WO2007013475A1 - Process for production of composition having organic particles dispersed therein - Google Patents

Process for production of composition having organic particles dispersed therein Download PDF

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Publication number
WO2007013475A1
WO2007013475A1 PCT/JP2006/314700 JP2006314700W WO2007013475A1 WO 2007013475 A1 WO2007013475 A1 WO 2007013475A1 JP 2006314700 W JP2006314700 W JP 2006314700W WO 2007013475 A1 WO2007013475 A1 WO 2007013475A1
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WIPO (PCT)
Prior art keywords
group
organic
pigment
solvent
meth
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Application number
PCT/JP2006/314700
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French (fr)
Japanese (ja)
Inventor
Naoya Shibata
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Fujifilm Corporation
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Priority to JP2007528487A priority Critical patent/JPWO2007013475A1/en
Publication of WO2007013475A1 publication Critical patent/WO2007013475A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0005—Coated particulate pigments or dyes the pigments being nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • 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
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

  • the present invention relates to a method for producing an organic particle dispersion composition by efficiently concentrating organic particles produced by an organic particle precipitation method. More specifically, the desalted organic particle dispersion composition is described above. It relates to a manufacturing method. Furthermore, in the production method described above, a method for producing an organic particle dispersion composition that suppresses changes in the particle size and monodispersity of the organic particles in the concentration step and can be easily redispersed even when aggregated by concentration. About.
  • nanometer-sized fine particles is different from that of larger nano particles and smaller molecules and atoms, and is located in the middle. Therefore, it has been pointed out that new characteristics that could not be predicted in the past can be extracted.
  • nanometer (nm) scale microcrystals exhibit various interesting properties such as catalytic effects based on unique surface structures, photophysical properties due to size effects, and nonlinear optical properties. However, if this monodispersity can be increased, the characteristics can be stabilized.
  • the potential of such nanoparticles is expected in various fields, and research is being actively conducted in a wide range of fields such as biochemistry, new materials, electronic devices, light-emitting display devices, printing, and medicine.
  • organic nanoparticles composed of organic compounds have a high potential as functional materials because the organic compounds themselves are diverse.
  • greater electrical insulation can be expected by combining finely divided substances such as polyimide that are excellent in electrical insulation.
  • organic pigments include, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like. It is now an important material that is indispensable in daily life. Among these, high performance is required, and pigments for inkjet ink and pigments for color filters are particularly important for practical use.
  • a gas phase method (a method in which a sample is sublimated in an inert gas atmosphere and particles are collected on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent is stirred) (Reprecipitation method to obtain fine particles by injecting into a poor solvent with controlled conditions and temperature), laser ablation method (a method to make particles fine by irradiating a sample dispersed in a solution with a laser) Etc. are being studied.
  • laser ablation method a method to make particles fine by irradiating a sample dispersed in a solution with a laser
  • the reprecipitation method is a method for producing organic particles excellent in simplicity and productivity, but is not yet sufficient as a method for producing particles with high industrial utilization.
  • sufficient research has not been conducted on how to separate and recover organic particles prepared by the reprecipitation method.
  • the prepared organic particles are obtained dispersed in a dilute solvent.
  • unnecessary salt is contained in a large amount with respect to organic particles, and for example, it may become a liquid crystal contaminant in color filter applications. Therefore, the ability to remove unnecessary salts and separate and recover organic particles becomes a problem. Even if the desired particles can be prepared in the dispersion, In the collecting process, the particle size is changed, the monodispersity of the particles is deteriorated, and it is impossible to put it to practical use if the collection requires a large cost.
  • Patent Document 4 discloses a method of adding an evaporation promoting liquid to a particle-containing aqueous dispersion and concentrating it by distillation.
  • this method is applied to organic particle-containing aqueous dispersions prepared by the reprecipitation method, when the boiling point of the good solvent of the organic material is higher than that of water, only the water evaporates. There is a concern that the concentration increases and the particle size of the organic particles increases during concentration.
  • Patent Document 5 discloses a method in which an ionic liquid that does not substantially dissolve in the dispersion medium is added to a dispersion containing fine particles, and the fine particles are concentrated in the ionic liquid. However, this method alone cannot sufficiently concentrate the organic particle dispersion to the desired concentration.
  • Patent Document 6 discloses a method of obtaining fine organic particles by dissolving an organic pigment and a dispersant together and precipitating the particles in a poor solvent. In this method, if the organic particles are then agglomerated by adding acid, and concentration and desalting are performed, the change in particle size due to redispersion is relatively small. However, the redispersion liquid obtained by this method has a large amount of particles contained therein, and when applied to, for example, a CCD color filter, the density of a specific pixel is lowered.
  • Patent Document 1 Japanese Translation of Special Publication 2002-092700
  • Patent Document 2 JP-A-6-79168
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-91560
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2004-181312
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2004-292632
  • Patent Document 6 Japanese Unexamined Patent Application Publication No. 2004-43776
  • An object of the present invention is to provide a method for producing an organic particle dispersion composition by efficiently concentrating organic particles produced by an organic particle precipitation method, and particularly desalting to provide an organic particle dispersion composition. It is an object to provide a manufacturing method for obtaining.
  • a method for producing an organic particle dispersion composition that suppresses changes in the particle size and monodispersity of organic particles in the concentration step and can be easily redispersed even when aggregated by concentration is provided. Is an issue. According to the present invention, the following means are provided:
  • R 1 represents a (m + n) -valent linking group
  • R 2 represents a single bond or a divalent linking group
  • a 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, or an isocyanate group.
  • a monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group which may have a substituent, or an organic dye structure or a heterocyclic ring.
  • n A 1 s may be the same or different.
  • m represents a number from 1 to 8
  • n represents a number from 2 to 9
  • P 1 represents a polymer skeleton.
  • the polymer compound represented by the general formula (1) is formed when organic nanoparticles are formed, extracted or concentrated, and when aggregated organic particles are dispersed after concentration.
  • An inkjet ink for a color filter characterized in that an inkjet ink for a color filter is prepared from the organic nanoparticle dispersion composition produced by the production method according to any one of (1) to (10). Production method.
  • a photosensitive transfer material wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (12) is provided on a temporary support.
  • a light-shielding partition is formed on the substrate, and a plurality of recesses separated by the partition are provided, and R (red) ink, G (green) ink, and B (blue) ink are formed by an inkjet method.
  • a method of manufacturing a color filter in which each of the recesses is sprayed and deposited to form a colored resin layer of each color in each recess, and at least the R ink, the G ink, and the B ink A color filter characterized by using an inkjet ink obtained by the production method described in (11) as one type.
  • a liquid crystal display device comprising the color filter according to (14) or (15).
  • a CCD device comprising the color filter according to (14) or (15).
  • organic particles are produced by an organic particle precipitation method, and the dispersion solvent and unnecessary salts in the dispersion are removed to make the organic particles efficient. It can be well concentrated to the desired concentration.
  • the method for producing an organic nanoparticle dispersion composition of the present invention when producing organic particles by the organic particle precipitation method, when increasing the amount of good solvent relative to the poor solvent, or when increasing the production scale. However, it can be concentrated and desalted without substantially increasing the particle size and the monodispersity, and the aggregated organic particles can be easily redispersed with high efficiency. Organic particles can be produced.
  • the concentrated organic particle paste produced by the method for producing an organic particle dispersion composition of the present invention and the organic particles obtained therefrom are suitable inkjet inks or raw material fine particles thereof, or color filter coating liquids or fine raw material particles thereof. Is available as In addition, the color filter, the liquid crystal display device, and the CCD device of the present invention exhibit excellent effects when exhibiting high display characteristics.
  • FIG. 1-1 is a cross-sectional view schematically showing a preferred embodiment of a production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
  • FIG. 1-2 is an enlarged partial cross-sectional view schematically showing a mixing chamber in a partial cross section as one embodiment of the manufacturing apparatus of FIG.
  • FIG. 1-3 is an enlarged partial cross-sectional view schematically showing a mixing chamber in a partial cross section as another embodiment of the manufacturing apparatus of FIG.
  • FIG. 2 is a cross-sectional view schematically showing another preferred embodiment of a production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing still another preferred embodiment of a production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
  • FIG. 4-1 is a front view schematically showing an example of a dissolver stirring blade used in the method for producing an organic particle dispersion composition of the present invention.
  • FIG. 4-2 This is a drawing-substituting photograph of the dissolver stirring blade shown in Fig. 41.
  • FIG. 5 A stirrer 1 composed of a rotatable turbine part used in the method for producing an organic particle dispersion composition of the present invention and a fixed stator part with a slight gap around it. It is sectional drawing which shows an example schematically.
  • FIG. 6 is an explanatory diagram showing a structural example of an ultrafiltration device used in the method for producing an organic particle dispersion composition of the present invention.
  • FIG. 7 is an apparatus explanatory view schematically showing an example of a preferred embodiment of a production apparatus used in the production method of the present invention.
  • the present invention relates to an organic particle precipitation method for obtaining organic particles by injecting an organic material dissolved in a good solvent into a poor solvent preferably controlled in stirring conditions and temperature, and the organic particle precipitation method
  • the present invention relates to a method for efficiently concentrating organic particles produced by the above, and particularly to a method for producing an organic particle dispersion composition by removing unnecessary ions.
  • the present invention also relates to a method for producing an organic particle dispersion composition that does not change the particle size and monodispersity of organic particles in the concentration step, and that can be easily redispersed when the organic particles aggregate due to concentration.
  • the present invention will be described in detail.
  • the organic material used as the organic particles is not particularly limited as long as it can be produced by a conventional reprecipitation method.
  • Powerful organic hydrocarbons such as organic pigments, organic dyes, or polymer compounds are particularly preferable. A combination of these may also be used.
  • the organic pigment is not limited in terms of hue.
  • perylene pigments such as CI Pigment Red 190 (CI No. 71140), CI Pigment Red 224 (CI No. 71127), CI Pigment Noorette 29 (CI No. 711 29), CI Pigment Orange 43 (CI No. 71105), or perinone pigments such as CI Pigment® Red 194 (CI No. 71100), CI Pigment® Noorette 19 (CI No.
  • CI Pigment Nooret 42 CI CI pigment red 122 (CI number 73915), CI pigment red 192, CI pigment red 202 (CI number 73907), CI pigment red 207 (CI number 73900, 73906), or CI CI pigment red 209 ( CI No. 73905) quinacridone pigment, CI Pigment Red 206 (CI No. 73900, 73920), CI Big Men Orange 48 (CI No. 73900, 73920), CI Big Men Orange 49 (CI No. 73900, 73920), etc. Quinacridonequinone series C. I. Pigment Yellow 147 (CI No.
  • Pigment Red 185 (CI number 12516) and other benzimidazole pigments, CI Pigment Yellow 93 (CI number 20710), CI Pigment Yellow 94 (CI number 20038), CI Pigment Yellow 95 (CI number 20034) CI big yellow 128 (CI number 20037), CI big yellow 166 (CI number 20035), CI big orange 34 (CI number 21115), CI big orange 13 (CI number 21110), CI big blue Orange 31 (CI number 20050), C.I.Bigmen ⁇ Red 144 (CI number 20735), CI Bigmen ⁇ Red 166 (CI number 20 730), CI Pigment Red 220 (CI No. 20055), CI Big Pigment Red 221 (C.I.No.
  • CI Pigment Red 242 (CI No. 20067), CI Pigment Red 248, CI Pigment Red 262 or CI pigment brown 23 (CI number 2 0060) and other disazo condensation pigments, CI pigment yellow 13 (CI number 21100), CI pigment yellow 83 (CI number 21108), or CI pigment yellow 18 8 (CI number 21094), etc., CI pigment red 187 (CI number 12 486), CI pigment red 170 (CI number 12475), CI big men yellow 74 (CI number 11714), CI big men yellow 150 (CI number 48545), CI Pigment Red 48 (CI number 15865), CI Pigment Red 53 (CI number 15585), CI Pigment ⁇ Orange 64 (CI number 12760), or.
  • Azo pigments such as I. Big Men ⁇ Red 247 (C.I.No. 15915), indantron pigments such as CI Big Men ⁇ Blue 60 (CI No. 69800), CI Pigment Green 7 (CI No. 74260), CI Pigment Green 36 (CI number 74265), Pigment Green 37 (CI number 74255), Pigment Blue 16 (CI number 74100), CI Pigment Blue 75 (CI number 74160: 2), or 15 (CI number 74160) Phthalocyanine pigments such as CI pigment blue 56 (CI number 42800), or the like.
  • I. Big Men ⁇ Blue 61 CI No. 42765: 1), etc., triaryl carbo-based pigments, CI Pigment Violet 23 (CI No.
  • Dioxazine pigments such as CI Pigment Red 177 (CI No. 65300), CI Big Men Men Red 254 (CI No. 56110), CI Big Men Men Red 255 (CI No.
  • two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.
  • organic dyes include azo dyes, cyanine dyes, merocyanine dyes, and coumarin dyes.
  • polymer compound examples include polydiacetylene and polyimide.
  • the good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent used in preparing the organic pigment particles.
  • the solubility of the organic pigment in a good solvent is preferably such that the solubility of the organic material is 0.2% by mass or more, and more preferably 0.5% by mass or more. This solubility may be the solubility when dissolved in an acidic or alkaline manner.
  • the compatibility or homogeneous mixing of the good solvent with the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more. ,.
  • the good solvent examples include an aqueous solvent (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvent, amide solvent, ketone solvent, ether solvent, aromatic solvent, carbon disulfide. , Aliphatic solvents, nitrile solvents, sulfoxide solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol solvents, ester solvents, sulfoxide solvents.
  • a water-based solvent in which a solvent or an amide solvent is preferred, a sulfoxide solvent or an amide solvent in which a sulfoxide solvent or an amide solvent is more preferred is particularly preferred.
  • Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy 2-propanol and the like.
  • Examples of amide solvents include N, N dimethylformamide, 1-methyl-2-pyrrolidone, 2 pyrrolidinone, 1,3 dimethyl-2-imidazolidinone, 2 pyrrolidinone, ⁇ -prolactam, formamide, ⁇ -methylformamide, Acetamide, ⁇ -methylacetamide, ⁇ , ⁇ ⁇ ⁇ dimethylacetamide, ⁇ methylpropanamide, hexamethylphosphoric tri Examples include amides.
  • Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the ether solvent include dimethyl ether, jetyl ether, tetrahydrofuran and the like.
  • Examples of the aromatic solvent include benzene and toluene.
  • Examples of the aliphatic solvent include hexane.
  • the nitrile solvent include acetonitrile.
  • Examples of the sulfoxide solvent include dimethyl sulfoxide, jetyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.
  • Examples of the halogen solvent include dichloromethane and trichloroethylene.
  • ester solvent examples include ethyl acetate, ethyl lactate, and 2- (1-methoxy) propyl acetate.
  • ionic liquid examples include a salt of 1-petitor 3-methylimidazolium and PF-.
  • the concentration of the organic material solution in which the organic material is dissolved in the good solvent is preferably in the range of the saturated concentration of the organic material to the good solvent or the lZioo range under the dissolution conditions.
  • the conditions for preparing the organic material solution can be selected from a range of normal pressure to subcritical and supercritical conditions, with no particular restrictions on the conditions for preparing the organic material solution.
  • the temperature at normal pressure is preferably 10 to 150 ° C, more preferably 5 to 130 ° C, and particularly preferably 0 to 100 ° C.
  • the organic material is uniformly dissolved in a good solvent, but it is also preferable that the organic material is dissolved in an acidic or alkaline manner.
  • a pigment having an alkaline and dissociable group in the molecule it is alkaline, and when there is no alkaline and dissociable group and there are many nitrogen atoms in the molecule where protons can easily be added, acidity is used.
  • quinacridone, diketopyrrolopyrrole, and disazo condensation pigments are alkaline, and phthalocyanine pigments are acidic.
  • the base used for the alkaline dissolution is an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or a trialkylamine.
  • Power which is an organic base such as diazabicycloundecene (DBU) and metal alkoxide, preferably an inorganic base.
  • DBU diazabicycloundecene
  • metal alkoxide preferably an inorganic base.
  • the amount of the base used is an amount capable of uniformly dissolving the pigment, and is not particularly limited.
  • an inorganic base it is preferably 1.0 to 30 molar equivalents relative to the organic material, more preferably 1.0 to 25 molar equivalents, and even more preferably 1.0 to 20 molar equivalents.
  • an organic base it is preferably 1.0 to: LOO molar equivalent, more preferably 5.0 to 100 molar equivalent, and further preferably 20 to 100 molar equivalent with respect to the organic material.
  • the acid used in the case of acidic dissolution is preferably an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid.
  • an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid
  • an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid.
  • sulfuric acid is preferably sulfuric acid.
  • the amount of the acid used is an amount that can dissolve the organic material uniformly, and is not particularly limited. Regardless of the inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, still more preferably 30 to 200 molar equivalents relative to the organic material.
  • the poor solvent is not particularly limited as long as it does not dissolve the organic pigment to be used, is compatible with the good solvent used in the preparation of the organic pigment particles, or is mixed uniformly.
  • the poor solvent when the poor solvent is compatible with the organic material solution in this way, it acts on the organic material molecules in the organic material solution, and the organic material is deposited.
  • the solubility of the organic material in the poor solvent is preferably 0.02% by mass or less, more preferably 0.01% by mass or less.
  • the preferred range of compatibility or uniform mixing of the poor solvent with the good solvent is as described above.
  • the poor solvent examples include aqueous solvents (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvents, ketone solvents, ether solvents, aromatic solvents, carbon dioxide, fatty acids Group solvents, nitrile solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof and the like, and aqueous solvents, alcohol solvents, and ester solvents are preferred.
  • aqueous solvents for example, water or hydrochloric acid, sodium hydroxide aqueous solution
  • alcohol solvents for example, ketone solvents, ether solvents, aromatic solvents, carbon dioxide, fatty acids
  • Group solvents nitrile solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof and the like
  • aqueous solvents, alcohol solvents, and ester solvents are preferred.
  • Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy 2-propanol and the like.
  • Keto Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Examples of the ether solvent include dimethyl ether, jetyl ether, and tetrahydrofuran.
  • Examples of the aromatic solvent include benzene and toluene.
  • Examples of the aliphatic solvent include hexane.
  • Examples of the nitrile solvent include acetonitrile.
  • Examples of the halogen solvent include dichloromethane, trichloroethylene, and the like.
  • ester solvent examples include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl pyracetate, and the like.
  • ionic liquid examples include a salt of 1-butyl-3-methylimidazolium and PF.
  • Examples of the solvent used as the supercritical fluid or subcritical fluid preferably used in the production method of the embodiment of the above (2) include, for example, water, alcohol compound solvent, ketone compound solvent, monolithic compound solvent, aromatic compound solvent. , Carbon disulfide, aliphatic compound solvent, nitrile compound solvent, sulfoxide compound solvent, halogen compound solvent, ester compound solvent, ionic solution, or a mixed solvent of two or more of these, water, alcohol compound solvent Ketone compound solvents, aromatic compounds and nitrile compound solvents are preferred. Water, ketone compound compounds solvents and aromatic compound solvents are more preferred.
  • the conditions for making the solvent a supercritical fluid or subcritical fluid may be appropriately determined depending on the solvent to be used (in the present invention, "supercritical fluid” means a critical temperature or higher and a critical temperature).
  • a subcritical fluid is a force in which only one of temperature and pressure reaches a critical state, or the other is not in a critical state, or both temperature and pressure are in a critical state.
  • the temperature does not reach, but at least one of temperature and pressure is sufficiently higher than normal temperature and close to the critical state.
  • the pressure is preferably 2 to 30 MPa. 3 to 25 MPa is more preferable. 4 to 20 MPa is particularly preferable.
  • the temperature is preferably 150 to 400 ° C, more preferably 180 to 350 ° C, and particularly preferably 200 to 300 ° C.
  • the amount of pigment dissolved in the supercritical fluid or subcritical fluid depends on the type of solvent and pigment used, but for example, 0.1 kg or more in 1 kg of supercritical fluid or subcritical fluid. It is preferable to dissolve pigments of Og or less. It is more preferable to dissolve 1 mg to 50 g of pigment.
  • a precipitation solvent is used as a poor solvent.
  • Preferred precipitation solvents include, for example, water, alcohol compound solvents, ketone compound solvents, monolithic compound solvents, aromatic compound solvents, carbon disulfide, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents. , Halogen compound solvent, ester compound solvent, ionic solution, or a mixed solvent of two or more of these, water, alcohol compound solvent, ketone compound solvent, ester compound solvent, aromatic compound solvent, halogen compound Water, alcohol compound solvents, and ketonic compound solvents are more preferred.
  • a polymer compound that can be preferably used in the production method of the present invention refers to an organic compound having a mass average molecular weight of 1000 or more, although there is no particular upper limit).
  • the mass average molecular weight is practically 500,000 or less, preferably 100,000 or less, more preferably 50,000 or less.
  • the production method of the present invention is preferred.
  • the polymer compound that can be used has a mass average molecular weight of 1000 or more, and is preferably a polymer compound represented by the following general formula (1).
  • a 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urea group, a group having a coordinating oxygen atom, or a hydrocarbon group having 4 or more carbon atoms.
  • An organic group, which may have a substituent, represents a monovalent organic group containing an organic dye structure or a heterocyclic ring.
  • n A 1 may be the same or different.
  • a 1 is not particularly limited, and examples of the “monovalent organic group having an acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, and a phosphoric acid group. And monovalent organic groups having a monophosphate group and a boric acid group. Further, as the “monovalent organic group having a group having a basic nitrogen atom”, for example, a monovalent organic group having an amino group (one NH 3), a substituted imino group (one NHR 8 , —NR 9 R 1C > ) Monovalent organic group having
  • R 8 , R 9 and R 1G each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.
  • the “monovalent organic group having a urea group” is, for example, —NHCONHR (where R 15 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms) An aryl group of 7 to 30 carbon atoms).
  • Examples of the “monovalent organic group having a urethane group” include: —NHCOOR 16 , —OCO NHR 17 (wherein R 16 and R 17 are each independently an alkyl group having 1 to 20 carbon atoms, carbon number) Represents an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.).
  • Examples of the “group having a group having a coordinating oxygen atom” include a group having an acetylethylacetonate group and a group having a crown ether.
  • Examples of the “group having a hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms (for example, octyl group, dodecyl group, etc.), an aryl group having 6 or more carbon atoms (for example, a phenyl group, Naphthyl group) and aralkyl groups having 7 or more carbon atoms (for example, benzyl group). At this time, there is no upper limit to the number of carbon atoms, but it is preferably 30 or less.
  • Examples of the “group having an alkoxysilyl group” include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.
  • Examples of the “group having an epoxy group” include a group having a glycidyl group and the like.
  • Examples of the “group having an isocyanate group” include a 3-isocyanatopropyl group.
  • Examples of the “group having a hydroxyl group” include a 3-hydroxypropyl group.
  • a 1 a monovalent organic group having an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms, a group selected. Preferably it is.
  • the organic dye structure or heterocyclic ring is not particularly limited, and more specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinones. Compounds, quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, thioindigo compounds, etc. It is done.
  • heterocyclic ring examples include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, vilazolidin, imidazole, oxazole, thiazole, oxazidazole, triazole, thiadiazole, pyran, pyridine, piperidine.
  • the organic dye structure or the heterocyclic ring may have a substituent which may have a substituent.
  • substituent for example, alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group, aryl groups having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl groups, amino groups, carboxyl groups, sulfones.
  • 1 to 6 carbon atoms such as amide group, N-sulfolamide group, and acetoxy group, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, C2-C7 alkoxy carbonyl groups such as methoxy carbo yl group, ethoxy carbo yl group, cyclohex oxy carbo yl group, etc.
  • Carbonate ester group such as cyano group, t-butyl carbonate, etc. Can be mentioned.
  • the A 1 is preferably a monovalent organic group represented by the following general formula (4).
  • B 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, A group selected from an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group, or an organic dye structure or a heterocyclic ring which may have a substituent.
  • R 18 represents a single bond or an alvalent organic or inorganic group. Represents a linking group. al represents 1 to 5, and al B 1 may be the same or different.
  • B 1 has the same meaning as A 1 in formula (4), and the preferred embodiment is also similar.
  • the organic dye structure or heterocyclic ring include phthalocyanine compounds and insoluble azo compounds.
  • Organic dye structures such as thioindigo compounds such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, virazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine
  • the organic dye structure or heterocyclic ring may have a substituent.
  • substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group. , Phenyl groups, naphthyl groups and the like having 6 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfolamide groups, and acetoxy groups.
  • alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, halogen atom such as chlorine, bromine, methoxy carbo yl group, ethoxy carbo yl group, cyclohex oxy carbo yl group, etc.
  • R 18 represents a single bond or an al + monovalent linking group, and al represents 1 to 5.
  • the linking group R 18 includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0. Groups comprising from 20 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
  • R 18 is preferably an organic linking group.
  • R 18 include the following structural units or groups formed by combining the structural units.
  • R 1B has a substituent
  • substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group and a naphthyl group having 6 to 6 carbon atoms.
  • Up to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfo-lumamide groups, acetoxy groups, etc.
  • 1 to 6 carbon atoms such as acyloxy groups, methoxy groups, ethoxy groups, etc.
  • Alkoxy groups of up to 6 carbon atoms halogen atoms such as chlorine and bromine, alkoxycarbon groups of up to 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexylcarbonyl groups, etc.
  • alkoxycarbon groups of up to 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexylcarbonyl groups, etc.
  • Examples include cyano groups and ester carbonate groups such as t-butyl carbonate.
  • R 1 represents an (m + n) -valent linking group. m + n satisfies 3 ⁇ : L0.
  • Examples of the (m + n) -valent linking group represented by R 1 include: 1 to: L00 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 From 1 to 200 hydrogen atoms, and from 0 to 20 sulfur atomic groups are included, which may be unsubstituted or further substituted.
  • R 1 is preferably an organic linking group.
  • R 1 include the structural units (t-1) to (t-34) or a group composed of a combination of the structural units (which may form a ring structure). ⁇ .)
  • substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group and a naphthyl group having 6 to 6 carbon atoms. Carbon number up to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfol amide group, acetooxy group, etc.
  • R 2 represents a single bond or a divalent linking group.
  • R 2 includes: 1 to: LOO carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to Up to 20 sulfur nuclear power groups are included, which may be unsubstituted or further substituted.
  • R 2 is preferably an organic linking group.
  • R 2 include the structural units of the above t-3, 4, 7-18, 22-26, 32, 34, or groups configured by combining the structural units.
  • R 2 has a substituent
  • substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group and a naphthyl group having 6 to 6 carbon atoms.
  • Carbon number up to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfol amide group, acetooxy group, etc.
  • alkoxy groups such as halogen atoms such as chlorine and bromine, methoxy carbo yl groups, ethoxy carbo yl groups, cyclohexyl carboxy groups, etc.
  • carbonic acid ester groups such as t-butyl carbonate.
  • m represents 1 to 8. As m, 1-5 is preferable, 1-3 is more preferable, and 1-2 is particularly preferable.
  • N represents 2-9.
  • n is preferably 2 to 8 forces S, more preferably 3 to 6 with 2 to 7 being more preferable.
  • P 1 represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like.
  • the polymer skeleton is composed of a polymer or copolymer of a bull monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and these.
  • a modified product or copolymer for example, a copolymer of a polyether Z polyurethane copolymer, a polymer of a polyether z butyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be present).
  • a polymer or copolymer of a bulle monomer Selected from the group consisting of a polymer or copolymer of a bulle monomer, an ester polymer, an ether polymer, a urethane polymer, and a modified product or a copolymer thereof.
  • Particularly preferred are polymers or copolymers of vinyl monomers, at least one of which is more preferred.
  • the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for dispersion stability.
  • a high molecular compound represented by the following general formula (2) is more preferable.
  • the general formula (2) has the same meaning as A 1 in ⁇ or the general formula (1) is the same also its concrete preferred embodiment, specific examples of the organic dye structure, Heterocycles that are more preferred are phthalocyanine compounds, azo lake compounds, anthraquinone compounds, dioxazine compounds, diketopyrrolopyrrol compounds, imidazole, triazole, pyridine, piperidine, Monoreforin, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, atalidine, attaridone and anthraquinone are more preferred.
  • the substituent which may have a substituent as in A 1 is the same as that in A 1 , and the preferred embodiment is also the same.
  • a 2 the monovalent organic group represented by the general formula (4) is preferred, and details and specific examples, preferred and embodiments of the organic group are the same.
  • R 3 represents a (x + y) -valent linking group. Represented by R 3 (x
  • + y) valent linking groups include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and Groups comprising 0 to 20 sulfur atoms are included and may be unsubstituted or further substituted.
  • the linking group of the represented by R 3 (x + y) value has the same meaning as the linking group of (m + n) valent in the R 1, it is the same a preferred embodiment thereof. Further, specific examples include the same structural unit as described above or a group constituted by combining the structural units.
  • the linking group represented by R 3 is preferably an organic linking group. Preferred specific examples of the organic linking group are shown below. However, the present invention is not limited to these.
  • R 3 has a substituent
  • substituents include carbon such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Number 6 to 16 aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfolamide groups, acetoxy groups, etc.
  • acyl groups having 1 to 6 carbon atoms such as acyl groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups, etc. C1-C6 alkoxy groups, halogen atoms such as chlorine and bromine, methoxycarbol groups, ethoxycarbon groups, cyclohexylcarboxy groups, etc.
  • -Carbonate group such as -l group, cyano group and t-butyl carbonate.
  • R 4 and R 5 each independently represents a single bond or a divalent linking group.
  • Preferred examples include SO or a divalent group in which two or more of these groups are combined.
  • the R 19 and R 2G is, independently,. Represents a hydrogen atom or a number 1-4 ⁇ alkyl group carbon atoms) is preferably 0 Among these organic linking group.
  • R 4 a linear or branched alkylene group, an aralkylene group, OC (
  • the divalent group combined above is particularly preferred.
  • R 5 a single bond, a linear or branched alkylene group, Ararukiren group, -O
  • a divalent group in which two or more of these groups are combined is particularly preferred.
  • R 5 has a substituent
  • substituents include carbon such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group.
  • Number 6 Up to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfolamide group, acetoxy group, etc. carbon number up to 1-6, such as acyloxy group, methoxy group, ethoxy group, etc.
  • alkoxy groups such as halogen atoms such as chlorine and bromine, methoxy carbo yl groups, ethoxy carbo yl groups, cyclohexyl carboxy groups, etc.
  • y represents 1 to 8, 1 to 5 is preferable, and 1 to 3 is more preferable, and 1 to 2 is particularly preferable.
  • X represents 2-9, 2-8 are preferred, 2-7 are more preferred, and 3-6 are particularly preferred.
  • P 2 in the general formula (2) represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like.
  • the preferred embodiment of the polymer is the same as P 1 in the general formula (1), and the preferred embodiment is also the same.
  • R 21 represents a hydrogen atom or a methyl group
  • 1 represents 1 or 2.
  • the polymer compound has a mass average molecular weight of lOOO or more, but the mass average molecular weight is 1000 to 500,000 force S preferred ⁇ , 3000 to 100000 preferred ⁇ , 5000 to 80000 force S more preferred. 7000 to 60000 is particularly preferable.
  • the mass average molecular weight is within the above range, the effects of the plurality of functional groups introduced at the ends of the polymer are sufficiently exerted, and the performance of adsorbing on the solid surface, micelle forming ability, and surface activity is excellent. Demonstrate.
  • a polymer compound is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.
  • the polymer compound represented by the general formula (1) (including the polymer compound represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 3, 4, 5, etc. are particularly preferred because of the ease of synthesis, and the following synthesis methods such as 2, 3, 4, 5 are more preferred.
  • a method in which a polymer in which a plurality of mercabtans are introduced at the terminal and a functional group in which a carbon-carbon double bond is introduced are reacted in the presence of a radical generator.
  • the polymer compound (preferably the polymer compound represented by the general formula (2)) used in the production method of the present invention is, for example, any one of the above 2, 3, 4, and 5 Although it can be synthesized by a method, it is more preferred to synthesize by the above method 5 because of ease of synthesis.
  • radical polymerization using a compound represented by the following general formula (3) as a chain transfer agent.
  • R 6 , R 7 , A 3 , g, and h are each R 3 in the general formula ( 2 ), It is synonymous with x and y, The preferable aspect is also the same.
  • the bull monomer is not particularly limited !, but, for example, (meth) acrylic acid esters, crotonic acid esters, buresters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters , (Meth) acrylamides, butyl ethers, esters of butyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.
  • Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid t- Butyl cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, ( Dodecyl (meth) acrylate, Octadecyl (meth) acrylate, Acetoxyethyl (meth) acrylate, Phenyl (meth) acrylate, 2-Hydroxyethyl (meth) acryl
  • crotonic acid esters examples include butyl crotonic acid and hexyl crotonic acid.
  • vinyl esters examples include butyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
  • maleic diesters examples include dimethyl maleate, diethyl maleate, and dibutyl maleate.
  • Examples of the fumaric acid diesters include dimethyl fumarate, jetyl fumarate, dibutyl fumarate, and the like.
  • Examples of the itaconic acid diesters include dimethyl itaconate, jetyl itaconate, and dibutyl itaconate.
  • Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide, N-n-butylacrylic (meth) amide, N-t-butyl (meth) acrylamide, N cyclohexyl (meth) acrylamide, N- (2-methoxyethyl ) (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-jetyl (meth) acrylamide, N-phenol (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atari Roylmorpholine, diacetone acrylamide, etc. are mentioned.
  • styrenes examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropylino styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene.
  • Examples thereof include low styrene, promostyrene, chloromethyl styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, and a-methylstyrene.
  • butyl ethers examples include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
  • (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups for example, bullpyridine, bull pyrrolidone, bull force rubazole, etc.
  • N-buluformamide, N-bulacetoamide N-Buylimidazole, bull force prolatatone, etc. can be used.
  • butyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used.
  • a monomer having a urethane group or urea group can be appropriately synthesized by utilizing, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group.
  • an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group It can be appropriately synthesized by an addition reaction between a group-containing monomer and a monoisocyanate.
  • the above-mentioned radical monomers which may be polymerized by only one kind, or may be used in combination of two or more kinds, may be the usual bulle monomers. It can be obtained by polymerization according to a conventional method.
  • these vinyl monomers and chain transfer agents are dissolved in a suitable solvent, It is obtained by using a method (solution polymerization method) in which a radical polymerization initiator is added to the polymer and polymerized in a solution at about 50 ° C to 220 ° C.
  • Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer.
  • solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer.
  • the radical polymerization initiator may be an azo such as 2,2'-azobis (isobutyoxy-tolyl) (AIBN) or 2,2, -azobis- (2,4, -dimethylbare-tolyl).
  • AIBN 2,2'-azobis (isobutyoxy-tolyl)
  • 2,2, -azobis- (2,4, -dimethylbare-tolyl) Compounds, peroxyacid compounds such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.
  • the compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
  • a method of converting a halide compound having a plurality of functional groups (A 1 or A 2 in the above general formula) into a mercabtan compound (a method of reacting with thiourea and hydrolyzing, a method of directly reacting with NaSH, Examples include a method of reacting with CH COSNa and hydrolyzing.
  • Preferred examples of the "functional group capable of reacting with a mercapto group" in Method 7 include an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond, and the like.
  • the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is synthesized by a radical addition reaction.
  • Carbon The carbon double bond is more preferably a mono- or di-substituted bur group in terms of reactivity with the mercapto group.
  • the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and the above “having an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, and a coordinating oxygen atom” A compound having at least one functional group selected from a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and having a carbon-carbon double bond.
  • the radical addition reaction product includes, for example, the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “acid group, group having basic nitrogen atom, urea group, urethane group, coordinating oxygen”.
  • Examples of preferable solvents used in the above method include "a compound having 3 to LO mercapto groups in one molecule", "an acidic group, a group having a basic nitrogen atom, a urea group, a Lethane group, group having a coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilane A compound having at least one functional group selected from the group consisting of an alkyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and a functional group capable of reacting with a mercapto group (for example, a carbon-carbon double bond), and It can be arbitrarily selected according to the solubility of the radical addition reaction product.
  • methanol, ethanol, propanol, isopropanol, 1 methoxy 2-propanol, 1-methoxy 2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, Kuroguchi Holm and Toluen are listed.
  • These solvents may be used as a mixture of two or more.
  • radical generators such as 2,2'-azobis (isobutyoroxy-tolyl) (AIBN) 2,2, -azobis (2,4, -dimethylvalerin-tolyl), and benzoyl peroxide can be used.
  • Peracids such as potassium persulfate and persulfates such as ammonium persulfate can be used.
  • the polymer compound is preferably a polymer compound having an acidic group, and more preferably a polymer compound having a lpoxyl group.
  • A Compound compound having a carboxyl group Particularly preferred are copolymer compounds containing at least one of the repeating units and (B) at least one of the derived repeating units.
  • a repeating unit derived from acrylic acid or methacrylic acid which is preferably a repeating unit represented by the following general formula (I):
  • a repeating unit derived from tacrylate is particularly preferred.
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R represents the following general formula (III)
  • R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group
  • R and R are hydroxyalkyl groups or an aryl group having 6 to 20 carbon atoms.
  • Each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • i represents a number from 1 to 5.
  • R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • R represents the following general formula (V):
  • R represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • j is a number between 1 and 5
  • the polymerization ratio of (A) a repeating unit derived from a compound having a carboxyl group and a repeating unit derived from the compound (B) having a carboxylic acid ester group is the total of repeating units (A). It is more preferable that the quantity ratio% to the number of repeating units is 3 to 40, and 5 to 35 is more preferable.
  • the molecular weight of the polymer means a mass average molecular weight unless otherwise specified.
  • the method for measuring the molecular weight of the polymer include a chromatography method, a viscosity method, a light scattering method, and a sedimentation rate method.
  • a mass average molecular weight measured by a chromatography method is used unless otherwise specified.
  • the polymer compound may be either water-soluble or oil-soluble, water-soluble and oil-soluble.
  • the polymer compound may be added in a solution in an aqueous solvent or an organic solvent, in a solid state, or a combination thereof.
  • Examples of the method of adding a solution dissolved in a solvent include, for example, a method of adding to an aggregated organic particle solution in a state dissolved in the same solvent as the solvent of the aggregated organic particle solution, and a compatibility with the solvent of the aggregated organic particle solution.
  • An example is a method in which it is dissolved in a different solvent.
  • the concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but 1 to 70% by mass is preferable, 2 to 65% by mass is more preferable, and 3 to 60% by mass is particularly preferable. preferable.
  • Polymer compounds are added when organic nanoparticles are formed (or before and after) by organic particle precipitation, during extraction or concentration (or before and after), and when dispersed organic particles after concentration (or before and after). ) After these steps are completed, they may be added to any of them or a combination thereof.
  • a polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, after concentrating the organic particle deposition liquid, finely dispersing the aggregated organic particles. Sometimes added It is preferable.
  • organic particles are formed in the presence of a polymer compound having an acidic group.
  • the polymer compound having an acidic group can be added to both or one of the poor solvents for adding the organic material solution and the organic material solution to produce organic particles.
  • the amount of the polymer compound added is preferably 0.1 to: L000 parts by mass, more preferably 5 to 500 parts by mass, when the organic particles contained in the aggregated organic particles are 100 parts by mass. 10 to 300 parts by mass are particularly preferred.
  • Examples of the high molecular compound having a molecular weight of 1000 or more include polybutyropyrrolidone, polyvinyl alcohol, polybutyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, butyl alcohol acetate butyl copolymer, poly Examples include a partially formalized butyl alcohol, a partially butylated butyl alcohol, a butylpyrrolidone acetate butyl copolymer, a polyethylene oxide z propylene oxide block copolymer, a polyamide, a cellulose derivative, and a starch derivative.
  • polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignosulfonate can also be used.
  • polymer compound having an acidic group examples include polyvinyl sulfate and condensed naphthalene sulfonic acid.
  • Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, a cellulose derivative having a carboxyl group in a side chain, and the like.
  • a copolymer compound containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a rubonic acid ester group JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836 and JP-A-59-71048
  • acrylic acid-acrylic acid ester copolymer methacrylic acid acrylic acid ester copolymer, acrylic acid-methacrylic acid ester copolymer, methacrylic acid-methacrylic acid ester copolymer, examples thereof include multi-component copolymers of acrylic acid or methacrylic acid, acrylic acid ester or methacrylic acid ester, and other bur compounds.
  • bur compound examples include styrene or substituted styrene (for example, butyl benzene and butyl benzene), bur naphthalene or substituted bur naphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. Len is preferred.
  • polymer compounds may be used alone or in combination of two or more, and may be used in combination with a compound having a molecular weight of less than 1000.
  • the organic nanoparticle dispersion preferably contains 60% by mass or more of an organic solvent, more preferably 65% by mass or more.
  • an organic solvent there can be appropriately selected a normal medium force without particular limitation.
  • ester compound solvents, ketone compound solvents, and ester compound solvents, and ketone compound solvents are particularly preferred, which are ester compound solvents, alcohol compound solvents, aromatic compound solvents, aliphatic compound solvents, and ketone compound solvents. These may be used alone or in combination of two or more.
  • Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate.
  • Examples of the alcohol compound solvent include n-butanol and isobutanol.
  • Examples of the aromatic compound solvent include benzene, toluene, xylene and the like.
  • Examples of the aliphatic compound solvent include n-xane and cyclohexane.
  • Examples of the ketone compound solvent include methyl ethyl ketone, acetone, cyclohexanone, and the like.
  • a dispersant can be added to both or one of the poor solvent for adding organic material solution and organic material solution to produce organic particles.
  • Dispersant (1) Quickly adsorbs on the deposited pigment surface to form fine pigment particles And (2) has an effect of preventing these particles from aggregating again.
  • a dispersant a low-molecular or high-molecular dispersant having a ionic, cationic, amphoteric, nonionic or pigment property can be used.
  • the molecular weight of the polymer dispersant should be used without limitation as long as it can be dissolved uniformly in the solution. Force over S. Preferable ⁇ Molecular weight of 1,000 to 2,000,000, 5,000 to 5,000 1, 000,000 0 force S preferred ⁇ , 10,000-500,000 force S more preferred ⁇ 10, 000-100,000 force s, particularly preferred. (In the present invention, unless otherwise specified, molecular weight means mass average molecular weight.
  • a polymer compound is a polydisperse system and does not necessarily have the same molecular weight or particle weight.
  • the values obtained are average molecular weights averaged in some form, the main three being: 1) number average molecular weight ⁇ , 2) mass average molecular weight Mw, 3) Z average molecular weight Mz And the relationship of Mn ⁇ Mw ⁇ Mz holds.
  • polymer dispersant examples include polyvinyl pyrrolidone, polyvinyl alcohol, polybutyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, butyl alcohol, acetic acid butyl copolymer, poly Butyl alcohol partially formalized, polybull alcohol partially butyral, bull pyrrolidone acetic acid bull copolymer, polyethylene oxide z propylene oxide block copolymer, polyacrylate, polybul sulfate, poly (4 bull pyridine)
  • Examples include salts, polyamides, polyallylamine salts, condensed naphthalene sulfonates, cellulose derivatives, and starch derivatives.
  • N-acyl-N alkyl taurine salt fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate , Alkyl phosphate ester Salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like.
  • N-acyl-N alkyltaurine salts are preferred.
  • the N-acyl N alkyltaurine salt those described in JP-A-3-273067 are preferable. These char-on dispersants can be used singly or in combination of two or more.
