剤と、 顔料分散剤とを含有する混合液を、 加圧下、 1 0 0〜 1 0 0 O in/ s e cの流速で該オリフィスを通過させた後、 更 に該混合物を該オリフィスから該中空部材の中で滞留している、 先に流出した混 合液中に吐出させて、 顔料を分散させたものである The pigment dispersion is obtained by using a high-pressure emulsifier having a linear orifice having no curved portion or bent portion and a linear hollow member having a diameter larger than the diameter of the orifice connected to the orifice. And ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon solvents, and nitrogen-containing organic solvents having a boiling point at normal pressure of 100 to 220 ° C. A mixed solution containing at least one organic solvent selected from the group consisting of a solvent and a pigment dispersant, under pressure, at a flow rate of 100 to 100 Oin / sec through the orifice. After passing through the orifice, the mixture is discharged from the orifice into the mixed liquid that has flown out and stays in the hollow member, and the pigment is dispersed.
ことを特徴とするカラーフィルタ一用顔料分散レジス ト組成物。 What is claimed is: 1. A pigment dispersion resist composition for a color filter.
2 . 前記顔料分散剤として、 塩基性基を含有する顔料分散剤を用いる ことを特徴とする請求の範囲第 1項記載のカラーフィルター用顔料分散レジスト 組成物。 2. The pigment dispersion resist composition for a color filter according to claim 1, wherein a pigment dispersant having a basic group is used as the pigment dispersant.
3 . 前記混合液として、 非メディア型混合装置でプレミックス処理してなる混 合液を使用する 3. Use a mixture that has been premixed with a non-media type mixing device as the mixture.
ことを特徴とする請求の範囲第 1又は 2項記載のカラーフィルター用顔料分散レ ジス ト組成物。 3. The pigment dispersion resist composition for a color filter according to claim 1 or 2, characterized in that:
PCT/JP2003/003781 2002-03-27 2003-03-27 Pigment-dispersed resist composition for color filters WO2003081298A1 (en)

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JP2005221804A (en) * 2004-02-06 2005-08-18 Toyo Ink Mfg Co Ltd Method for manufacturing coloring material for color filter,coloring material for color filter manufactured by the method and color filter
JP2006243409A (en) * 2005-03-03 2006-09-14 Fuji Photo Film Co Ltd Light shielding film for display apparatus, particulate-containing composition for black material, material, substrate with light shielding film, color filter, liquid crystal display element, liquid crystal display and display apparatus
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JP2009222761A (en) * 2008-03-13 2009-10-01 Tokyo Ohka Kogyo Co Ltd Colored photosensitive resin composition, black matrix, color filter and liquid crystal display
JP2011111616A (en) * 2009-11-30 2011-06-09 Fujifilm Corp Black curable composition for wafer-level lens and wafer-level lens
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WO2019131455A1 (en) * 2017-12-27 2019-07-04 花王株式会社 Production method for pigment aqueous dispersion
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