  • Cationic dispersants include quaternary ammonium salts, alkoxy Louis polyamines, aliphatic amine polyglycol ethers, aliphatic amines, aliphatic amines and fatty alcohol power induction. And diamines derived from fatty acids, imidazolines derived from fatty acids, and salts of these cationic substances. These cationic dispersants can be used alone or in combination of two or more.
  • the amphoteric dispersant is a dispersant having both the cation group part of the cation-dispersing agent in the molecule and the cation group part of the cation-dispersing agent in the molecule. .
  • Non-ionic dispersants include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Examples thereof include oxyethylene alkylamine and glycerin fatty acid ester. Of these, polyoxyethylene alkylaryl ether is preferred. These nonionic dispersants can be used singly or in combination of two or more.
  • a pigment-based dispersant is defined as a pigment-based dispersant derived from an organic pigment as a parent substance and produced by chemically modifying the parent structure.
  • a pigment-based dispersant derived from an organic pigment as a parent substance and produced by chemically modifying the parent structure.
  • sugar-containing pigment dispersants for example, sugar-containing pigment dispersants, piperidyl-containing pigment dispersants, naphthalene or perylene-derived pigment dispersants, pigment dispersants having functional groups linked to the pigment parent structure via methylene groups, and chemically modified with polymers.
  • a compound represented by the general formula (I) described in JP-A-2000-239554 is also preferably used.
  • the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of the amino groups may be one or plural.
  • It may be a pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component. Examples of these include, for example, compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-B-5-72943. Forces that are not limited to these
  • the amino group-containing dispersant used in the production method of the present invention is not limited thereto, but is represented by the following general formulas (Dl), (D3), and (D4). At least one selected from compounds can be used.
  • A-N N-X- Y
  • A represents a component capable of forming an azo dye together with X—Y.
  • A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazo-um compound. Specific examples of A will be shown below, but the present invention is not limited thereto.
  • X represents a single bond or a group selected from divalent linking groups represented by structural formulas of the following formulas (i) to (v).
  • Z represents a lower alkylene group.
  • Z is the force expressed as one (CH) —
  • the b represents an integer of 1 to 5, preferably 2 or 3.
  • NR is
  • —NR represents a lower alkylamino group, it is represented as —N (C H), and r is an integer of 1 to 4.
  • any of the heterocyclic groups represented by the following structural formula is preferred.
  • Z and -NR are each a lower alkyl group or an alcohol
  • a represents 1 or 2, preferably 2.
  • the compound represented by the general formula (Dl) can be synthesized, for example, by the method described in JP-A-2000-239554.
  • Q is an anthraquinone compound dye, an azo compound compound dye, a phthalocyanine compound dye, a quinacridone compound compound dye, a dioxazine compound compound dye, an anthrapyrimidine compound compound dye, an anthrone compound compound, an indanthrone compound Represents an organic dye residue selected from a dye, a flavanthrone compound dye, a pyranthrone compound dye, a perinone compound dye, a perylene compound dye, and a thioindigo compound dye, particularly an azo compound dye or a dioxazine compound dye. It is more preferred that it is an azo compound pigment. Yes.
  • X is CO—, —CONH-Y one, SO NH-Y one, or CH NHCOCH
  • NH-Y— represents CO— and —CONH-Y—.
  • Y represents an alkylene group or an arylene group which may have a substituent.
  • More preferred is phenylene, toluylene or hexylene.
  • R and R are each independently a substituted or unsubstituted alkyl group or R and R
  • a methyl group, an ethyl group, a propyl group, or a pyrrolidyl group including a nitrogen atom is preferable, and an ethyl group is more preferable!
  • Y represents —NH 2 or —O 2.
  • Z represents a hydroxyl group or a group represented by the general formula (D3a), or when nl is 1, —NH 2 —X Q may be used.
  • ml represents an integer of 1 to 6, preferably 2 to 3.
  • nl represents an integer of 1 to 4, preferably 1 or 2.
  • the compound represented by the general formula (D3) is represented by the following general formula, for example.
  • the compound represented by the general formula (D3) is, for example, an amine compound having R and R and R
  • JP-B-5-72943 can also be referred to.
  • the graft copolymer may have at least an amino group and an ether group, and may contain other monomers as copolymer units.
  • the weight average molecular weight (Mw) of the graft copolymer is preferably 300 to 100,000 particles ⁇ , more preferably 5000 to 50,000 force! / ⁇ . If the mass average molecular weight (Mw) force is less than 3000, the aggregation of pigment nanoparticles cannot be prevented, and the viscosity may increase. When it exceeds 0000, the solubility in an organic solvent is insufficient, and the viscosity may increase.
  • the mass average molecular weight is a polystyrene-reduced mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).
  • the graft copolymer comprises: (i) a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal; (ii) a monomer having an amino group and an ethylenically unsaturated double bond; (iii) It preferably contains at least a polymerizable monomer having an ether group as a copolymer unit, and (iv) optionally contains other monomers as copolymer units.
  • the content of the graft copolymer, (i) the polymerizable oligomer is preferably to be 15 to 98 mass 0/0 device 25 to 90 weight 0 / 0 is it forces Ri preferably fixture (ii) preferably be an amino group-containing monomer is 1 to 40 wt% instrument 5 to 3 0% by weight and is more preferably tool the (iii) the ether group
  • the polymerizable monomer is preferably 1 to 70% by mass, more preferably 5 to 60% by mass.
  • the content of the polymerizable oligomer is less than 15% by mass, a steric repulsion effect as a dispersant may not be obtained, and aggregation of pigment nanoparticles may not be prevented. In some cases, the ratio of the nitrogen-containing monomer is reduced, the adsorption ability to the pigment particles is lowered, and the dispersibility is not sufficient. If the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption capacity for organic particles may be reduced and dispersibility may not be sufficient, and if it exceeds 40% by mass, the proportion of the polymerizable oligomer will decrease.
  • the solid repulsion effect as a dispersant cannot be obtained, and the aggregation of pigment particles may not be sufficiently prevented.
  • the content of the polymerizable monomer having an ether group is less than 1% by mass, the development suitability in the production of a color filter or the like may not be sufficient, and when it exceeds 70% by mass, the dispersant is used as a dispersant. Your ability may decline.
  • the polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a group having an ethylenically unsaturated double bond at the terminal.
  • the oligomer generally includes, for example, alkyl (meth) acrylate, hydroxy.
  • Cialkyl (meth) acrylate, styrene, acrylonitrile, butyl acetate, and butagen force At least one selected monomer force A homopolymer or a copolymer formed, and among them, alkyl (meth) acrylate Preferred are rate homopolymers or copolymers, polystyrene and the like.
  • these oligomers which may be substituted with a substituent are not particularly limited, and examples thereof include a halogen atom.
  • Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) atalyloyl group, a bure group, and the like, and among these, a (meth) atalyloyl group is particularly preferred.
  • an oligomer represented by the following general formula (E6) is preferable.
  • R 61 and R 63 represent a hydrogen atom or a methyl group.
  • R 62 represents an alkylene group which may be substituted with an alcoholic hydroxyl group having 1 to 8 carbon atoms, and an alkylene group having 2 to 4 carbon atoms is preferable.
  • Y 6 is a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or —COOR 64 (where R 64 is an alcoholic hydroxyl group having 1 to 6 carbon atoms, halogen, Represents an optionally substituted alkyl group, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms.), A phenyl group or —COOR 64 (where R 64 is a carbon number of 1). Represents an alkyl group which may be substituted with ⁇ 4 alcoholic hydroxyl groups). q represents 20-200.
  • polymerizable oligomer examples include poly-2-hydroxyethyl (meth) atrelate, polystyrene, polymethyl (meth) acrylate, poly n-butyl (meth) acrylate, poly i butyl.
  • a (meth) acrylate, a copolymer thereof, and a polymer in which a (meth) taliloyl group is bonded to one of the molecular terminals is preferred.
  • the polymerizable oligomer may be a commercially available product or an appropriately synthesized one.
  • Preferred examples of the polymerizable oligomer in the present invention include, as specific examples, polymers of alkyl (meth) acrylate and copolymers of alkyl (meth) acrylate and polystyrene. And those having a number average molecular weight of 1000 to 20000 and having a (meth) atallyloyl group at the terminal.
  • Suitable examples of the amino group-containing monomer include at least one selected from compounds represented by the following general formula (E2).
  • R 21 represents a hydrogen atom or a methyl group.
  • R 22 represents an alkylene group having 1 to 8 carbon atoms, and among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable.
  • X 2 represents N (R 23 ) (R 24 ), and one R 25 N (R 26 ) (R 27 ).
  • R 23 and R 24 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • R 25 represents an alkylene group having 1 to 6 carbon atoms
  • R 26 and R 27 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. Represents a group.
  • - N (R 23) R 23 and R 24 of (R 24) is a hydrogen atom or 1 to 4 carbon atoms alkyl Le group or Hue - Le group preferably tool -R 25 - R 25 of N (R 26 ) (R 27 ) is preferably an alkylene group having 2 to 6 carbon atoms.
  • R 26 and R 27 are preferably an alkyl group having 1 to 4 carbon atoms.
  • R 31 has the same meaning as R 21 .
  • R 32 is synonymous with R 22 .
  • X 3 is synonymous with X 2 .
  • R 41 has the same meaning as R 21 .
  • X 4 is synonymous with X 2 — N
  • R 43 (R 43 ) (R 44 ) (where R 43 and R 44 are synonymous with R 23 and R 24 ), or -R 45 -N (R 46 ) (R 47 ) (where R 45 , R 46 and R 47 are synonymous with 5 , R 26 and R 27 , respectively.
  • Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, jetyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, di- — I-butyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenol (meth) acrylamide (above ( (Meth) acrylamides); 2— (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-demethylamino) ethyl (meth) acrylamide, 3 -— (N, N-demethylamino) propyl (meth) acrylamide, 3 -— (N, N-dimethylamino) propyl (meth) acryl
  • Suitable examples of the polymerizable monomer having an ether group include at least one selected from monomers represented by the following general formula ( E 1 ).
  • R 11 represents a hydrogen atom or a methyl group.
  • R 12 represents an alkylene group having 1 to 8 carbon atoms, and among them, an alkylene group having 2 to 3 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, is more preferable.
  • X 1 represents OR 13 or one OCOR 14 .
  • R 13 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenol group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms.
  • R 14 represents an alkyl group having 1 to 18 carbon atoms.
  • m3i represents 2 to 200, 5 ⁇ : L00 force preferred, 10 ⁇ : L00 force ⁇ Especially preferred! / ,.
  • the polymerizable monomer having an ether group can be appropriately selected from the usual intermediate forces that are not particularly limited as long as they have an ether group and are polymerizable.
  • the commercially available products include methoxypolyethylene glycol metatalylate (trade names: NK ester M-40G, M-90G, M-230G (above, manufactured by Toa Gosei Chemical Co., Ltd.); trade name: BLEMMER PME— 100, PME-200, PME-400, PME-1000, PME—2000, PME—4000 (Enomoto Yushi Co., Ltd.) Polyethylene glycol monometatalylate (trade name: Blemmer PE-90, PE 200, PE-350, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol monometatalylate (trade name: Blemmer PP-500) , PP-800, PP-1000, manufactured by Nippon Oil & Fats Co., Ltd.), Polyethylene Glycol Polypropylene Glycol Monometatalylate (Brandmer 70 PEP-370B, manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol polytetra M
  • the graft copolymer may further contain the other monomer as a copolymer unit, and the other monomer may be appropriately selected according to the purpose without any particular limitation.
  • Aromatic vinyl compounds eg, styrene, a-methylstyrene and butyltoluene
  • acrylic acid alkyl esters eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate and i-butyl (meth) acrylate
  • (meth) acrylate alkyl aryl ester eg, benzyl (meth) acrylate
  • glycidyl (meth) acrylate carboxylate butyl ester (eg Butyl acetate and propionate)
  • cyanide butyl eg, (meth) acrylonitrile and chloroformate trityl
  • Fine aliphatic conjugated diene
  • the content of the other monomer in the graft copolymer is, for example, 5 to
  • 70% by mass is preferred. When the content is less than 5% by mass, the physical properties of the coating film may not be controlled. When the content exceeds 70% by mass, the ability as a dispersant may not be sufficiently exhibited.
  • Preferred examples of the graft copolymer include:
  • the graft copolymer can be obtained by, for example, performing radical polymerization of the components to be the respective copolymer units in a solvent.
  • a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used.
  • JP-A-2001-31885 can also be referred to for the pigment dispersant containing the graft copolymer.
  • the content of the dispersant may be in the range of 0.1 to L000 parts by mass with respect to 100 parts by mass of the pigment in order to further improve the uniform dispersibility and storage stability of the pigment particles. More preferably, it is in the range of 1 to 500 parts by mass, and still more preferably in the range of 5 to 20 parts by mass. If the amount is less than 1 part by mass, the dispersion stability of the organic nanoparticles may not be improved.
  • a dispersing agent may be used independently or may be used in combination of multiple things.
  • the organic particle of the present invention is a step of obtaining an organic particle by mixing an organic material solution obtained by dissolving an organic material in a good solvent and a poor solvent for the organic material (hereinafter also simply referred to as “poor solvent for organic particles”). (Hereinafter, this method is also referred to as “organic particle precipitation method”, and the organic particle liquid obtained by this method is referred to as “organic particle dispersion”).
  • the normal pressure can be selected from the subcritical and supercritical conditions.
  • the temperature at normal pressure is preferably ⁇ 30 to 100 ° C. ⁇ 10 to 60 ° C. is more preferable, and 0 to 30 ° C. is particularly preferable.
  • the method of mixing the organic material solution and the poor solvent it is preferable to add one organic material solution to the stirred poor solvent. Particularly preferred.
  • a pump or the like may be used for the addition, or it may not be used. Further, it may be added in the liquid or outside the liquid, but the addition in the liquid is more preferable.
  • One or more addition ports may be used for the submerged addition. It is preferable that the accessory diameter is 20 mm or less. More preferably, it is 10 mm or less.
  • the stirring speed when stirring one is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm.
  • the ratio of the organic material solution to the poor solvent is preferably 1Z50 to 2Z3 by volume ratio, 1Z40 to: LZ2 is more preferred, and 1Z20 to 3Z8 is particularly preferred.
  • the concentration of the dispersion liquid prepared as organic particles is not particularly limited as long as the organic particles can be dispersed, but it is more preferable that the particle force is in the range of 10 to 40,000 mg per 1000 ml of the dispersion solvent. Is in the range of 20-30000 mg, particularly preferably in the range of 50-25000 mg.
  • the conditions when the organic pigment-containing fluid and the precipitation solvent are mixed are not particularly limited, but the solubility of the pigment as the state is not the organic pigment-containing fluid in a supercritical state or subcritical fluid state. It is preferable that the conditions are such that the pigment is precipitated and the pigment is precipitated.
  • the mixing temperature is preferably lower than the supercritical temperature of the solvent used. For example, when using acetone, it is preferable to set the temperature within the range of 15 ° C to 180 ° C, more preferably 40 ° C to 180 ° C, and particularly preferably 60 ° C to 150 ° C. preferable.
  • the pressure at the time of mixing is preferably near the supercritical pressure of the solvent to be used or higher than the supercritical pressure.
  • the pressure is preferably 2 to 30 MPa, more preferably 3 to 25 MPa, and particularly preferably 4 to 20 MPa.
  • the mixing ratio between the organic pigment-containing fluid and the precipitation solvent is preferably 20: 1 to 1:20, more preferably 10: 1 to 1:10, and more preferably 5: 1 to 1: 5. preferable.
  • the particle concentration of the mixed liquid in which the organic pigment is precipitated is not particularly limited, but is preferably in the range of 0.01 to 500 mgZml, more preferably 0.1 to: in the range of LOOmgZml, particularly preferably 0. 5 ⁇ : It is in the range of LOmgZml.
  • a supercritical fluid or When using a field fluid it exhibits different properties from melting at room temperature and pressure. For example, the ability to dissolve poorly soluble materials such as facial materials is enhanced.
  • the particle size of organic particles there is a method of expressing the average size of the population by numerical values by measurement methods, but as a common method, the mode diameter indicating the maximum value of distribution, the integral distribution curve Median diameter corresponding to the median value of each other, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. in the present invention, unless otherwise specified. Means the number average diameter.
  • the average particle size of the organic particles (primary particles) contained in the organic particle dispersion used in the organic particle concentration method of the present invention is nanometer size, and the particle size is preferably 1 ⁇ to 1 / ⁇ ⁇ . More preferably, it is 1 to 200 nm. 2-: It is particularly preferable that LOOnm is 5 to 80 nm.
  • the formed particles may be crystalline particles, non-crystalline particles, or a mixture thereof.
  • the ratio ( ⁇ ) of the volume average particle size (Mv) and the number average particle size ( ⁇ ) is used as an index representing the monodispersity of the particles unless otherwise specified.
  • the monodispersity of particles (primary particles) contained in the organic particle dispersion used in the organic particle concentration method of the present invention that is, ⁇ / ⁇ is preferably 1.0 to 2.0, and preferably 1.0 to 1.8. Is more preferably 1.0 to 1.5.
  • Methods for measuring the particle size of organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred.
  • Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope.
  • Examples of the particle measuring apparatus by the dynamic light scattering method include Nikkiso Co., Ltd. Nanotrac UPA-150, Otsuka Electronics Co., Ltd. dynamic light scattering photometer DLS-7000 series, and the like.
  • FIG. 11 is a schematic view of a production apparatus used as an embodiment in the present invention.
  • the organic material solution is continuously supplied from the supply pipe 14 into the mixing chamber 13 provided in the container 11.
  • the container 11 is filled with the poor solvent 11a
  • the mixing chamber 13 is provided under the surface of the poor solvent
  • the inside thereof is filled with the poor solvent.
  • the Balta poor solvent in the reaction vessel 11 is constantly convected across the mixing chamber 13 from below to above (in the direction of the arrow in the figure) by the action of stirring in the mixing chamber 13. Yes.
  • FIG. 1-2 is an enlarged partial sectional view schematically showing the mixing chamber 13 in an enlarged manner as an embodiment of the manufacturing apparatus of FIG. 1-1.
  • the organic material solution is supplied from the supply pipe 14 into the mixing chamber 13.
  • the mixing chamber 13 is formed by a casing 17 made of a rectangular cylinder having a constant cross-sectional area.
  • the upper end of the casing 17 is an open end, and a circular hole 18 is provided at the lower end so that the poor solvent in the mixer 13 It becomes connected with the poor solvent.
  • the organic material solution supply pipe 14 is provided in a wall constituting the lower end of the casing 17 and opens toward the circular hole.
  • a stirring blade 12 is provided in the mixer 13, and the stirring blade is attached to a shaft 15 and is rotated by a motor (not shown). By the rotation of the stirring blade 12, the poor solvent is constantly circulated through the circular hole 18, and the downward force is always directed upward in the mixer 13.
  • the stirring blade 12 provided in the mixing chamber 13 must produce a desired mixing strength in the mixing chamber. This mixing strength is estimated to be an important operating factor for the size of the droplet when the organic material solution is mixed.
  • stirring blades 12 can be combined with other organic particles to form larger particles when the organic particles generated in the mixing space remain in the mixing chamber 13, or to the organic material solution supplied to the mixing chamber 13. It has the ability to quickly draw out the generated organic particles and quickly discharge them out of the mixing chamber 13 so that they do not become large particles when exposed. It is preferable to choose what to do!
  • any type can be used as long as the above object is achieved.
  • a turbine type, a fan turbine type or the like can be used.
  • the casing 17 is preferably composed of a rectangular tube as described above. By doing so, the corners of the casing 17 disturb the flow created by the stirring blades 12, and the mixing effect without requiring additional products such as baffles can be further enhanced.
  • Figure 13 shows another embodiment of the production apparatus of Figure 11 with two stirring blades in the mixing chamber.
  • FIG. 5 is an enlarged partial cross-sectional view of a mixer (mixing stirring blade 19a, discharging stirring blade 19b).
  • FIG. 2 is a cross-sectional view schematically showing another embodiment of the production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
  • the organic material solution and the poor solvent are continuously supplied into the stirring tank 21a through the supply pipes 24a and 24b, respectively.
  • the organic particles generated in the stirring tank 21a remain in the stirring tank 21a, so that they are combined with other organic particles to become larger particles or exposed to the organic material solution supplied from the supply pipes 24a and 24b.
  • the generated organic particle dispersion is quickly withdrawn from the discharge pipe 23 so that large particles are not generated due to large particles.
  • FIG. 3 is a cross-sectional view schematically showing still another embodiment of the apparatus used in the method for producing an organic particle dispersion composition of the present invention.
  • the stirring device 50 includes two liquid supply ports 32 and 33 for allowing the organic material solution and the poor solvent to flow in, and a liquid discharge port 36 for discharging the mixed liquid after the stirring treatment, respectively.
  • a cylindrical stirring tank 38 provided, and a pair of stirring blades 41 and 42 as stirring means for controlling the stirring state of the liquid in the stirring tank 38 by being driven to rotate in the stirring tank 38. Become.
  • the agitation tank 38 includes a cylindrical tank body 39 whose central axis is directed in the vertical direction, and a seal plate 40 serving as a tank wall that closes the upper and lower opening ends of the tank body 39. Further, the agitation tank 38 and the tank body 39 are made of a nonmagnetic material having excellent magnetic permeability. 2 liquid supply The ports 32 and 33 are provided at a position near the lower end of the tank body 39, and the liquid discharge port 36 is provided at a position near the upper end of the tank body 39.
  • each stirring blade 41, 42 constitutes an external magnet 46 and a magnetic coupling C arranged outside the tank wall (seal plate 40) where the stirring blade 41, 42 is close. That is, the stirring blades 41 and 42 are coupled to the respective external magnets 46 by magnetic force, and are rotated in opposite directions by being driven by the independent motors 48 and 49. Operated.
  • the pair of stirring blades 41, 42 arranged opposite to each other in the tank 38 are provided with stirring flows having different directions as indicated by the wavy arrow (X) and the solid arrow (Y) in FIG. Form in tank 38. Since the stirring flows formed by the respective stirring blades 41 and 42 have different flow directions, they collide with each other to generate a high-speed turbulent flow in the tank 38 that promotes stirring in the tank 38, 38 prevents the flow in the steady state and prevents the formation of a cavity around the rotation axis of the stirring blades 41 and 42 even when the stirring blades 41 and 42 are rotated at high speed. It is possible to prevent the inconvenience that a steady flow flowing in the tank 38 along the inner peripheral surface of the stirring tank 38 is formed without being sufficiently affected. Therefore, the processing speed can be easily improved by the high-speed rotation of the stirring blades 41 and 42, and further, the liquid flow in the tank 38 becomes steady and liquid with insufficient stirring and mixing at that time. Can be prevented, and the degradation of the processing quality can be prevented.
  • the stirring blades 41 and 42 in the stirring tank 38 are connected to the motors 48 and 49 disposed outside the stirring tank 38 by the magnetic coupling C, the rotating shaft is connected to the tank wall of the stirring tank 38.
  • the stirring tank 38 can be made into a closed container structure without the insertion part of the rotating shaft, preventing leakage of the stirred and mixed liquid to the outside of the tank, and at the same time, lubricating oil for the rotating shaft. It is possible to prevent deterioration in processing quality due to (sealing liquid) or the like being mixed into the liquid in the tank 38 as an impurity.
  • an organic pigment particle can be produced not only in a batch method but also in a continuous flow method using a production apparatus having these configurations. It can handle mass production.
  • the generated organic particle dispersion is quickly discharged.
  • the ratio of the organic material solution and the poor solvent solution supplied into the stirring tank can be kept constant. For this reason, it becomes possible to make the solubility of the organic material of the dispersion liquid constant from the start of manufacture to the end of manufacture, and monodisperse organic particles can be stably produced.
  • the liquid flow in the tank becomes steady, preventing the organic particle dispersion liquid with insufficient stirring and mixing from being discharged, and the lubricating liquid (seal liquid) for the rotating shaft is used as an impurity as the liquid in the tank. By preventing it from being mixed in, monodispersed organic particles can be produced more stably.
  • the shearing force referred to in the present invention is a shear that the stirring blade exerts on droplets generated after the organic pigment solution is mixed in a poor solvent.
  • the shape of the stirring unit usable in the present invention is not particularly limited as long as it can be subjected to a high shearing force, but generally includes paddle blades, turbine blades, screw blades, fowler blades, etc.
  • An agitator, an emulsifier, and a disperser are preferably used in the agitating portion that is constituted by a turbine portion that can rotate and a fixed stator portion that is positioned with a small gap around it.
  • the dissolver blade is a special stirring blade having a function capable of forming a high shear force.
  • One example is schematically shown in the front view in FIG. 41, and a photograph in place of the drawing is shown in FIG.
  • a device having a stirring portion constituted by a turbine portion that can rotate as shown in FIG. 5 and a fixed stator portion that is positioned with a slight gap around the turbine portion is also preferably used.
  • the stirrer, emulsifier, and disperser include, for example, Histotron manufactured by Microtech-Thion Co., Ltd., T. K Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd., and ULTRA-TURRAX manufactured by IKA.
  • the stirring speed at which the effects of the present invention can be manifested is a force that varies depending on the viscosity of the poor solvent, the temperature, the type of surfactant and the amount of additive, and a force of 100 to 10,000 rpm S, preferably 150 to 8000 rpm 200-6000rpm force S is more preferable. If the rotation speed is less than this range In other words, the effect of the present invention is not sufficiently exhibited. On the other hand, if it exceeds this range, bubbles are introduced into the poor solvent, which is not preferable.
  • the manufacturing apparatus used in the manufacturing method of the embodiment of the above (2) of the present invention is to mix a pigment dissolving fluid obtained by dissolving a pigment in a supercritical fluid or a subcritical fluid and a precipitation solvent to precipitate particles.
  • a pigment dissolving fluid obtained by dissolving a pigment in a supercritical fluid or a subcritical fluid and a precipitation solvent to precipitate particles.
  • FIG. 7 demonstrates an example of the preferable embodiment.
  • the supercritical fluid or subcritical fluid 101 is put in a container, and is pumped by the pump 104a, heated by the heater 106, and the pressure is adjusted by the back pressure valve 114.
  • the sample pipe 1 07 is injected through the mesh 109a.
  • the sample 103 such as the pigment that has been charged into the supercritical fluid or subcritical fluid injected into the supercritical fluid or subcritical fluid is dissolved, passes through the pigment dissolving fluid cache 109b, and is sent to the mixer 111. It is done.
  • the pigment-dissolved fluid sent by the pump 104a and the precipitation solvent 102 sent by the pump 104b are mixed, and the solvent composition and the solvent temperature change rapidly.
  • the nanoparticle dispersion produced in the mixer section is cooled to near room temperature with a cooling pipe 112 and can be taken out of the system as a nanoparticle dispersion 115 at normal temperature and normal pressure (note that arrow B in Fig. 7 is sent). Indicates the direction of the liquid).
  • the organic particle dispersion is desalted and concentrated to obtain an organic particle dispersion having a concentration suitable for a color filter coating liquid and an inkjet ink on an industrial scale. It is possible to produce.
  • the dispersion is concentrated by ultrafiltration. If the particle-containing liquid formed simply by the organic particle precipitation method is concentrated by ultrafiltration, the particle size distribution changes greatly during the concentration process.
  • the method for producing an organic particle dispersion composition of the present invention suppresses such a change in the particle size distribution, and enables efficient removal and concentration of salt that does not require force. Also after ultrafiltration, further vacuum freezing It is also very preferable to combine the methods of sublimating the solvent by freeze drying, concentrating and drying. Furthermore, you may combine with the concentration methods other than ultrafiltration.
  • an extraction solvent is added to and mixed with an organic particle dispersion, the organic particles are concentrated and extracted into the extraction solvent phase, and the concentrated extract is filtered through a filter or the like to obtain a concentrated particle liquid. Therefore, a method of precipitating and concentrating the organic particles, a method of drying and concentrating the solvent by heating or decompression, etc. are preferred. Or a combination of these is very preferably used.
  • concentration of organic particles after concentration 1 to 100% by mass is preferable 5 to: LOO% by mass is more preferable 10 to: LOO% by mass is particularly preferable.
  • a specific ultrafiltration method can be applied, for example, a method used for desalting / concentrating a silver halide emulsion.
  • Research Disclosure No. 10208 (1972), No. 13122 (1975) and No. 16 351 (1977) are known.
  • the pressure difference and flow rate which are important as operating conditions, can be selected with reference to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology No. Book” Koshobo Publishing (1978), p275.
  • FIG. 6 shows a configuration example of an apparatus for performing ultrafiltration.
  • this apparatus has a tank 81 for storing the organic particle dispersion, a circulation pump 82 for circulating the dispersion in the tank 81, and a secondary liquid in the dispersion introduced by the circulation pump 82.
  • It has an ultrafiltration module 83 that removes generated organic salt as permeate.
  • the dispersion from which the permeated water has been separated is returned to the tank 81 again, and the same operation is repeated until the predetermined purpose of removing the by-product inorganic salt is achieved.
  • this device has a replenishment pure water measurement flow meter used to replenish a certain amount of solvent lost by permeate as pure water. 4 is installed, and a permeate flow meter 85 used to determine the amount of pure water replenishment is installed.
  • a reverse cleaning pump 86 is installed to introduce water for diluting the permeate.
  • the ultrafiltration membrane flat plate type, spiral type, cylindrical type, hollow fiber type, holo fiber type, etc., which are already incorporated as modules, include Asahi Kasei Co., Ltd., Daicel Chemical Co., Ltd., Toray Industries, Inc. Nitto Denko Co., Ltd. is commercially available, but a spiral type or hollow fiber type is preferred from the viewpoint of the total membrane area and detergency.
  • the molecular weight cut-off which serves as an index for the threshold value of the component that can permeate the membrane, must be determined from the molecular weight of the dispersant used, but the force after 5,000 to 50,000 is preferred. , More than 5,000 and less than 15,000.
  • the freeze-drying method is not particularly limited, and any method that can be used by those skilled in the art may be adopted.
  • a refrigerant direct expansion method, an overlapping freezing method, a heat medium circulation method, a triple heat exchange method, and an indirect heating freezing method can be mentioned, preferably a refrigerant direct expansion method, an indirect calothermal heat freezing method, more preferably an indirect heating freezing method.
  • the pre-freezing conditions are not particularly limited, but the sample to be lyophilized needs to be completely frozen.
  • Indirect heating freezing methods include small freeze dryer, FTS freeze dryer, LYOVA C freeze dryer, experimental freeze dryer, research freeze dryer, triple heat exchange vacuum freeze dryer, monocooling Lyophilizer and HULL lyophilizer are preferable, but preferably a small lyophilizer, a laboratory lyophilizer, a research lyophilizer, a monocooling lyophilizer, more preferably a small lyophilizer, A cooling freeze dryer may be used.
  • the temperature of lyophilization is not particularly limited, but is, for example, -190 to -4 ° C, preferably -120 to -20 ° C, more preferably about -80 to -60 ° C.
  • the pressure of lyophilization is not particularly limited, and can be appropriately selected by those skilled in the art. For example, 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably 5 to about LOPa.
  • the freeze-drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, and more preferably about 16 to 26 hours. However, these conditions can be appropriately selected by those skilled in the art.
  • the extraction solvent used for this concentration extraction is not particularly limited, but does not substantially mix with the dispersion solvent (for example, aqueous solvent) of the organic particle dispersion (in the present invention, it does not mix substantially)
  • Low solubility means 50% by mass or less is preferable, and 30% by mass or less is more preferable.
  • this extraction solvent must be a solvent that produces weak aggregation (re-dispersion is possible without applying high shearing force such as milling or high-speed stirring) in which organic particles can be re-dispersed in the extraction solvent. preferable.
  • the target organic particles are moistened with the extraction solvent without causing strong aggregation that changes the particle size, and the dispersion solvent such as water can be easily removed by filter filtration or the like.
  • the dispersion solvent such as water can be easily removed by filter filtration or the like.
  • the extraction solvent is preferably an ester solvent, an alcohol solvent, an aromatic solvent or an aliphatic solvent, more preferably an ester solvent, an aromatic solvent or an aliphatic solvent, and particularly preferably an ester solvent.
  • ester solvent examples include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate.
  • alcohol solvent examples include n-butanol and isobutanol.
  • aromatic solvent examples include benzene, toluene, xylene and the like.
  • aliphatic solvent examples include n-hexane and cyclohexane.
  • extraction solvent may be a pure solvent based on the above preferred solvent or a mixed solvent composed of a plurality of solvents.
  • the amount of the extraction solvent is not particularly limited as long as the organic particles can be extracted, but it is preferable that the amount of the extraction solvent is smaller than that of the organic particle dispersion in consideration of concentration and extraction.
  • the extraction solvent added is preferably in the range of 1 to: LOO, more preferably in the range of 10 to 90, and 20 to A range of 80 is particularly preferred. If it is too much, it will take a lot of time to concentrate, and if it is too little, extraction will be insufficient and the particles will be dispersed in the dispersion solvent. The child remains.
  • the temperature at which the extraction solvent is added and mixed is not particularly limited, but is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. Any device may be used for adding and mixing the extraction solvent as long as each step can be preferably performed. For example, a separation funnel type device can be used.
  • filter filtration apparatus for example, an apparatus such as pressure filtration can be used.
  • Preferred filters include nanofilters and ultrafilters. It is preferable to remove the remaining dispersion solvent by filter filtration and further concentrate the organic particles in the concentrated extract to obtain a concentrated particle solution.
  • centrifuge used for concentration of organic particles by centrifugation may be any device as long as it can precipitate organic particles in an organic particle dispersion (or organic particle concentrated extract).
  • a centrifuge for example, in addition to a general-purpose device, one with a skimming function (function of sucking the supernatant layer during rotation and discharging it out of the system) or continuous centrifugation that continuously discharges solid matter.
  • Centrifugation conditions include centrifugal force (a value that represents the force at which centrifugal acceleration is multiplied by the gravitational acceleration) 50 ⁇ : LOOOO force preference ⁇ , 100 ⁇ 8000 force preference ⁇ , 150 ⁇ 6000 is especially preferred ⁇ .
  • the temperature at the time of centrifugation is a force depending on the solvent type of the dispersion liquid—preferably 10 to 80 ° C.—preferably 5 to 70 ° C. Particularly preferably 0 to 60 ° C.
  • the apparatus used for concentration of organic particles by drying under reduced pressure is not particularly limited as long as the solvent of the organic particle dispersion (or organic particle concentrated extract) can be evaporated.
  • a general-purpose vacuum dryer and a rotary pump a device capable of drying under heating and heating while stirring the liquid, and a device capable of continuous drying by passing the liquid through a heat-depressurized tube.
  • Heating vacuum drying temperature is preferably 30-230 ° C 35-200 ° C is more preferred 40-18 0 ° C force S Especially preferred ⁇ .
  • Pressure during decompression ⁇ 100-100,000 Pa force preferred ⁇ , 300-90000 Pa force more preferred, 500-80000 Pa force particularly preferred! / ,.
  • organic particles can be efficiently concentrated from the organic particle dispersion by combination with ultrafiltration or the above-described concentration method.
  • concentration factor for example, if the concentration of the particles in the organic particle dispersion as the raw material is 1, the concentration in the concentrated organic particle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. be able to.
  • ions unnecessary for the organic particle dispersion force can be removed.
  • the ions to be removed are not particularly limited, but it is preferable to remove ions having a low molecular weight such as sodium (Na), potassium (K), calcium (Ca), chlorine (C1) and the like.
  • the molecular weight is small and it is easy to move.
  • the total amount of ions after removal is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, relative to the organic material.
  • fine dispersion means to increase the degree of dispersion by deaggregating particles in a dispersion.
  • the vehicle refers to a portion of a medium in which organic particles are dispersed in a liquid state, a portion that is liquid and hardens by acting with the organic particles (binder), and a component that dissolves and dilutes this (organic) Solvent).
  • the present invention it is preferable to perform redispersion in an organic solvent containing the above-described polymer compound or a polymer compound having an acidic group.
  • an organic compound is used as for the polymer compound or the polymer compound having an acidic group. It is preferable to add the same type or different type used during grain formation during redispersion. More preferred to add.
  • the organic particle concentration of the organic particle dispersion composition after redispersion is appropriately determined according to the purpose.
  • the organic particle concentration is 2 to 30% by mass with respect to the total amount of the dispersion composition. 4 to 20% by mass It is particularly preferable that the content is 5 to 15% by mass.
  • the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic material, etc., but the binder is preferably 1 to 30% by mass with respect to the total amount of the organic particle dispersion composition, and is 3 to 20% by mass. It is particularly preferable that the content is 5 to 15% by mass.
  • the dissolution dilution component is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
  • organic particles are usually agglomerated due to concentration in a state where rapid filter filtration is possible.
  • Organic particles concentrated by centrifugation or drying are also aggregated by the concentration.
  • agglomerated organic particles are particles in which particles such as agglomerates are gathered by a secondary force
  • a dispersion method using ultrasonic waves or physical It is possible to use a method of adding energy.
  • the ultrasonic irradiation device preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner.
  • the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the particles occurs (see Pigment Dispersion Technology, Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation Technical Information Association 1999), so the liquid temperature is 1 to 100 ° C. 5-60 ° C is more preferable.
  • the temperature can be controlled by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
  • the dispersing machine used to disperse the concentrated organic particles by applying physical energy. For example, kneaders, roll mills, atriders, super mills, dissolvers, homomixers, sand mills, etc. Examples include a disperser.
  • finely dispersed particles of redispersed organic particles (primary particles) can be obtained.
  • Japanese Patent Application Laid-Open No. 2004-43776 describes a method for obtaining fine particles with a small change in particle size after redispersion. When evaluated finely, a considerable amount (for example, about 0.1%) of particles exceeding 0.50 m is observed, which may cause a decrease in performance in a CCD color filter or the like.
  • This method includes a step of causing agglomeration rapidly in a poor solvent by adding an acid, and this is presumed to cause association of pigment particles.
  • the average particle size can be nanometer size, preferably 1 to 200 nm, more preferably 2 to 100 nm, and 5 to 50 nm. Is particularly preferred.
  • the Mv / Mn of the particles after redispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5.
  • the organic particles are reconcentrated and reconstituted at the intended particle size, despite a nanometer size (for example, 10 to: LOOnm). Can be dispersed. For this reason, when an ink for inkjet is used, it is possible to obtain a clear ink having high optical density, excellent uniformity of the image surface, high saturation, and high clarity. Furthermore, when used in a color filter, the filter surface with high optical density is excellent in uniformity, the contrast is high, and image noise can be reduced.
  • a nanometer size for example, 10 to: LOOnm
  • the colored photosensitive resin composition of the present invention comprises at least (a) organic nanoparticles, (b) a binder, (c) a polyfunctional monomer (monomer or oligomer), and (d) a photopolymerization initiator or light. Includes a polymerization initiator system.
  • the method for producing organic nanoparticles has already been described in detail.
  • the content of the organic nanoparticles is 3 to 90% by mass with respect to the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content refers to the total composition excluding the organic solvent). 20 to 80% by mass is more preferable and 25 to 60% by mass is more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient.
  • the organic nanoparticles (pigment particles) functioning as a colorant preferably have a particle size of 0.1 ⁇ m or less, and particularly preferably a particle size of 0.08 m or less. Also in combination with ordinary pigments for toning Use it. As the pigment, those described above can be used.
  • the above-described polymer compound having a mass average molecular weight of 1000 or more can be preferably used as the binder in the colored photosensitive resin composition.
  • the content of the binder is generally 15 to 50% by mass, preferably 20 to 45% by mass, based on the total solid content of the colored photosensitive resin composition. If this amount is too large, the viscosity of the composition becomes too high, which causes a problem in production suitability. If the amount is too small, there is a problem in forming the coating film.
  • the polyfunctional monomer to be contained in the colored photosensitive resin composition of the present invention is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light.
  • polyfunctional monomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
  • Examples include monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxychetyl (meth) acrylate, and monofunctional methacrylates.
  • monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxychetyl (meth) acrylate, and monofunctional methacrylates.
  • Tacrylate Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane diatalate, neopentyl glycol di ( (Meth) atalylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (meth) acrylate, dipen Taerythritol Penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol propantri (atallylooxypropyl) ether, tri (atallylooxychetyl) isocyanurate, tri (atalylooxy) (Cetyl) cyanurate, glycerin tri (meth) at
  • urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B 49-43191 and Japanese Patent Publication No. 52-30490 such as polyester acrylates; polyfunctional acrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid; Metatalates can be mentioned.
  • trimethylolpropane tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred.
  • polymerizable compound B described in JP-A-11-133600 can also be mentioned as a preferable example.
  • These polyfunctional monomers are preferable.
  • Colored photosensitive resin compositions that can be used alone or in combination of two or more.
  • the content of the total solid content is generally 5 to 50% by mass, and preferably 10 to 40% by mass. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure will be insufficient.
  • Photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention expresses the function of initiation of photopolymerization by a combination of a plurality of compounds.
  • polymerization initiator C described in JP-A-11-133600, or oxime-based 1-Ferru 1, 2-propanedione 1- (o ethoxycarbol) ) Oxim, O Benzyl-4,-(Benzmercapto) Benzyl Hexyl-Ketoxime, 2, 4, 6 Trimethylphenol-Lulphyl-Folphosphate Oxide, Hexafluorophospho-Trialkylphenol Phospho- Umu salt and the like can also be mentioned as suitable.
  • photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two types of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
  • the content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If it is too low, the exposure sensitivity will be too low.
  • an organic solvent may be used in addition to the above components.
  • organic solvents include, but are not limited to, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate.
  • Alkyl esters methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropion Alkyl 3-alkylpropionates such as methyl 3-ethylpropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, 2 Methyl oxypropionate 2 Okishipuropio phosphate Echiru, 2 Okishipuropion propyl, 2-methyl methoxypropionate, 2- Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethyl ethoxy
  • methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, solvate acetate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, 2 heptanone, cyclohexanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention.
  • These solvents may be used alone or in combination of two or more.
  • a solvent having a boiling point of 180 ° C. to 250 ° C. may be used as necessary. Examples of these high boiling point solvents are as follows.
  • Diethylene glycol monobutyl ester diethylene glycol monoethyl enoate acetate, diethylene glycol monoethyl ether, 3, 5, 5 trimethyl-2-cyclohexene 1-one, butyl lactate, dipropylene glycol monomethenoylate
  • the content of the solvent is preferably 10 to 95% by mass with respect to the total amount of the resin composition.
  • the color filters that have been used in the past have a problem that the color of each pixel becomes darker in order to achieve high color purity, and the uneven power of the pixel film thickness is recognized as color unevenness as it is. . For this reason, it has been demanded to improve the film thickness fluctuation when forming (coating) the photosensitive resin layer, which directly affects the film thickness of the pixel.
  • the color filter of the present invention or the photosensitive resin transfer material of the present invention can be controlled to have a uniform film thickness, and from the viewpoint of effectively preventing coating unevenness (color unevenness due to film thickness variation), It is preferable to include an appropriate surfactant in the greave composition.
  • the surfactant include those disclosed in JP-A-2003-337424 and JP-A-11-133600.
  • the content of the surfactant is preferably 5% by mass or less based on the total amount of the resin composition.
  • the colored photosensitive resin composition of the present invention preferably contains a thermal polymerization inhibitor.
  • the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxy fenenore, di-t-butinole p-crezo-monore, pyrogalonore, tert-tinole teconole, benzoquinone, 4, 4'-thiobis (3-methyl-6 — T-Butylphenol), 2,2, -Methylenebis (4-methyl-6-t-butylphenol), 2-Mercaptobens imidazole, and Funothiazine.
  • the content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition.
  • a colorant in addition to the colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition of the present invention as necessary.
  • a pigment among the colorants it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition, so that the particle size is 0.1 ⁇ m or less, particularly 0.0 ⁇ m or less. It is preferable that
  • the dye or pigment include the colorant described in JP-A-2005-17716, [0038]-[0040], and JP-A-2005-361447 [0068]-[0]. [072] and the colorants described in JP-A-2005-17521, [0080] to [0088] can be suitably used.
  • the auxiliary dye or pigment content is preferably 5% by weight or less, based on the total amount of the resin composition.
  • the colored photosensitive resin composition of the present invention can contain an ultraviolet absorber as necessary.
  • the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, -chelate-chelated, and hindered amine-based compounds in addition to the compounds described in JP-A-5-72724.
  • ferric salicylate 4 t-butyl ferric salicylate, 2,4-di-t-butyl ferrule 3 ', 5'-di-t-4'-hydroxybenzoate, 4-t-butyl fuel Salicylate, 2,4-Dihydroxybenzophenone, 2 Hydroxy-4-methoxybenzophenone, 2 Hydroxy 4-n-Otoxybenzophenone, 2 -— (2′-Hydroxy-5′-methylphenyl) benzotriazole, 2 -— (2 '—Hydroxy 3' t-butyl-5, 1-methylphenol) 5 Chronobenzozoazole, Ethyl 2 Cyan 3, 3—Diphenyl acrylate, 2, 2, 1-hydroxy 4-methoxybenzophenone, Nickel dibutyl Dithiocarbamate, bis (2, 2, 6, 6-tetramethyl-4-pyridine) sebacate, 4 t-butylphenol salicylate, salicylate, 4-hydroxy 2, 2, 6, 6-tetramethyl
  • the colored photosensitive resin composition of the present invention contains "adhesion aid" described in JP-A-11-133600, other additives and the like in addition to the above-mentioned additives. It can be made.
  • the components contained in the coating film using the colored photosensitive resin composition of the present invention are the same as those already described in the section of [Colored photosensitive resin composition].
  • this departure The thickness of the coating film using the bright colored photosensitive resin composition can be determined as appropriate according to the application force S capable of being S, 0.5-5.O / zm force S, preferably 1. It is more preferably 0 to 3.0 m than force S.
  • a monomer or oligomer contained therein is polymerized to form a colored photosensitive resin composition polymer film, and a color filter having the same (The production of the color filter will be described later.)
  • O Polymerization of the polymerizable monomer or polymerizable oligomer is effected by (d) photopolymerization initiator or photopolymerization initiator system by light irradiation. Can be done.
  • the coating film can be formed by applying a colored photosensitive resin composition by a normal coating method and drying, but in the present invention, a slit-like hole is formed in a portion from which the liquid is discharged. It is preferable to apply with a slit-shaped nozzle.
  • JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-7 Slit nozzles and slit coaters described in 9163, JP 2001-310147, and the like are preferably used.
  • the coating method of the colored photosensitive resin composition on the substrate is superior in spin coating because it can uniformly and precisely coat a thin film of 1 to 3 ⁇ m, and is widely used for the production of color filters. Can be used generally.
  • slit coating suitable for coating a substrate that is wider and larger than spin coating has been developed in order to increase manufacturing efficiency and manufacturing cost. It has come to be used for the production of filters. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.
  • a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is used, and the clearance (gap) with the substrate is several tens to several hundreds.
  • This slit coating is (1) less liquid loss than spin coating, (2) no coating liquid jumping, reducing the cleaning process, and (3) respraying scattered liquid components to the coating film.
  • slit coating is suitable for producing color filters for large-screen liquid crystal display devices, and is expected to be an advantageous coating method for reducing the amount of coating liquid.
  • slit coating forms a coating film with a much larger area than spin coating, a wide slit exit force When discharging coating liquid, a certain degree of relative speed is applied between the coater and the object to be coated. Need to keep. For this reason, good fluidity is required for the coating solution used in the slit coating method.
  • the slit coating is particularly required to keep the conditions of the coating solution supplied to the substrate from the slit of the coating head constant over the entire coating width. If the liquid properties such as fluidity and viscoelastic properties of the coating liquid are insufficient, uneven coating will occur and it will be difficult to keep the coating thickness constant in the coating width direction, and a uniform coating film will be obtained. I can't do that!
  • the photosensitive transfer material of the present invention is preferably formed using a photosensitive resin transfer material described in JP-A-5-72724, that is, an integrated film.
  • a photosensitive resin transfer material described in JP-A-5-72724, that is, an integrated film.
  • the constitution of the body-type film include a constitution in which the temporary support Z, the thermoplastic resin layer Z, the intermediate layer Z, the photosensitive resin layer Z, and the protective film are laminated in this order, and the photosensitive transfer of the present invention.
  • a photosensitive photosensitive resin is provided by using the above-described colored photosensitive resin composition of the present invention.
  • the temporary support is flexible and can be marked even under pressure, or even under pressure and heating! /, Deformation, shrinkage or elongation. Does not occur It is necessary.
  • Examples of such a temporary support include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like, and among them, biaxially stretched polyethylene terephthalate film is particularly preferable.
  • an organic polymer substance described in JP-A-5-72724 is preferred as a component used for the thermoplastic resin layer.
  • the Vicat method specifically, the American Material Testing Method, Est. It is particularly preferred that the polymer is selected from organic polymer materials having a soft softening point measured by ASTM D1235 of about 80 ° C. or less.
  • polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and butyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, and vinyl chloride.
  • Salt-vinyl copolymer such as butyl acetate and its ken hydrate, poly-salt vinylidene, vinylidene chloride copolymer, polystyrene, styrene and (meth) acrylic acid ester or saponified product thereof Styrene copolymer, polytoluene toluene, vinyl toluene and (meth) acrylic acid ester or saponified butyltoluene copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid butyl and vinyl acetate
  • organic polymers such as polyamide resin such as dimethyl methyl nylon and N-dimethylaminolated nylon.
  • an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application.
  • an oxygen-blocking film having an oxygen-blocking function described in JP-A-5-72724 as a “separation layer”. The time load of the exposure machine is reduced and the productivity is improved.
  • oxygen-blocking membrane As the oxygen-blocking membrane, a normal medium force that exhibits low oxygen permeability and is preferably dispersed or dissolved in water or an aqueous alkali solution can be appropriately selected. Of these, the combination of polybulal alcohol and polybulurpyrrolidone is particularly preferred. It is.
  • the protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer.
  • silicone paper, polyolefin, or polytetrafluoroethylene sheet is suitable as the protective film material.
  • the photosensitive transfer material of the present invention is obtained by applying a coating solution in which an additive for a thermoplastic resin layer is dissolved on a temporary support (a coating solution for a thermoplastic resin layer) and drying the thermoplastic resin layer. After that, a solution of an intermediate layer material that also has solvent power is applied and dried on the thermoplastic resin layer without dissolving the thermoplastic resin layer, and then the photosensitive resin layer is coated with a solvent that does not dissolve the intermediate layer. It can be prepared by coating and drying.
  • thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other.
  • a sheet provided with a thermoplastic resin layer on the temporary support, and a photosensitive resin layer and an intermediate layer were provided on a protective film. It can also be produced by preparing a sheet and bonding them together so that the thermoplastic resin layer and the intermediate layer are in contact with each other.
  • the thickness of the photosensitive resin layer is preferably 1.0 to 5. ⁇ m force, more preferably 1.0 to 4. O / zm force. 0 ⁇ 3.0 m force ⁇ Especially preferred! / ⁇ . Further, although not particularly limited, the preferred film thickness of each of the other layers is as follows: Temporary support 15 to: LOO / zm Also 0.5-3. O / zm, protective film 4-40 m force is generally preferred.
  • the coating in the above production method can be performed by a normal coating apparatus or the like.
  • the coating is preferably performed by the coating apparatus (slit coater) using the slit-like nozzle already described in the section of [Coating film of colored photosensitive resin composition].
  • the coating apparatus slit coater
  • Preferred specific examples of the slit coater are the same as described above.
  • contrast refers to the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 7th Color Optical Conference, 512 color display 10 See 4 "size TFT — color filters for LCD, Ueki, Koseki, Fukunaga, Yamanaka” etc.
  • the high contrast of the color filter means that the brightness and darkness discrimination when combined with the liquid crystal can be increased. This is a very important performance in order to replace the liquid crystal display with a CRT.
  • the chromaticity power of each single color of red (R), green (G), and blue (B) by the F10 light source is as described in the table below.
  • the difference ( ⁇ E) from the value (hereinafter referred to as “target chromaticity” in the present invention) is preferably within a range of 5 or less, and more preferably 3 or less. It is particularly preferable that the number is within 2.
  • the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system.
  • the difference from the target chromaticity is expressed by the color difference of the La * b * color system.
  • the color filter of the present invention can be produced by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.
  • an ordinary coating apparatus can be used for coating the colored photosensitive resin composition, but among others, already [coated film of colored photosensitive resin composition]
  • the slit coater described in the section can be preferably used. Preferred examples of the slit coater are the same as described above.
  • the film thickness is preferably 1.0 to 3. O / zm, more preferably 1.0 to 2.5 / zm, 1.5 to 2.5 5 111 especially preferred 1 ⁇ 0
  • a photosensitive resin layer formed into a film is pressure-bonded or heat-pressed with a roller or flat plate heated and Z or pressurized on a substrate described later.
  • Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575.
  • the preferable film thickness is the preferred U film thickness described in the section of [Photosensitive resin transfer material]. It is the same.
  • the substrate on which the color filter is formed for example, a transparent substrate is used, and a known soda glass plate, low expansion glass, non-alkaline glass, quartz glass plate, etc., having an acid silicon film on the surface. Glass plate or plastic film.
  • substrate can make favorable adhesion
  • a method described in JP-A-2000-39033 is preferably used.
  • the film thickness of the substrate is generally preferably 700 to 1200 / ⁇ ⁇ , and 500 to: L 100 m force is particularly preferable! / ⁇ . [0281] (Oxygen barrier membrane)
  • an oxygen-blocking film can be further provided on the photosensitive resin layer.
  • the oxygen-blocking film include those already described in the section (intermediate layer) of [Photosensitive resin transfer material].
  • the thickness of the oxygen blocking film is generally preferably 0.5 to 3. ⁇ m.
  • a predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then the mask upward force is also exposed through the mask, the thermoplastic resin layer, and the intermediate layer, and then development with a developer is performed. It is possible to obtain the color filter of the present invention by repeating the process of performing as many times as the number of colors.
  • the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.).
  • a wavelength region capable of curing the photosensitive resin layer for example, 365 nm, 405 nm, etc.
  • an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned.
  • the amount of exposure is usually about 5 to 200 mjZcm 2 , preferably 10 to about LOOmjZcm 2 .
  • the developer a normal developer such as that described in JP-A-5-72724, which is not particularly limited, can be used.
  • the developer has a developing behavior in which the photosensitive resin layer is dissolved.
  • a developer containing 1 ⁇ & 7 to 13 in a concentration of 0. O5 to 5mo 1ZL.
  • a small amount of an organic solvent miscible with water may be added.
  • organic solvents that are miscible with water include methanol, ethanol, 2-propanol, 1 propanol, butanol, diacetone alcohol, ethylene glycol monomethino ethenole, ethylene glycol monomethino enotenole, and ethylene glycol monomethanol.
  • the concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
  • a normal surfactant can be further added to the developer.
  • concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
  • development method methods such as paddle development, shower development, shower & spin development, and dip imaging can be used.
  • the uncured portion can be removed by spraying a developer onto the photosensitive resin layer after exposure.
  • a developer onto the photosensitive resin layer after exposure.
  • the developer temperature is preferably 20 ° C to 40 ° C, and the developer pH is preferably 8 to 13.
  • a colored photosensitive resin composition that forms a color filter is stacked. From the viewpoint of cost reduction, it is preferable to form a base, form a transparent electrode on it, and then form a spacer by overlapping projections for split orientation.
  • the film thickness becomes thinner each time it is stacked due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors K (black) 'R'G'B, and further overlap the divisional alignment protrusions.
  • the thickness is kept constant, so that the overlapping color is preferably 3 or 2 colors.
  • the size of the base is preferably 25 m or more and particularly preferably 30 m or more from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and maintaining a constant thickness. .
  • the CCD device of the present invention is manufactured using the pigment nanoparticles obtained by the production method of the present invention.
  • the manufactured color filter is provided.
  • the CCD device of the present invention will be described in detail.
  • the alkali-soluble resin used in the CCD device is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution.
  • linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54- Nos.
  • methacrylic acid copolymer examples include maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain.
  • a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group is also useful.
  • benzyl (meth) atarylate Z (meth) acrylic acid copolymer and benzyl (meth) atarylate Z (meth) acrylic acid / and multi-component copolymers with other monomers are particularly suitable.
  • Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polybutyl pyrrolidone, polyethylene oxide, and polybutyl alcohol.
  • the polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. That's right.
  • Compounds having at least one addition-polymerizable ethylenically unsaturated group and a boiling point of 100 ° C or higher at normal pressure include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.
  • Monofunctional acrylates and meta acrylates such as phenoxychetyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, penta erythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (atalylooxypropyl) ether, toluene (Meth) atelar toy after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as isocyanurate, glycerin and trimethylolethane
  • a compound represented by the following general formula (B-1) or (B-2) can also be used.
  • B is each independently one (CH CH O)-and one (CH CH (
  • CH)) ⁇ ) — represents one of the following: X represents each independently an taliloyl group, a methacryloyl group, and
  • the total of the allyloyl group and the metathalyl group is 5 or 6, and that in the formula (B-2) is 3 or 4 N represents an integer of 0 to 6 each independently, and the sum of each force n is 3 to 24; m represents an integer of 0 to 6 each independently, and the force represents each m
  • the total is 2-16.
  • These polymerizable monomers can be used in any ratio as long as they can form a coating film having adhesiveness upon irradiation with radiation.
  • the amount used is usually 5 to 90% by mass, preferably 10 to 50% by mass, based on the total solid content of the composition.
  • colorant various conventionally known dyes, inorganic pigments or organic pigments can be used singly or in combination.
  • dye known dyes for conventional color filters can be used without any particular limitation.
  • dye currently disclosed by the gazette etc. can be used.
  • the chemical structure is pyrazole azo, lino azo, triphenyl methane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. Etc. can be used.
  • the curable composition can be cured at a relatively low temperature, even a dye that is inferior in heat resistance compared to a pigment has a high temperature during post-beta to impart durability to the cured film. It is possible to reduce problems such as decomposition even when exposed to water.
  • the inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt, or the like, and specifically iron, conoleto, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony.
  • Metal oxides such as the above, and complex oxides of the above metals.
  • Organic pigments include CI Pigment Yellow 11, 24, 31, 53, 83, 8 5, 99, 108, 109, 110, 138, 139, 150, 151, 154, 167, 18 5, CI Pigment Orange 36, 38, 43, 71, CI Pigment Red 1 05, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254, CI Pigment Violet 19, 23, 32, 39, CI Pigmen t Blue 1, 2, 15, 16, 22, 60, 66, 15: 3, 15: 6, CI Pigmen t Green 7, 36, 37, CI Pigment Brown 25, 28, CI Pigment Black 1, 7, carbon Black etc. can be mentioned.
  • red pigment an anthraquinone pigment, a perylene pigment alone or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used.
  • CI pigment red 177 is used as an anthraquinone pigment
  • CI pigment red 155 is used as a perylene pigment.
  • Mixing with CI pigment yellow 83 or CI pigment yellow 139 is preferable in terms of color reproducibility. It is.
  • the mass ratio of red pigment to yellow pigment is good from 100: 5 to 100: 50. Within this range, it is preferable because the light transmittance of 400 nm to 500 nm can be suppressed and the color purity can be increased.
  • the green pigment a halogenated phthalocyanine pigment alone or a mixture of a disazo yellow pigment, a quinophthalone yellow dye or an isoindoline yellow pigment is used.
  • CI Pigment Green 7, 36 37 and CI Pigment Yellow 83, 138, 139 are preferred.
  • the mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to L00: 100. Within this range, the light transmittance from 400 nm to 450 nm can be suppressed and good color purity can be obtained.
  • the blue pigment a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used.
  • CI pigment blue 15: 6 and CI pigment violet 23 are preferably mixed.
  • the mass ratio of blue pigment to purple pigment is preferably 100: 0 to 100: 50. Within this range, the light transmittance from 400 nm to 420 nm can be suppressed and the color purity can be increased. Togashi.
  • pigment for the black matrix carbon, titanium oxide, iron oxide, alone or a mixture thereof is used, and carbon and titanium oxide are preferable. Mass ratio from 100: 5
  • a range of 100: 40 is preferred. Within this range, the light transmittance at long wavelengths is small and the dispersion stability is also good.
  • Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate.
  • Ethyl lactate methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxy Alkyl esters of 3-oxypropionic acid such as ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, methyl 2-oxypropionate, 2 —Oxypropionate 2-propylpropionate, 2-methoxymethyl propionate, 2-methoxypropionate, 2-methoxypropionate, 2-methoxypropylpropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-oxypropionate 2-methyl methyl propionate, 2-oxy-2-e
  • methyl ethoxypropionate, 3 ethyl ethoxypropionate, ethyl solvate sorb acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 heptanone, cyclohexanone, Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used.
  • the amount of the solvent added is usually 60 to 90% by mass, preferably 70 to 90% by mass in the composition.
  • a sensitizer can be used in combination.
  • Specific examples include 9 fluorenone, 2 chloro 9 fluorenone, 2-methyl 9 fluorenone, 9 anthrone, 2 bromo 9 —anthrone, 2 ethyl 9 anthrone, 9, 10 anthraquinone, 2 ethyl 9, 10 anthraquinone, 2— t-butyl-9,10 anthraquinone, 2,6 dichloro-9,10-anthraquinone, benzyl, dibenzalacetone, p- (dimethylamino) phenol ketol, P- (dimethylamino) phenol ⁇ -methylstyryl ketone, benzo Anthrone and the like include benzothiazole compounds described in JP-B 51-48516.
  • a general manufacturing method of a color filter used in a CCD device is as follows. A step of applying and drying the composition (color resist solution) of the present invention on a substrate, a step of pattern exposure of the obtained dry coating film with an i-line stepper, a step of alkali development after exposure, and a heat treatment A color filter is obtained by sequentially performing the steps and repeating the above steps for each color (three or four colors) to produce a cured film.
  • the curable composition is generally dried on a suitable substrate with a spinner or the like so that the film thickness when dried is generally 0.1 to 5111, preferably 0.2 to Apply to 2 m and leave in oven at 85 ° C for 2 minutes to obtain a smooth coating.
  • the substrate is not particularly limited, but it is a substrate for electronic parts such as a glass plate, a plastic plate, an aluminum plate, a silicon wafer for an imaging element, and further a transparent resin plate, a resin film, a brush.
  • Duct tube display surface light-sensitive surface for image sensing, wafers with solid-state image sensors such as CCD, BBD, CID, BASIS, contact image sensor using thin film semiconductors, liquid crystal display surface, color electrophotographic photosensitive Body, Electrum Chromy (EC) display substrate.
  • a pattern of the curable composition is formed after thinly coating with a silane coupling agent or the like on the substrate in advance, or in some cases, a silane coupling agent is previously contained in the curable composition.
  • a flattening film for eliminating the step and smoothing the coating surface is applied on the substrate, and then the curable composition of the present invention is applied.
  • an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate according to the amount of light received, and a readout gate unit that outputs the generated electrons. If the gate is exposed to light, it will cause noise and accurate data will not be output.Therefore, a light-shielding film layer is formed on the top of the readout gate, and there is a step between the photodiode part without the light-shielding film layer. May have occurred.
  • the optical path length becomes long, so that the image becomes dark and the light condensing property becomes poor.
  • the material for the flat film include a photo-curable resist solution as in the present invention, thermosetting resins such as acrylic and epoxy resins, and the like.
  • the solvent is evaporated and a normal baking is performed to obtain a dry coating film.
  • This prebeta method includes drying under reduced pressure, indirect hot heat drying with high-temperature air, etc., and direct heat drying (about 80 to 140 ° C, 50 to 200 seconds) with a hot plate.
  • post-beta is performed in order to sufficiently cure the pattern obtained after development to increase the mechanical strength and form a permanent film.
  • the first formed pattern is then subjected to application, exposure and development of another color resist solution twice. In this case, pattern loss due to color mixing, exposure, and development with the applied resist solution Post-beta is performed so as not to occur.
  • This post-beta is used in the same way as pre-beta, but at a higher temperature and longer time than pre-beta conditions.
  • indirect heating by oven is performed at about 180 to 250 ° C. for about 0.5 to 2 hours
  • direct heating by hot plate is performed at about 180 to 250 ° C. for about 2 to 10 minutes.
  • the light source for exposure is not particularly limited, i-line of a mercury lamp can be cited as a light source that has a significant effect on pattern formation.
  • the feature of the present invention is an appropriate surface power of the process. The feature is particularly remarkable in the production of a color filter for an image sensor using i-line, which is one of the line spectrum of a mercury lamp, but it is also used for an LCD. Of course, it can be used.
  • the developer used for the development of the curable composition is not particularly limited, and a conventionally known developer can be used. Among them, an organic alkaline developer of a quaternary ammonium salt such as tetramethyl ammonium hydroxide (TMAH) is preferable for achieving the object of the present invention.
  • TMAH tetramethyl ammonium hydroxide
  • a normal photopolymerization initiator can be used as the polymerization initiator.
  • the vicinal polykettle aldo two Louis compound described in US Pat. No. 2,367,660, US Pat. Nos. 2,367,661 and 2,367,670 Substituted with the ⁇ -hydrocarbon described in US Pat. No. 2,722,512, the acylo ether described in US Pat. No. 2,448,828.
  • the content of the photopolymerization initiator (including the above-mentioned ordinary photopolymerization initiator) in the dye-containing negative curable composition is 0 with respect to the solid content (mass) of the radical polymerizable monomer. 0 1 to 50% by weight is preferred 1 to 30% by weight is more preferred 1 to 20% by weight is particularly preferred. When the content is in the above range, sufficient polymerization and curing can be performed, and polymerization is difficult to proceed. In addition, the polymerization rate increases but the molecular weight does not decrease and the film strength does not decrease.
  • a sensitizer or a light stabilizer can be used in combination with the photopolymerization initiator.
  • benzoin benzoin methyl ether, 9 fluorenone, 2 chloro 9 fluorenone, 2—methyl 9 fluorenone, 9 anthrone, 2 bromo 9 —anthrone, 2 ethyl 9 anthrone, 9, 10 anthraquinone, 2 ethyl 9, 1 0 Anthraquinone, 2-t-butyl-9, 10 Anthraquinone, 2, 6 Dichloro-9, 10 Anthraquinone, Xanthone, 2-Methylxanthone, 2-Methoxyxanthone, 2-Ethoxyxanthone, Thioxanthone, 2, 4 Jetylthioxanthone, Atalidone 10 butyl 2 -chloroataridon, benzyl, dibenzalacetone, p- (dimethylamino) phenol styryl ketone, p- (dimethylamino) phenol-p-methylstyryl
  • the liquid crystal display device of the present invention uses the color filter of the present invention having excellent contrast and is excellent in descriptive power such as black spots.
  • the color filter of the present invention is preferably a VA system. It can also be suitably used as a large screen liquid crystal display device such as a notebook personal computer display or a television monitor.
  • the color filter of the present invention can be used for a CCD device and exhibits excellent performance.
  • Another preferred embodiment of the present invention includes the following examples.
  • a method for producing an organic particle dispersion composition comprising producing a material as organic particles and concentrating the material, by concentrating the dispersion containing the organic particles by ultrafiltration.
  • the organic material is an organic pigment, wherein (A) to (C) The manufacturing method of the organic-particle dispersion composition of description.
  • a pigment solution was prepared by dissolving 0.6 g of Pigment (Vigment Red 254) in a solution prepared by mixing 1-methyl-2-pyrrolidone and ImolZL-sodium hydroxide aqueous solution 6: 1 to 15 mmol, L. Also, methacrylic acid / benzyl methacrylate copolymer 0.75 g (molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution), pigment dispersant A 0.3 g, dispersant Polybulpyrrolidone 0.6 g (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) was dissolved in the above solution. Separately from this, water was prepared as a poor solvent.
  • the temperature of the solution was controlled at 25 ° C, and the pigment solution was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type ramond stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd., manufactured by Nippon Seimitsu Chemical Co., Ltd.
  • An organic pigment particle dispersion was prepared by injecting 22 Oml at a flow rate of 50 mlZmin using an NP-KX-500 large capacity non-pulsating pump.
  • the prepared organic particle dispersion was measured using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated. The number average particle size was 32 nm and MvZMnl.35.
  • the prepared organic pigment particle dispersion (pigment particle concentration of about 0.05% by mass) was desalted and concentrated using CIO-TZRUM-2, an ultrafiltration machine manufactured by Nitto Denko. The conditions were as follows: liquid flow rate lL / min, liquid feed pressure 0.2 MPa, ultrafiltration filter molecular weight cut off 500,000. As a result, 400 ml of an organic pigment particle dispersion (pigment particle concentration: about 1.5% by mass) was obtained.
  • the concentrated extract from which organic pigment particles have been extracted is filtered using a FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co., Ltd. The amount 0/0) was obtained. At this time, the sodium (Na) ion concentration was 0.01% by mass with respect to the pigment.
  • the pigment composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger) at a peripheral speed of 9 m / s using Zirco Your beads having a diameter of 0.65 mm.
  • the pigment composition thus prepared was measured as a pigment dispersion composition A using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated.
  • Pigment Dispersion Composition A the methacrylic acid / benzyl methacrylate copolymer used for preparing Pigment Dispersion Composition A using the paste was replaced with methacrylic acid / benzyl methacrylate / styrene copolymer 15 Pigment dispersion composition as in Pigment dispersion composition A, except that 8 g (molar ratio 27:60:13, mass average molecular weight: 28,000, 40% 1-methoxy-2-propyl acetate solution) was used.
  • Object B was made.
  • Pigment Dispersion Composition A 15.8 g (weight average) of the methacrylic acid / benzyl methacrylate copolymer used in preparing Pigment Dispersion Composition A using the paste was used.
  • Pigment Dispersion Composition C was prepared in the same manner as Pigment Dispersion Composition A, except that the average molecular weight was 33,000 and a 40% 1-methoxy-2-propyl acetate solution was used.
  • Pigment dispersion composition B was the same as pigment dispersion composition B except that the methacrylic acid / benzyl methacrylate copolymer used in preparing the organic pigment particle dispersion was used. D was produced.
  • Pigment Dispersion Composition B instead of using the methacrylic acid / benzyl methacrylate copolymer used in preparing the organic pigment particle dispersion, 0.75 g of methacrylic acid / benzyl methacrylate copolymer was dispersed in the pigment.
  • Pigment dispersion composition E was prepared in the same manner as pigment dispersion composition B, except that it was added during preparation of the composition.
  • An organic pigment particle dispersion was prepared in the same manner as in Example 1.
  • the obtained pigment dispersion compositions A to F were each applied onto a glass substrate so as to have a thickness of 2 ⁇ m, thereby preparing samples. This sample was observed with an optical microscope, and the number of particles with a diameter of 0.5 ⁇ m or more (coarse particle number) at 1 mm 2 was evaluated.
  • the particle size and particle size distribution MvZMn are shown in Table 1.
  • a pigment solution was prepared by dissolving 0.6 g of Pigment (Vigment Red 254) in a solution prepared by mixing 1-methyl-2-pyrrolidone and ImolZL-sodium hydroxide aqueous solution 6: 1 to 15 mmol, L. Also, methacrylic acid / benzyl methacrylate copolymer 0.75 g (molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution), pigment dispersant A 0.3 g, dispersant Polybulpyrrolidone 0.6 g (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) was dissolved in the above solution. Separately from this, water was prepared as a poor solvent.
  • the temperature was controlled at 25 ° C, and the pigment solution was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type ramond stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd., manufactured by Nippon Seimitsu Chemical Co., Ltd.
  • An organic pigment particle dispersion was prepared by injecting 22 Oml at a flow rate of 50 mlZmin using an NP-KX-500 large capacity non-pulsating pump.
  • the prepared organic particle dispersion was measured using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated.
  • the number average particle size was 32 nm and MvZMnl.35.
  • the prepared organic pigment particle dispersion (pigment particle concentration: about 0.05 mass%) was used with an ultrafilter to obtain a concentrated pigment liquid (pigment particle concentration: 10 mass%).
  • sodium (Na) The ion concentration was 0.02% by mass.
  • VF35 manufactured by Advantech Toyo Co., Ltd., it was frozen at ⁇ 35 ° C., and then freeze-dried with 6 ⁇ 10 torr for 16 hours to obtain a granular pigment.
  • the pigment composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger) at a peripheral speed of 9 m / s using Zircoyu beads having a diameter of 0.65 mm.
  • the pigment composition thus prepared was measured using a nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. as a pigment dispersion composition A1, and the particle size and monodispersity were evaluated.
  • a methacrylic acid / benzyl methacrylate copolymer was used to prepare the pigment dispersion composition A1 by using a paste, and a methacrylic acid / benzyl methacrylate / styrene copolymer 15 Pigment dispersion composition as in Pigment dispersion composition A1, except that 8 g (molar ratio 27:60:13, weight average molecular weight: 28,000, 40% 1-methoxy-2-propyl acetate solution) was used.
  • Material B1 was produced.
  • pigment dispersion composition A1 methacrylic acid / benzyl methacrylate copolymer used for preparing the pigment dispersion composition A1 using a paste was added with 15.8 g of polyacrylic acid (mass average molecular weight: 33,3)
  • a pigment dispersion composition C1 was prepared in the same manner as the pigment dispersion composition A1, except that the solution was 1,000, 40% 1-methoxy-2-propyl acetate solution.
  • Pigment dispersion composition B1 was the same as pigment dispersion composition A1 except that when the organic pigment particle dispersion was prepared, a methacrylic acid / benzyl methacrylate copolymer was used. Thus, a pigment dispersion composition Dl was prepared.
  • pigment dispersion composition B1 0.75 g of methacrylic acid / benzyl methacrylate copolymer was used instead of the methacrylic acid / benzyl methacrylate copolymer used in preparing the organic pigment particle dispersion.
  • a pigment dispersion composition E1 was produced in the same manner as the pigment dispersion composition A1, except that it was added during preparation of the product.
  • Table 2 shows the particle size distributions MvZMn of the pigment dispersion compositions A1 to E1.
  • the particle size distribution re-dispersed after ultrafiltration and lyophilization for the purpose of removing salt is organic in the presence of the polymer compound having an acidic group of the present invention.
  • the particles were prepared (pigment dispersion compositions A1 to C1), there was almost no change.
  • pigment dispersion composition D1 When there is no polymer compound having an acidic group when preparing organic particles (pigment dispersion composition D1), or when there is no polymer compound having an acidic group when preparing organic particles, and preparing a pigment dispersion composition
  • a polymer compound having an acidic group corresponding to that amount is sometimes added (pigment dispersion composition E1), the particle size distribution Mv / Mn is slightly changed, but it can be said that there is almost no problem in practical use.
  • Reagent Manufacturer Pigment Red 254 (Ilga Fore Red) Ciba 'Specialty'
  • An organic pigment having a dioxazine structure (C.I. Pigment Violet 23, manufactured by Dainichi Seika Co., Ltd., trade name: NOOLET RE) lg was charged into a sample tube 107 of an apparatus having the configuration shown in FIG.
  • Acetone prepared as solvent 1 to be used as a supercritical fluid was supplied to the sample tube 107 and supplied to the mixer 111 as a pigment-dissolving fluid.
  • water containing 1% by weight of polyvinyl pyrrolidone (trade name: Polybulol pyrrolidone K-30, mass average molecular weight 40, 000, manufactured by Wako Pure Chemical Industries, Ltd.) is prepared as precipitation solvent 2 and supplied to mixer 111. did.
  • the pigment nanoparticle dispersion liquid 115 was prepared and collected by mixing the pigment-dissolving fluid and the precipitation solvent with a mixer.
  • mass ratio of acetone and a precipitation solvent might be set to 1: 1.
  • the temperature of acetone for dissolving pigment (the temperature in sample tube 107) was 245 ° C, and the pressure was 15 MPa.
  • the temperature after mixing with the precipitation solvent was 90 ° C. (outlet temperature of mixer 111).
  • the prepared pigment particle dispersion was evaluated in the same manner as in Example 1. As a result, the pigment particle concentration was about 0.05% by mass.
  • the prepared pigment particles were observed in the same manner as in Example 1. As a result, the number average particle diameter was about 36 nm and Mv / Mn was 1.40.
  • a paste-like concentrated pigment dispersion (pigment particle concentration 33% by mass) was obtained in the same manner as in Example 1.
  • a pigment dispersion composition having the following composition was prepared.
  • the sodium (Na) ion concentration was 0.01 mass% with respect to the pigment.
  • Pigment dispersion from the pigment dispersion composition of the above composition using a motor mill in the same manner as in Example 1.
  • Composition G was made.
  • Example 11 instead of the polymer compound C 1 represented by the general formula (1), methacrylic acid 'benzyl methacrylate copolymer (molar ratio 28Z72, mass average molecular weight 30000, 40% 1-methoxy 2-propyl A pigment dispersion composition H was prepared in the same manner as the pigment dispersion composition G except that the acetate solution was used.
  • An organic pigment particle dispersion was prepared in the same manner as in Example 11.
  • the aqueous dispersion was then agglomerated, washed and filtered in the same manner as in Comparative Example 1 to obtain a desalted and dehydrated paste-like concentrated pigment liquid (pigment particle concentration 31% by mass).
  • the sodium (Na) ion concentration was 0.03 mass 0 / with respect to the pigment. Met.
  • Example 1 Table 3 shows the particle size, the particle size distribution and the number of coarse particles, and the contrast of the pigment dispersion compositions G to I measured in the same manner as in others.
  • the obtained pigment dispersion compositions G to I were each coated on a glass substrate so as to have a thickness of 2 m, thereby preparing samples.
  • a knocklight unit a three-wavelength cold-cathode tube light source (FWL18EX—N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plate manufactured by Sanritsu Co., Ltd.
  • the pigment dispersion composition of the present invention redispersed in the presence of the compound of the general formula (1) after performing ultrafiltration exhibits a particularly high contrast value, which is a more preferable result.
  • the change in the force at the time of particle formation is large, especially the number of coarse particles is large, and the contrast value is low.
  • thermoplastic resin layer having the following formulation HI On a 75 ⁇ m-thick polyethylene terephthalate film temporary support, using a slit nozzle, a coating solution for a thermoplastic resin layer having the following formulation HI was applied and dried. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, a light-shielding resin composition K1 having the composition described in Table 4 below was applied and dried, and a thermoplastic resin layer having a dry film thickness of 15 m on the temporary support and a dry film. An intermediate layer with a thickness of 1.6 m and a light-shielding resin layer with a dry film thickness of 2.4 m were provided, and a protective film (polypropylene phenol with a thickness of 12 m) was pressure-bonded.
  • a protective film polypropylene phenol with a thickness of 12 m
  • a photosensitive resin transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a light-shielding resin layer was prepared, and the sample name was photosensitive resin.
  • the transfer material was K1.
  • the resin composition Kl having a light-shielding property is obtained by first removing the amount of K pigment dispersion 1 and polypropylene alcohol monomethyl ether acetate in the amounts shown in Table 4 and mixing them at a temperature of 24 ° C ( ⁇ 2 ° C).
  • the surfactant 1 is the same as the surfactant 1 used in the coating solution HI for thermoplastic resin layer.
  • silane coupling liquid N- ⁇ (aminoethyl) y-aminopropyltrimethoxysilane 0.3 mass
  • % Aqueous solution trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.
  • KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.
  • a rubber roller temperature is applied to the substrate heated at 100 ° C for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). Lamination was performed at 130 ° C, linear pressure 100 NZcm, conveyance speed 2. 2 mZ min.
  • a proximity type exposure machine manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd. having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically.
  • the distance between the mask surface and the thermoplastic resin layer is set to 20 O / zm, and an exposure energy of lOOmjZcm 2.
  • the mask shape is a lattice shape, and the radius of curvature of the corner that protrudes toward the light-shielding partition wall at the boundary line between the pixel and the light-shielding barrier is 0.6 m.
  • a triethanolamine developer (containing 2.5% triethanolamine, containing a non-ionic surfactant, containing a polypropylene antifoaming agent, trade name: TPD1, Fuji Photo Film) Made by showering at 30 ° C for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
  • a sodium carbonate developer (0.06 mol Z liters of sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, ionic surfactant, antifoaming agent, stabilizer, Product name: TCD1, manufactured by Fuji Photo Film Co., Ltd., shower developed at 29 ° C for 30 seconds, cone type nozzle pressure 0.15 MPa, developing a light-shielding resin layer, and patterning separation wall (light-shielding property) Partition wall pattern).
  • plasma water repellency treatment was performed by the following method.
  • Plasma water repellency treatment was performed on the substrate on which the light-shielding partition walls were formed using a force sword coupling parallel plate type plasma processing apparatus under the following conditions.
  • An ink was prepared according to the following formulation with reference to Example 1 of JP-A-2002-201387.
  • composition component content (parts by mass) B ink 1 B ink 2 B ink 3 R ink 1 G ink 1 Pigment dispersion composition G (CIPV 23) 8 Pigment dispersion composition H (CIPV 23) 8 Pigment dispersion composition I (CIPV 23) 8 Pigment dispersion composition J (C. L PR 254) 75 Pigment dispersion composition K (CIPG 36) 75 Pigment dispersion composition (CIPB 15: 6) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
  • the pigment and the polymer dispersant were first charged and mixed in a part of the solvent, and the mixture was stirred using a three-roll and bead mill, and then the pigment dispersion liquid was mixed. Got. On the other hand, other compounding ingredients were added to the remainder of the solvent, and dissolved and dispersed by stirring to obtain a binder solution. Then, the pigment dispersion was added little by little to the binder solution and sufficiently stirred with a dissolver to prepare an ink-jet ink for a color filter.
  • Pigment dispersion compositions J, K and L in the same manner as in Example 11 except that Pigment Red 254, Pigment Green 36, or Pigment Blue 15: 6 was used instead of Pigment Violet 23. , Respectively.
  • the R ink 1, G ink 1, and B ink 1 obtained above were first ejected into a recess surrounded by a light-shielding partition as follows using a piezo-type head. And the color filter 1 of this invention was obtained as follows.
  • the head has 2 nozzles with a nozzle density of 25.4 mm and 318 nozzles. Two of these are fixed in the nozzle row direction by shifting the nozzle spacing by 1 Z2 and 25 on the substrate in the nozzle row direction. 300 drops per 4mm.
  • the head and the ink are controlled so that the vicinity of the discharge portion is 50 ° C 0.5 ° C by circulating hot water in the head.
  • the ink ejection of the head force is controlled by a piezo drive signal applied to the head, and it is possible to eject 6 to 42 pl per drop.
  • the glass substrate is conveyed at a position lmm below the head. However, it is ejected from the head.
  • the conveyance speed can be set in the range of 50 to 200 mmZs.
  • the piezo drive frequency can be up to 4.6 KHz, and the droplet ejection volume can be controlled by these settings.
  • the transport speed and drive frequency are controlled so that the amount of pigment applied is 1.1, 1.8, and 0.75gZm 2 for each of R, G, and B.
  • the desired R, G, and B R, G, and B inks were ejected into the recesses corresponding to.
  • UV—LED ultraviolet light emitting diode
  • NCCU033 manufactured by Nichia Corporation was used. This LED outputs ultraviolet light with a wavelength of 365 nm from a single chip.
  • a current of about 500 mA is applied, about lOOmW of light is emitted from the chip.
  • a plurality of these are arranged at intervals of 7 mm, and a power of 0.3 WZcm 2 can be obtained on the surface.
  • the exposure time after droplet ejection and the exposure time can be changed according to the transport speed of the media and the distance between the head and the LED transport direction. After landing, it was dried at 100 degrees for 10 minutes and then exposed.
  • the exposure energy on the media can be adjusted between 0.01 and 15 J Zcm 2 .
  • the exposure energy was adjusted according to the conveyance speed.
  • Spectroradiome A value obtained by integrating the wavelength between 220 nm and 400 nm using URS-40D was used.
  • the glass substrate after droplet ejection was beta-cured in an oven at 230 ° C for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.
  • ITO indium stannate
  • a spacer was formed on the ITO transparent electrode produced in the same manner as the spacer forming method described in [Example 1] of JP-A-2004-240335.
  • a liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.

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Abstract

A process for producing a composition having organic nanoparticles dispersed therein, the process comprising the steps of mixing a solution of an organic material dissolved in a good solvent with a poor solvent for the organic material which is compatible with the good solvent to generate nano-sized organic particles from the organic material, and concentrating the resulting dispersion solution containing the organic particles, the concentrating step being performed by the ultrafiltration of the dispersion solution.

Description

明 細 書  Specification
有機粒子分散組成物の製造方法  Method for producing organic particle dispersion composition
技術分野  Technical field
[0001] 本発明は、有機粒子析出法により作製した有機粒子を効率よく濃縮して有機粒子 分散組成物を製造する方法に関し、さら〖こ詳しくは、脱塩した上記有機粒子分散組 成物の製造方法に関する。さらには上記の製造方法において、その濃縮工程での 有機粒子の粒径および単分散性の変化を抑え、また濃縮により凝集したときにも容 易に再分散化できる有機粒子分散組成物の製造方法に関する。  [0001] The present invention relates to a method for producing an organic particle dispersion composition by efficiently concentrating organic particles produced by an organic particle precipitation method. More specifically, the desalted organic particle dispersion composition is described above. It relates to a manufacturing method. Furthermore, in the production method described above, a method for producing an organic particle dispersion composition that suppresses changes in the particle size and monodispersity of the organic particles in the concentration step and can be easily redispersed even when aggregated by concentration. About.
背景技術  Background art
[0002] 近年、粒子を小サイズィ匕する取り組みが進められて 、る。特に、粉砕法、析出法な どでは製造することが困難なナノメートルサイズ (例えば、 10〜： LOOnmの範囲）にま で小サイズィ匕する研究が進められている。さら〖こ、ナノメートルサイズに小サイズィ匕し た上で、し力も単分散性 (本発明において、単分散性とは粒径が揃っている度合いを いう。）の高い粒子とすることが試みられている。  [0002] In recent years, efforts have been made to reduce the size of particles. In particular, research is underway to reduce the size to nanometer size (for example, 10 to LOONm range), which is difficult to produce by pulverization and precipitation methods. Furthermore, while trying to reduce the size to a nanometer size, the force is also monodispersed (in the present invention, monodispersity refers to the degree of uniform particle size). It has been.
このようなナノメートルサイズの微粒子の大きさは、より大きなノ レク粒子や、より小さ な分子や原子と異なり、その中間に位置する。したがって、従来予想できな力 た新 たな特性を引き出しうることが指摘されている。例えば、ナノメートル (nm)スケールの 微結晶は、特異な表面構造に基づく触媒効果、サイズ効果による光物性、非線形光 学特性等の極めて興味深い様々な性質を発現する。し力も、この単分散性を高くで きれば、その特性を安定ィ匕することも可能である。このようなナノ粒子のもつ可能性は さまざまな分野で期待され、生化学、新規材料、電子素子、発光表示素子、印刷、医 療などの広い分野で研究が盛んになりつつある。  The size of such nanometer-sized fine particles is different from that of larger nano particles and smaller molecules and atoms, and is located in the middle. Therefore, it has been pointed out that new characteristics that could not be predicted in the past can be extracted. For example, nanometer (nm) scale microcrystals exhibit various interesting properties such as catalytic effects based on unique surface structures, photophysical properties due to size effects, and nonlinear optical properties. However, if this monodispersity can be increased, the characteristics can be stabilized. The potential of such nanoparticles is expected in various fields, and research is being actively conducted in a wide range of fields such as biochemistry, new materials, electronic devices, light-emitting display devices, printing, and medicine.
特に、有機化合物からなる有機ナノ粒子は、有機化合物自体が多様性を有するた め、機能性材料としてのそのポテンシャルは高い。例えば、ポリイミド等の電気絶縁性 に優れた物質を微粒子化して組み合わせればより大きな電気絶縁性が期待できる。  In particular, organic nanoparticles composed of organic compounds have a high potential as functional materials because the organic compounds themselves are diverse. For example, greater electrical insulation can be expected by combining finely divided substances such as polyimide that are excellent in electrical insulation.
[0003] 有機ナノ粒子のなかでも有機顔料にっ 、てみると、例えば、塗料、印刷インク、電 子写真用トナー、インクジェットインク、カラーフィルタ一等を用途として挙げることが でき、今や、生活上欠くことができない重要な材料となっている。なかでも高性能が要 求され、実用上特に重要なものとしては、インクジェットインク用顔料およびカラーフィ ルター用顔料が挙げられる。 [0003] Among organic nanoparticles, organic pigments include, for example, paints, printing inks, electrophotographic toners, inkjet inks, color filters, and the like. It is now an important material that is indispensable in daily life. Among these, high performance is required, and pigments for inkjet ink and pigments for color filters are particularly important for practical use.
インクジェット用インクの色材については、従来、染料が用いられてきた力 耐水性 ゃ耐光性の面で問題があり、それを改良するために顔料が用いられるようになってき ている。顔料インクにより得られた画像は、染料系のインクによる画像に較べて耐光 性、耐水性に優れるという利点を有する。し力しながら、紙表面の空隙に染み込むこ とが可能なナノメートルサイズで単分散性を高くすることは難しぐ紙への密着性に劣 る。  With respect to coloring materials for ink-jet inks, there have been problems in terms of water resistance and light resistance, in which dyes have conventionally been used, and pigments have been used to improve them. Images obtained with pigment inks have the advantage that they are superior in light resistance and water resistance compared to images obtained with dye-based inks. However, it is difficult to increase the monodispersity at a nanometer size that can penetrate into the voids on the paper surface.
また、デジタルカメラの高画素化に伴い、 CCDセンサーなどの光学素子や表示素 子に用いるカラーフィルターの薄層化が望まれている。カラーフィルターには有機顔 料が用いられている力 フィルターの厚さは有機顔料の粒子径に大きく依存するため 、ナノメートルサイズレベルで、し力も単分散で安定な微粒子の製造が望まれている  In addition, with the increase in the number of pixels in digital cameras, it is desired to reduce the thickness of color filters used in optical elements such as CCD sensors and display elements. The power of organic pigments used in color filters The thickness of the filter greatly depends on the particle size of the organic pigment. Therefore, it is desired to produce fine particles that are nanometer-sized, stable and monodisperse.
[0004] 有機粒子の製造に関しては、気相法 (不活性ガス雰囲気下で試料を昇華させ、粒 子を基板上に回収する方法)、液相法 (例えば、良溶媒に溶解した試料を攪拌条件 や温度を制御した貧溶媒に注入することにより、微粒子を得る再沈法)、レーザーァ ブレーシヨン法 (溶液中に分散させた試料に、レーザーを照射しアブレーシヨンさせる ことにより粒子を微細化する方法)などが研究されている。また、これらの方法により、 所望のサイズで単分散化を試みた製造例が報告されて 、る。（特許文献 1〜3など参 照)。 [0004] Regarding the production of organic particles, a gas phase method (a method in which a sample is sublimated in an inert gas atmosphere and particles are collected on a substrate), a liquid phase method (for example, a sample dissolved in a good solvent is stirred) (Reprecipitation method to obtain fine particles by injecting into a poor solvent with controlled conditions and temperature), laser ablation method (a method to make particles fine by irradiating a sample dispersed in a solution with a laser) Etc. are being studied. In addition, production examples in which monodispersion with a desired size is attempted by these methods are reported. (See Patent Documents 1-3).
[0005] 中でも再沈法は、簡易性および生産性に優れた有機粒子の製造法であるが、工業 利用性の高い粒子製法としては未だ十分ではない。例えば、再沈法により調製した 有機粒子をどのように分離回収するか、十分な研究がなされていない。再沈法では 調製した有機粒子は希薄な溶媒中に分散した状態で得られる。また、不要な塩が有 機粒子に対して多く含まれ、例えばカラーフィルター用途においては液晶汚染物質 となる可能性がある。そのため、不要な塩を除去し,有機粒子をいかに分離回収する 力が問題となる。またせつ力べ所望の粒子を分散液中で調製できたとしても、分離回 収する工程において、粒子サイズが変化し、粒子の単分散性が悪ィ匕してしまったり、 その回収に多大なコストを要したりするのでは実用化することはできない。 [0005] Among them, the reprecipitation method is a method for producing organic particles excellent in simplicity and productivity, but is not yet sufficient as a method for producing particles with high industrial utilization. For example, sufficient research has not been conducted on how to separate and recover organic particles prepared by the reprecipitation method. In the reprecipitation method, the prepared organic particles are obtained dispersed in a dilute solvent. In addition, unnecessary salt is contained in a large amount with respect to organic particles, and for example, it may become a liquid crystal contaminant in color filter applications. Therefore, the ability to remove unnecessary salts and separate and recover organic particles becomes a problem. Even if the desired particles can be prepared in the dispersion, In the collecting process, the particle size is changed, the monodispersity of the particles is deteriorated, and it is impossible to put it to practical use if the collection requires a large cost.
[0006] 分散液中の有機粒子を濃縮して回収する方法が、いくつか開示されているものの、 工業的な生産規模まで見据えたときに現実的な技術は 、まだ確立されて 、な!/、。 例えば、特許文献 4には粒子含有水分散液に蒸発促進液を添加し、蒸留すること により濃縮する方法が開示されている。しかし、この方法を再沈法で作製した有機粒 子含有水分散液に適用することを考えると、有機材料の良溶媒の沸点が水より高い 場合、水のみが蒸発してしまうことにより良溶媒濃度が増加し、濃縮中に有機粒子の 粒径が大きくなつてしまう懸念がある。  [0006] Although several methods for concentrating and recovering organic particles in a dispersion have been disclosed, the practical technology has not yet been established when looking at the industrial production scale! ,. For example, Patent Document 4 discloses a method of adding an evaporation promoting liquid to a particle-containing aqueous dispersion and concentrating it by distillation. However, considering that this method is applied to organic particle-containing aqueous dispersions prepared by the reprecipitation method, when the boiling point of the good solvent of the organic material is higher than that of water, only the water evaporates. There is a concern that the concentration increases and the particle size of the organic particles increases during concentration.
特許文献 5には、微粒子を含有する分散液に、その分散媒と実質的に溶解しない イオン性液体を添加して、当該イオン性液体中に微粒子を濃縮する方法が開示され ている。し力しながら、この方法のみでは有機粒子分散液を十分に所望の濃度まで 濃縮できない。  Patent Document 5 discloses a method in which an ionic liquid that does not substantially dissolve in the dispersion medium is added to a dispersion containing fine particles, and the fine particles are concentrated in the ionic liquid. However, this method alone cannot sufficiently concentrate the organic particle dispersion to the desired concentration.
特許文献 6には、有機顔料と分散剤を一緒に溶解させ、貧溶媒中で粒子を析出さ せることで微細な有機粒子を得る方法が開示されている。この方法では、その後酸の 添カ卩により有機粒子を凝集させることで、濃縮、脱塩を行えば、再分散による粒子サ ィズの変化が比較的小さくなるとされている。しかし、この手法により得られた再分散 液は、含まれる粒子の相当量が粒径の大きなものであり、例えば CCDのカラーフィル ターに適用する場合には特定の画素の濃度を下げてしまう。  Patent Document 6 discloses a method of obtaining fine organic particles by dissolving an organic pigment and a dispersant together and precipitating the particles in a poor solvent. In this method, if the organic particles are then agglomerated by adding acid, and concentration and desalting are performed, the change in particle size due to redispersion is relatively small. However, the redispersion liquid obtained by this method has a large amount of particles contained therein, and when applied to, for example, a CCD color filter, the density of a specific pixel is lowered.
特許文献 1：特表 2002— 092700号公報  Patent Document 1: Japanese Translation of Special Publication 2002-092700
特許文献 2：特開平 6— 79168号公報  Patent Document 2: JP-A-6-79168
特許文献 3：特開 2004 - 91560号公報  Patent Document 3: Japanese Patent Application Laid-Open No. 2004-91560
特許文献 4：特開 2004 - 181312号公報  Patent Document 4: Japanese Patent Application Laid-Open No. 2004-181312
特許文献 5：特開 2004— 292632号公報  Patent Document 5: Japanese Patent Application Laid-Open No. 2004-292632
特許文献 6：特開 2004— 43776号公報  Patent Document 6: Japanese Unexamined Patent Application Publication No. 2004-43776
発明の開示  Disclosure of the invention
[0007] 本発明は、有機粒子析出法により作製した有機粒子を効率よく濃縮して有機粒子 分散組成物を製造する方法の提供を課題とし、特に脱塩して有機粒子分散組成物 を得る製造方法の提供を課題とする。また上記の製造方法において、その濃縮工程 での有機粒子の粒径および単分散性の変化を抑え、また濃縮により凝集したときに も容易に再分散化できる有機粒子分散組成物の製造方法の提供を課題とする。 本発明によれば、以下の手段が提供される： [0007] An object of the present invention is to provide a method for producing an organic particle dispersion composition by efficiently concentrating organic particles produced by an organic particle precipitation method, and particularly desalting to provide an organic particle dispersion composition. It is an object to provide a manufacturing method for obtaining In addition, in the above production method, a method for producing an organic particle dispersion composition that suppresses changes in the particle size and monodispersity of organic particles in the concentration step and can be easily redispersed even when aggregated by concentration is provided. Is an issue. According to the present invention, the following means are provided:
(1)良溶媒に溶解した有機材料の溶液と、該溶媒と相溶する前記有機材料の貧溶 媒とを混合し、該有機材料をナノサイズの有機粒子として生成させ、これを濃縮する にあたり、前記有機粒子を含む分散液を限外ろ過によって濃縮することを特徴とする 有機ナノ粒子分散組成物の製造方法。  (1) When mixing a solution of an organic material dissolved in a good solvent and a poor solvent of the organic material compatible with the solvent to produce the organic material as nano-sized organic particles, and concentrating it. A method for producing an organic nanoparticle dispersion composition, wherein the dispersion containing the organic particles is concentrated by ultrafiltration.
(2)前記有機材料溶液が、有機顔料を超臨界流体もしくは亜臨界流体に溶解した顔 料含有流体であることを特徴とする、 (1)に記載の有機ナノ粒子分散組成物の製造 方法。  (2) The method for producing an organic nanoparticle dispersion composition according to (1), wherein the organic material solution is a pigment-containing fluid in which an organic pigment is dissolved in a supercritical fluid or a subcritical fluid.
(3)酸性基を持つ高分子化合物を含有する事を特徴とする（1)又は (2)に記載の有 機ナノ粒子分散組成物の製造方法。  (3) The method for producing an organic nanoparticle dispersion composition according to (1) or (2), comprising a polymer compound having an acidic group.
(4)酸性基を持つ高分子化合物の存在下、前記有機材料液と貧溶媒の混合を行う ことを特徴とする（1)〜（3)の 、ずれかに記載の有機ナノ粒子分散組成物の製造方 法。  (4) The organic nanoparticle dispersion composition according to any one of (1) to (3), wherein the organic material liquid and a poor solvent are mixed in the presence of a polymer compound having an acidic group. Manufacturing method.
(5)前記有機粒子の数平均粒径が 1 μ m以下であることを特徴とする（1)〜 (4)のい ずれ力 1項に記載の有機ナノ粒子分散組成物の製造方法。  (5) The method for producing an organic nanoparticle dispersion composition according to any one of (1) to (4), wherein the number average particle diameter of the organic particles is 1 μm or less.
(6)前記限外ろ過の後さらに凍結乾燥を行うことを特徴とする（1)〜（5)の 、ずれか 1 項に記載の有機ナノ粒子分散組成物の製造方法。  (6) The method for producing an organic nanoparticle dispersion composition according to any one of (1) to (5), wherein freeze drying is further performed after the ultrafiltration.
(7)前記有機材料が、有機顔料であることを特徴とする（1)〜 (6)の ヽずれか 1項に 記載の有機ナノ粒子分散組成物の製造方法。  (7) The method for producing an organic nanoparticle dispersion composition according to (1), wherein the organic material is an organic pigment.
(8)酸性基を有する高分子化合物を含む有機溶媒中で再分散化することを特徴とす る（1)〜（7)の 、ずれ力 1項に記載の有機ナノ粒子分散組成物の製造方法。  (8) Production of the organic nanoparticle dispersion composition according to (1) to (7) above, wherein redispersion is performed in an organic solvent containing a polymer compound having an acidic group. Method.
(9)一般式 (1)で表される高分子化合物を含有することを特徴とする（1)〜 (8)の 、 ずれ力に記載の有機ナノ粒子分散組成物の製造方法。  (9) The method for producing an organic nanoparticle dispersion composition according to any one of (1) to (8), which comprises a polymer compound represented by the general formula (1).
[化 1]
Figure imgf000006_0001
[Chemical 1]
Figure imgf000006_0001
〔式中、 R1は、（m+n)価の連結基を表し、 R2は単結合あるいは 2価の連結基を表す 。 A1は、酸性基、塩基性窒素原子を有する基、ウレァ基、ウレタン基、配位性酸素原 子を有する基、炭素数 4以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシ ァネート基、および水酸基からなる群より選ばれる基を有する 1価の有機基、または 置換基を有してもよ!ヽ有機色素構造もしくは複素環を含有する 1価の有機基を表す。 ただし、 n個の A1は互いに同一であっても、異なっていてもよい。 mは 1〜8の数を表 し、 nは 2〜9の数を表し、 m+nは 3〜： LOを満たす。 P1は高分子骨格を表す。〕[Wherein, R 1 represents a (m + n) -valent linking group, and R 2 represents a single bond or a divalent linking group. A 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, or an isocyanate group. And a monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group which may have a substituent, or an organic dye structure or a heterocyclic ring. However, n A 1 s may be the same or different. m represents a number from 1 to 8, n represents a number from 2 to 9, and m + n satisfies 3 to: LO. P 1 represents a polymer skeleton. ]
(10)前記一般式 (1)で表される高分子化合物を有機ナノ粒子の形成時、抽出また は濃縮時、濃縮後の凝集有機粒子の分散時、これらの工程が終了したのちのいず れかの工程にお!、て含有させることを特徴とする（9)に記載の有機ナノ粒子分散組 成物の製造方法。 (10) After the completion of these steps, the polymer compound represented by the general formula (1) is formed when organic nanoparticles are formed, extracted or concentrated, and when aggregated organic particles are dispersed after concentration. (9) The method for producing an organic nanoparticle dispersion composition according to (9), which is contained in any of the steps.
(11) (1)〜（10)のいずれか 1項に記載の製造方法で製造された有機ナノ粒子分散 組成物よりカラーフィルタ用インクジェットインクを調製することを特徴とするカラーフィ ルタ用インクジェットインクの製造方法。  (11) An inkjet ink for a color filter, characterized in that an inkjet ink for a color filter is prepared from the organic nanoparticle dispersion composition produced by the production method according to any one of (1) to (10). Production method.
(12) (1)〜（10)の ヽずれか 1項に記載の製造方法で製造された有機ナノ粒子分散 組成物中の有機粒子と、バインダーと、多官能モノマーと、光重合開始剤または光重 合開始剤系とを少なくとも含むことを特徴とする着色感光性榭脂組成物。  (12) Any one of (1) to (10) Organic nanoparticle dispersion produced by the production method according to Item 1, Organic particles in the composition, binder, polyfunctional monomer, photopolymerization initiator or A colored photosensitive resin composition comprising at least a photopolymerization initiator system.
(13)仮支持体上に、少なくとも、（12)に記載の着色感光性榭脂組成物を含む感光 性榭脂層を設けたことを特徴とする感光性転写材料。  (13) A photosensitive transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (12) is provided on a temporary support.
(14) (12)記載の着色感光性榭脂組成物または（13)記載の感光性転写材料を用 V、て作製したことを特徴とするカラーフィルタ。  (14) A color filter produced by using the colored photosensitive resin composition according to (12) or the photosensitive transfer material according to (13).
(15)基板上に遮光性を有する隔壁を形成し、該隔壁により区切られた複数の凹部 を設け、インクジェット方式により R (赤)インク、 G (緑)インク、および B (青)インクのそ れぞれを前記凹部に吹き付けて堆積させ、各凹部に各色の着色榭脂層を形成する カラーフィルタの製造方法であって、前記 Rインク、 Gインク、および Bインクの少なくと も 1種に（11)に記載の製造方法で得られるインクジェットインクを用いることを特徴と するカラーフィルタ。 (15) A light-shielding partition is formed on the substrate, and a plurality of recesses separated by the partition are provided, and R (red) ink, G (green) ink, and B (blue) ink are formed by an inkjet method. A method of manufacturing a color filter in which each of the recesses is sprayed and deposited to form a colored resin layer of each color in each recess, and at least the R ink, the G ink, and the B ink A color filter characterized by using an inkjet ink obtained by the production method described in (11) as one type.
(16) (14)または（15)に記載のカラーフィルタを備えたことを特徴とする液晶表示装 置。  (16) A liquid crystal display device comprising the color filter according to (14) or (15).
(17)前記液晶表示装置が、 VA方式であることを特徴とする（16)に記載の液晶表 示装置。  (17) The liquid crystal display device according to (16), wherein the liquid crystal display device is a VA system.
(18) (14)または（15)に記載のカラーフィルタを備えたことを特徴とする CCDデバイ ス。  (18) A CCD device comprising the color filter according to (14) or (15).
[0009] 本発明の有機ナノ粒子分散組成物の製造方法によれば、有機粒子析出法により 有機粒子を生成させ、その分散液の分散溶媒および不要な塩を除去して、有機粒 子を効率よく所望の濃度に濃縮することができる。また本発明の有機ナノ粒子分散組 成物の製造方法によれば、有機粒子析出法による有機粒子作製時、貧溶媒に対す る良溶媒の量を増やした際や、製造スケールを上げた際にも、粒子サイズの増加、 単分散性の悪ィ匕を実質的に生じることなく濃縮脱塩することができ、また濃縮により 凝集させた有機粒子を容易に再分散することができ、高効率な有機粒子の作製が可 能となる。  [0009] According to the method for producing an organic nanoparticle dispersion composition of the present invention, organic particles are produced by an organic particle precipitation method, and the dispersion solvent and unnecessary salts in the dispersion are removed to make the organic particles efficient. It can be well concentrated to the desired concentration. In addition, according to the method for producing an organic nanoparticle dispersion composition of the present invention, when producing organic particles by the organic particle precipitation method, when increasing the amount of good solvent relative to the poor solvent, or when increasing the production scale. However, it can be concentrated and desalted without substantially increasing the particle size and the monodispersity, and the aggregated organic particles can be easily redispersed with high efficiency. Organic particles can be produced.
本発明の有機粒子分散組成物の製造方法で製造された濃縮有機粒子ペーストお よびそこカゝら得られる有機粒子は、好適なインクジェットインクもしくはその原料微粒 子、またはカラーフィルター塗布液もしくはその原料微粒子として利用可能である。 また、本発明のカラーフィルタ、液晶表示装置、及び CCDデバイスは高い表示'撮 像特性を発揮すると!ヽぅ優れた効果を奏する。  The concentrated organic particle paste produced by the method for producing an organic particle dispersion composition of the present invention and the organic particles obtained therefrom are suitable inkjet inks or raw material fine particles thereof, or color filter coating liquids or fine raw material particles thereof. Is available as In addition, the color filter, the liquid crystal display device, and the CCD device of the present invention exhibit excellent effects when exhibiting high display characteristics.
[0010] 本発明の上記及び他の特徴及び利点は、適宜添付の図面を参照して、下記の記 載力もより明らかになるであろう。 [0010] The above and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings as needed.
図面の簡単な説明  Brief Description of Drawings
[0011] [図 1-1]本発明の有機粒子分散組成物の製造方法に用いられる製造装置の好まし い実施態様を概略的に示す断面図である。  [0011] FIG. 1-1 is a cross-sectional view schematically showing a preferred embodiment of a production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
[図 1-2]図 1 1の製造装置の一実施態様として混合室を一部断面により概略的に示 す拡大部分断面図である。 [図 1-3]図 1 1の製造装置の別の実施態様として混合室を一部断面により概略的に 示す拡大部分断面図である。 FIG. 1-2 is an enlarged partial cross-sectional view schematically showing a mixing chamber in a partial cross section as one embodiment of the manufacturing apparatus of FIG. FIG. 1-3 is an enlarged partial cross-sectional view schematically showing a mixing chamber in a partial cross section as another embodiment of the manufacturing apparatus of FIG.
[図 2]本発明の有機粒子分散組成物の製造方法に用いられる製造装置の別の好ま しい実施態様を概略的に示す断面図である。  FIG. 2 is a cross-sectional view schematically showing another preferred embodiment of a production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
[図 3]本発明の有機粒子分散組成物の製造方法に用いられる製造装置のさらに別の 好ましい実施態様を概略的に示す断面図である。  FIG. 3 is a cross-sectional view schematically showing still another preferred embodiment of a production apparatus used in the method for producing an organic particle dispersion composition of the present invention.
[図 4-1]本発明の有機粒子分散組成物の製造方法に用いられるディゾルバー撹拌 羽根の 1例を概略的に示す正面図である。  FIG. 4-1 is a front view schematically showing an example of a dissolver stirring blade used in the method for producing an organic particle dispersion composition of the present invention.
[図 4-2]図 4 1に示したディゾルバー撹拌羽根の図面代用写真である。  [Fig. 4-2] This is a drawing-substituting photograph of the dissolver stirring blade shown in Fig. 41.
[図 5]本発明の有機粒子分散組成物の製造方法に用いられる回転し得るタービン部 とその周囲にわずかな間隙を置いて位置する固定化されたステータ部から構成され ている撹拌部の 1例を概略的に示す断面図である。 [FIG. 5] A stirrer 1 composed of a rotatable turbine part used in the method for producing an organic particle dispersion composition of the present invention and a fixed stator part with a slight gap around it. It is sectional drawing which shows an example schematically.
[図 6]本発明の有機粒子分散組成物の製造方法に用いられる限外ろ過装置の一構 成例を示す説明図である。  FIG. 6 is an explanatory diagram showing a structural example of an ultrafiltration device used in the method for producing an organic particle dispersion composition of the present invention.
[図 7]本発明の製造方法に用いられる製造装置の好ましい実施態様の一例を概略的 に示す装置説明図である。  FIG. 7 is an apparatus explanatory view schematically showing an example of a preferred embodiment of a production apparatus used in the production method of the present invention.
図中、主要な符号は以下のとおりである。  In the figure, the main symbols are as follows.
11 容器  11 containers
11a 液槽 (溶媒）、 l ib 液面  11a Liquid tank (solvent), l ib liquid level
12 撹拌羽根  12 Stir blade
13 混合室  13 Mixing chamber
14 供給管、 14a 供給管開口部  14 Supply pipe, 14a Supply pipe opening
15 シャフト  15 shaft
16 モーター  16 motor
17 ケーシング (混合室壁）  17 Casing (mixing chamber wall)
18 孔（円形孔）  18 holes (circular holes)
19a, 19b 撹拌羽根  19a, 19b stirring blade
21 容器 (攪拌槽外壁） 21a 攪拌槽 21 container (outer wall of stirring tank) 21a Mixing tank
22 撹拌羽根 22 Stirring blade
23 排出管 23 discharge pipe
24a、 24b 供給管 24a, 24b supply pipe
25 シャフト 25 shaft
50 撹拌装置 50 Stirrer
32, 33 供給口 32, 33 Supply port
36 排出口 36 outlet
38 撹拌槽 38 Mixing tank
39 槽本体39 Tank body
0 シールプレート 0 Seal plate
1, 42 撹拌羽根 1, 42 Stirrer blade
6 外部磁石 6 External magnet
8, 49 モータ  8, 49 motor
(X) 撹拌流 (X) Stir flow
(Y) 撹拌流(Y) Stir flow
1 円盤部 1 Disc part
2 羽根 2 feathers
3 シャフト 3 shaft
4 回転し得るタービン部 4 Turbine that can rotate
5 固定ィ匕されたステータ部 5 Fixed stator part
1 分散物を収納する容器 1 Container for storing dispersion
2 循環用ポンプ 2 Circulation pump
3 限外ろ過モジュール 3 Ultrafiltration module
4 補充純粋計測用流量計 4 Replenishment pure flow meter
5 透過水計測用流量計 5 Flow meter for permeate measurement
6 逆方向洗浄用ポンプ 6 Reverse cleaning pump
01 超臨界流体もしくは亜臨界流体とする溶媒 102 析出用溶媒 01 Solvent for supercritical fluid or subcritical fluid 102 Precipitation solvent
103 顔料等の試料  103 Samples such as pigments
104a, 104b ポンプ  104a, 104b pump
106 ヒーター  106 heater
107 試料管  107 Sample tube
108 ハステロィ配管  108 Hastelloy piping
109a, 109b メッシュ（2 m)  109a, 109b mesh (2 m)
111 ミキサー  111 mixer
112 冷却管  112 Cooling pipe
114 背圧弁  114 Back pressure valve
115 顔料ナノ粒子分散液  115 Pigment nanoparticle dispersion
B 送液の方向  B Direction of liquid delivery
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0013] 本発明は、良溶媒に溶解した有機材料を好ましくは攪拌条件や温度を制御した貧 溶媒に注入することにより、有機粒子を得る有機粒子析出法に関するものであり、有 機粒子析出法により作製した有機粒子を効率よく濃縮する方法、特に不要なイオン を除去して有機粒子分散組成物を製造する方法に関する。また、濃縮工程において 有機粒子の粒径および単分散性が変化せず、また濃縮により有機粒子が凝集したと きにも容易に再分散化できる有機粒子分散組成物の製造方法に関するものである。 以下、本発明について詳細に説明する。 [0013] The present invention relates to an organic particle precipitation method for obtaining organic particles by injecting an organic material dissolved in a good solvent into a poor solvent preferably controlled in stirring conditions and temperature, and the organic particle precipitation method The present invention relates to a method for efficiently concentrating organic particles produced by the above, and particularly to a method for producing an organic particle dispersion composition by removing unnecessary ions. The present invention also relates to a method for producing an organic particle dispersion composition that does not change the particle size and monodispersity of organic particles in the concentration step, and that can be easily redispersed when the organic particles aggregate due to concentration. Hereinafter, the present invention will be described in detail.
[0014] [有機粒子として用いられる材料]  [0014] [Material used as organic particles]
本発明の有機粒子分散組成物の製造方法にぉ 、て、有機粒子とする有機材料は 従来の再沈法で作製することができるものであれば特に制約はない。例えば、有機 顔料、有機色素、フラーレン、ポリジアセチレン、ポリイミドなどの高分子化合物、芳香 族炭化水素もしくは脂肪族炭化水素 (例えば、配向性を有する芳香族炭化水素もし くは脂肪族炭化水素、または昇華性を有する芳香族炭化水素もしくは脂肪族炭化水 素)など力 なる粒子が挙げられ、有機顔料、有機色素、または高分子化合物が好ま しぐ有機顔料が特に好ましい。また、これらを組み合わせたものでもよい。 [0015] 有機顔料は、色相的に限定されるものではない。詳しくは、ペリレン、ペリノン、キナ クリドン、キナクリドンキノン、アントラキノン、アントアントロン、ベンズイミダゾロン、ジス ァゾ縮合、ジスァゾ、ァゾ、インダントロン、フタロシアニン、トリアリーノレカノレボニゥム、 ジォキサジン、アミノアントラキノン、ジケトピロロピロール、チォインジゴ、イソインドリン 、イソインドリノン、ピラントロンもしくはイソビオラントロン系顔料、またはそれらの混合 物などが挙げられる。 In the method for producing the organic particle dispersion composition of the present invention, the organic material used as the organic particles is not particularly limited as long as it can be produced by a conventional reprecipitation method. For example, organic pigments, organic dyes, fullerenes, polydiacetylenes, polymer compounds such as polyimide, aromatic hydrocarbons or aliphatic hydrocarbons (for example, oriented aromatic hydrocarbons or aliphatic hydrocarbons, or sublimation) Powerful organic hydrocarbons such as organic pigments, organic dyes, or polymer compounds are particularly preferable. A combination of these may also be used. [0015] The organic pigment is not limited in terms of hue. For details, perylene, perinone, quinacridone, quinacridone quinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarino decanolone, dioxazine, aminoanthraquinone, Examples thereof include diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone pigment, or a mixture thereof.
[0016] 更に詳しくは、たとえば、 C. I.ビグメントレッド 190 (C. I.番号 71140)、 C. I.ビグ メントレッド 224 (C. I.番号 71127)、 C. I.ピグメントノィォレット 29 (C. I.番号 711 29)等のペリレン系顔料、 C. I.ビグメントオレンジ 43 (C. I.番号 71105)、もしくは C . I.ビグメン卜レッド 194 (C. I.番号 71100)等のペリノン系顔料、 C. I.ピグメン卜ノ ィォレット 19 (C. I.番号 73900)、 C. I.ピグメントノィォレット 42、 C. I.ビグメントレ ッド 122 (C. I.番号 73915)、 C. I.ビグメン卜レッド 192、 C. I.ビグメン卜レッド 202 ( C. I.番号 73907)、 C. I.ビグメン卜レッド 207 (C. I.番号 73900、 73906)、もしく ίま C. I.ビグメントレッド 209 (C. I.番号 73905)のキナクリドン系顔料、 C. I.ピグメ ン卜レッド 206 (C. I.番号 73900,73920)、 C. I.ビグメン卜オレンジ 48 (C. I.番号 73900,73920)、もしくは C. I.ビグメン卜オレンジ 49 (C. I.番号 73900,73920 )等のキナクリドンキノン系顔料、 c. I.ビグメントイエロー 147 (C. I.番号 60645)等 のアントラキノン系顔料、 C. I.ビグメントレッド 168 (C. I.番号 59300)等のアントァ ントロン系顔料、 C. I.ビグメントブラウン 25 (C. I.番号 12510)、 C. I.ビグメントバイ ォレツ卜 32 (C. I.番号 12517)、 C. I.ビグメン卜イェロー 180 (C. I.番号 21290)、 C. I.ビグメン卜イェロー 181 (C. I.番号 11777)、 C. I.ビグメン卜オレンジ 62 (C. I. 番号 11775)、もしくは。. I.ビグメントレッド 185 (C. I.番号 12516)等のベンズイミ ダゾロン系顔料、 C. I.ビグメントイエロー 93 (C. I.番号 20710)、 C. I.ビグメントイ エロー 94 (C. I.番号 20038)、 C. I.ビグメン卜イェロー 95 (C. I.番号 20034)、 C. I.ビグメン卜イェロー 128 (C. I.番号 20037)、 C. I.ビグメン卜イェロー 166 (C. I. 番号 20035)、 C. I.ビグメン卜オレンジ 34 (C. I.番号 21115)、 C. I.ビグメン卜ォレ ンジ 13 (C. I.番号 21110)、 C. I.ビグメン卜オレンジ 31 (C. I.番号 20050)、 C. I .ビグメン卜レッド 144 (C. I.番号 20735)、 C. I.ビグメン卜レッド 166 (C. I.番号 20 730)、 C. I.ビグメン卜レッド 220 (C. I.番号 20055)、 C. I.ビグメン卜レッド 221 (C . I.番号 20065)、 C. I.ビグメン卜レッド 242 (C. I.番号 20067)、 C. I.ピグメン卜レ ッド 248、 C. I.ビグメントレッド 262、もしくは C. I.ビグメントブラウン 23 (C. I.番号 2 0060)等のジスァゾ縮合系顔料、 C. I.ビグメントイエロー 13 (C. I.番号 21100)、 C. I.ビグメントイエロー 83 (C. I.番号 21108)、もしくは C. I.ビグメントイエロー 18 8 (C. I.番号 21094)等のジスァゾ系顔料、 C. I.ビグメントレッド 187 (C. I.番号 12 486)、 C. I.ビグメン卜レッド 170 (C. I.番号 12475)、 C. I.ビグメン卜イェロー 74 ( C. I.番号 11714)、 C. I.ビグメン卜イェロー 150 (C. I.番号 48545)、 C. I.ピグメ ントレッド 48 (C. I.番号 15865)、 C. I.ビグメントレッド 53 (C. I.番号 15585)、 C. I.ビグメン卜オレンジ 64 (C. I.番号 12760)、もしくは。. I.ビグメン卜レッド 247 (C. I .番号 15915)等のァゾ系顔料、 C. I.ビグメン卜ブルー 60 (C. I.番号 69800)等の インダントロン系顔料、 C. I.ビグメントグリーン 7 (C. I.番号 74260)、 C. I.ビグメン トグリーン 36 (C. I.番号 74265)、ビグメントグリーン 37 (C. I.番号 74255)、ピグメ ントブルー 16 (C. I.番号 74100)、 C. I.ビグメントブルー 75 (C. I.番号 74160 : 2 )、もしくは 15 (C. I.番号 74160)等のフタロシアニン系顔料、 C. I.ビグメントブルー 56 (C. I.番号 42800)、もしくは。. I.ビグメン卜ブルー 61 (C. I.番号 42765 : 1)等 のトリアリールカルボ-ゥム系顔料、 C. I.ビグメントバイオレット 23 (C. I.番号 5131 9)、もしくは C. I.ビグメントバイオレット 37 (C. I.番号 51345)等のジォキサジン系 顔料、 C. I.ビグメントレッド 177 (C. I.番号 65300)等のアミノアントラキノン系顔料 、 C. I.ビグメン卜レッド 254 (C. I.番号 56110)、 C. I.ビグメン卜レッド 255 (C. I.番 号 561050)、 C. I.ビグメン卜レッド 264、 C. I.ビグメン卜レッド 272 (C. I.番号 5611 50)、 C. I.ビグメントオレンジ 71、もしくは C. I.ビグメントオレンジ 73等のジケトピロ ロピロール系顔料、 C. I.ビグメントレッド 88 (C. I.番号 73312)等のチォインジゴ系 顔料、 C丄ピグメントイエロー 139 (C. I.番号 56298)、 C. I.ビグメントオレンジ 66 ( C. I.番号 48210)等のイソインドリン系顔料、 C. I.ビグメントイエロー 109 (C. I.番 号 56284)、もしくは。. I.ビグメントオレンジ 61 (C. I.番号 11295)等のイソインドリノ ン系顔料、 C. I.ビグメン卜オレンジ 40 (C. I.番号 59700)、もしくは。. I.ビグメン卜 レッド 216 (C. I.番号 59710)等のピラントロン系顔料、または C. I.ビグメントバイオ レット 31 (60010)等のイソビオラントロン系顔料が挙げられる。 [0016] More specifically, for example, perylene pigments such as CI Pigment Red 190 (CI No. 71140), CI Pigment Red 224 (CI No. 71127), CI Pigment Noorette 29 (CI No. 711 29), CI Pigment Orange 43 (CI No. 71105), or perinone pigments such as CI Pigment® Red 194 (CI No. 71100), CI Pigment® Noorette 19 (CI No. 73900), CI Pigment Nooret 42, CI CI pigment red 122 (CI number 73915), CI pigment red 192, CI pigment red 202 (CI number 73907), CI pigment red 207 (CI number 73900, 73906), or CI CI pigment red 209 ( CI No. 73905) quinacridone pigment, CI Pigment Red 206 (CI No. 73900, 73920), CI Big Men Orange 48 (CI No. 73900, 73920), CI Big Men Orange 49 (CI No. 73900, 73920), etc. Quinacridonequinone series C. I. Pigment Yellow 147 (CI No. 60645) and other anthraquinone pigments, CI Pigment Red 168 (CI No. 59300) and other anthrone pigments, CI Pigment Brown 25 (CI No. 12510), CI Pigment Biolet 32 (CI number 12517), CI Big Yellow 180 (CI number 21290), CI Big Yellow 181 (CI number 11777), CI Big Orange 62 (CI number 11775), or. I. Pigment Red 185 (CI number 12516) and other benzimidazole pigments, CI Pigment Yellow 93 (CI number 20710), CI Pigment Yellow 94 (CI number 20038), CI Pigment Yellow 95 (CI number 20034) CI big yellow 128 (CI number 20037), CI big yellow 166 (CI number 20035), CI big orange 34 (CI number 21115), CI big orange 13 (CI number 21110), CI big blue Orange 31 (CI number 20050), C.I.Bigmen 卜 Red 144 (CI number 20735), CI Bigmen 卜 Red 166 (CI number 20 730), CI Pigment Red 220 (CI No. 20055), CI Big Pigment Red 221 (C.I.No. 20065), CI Big Pigment Red 242 (CI No. 20067), CI Pigment Red 248, CI Pigment Red 262 or CI pigment brown 23 (CI number 2 0060) and other disazo condensation pigments, CI pigment yellow 13 (CI number 21100), CI pigment yellow 83 (CI number 21108), or CI pigment yellow 18 8 (CI number 21094), etc., CI pigment red 187 (CI number 12 486), CI pigment red 170 (CI number 12475), CI big men yellow 74 (CI number 11714), CI big men yellow 150 (CI number 48545), CI Pigment Red 48 (CI number 15865), CI Pigment Red 53 (CI number 15585), CI Pigment ビ Orange 64 (CI number 12760), or. Azo pigments such as I. Big Men 卜 Red 247 (C.I.No. 15915), indantron pigments such as CI Big Men 卜 Blue 60 (CI No. 69800), CI Pigment Green 7 (CI No. 74260), CI Pigment Green 36 (CI number 74265), Pigment Green 37 (CI number 74255), Pigment Blue 16 (CI number 74100), CI Pigment Blue 75 (CI number 74160: 2), or 15 (CI number 74160) Phthalocyanine pigments such as CI pigment blue 56 (CI number 42800), or the like. I. Big Men 卜 Blue 61 (CI No. 42765: 1), etc., triaryl carbo-based pigments, CI Pigment Violet 23 (CI No. 5131 9), or CI Pigment Violet 37 (CI No. 51345) Dioxazine pigments, aminoanthraquinone pigments such as CI Pigment Red 177 (CI No. 65300), CI Big Men Men Red 254 (CI No. 56110), CI Big Men Men Red 255 (CI No. 561050), CI Big Men Men Red 264, CI pigment red 272 (CI number 5611 50), CI pigment orange 71, or diketopyrrolopyrrole pigments such as CI pigment orange 73, thioindigo pigments such as CI pigment red 88 (CI number 73312), C pigment Isoindoline pigments such as yellow 139 (CI number 56298), CI pigment orange 66 (CI number 48210), CI pigment yellow 109 (CI number 56284), or the like. I. Pigment Orange 61 (CI No. 11295) and other isoindolinone pigments, CI Pigment Orange 40 (CI No. 59700), or I. Big Men 卜 Red 216 (CI No. 59710) and other pyranthrone pigments, or CI Pigment Bio And isoviolanthrone-based pigments such as Let 31 (60010).
本発明の有機粒子分散組成物の製造方法にぉ 、て、 2種類以上の有機顔料また は有機顔料の固溶体を組み合わせて用いることもできる。  In the method for producing an organic particle dispersion composition of the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.
[0017] 有機色素としては、例えば、ァゾ色素、シァニン色素、メロシアニン色素、クマリン系 色素などが挙げられる。高分子化合物としては、例えば、ポリジアセチレン、ポリイミド などが挙げられる。 [0017] Examples of organic dyes include azo dyes, cyanine dyes, merocyanine dyes, and coumarin dyes. Examples of the polymer compound include polydiacetylene and polyimide.
[0018] [有機粒子形成時の良溶媒] [0018] [Good solvent for forming organic particles]
次に、有機粒子作製時の好ましい良溶媒について説明する。  Next, the preferable good solvent at the time of organic particle preparation is demonstrated.
良溶媒は用いる有機顔料を溶解することが可能で、有機顔料粒子作製時に用いる 貧溶媒と相溶するもしくは均一に混ざるものであれば特に制限はない。有機顔料の 良溶媒への溶解性は有機材料の溶解度が 0. 2質量％以上であることが好ましぐ 0. 5質量％以上であることがより好ま ヽ。この溶解度は酸性またはアルカリ性で溶解さ れた場合の溶解度であってもよい。また、良溶媒と貧溶媒との相溶性もしくは均一混 合性は、良溶媒の貧溶媒に対する溶解度が 30質量％以上であることが好ましぐ 50 質量％以上であることがより好まし!/、。  The good solvent is not particularly limited as long as it can dissolve the organic pigment to be used and is compatible with or uniformly mixed with the poor solvent used in preparing the organic pigment particles. The solubility of the organic pigment in a good solvent is preferably such that the solubility of the organic material is 0.2% by mass or more, and more preferably 0.5% by mass or more. This solubility may be the solubility when dissolved in an acidic or alkaline manner. In addition, the compatibility or homogeneous mixing of the good solvent with the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more. ,.
良溶媒としては、例えば、水系溶媒 (例えば、水、または塩酸、水酸ィ匕ナトリウム水 溶液)、アルコール系溶媒、アミド系溶媒、ケトン系溶媒、エーテル系溶媒、芳香族系 溶媒、二硫化炭素、脂肪族系溶媒、二トリル系溶媒、スルホキシド系溶媒、ハロゲン 系溶媒、エステル系溶媒、イオン性液体、これらの混合溶媒などが挙げられ、水系溶 媒、アルコール系溶媒、エステル系溶媒、スルホキシド系溶媒またはアミド系溶媒が 好ましぐ水系溶媒、スルホキシド系溶媒またはアミド系溶媒がより好ましぐスルホキ シド系溶媒またはアミド系溶媒が特に好まし 、。  Examples of the good solvent include an aqueous solvent (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvent, amide solvent, ketone solvent, ether solvent, aromatic solvent, carbon disulfide. , Aliphatic solvents, nitrile solvents, sulfoxide solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol solvents, ester solvents, sulfoxide solvents. A water-based solvent in which a solvent or an amide solvent is preferred, a sulfoxide solvent or an amide solvent in which a sulfoxide solvent or an amide solvent is more preferred is particularly preferred.
アルコール系溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコー ル、 n—プロピルアルコール、 1ーメトキシ 2—プロパノールなどが挙げられる。アミド 系溶媒としては、例えば、 N, N ジメチルホルムアミド、 1—メチル—2—ピロリドン、 2 ピロリジノン、 1, 3 ジメチルー 2 イミダゾリジノン、 2 ピロリジノン、 ε 一力プロ ラタタム、ホルムアミド、 Ν—メチルホルムアミド、ァセトアミド、 Ν—メチルァセトアミド、 Ν, Ν ジメチルァセトアミド、 Ν メチルプロパンアミド、へキサメチルホスホリックトリ アミドなどが挙げられる。ケトン系溶媒としては、例えば、アセトン、メチルェチルケトン 、メチルイソブチルケトン、シクロへキサノンが挙げられる。エーテル系溶媒としては、 例えば、ジメチルエーテル、ジェチルエーテル、テトラヒドロフランなどが挙げられる。 芳香族系溶媒としては、例えば、ベンゼン、トルエンなどが挙げられる。脂肪族系溶 媒としては、例えば、へキサンなどが挙げられる。二トリル系溶媒としては、例えば、ァ セトニトリルなどが挙げられる。スルホキシド系溶媒としては、例えば、ジメチルスルホ キシド、ジェチルスルホキド、へキサメチレンスルホキシド、スルホランなどが挙げられ る。ハロゲン系溶媒としては、例えば、ジクロロメタン、トリクロロエチレンなどが挙げら れる。エステル系溶媒としては、例えば、酢酸ェチル、乳酸ェチル、 2- (1—メトキシ )プロピルアセテートなどが挙げられる。イオン性液体としては、例えば、 1—プチルー 3—メチルイミダゾリゥムと PF—との塩などが挙げられる。 Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy 2-propanol and the like. Examples of amide solvents include N, N dimethylformamide, 1-methyl-2-pyrrolidone, 2 pyrrolidinone, 1,3 dimethyl-2-imidazolidinone, 2 pyrrolidinone, ε-prolactam, formamide, Ν-methylformamide, Acetamide, Ν-methylacetamide, Ν, ジ メ チ ル dimethylacetamide, Ν methylpropanamide, hexamethylphosphoric tri Examples include amides. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether solvent include dimethyl ether, jetyl ether, tetrahydrofuran and the like. Examples of the aromatic solvent include benzene and toluene. Examples of the aliphatic solvent include hexane. Examples of the nitrile solvent include acetonitrile. Examples of the sulfoxide solvent include dimethyl sulfoxide, jetyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the halogen solvent include dichloromethane and trichloroethylene. Examples of the ester solvent include ethyl acetate, ethyl lactate, and 2- (1-methoxy) propyl acetate. Examples of the ionic liquid include a salt of 1-petitor 3-methylimidazolium and PF-.
6  6
また、良溶媒に有機材料を溶解した有機材料溶液の濃度としては、溶解時の条件 における有機材料の良溶媒に対する飽和濃度乃至これの lZioo程度の範囲が望 ましい。  In addition, the concentration of the organic material solution in which the organic material is dissolved in the good solvent is preferably in the range of the saturated concentration of the organic material to the good solvent or the lZioo range under the dissolution conditions.
有機材料溶液の調製条件は、有機材料溶液の調製条件に特に制約はなぐ常圧 から亜臨界、超臨界条件の範囲を選択できる。常圧での温度は— 10〜150°Cが好 ましぐ—5〜130°Cがより好ましぐ 0〜100°Cが特に好ましい。  The conditions for preparing the organic material solution can be selected from a range of normal pressure to subcritical and supercritical conditions, with no particular restrictions on the conditions for preparing the organic material solution. The temperature at normal pressure is preferably 10 to 150 ° C, more preferably 5 to 130 ° C, and particularly preferably 0 to 100 ° C.
[0019] 本発明の有機粒子分散組成物の製造方法において、有機材料は良溶媒中に均一 に溶解するが、酸性でもしくはアルカリ性で溶解することも好ましい。一般に分子内に アルカリ性で解離可能な基を有する顔料の場合はアルカリ性が、アルカリ性で解離 する基が存在せず、プロトンが付加しやすい窒素原子を分子内に多く有するときは 酸性が用いられる。例えば、キナクリドン、ジケトピロロピロール、ジスァゾ縮合系顔料 はアルカリ性で、フタロシアニン系顔料は酸性で溶解される。  [0019] In the method for producing an organic particle dispersion composition of the present invention, the organic material is uniformly dissolved in a good solvent, but it is also preferable that the organic material is dissolved in an acidic or alkaline manner. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, it is alkaline, and when there is no alkaline and dissociable group and there are many nitrogen atoms in the molecule where protons can easily be added, acidity is used. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation pigments are alkaline, and phthalocyanine pigments are acidic.
[0020] アルカリ性で溶解させる場合に用いられる塩基は、水酸化リチウム、水酸化ナトリウ ム、水酸ィ匕カリウム、水酸ィ匕カルシウム、もしくは水酸化バリウムなどの無機塩基、また はトリアルキルァミン、ジァザビシクロウンデセン（DBU)、金属アルコキシドなどの有 機塩基である力 好ましくは無機塩基である。  [0020] The base used for the alkaline dissolution is an inorganic base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or a trialkylamine. Power which is an organic base such as diazabicycloundecene (DBU) and metal alkoxide, preferably an inorganic base.
[0021] 使用される塩基の量は、顔料を均一に溶解可能な量であり、特に限定されないが、 無機塩基の場合、好ましくは有機材料に対して 1. 0〜30モル当量であり、より好まし くは 1. 0〜25モル当量であり、さらに好ましくは 1. 0〜20モル当量である。有機塩基 の場合、好ましくは有機材料に対して 1. 0〜： LOOモル当量であり、より好ましくは 5. 0 〜100モル当量であり、さらに好ましくは 20〜100モル当量である。 [0021] The amount of the base used is an amount capable of uniformly dissolving the pigment, and is not particularly limited. In the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents relative to the organic material, more preferably 1.0 to 25 molar equivalents, and even more preferably 1.0 to 20 molar equivalents. In the case of an organic base, it is preferably 1.0 to: LOO molar equivalent, more preferably 5.0 to 100 molar equivalent, and further preferably 20 to 100 molar equivalent with respect to the organic material.
[0022] 酸性で溶解させる場合に用いられる酸は、硫酸、塩酸、もしくは燐酸などの無機酸 、または酢酸、トリフルォロ酢酸、シユウ酸、メタンスルホン酸、もしくはトリフルォロメタ ンスルホン酸等の有機酸であるが好ましくは無機酸である。特に好ましくは硫酸であ る。 [0022] The acid used in the case of acidic dissolution is preferably an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid. Is an inorganic acid. Particularly preferred is sulfuric acid.
使用される酸の量は、有機材料を均一に溶解可能な量であり、特に限定されない 力 塩基に比べて過剰量用いられる場合が多い。無機酸および有機酸の場合を問 わず、好ましくは有機材料に対して 3〜500モル当量であり、より好ましくは 10〜500 モル当量であり、さらに好ましくは 30〜200モル当量である。  The amount of the acid used is an amount that can dissolve the organic material uniformly, and is not particularly limited. Regardless of the inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, still more preferably 30 to 200 molar equivalents relative to the organic material.
[0023] [有機粒子形成時の貧溶媒] [0023] [Poor solvent for forming organic particles]
次に、有機粒子作製時の好ま 、貧溶媒につ!、て説明する。  Next, the preferred and poor solvent at the time of preparing the organic particles will be described.
貧溶媒は用いる有機顔料を溶解せず、有機顔料粒子作製時に用いる良溶媒と相 溶する、あるいは均一に混ざるものであれば特に制約はない。本発明の製造方法に おいては、このように貧溶媒が有機材料溶液に相溶することにより、有機材料溶液中 の有機材料分子に作用し、有機材料が析出生成する。有機材料の貧溶媒に対する 溶解度は 0. 02質量％以下であることが好ましぐ 0. 01質量％以下であることがより 好ま ヽ。貧溶媒と良溶媒との相溶性もしくは均一混合性の好ま ヽ範囲は前述のと おりである。  The poor solvent is not particularly limited as long as it does not dissolve the organic pigment to be used, is compatible with the good solvent used in the preparation of the organic pigment particles, or is mixed uniformly. In the production method of the present invention, when the poor solvent is compatible with the organic material solution in this way, it acts on the organic material molecules in the organic material solution, and the organic material is deposited. The solubility of the organic material in the poor solvent is preferably 0.02% by mass or less, more preferably 0.01% by mass or less. The preferred range of compatibility or uniform mixing of the poor solvent with the good solvent is as described above.
貧溶媒としては、例えば、水系溶媒 (例えば、水、または塩酸、水酸ィ匕ナトリウム水 溶液)、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、芳香族系溶媒、二硫ィ匕 炭素、脂肪族系溶媒、二トリル系溶媒、ハロゲン系溶媒、エステル系溶媒、イオン性 液体、これらの混合溶媒などが挙げられ、水系溶媒、アルコール系溶媒またはエステ ル系溶媒が好ましい。  Examples of the poor solvent include aqueous solvents (for example, water or hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvents, ketone solvents, ether solvents, aromatic solvents, carbon dioxide, fatty acids Group solvents, nitrile solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof and the like, and aqueous solvents, alcohol solvents, and ester solvents are preferred.
アルコール系溶媒としては、例えば、メタノール、エタノール、イソプロピルアルコー ル、 n—プロピルアルコール、 1ーメトキシ 2—プロパノールなどが挙げられる。ケト ン系溶媒としては、例えば、アセトン、メチルェチルケトン、メチルイソブチルケトン、シ クロへキサノンが挙げられる。エーテル系溶媒としては、例えば、ジメチルエーテル、 ジェチルエーテル、テトラヒドロフランなどが挙げられる。芳香族系溶媒としては、例え ば、ベンゼン、トルエンなどが挙げられる。脂肪族系溶媒としては、例えば、へキサン などが挙げられる。二トリル系溶媒としては、例えば、ァセトニトリルなどが挙げられる。 ハロゲン系溶媒としては、例えば、ジクロロメタン、トリクロロエチレンなどが挙げられるExamples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy 2-propanol and the like. Keto Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether solvent include dimethyl ether, jetyl ether, and tetrahydrofuran. Examples of the aromatic solvent include benzene and toluene. Examples of the aliphatic solvent include hexane. Examples of the nitrile solvent include acetonitrile. Examples of the halogen solvent include dichloromethane, trichloroethylene, and the like.
。エステル系溶媒としては、例えば、酢酸ェチル、乳酸ェチル、 2- (1ーメトキシ)プ 口ピルアセテートなどが挙げられる。イオン性液体としては、例えば、 1ーブチルー 3 —メチルイミダゾリゥムと PF —との塩などが挙げられる。 . Examples of the ester solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl pyracetate, and the like. Examples of the ionic liquid include a salt of 1-butyl-3-methylimidazolium and PF.
6  6
[0024] [超臨界流体]  [0024] [Supercritical fluid]
上記（2)の実施態様の製造方法において好ましく用いられる超臨界流体もしくは亜 臨界流体とする溶媒としては、例えば、水、アルコール化合物溶媒、ケトン化合物溶 媒、ヱ一テル化合物溶媒、芳香族化合物溶媒、二硫化炭素、脂肪族化合物溶媒、 二トリル化合物溶媒、スルホキシド化合物溶媒、ハロゲン化合物溶媒、エステル化合 物溶媒、イオン性溶液、またはこれら 2種以上の混合溶媒が挙げられ、水、アルコー ル化合物溶媒、ケトンィ匕合物溶媒、芳香族化合物、二トリル化合物溶媒が好ましぐ 水、ケトンィ匕合物溶媒、芳香族化合物溶媒がより好ましい。  Examples of the solvent used as the supercritical fluid or subcritical fluid preferably used in the production method of the embodiment of the above (2) include, for example, water, alcohol compound solvent, ketone compound solvent, monolithic compound solvent, aromatic compound solvent. , Carbon disulfide, aliphatic compound solvent, nitrile compound solvent, sulfoxide compound solvent, halogen compound solvent, ester compound solvent, ionic solution, or a mixed solvent of two or more of these, water, alcohol compound solvent Ketone compound solvents, aromatic compounds and nitrile compound solvents are preferred. Water, ketone compound compounds solvents and aromatic compound solvents are more preferred.
[0025] 溶媒を超臨界流体もしくは亜臨界流体とする条件 (圧力 Z温度）は、用いる溶媒に より適宜定めればよい (本発明において、「超臨界流体」とは臨界温度以上でかつ臨 界圧力以上の状態の流体をいう。亜臨界流体とは、温度及び圧力の一方のみが臨 界状態に達している力 他方は臨界状態に達していない状態、あるいは、温度及び 圧力の両方が臨界状態に達していないが、温度及び圧力の少なくとも一方が常温常 圧より十分高く臨界状態に近い状態をいう。 ) o例えば、溶媒としてアセトンを用いる 場合、圧力は 2〜30MPaとすることが好ましぐ 3〜25MPaとすることがより好ましぐ 4〜20MPaとすることが特に好ましい。温度は 150〜400°Cとすることが好ましぐ 18 0°C〜350°Cとすることがより好ましぐ 200〜300°Cとすることが特に好ましい。  [0025] The conditions for making the solvent a supercritical fluid or subcritical fluid (pressure Z temperature) may be appropriately determined depending on the solvent to be used (in the present invention, "supercritical fluid" means a critical temperature or higher and a critical temperature). A subcritical fluid is a force in which only one of temperature and pressure reaches a critical state, or the other is not in a critical state, or both temperature and pressure are in a critical state. Although the temperature does not reach, but at least one of temperature and pressure is sufficiently higher than normal temperature and close to the critical state.) O For example, when acetone is used as a solvent, the pressure is preferably 2 to 30 MPa. 3 to 25 MPa is more preferable. 4 to 20 MPa is particularly preferable. The temperature is preferably 150 to 400 ° C, more preferably 180 to 350 ° C, and particularly preferably 200 to 300 ° C.
超臨界流体もしくは亜臨界流体に顔料を溶解する量は、用いられる溶媒や顔料の 種類等にもよるが、例えば、 1kgの超臨界流体または亜臨界流体に 0. lmg以上 10 Og以下の顔料を溶解することが好ましぐ lmg〜50gの顔料を溶解することがより好 ましい。 The amount of pigment dissolved in the supercritical fluid or subcritical fluid depends on the type of solvent and pigment used, but for example, 0.1 kg or more in 1 kg of supercritical fluid or subcritical fluid. It is preferable to dissolve pigments of Og or less. It is more preferable to dissolve 1 mg to 50 g of pigment.
[0026] [析出用溶媒] [0026] [Solvent for precipitation]
上記（2)の実施態様の製造方法にぉ 、ては、貧溶媒として析出用溶媒を用いる。 好ましく用いられる析出用溶媒は、例えば、水、アルコール化合物溶媒、ケトン化合 物溶媒、ヱ一テル化合物溶媒、芳香族化合物溶媒、二硫化炭素、脂肪族化合物溶 媒、二トリル化合物溶媒、スルホキシド化合物溶媒、ハロゲンィ匕合物溶媒、エステル 化合物溶媒、イオン性溶液、またはこれら 2種以上の混合溶媒が挙げられ、水、アル コール化合物溶媒、ケトン化合物溶媒、エステル化合物溶媒、芳香族化合物溶媒、 ハロゲンィ匕合物溶媒、二トリル化合物溶媒が好ましぐ水、アルコール化合物溶媒、 ケトンィ匕合物溶媒がより好まし 、。  In the manufacturing method of the embodiment of the above (2), a precipitation solvent is used as a poor solvent. Preferred precipitation solvents include, for example, water, alcohol compound solvents, ketone compound solvents, monolithic compound solvents, aromatic compound solvents, carbon disulfide, aliphatic compound solvents, nitrile compound solvents, sulfoxide compound solvents. , Halogen compound solvent, ester compound solvent, ionic solution, or a mixed solvent of two or more of these, water, alcohol compound solvent, ketone compound solvent, ester compound solvent, aromatic compound solvent, halogen compound Water, alcohol compound solvents, and ketonic compound solvents are more preferred.
本発明の製造方法においては、析出溶媒に分散剤を含有させることも好ましい。こ のときに用いられる分散剤にっ ヽては、後記「分散剤」の項にお!ヽて詳しく述べる。  In the production method of the present invention, it is also preferable to add a dispersant to the precipitation solvent. The dispersant used at this time will be described in detail in the section “Dispersant” below.
[0027] [高分子化合物] [0027] [Polymer compound]
次に、本発明の製造方法に好ましく用いることができる高分子化合物 (本発明にお V、て「高分子化合物」とは質量平均分子量 1000以上の有機化合物を 、 、、特に上 限はないが、質量平均分子量 500, 000以下であることが実際的であり、好ましくは 1 00, 000以下であり、より好ましくは 50, 000以下である。）について詳細に説明する 本発明の製造方法に好ましく用いることができる高分子化合物は質量平均分子量 1000以上であり、下記一般式（1)で表される高分子化合物であることが好ましい。  Next, a polymer compound that can be preferably used in the production method of the present invention (in the present invention, the term “polymer compound” refers to an organic compound having a mass average molecular weight of 1000 or more, although there is no particular upper limit). The mass average molecular weight is practically 500,000 or less, preferably 100,000 or less, more preferably 50,000 or less.) The production method of the present invention is preferred. The polymer compound that can be used has a mass average molecular weight of 1000 or more, and is preferably a polymer compound represented by the following general formula (1).
[化 2]  [Chemical 2]
(A^R^-R1-^ P1 ) —般式 （1 ) (A ^ R ^ -R 1- ^ P 1 ) — General formula (1)
[0028] 前記一般式（1)中、 A1は、酸性基、塩基性窒素原子を有する基、ウレァ基、ウレタ ン基、配位性酸素原子を有する基、炭素数 4以上の炭化水素基、アルコキシシリル 基、エポキシ基、イソシァネート基、および水酸基から選択される基を有する 1価の有 機基、または置換基を有してもよ!ヽ有機色素構造もしくは複素環を含有する 1価の有 機基を表す。 n個の A1は同一であっても、異なっていてもよい。 In the general formula (1), A 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urea group, a group having a coordinating oxygen atom, or a hydrocarbon group having 4 or more carbon atoms. A monovalent group having a group selected from an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. An organic group, which may have a substituent, represents a monovalent organic group containing an organic dye structure or a heterocyclic ring. n A 1 may be the same or different.
具体的には、 A1は特に制限されるものではないが、前記「酸性基を有する 1価の有 機基」として、例えば、カルボン酸基、スルホン酸基、モノ硫酸エステル基、リン酸基、 モノリン酸エステル基、ホウ酸基などを有する 1価の有機基が挙げられる。また、前記 「塩基性窒素原子を有する基を有する 1価の有機基」として、例えば、アミノ基（一 NH )を有する 1価の有機基、置換イミノ基（一 NHR8、— NR9R1C>)を有する 1価の有機基Specifically, A 1 is not particularly limited, and examples of the “monovalent organic group having an acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, and a phosphoric acid group. And monovalent organic groups having a monophosphate group and a boric acid group. Further, as the “monovalent organic group having a group having a basic nitrogen atom”, for example, a monovalent organic group having an amino group (one NH 3), a substituted imino group (one NHR 8 , —NR 9 R 1C > ) Monovalent organic group having
2 2
(ここで、 R8、 R9、および R1Gは各々独立に、炭素数 1〜20までのアルキル基、炭素数 6以上 20以下のァリール基、炭素数 7以上 30以下のァラルキル基を表す。 )、下記一 般式 (al)で表されるグァニジル基を有する 1価の有機基〔一般式 (al)中、 Ralおよび Ra2は各々独立に、炭素数 1〜20までのアルキル基、炭素数 6以上 20以下のァリー ル基、炭素数 7以上 30以下のァラルキル基を表す。〕、下記一般式 (a2)で表される アミジニル基を有する 1価の有機基〔一般式 (a2)中、 Ra3および Ra4は各々独立に、 炭素数 1〜20までのアルキル基、炭素数 6以上 20以下のァリール基、炭素数 7以上 30以下のァラルキル基を表す。〕などが挙げられる。 (Here, R 8 , R 9 and R 1G each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. ), A monovalent organic group having a guanidyl group represented by the following general formula (al) (in the general formula (al), R al and R a2 are each independently an alkyl group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 30 carbon atoms. A monovalent organic group having an amidinyl group represented by the following general formula (a2) [in the general formula (a2), R a3 and R a4 are each independently an alkyl group having 1 to 20 carbon atoms, carbon It represents an aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 30 carbon atoms. And the like.
[0029] [化 3]
Figure imgf000018_0001
[0029] [Chemical 3]
Figure imgf000018_0001
[0030] 前記「ウレァ基を有する 1価の有機基」として、例えば、— NHCONHR (ここで、 R 15は、水素原子あるいは、炭素数 1〜20までのアルキル基、炭素数 6以上 20以下の ァリール基、炭素数 7以上 30以下のァラルキル基を表す。）などが挙げられる。 The “monovalent organic group having a urea group” is, for example, —NHCONHR (where R 15 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms) An aryl group of 7 to 30 carbon atoms).
前記「ウレタン基を有する 1価の有機基」として、例えば、— NHCOOR16、 -OCO NHR17 (ここで、 R16および R17は各々独立に、炭素数 1〜20までのアルキル基、炭 素数 6以上 20以下のァリール基、炭素数 7以上 30以下のァラルキル基を表す。）な どが挙げられる。 Examples of the “monovalent organic group having a urethane group” include: —NHCOOR 16 , —OCO NHR 17 (wherein R 16 and R 17 are each independently an alkyl group having 1 to 20 carbon atoms, carbon number) Represents an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms.).
前記「'配位性酸素原子を有する基'を有する基」としては、例えば、ァセチルァセト ナト基を有する基、クラウンエーテルを有する基などが挙げられる。 前記「炭素数 4以上の炭化水素基を有する基」としては、炭素数 4以上のアルキル 基 (例えば、ォクチル基、ドデシル基など）、炭素数 6以上のァリール基 (例えば、フエ -ル基、ナフチル基など）、炭素数 7以上のァラルキル基 (例えばべンジル基など)な どが挙げられる。このとき炭素数に上限はないが、 30以下であることが好ましい。 前記「アルコキシシリル基を有する基」としては、例えば、トリメトキシシリル基、トリエ トキシシリル基などを有する基が挙げられる。 Examples of the “group having a group having a coordinating oxygen atom” include a group having an acetylethylacetonate group and a group having a crown ether. Examples of the “group having a hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms (for example, octyl group, dodecyl group, etc.), an aryl group having 6 or more carbon atoms (for example, a phenyl group, Naphthyl group) and aralkyl groups having 7 or more carbon atoms (for example, benzyl group). At this time, there is no upper limit to the number of carbon atoms, but it is preferably 30 or less. Examples of the “group having an alkoxysilyl group” include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.
前記「エポキシ基を有する基」としては、例えば、グリシジル基などを有する基が挙 げられる。  Examples of the “group having an epoxy group” include a group having a glycidyl group and the like.
前記「イソシァネート基を有する基」としては、例えば、 3—イソシアナトプロピル基な どが挙げられる。  Examples of the “group having an isocyanate group” include a 3-isocyanatopropyl group.
前記「水酸基を有する基」としては、例えば、 3—ヒドロキシプロピル基などが挙げら れる。  Examples of the “group having a hydroxyl group” include a 3-hydroxypropyl group.
[0031] 上記の中では、前記 A1として、酸性基、塩基性窒素原子を有する基、ウレァ基、お よび炭素数 4以上の炭化水素基力 選択される基を有する 1価の有機基であることが 好ましい。 In the above, as A 1 , a monovalent organic group having an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms, a group selected. Preferably it is.
[0032] また、前記有機色素構造または複素環としては、特に限定されないが、より具体的 には、有機色素構造としては、例えば、フタロシア-ンィ匕合物、不溶性ァゾ化合物、 ァゾレーキ化合物、アントラキノンィ匕合物、キナクリドンィ匕合物、ジォキサジンィ匕合物、 ジケトピロロピロール化合物、アントラピリジン化合物、アンサンスロン化合物、インダ ンスロン化合物、フラバンスロン化合物、ペリノン化合物、ペリレン化合物、チォインジ ゴ化合物等が挙げられる。また、複素環としては、例えばチォフェン、フラン、キサン テン、ピロール、ピロリン、ピロリジン、ジォキソラン、ピラゾール、ピラゾリン、ビラゾリジ ン、イミダゾール、ォキサゾール、チアゾール、ォキサジァゾール、トリァゾール、チア ジァゾール、ピラン、ピリジン、ピぺリジン、ジォキサン、モルホリン、ピリダジン、ピリミ ジン、ピぺラジン、トリアジン、トリチアン、イソインドリン、イソインドリノン、ベンズイミダ ゾロン、コハクイミド、フタルイミド、ナフタルイミド、ヒダントイン、インドール、キノリン、 カルバゾール、アタリジン、アタリドン、アントラキノン等が挙げられる。  [0032] The organic dye structure or heterocyclic ring is not particularly limited, and more specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinones. Compounds, quinacridone compounds, dioxazine compounds, diketopyrrolopyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, thioindigo compounds, etc. It is done. Examples of the heterocyclic ring include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, vilazolidin, imidazole, oxazole, thiazole, oxazidazole, triazole, thiadiazole, pyran, pyridine, piperidine. , Dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, atalidine, atalidone, anthraquinone, etc. Can be mentioned.
[0033] また、前記有機色素構造または複素環は、置換基を有していてもよぐ該置換基と しては、例えば、メチル基、ェチル基等の炭素数 1〜20までのアルキル基、フエニル 基、ナフチル基等の炭素数 6〜16までのァリール基、水酸基、アミノ基、カルボキシ ル基、スルホンアミド基、 N—スルホ-ルアミド基、ァセトキシ基等の炭素数 1〜6まで のァシルォキシ基、メトキシ基、エトキシ基等の炭素数 1〜6までのアルコキシ基、塩 素、臭素等のハロゲン原子、メトキシカルボ-ル基、エトキシカルボ-ル基、シクロへ キシルォキシカルボ-ル基等の炭素数 2〜7までのアルコキシカルボ-ル基、シァノ 基、 t ブチルカーボネート等の炭酸エステル基、等が挙げられる。 [0033] The organic dye structure or the heterocyclic ring may have a substituent which may have a substituent. For example, alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group, aryl groups having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl groups, amino groups, carboxyl groups, sulfones. 1 to 6 carbon atoms such as amide group, N-sulfolamide group, and acetoxy group, alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, C2-C7 alkoxy carbonyl groups such as methoxy carbo yl group, ethoxy carbo yl group, cyclohex oxy carbo yl group, etc. Carbonate ester group such as cyano group, t-butyl carbonate, etc. Can be mentioned.
[0034] また、前記 A1としては、下記一般式 (4)で表される 1価の有機基であることが好まし い。 [0034] In addition, the A 1 is preferably a monovalent organic group represented by the following general formula (4).
[0035] [化 4]
Figure imgf000020_0001
[0035] [Chemical 4]
Figure imgf000020_0001
[0036] 前記一般式 (4)において、 B1は、酸性基、塩基性窒素原子を有する基、ウレァ基、 ウレタン基、配位性酸素原子を有する基、炭素数 4以上の炭化水素基、アルコキシシ リル基、エポキシ基、イソシァネート基、および水酸基から選択される基、または置換 基を有してもよい有機色素構造または複素環を表し、 R18は単結合あるいは al価の 有機もしくは無機の連結基を表す。 alは、 1〜5を表し、 al個の B1は同一であっても 、異なっていてもよい。 In the general formula (4), B 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, A group selected from an alkoxy silyl group, an epoxy group, an isocyanate group, and a hydroxyl group, or an organic dye structure or a heterocyclic ring which may have a substituent. R 18 represents a single bond or an alvalent organic or inorganic group. Represents a linking group. al represents 1 to 5, and al B 1 may be the same or different.
[0037] B1は、一般式 (4)における前記 A1と同義であり、好ましい態様も同様である力 前 記有機色素構造または複素環としては、例えばフタロシア-ンィ匕合物、不溶性ァゾ 化合物、ァゾレーキ化合物、アントラキノンィ匕合物、キナクリドンィ匕合物、ジォキサジン 化合物、ジケトピロロピロール化合物、アントラピリジン化合物、アンサンスロン化合物 、インダンスロン化合物、フラバンスロン化合物、ペリノン化合物、ペリレン化合物、チ ォインジゴィ匕合物等の有機色素構造、例えばチォフェン、フラン、キサンテン、ピロ一 ル、ピロリン、ピロリジン、ジォキソラン、ピラゾール、ピラゾリン、ビラゾリジン、イミダゾ ール、ォキサゾール、チアゾール、ォキサジァゾール、トリァゾール、チアジアゾール 、ピラン、ピリジン、ピぺリジン、ジ才キサン、モノレホリン、ピリダジン、ピリミジン、ピペラ ジン、トリアジン、トリチアン、イソインドリン、イソインドリノン、ベンズイミダゾロン、コハ クイミド、フタルイミド、ナフタルイミド、ヒダントイン、インドール、キノリン、力ルバゾール 、アタリジン、アタリドン、アントラキノン等の複素環が挙げられる。 [0037] B 1 has the same meaning as A 1 in formula (4), and the preferred embodiment is also similar. Examples of the organic dye structure or heterocyclic ring include phthalocyanine compounds and insoluble azo compounds. Compound, azo lake compound, anthraquinone compound, quinacridone compound, dioxazine compound, diketopyrrolopyrrole compound, anthrapyridine compound, ansanthrone compound, indanthrone compound, flavanthrone compound, perinone compound, perylene compound, chi Organic dye structures such as thioindigo compounds such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, virazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine The Peridine, di-xane, monoreforin, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, koha Heterocycles such as quinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, force rubazole, atalidine, attaridone, anthraquinone and the like can be mentioned.
[0038] また、前記有機色素構造または複素環は、置換基を有していてもよぐ該置換基と しては、例えば、メチル基、ェチル基等の炭素数 1〜20までのアルキル基、フエニル 基、ナフチル基等の炭素数 6〜16までのァリール基、水酸基、アミノ基、カルボキシ ル基、スルホンアミド基、 N—スルホ-ルアミド基、ァセトキシ基等の炭素数 1〜6まで のァシルォキシ基、メトキシ基、エトキシ基等の炭素数 1〜6までのアルコキシ基、塩 素、臭素等のハロゲン原子、メトキシカルボ-ル基、エトキシカルボ-ル基、シクロへ キシルォキシカルボ-ル基等の炭素数 2〜7までのアルコキシカルボ-ル基、シァノ 基、 t ブチルカーボネート等の炭酸エステル基、等が挙げられる。  [0038] The organic dye structure or heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group. , Phenyl groups, naphthyl groups and the like having 6 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfolamide groups, and acetoxy groups. Group, alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, halogen atom such as chlorine, bromine, methoxy carbo yl group, ethoxy carbo yl group, cyclohex oxy carbo yl group, etc. And a carbonic acid ester group having 2 to 7 carbon atoms, a cyano group, t-butyl carbonate, and the like.
[0039] R18は、単結合あるいは al + 1価の連結基を表し、 alは 1〜5を表す。連結基 R18と しては、 1〜100個までの炭素原子、 0個〜 10個までの窒素原子、 0個〜 50個まで の酸素原子、 1個〜 200個までの水素原子、および 0個〜 20個までの硫黄原子から 成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。 R18は、有機連結 基であることが好ましい。 [0039] R 18 represents a single bond or an al + monovalent linking group, and al represents 1 to 5. The linking group R 18 includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0. Groups comprising from 20 to 20 sulfur atoms are included, which may be unsubstituted or further substituted. R 18 is preferably an organic linking group.
[0040] R18の具体的な例として、下記の構造単位又は該構造単位を組み合わせて構成さ れる基を挙げることがでさる。 [0040] Specific examples of R 18 include the following structural units or groups formed by combining the structural units.
[0041] [化 5] [0041] [Chemical 5]
-
Figure imgf000022_0001
-
Figure imgf000022_0001
(t-1) (t-2) (t-3) (t-4) (t-5) (t-6) (t-7) (t-8) (t-9) (t-10) (t-11) (t-12)
Figure imgf000022_0002
(t-1) (t-2) (t-3) (t-4) (t-5) (t-6) (t-7) (t-8) (t-9) (t-10) (t-11) (t-12)
Figure imgf000022_0002
(t-13) (t-14) (t-15) (t-16) (t-17) (t-18) (t-19)
Figure imgf000022_0003
(t-13) (t-14) (t-15) (t-16) (t-17) (t-18) (t-19)
Figure imgf000022_0003
(t-20) (t-21 ) (t-22) (t-23) (t-24) (t-25) (t-26)
Figure imgf000022_0004
(t-20) (t-21) (t-22) (t-23) (t-24) (t-25) (t-26)
Figure imgf000022_0004
(t-27) (t-28) (t-29) (t-30) (t-31) (t-32) (t-33) (t-34)  (t-27) (t-28) (t-29) (t-30) (t-31) (t-32) (t-33) (t-34)
[0042] R1Bが置換基を有する場合、該置換基としては、例えば、メチル基、ェチル基等の 炭素数 1〜20までのアルキル基、フエ-ル基、ナフチル基等の炭素数 6〜16までの ァリール基、水酸基、アミノ基、カルボキシル基、スルホンアミド基、 N—スルホ -ルァ ミド基、ァセトキシ基等の炭素数 1〜6までのァシルォキシ基、メトキシ基、エトキシ基 等の炭素数 1〜6までのアルコキシ基、塩素、臭素等のハロゲン原子、メトキシカルボ ニル基、エトキシカルボ-ル基、シクロへキシルォキシカルボ-ル基等の炭素数 2〜 7までのアルコキシカルボ-ル基、シァノ基、 t—ブチルカーボネート等の炭酸エステ ル基、等が挙げられる。 [0042] When R 1B has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group and a naphthyl group having 6 to 6 carbon atoms. Up to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfo-lumamide groups, acetoxy groups, etc. 1 to 6 carbon atoms such as acyloxy groups, methoxy groups, ethoxy groups, etc. Alkoxy groups of up to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbon groups of up to 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexylcarbonyl groups, etc. Examples include cyano groups and ester carbonate groups such as t-butyl carbonate.
[0043] 前記一般式（1)中、 R1は、（m+n)価の連結基を表す。 m+nは 3〜： L0を満たす。 In the general formula (1), R 1 represents an (m + n) -valent linking group. m + n satisfies 3 ~: L0.
前記 R1で表される（m+n)価の連結基としては、 1〜： L00個までの炭素原子、 0個 〜 10個までの窒素原子、 0個〜 50個までの酸素原子、 1個〜 200個までの水素原 子、および 0個〜 20個までの硫黄原子力 成り立つ基が含まれ、無置換でも置換基 を更に有して 、てもよ 、。 R1は有機連結基であることが好ま U、。 Examples of the (m + n) -valent linking group represented by R 1 include: 1 to: L00 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 From 1 to 200 hydrogen atoms, and from 0 to 20 sulfur atomic groups are included, which may be unsubstituted or further substituted. R 1 is preferably an organic linking group.
[0044] R1の具体的な例としては、前記 (t— 1)〜 (t— 34)の構造単位又は該構造単位を 組み合わせて構成される基 (環構造を形成して ヽてもよ ヽ。 )を挙げることができる。 [0045] R1が置換基を有する場合、該置換基としては、例えば、メチル基、ェチル基等の炭 素数 1〜20までのアルキル基、フエ-ル基、ナフチル基等の炭素数 6〜16までのァ リール基、水酸基、アミノ基、カルボキシル基、スルホンアミド基、 N—スルホ-ルアミ ド基、ァセトキシ基等の炭素数 1〜6までのァシルォキシ基、メトキシ基、エトキシ基等 の炭素数 1〜6までのアルコキシ基、塩素、臭素等のハロゲン原子、メトキシカルボ- ル基、エトキシカルボ-ル基、シクロへキシルォキシカルボ-ル基等の炭素数 2〜7ま でのアルコキシカルボ-ル基、シァノ基、 t—ブチルカーボネート等の炭酸エステル 基、等が挙げられる。 [0044] Specific examples of R 1 include the structural units (t-1) to (t-34) or a group composed of a combination of the structural units (which may form a ring structure).ヽ.) [0045] When R 1 has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group and a naphthyl group having 6 to 6 carbon atoms. Carbon number up to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfol amide group, acetooxy group, etc. Carbon group up to 1-6, methoxy group, ethoxy group, etc. 1 to 6 alkoxy groups, such as halogen atoms such as chlorine and bromine, methoxy carbo yl groups, ethoxy carbo yl groups, cyclohexyl carboxy groups, etc. And carbonic acid ester groups such as t-butyl carbonate.
[0046] R2は、単結合あるいは 2価の連結基を表す。 R2としては、 1〜： LOO個までの炭素原 子、 0個〜 10個までの窒素原子、 0個〜 50個までの酸素原子、 1個〜 200個までの 水素原子、および 0個〜 20個までの硫黄原子力 成り立つ基が含まれ、無置換でも 置換基を更に有して 、てもよ 、。 R2は有機連結基であることが好ま U、。 [0046] R 2 represents a single bond or a divalent linking group. R 2 includes: 1 to: LOO carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to Up to 20 sulfur nuclear power groups are included, which may be unsubstituted or further substituted. R 2 is preferably an organic linking group.
[0047] R2の具体的な例として、前記 t— 3、 4、 7〜18、 22〜26、 32、 34の構造単位又は 該構造単位を組み合わせて構成される基を挙げることができる。 [0047] Specific examples of R 2 include the structural units of the above t-3, 4, 7-18, 22-26, 32, 34, or groups configured by combining the structural units.
[0048] R2が置換基を有する場合、該置換基としては、例えば、メチル基、ェチル基等の炭 素数 1〜20までのアルキル基、フエ-ル基、ナフチル基等の炭素数 6〜16までのァ リール基、水酸基、アミノ基、カルボキシル基、スルホンアミド基、 N—スルホ-ルアミ ド基、ァセトキシ基等の炭素数 1〜6までのァシルォキシ基、メトキシ基、エトキシ基等 の炭素数 1〜6までのアルコキシ基、塩素、臭素等のハロゲン原子、メトキシカルボ- ル基、エトキシカルボ-ル基、シクロへキシルォキシカルボ-ル基等の炭素数 2〜7ま でのアルコキシカルボ-ル基、シァノ基、 t—ブチルカーボネート等の炭酸エステル 基、等が挙げられる。 [0048] When R 2 has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group and a naphthyl group having 6 to 6 carbon atoms. Carbon number up to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfol amide group, acetooxy group, etc. Carbon group up to 1-6, methoxy group, ethoxy group, etc. 1 to 6 alkoxy groups, such as halogen atoms such as chlorine and bromine, methoxy carbo yl groups, ethoxy carbo yl groups, cyclohexyl carboxy groups, etc. And carbonic acid ester groups such as t-butyl carbonate.
[0049] 前記一般式（1)中、 mは 1〜8を表す。 mとしては、 1〜5が好ましぐ 1〜3がより好 ましぐ 1〜2が特に好ましい。  [0049] In the general formula (1), m represents 1 to 8. As m, 1-5 is preferable, 1-3 is more preferable, and 1-2 is particularly preferable.
また、 nは 2〜9を表す。 nとしては、 2〜8力 S好ましく、 2〜7がより好ましぐ 3〜6が特 に好ましい。  N represents 2-9. n is preferably 2 to 8 forces S, more preferably 3 to 6 with 2 to 7 being more preferable.
[0050] 前記一般式（1)中、 P1は高分子骨格を表し、通常のポリマーなどから目的等に応じ て選択することができる。 ポリマーの中でも、高分子骨格を構成するには、ビュルモノマーの重合体もしくは 共重合体、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、アミド系ポ リマー、エポキシ系ポリマー、シリコーン系ポリマー、及びこれらの変性物、又は共重 合体〔例えば、ポリエーテル Zポリウレタン共重合体、ポリエーテル zビュルモノマー の重合体の共重合体など（ランダム共重合体、ブロック共重合体、グラフト共重合体 のいずれであってもよい。）を含む。〕からなる群より選択される少なくとも一種が好ま しぐビュルモノマーの重合体もしくは共重合体、エステル系ポリマー、エーテル系ポ リマー、ウレタン系ポリマー、およびこれらの変性物又は共重合体力 なる群より選択 される少なくとも一種がより好ましぐビニルモノマーの重合体もしくは共重合体が特 に好ましい。 [0050] In the general formula (1), P 1 represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like. Among the polymers, the polymer skeleton is composed of a polymer or copolymer of a bull monomer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and these. A modified product or copolymer (for example, a copolymer of a polyether Z polyurethane copolymer, a polymer of a polyether z butyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be present). Selected from the group consisting of a polymer or copolymer of a bulle monomer, an ester polymer, an ether polymer, a urethane polymer, and a modified product or a copolymer thereof. Particularly preferred are polymers or copolymers of vinyl monomers, at least one of which is more preferred.
更には、前記ポリマーは有機溶媒に可溶であることが好ましい。有機溶媒との親和 性が低いと、例えば、顔料分散剤として使用した場合、分散媒との親和性が弱まり、 分散安定ィ匕に十分な吸着層を確保できなくなることがある。  Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for dispersion stability.
[0051] 前記一般式（1)で表される高分子化合物の中でも、下記一般式 (2)で表される高 分子化合物がより好ましい。  [0051] Among the polymer compounds represented by the general formula (1), a high molecular compound represented by the following general formula (2) is more preferable.
[0052] [化 6]
Figure imgf000024_0001
[0052] [Chemical 6]
Figure imgf000024_0001
[0053] 前記一般式（2)において、 ΑΊま前記一般式（1)における A1と同義であり、その具 体的な好ましい態様も同様であるが、有機色素構造の具体的な例として、フタロシア ニンィ匕合物、ァゾレーキ化合物、アントラキノンィ匕合物、ジォキサジンィ匕合物、ジケト ピロ口ピロ一ルイ匕合物等がより好ましぐ複素環としては、イミダゾール、トリァゾール、 ピリジン、ピぺリジン、モノレホリン、トリアジン、イソインドリン、イソインドリノン、ベンズィ ミダゾロン、ベンゾチアゾール、コハクイミド、フタルイミド、ナフタルイミド、ヒダントイン 、インドール、キノリン、カルバゾール、アタリジン、アタリドン、アントラキノン等がより好 ましい。 [0053] In the general formula (2) has the same meaning as A 1 in ΑΊ or the general formula (1) is the same also its concrete preferred embodiment, specific examples of the organic dye structure, Heterocycles that are more preferred are phthalocyanine compounds, azo lake compounds, anthraquinone compounds, dioxazine compounds, diketopyrrolopyrrol compounds, imidazole, triazole, pyridine, piperidine, Monoreforin, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, atalidine, attaridone and anthraquinone are more preferred.
[0054] また、 A1と同様に置換基を有していてもよぐ該置換基については、 A1における場 合と同様であり、好ましい態様も同様である。 更に、 A2として、前記一般式 (4)で表される 1価の有機基が好ましぐ該有機基の詳 細および具体的な例、好ま 、態様にっ 、ては同様である。 [0054] The substituent which may have a substituent as in A 1 is the same as that in A 1 , and the preferred embodiment is also the same. Further, as A 2 , the monovalent organic group represented by the general formula (4) is preferred, and details and specific examples, preferred and embodiments of the organic group are the same.
[0055] 前記一般式（2)にお 、て、 R3は、 (x+y)価の連結基を表す。前記 R3で表される (x In the general formula (2), R 3 represents a (x + y) -valent linking group. Represented by R 3 (x
+y)価の連結基としては、 1〜60個までの炭素原子、 0個〜 10個までの窒素原子、 0個〜 50個までの酸素原子、 1個〜 100個までの水素原子、及び 0個〜 20個までの 硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有して 、てもよ 、。  + y) valent linking groups include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and Groups comprising 0 to 20 sulfur atoms are included and may be unsubstituted or further substituted.
[0056] 前記 R3で表される（x+y)価の連結基としては、前記 R1における（m+n)価の連結 基と同義であり、その好ましい態様も同様である。また、具体的な例として、前記同様 の構造単位又は該構造単位を組み合わせて構成される基が挙げられる。 [0056] The linking group of the represented by R 3 (x + y) value has the same meaning as the linking group of (m + n) valent in the R 1, it is the same a preferred embodiment thereof. Further, specific examples include the same structural unit as described above or a group constituted by combining the structural units.
[0057] これらのうち、 R3で表される連結基は有機連結基であることが好ましぐその有機連 結基の好ましい具体的な例を以下に示す。但し、本発明においては、これらに制限さ れるものではない。 Of these, the linking group represented by R 3 is preferably an organic linking group. Preferred specific examples of the organic linking group are shown below. However, the present invention is not limited to these.
[0058] [化 7] [0058] [Chemical 7]
〔置〕0059 [Position] 0059
Figure imgf000026_0001
Figure imgf000026_0001
H2— H2 - CH2— H 2 — H 2 -CH 2 —
Figure imgf000027_0001
Figure imgf000027_0001
上記の中でも、原料の入手性、合成の容易さ、各種溶媒への溶解性の観点から、 上記 (r一 1)、 (r一 2)、 (r-10), (r一 11)、 (r一 16)、 (r一 17)の基が好ましい。 [0061] また、上記の R3が置換基を有する場合、該置換基としては、例えば、メチル基、ェ チル基等の炭素数 1〜20までのアルキル基、フエニル基、ナフチル基等の炭素数 6 〜16までのァリール基、水酸基、アミノ基、カルボキシル基、スルホンアミド基、 N—ス ルホ-ルアミド基、ァセトキシ基等の炭素数 1〜6までのァシルォキシ基、メトキシ基、 エトキシ基等の炭素数 1〜6までのアルコキシ基、塩素、臭素等のハロゲン原子、メト キシカルボ-ル基、エトキシカルボ-ル基、シクロへキシルォキシカルボ-ル基等の 炭素数 2〜7までのアルコキシカルボ-ル基、シァノ基、 t—ブチルカーボネート等の 炭酸エステル基、等が挙げられる。 Among the above, from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents, the above (r 1), (r 1 2), (r-10), (r 1 11), ( R 1 16) and (r 1 17) are preferred. [0061] When R 3 has a substituent, examples of the substituent include carbon such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Number 6 to 16 aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfolamide groups, acetoxy groups, etc. such as acyl groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups, etc. C1-C6 alkoxy groups, halogen atoms such as chlorine and bromine, methoxycarbol groups, ethoxycarbon groups, cyclohexylcarboxy groups, etc. -Carbonate group such as -l group, cyano group and t-butyl carbonate.
[0062] 前記一般式（2)において、 R4および R5は、各々独立に、単結合あるいは 2価の連 結基を表す。 In the general formula (2), R 4 and R 5 each independently represents a single bond or a divalent linking group.
前記 、 R5で表される「2価の連結基」としては、無置換でも置換基を有していても よぐ直鎖、分岐、もしくは環状のアルキレン基、ァリーレン基、ァラルキレン基、 O S C ( = 0) N (R19) SO SO CO N (R20) As the above-mentioned “divalent linking group” represented by R 5 , a linear, branched, or cyclic alkylene group that may be unsubstituted or substituted, an arylene group, an aralkylene group, OSC ( = 0) N (R 19 ) SO SO CO N (R 20 )
2 2  twenty two
SO 又はこれらの基を 2つ以上組み合わせた 2価の基を好ましい例として挙げる Preferred examples include SO or a divalent group in which two or more of these groups are combined.
2 2
ことができる（前記 R19および R2Gは、各々独立に、水素原子又は炭素数 1〜4個のァ ルキル基を表す。 ) 0なかでも有機連結基であることが好ましい。 It can (the R 19 and R 2G is, independently,. Represents a hydrogen atom or a number 1-4 § alkyl group carbon atoms) is preferably 0 Among these organic linking group.
[0063] 前記 R4としては、直鎖もしくは分岐のアルキレン基、ァラルキレン基、 O C ( [0063] As R 4 , a linear or branched alkylene group, an aralkylene group, OC (
= 0)—、— N (R19)—、—SO —CO — N (R2。）SO—、又はこれらの基を 2 = 0) —, —N (R 19 ) —, —SO —CO — N (R 2. ) SO—, or these groups to 2
2 2 2  2 2 2
つ以上組み合わせた 2価の基がより好ましぐ直鎖もしくは分岐のアルキレン基、ァラ ルキレン基、 O—、— C ( = 0)—、— N (R19)—、—CO—、又はこれらの基を 2つ A linear or branched alkylene group, aralkylene group, O—, — C (= 0) —, — N (R 19 ) —, —CO—, or a combination of two or more divalent groups is more preferred Two of these groups
2  2
以上組み合わせた 2価の基が特に好まし 、。  The divalent group combined above is particularly preferred.
[0064] 前記 R5としては、単結合、直鎖もしくは分岐のアルキレン基、ァラルキレン基、—O[0064] Examples of R 5, a single bond, a linear or branched alkylene group, Ararukiren group, -O
C ( = 0) N (R19) SO CO N (R20) SO—、又はこれ C (= 0) N (R 19 ) SO CO N (R 20 ) SO— or this
2 2 2  2 2 2
らの基を 2つ以上組み合わせた 2価の基がより好ましく、直鎖もしくは分岐のアルキレ ン基、ァラルキレン基、 O C ( = 0) N (R19)― CO―、又はこれら A divalent group in which two or more of these groups are combined is more preferable, and a linear or branched alkylene group, an aralkylene group, OC (= 0) N (R 19 ) -CO-, or these
2  2
の基を 2つ以上組み合わせた 2価の基が特に好ましい。  A divalent group in which two or more of these groups are combined is particularly preferred.
[0065] また、前記 、 R5が置換基を有する場合、該置換基としては、例えば、メチル基、ェ チル基等の炭素数 1〜20までのアルキル基、フエニル基、ナフチル基等の炭素数 6 〜16までのァリール基、水酸基、アミノ基、カルボキシル基、スルホンアミド基、 N—ス ルホ-ルアミド基、ァセトキシ基等の炭素数 1〜6までのァシルォキシ基、メトキシ基、 エトキシ基等の炭素数 1〜6までのアルコキシ基、塩素、臭素等のハロゲン原子、メト キシカルボ-ル基、エトキシカルボ-ル基、シクロへキシルォキシカルボ-ル基等の 炭素数 2〜7までのアルコキシカルボ-ル基、シァノ基、 t—ブチルカーボネート等の 炭酸エステル基、等が挙げられる。 [0065] Further, when R 5 has a substituent, examples of the substituent include carbon such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Number 6 Up to 16 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfolamide group, acetoxy group, etc. carbon number up to 1-6, such as acyloxy group, methoxy group, ethoxy group, etc. 1 to 6 alkoxy groups, such as halogen atoms such as chlorine and bromine, methoxy carbo yl groups, ethoxy carbo yl groups, cyclohexyl carboxy groups, etc. Groups, cyano groups, carbonate groups such as t-butyl carbonate, and the like.
[0066] 前記一般式（2)中、 yは 1〜8を表し、 1〜5が好ましぐ 1〜3がより好ましぐ 1〜2が 特に好ましい。また、 Xは 2〜9を表し、 2〜8が好ましぐ 2〜7がより好ましぐ 3〜6が 特に好ましい。 In the general formula (2), y represents 1 to 8, 1 to 5 is preferable, and 1 to 3 is more preferable, and 1 to 2 is particularly preferable. X represents 2-9, 2-8 are preferred, 2-7 are more preferred, and 3-6 are particularly preferred.
[0067] また、一般式 (2)中の P2は、高分子骨格を表し、通常のポリマーなどから目的等に 応じて選択することができる。ポリマーの好ましい態様については、前記一般式（1) における P1と同義であり、その好ましい態様も同様である。 In addition, P 2 in the general formula (2) represents a polymer skeleton and can be selected from ordinary polymers according to the purpose and the like. The preferred embodiment of the polymer is the same as P 1 in the general formula (1), and the preferred embodiment is also the same.
[0068] 前記一般式 (2)で表される高分子化合物のうち、特に、 R3が前記具体例 (r— 1)、 ( r 2)、 (r 10)、 (r 11)、 (r— 16)、又は（r— 17)であって、 R4力 単結合、直鎖 もしくは分岐のアルキレン基、ァラルキレン基、一 O 、 一 C ( = 0)—、 一 N (R19)—、 — CO—、またはこれらの基を 2つ以上組み合わせた 2価の有機基であって、 R5が単[0068] Among the polymer compounds represented by the general formula (2), in particular, R 3 represents the specific examples (r-1), (r 2), (r 10), (r 11), (r — 16), or (r—17), wherein R 4 force single bond, linear or branched alkylene group, aralkylene group, one O, one C (= 0) —, one N (R 19 ) —, — CO— or a divalent organic group in which two or more of these groups are combined, and R 5 is
2 2
結合、エチレン基、プロピレン基、又は下記一般式 (s a)もしくは（s b)で表される 連結基であって、 P2がビニルモノマーの重合体もしくは共重合体、エステル系ポリマ 一、エーテル系ポリマー、ウレタン系ポリマー、又はこれらの変性物であって、 yが 1〜 2であって、 Xが 3〜6である高分子化合物が特に好ましい。なお、下記基中、 R21は 水素原子又はメチル基を表し、 1は 1又は 2を表す。 A bond, an ethylene group, a propylene group, or a linking group represented by the following general formula (s a ) or (sb), wherein P 2 is a polymer or copolymer of a vinyl monomer, an ester polymer, an ether type Polymers, urethane polymers, or modified products thereof, where y is 1 to 2 and X is 3 to 6 are particularly preferable. In the following groups, R 21 represents a hydrogen atom or a methyl group, and 1 represents 1 or 2.
[0069] [化 9] (s-a) [0069] [Chemical 9] (sa)
Figure imgf000030_0001
Figure imgf000030_0001
(s-b) (s-b)
Figure imgf000030_0002
Figure imgf000030_0002
[0070] 高分子化合物の質量平均分子量は lOOO以上であるが、質量平均分子量で 1000 〜500, 000力 S好まし <、 3000〜100000カょり好まし<、 5000〜80000力 Sさらに好 ましぐ 7000〜60000が特に好ましい。質量平均分子量が前記範囲内であると、ポ リマーの末端に導入された複数の官能基の効果が十分に発揮され、固体表面への 吸着性、ミセル形成能、界面活性性に優れた性能を発揮する。特にそのような高分 子化合物を顔料分散剤として用いた場合に、良好な分散性と分散安定性を達成す ることがでさる。 [0070] The polymer compound has a mass average molecular weight of lOOO or more, but the mass average molecular weight is 1000 to 500,000 force S preferred <, 3000 to 100000 preferred <, 5000 to 80000 force S more preferred. 7000 to 60000 is particularly preferable. When the mass average molecular weight is within the above range, the effects of the plurality of functional groups introduced at the ends of the polymer are sufficiently exerted, and the performance of adsorbing on the solid surface, micelle forming ability, and surface activity is excellent. Demonstrate. In particular, when such a polymer compound is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.
[0071] 前記一般式（1)で表される高分子化合物 (一般式 (2)で表されるものを含む）は、 特に制限されないが、下記方法などにより合成することができる。下記合成方法のう ち、合成上の容易さから、下記 2、 3、 4、 5等の合成方法がより好ましぐ下記 3、 4、 5 等の合成方法が特に好まし 、。  [0071] The polymer compound represented by the general formula (1) (including the polymer compound represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 3, 4, 5, etc. are particularly preferred because of the ease of synthesis, and the following synthesis methods such as 2, 3, 4, 5 are more preferred.
1.カルボキシル基、ヒドロキシル基、アミノ基等から選択される官能基を末端に導 入したポリマーと、複数の官能基 (前記一般式中の A1又は A2)を有する酸ノ、ライド、 あるいは複数の官能基 (前記一般式中の A1又は A2)を有するアルキルハライド、ある いは複数の官能基 (前記一般式中の A1又は A2)を有するイソシァネート等とを高分 子反応させる方法。 1. a polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group or the like is introduced at the end, and an acid group, a ride, or a plurality of functional groups (A 1 or A 2 in the above general formula), or alkyl halide having a plurality of functional groups (a 1 or a 2 in the formula), there have high-molecular reaction and Isoshianeto or the like having a plurality of functional groups (a 1 or a 2 in the general formula) How to make.
2.末端に炭素 炭素二重結合を導入したポリマーと、複数の官能基 (前記一般式 中の A1又は A2)を有するメルカプタンとをマイケル付加反応させる方法。 3.末端に炭素 炭素二重結合を導入したポリマーと、複数の官能基 (前記一般式 中の A1又は A2)を有するメルカブタンとをラジカル発生剤存在下で反応させる方法。2. A method in which a polymer having a carbon-carbon double bond introduced at a terminal and a mercaptan having a plurality of functional groups (A 1 or A 2 in the above general formula) are subjected to a Michael addition reaction. 3. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercabtan having a plurality of functional groups (A 1 or A 2 in the above general formula) are reacted in the presence of a radical generator.
4.末端に複数のメルカブタンを導入したポリマーと、炭素 炭素二重結合を導入 した官能基 (前記一般式中の A1又は A2)とをラジカル発生剤存在下で反応させる方 法。 4. A method in which a polymer in which a plurality of mercabtans are introduced at the terminal and a functional group in which a carbon-carbon double bond is introduced (A 1 or A 2 in the above general formula) are reacted in the presence of a radical generator.
5.複数の官能基 (前記一般式中の A1又は A2)を有するメルカブタンィ匕合物を連鎖 移動剤として、ビュルモノマーをラジカル重合する方法。 5. A method in which a bull monomer is radically polymerized using a mercabtan compound having a plurality of functional groups (A 1 or A 2 in the above general formula) as a chain transfer agent.
[0072] 上記のうち、本発明の製造方法に用いられる高分子化合物 (好ましくは一般式 (2) で表される高分子化合物）は、例えば、上記 2、 3、 4、 5のいずれかの方法で合成す ることができるが、合成上の容易さから、上記 5の方法で合成することがより好ましい。  [0072] Among the above, the polymer compound (preferably the polymer compound represented by the general formula (2)) used in the production method of the present invention is, for example, any one of the above 2, 3, 4, and 5 Although it can be synthesized by a method, it is more preferred to synthesize by the above method 5 because of ease of synthesis.
[0073] より具体的には、下記一般式 (3)で表される化合物を連鎖移動剤として用いて、ラ ジカル重合させることが好まし 、。  [0073] More specifically, it is preferable to perform radical polymerization using a compound represented by the following general formula (3) as a chain transfer agent.
[0074] [化 10]  [0074] [Chemical 10]
A— RLs R6- sH ) 一般式 （ 3 ) A— R L s R 6 -sH) General formula (3)
k ん  k
[0075] 前記一般式 ）にお 、て、 R6、 R7、 A3、 g、および hは、それぞれ前記一般式（2)に おける R3、
Figure imgf000031_0001
x、および yと同義であり、その好ましい態様も同様である。 [0075] In the general formula), R 6 , R 7 , A 3 , g, and h are each R 3 in the general formula ( 2 ),
Figure imgf000031_0001
It is synonymous with x and y, The preferable aspect is also the same.
[0076] 前記ビュルモノマーとしては、特に制限されな!、が、例えば、（メタ)アクリル酸エス テル類、クロトン酸エステル類、ビュルエステル類、マレイン酸ジエステル類、フマル 酸ジエステル類、ィタコン酸ジエステル類、（メタ）アクリルアミド類、ビュルエーテル類 、ビュルアルコールのエステル類、スチレン類、（メタ）アクリロニトリルなどが好ましい。 このような例としては、下記のような化合物が挙げられる。  [0076] The bull monomer is not particularly limited !, but, for example, (meth) acrylic acid esters, crotonic acid esters, buresters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters , (Meth) acrylamides, butyl ethers, esters of butyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.
[0077] 前記 (メタ）アクリル酸エステル類の例としては、（メタ）アクリル酸メチル、（メタ)アタリ ル酸ェチル、 （メタ）アクリル酸 n—プロピル、 （メタ）アクリル酸イソプロピル、 （メタ）ァク リル酸 n—ブチル、 （メタ）アクリル酸イソブチル、 （メタ）アクリル酸 tーブチル、 （メタ）ァ クリル酸 n—へキシル、 （メタ）アクリル酸シクロへキシル、 （メタ）アクリル酸 t—ブチルシ クロへキシル、 （メタ）アクリル酸 2—ェチルへキシル、 （メタ）アクリル酸 t—ォクチル、 （ メタ）アクリル酸ドデシル、（メタ）アクリル酸ォクタデシル、（メタ）アクリル酸ァセトキシ ェチル、（メタ）アクリル酸フエ-ル、（メタ）アクリル酸 2—ヒドロキシェチル、（メタ）アタリ ル酸 2—メトキシェチル、（メタ）アクリル酸 2—エトキシェチル、（メタ）アクリル酸 2—（2 —メトキシエトキシ）ェチル、（メタ）アクリル酸 3 -フエノキシ 2 ヒドロキシプロピル、 (メタ）アクリル酸ベンジル、（メタ）アクリル酸ジエチレングリコールモノメチルエーテル 、（メタ）アクリル酸ジエチレングリコールモノェチルエーテル、（メタ）アクリル酸トリェチ レングリコールモノメチルエーテル、（メタ）アクリル酸トリエチレングリコールモノェチ ルエーテル、（メタ）アクリル酸ポリエチレングリコールモノメチルエーテル、（メタ）ァク リル酸ポリエチレングリコールモノェチルエーテル、（メタ）アクリル酸 j8ーフエノキシェ トキシェチル、（メタ）アクリル酸ノ-ルフエノキシポリエチレングリコール、（メタ）アタリ ル酸ジシクロペンテ-ル、（メタ）アクリル酸ジシクロペンテ-ルォキシェチル、（メタ）ァ クリル酸トリフロロェチル、（メタ）アクリル酸オタタフロロペンチル、（メタ）アクリル酸パ 一フロロォクチルェチル、（メタ）アクリル酸ジシクロペンタ -ル、（メタ）アクリル酸トリブ ロモフエ-ル、（メタ）アクリル酸トリブロモフエ-ルォキシェチルなどが挙げられる。 [0077] Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid t- Butyl cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, ( Dodecyl (meth) acrylate, Octadecyl (meth) acrylate, Acetoxyethyl (meth) acrylate, Phenyl (meth) acrylate, 2-Hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate , (Meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2-methoxyethoxy) ethyl, (meth) acrylic acid 3-phenoxy 2 hydroxypropyl, (meth) acrylic acid benzyl, (meth) acrylic acid diethylene glycol Monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (Meth) acrylic acid polyethylene glycol monoethyl ether, (meth) acrylic acid j8-phenoxytoxychetylyl, (meth) acrylic acid norphenoxypolyethylene glycol, (meth) acrylic acid dicyclopental, (meth) acrylic Dicyclopentyl-oxychetyl acid, trifluoroethyl (meth) acrylate, otafluorofluoropentyl (meth) acrylate, trifluorooctyl (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) acrylic acid Examples include tribromophenol, tribromophenol (meth) acrylate, and so on.
[0078] 前記クロトン酸エステル類の例としては、クロトン酸ブチル、クロトン酸へキシル等が 挙げられる。 [0078] Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
[0079] 前記ビニルエステル類の例としては、ビュルアセテート、ビニルプロピオネート、ビニ ルブチレート、ビニルメトキシアセテート、安息香酸ビニルなどが挙げられる。  [0079] Examples of the vinyl esters include butyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
[0080] 前記マレイン酸ジエステル類の例としては、マレイン酸ジメチル、マレイン酸ジェチ ル、マレイン酸ジブチルなどが挙げられる。  [0080] Examples of the maleic diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
[0081] 前記フマル酸ジエステル類の例としては、フマル酸ジメチル、フマル酸ジェチル、フ マル酸ジブチルなどが挙げられる。  [0081] Examples of the fumaric acid diesters include dimethyl fumarate, jetyl fumarate, dibutyl fumarate, and the like.
[0082] 前記ィタコン酸ジエステル類の例としては、ィタコン酸ジメチル、ィタコン酸ジェチル 、ィタコン酸ジブチルなどが挙げられる。  [0082] Examples of the itaconic acid diesters include dimethyl itaconate, jetyl itaconate, and dibutyl itaconate.
[0083] 前記 (メタ）アクリルアミド類の例としては、（メタ）アクリルアミド、 N—メチル (メタ)ァク リルアミド、 N ェチル (メタ）アクリルアミド、 N—プロピル (メタ）アクリルアミド、 N—ィ ソプロピル (メタ）アクリルアミド、 N—n—ブチルアクリル (メタ）アミド、 N— t—ブチル（ メタ）アクリルアミド、 N シクロへキシル (メタ）アクリルアミド、 N— (2—メトキシェチル ) (メタ）アクリルアミド、 N, N—ジメチル (メタ）アクリルアミド、 N, N—ジェチル (メタ）ァ クリルアミド、 N—フエ-ル (メタ）アクリルアミド、 N—ベンジル (メタ）アクリルアミド、 （メ タ）アタリロイルモルホリン、ジアセトンアクリルアミドなどが挙げられる。 [0083] Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) ) Acrylamide, N-n-butylacrylic (meth) amide, N-t-butyl (meth) acrylamide, N cyclohexyl (meth) acrylamide, N- (2-methoxyethyl ) (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-jetyl (meth) acrylamide, N-phenol (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) atari Roylmorpholine, diacetone acrylamide, etc. are mentioned.
[0084] 前記スチレン類の例としては、スチレン、メチルスチレン、ジメチルスチレン、トリメチ ノレスチレン、ェチルスチレン、イソプロピノレスチレン、ブチルスチレン、ヒドロキシスチ レン、メトキシスチレン、ブトキシスチレン、ァセトキシスチレン、クロロスチレン、ジクロ ロスチレン、プロモスチレン、クロロメチルスチレン、酸性物質により脱保護可能な基（ 例えば t— Bocなど）で保護されたヒドロキシスチレン、ビニル安息香酸メチル、及び a—メチルスチレンなどが挙げられる。  [0084] Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropylino styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene. Examples thereof include low styrene, promostyrene, chloromethyl styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinylbenzoate, and a-methylstyrene.
[0085] 前記ビュルエーテル類の例としては、メチルビ-ルエーテル、ブチルビニルエーテ ル、へキシルビ-ルエーテル、及びメトキシェチルビ-ルエーテルなどが挙げられる  [0085] Examples of the butyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
[0086] 上記の化合物以外にも、（メタ）アクリロニトリル、ビニル基が置換した複素環式基（ 例えば、ビュルピリジン、ビュルピロリドン、ビュル力ルバゾールなど）、 N—ビュルホ ルムアミド、 N—ビュルァセトアミド、 N—ビュルイミダゾール、ビュル力プロラタトン等 ち使用でさる。 [0086] In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, bullpyridine, bull pyrrolidone, bull force rubazole, etc.), N-buluformamide, N-bulacetoamide N-Buylimidazole, bull force prolatatone, etc. can be used.
また、上記の化合物以外に、例えばウレタン基、ウレァ基、スルホンアミド基、フエノ ール基、イミド基などの官能基を有するビュルモノマーも用いることができる。このよう なウレタン基、又はウレァ基を有する単量体としては、例えばイソシアナ一ト基と水酸 基、又はアミノ基の付加反応を利用して、適宜合成することが可能である。具体的に は、イソシアナート基含有モノマーと水酸基を 1個含有する化合物または 1級あるい は 2級アミノ基を 1個含有する化合物との付加反応、又は水酸基含有モノマーまたは 1級あるいは 2級ァミノ基含有モノマーとモノイソシァネートとの付加反応等により適宜 合成することができる。  In addition to the above compounds, butyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or urea group can be appropriately synthesized by utilizing, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group. It can be appropriately synthesized by an addition reaction between a group-containing monomer and a monoisocyanate.
[0087] 上記のビュルモノマーは一種のみで重合させてもよいし、二種以上を併用して共重 合させてもよぐこのようなラジカル重合体は、それぞれ相当するビュルモノマーを通 常の方法で常法に従って重合させることで得られる。  [0087] The above-mentioned radical monomers, which may be polymerized by only one kind, or may be used in combination of two or more kinds, may be the usual bulle monomers. It can be obtained by polymerization according to a conventional method.
例えばこれらのビニルモノマー、および連鎖移動剤を適当な溶媒中に溶解し、ここ にラジカル重合開始剤を添加して、約 50°C〜220°Cで、溶液中で重合させる方法（ 溶液重合法)を利用して得られる。 For example, these vinyl monomers and chain transfer agents are dissolved in a suitable solvent, It is obtained by using a method (solution polymerization method) in which a radical polymerization initiator is added to the polymer and polymerized in a solution at about 50 ° C to 220 ° C.
[0088] 溶液重合法で用いられる適当な溶媒の例としては、用いる単量体、及び生成する 共重合体の溶解性に応じて任意に選択できる。例えば、メタノール、エタノール、プロ パノール、イソプロパノール、 1ーメトキシー2—プロパノール、 1ーメトキシー2—プロ ピルアセテート、アセトン、メチルェチルケトン、メチルイソブチルケトン、メトキシプロピ ルアセテート、乳酸ェチル、酢酸ェチル、ァセトニトリル、テトラヒドロフラン、ジメチル ホルムアミド、クロ口ホルム、トルエンが挙げられる。これらの溶媒は、二種以上を混合 して使用してちょい。 [0088] Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, lactic acid ethyl, ethyl acetate, acetonitrile, tetrahydrofuran , Dimethylformamide, black mouth form, and toluene. Use a mixture of two or more of these solvents.
[0089] また、ラジカル重合開始剤としては、 2, 2'—ァゾビス (イソブチ口-トリル）（AIBN) 、 2, 2，—ァゾビス— (2, 4，—ジメチルバレ口-トリル）のようなァゾ化合物、ベンゾィ ルバーオキシドのような過酸ィ匕物、及び過硫酸カリウム、過硫酸アンモ-ゥムのような 過硫酸塩などが利用できる。  [0089] The radical polymerization initiator may be an azo such as 2,2'-azobis (isobutyoxy-tolyl) (AIBN) or 2,2, -azobis- (2,4, -dimethylbare-tolyl). Compounds, peroxyacid compounds such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.
[0090] 前記一般式（3)で表される化合物は、以下の方法等で合成することができるが、合 成上の容易さから、下記 7の方法がより好ましい。  [0090] The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6.複数の官能基 (前記一般式中の A1又は A2)を有するハライド化合物からメルカ ブタン化合物に変換する方法 (チォ尿素と反応させ、加水分解する方法、 NaSHと直 接反応させる方法、 CH COSNaと反応させ、加水分解させる方法などが挙げられる 6.A method of converting a halide compound having a plurality of functional groups (A 1 or A 2 in the above general formula) into a mercabtan compound (a method of reacting with thiourea and hydrolyzing, a method of directly reacting with NaSH, Examples include a method of reacting with CH COSNa and hydrolyzing.
3  Three
)  )
7.一分子中に 3〜10個のメルカプト基を有する化合物と、官能基 (前記一般式中 の A1又は A2)を有し、かつメルカプト基と反応可能な官能基を有する化合物、とを付 加反応させる方法 7. A compound having 3 to 10 mercapto groups in one molecule, a compound having a functional group (A 1 or A 2 in the above general formula) and a functional group capable of reacting with a mercapto group, and Addition reaction method
[0091] 前記方法 7における「メルカプト基と反応可能な官能基」としては、酸ノヽライド、アル キルハライド、イソシァネート、炭素 炭素二重結合などが好適に挙げられる。  [0091] Preferred examples of the "functional group capable of reacting with a mercapto group" in Method 7 include an acid halide, an alkyl halide, an isocyanate, a carbon-carbon double bond, and the like.
「メルカプト基と反応可能な官能基」が炭素 炭素二重結合であり、付加反応がラ ジカル付加反応で合成することが特に好ましい。炭素 炭素二重結合としては、メル カプト基との反応性の点で、 1置換もしくは 2置換のビュル基がより好ま U、。  It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is synthesized by a radical addition reaction. Carbon The carbon double bond is more preferably a mono- or di-substituted bur group in terms of reactivity with the mercapto group.
[0092] 前記「一分子中に 3〜： L0個のメルカプト基を有する化合物」の具体的な例として、 以下の化合物が挙げられる c[0092] As a specific example of the "compound having 3 to L0 mercapto groups in one molecule", The following compounds are mentioned c
[化 11] [Chemical 11]
(u-5 ) (u-B )
Figure imgf000035_0001
(u-5) (uB)
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000035_0002
[化 12]
Figure imgf000036_0001
[Chemical 12]
Figure imgf000036_0001
O o  O o
II II  II II
(u-11) HS - CH2-C -。- CH2、rzCH2-0 - C - CH2— SH (u-11) HS-CH 2 -C-. -CH 2 , r zCH 2 -0-C-CH 2 — SH
HS-CH2-C-0-CH CH2-0-C-CH2-SH HS-CH 2 -C-0-CH CH 2 -0-C-CH 2 -SH
II II  II II
o o  o o
(u-12) o o  (u-12) o o
II II II II
HS-CH2-CH2-NH-C-0- CH2、 CH2- O - C - N H- CH2_ CH2 - SH HS-CH 2 -CH 2 -NH-C-0- CH 2 , CH 2 -O-C-N H- CH 2 _ CH 2 -SH
HS CH2— CH2-NH-C- O— CH0 CH2-0— C_NH一 CH2— CH2— SH HS CH 2 — CH 2 —NH—C— O— CH0 CH 2 —0— C_NH CH 2 — CH 2 — SH
II O O  II O O
OM
Figure imgf000036_0002
OM
Figure imgf000036_0002
(U—16) ( U —16)
HS-CH2-CHZ- C - O - CH2、 z CH2— O- C - CH2— CH2— SH HS-CH 2 -CH Z -C-O-CH 2 , z CH 2 — O- C-CH 2 — CH 2 — SH
0 じヘ、  0
II ノ CH 2 CH2— O- C一 CH2- CH SH II 2 CH 2 CH 2 — O-C 1 CH 2 -CH SH
HS-CH2— CH2— C - O - CH2、 CH2— Ο' HS-CH 2 — CH 2 — C-O-CH 2 , CH 2 — Ο '
パゝ 0  Parr 0
HS- CH— CH2- C— O— CH CH2-0-C-CH2-CH2-SH HS- CH— CH 2 -C— O— CH CH 2 -0-C-CH 2 -CH 2 -SH
II II  II II
0 o  0 o
Figure imgf000036_0003
Figure imgf000036_0003
[0095] 上記の中でも、原料の入手性、合成の容易さ、各種溶媒への溶解性の観点から、 ( u— 1)、 (u— 2)、 (u— 10)、 (u-11), (u— 16)、 (u— 17)が好ましい。 [0095] Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, (u—1), (u—2), (u—10), (u-11) , (u-16), (u-17) are preferred.
[0096] 官能基 (前記一般式中の A1又は A2)を有し、かつ、炭素 炭素二重結合を有する 化合物としては、特に制限されないが、以下のようなものが挙げられる。 [0096] Has a functional group (A 1 or A 2 in the above general formula) and has a carbon-carbon double bond Although it does not restrict | limit especially as a compound, The following are mentioned.
[化 13] [Chemical 13]
Figure imgf000037_0001
Figure imgf000037_0001
Ck-11) (k-12) (k-13)
Figure imgf000037_0002
Ck-11) (k-12) (k-13)
Figure imgf000037_0002
[化 14] (k-17) (k-18)[Chemical 14] (k-17) (k-18)
Figure imgf000038_0001
Figure imgf000038_0001
(k- 20) (k-21 )
Figure imgf000038_0002
(k-20) (k-21)
Figure imgf000038_0002
(k-24) (k-25) (k-26) (k-24) (k-25) (k-26)
Figure imgf000038_0003
Figure imgf000038_0003
( 27) Ck-28) (k-29)  (27) Ck-28) (k-29)
0 o
Figure imgf000038_0004
0 o
Figure imgf000038_0004
(k-30) (k-31 ) (k-32)
Figure imgf000038_0005
(k-30) (k-31) (k-32)
Figure imgf000038_0005
(k-33) (k-34) (k-35)
Figure imgf000038_0006
(k-33) (k-34) (k-35)
Figure imgf000038_0006
[化 15] //: O 00/-Ηε900ί1£ εϊο-οοίAV 8ε
Figure imgf000039_0001
[Chemical 15] //: O 00 / -Ηε900ί1 £ εϊο-οοίAV 8ε
Figure imgf000039_0001
96600 OAV 96600 OAV
()- ()丄>ε9—
Figure imgf000040_0001
()-() 丄> ε9—
Figure imgf000040_0001
〔星0 [Star 0
Figure imgf000041_0001
Figure imgf000041_0001
[0101] 例えば、前記「一分子中に 3〜 10個のメルカプト基を有する化合物」と、前記「酸性 基、塩基性窒素原子を有する基、ウレァ基、ウレタン基、配位性酸素原子を有する基 、炭素数 4以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシァネート基、 および水酸基から選択される少なくとも 1種の官能基を有し、かつ、炭素 炭素二重 結合を有する化合物」とのラジカル付加反応生成物は、例えば、上記の「一分子中に 3〜10個のメルカプト基を有する化合物」および「酸性基、塩基性窒素原子を有する 基、ウレァ基、ウレタン基、配位性酸素原子を有する基、炭素数 4以上の炭化水素基 、アルコキシシリル基、エポキシ基、イソシァネート基、および水酸基から選択される 少なくとも 1種の官能基を有し、かつ、炭素 炭素二重結合を有する化合物」を適当 な溶媒中に溶解し、ここにラジカル発生剤を添加して、約 50°C〜100°Cで、付加させ る方法 (チオールーェン反応法)を利用して得られる。  [0101] For example, the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and the above “having an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, and a coordinating oxygen atom” A compound having at least one functional group selected from a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and having a carbon-carbon double bond. The radical addition reaction product includes, for example, the above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “acid group, group having basic nitrogen atom, urea group, urethane group, coordinating oxygen”. A group having an atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and having at least one functional group and a carbon-carbon double bond Dissolved compounds "a in a suitable solvent with, here by adding a radical generator, at about 50 ° C~100 ° C, obtained using the added was Ru method (Chioruen reaction method).
[0102] 前記方法で用いられる好ましい溶媒の例としては、用いる「一分子中に 3〜： LO個の メルカプト基を有する化合物」、「酸性基、塩基性窒素原子を有する基、ウレァ基、ゥ レタン基、配位性酸素原子を有する基、炭素数 4以上の炭化水素基、アルコキシシリ ル基、エポキシ基、イソシァネート基、および水酸基から選択される少なくとも 1種の 官能基を有し、かつメルカプト基と反応可能な官能基 (例えば炭素 炭素二重結合) を有する化合物」、および生成するラジカル付加反応生成物の溶解性に応じて任意 に選択できる。例えば、メタノール、エタノール、プロパノール、イソプロパノール、 1 メトキシ 2—プロパノール、 1ーメトキシ 2—プロピルアセテート、アセトン、メチル ェチルケトン、メチルイソブチルケトン、メトキシプロピルアセテート、乳酸ェチル、酢 酸ェチル、ァセトニトリル、テトラヒドロフラン、ジメチルホルムアミド、クロ口ホルム、トル ェンが挙げられる。これらの溶媒は、二種以上を混合して使用してもよい。 [0102] Examples of preferable solvents used in the above method include "a compound having 3 to LO mercapto groups in one molecule", "an acidic group, a group having a basic nitrogen atom, a urea group, a Lethane group, group having a coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilane A compound having at least one functional group selected from the group consisting of an alkyl group, an epoxy group, an isocyanate group, and a hydroxyl group, and a functional group capable of reacting with a mercapto group (for example, a carbon-carbon double bond), and It can be arbitrarily selected according to the solubility of the radical addition reaction product. For example, methanol, ethanol, propanol, isopropanol, 1 methoxy 2-propanol, 1-methoxy 2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, Kuroguchi Holm and Toluen are listed. These solvents may be used as a mixture of two or more.
[0103] また、ラジカル発生剤としては、 2, 2'—ァゾビス (イソブチ口-トリル）（AIBN) 2, 2，ーァゾビス (2, 4，ージメチルバレ口-トリル）のようなァゾ化合物、ベンゾィルパ ーォキシドのような過酸ィ匕物、及び過硫酸カリウム、過硫酸アンモ-ゥムのような過硫 酸塩などが利用できる。  [0103] In addition, as radical generators, azo compounds such as 2,2'-azobis (isobutyoroxy-tolyl) (AIBN) 2,2, -azobis (2,4, -dimethylvalerin-tolyl), and benzoyl peroxide can be used. Peracids such as potassium persulfate and persulfates such as ammonium persulfate can be used.
[0104] 本発明の製造方法に好ましく用いられる一般式（1)で表される化合物の具体例を 以下に示す。但し本発明はこれらの具体例に何ら限定されるものではない。  [0104] Specific examples of the compound represented by the general formula (1) preferably used in the production method of the present invention are shown below. However, the present invention is not limited to these specific examples.
[0105] [化 18]  [0105] [Chemical 18]
Figure imgf000042_0002
Figure imgf000042_0002
Figure imgf000042_0001
Figure imgf000042_0001
[0106] [化 19] [0106] [Chemical 19]
Figure imgf000043_0001
Figure imgf000043_0001
CC-4) CC-4)
Figure imgf000043_0002
Figure imgf000043_0002
[0107] [化 20]
Figure imgf000043_0003
Figure imgf000043_0004
[0107] [Chemical 20]
Figure imgf000043_0003
Figure imgf000043_0004
(n=5, m=1)  (n = 5, m = 1)
[0108] [化 21]
Figure imgf000044_0001
[0108] [Chemical 21]
Figure imgf000044_0001
(n=5, m=1)
Figure imgf000044_0002
(n = 5, m = 1)
Figure imgf000044_0002
(n=5 , m=1)  (n = 5, m = 1)
[0109] [化 22] [0109] [Chemical 22]
Figure imgf000044_0003
Figure imgf000044_0003
(n=5,m=1)
Figure imgf000044_0004
(n = 5, m = 1)
Figure imgf000044_0004
[0110] [化 23]
Figure imgf000045_0001
[0110] [Chemical 23]
Figure imgf000045_0001
(n= , m=1 }
Figure imgf000045_0002
(n =, m = 1}
Figure imgf000045_0002
(n=5, m:1)  (n = 5, m: 1)
[0111] [化 24] [0111] [Chemical 24]
Figure imgf000045_0003
Figure imgf000045_0003
(n=5, m=1)
Figure imgf000045_0004
(n = 5, m = 1)
Figure imgf000045_0004
(n=5, m=l)  (n = 5, m = l)
[0112] [化 25] [0112] [Chemical 25]
Figure imgf000046_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000047_0001
(n=5, m=1)  (n = 5, m = 1)
[0115] [化 28] [0115] [Chemical 28]
Figure imgf000047_0002
Figure imgf000047_0002
(n=5, m=1)
Figure imgf000047_0003
(n = 5, m = 1)
Figure imgf000047_0003
[0116] [化 29] 奮¾〔〕011 [0116] [Chemical 29] Intense [] 011
Figure imgf000048_0001
Figure imgf000048_0001
[0119] [0119]
Figure imgf000049_0001
Figure imgf000049_0001
[0120] [化 33]
Figure imgf000050_0001
Figure imgf000050_0002
[0120] [Chemical 33]
Figure imgf000050_0001
Figure imgf000050_0002
[0121] [化 34] [0121] [Chemical 34]
Figure imgf000050_0003
Figure imgf000050_0003
(n=4.5， m= .5)
Figure imgf000050_0004
(n = 4.5, m = .5)
Figure imgf000050_0004
[0122] [化 35] (C-35) [0122] [Chemical 35] (C-35)
Figure imgf000051_0001
Figure imgf000051_0001
[0123] またこの高分子化合物は、酸性基を有する高分子化合物であることが好ましぐ力 ルポキシル基を有する高分子化合物であることがより好ましぐ (A)カルボキシル基を 有する化合物力 導かれた繰り返し単位の少なくとも 1種および (B)カルボン酸エス テル基を有する化合物力 導かれた繰り返し単位の少なくとも 1種を含有する共重合 化合物が特に好ましい。 [0123] The polymer compound is preferably a polymer compound having an acidic group, and more preferably a polymer compound having a lpoxyl group. (A) Compound compound having a carboxyl group Particularly preferred are copolymer compounds containing at least one of the repeating units and (B) at least one of the derived repeating units.
前記 (A)カルボキシル基を有する化合物力 導かれた繰り返し単位として、下記一 般式 (I)で表される繰り返し単位であることが好ましぐアクリル酸またはメタクリル酸か ら導かれた繰り返し単位であることがより好ましぐ前記 (B)カルボン酸エステル基を 有する化合物力 導かれた繰り返し単位として、下記一般式 (Π)で表される繰り返し 単位であることが好ましぐ下記一般式 (IV)で表される繰り返し単位であることがより 好ましく、ベンジルアタリレート、ベンジルメタタリレート、フエネチルアタリレート、フエ ネチルメタタリレート、 3—フエ-ルプロピルアタリレート、または 3—フエ-ルプロピルメ タクリレートから導かれた繰り返し単位であることが特に好ましい。  (A) Compound force having a carboxyl group As the derived repeating unit, a repeating unit derived from acrylic acid or methacrylic acid, which is preferably a repeating unit represented by the following general formula (I): (B) Compound Power Having Carboxylic Acid Ester Groups More Preferred As Derived Repeating Units, the following General Formula (IV) It is more preferable that the repeating unit is represented by the following formula: benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, 3-phenylpropyl acrylate, or 3-phenol propyl methacrylate. A repeating unit derived from tacrylate is particularly preferred.
[0124] [化 36] 一般式 （I )
Figure imgf000052_0001
[0124] [Chemical 36] Formula (I)
Figure imgf000052_0001
(Rは水素原子又は炭素原子数 1〜5のアルキル基を表す。 )  (R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
[0125] [化 37]  [0125] [Chemical 37]
一般式 ( I I )  General formula (I I)
Figure imgf000052_0002
Figure imgf000052_0002
(Rは水素原子又は炭素原子数 1〜5のアルキル基を表す。 Rは下記一般式 (III) (R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R represents the following general formula (III)
2 3 twenty three
で表される基を表す。 )  Represents a group represented by )
[0126] [化 38] [0126] [Chemical 38]
一般式 （I I I )
Figure imgf000052_0003
General formula (III)
Figure imgf000052_0003
(Rは水素原子、炭素原子数 1〜5のアルキル基、ヒドロキシ基、炭素原子数 1〜5の (R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxy group,
4 Four
ヒドロキシアルキル基、又は炭素原子数 6〜20のァリール基を表す。 R及び Rはそ  It represents a hydroxyalkyl group or an aryl group having 6 to 20 carbon atoms. R and R are
5 6 れぞれ水素原子又は炭素原子数 1〜5のアルキル基を表す。 iは 1〜5の数を表す。 ) 5 6 Each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. i represents a number from 1 to 5. )
[0127] [化 39] [0127] [Chemical 39]
Figure imgf000052_0004
Figure imgf000052_0004
(Rは水素原子又は炭素原子数 1〜5のアルキル基を表す。 Rは下記一般式 (V)で (R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R represents the following general formula (V):
7 8 7 8
表される基を表す。 )  Represents the group represented. )
[0128] [化 40] 一般式 （V)
Figure imgf000053_0001
[0128] [Chemical 40] General formula (V)
Figure imgf000053_0001
(Rは炭素原子数 2〜5のアルキル基又は炭素原子数 6〜20のァリール基を表す。  (R represents an alkyl group having 2 to 5 carbon atoms or an aryl group having 6 to 20 carbon atoms.
9  9
R 及び R は水素原子又は炭素原子数 1〜5のアルキル基を表す。 jは 1〜5の数を R 1 and R 2 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. j is a number between 1 and 5
10 11 10 11
表す。） To express. )
また、（A)カルボキシル基を有する化合物力も導かれた繰り返し単位と、前記 (B) カルボン酸エステル基を有する化合物から導かれた繰り返し単位との重合比率として いえば、繰り返し単位 (A)の全繰り返し単位数に対する数量比％が 3〜40であること が好ましぐ 5〜35であることがより好ましい。  Further, the polymerization ratio of (A) a repeating unit derived from a compound having a carboxyl group and a repeating unit derived from the compound (B) having a carboxylic acid ester group is the total of repeating units (A). It is more preferable that the quantity ratio% to the number of repeating units is 3 to 40, and 5 to 35 is more preferable.
本発明の製造方法において高分子の分子量とは、特に断らない限り、質量平均分 子量をいう。高分子の分子量の測定方法としては、クロマトグラフィー法、粘度法、光 散乱法、沈降速度法等が挙げられる。本発明では、特に断らない限りクロマトグラフィ 一法により測定した質量平均分子量を用いる。  In the production method of the present invention, the molecular weight of the polymer means a mass average molecular weight unless otherwise specified. Examples of the method for measuring the molecular weight of the polymer include a chromatography method, a viscosity method, a light scattering method, and a sedimentation rate method. In the present invention, a mass average molecular weight measured by a chromatography method is used unless otherwise specified.
高分子化合物は、水溶性、油溶性いずれでもよぐ水溶性かつ油溶性でもよい。 高分子化合物の添加方法は、水性溶媒または有機溶媒に溶解した溶液でも、固体 状態でもよぐまた、これらの組み合わせでもよい。溶媒に溶解した溶液で添加する 方法としては、例えば、凝集有機粒子液に、凝集有機粒子液の溶媒と同様の溶媒に 溶解した状態で添加する方法、凝集有機粒子液の溶媒と相溶する、異なる溶媒に溶 解した状態で添加する方法が挙げられる。溶媒に溶解した溶液で添加する場合の、 高分子化合物の濃度は、特に制限されないが、 1〜70質量％が好ましぐ 2〜65質 量％がより好ましぐ 3〜60質量％が特に好ましい。  The polymer compound may be either water-soluble or oil-soluble, water-soluble and oil-soluble. The polymer compound may be added in a solution in an aqueous solvent or an organic solvent, in a solid state, or a combination thereof. Examples of the method of adding a solution dissolved in a solvent include, for example, a method of adding to an aggregated organic particle solution in a state dissolved in the same solvent as the solvent of the aggregated organic particle solution, and a compatibility with the solvent of the aggregated organic particle solution. An example is a method in which it is dissolved in a different solvent. The concentration of the polymer compound when added in a solution dissolved in a solvent is not particularly limited, but 1 to 70% by mass is preferable, 2 to 65% by mass is more preferable, and 3 to 60% by mass is particularly preferable. preferable.
高分子化合物の添カ卩は、有機粒子析出法による有機ナノ粒子の形成時 (またはそ の前後）、抽出または濃縮時 (またはその前後）、濃縮後の凝集有機粒子の分散時（ またはその前後）、それらの工程が終了したのち、のいずれに添加してもよぐまた、 これらの組み合わせでもよい。本発明の製造方法において、質量平均分子量 1000 以上の高分子化合物は後述するバインダーとして組成物中に含有させてもよぐ例 えば有機粒子析出液を濃縮した後、凝集有機粒子の微細分散化のときに添加する ことが好ましい。 Polymer compounds are added when organic nanoparticles are formed (or before and after) by organic particle precipitation, during extraction or concentration (or before and after), and when dispersed organic particles after concentration (or before and after). ) After these steps are completed, they may be added to any of them or a combination thereof. In the production method of the present invention, a polymer compound having a mass average molecular weight of 1000 or more may be contained in the composition as a binder to be described later. For example, after concentrating the organic particle deposition liquid, finely dispersing the aggregated organic particles. Sometimes added It is preferable.
[0130] 本発明の上記 (4)の有機粒子分散組成物の製造方法においては、酸性基をもつ 高分子化合物の存在下で有機粒子形成を行う。この場合、有機材料溶液および有 機材料溶液を添加して有機粒子を生成させるための貧溶媒の両方もしくは一方に、 酸性基をもつ高分子化合物を添加することができる。または酸性基をもつ高分子化 合物の溶液を別系統で有機粒子形成時に添加することも好ましい。  In the method (4) for producing an organic particle dispersion composition of the present invention, organic particles are formed in the presence of a polymer compound having an acidic group. In this case, the polymer compound having an acidic group can be added to both or one of the poor solvents for adding the organic material solution and the organic material solution to produce organic particles. Alternatively, it is also preferable to add a solution of a polymer compound having an acidic group in another system when forming organic particles.
[0131] 高分子化合物の添加量は、凝集有機粒子に含まれる有機粒子を 100質量部とした ときに、好ましくは 0. 1〜： L000質量部が好ましぐ 5〜500質量部がより好ましぐ 10 〜 300質量部が特に好まし 、。  [0131] The amount of the polymer compound added is preferably 0.1 to: L000 parts by mass, more preferably 5 to 500 parts by mass, when the organic particles contained in the aggregated organic particles are 100 parts by mass. 10 to 300 parts by mass are particularly preferred.
分子量 1000以上の高分子化合物としては、例えば、ポリビュルピロリドン、ポリビ- ルアルコール、ポリビュルメチルエーテル、ポリエチレンォキシド、ポリエチレングリコ ール、ポリプロピレングリコール、ポリアクリルアミド、ビュルアルコール 酢酸ビュル 共重合体、ポリビュルアルコール一部分ホルマール化物、ポリビュルアルコール一部 分ブチラール化物、ビュルピロリドン 酢酸ビュル共重合体、ポリエチレンォキシド z プロピレンォキシドブロック共重合体、ポリアミド、セルロース誘導体、澱粉誘導体など が挙げられる。その他、アルギン酸塩、ゼラチン、アルブミン、カゼイン、アラビアゴム 、トンガントゴム、リグ-ンスルホン酸塩などの天然高分子化合物類も使用できる。 酸性基を有する高分子化合物としては、ポリビニル硫酸、縮合ナフタレンスルホン 酸等が挙げられる。  Examples of the high molecular compound having a molecular weight of 1000 or more include polybutyropyrrolidone, polyvinyl alcohol, polybutyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, butyl alcohol acetate butyl copolymer, poly Examples include a partially formalized butyl alcohol, a partially butylated butyl alcohol, a butylpyrrolidone acetate butyl copolymer, a polyethylene oxide z propylene oxide block copolymer, a polyamide, a cellulose derivative, and a starch derivative. In addition, natural polymer compounds such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignosulfonate can also be used. Examples of the polymer compound having an acidic group include polyvinyl sulfate and condensed naphthalene sulfonic acid.
[0132] カルボキシル基を有する高分子化合物としては、例えば、ポリアクリル酸、ポリメタク リル酸、側鎖にカルボキシル基を有するセルロース誘導体等があげられる。（A)カル ボキシル基を有する化合物から導かれた繰り返し単位の少なくとも 1種および (B)力 ルボン酸エステル基を有する化合物から導かれた繰り返し単位の少なくとも 1種を含 む共重合化合物としては、特開昭 59— 44615号公報、特公昭 54— 34327号公報 、特公昭 58— 12577号公報、特公昭 54— 25957号公報、特開昭 59— 53836号 公報及び特開昭 59— 71048号公報に記載されて 、るようなメタクリル酸共重合体、 アクリル酸共重合体、ィタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体 、部分エステルイ匕マレイン酸共重合体等を挙げることができる。また、特に好ましい例 として、米国特許第 4139391号明細書に記載のアクリル酸—アクリル酸エステル共 重合体、メタクリル酸 アクリル酸エステル共重合体、アクリル酸ーメタクリル酸エステ ル共重合体、メタクリル酸ーメタクリル酸エステル共重合体や、アクリル酸またはメタク リル酸と、アクリル酸エステルまたはメタクリル酸エステルと、他のビュル化合物の多 元共重合体を挙げることができる。 [0132] Examples of the polymer compound having a carboxyl group include polyacrylic acid, polymethacrylic acid, a cellulose derivative having a carboxyl group in a side chain, and the like. As a copolymer compound containing (A) at least one repeating unit derived from a compound having a carboxyl group and (B) at least one repeating unit derived from a compound having a rubonic acid ester group, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836 and JP-A-59-71048 A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Can do. Also particularly preferred examples As described in US Pat. No. 4,139,391, acrylic acid-acrylic acid ester copolymer, methacrylic acid acrylic acid ester copolymer, acrylic acid-methacrylic acid ester copolymer, methacrylic acid-methacrylic acid ester copolymer, Examples thereof include multi-component copolymers of acrylic acid or methacrylic acid, acrylic acid ester or methacrylic acid ester, and other bur compounds.
ビュル化合物の例としては、スチレン又は置換されたスチレン（例えばビュルトルェ ン、ビュルェチルベンゼン）、ビュルナフタリン又は置換されたビュルナフタリン、ァク リルアミド、メタアクリルアミド、アクリロニトリル、メタアクリロニトリル等が挙げられ、スチ レンが好ましい。  Examples of the bur compound include styrene or substituted styrene (for example, butyl benzene and butyl benzene), bur naphthalene or substituted bur naphthalene, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and the like. Len is preferred.
これらの高分子化合物は 1種のみを用いてもよいし、 2種以上組み合わせて使用し てもよく、分子量 1000未満の化合物と併用してもよい。  These polymer compounds may be used alone or in combination of two or more, and may be used in combination with a compound having a molecular weight of less than 1000.
[0133] 本発明の製造方法においては、有機ナノ粒子分散物が 60質量％以上の有機溶剤 を含有することが好ましぐ 65質量％以上であることがより好ましい。有機溶剤として は、特に制限はなぐ通常のものの中力も適宜選択することができる。例えば、エステ ル化合物溶媒、アルコール化合物溶媒、芳香族化合物溶媒、脂肪族化合物溶媒、 ケトンィ匕合物溶媒が好ましぐエステル化合物溶媒、ケトンィ匕合物溶媒が特に好まし い。これらは、 1種単独で使用してもよいし、 2種以上併用してもよい。  [0133] In the production method of the present invention, the organic nanoparticle dispersion preferably contains 60% by mass or more of an organic solvent, more preferably 65% by mass or more. As the organic solvent, there can be appropriately selected a normal medium force without particular limitation. For example, ester compound solvents, ketone compound solvents, and ester compound solvents, and ketone compound solvents are particularly preferred, which are ester compound solvents, alcohol compound solvents, aromatic compound solvents, aliphatic compound solvents, and ketone compound solvents. These may be used alone or in combination of two or more.
[0134] エステルイ匕合物溶媒としては、例えば、 2- (1ーメトキシ）プロピルアセテート、酢酸 ェチル、乳酸ェチルなどが挙げられる。アルコール化合物溶媒としては、例えば、 n ーブタノール、イソブタノールなどが挙げられる。芳香族化合物溶媒としては、例えば 、ベンゼン、トルエン、キシレンなどが挙げられる。脂肪族化合物溶媒としては、例え ば、 n キサン、シクロへキサンなどが挙げられる。ケトンィ匕合物溶媒としては、例え ば、メチルェチルケトン、アセトン、シクロへキサノンなどが挙げられる。  [0134] Examples of the ester compound solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol compound solvent include n-butanol and isobutanol. Examples of the aromatic compound solvent include benzene, toluene, xylene and the like. Examples of the aliphatic compound solvent include n-xane and cyclohexane. Examples of the ketone compound solvent include methyl ethyl ketone, acetone, cyclohexanone, and the like.
[0135] [分散剤]  [0135] [Dispersant]
本発明の有機粒子分散組成物の製造方法では、有機材料溶液および有機材料溶 液を添加して有機粒子を生成させるための貧溶媒の両方もしくは一方に分散剤を添 加することができる。または分散剤溶液を別系統で有機粒子形成時に添加することも 好ましい。分散剤は（1)析出した顔料表面に素早く吸着して、微細な顔料粒子を形 成し、かつ（2)これらの粒子が再び凝集することを防ぐ作用を有するものである。 本発明では、このような分散剤として、ァ-オン性、カチオン性、両イオン性、ノ-ォ ン性もしくは顔料性の、低分子または高分子分散剤を使用することができる。なお、 高分子分散剤の分子量は溶液に均一に溶解できるものであれば制限なく用いること 力 Sでさる力 好まし < ίま分子量 1, 000〜2, 000, 000であり、 5, 000〜1, 000, 00 0力 Sより好まし <、 10, 000〜500, 000力 Sさらに好まし <、 10, 000〜100, 000力 s特 に好ましい。（本発明においては、特に断りのない限り、分子量とは質量平均分子量 を意味する。高分子化合物は多分散系であり、必ずしも同一の分子量または粒子量 を持たない。したがって、分子量を測定すると得られた値はなんらかの形で平均され た平均分子量になる。その主なものは次の 3種類である。すなわち、 1)数平均分子 量 Μη、 2)質量平均分子量 Mw、 3) Z平均分子量 Mzであり、 Mn< Mw< Mzの関 係が成立する。）高分子分散剤としては、具体的には、ポリビニルピロリドン、ポリビ- ルアルコール、ポリビュルメチルエーテル、ポリエチレンォキシド、ポリエチレングリコ ール、ポリプロピレングリコール、ポリアクリルアミド、ビュルアルコール 酢酸ビュル 共重合体、ポリビュルアルコール一部分ホルマール化物、ポリビュルアルコール一部 分ブチラール化物、ビュルピロリドン 酢酸ビュル共重合体、ポリエチレンォキシド z プロピレンォキシドブロック共重合体、ポリアクリル酸塩、ポリビュル硫酸塩、ポリ（4 ビュルピリジン)塩、ポリアミド、ポリアリルアミン塩、縮合ナフタレンスルホン酸塩、セ ルロース誘導体、澱粉誘導体などが挙げられる。その他、アルギン酸塩、ゼラチン、 アルブミン、カゼイン、アラビアゴム、トンガントゴム、リグ-ンスルホン酸塩などの天然 高分子類も使用できる。なかでも、ポリビニルピロリドンが好ましい。これらの分散剤は 、 1種単独であるいは 2種以上を組み合わせて用いることができる。これらの分散剤は 、単独あるいは併用して使用することができる。顔料の分散に用いる分散剤に関して は、「顔料分散安定化と表面処理技術，評価」（化学情報協会、 2001年 12月発行） の 29〜46頁に詳しく記載されている。 In the method for producing an organic particle dispersion composition of the present invention, a dispersant can be added to both or one of the poor solvent for adding organic material solution and organic material solution to produce organic particles. Alternatively, it is also preferable to add the dispersant solution at the time of forming the organic particles in a separate system. Dispersant (1) Quickly adsorbs on the deposited pigment surface to form fine pigment particles And (2) has an effect of preventing these particles from aggregating again. In the present invention, as such a dispersant, a low-molecular or high-molecular dispersant having a ionic, cationic, amphoteric, nonionic or pigment property can be used. The molecular weight of the polymer dispersant should be used without limitation as long as it can be dissolved uniformly in the solution. Force over S. Preferable <Molecular weight of 1,000 to 2,000,000, 5,000 to 5,000 1, 000,000 0 force S preferred <, 10,000-500,000 force S more preferred <10, 000-100,000 force s, particularly preferred. (In the present invention, unless otherwise specified, molecular weight means mass average molecular weight. A polymer compound is a polydisperse system and does not necessarily have the same molecular weight or particle weight. The values obtained are average molecular weights averaged in some form, the main three being: 1) number average molecular weight Μη, 2) mass average molecular weight Mw, 3) Z average molecular weight Mz And the relationship of Mn <Mw <Mz holds. ) Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polybutyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, butyl alcohol, acetic acid butyl copolymer, poly Butyl alcohol partially formalized, polybull alcohol partially butyral, bull pyrrolidone acetic acid bull copolymer, polyethylene oxide z propylene oxide block copolymer, polyacrylate, polybul sulfate, poly (4 bull pyridine) Examples include salts, polyamides, polyallylamine salts, condensed naphthalene sulfonates, cellulose derivatives, and starch derivatives. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignosulfonate can also be used. Of these, polyvinylpyrrolidone is preferable. These dispersants can be used alone or in combination of two or more. These dispersants can be used alone or in combination. The dispersants used for dispersing the pigment are described in detail on pages 29 to 46 of “Pigment dispersion stabilization and surface treatment technology, evaluation” (Chemical Information Association, issued in December 2001).
ァ-オン性分散剤（ァ-オン性界面活性剤）としては、 N ァシル—N アルキルタ ゥリン塩、脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、ァ ルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキルリン酸エステ ル塩、ナフタレンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキル硫酸エス テル塩等を挙げることができる。なかでも、 N ァシル—N アルキルタウリン塩が好 ましい。 N ァシル N アルキルタウリン塩としては、特開平 3— 273067号明細書 に記載されているものが好ましい。これらァ-オン性分散剤は、 1種単独であるいは 2 種以上を組み合わせて用いることができる。 As the ionic dispersant (the ionic surfactant), N-acyl-N alkyl taurine salt, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate , Alkyl phosphate ester Salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Of these, N-acyl-N alkyltaurine salts are preferred. As the N-acyl N alkyltaurine salt, those described in JP-A-3-273067 are preferable. These char-on dispersants can be used singly or in combination of two or more.
[0137] カチオン性分散剤 (カチオン性界面活性剤）には、四級アンモ-ゥム塩、アルコキシ ルイ匕ポリアミン、脂肪族アミンポリグリコールエーテル、脂肪族ァミン、脂肪族ァミンと 脂肪族アルコール力 誘導されるジァミンおよびポリアミン、脂肪酸から誘導されるィ ミダゾリンおよびこれらのカチオン性物質の塩が含まれる。これらカチオン性分散剤 は、 1種単独であるいは 2種以上を組み合わせて用いることができる。  [0137] Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxy Louis polyamines, aliphatic amine polyglycol ethers, aliphatic amines, aliphatic amines and fatty alcohol power induction. And diamines derived from fatty acids, imidazolines derived from fatty acids, and salts of these cationic substances. These cationic dispersants can be used alone or in combination of two or more.
[0138] 両イオン性分散剤は、前記ァ-オン性分散剤が分子内に有するァ-オン基部分と カチオン性分散剤が分子内に有するカチオン基部分を共に分子内に有する分散剤 である。  [0138] The amphoteric dispersant is a dispersant having both the cation group part of the cation-dispersing agent in the molecule and the cation group part of the cation-dispersing agent in the molecule. .
ノ-オン性分散剤（ノ-オン性界面活性剤）としては、ポリオキシエチレンアルキル エーテル、ポリオキシエチレンアルキルァリールエーテル、ポリオキシエチレン脂肪酸 エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル 、ポリオキシエチレンアルキルァミン、グリセリン脂肪酸エステルなどを挙げることがで きる。なかでも、ポリオキシエチレンアルキルァリールエーテルが好ましい。これらノニ オン性分散剤は、 1種単独であるいは 2種以上を組み合わせて用いることができる。  Non-ionic dispersants (non-ionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Examples thereof include oxyethylene alkylamine and glycerin fatty acid ester. Of these, polyoxyethylene alkylaryl ether is preferred. These nonionic dispersants can be used singly or in combination of two or more.
[0139] 顔料性分散剤とは、親物質としての有機顔料から誘導され、その親構造を化学修 飾することで製造される顔料性分散剤と定義する。例えば、糖含有顔料分散剤、ピぺ リジル含有顔料分散剤、ナフタレンまたはペリレン誘導顔料分散剤、メチレン基を介 して顔料親構造に連結された官能基を有する顔料分散剤、ポリマーで化学修飾され た顔料親構造、スルホン酸基を有する顔料分散剤、スルホンアミド基を有する顔料分 散剤、エーテル基を有する顔料分散剤、あるいはカルボン酸基、カルボン酸エステ ル基またはカルボキサミド基を有する顔料分散剤などがある。 [0139] A pigment-based dispersant is defined as a pigment-based dispersant derived from an organic pigment as a parent substance and produced by chemically modifying the parent structure. For example, sugar-containing pigment dispersants, piperidyl-containing pigment dispersants, naphthalene or perylene-derived pigment dispersants, pigment dispersants having functional groups linked to the pigment parent structure via methylene groups, and chemically modified with polymers. Pigment parent structure, pigment dispersant having sulfonic acid group, pigment dispersant having sulfonamide group, pigment dispersant having ether group, pigment dispersant having carboxylic acid group, carboxylic ester group or carboxamide group, etc. There is.
また、特開 2000— 239554に記載の一般式 (I)で表される化合物も非常に好ましく 用いられる。 [0140] 本発明の製造方法においては、分散剤として、アミノ基を含有する顔料分散剤を用 いることも好ましい。ここで、ァミノ基とは一級アミノ基、二級アミノ基、三級アミノ基を含 み、ァミノ基の数は一つでも複数でもよい。顔料骨格にアミノ基を有する置換基を導 入した顔料誘導体化合物でも、アミノ基を有するモノマーを重合成分としたポリマー 化合物でもよい。これらの例として、例えば、特開 2000— 239554号公報、 2003— 96329号公報、 2001— 31885号公報、特開平 10— 339949号公報、特公平 5— 7 2943号公報に記載の化合物などが挙げられる力 これらに限定されるものではない Further, a compound represented by the general formula (I) described in JP-A-2000-239554 is also preferably used. [0140] In the production method of the present invention, it is also preferable to use a pigment dispersant containing an amino group as the dispersant. Here, the amino group includes a primary amino group, a secondary amino group, and a tertiary amino group, and the number of the amino groups may be one or plural. It may be a pigment derivative compound in which a substituent having an amino group is introduced into the pigment skeleton, or a polymer compound having a monomer having an amino group as a polymerization component. Examples of these include, for example, compounds described in JP-A Nos. 2000-239554, 2003-96329, 2001-31885, JP-A-10-339949, and JP-B-5-72943. Forces that are not limited to these
[0141] 本発明の製造方法に用いられるアミノ基を有する分散剤としては、それに限定され るものではないが、下記の一般式 (Dl)、（D3)、および式 (D4)で表される化合物か ら選ばれる少なくとも一種を用いることができる。 [0141] The amino group-containing dispersant used in the production method of the present invention is not limited thereto, but is represented by the following general formulas (Dl), (D3), and (D4). At least one selected from compounds can be used.
< 1.一般式 (D1)で表される化合物 >  <1. Compounds represented by general formula (D1)>
[0142] [化 41] 一般式（D1)  [0142] [Chemical Formula 41] General formula (D1)
A-N=N-X- Y  A-N = N-X- Y
[0143] 一般式 (D1)中、 Aは X—Yとともにァゾ色素を形成しうる成分を表す。前記 Aは、ジ ァゾ -ゥム化合物とカップリングしてァゾ色素を形成しうる化合物であれば任意に選 択することができる。前記 Aの具体例を以下に示すが、本発明はこれらにより何ら限 定されるものではない。  In general formula (D1), A represents a component capable of forming an azo dye together with X—Y. A can be arbitrarily selected as long as it is a compound capable of forming an azo dye by coupling with a diazo-um compound. Specific examples of A will be shown below, but the present invention is not limited thereto.
[0144] [化 42] [0144] [Chemical 42]
CHaCOCHCONhCH a COCHCONh
Figure imgf000059_0001
Figure imgf000059_0001
式 1—1  Formula 1-1
式 1—2  Formula 1-2
-COCHCONh -COCHCONh
Figure imgf000059_0002
Figure imgf000059_0002
式 1 _3  Formula 1 _3
式 1—4
Figure imgf000059_0003
式 1 _5 式 1— 式 1 _' Formula 1-4
Figure imgf000059_0003
Equation 1 _5 Equation 1—Equation 1 _ '
[0145] [化 43]
Figure imgf000059_0004
[0145] [Chemical 43]
Figure imgf000059_0004
式 1—8 式 1—9 式 1 -10  Formula 1-8 Formula 1-9 Formula 1 -10
Figure imgf000059_0005
Figure imgf000059_0005
1一 11 式 1— 12  1 1 11 Formula 1— 12
[0146] 一般式 (Dl)中、 Xは単結合又は下記式 (i)〜(v)の構造式で表される二価の連結 基から選択される基を表す。 [0146] In the general formula (Dl), X represents a single bond or a group selected from divalent linking groups represented by structural formulas of the following formulas (i) to (v).
[0147] [化 44] [0147] [Chemical 44]
、C0NH—
Figure imgf000059_0006
NH- 式（ i ) 式 (ii) 式（iii)
Figure imgf000059_0007
, C0NH—
Figure imgf000059_0006
NH- Formula (i) Formula (ii) Formula (iii)
Figure imgf000059_0007
式 (iv) 式（v) [0148] 一般式 (Dl)中、 Yは下記一般式 (D2)で表される基を表す。 Formula (iv) Formula (v) [0148] In the general formula (Dl), Y represents a group represented by the following general formula (D2).
[0149] [化 45] [0149] [Chemical 45]
-般式（D 2 ) 广 -General formula (D 2) 广
(C0NH-;  (C0NH-;
[0150] -般式 (D2)中、 Zは、低級アルキレン基を表す。 Zは、一（CH ) —と表される力  -In the general formula (D2), Z represents a lower alkylene group. Z is the force expressed as one (CH) —
2 b  2 b
該 bは 1〜5の整数を表し、好ましくは 2又は 3を表す。一般式 (D2)中、 NR は、  The b represents an integer of 1 to 5, preferably 2 or 3. In the general formula (D2), NR is
21 低級アルキルアミノ基、又は窒素原子を含む 5乃至 6員飽和へテロ環基を表す。該ー NR は、低級アルキルアミノ基を表す場合、— N (C H ) と表され、 rは 1〜4の整 21 represents a lower alkylamino group or a 5- to 6-membered saturated heterocyclic group containing a nitrogen atom. When —NR represents a lower alkylamino group, it is represented as —N (C H), and r is an integer of 1 to 4.
21 r 2r+ l 2 21 r 2r + l 2
数を表し、好ましくは 1又は 2を表す。 -NR 1S 窒素原子を含む 5乃至 6員飽和へ  Represents a number, preferably 1 or 2. -NR 1S 5 to 6-membered saturation containing nitrogen atoms
21  twenty one
テロ環基を表す場合、下記構造式で表される 、ずれかのへテロ環基が好まし 、。  When a heterocyclic group is represented, any of the heterocyclic groups represented by the following structural formula is preferred.
[0151] [化 46] ーリ ， > ,
Figure imgf000060_0001
[0151] [Chemical 46]-,>,
Figure imgf000060_0001
ピロリジン環 ビベリジン璣 モルホリン環  Pyrrolidine ring Biveridine 璣 Morpholine ring
[0152] 前記一般式 (D2)における、 Z及び—NR は、それぞれ、低級アルキル基、アルコ  [0152] In the general formula (D2), Z and -NR are each a lower alkyl group or an alcohol;
21  twenty one
キシ基を置換基として有していてもよい。前記一般式 (D2)中、 aは、 1又は 2を表し、 好ましくは 2を表す。  You may have a xy group as a substituent. In the general formula (D2), a represents 1 or 2, preferably 2.
[0153] 以下に、前記一般式 (D1)で表される化合物の具体例を示すが、本発明はこれら の具体例に何ら限定されるものではな 、。  [0153] Specific examples of the compound represented by the general formula (D1) are shown below, but the present invention is not limited to these specific examples.
[0154] [化 47] [0154] [Chemical 47]
Figure imgf000061_0001
Figure imgf000061_0001
Figure imgf000061_0002
Figure imgf000061_0002
Figure imgf000061_0003
" V
Figure imgf000061_0004
Figure imgf000061_0003
"V
Figure imgf000061_0004
/.1"lC/900Zdf/X3«i 09 sz.teio//.ooz ΟΛ /.1"lC/900Zdf/X3«i 09 sz.teio //. Ooz ΟΛ
Figure imgf000062_0001
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000062_0002
Figure imgf000062_0003
Figure imgf000062_0003
Ltl£/900ld£/lDd V9 Ltl £ / 900ld £ / lDd V9
Figure imgf000063_0001
Figure imgf000063_0001
Figure imgf000063_0002
2 0
Figure imgf000063_0002
2 0
Figure imgf000064_0001
Figure imgf000064_0001
Figure imgf000064_0002
Figure imgf000064_0002
[0158] 一般式 (Dl)で表される化合物は例えば特開 2000— 239554号公報に記載され た方法により合成することができる。 [0158] The compound represented by the general formula (Dl) can be synthesized, for example, by the method described in JP-A-2000-239554.
[0159] < 2.一般式 (D3)で表される化合物 > [0159] <2. Compound represented by general formula (D3)>
[0160] [化 51] 一般式（D 3 [0160] [Chemical formula 51] General formula (D 3
ii
Figure imgf000064_0003
Figure imgf000064_0003
[0161] 一般式 (D3)中、  [0161] In general formula (D3),
Qは、アントラキノンィ匕合物色素、ァゾィ匕合物色素、フタロシアニン化合物色素、キ ナクリドンィ匕合物色素、ジォキサジンィ匕合物色素、アントラピリミジンィ匕合物色素、ァ ンサンスロン化合物色素、インダンスロン化合物色素、フラバンスロン化合物色素、ピ ランスロン化合物色素、ペリノン化合物色素、ペリレン化合物色素、及びチォインジゴ 化合物色素から選ばれる有機色素残基を表し、なかでもァゾィ匕合物色素、またはジ ォキサジンィ匕合物色素であることが好ましぐァゾィ匕合物色素であることがより好まし い。 Q is an anthraquinone compound dye, an azo compound compound dye, a phthalocyanine compound dye, a quinacridone compound compound dye, a dioxazine compound compound dye, an anthrapyrimidine compound compound dye, an anthrone compound compound, an indanthrone compound Represents an organic dye residue selected from a dye, a flavanthrone compound dye, a pyranthrone compound dye, a perinone compound dye, a perylene compound dye, and a thioindigo compound dye, particularly an azo compound dye or a dioxazine compound dye. It is more preferred that it is an azo compound pigment. Yes.
Xは、 CO—、 -CONH-Y 一、 SO NH-Y 一、又は CH NHCOCH X is CO—, —CONH-Y one, SO NH-Y one, or CH NHCOCH
I 2 2 2 2 2I 2 2 2 2 2
NH-Y—を表し、 CO—、 -CONH-Y—であることが好ましい。 NH-Y— represents CO— and —CONH-Y—.
2 2  twenty two
Yは置換基を有してもよいアルキレン基又はァリーレン基を表し、なかでもフエ-レ Y represents an alkylene group or an arylene group which may have a substituent.
2 2
ン、トルイレン、またはへキシレンであることが好ましぐフエ-レンであることがより好ま しい。  More preferred is phenylene, toluylene or hexylene.
R および R はそれぞれ独立に置換もしくは無置換のアルキル基または R と R と R and R are each independently a substituted or unsubstituted alkyl group or R and R
II 12 11 12 で少なくとも窒素原子を含むヘテロ環基を形成してもよい。なかでもメチル基、ェチル 基、プロピル基、または窒素原子を含めたピロリジ -ル基であることが好ましぐェチ ル基であることがより好まし!/、。 II 12 11 12 may form a heterocyclic group containing at least a nitrogen atom. Among them, a methyl group, an ethyl group, a propyl group, or a pyrrolidyl group including a nitrogen atom is preferable, and an ethyl group is more preferable!
Yは—NH 又は—O を表す。  Y represents —NH 2 or —O 2.
Zは水酸基又は一般式（D3a)で表される基を表し、あるいは nlが 1の場合—NH —X Qでもよい。 mlは 1〜6の整数を表し、 2〜3が好ましい。 nlは 1〜4の整数を 表し、 1〜2が好ましい。  Z represents a hydroxyl group or a group represented by the general formula (D3a), or when nl is 1, —NH 2 —X Q may be used. ml represents an integer of 1 to 6, preferably 2 to 3. nl represents an integer of 1 to 4, preferably 1 or 2.
[0162] [化 52] [0162] [Chemical 52]
—般式（D 3 a) Rn  —General formula (D 3 a) Rn
— Y3-(CH2)- ml \ — Y 3- (CH 2 )-ml \
Γ 12 Γ 12
[0163] 一般式（D3a)中、 Yは NH 又は—Ο を表し、 ml、 R 、および R は一般式 [0163] In the general formula (D3a), Y represents NH or —Ο, and ml, R 1 and R 2 represent the general formula
3 11 12  3 11 12
(D3)におけるそれらと同じ意味である。  It has the same meaning as those in (D3).
[0164] 一般式 (D3)で表される化合物はより具体的には例えば下記一般式により表される [0164] More specifically, the compound represented by the general formula (D3) is represented by the following general formula, for example.
[0165] [化 53] -般式（D3— 1) 一般式（D3—2)[0165] [Chemical 53] -General formula (D3-1) General formula (D3-2)
—般式（D 3—3) 般式（D3 - 4)—General formula (D 3-3) General formula (D3-4)
—般式（D 3— 5)
Figure imgf000066_0001
—General formula (D 3— 5)
Figure imgf000066_0001
一般式（D 3— 6)
Figure imgf000066_0002
General formula (D 3-6)
Figure imgf000066_0002
なぉー般式（03— 1)〜（03— 6)にぉぃて、<3 1111 111 1 R は一般式（D3)  In general formulas (03-1) to (03-6), <3 1111 111 1 R is the general formula (D3)
11 12  11 12
におけるそれらと同じ意味である。以下に一般式 (D3)で表される化合物の具体例を 挙げるが、本発明はこれらにより限定されるものではない。なお、式中 Cu—Pcは銅フ タロシアニンを表す。 [0167] [化 54] It is the same meaning as those in Specific examples of the compound represented by the general formula (D3) are listed below, but the present invention is not limited thereto. In the formula, Cu-Pc represents copper phthalocyanine. [0167] [Chemical 54]
(a) NHヤ 響 (a) NH Ya Hibiki
N< V.N  N <V.N
NH(CH2)3N、 NH (CH 2 ) 3 N,
C2H5 1~3 C 2 H 5 1-3
(b) (b)
Figure imgf000067_0001
Figure imgf000067_0001
(c)  (c)
Figure imgf000067_0002
Figure imgf000067_0002
[0168] [化 55] [0168] [Chemical 55]
Figure imgf000068_0001
Figure imgf000068_0001
Figure imgf000068_0002
Figure imgf000068_0002
[0169] 一般式 (D3)で表される化合物は、例えば R および R を有するァミン化合物と R  [0169] The compound represented by the general formula (D3) is, for example, an amine compound having R and R and R
11 12 11 および R を有するアルコールィ匕合物とをハロゲンィ匕トリアジンィ匕合物と反応させ、得 11 12 11 and an alcohol compound having 11 and R are reacted with a halogenated triazine compound.
12 12
られた中間体に色素化合物を反応させて得ることができる。また、特公平 5— 72943 号明細書の記載も参考にすることができる。  It can be obtained by reacting the obtained intermediate with a dye compound. The description in the specification of JP-B-5-72943 can also be referred to.
[0170] < 3.グラフト共重合体を含有する顔料分散剤 > [0170] <3. Pigment Dispersant Containing Graft Copolymer>
本発明の製造方法にお！ヽては、アミノ基及びエーテル基を有するグラフト共重合体 を含有し、必要に応じて適宜選択したその他の成分を含有する分散剤を用いることも 好ましい。  In the manufacturing method of the present invention! It is also preferable to use a dispersant containing a graft copolymer having an amino group and an ether group and containing other components appropriately selected as necessary.
前記グラフト共重合体は、アミノ基及びエーテル基を少なくとも有してなり、その他 のモノマー等を共重合体単位として含んで 、てもよ 、。  The graft copolymer may have at least an amino group and an ether group, and may contain other monomers as copolymer units.
前記グラフト共重合体の質量平均分子量（Mw)としては、 3000〜100000カ 子ま し <、 5000〜50000力より好まし!/ヽ。前記質量平均分子量（Mw)力 3000未満で あると、顔料ナノ粒子の凝集を防ぐことができず、粘度が上昇してしまうことがあり、 10 0000を超えると有機溶剤への溶解性が不足し、粘度が上昇してしまうことがある。な お、該質量平均分子量は、ゲルパーミエーシヨンクロマトグラフィ (キャリア:テトラヒドロ フラン）により測定されるポリスチレン換算質量平均分子量である。 The weight average molecular weight (Mw) of the graft copolymer is preferably 300 to 100,000 particles <, more preferably 5000 to 50,000 force! / ヽ. If the mass average molecular weight (Mw) force is less than 3000, the aggregation of pigment nanoparticles cannot be prevented, and the viscosity may increase. When it exceeds 0000, the solubility in an organic solvent is insufficient, and the viscosity may increase. The mass average molecular weight is a polystyrene-reduced mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).
[0171] 前記グラフト共重合体は、 (i)末端にエチレン性不飽和二重結合を有する重合性ォ リゴマーと、（ii)ァミノ基とエチレン性不飽和二重結合とを有するモノマーと、（iii)エー テル基を有する重合性モノマーとを共重合体単位として少なくとも含み、必要に応じ て（iv)その他のモノマーを共重合単位として含むことが好まし 、。  [0171] The graft copolymer comprises: (i) a polymerizable oligomer having an ethylenically unsaturated double bond at a terminal; (ii) a monomer having an amino group and an ethylenically unsaturated double bond; (iii) It preferably contains at least a polymerizable monomer having an ether group as a copolymer unit, and (iv) optionally contains other monomers as copolymer units.
[0172] これらの共重合体単位の、前記グラフト共重合体における含有量としては、（i)前記 重合性オリゴマーが 15〜98質量0 /0であることが好ましぐ 25〜90質量0 /0であること 力 り好ましぐ（ii)アミノ基含有モノマーが 1〜40質量％であることが好ましぐ 5〜3 0質量％であることがより好ましぐ (iii)前記エーテル基を有する重合性モノマーが 1 〜70質量％であることが好ましぐ 5〜60質量％であることがより好ましい。 [0172] These copolymers unit, The content of the graft copolymer, (i) the polymerizable oligomer is preferably to be 15 to 98 mass 0/0 device 25 to 90 weight 0 / 0 is it forces Ri preferably fixture (ii) preferably be an amino group-containing monomer is 1 to 40 wt% instrument 5 to 3 0% by weight and is more preferably tool the (iii) the ether group The polymerizable monomer is preferably 1 to 70% by mass, more preferably 5 to 60% by mass.
[0173] 前記重合性オリゴマーの含有量が、 15質量％未満であると、分散剤としての立体 反発効果が得られず、顔料ナノ粒子の凝集が防止できないことがあり、 98質量％を 超えると、前記窒素含有モノマーの割合が減り顔料粒子に対する吸着能力が低下し 、分散性が十分でないことがある。前記窒素含有モノマーの含有量が、 1質量％未満 であると、有機粒子に対する吸着能力が低下し、分散性が十分でないことがあり、 40 質量％を超えると、前記重合性オリゴマーの割合が減ることから、分散剤としての立 体反発効果が得られず、顔料粒子の凝集を十分に防止できないことがある。前記ェ 一テル基を有する重合性モノマーの含有量力 1質量％未満であると、カラーフィル タ等の製造の際の現像適性が十分でないことがあり、 70質量％を超えると、分散剤と しての能力が低下することがある。  [0173] If the content of the polymerizable oligomer is less than 15% by mass, a steric repulsion effect as a dispersant may not be obtained, and aggregation of pigment nanoparticles may not be prevented. In some cases, the ratio of the nitrogen-containing monomer is reduced, the adsorption ability to the pigment particles is lowered, and the dispersibility is not sufficient. If the content of the nitrogen-containing monomer is less than 1% by mass, the adsorption capacity for organic particles may be reduced and dispersibility may not be sufficient, and if it exceeds 40% by mass, the proportion of the polymerizable oligomer will decrease. For this reason, the solid repulsion effect as a dispersant cannot be obtained, and the aggregation of pigment particles may not be sufficiently prevented. When the content of the polymerizable monomer having an ether group is less than 1% by mass, the development suitability in the production of a color filter or the like may not be sufficient, and when it exceeds 70% by mass, the dispersant is used as a dispersant. Your ability may decline.
[0174] (i) 重合性オリゴマー  [0174] (i) Polymerizable oligomer
前記重合性オリゴマー（以下、「マクロモノマー」と称することがある。）は、エチレン 性不飽和二重結合を有する基を末端に有するオリゴマーである。本発明にお 、ては 、前記重合性オリゴマーの中でも、該オリゴマーの両末端の内の一方にのみ前記ェ チレン性不飽和二重結合を有する基を有するのが好ましい。  The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.
[0175] 前記オリゴマーとしては、一般的には、例えば、アルキル (メタ)アタリレート、ヒドロキ シアルキル (メタ）アタリレート、スチレン、アクリロニトリル、酢酸ビュル、及びブタジェ ン力 選択された少なくとも一種のモノマー力 形成された単独重合体又は共重合 体などが挙げられ、これらの中でも、アルキル (メタ）アタリレートの単独重合体又は共 重合体、ポリスチレンなどが好ましい。本発明において、これらのオリゴマーは、置換 基で置換されていてもよぐ該置換基としては、特に制限はないが、例えば、ハロゲン 原子などが挙げられる。 [0175] The oligomer generally includes, for example, alkyl (meth) acrylate, hydroxy. Cialkyl (meth) acrylate, styrene, acrylonitrile, butyl acetate, and butagen force At least one selected monomer force A homopolymer or a copolymer formed, and among them, alkyl (meth) acrylate Preferred are rate homopolymers or copolymers, polystyrene and the like. In the present invention, these oligomers which may be substituted with a substituent are not particularly limited, and examples thereof include a halogen atom.
[0176] 前記エチレン性不飽和二重結合を有する基としては、例えば、（メタ)アタリロイル基 、ビュル基、などが好適に挙げられ、これらの中でも (メタ）アタリロイル基が特に好ま しい。  [0176] Preferred examples of the group having an ethylenically unsaturated double bond include a (meth) atalyloyl group, a bure group, and the like, and among these, a (meth) atalyloyl group is particularly preferred.
[0177] 本発明においては、前記重合性オリゴマーの中でも、下記一般式 (E6)で表される オリゴマーが好ましい。  In the present invention, among the polymerizable oligomers, an oligomer represented by the following general formula (E6) is preferable.
[0178] [化 56]  [0178] [Chemical 56]
—般式 （E 6 )—General formula (E 6)
Figure imgf000070_0001
Figure imgf000070_0001
[0179] 前記一般式 (E6)において、 R61及び R63は、水素原子又はメチル基を表す。 R62は 、炭素数 1〜8のアルコール性水酸基で置換されてもよいアルキレン基を表し、炭素 数 2〜4のアルキレン基が好ましい。 Y6は、フエ-ル基、炭素数 1〜4のアルキル基を 有するフエ-ル基、又は— COOR64 (ここで、 R64は、炭素数 1〜6のアルコール性水 酸基、ハロゲンで置換されてもよいアルキル基、フエ-ル基、又は炭素数 7〜 10のァ リールアルキル基を表す。）を表し、フエ-ル基又は— COOR64 (ここで、 R64は、炭素 数 1〜4のアルコール性水酸基で置換されてもよいアルキル基を表す。）が好ましい。 qは、 20〜200を表す。 In the general formula (E6), R 61 and R 63 represent a hydrogen atom or a methyl group. R 62 represents an alkylene group which may be substituted with an alcoholic hydroxyl group having 1 to 8 carbon atoms, and an alkylene group having 2 to 4 carbon atoms is preferable. Y 6 is a phenyl group, a phenyl group having an alkyl group having 1 to 4 carbon atoms, or —COOR 64 (where R 64 is an alcoholic hydroxyl group having 1 to 6 carbon atoms, halogen, Represents an optionally substituted alkyl group, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms.), A phenyl group or —COOR 64 (where R 64 is a carbon number of 1). Represents an alkyl group which may be substituted with ~ 4 alcoholic hydroxyl groups). q represents 20-200.
[0180] 前記重合性オリゴマーの具体例としては、ポリ― 2ヒドロキシェチル (メタ)アタリレー ト、ポリスチレン、ポリメチル (メタ）アタリレート、ポリ一 n—ブチル (メタ）アタリレート、ポ リ— i ブチル (メタ)アタリレート、それらの共重合体であって、分子末端の一個に (メ タ）アタリロイル基が結合したポリマーが好まし 、。  [0180] Specific examples of the polymerizable oligomer include poly-2-hydroxyethyl (meth) atrelate, polystyrene, polymethyl (meth) acrylate, poly n-butyl (meth) acrylate, poly i butyl. A (meth) acrylate, a copolymer thereof, and a polymer in which a (meth) taliloyl group is bonded to one of the molecular terminals is preferred.
[0181] 前記重合性オリゴマーは、市販品であってもよいし、適宜合成したものであってもよ ぐ該市販品としては、例えば、片末端メタタリロイルイ匕ポリスチレンオリゴマー（Mn= 6000、商品名： AS— 6,東亜合成化学工業 (株)社製)、片末端メタタリロイルイ匕ポリ メチルメタタリレートオリゴマー（Mn= 6000、商品名： AA—6,東亜合成化学工業（ 株)社製）、片末端メタクリロイル化ポリ n ブチルアタリレートオリゴマー（Mn = 60 00、商品名： AB— 6,東亜合成化学工業 (株)社製)、片末端メタタリロイルイ匕ポリメチ ノレメタタリレート /2 ヒドロキシェチノレメタタリレートオリゴマー（Mn= 7000、商品名 ： AA- 714,東亜合成化学工業 (株)社製)、片末端メタタリロイルイ匕ポリプチルメタク リレート /2 ヒドロキシェチノレメタタリレートオリゴマー（Mn= 7000、商品名： 707S ,東亜合成化学工業 (株)社製)、片末端メタタリロイルイ匕ポリ 2—ェチルへキシルメタ タリレート /2 ヒドロキシェチノレメタタリレートオリゴマー（Mn= 7000、商品名： AY — 707S、 AY- 714S,東亜合成化学工業 (株)社製)、などが挙げられる。 [0181] The polymerizable oligomer may be a commercially available product or an appropriately synthesized one. Examples of commercially available products include, for example, one-end metatalloy roy polystyrene styrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toa Gosei Chemical Co., Ltd.), one-end metataryl roy potato polymethyl metatalylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Industry Co., Ltd., one-terminal methacryloylated poly n butyl acrylate oligomer (Mn = 600,0, trade name: AB— 6, Toa Gosei Chemical Co., Ltd. )), One-end metatarery roy Louis チ polymethenoremetatalylate / 2 hydroxy ethenoremetatalylate oligomer (Mn = 7000, trade name: AA-714, manufactured by Toa Gosei Chemical Co., Ltd.) Polymethyl methacrylate / 2 Hydroxy ethenore methacrylate oligomer (Mn = 7000, trade name: 707S, manufactured by Toa Gosei Chemical Co., Ltd.) To Kishirumeta Tarireto / 2-hydroxy-E Chino Leme Tatari rate oligomer (Mn = 7000, trade name: AY - 707S, AY- 714S, manufactured by Toa Synthetic Chemical Industry Co., Ltd.), and the like.
[0182] 本発明における前記重合性オリゴマーの好ま 、具体例としては、アルキル (メタ） アタリレートの重合体、及び、アルキル (メタ）アタリレートとポリスチレンとの共重合体 力 選択される少なくとも 1種のオリゴマーであって、数平均分子量が 1000〜20000 であり、末端に (メタ)アタリロイル基を有するものが挙げられる。  [0182] Preferred examples of the polymerizable oligomer in the present invention include, as specific examples, polymers of alkyl (meth) acrylate and copolymers of alkyl (meth) acrylate and polystyrene. And those having a number average molecular weight of 1000 to 20000 and having a (meth) atallyloyl group at the terminal.
[0183] (ii) アミノ基含有モノマー  [0183] (ii) Amino group-containing monomer
前記アミノ基含有モノマーとしては、例えば、下記一般式 (E2)で表される化合物よ り選択される少なくとも 1種が好適に挙げられる。  Suitable examples of the amino group-containing monomer include at least one selected from compounds represented by the following general formula (E2).
[0184] [化 57] —般式 （ E 2 ) [0184] [Chemical formula 57] — General formula (E 2)
Figure imgf000071_0001
Figure imgf000071_0001
[0185] 前記一般式 (E2)において、 R21は、水素原子又はメチル基を表す。 R22は、炭素数 1〜8のアルキレン基を表し、これらの中でも、炭素数 1〜6のアルキレン基が好ましく 、炭素数 2〜3のアルキレン基が特に好ましい。 In the general formula (E2), R 21 represents a hydrogen atom or a methyl group. R 22 represents an alkylene group having 1 to 8 carbon atoms, and among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable.
[0186] X2は、 N (R23) (R24)、 一 R25N (R26) (R27)を表す。ここで、 R23及び R24は、水素 原子、炭素数 1〜6のアルキル基又はフエ-ル基を表す。 R25は、炭素数 1〜6のアル キレン基を表し、 R26及び R27は、水素原子、炭素数 1〜6のアルキル基又はフエニル 基を表す。 X 2 represents N (R 23 ) (R 24 ), and one R 25 N (R 26 ) (R 27 ). Here, R 23 and R 24 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. R 25 represents an alkylene group having 1 to 6 carbon atoms, and R 26 and R 27 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or phenyl. Represents a group.
[0187] 上記のうち、— N (R23) (R24)の R23及び R24は、水素原子又は炭素数 1〜4のアルキ ル基若しくはフエ-ル基が好ましぐ -R25-N (R26) (R27)の R25は、炭素数 2〜6の アルキレン基が好ましぐ R26及び R27は、炭素数 1〜4のアルキル基が好ましい。 m2 及び n2は、 1又は 0を表し、 m2= lかつ n2= l、又は、 m2= 1かつ n2 = 0が好まし い（即ち、下記一般式 (E3)、 （E4)で表されるモノマーに対応する）。 [0187] Among the above, - N (R 23) R 23 and R 24 of (R 24) is a hydrogen atom or 1 to 4 carbon atoms alkyl Le group or Hue - Le group preferably tool -R 25 - R 25 of N (R 26 ) (R 27 ) is preferably an alkylene group having 2 to 6 carbon atoms. R 26 and R 27 are preferably an alkyl group having 1 to 4 carbon atoms. m2 and n2 represent 1 or 0, and m2 = l and n2 = 1, or m2 = 1 and n2 = 0 are preferred (that is, monomers represented by the following general formulas (E3) and (E4) Corresponding to).
[0188] 本発明においては、前記一般式 (E2)で表されるモノマーの中でも、下記一般式（ E3)及び (E4)の 、ずれかで表されるモノマー力 選択される少なくとも 1種が好まし い。  [0188] In the present invention, among the monomers represented by the general formula (E2), at least one selected from the following general formulas (E3) and (E4) having a monomer power represented by a shift is preferred. Good.
[0189] [化 58]  [0189] [Chemical 58]
—般式 （E 3 )—General formula (E 3)
Figure imgf000072_0001
Figure imgf000072_0001
[0190] 前記一般式 (Ε3)において、 R31は、 R21と同義である。 R32は、 R22と同義である。 X3 は、 X2と同義である。 In the general formula (一般 3), R 31 has the same meaning as R 21 . R 32 is synonymous with R 22 . X 3 is synonymous with X 2 .
[0191] [化 59] [0191] [Chemical 59]
一般式 （E 4 )General formula (E 4)
Figure imgf000072_0002
Figure imgf000072_0002
[0192] 前記一般式 (E4)において、 R41は、 R21と同義である。 X4は、 X2と同義であり、— N In the general formula (E4), R 41 has the same meaning as R 21 . X 4 is synonymous with X 2 — N
(R43) (R44) (ここで、 R43及び R44は、 R23及び R24と同義である。）、又は、 -R45-N ( R46) (R47) (ここで、 R45、 R46及び R47は、それぞれ 5、 R26及び R27と同義である。 )が 好ましい。 (R 43 ) (R 44 ) (where R 43 and R 44 are synonymous with R 23 and R 24 ), or -R 45 -N (R 46 ) (R 47 ) (where R 45 , R 46 and R 47 are synonymous with 5 , R 26 and R 27 , respectively.
[0193] 前記一般式 (E2)で表されるモノマーの具体例としては、ジメチル (メタ)アクリルアミ ド、ジェチル (メタ）アクリルアミド、ジイソプロピル (メタ）アクリルアミド、ジー n—ブチル (メタ）アクリルアミド、ジ— i—ブチル (メタ）アクリルアミド、モルホリノ (メタ）アクリルアミ ド、ピペリジノ (メタ）アクリルアミド、 N—メチル—2—ピロリジル (メタ）アクリルアミド及 び N, N—メチルフエ-ル (メタ）アクリルアミド（以上 (メタ）アクリルアミド類）；2— (N, N ジメチルァミノ）ェチル (メタ）アクリルアミド、 2- (N, N ジェチルァミノ）ェチル（ メタ）アクリルアミド、 3— (N, N ジェチルァミノ）プロピル (メタ）アクリルアミド、 3— ( N, N ジメチルァミノ）プロピル (メタ）アクリルアミド、 1— (N, N ジメチルァミノ）— 1 , 1ージメチルメチル (メタ）アクリルアミド、 6—（N, N ジェチルァミノ）へキシル (メタ )アクリルアミド (以上アミノアルキル (メタ)アクリルアミド類)などが好まし!/、ものとして 挙げられる。 [0193] Specific examples of the monomer represented by the general formula (E2) include dimethyl (meth) acrylamide, jetyl (meth) acrylamide, diisopropyl (meth) acrylamide, di-n-butyl (meth) acrylamide, di- — I-butyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and N, N-methylphenol (meth) acrylamide (above ( (Meth) acrylamides); 2— (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-demethylamino) ethyl (meth) acrylamide, 3 -— (N, N-demethylamino) propyl (meth) acrylamide, 3 -— (N, N-dimethylamino) propyl (meth) acrylamide 1- (N, N dimethylamino) — 1,1-dimethylmethyl (meth) acrylamide, 6- (N, N dimethylamino) hexyl (meth) acrylamide (above aminoalkyl (meth) acrylamides) are preferred! /, Can be cited as
[0194] (iii) エーテル基を有する重合性モノマー  [0194] (iii) A polymerizable monomer having an ether group
前記エーテル基を有する重合性モノマーとしては、例えば、下記一般式 (E 1)で表 されるモノマーより選択される少なくとも 1種が好適に挙げられる。 Suitable examples of the polymerizable monomer having an ether group include at least one selected from monomers represented by the following general formula ( E 1 ).
[0195] [化 60] —般式 （ E 1 )[0195] [Chemical Formula 60] — General Formula (E 1)
Figure imgf000073_0001
Figure imgf000073_0001
[0196] 前記一般式 (El)において、 R11は、水素原子又はメチル基を表す。 R12は、炭素数 1〜8のアルキレン基を表し、中でも、炭素数 1〜6のアルキレン基が好ましぐ炭素数 2〜3のアルキレン基がより好ましい。 X1は、 OR13又は一 OCOR14を表す。ここで、 R13は、水素原子、炭素数 1〜18のアルキル基、フエ-ル基、又は炭素数 1〜18のァ ルキル基で置換されたフエ二ル基を表す。 R14は、炭素数 1〜18のアルキル基を表 す。また、 m3iま、 2〜200を表し、 5〜： L00力好ましく、 10〜： L00力 ^特に好まし!/、。 In the general formula (El), R 11 represents a hydrogen atom or a methyl group. R 12 represents an alkylene group having 1 to 8 carbon atoms, and among them, an alkylene group having 2 to 3 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, is more preferable. X 1 represents OR 13 or one OCOR 14 . Here, R 13 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenol group, or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms. R 14 represents an alkyl group having 1 to 18 carbon atoms. Also, m3i represents 2 to 200, 5 ~: L00 force preferred, 10 ~: L00 force ^ Especially preferred! / ,.
[0197] 前記エーテル基を有する重合性モノマーとしては、エーテル基を有し、且つ重合性 のものであれば特に制限はなぐ通常のものの中力も適宜選択することができ、例え ば、ポリエチレングリコールモノ（メタ）アタリレート、ポリプロピレングリコールモノ（メタ） アタリレート、ポリエチレングリコールポリプロピレングリコールモノ（メタ）アタリレート、 ポリテトラメチレングリコールモノメタタリレートなどが挙げられ、これらは市販品であつ てもよいし、適宜合成したものであってもよい。該市販品としては、メトキシポリエチレ ングリコールメタタリレート（商品名： NKエステル M— 40G, M- 90G, M— 230G ( 以上、東亜合成化学工業 (株)社製）；商品名：ブレンマー PME— 100, PME- 200 , PME-400, PME- 1000, PME— 2000、 PME— 4000 (以上、 曰本油脂（株） 社製））、ポリエチレングリコールモノメタタリレート（商品名：ブレンマー PE— 90、 PE 200、 PE- 350, 日本油脂 (株)社製）、ポリプロピレングリコールモノメタタリレート (商品名：ブレンマー PP— 500、 PP— 800、 PP— 1000, 日本油脂（株）社製）、ポリ エチレングリコールポリプロピレングリコールモノメタタリレート（商品名：ブレンマー 70 PEP- 370B, 日本油脂 (株)社製）、ポリエチレングリコールポリテトラメチレングリコ ールモノメタタリレート（商品名：ブレンマー 55PET— 800, 日本油脂（株）社製）、ポ リプロピレングリコールポリテトラメチレングリコールモノメタタリレート（商品名：ブレン マー NHK— 5050, 日本油脂 (株)社製)などが挙げられる。 [0197] The polymerizable monomer having an ether group can be appropriately selected from the usual intermediate forces that are not particularly limited as long as they have an ether group and are polymerizable. (Meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polytetramethylene glycol monomethacrylate, etc., these may be commercially available products, It may be appropriately synthesized. The commercially available products include methoxypolyethylene glycol metatalylate (trade names: NK ester M-40G, M-90G, M-230G (above, manufactured by Toa Gosei Chemical Co., Ltd.); trade name: BLEMMER PME— 100, PME-200, PME-400, PME-1000, PME—2000, PME—4000 (Enomoto Yushi Co., Ltd.) Polyethylene glycol monometatalylate (trade name: Blemmer PE-90, PE 200, PE-350, manufactured by Nippon Oil & Fats Co., Ltd.), polypropylene glycol monometatalylate (trade name: Blemmer PP-500) , PP-800, PP-1000, manufactured by Nippon Oil & Fats Co., Ltd.), Polyethylene Glycol Polypropylene Glycol Monometatalylate (Brandmer 70 PEP-370B, manufactured by Nippon Oil & Fats Co., Ltd.), polyethylene glycol polytetra Methylene glycol monometatalylate (trade name: Blenmer 55PET-800, manufactured by Nippon Oil & Fats Co., Ltd.), Polypropylene glycol polytetramethylene glycol monometatalylate (trade name: Blenmer NHK-5050, Nippon Oil & Fats ( Etc.).
[0198] (iv) その他のモノマー [0198] (iv) Other monomers
前記グラフト共重合体は、前記その他のモノマーを更に共重合体単位として含有し ていてもよぐ該その他のモノマーとしては、特に制限はなぐ 目的に応じて適宜選択 することができるが、例えば、芳香族ビ-ルイ匕合物（例、スチレン、 a—メチルスチレ ン及びビュルトルエン）、（メタ）アクリル酸アルキルエステル（例、メチル (メタ）アタリレ ート、ェチル (メタ）アタリレート、 n—ブチル (メタ）アタリレート及び i—ブチル (メタ）ァク リレート）、（メタ）アクリル酸アルキルァリールエステル（例、ベンジル (メタ）アタリレート )、グリシジル（メタ）アタリレート、カルボン酸ビュルエステル（例、酢酸ビュル及びプロ ピオン酸ビュル）、シアン化ビュル（例、（メタ）アクリロニトリル及びひ クロロアタリ口- トリル)、及び脂肪族共役ジェン (例、 1, 3 ブタジエン及びイソプレン)、（メタ)アタリ ル酸、などが挙げられる。これらの中でも、不飽和カルボン酸、（メタ）アクリル酸アル キルエステル、（メタ）アクリル酸アルキルァリールエステル及びカルボン酸ビュルエス テルが好ましい。  The graft copolymer may further contain the other monomer as a copolymer unit, and the other monomer may be appropriately selected according to the purpose without any particular limitation. Aromatic vinyl compounds (eg, styrene, a-methylstyrene and butyltoluene), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate and i-butyl (meth) acrylate), (meth) acrylate alkyl aryl ester (eg, benzyl (meth) acrylate), glycidyl (meth) acrylate, carboxylate butyl ester (eg Butyl acetate and propionate), cyanide butyl (eg, (meth) acrylonitrile and chloroformate trityl), Fine aliphatic conjugated diene (e.g., 1, 3-butadiene and isoprene), (meth) Atari le acid, and the like. Among these, unsaturated carboxylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid alkyl aryl ester, and carboxylic acid bull ester are preferable.
[0199] 前記グラフト共重合体における該その他のモノマーの含有量としては、例えば、 5〜  [0199] The content of the other monomer in the graft copolymer is, for example, 5 to
70質量％が好ましい。前記含有率が、 5質量％未満であると、塗布膜の物性の制御 ができなくなることがあり、 70質量％を超えると、分散剤としての能力が十分に発揮さ れないことがある。  70% by mass is preferred. When the content is less than 5% by mass, the physical properties of the coating film may not be controlled. When the content exceeds 70% by mass, the ability as a dispersant may not be sufficiently exhibited.
[0200] 前記グラフト共重合体の好ま 、具体例としては、  [0200] Preferred examples of the graft copolymer include:
(11) 3—(N, N ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールモ ノ (メタ)アタリレート Z末端メタタリロイルイ匕ポリメチル (メタ)アタリレート共重合体、 (12) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールモ ノ (メタ)アタリレート Z末端メタクリロイルイ匕ポリスチレン共重合体、 (11) 3— (N, N dimethylamino) propylacrylamide Z polyethylene glycol mono (meth) atalylate Z-terminal metatalloy leucopolymethyl (meth) atalylate copolymer, (12) 3- (N, N-dimethylamino) propyl acrylamide Z polyethylene glycol mono (meth) atarylate Z-terminal methacryloyl-polystyrene copolymer,
[0201] (13) 3— (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールモ ノ (メタ)アタリレート Zメチル (メタ)アタリレート末端メタタリロイルイ匕ポリスチレン共重合 体、 [0201] (13) 3— (N, N-dimethylamino) propyl acrylamide Z polyethylene glycol mono (meth) atalylate Z methyl (meth) acrylate terminal-terminated metatalloy Louis polystyrene copolymer,
(14) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールモ ノ (メタ)アタリレート Z末端メタクリロイル化メチル (メタ)アタリレート及び 2—ヒドロキシ ェチルメタタリレートの共重合体の共重合体、  (14) 3- (N, N-Dimethylamino) propylacrylamide Z Polyethylene glycol mono (meth) atalylate Copolymer of copolymer of Z-terminal methacryloylated methyl (meth) acrylate and 2-hydroxyethyl methacrylate Coalescence,
(15) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールモ ノ (メタ)アタリレート/末端メタクリロイル化メチルメタアタリレート及び 2—ヒドロキシェ チルメタタリレートの共重合体の共重合体、  (15) a copolymer of 3- (N, N-dimethylamino) propylacrylamide Z polyethylene glycol mono (meth) atalylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate
(16) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールモ ノ (メタ)アタリレート/末端メタクリロイル化メチルメタアタリレート及び 2—ヒドロキシェ チルメタタリレートの共重合体の共重合体、  (16) 3- (N, N-dimethylamino) propylacrylamide Z polyethylene glycol mono (meth) atalylate / terminated methacryloylated methyl methacrylate and 2-hydroxyethyl methacrylate copolymer
[0202] (17) 3— (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリプロピレングリコール モノ (メタ）アタリレート Z末端メタクロィルイ匕ポリメチル (メタ)アタリレート共重合体、 [0202] (17) 3— (N, N-dimethylamino) propylacrylamide Z polypropylene glycol mono (meth) acrylate, Z-terminal metachloro 匕 polymethyl (meth) acrylate copolymer,
(18) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールポ リプロピレングリコールモノ (メタ）アタリレート/末端メタクロィルイ匕ポリメチル (メタ)ァク リレート共重合体、 (18) 3- (N, N-dimethylamino) propylacrylamide Z polyethylene glycol polypropylene glycol mono (meth) acrylate / terminated methacryloyl polymethyl (meth) acrylate copolymer,
(19) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリエチレングリコールポ リテトラメチレングリコールモノ (メタ)アタリレート Z末端メタクロィルイ匕ポリメチル (メタ） アタリレート共重合体、  (19) 3- (N, N-dimethylamino) propyl acrylamide Z polyethylene glycol polytetramethylene glycol mono (meth) atarylate Z-terminal metachlorine 匕 polymethyl (meth) acrylate copolymer,
(20) 3- (N, N—ジメチルァミノ）プロピルアクリルアミド Zポリプロピレングリコール ポリテトラメチレングリコールモノ (メタ)アタリレート Z末端メタクロィルイ匕ポリメチル (メ タ）アタリレート共重合体、などが挙げられる。  (20) 3- (N, N-dimethylamino) propylacrylamide Z polypropylene glycol polytetramethylene glycol mono (meth) acrylate The Z-terminal metachlorine 匕 polymethyl (meth) acrylate copolymer.
なかでも、（11)、（14)、（18)が好ましぐ下記式 (D4)で表される化合物がより好ま しい。式（D4)中、 Meはメチル基を表す。  Of these, compounds represented by the following formula (D4), in which (11), (14), and (18) are preferred, are more preferred. In formula (D4), Me represents a methyl group.
[0203] [化 61]
Figure imgf000076_0001
[0203] [Chemical 61]
Figure imgf000076_0001
[0204] 前記グラフト共重合体は、前記各共重合体単位となる成分を、例えば、溶媒中でラ ジカル重合させることにより得ることができる。該ラジカル重合の際、ラジカル重合開 始剤を使用することができ、また、更に連鎖移動剤（例、 2—メルカプトエタノール及 びドデシルメルカブタン)を使用することができる。グラフト共重合体を含有する顔料 分散剤については特開 2001— 31885号公報の記載を参考にすることもできる。 [0204] The graft copolymer can be obtained by, for example, performing radical polymerization of the components to be the respective copolymer units in a solvent. In the radical polymerization, a radical polymerization initiator can be used, and a chain transfer agent (eg, 2-mercaptoethanol and dodecyl mercaptan) can be further used. JP-A-2001-31885 can also be referred to for the pigment dispersant containing the graft copolymer.
[0205] 分散剤の含有量は、顔料粒子の均一分散性および保存安定性をより一層向上さ せるために、顔料 100質量部に対して 0. 1〜： L000質量部の範囲であることが好まし ぐより好ましくは 1〜500質量部の範囲であり、さらに好ましくは 5〜20質量部の範 囲である。 0. 1質量部未満であると有機ナノ粒子の分散安定性の向上が見られない 場合がある。また、分散剤は、単独で用いても、複数のものを組み合わせて用いても よい。 [0205] The content of the dispersant may be in the range of 0.1 to L000 parts by mass with respect to 100 parts by mass of the pigment in order to further improve the uniform dispersibility and storage stability of the pigment particles. More preferably, it is in the range of 1 to 500 parts by mass, and still more preferably in the range of 5 to 20 parts by mass. If the amount is less than 1 part by mass, the dispersion stability of the organic nanoparticles may not be improved. Moreover, a dispersing agent may be used independently or may be used in combination of multiple things.
[0206] [有機粒子形成時の条件]  [0206] [Conditions for forming organic particles]
本発明の有機粒子は、有機材料を良溶媒に溶解した有機材料溶液と、有機材料 に対する貧溶媒 (以下、単に「有機粒子の貧溶媒」ともいう。）とを混合して有機粒子 を得る工程を経て形成される（以下、この方法を「有機粒子析出法」ともいい、これに より得られた有機粒子液を「有機粒子分散液」 ヽぅ。 )。  The organic particle of the present invention is a step of obtaining an organic particle by mixing an organic material solution obtained by dissolving an organic material in a good solvent and a poor solvent for the organic material (hereinafter also simply referred to as “poor solvent for organic particles”). (Hereinafter, this method is also referred to as “organic particle precipitation method”, and the organic particle liquid obtained by this method is referred to as “organic particle dispersion”).
有機材料を有機粒子として生成させる際の条件に特に制限はなぐ常圧力も亜臨 界、超臨界条件の範囲を選択できる。常圧での温度は— 30〜100°Cが好ましぐ - 10〜60°Cがより好ましぐ 0〜30°Cが特に好ましい。  There are no particular restrictions on the conditions for generating organic materials as organic particles, and the normal pressure can be selected from the subcritical and supercritical conditions. The temperature at normal pressure is preferably −30 to 100 ° C. −10 to 60 ° C. is more preferable, and 0 to 30 ° C. is particularly preferable.
有機材料溶液と貧溶媒との混合方法に特に制約はな ヽが、一方を撹拌しておき、 そこに他方を添加することが好ましぐ有機材料溶液を撹拌された貧溶媒に添加する ことが特に好ましい。添加にはポンプ等を用いることもできるし、用いなくてもよい。ま た、液中添加でも液外添加でもよいが、液中添加がより好ましい。液中添カ卩の際の添 加口は 1つでもよいし、複数用いてもよい。添カ卩口径は 20mm以下であることが好ま しぐ 10mm以下であることがより好ましい。 Although there is no particular limitation on the method of mixing the organic material solution and the poor solvent, it is preferable to add one organic material solution to the stirred poor solvent. Particularly preferred. A pump or the like may be used for the addition, or it may not be used. Further, it may be added in the liquid or outside the liquid, but the addition in the liquid is more preferable. One or more addition ports may be used for the submerged addition. It is preferable that the accessory diameter is 20 mm or less. More preferably, it is 10 mm or less.
一方を撹拌する際の撹拌速度は 100〜10000rpmが好ましく 150〜8000rpmが より好ましく、 200〜6000rpm力特に好まし!/ヽ。  The stirring speed when stirring one is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm.
有機材料溶液と貧溶媒の比（良溶媒 Z貧溶媒)は体積比で 1Z50〜2Z3が好まし く、 1Z40〜： LZ2がより好ましぐ 1Z20〜3Z8が特に好ましい。  The ratio of the organic material solution to the poor solvent (good solvent Z poor solvent) is preferably 1Z50 to 2Z3 by volume ratio, 1Z40 to: LZ2 is more preferred, and 1Z20 to 3Z8 is particularly preferred.
有機粒子として調製したのちの分散液の濃度は有機粒子を分散させることができ れば特に制限されないが、分散溶媒 1000mlに対して粒子力 l0〜40000mgの範 囲であることが好ましぐより好ましくは 20〜30000mgの範囲であり、特に好ましくは 50〜25000mgの範囲である。  The concentration of the dispersion liquid prepared as organic particles is not particularly limited as long as the organic particles can be dispersed, but it is more preferable that the particle force is in the range of 10 to 40,000 mg per 1000 ml of the dispersion solvent. Is in the range of 20-30000 mg, particularly preferably in the range of 50-25000 mg.
[0207] [超臨界流体を用いた有機粒子の析出時の条件] [0207] [Conditions for deposition of organic particles using supercritical fluid]
次に、有機顔料含有流体と析出溶媒とを混合するときの条件について説明する。 本発明の製造方法において、有機顔料含有流体と析出溶媒とを混合するときの条 件は特に限定されないが、有機顔料含有流体を超臨界状態もしくは亜臨界流体状 態でな 、状態として顔料の溶解度を下げ、顔料を析出させる条件であることが好まし い。具体的には、混合時の温度は、用いる溶媒の超臨界温度より低くすることが好ま しい。例えば、アセトンを用いる場合、 15°C〜180°Cの範囲とすることが好ましぐ 40 °C〜180°Cとすることがより好ましぐ 60°C〜150°Cとすることが特に好ましい。  Next, conditions for mixing the organic pigment-containing fluid and the precipitation solvent will be described. In the production method of the present invention, the conditions when the organic pigment-containing fluid and the precipitation solvent are mixed are not particularly limited, but the solubility of the pigment as the state is not the organic pigment-containing fluid in a supercritical state or subcritical fluid state. It is preferable that the conditions are such that the pigment is precipitated and the pigment is precipitated. Specifically, the mixing temperature is preferably lower than the supercritical temperature of the solvent used. For example, when using acetone, it is preferable to set the temperature within the range of 15 ° C to 180 ° C, more preferably 40 ° C to 180 ° C, and particularly preferably 60 ° C to 150 ° C. preferable.
混合時の圧力は、用いる溶媒の超臨界圧付近または超臨界圧以上の圧力とするこ とが好ましい。例えば、溶媒としてアセトンを用いる場合、圧力を 2〜30MPaとするこ と力 子ましく、 3〜25MPaとすることがより好ましぐ 4〜20MPaとすることが特に好ま しい。ただし装置の構成によって、装置内の圧力が一定のため任意に調製すること はできない場合もあり、圧力一定条件としてもよい。  The pressure at the time of mixing is preferably near the supercritical pressure of the solvent to be used or higher than the supercritical pressure. For example, when acetone is used as the solvent, the pressure is preferably 2 to 30 MPa, more preferably 3 to 25 MPa, and particularly preferably 4 to 20 MPa. However, depending on the configuration of the device, it may not be possible to adjust the pressure inside the device because it is constant.
[0208] 有機顔料含有流体と析出溶媒との混合比は体積比で 20: 1〜1 : 20が好ましぐ 10 ： 1〜1： 10がより好ましぐ 5 : 1〜1： 5が特に好ましい。 [0208] The mixing ratio between the organic pigment-containing fluid and the precipitation solvent is preferably 20: 1 to 1:20, more preferably 10: 1 to 1:10, and more preferably 5: 1 to 1: 5. preferable.
有機顔料を析出させた混合液の粒子濃度は特に限定されないが、 0. 01〜500m gZmlの範囲であることが好ましぐより好ましくは 0. 1〜： LOOmgZmlの範囲であり、 特に好ましくは 0. 5〜： LOmgZmlの範囲である。  The particle concentration of the mixed liquid in which the organic pigment is precipitated is not particularly limited, but is preferably in the range of 0.01 to 500 mgZml, more preferably 0.1 to: in the range of LOOmgZml, particularly preferably 0. 5 ~: It is in the range of LOmgZml.
[0209] 本発明の製造方法にお!、て、有機顔料を溶解するために超臨界流体もしくは亜臨 界流体を用いる場合には、常温 ·常圧での溶解とは異なる性質を示す。例えば、顔 料など難溶性材料を溶解する能力が高まる。このような性質を活かすことにより、析出 現象を利用して、これまで顔料を溶解する好ましい良溶媒がなぐその溶解が困難で あった難溶性の材料であってもナノ粒子化が可能となる。また、アセトンや水のように 安価で環境負荷が小さ 、溶媒を用いてナノ粒子を調製できると!、う利点を有する。 [0209] In the production method of the present invention, in order to dissolve the organic pigment, a supercritical fluid or When using a field fluid, it exhibits different properties from melting at room temperature and pressure. For example, the ability to dissolve poorly soluble materials such as facial materials is enhanced. By taking advantage of such properties, it is possible to make nanoparticles even by using a precipitation phenomenon, even if it is a hardly soluble material that has been difficult to dissolve, because there is a good solvent that dissolves the pigment. In addition, it is inexpensive and has a low environmental impact, such as acetone and water, and has the advantage that nanoparticles can be prepared using a solvent.
[0210] [有機粒子の粒径、単分散性]  [0210] [Particle size and monodispersity of organic particles]
有機粒子の粒径に関しては、計測法により数値ィ匕して集団の平均の大きさを表現 する方法があるが、よく使用されるものとして、分布の最大値を示すモード径、積分分 布曲線の中央値に相当するメジアン径、各種の平均径 (数平均、長さ平均、面積平 均、質量平均、体積平均等)などがあり、本発明においては、特に断りのない限り、粒 径とは数平均径をいう。本発明の有機粒子の濃縮方法に用いられる有機粒子分散 液に含まれる有機粒子（一次粒子）の平均粒径はナノメートルサイズであり、該粒径 は 1ηπι〜1 /ζ πιであることが好ましぐ l〜200nmであることがより好ましぐ 2〜： LOOn mであることがさらに好ましぐ 5〜80nmであることが特に好ましい。なお本発明の製 造方法において、形成される粒子は結晶質粒子でも非結晶質粒子でもよぐまたこれ らの混合物でもよい。  Regarding the particle size of organic particles, there is a method of expressing the average size of the population by numerical values by measurement methods, but as a common method, the mode diameter indicating the maximum value of distribution, the integral distribution curve Median diameter corresponding to the median value of each other, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. in the present invention, unless otherwise specified. Means the number average diameter. The average particle size of the organic particles (primary particles) contained in the organic particle dispersion used in the organic particle concentration method of the present invention is nanometer size, and the particle size is preferably 1ηπι to 1 / ζ πι. More preferably, it is 1 to 200 nm. 2-: It is particularly preferable that LOOnm is 5 to 80 nm. In the production method of the present invention, the formed particles may be crystalline particles, non-crystalline particles, or a mixture thereof.
また、粒子の単分散性を表す指標として、本発明においては、特に断りのない限り 、体積平均粒径 (Mv)と数平均粒径 (Μη)の比（ΜνΖΜη)を用いる。本発明の有機 粒子の濃縮方法に用いられる有機粒子分散液に含まれる粒子 (一次粒子)の単分散 性、つまり Μν/Μηは、 1.0〜2.0であることが好ましぐ 1.0〜 1.8であることがより好ま しぐ 1.0〜1.5であることが特に好ましい。  Further, in the present invention, the ratio (ΜνΖΜη) of the volume average particle size (Mv) and the number average particle size (Μη) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of particles (primary particles) contained in the organic particle dispersion used in the organic particle concentration method of the present invention, that is, Μν / Μη is preferably 1.0 to 2.0, and preferably 1.0 to 1.8. Is more preferably 1.0 to 1.5.
有機粒子の粒径の測定方法としては、顕微鏡法、質量法、光散乱法、光遮断法、 電気抵抗法、音響法、動的光散乱法が挙げられ、顕微鏡法、動的光散乱法が特に 好ましい。顕微鏡法に用いられる顕微鏡としては、例えば、走査型電子顕微鏡、透過 型電子顕微鏡などが挙げられる。動的光散乱法による粒子測定装置として、例えば 、 日機装社製ナノトラック UPA— ΕΧ150、大塚電子社製ダイナミック光散乱光度計 DLS— 7000シリーズなどが挙げられる。  Methods for measuring the particle size of organic particles include microscopy, mass method, light scattering method, light blocking method, electrical resistance method, acoustic method, and dynamic light scattering method. Particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus by the dynamic light scattering method include Nikkiso Co., Ltd. Nanotrac UPA-150, Otsuka Electronics Co., Ltd. dynamic light scattering photometer DLS-7000 series, and the like.
[0211] [有機粒子形成法 (製造装置) ] 本発明の有機粒子分散組成物の製造の際、有機粒子の形成に用いられる製造装 置の好ましい実施態様を図面を参照して説明するが、これにより本発明が限定的に 解釈されるものではない。 [0211] [Organic Particle Forming Method (Manufacturing Equipment)] In the production of the organic particle dispersion composition of the present invention, a preferred embodiment of the production apparatus used for forming the organic particles will be described with reference to the drawings. However, the present invention is not construed as being limited thereto. Absent.
[0212] (製造装置例 1)  [0212] (Example of manufacturing equipment 1)
図 1 1は本発明にお 、て、一実施態様として用いられる製造装置の概略図である 。図 1 1にお 、て有機材料溶液は供給管 14により容器 11内に設けられた混合室 1 3内へ連続的に供給される。ここに容器 11内には貧溶媒 11aが容れられており、該 混合室 13は貧溶媒の液面下に設けられ、その内部は該貧溶媒により満たされている 。また反応容器 11内のバルタ貧溶媒は該混合室 13内での攪拌の作用により、該混 合室 13内を下方から上方へ（図中矢印の方向へ)横切るようにつねに対流せしめら れている。  FIG. 11 is a schematic view of a production apparatus used as an embodiment in the present invention. In FIG. 11, the organic material solution is continuously supplied from the supply pipe 14 into the mixing chamber 13 provided in the container 11. Here, the container 11 is filled with the poor solvent 11a, the mixing chamber 13 is provided under the surface of the poor solvent, and the inside thereof is filled with the poor solvent. Also, the Balta poor solvent in the reaction vessel 11 is constantly convected across the mixing chamber 13 from below to above (in the direction of the arrow in the figure) by the action of stirring in the mixing chamber 13. Yes.
[0213] 図 1—2は、図 1—1の製造装置の一実施態様として混合室 13を拡大して概略的に 示した拡大部分断面図である。有機材料溶液は供給管 14より混合室 13内へ供給さ れる。該混合室 13は断面積一定の直四角筒よりなるケーシング 17により形成され、 ケーシング 17の上端は開放端とされ、下端には円形孔 18が設けられて該混合器 13 内の貧溶媒がバルタ貧溶媒と互いに連結するようになって 、る。ここに有機材料溶液 供給管 14はケーシング 17の下端を構成する壁内に設けられ、前記円形孔に向けて 開口している。また前記混合器 13内には撹拌羽根 12が設けられており、撹拌羽根 はシャフト 15に取り付けられ、モーター（図示せず）により回転せしめられる。この攪 拌羽根 12の回転により、貧溶媒は円形孔 18を通り混合器 13内を下方力も上方へ向 力つてつねに循環運動せしめられている。  [0213] FIG. 1-2 is an enlarged partial sectional view schematically showing the mixing chamber 13 in an enlarged manner as an embodiment of the manufacturing apparatus of FIG. 1-1. The organic material solution is supplied from the supply pipe 14 into the mixing chamber 13. The mixing chamber 13 is formed by a casing 17 made of a rectangular cylinder having a constant cross-sectional area. The upper end of the casing 17 is an open end, and a circular hole 18 is provided at the lower end so that the poor solvent in the mixer 13 It becomes connected with the poor solvent. Here, the organic material solution supply pipe 14 is provided in a wall constituting the lower end of the casing 17 and opens toward the circular hole. A stirring blade 12 is provided in the mixer 13, and the stirring blade is attached to a shaft 15 and is rotated by a motor (not shown). By the rotation of the stirring blade 12, the poor solvent is constantly circulated through the circular hole 18, and the downward force is always directed upward in the mixer 13.
[0214] 上記の混合室 13に設けられた撹拌羽根 12は、混合室内に所望の混合強さをつく り出すものでなければならない。この混合強さは、有機材料溶液が混入した際の液滴 (ドロップレット）の大きさに対する重要な操作因子であることが推定される。  [0214] The stirring blade 12 provided in the mixing chamber 13 must produce a desired mixing strength in the mixing chamber. This mixing strength is estimated to be an important operating factor for the size of the droplet when the organic material solution is mixed.
また、撹拌羽根 12は、混合空間内で生成した有機粒子が混合室 13にとどまること により、他の有機粒子と結合して更に大きな粒子となったり、混合室 13に供給される 有機材料溶液にさらされて大きな粒子となったりして巨大粒子が生成することがない よう、生成した有機粒子を迅速に引き出し、迅速に混合室 13外へ排出する能力を有 するものが選ばれることが好まし!/、。 In addition, the stirring blades 12 can be combined with other organic particles to form larger particles when the organic particles generated in the mixing space remain in the mixing chamber 13, or to the organic material solution supplied to the mixing chamber 13. It has the ability to quickly draw out the generated organic particles and quickly discharge them out of the mixing chamber 13 so that they do not become large particles when exposed. It is preferable to choose what to do!
撹拌羽根 12としては上記目的が達成されれば、いかなる形式のものでもよぐ例え ばタービン型、ファンタービン型等が用いられうる。  As the stirring blade 12, any type can be used as long as the above object is achieved. For example, a turbine type, a fan turbine type or the like can be used.
またケーシング 17は、前述のごとく四角筒により構成されていることが好ましい。こ のようにすることで、撹拌羽根 12によりつくられた流れをケーシング 17の角が乱し、 邪魔板のごとき付加物を要することなぐ混合効果を一層高めることができる。  The casing 17 is preferably composed of a rectangular tube as described above. By doing so, the corners of the casing 17 disturb the flow created by the stirring blades 12, and the mixing effect without requiring additional products such as baffles can be further enhanced.
[0215] 図 1 3は、図 1 1の製造装置の別の実施態様として混合室内の撹拌羽根を二つ [0215] Figure 13 shows another embodiment of the production apparatus of Figure 11 with two stirring blades in the mixing chamber.
(混合用撹拌羽根 19a、排出用撹拌羽根 19b)にした混合器の拡大部分断面図であ る。このように撹拌羽根を二つ設けることによって、混合強さをコントロールする能力と 、生成した有機粒子を混合器外へ排出する能力を独立に選択することができるように し、混合の強さ、循環量を独立に所望の値に設定して操作することが可能となる。  FIG. 5 is an enlarged partial cross-sectional view of a mixer (mixing stirring blade 19a, discharging stirring blade 19b). By providing two stirring blades in this way, the ability to control the mixing strength and the ability to discharge the generated organic particles out of the mixer can be selected independently. It is possible to operate by setting the circulation amount to a desired value independently.
[0216] (製造装置例 2) [0216] (Manufacturing device example 2)
図 2は、本発明の有機粒子分散組成物の製造方法に用いられる、製造装置の別の 実施態様を概略的に示す断面図である。図 2において有機材料溶液および貧溶媒 はそれぞれ供給管 24a、 24bにより撹拌槽 21a内に連続的に供給される。撹拌槽 21 a内で生成した有機粒子が撹拌槽 21a内にとどまることにより、他の有機粒子と結合し て更に大きな粒子となったり、供給管 24a、 24bより供給される有機材料溶液にさらさ れて大きな粒子となったりして巨大粒子が生成することがないよう、生成した有機粒 子分散液は排出管 23より迅速に引き出される。  FIG. 2 is a cross-sectional view schematically showing another embodiment of the production apparatus used in the method for producing an organic particle dispersion composition of the present invention. In FIG. 2, the organic material solution and the poor solvent are continuously supplied into the stirring tank 21a through the supply pipes 24a and 24b, respectively. The organic particles generated in the stirring tank 21a remain in the stirring tank 21a, so that they are combined with other organic particles to become larger particles or exposed to the organic material solution supplied from the supply pipes 24a and 24b. The generated organic particle dispersion is quickly withdrawn from the discharge pipe 23 so that large particles are not generated due to large particles.
[0217] 図 3は、本発明の有機粒子分散組成物の製造方法に用いられる装置の、さらに別 の実施態様を概略的に示す断面図である。図 3の製造装置においては、撹拌装置 5 0は、有機材料溶液および貧溶媒をそれぞれ流入させる 2つの液供給口 32, 33と撹 拌処理を終えた混合液体を排出する液排出口 36とを備えた円筒状の撹拌槽 38と、 該撹拌槽 38内で回転駆動されることで該撹拌槽 38内の液体の撹拌状態を制御する 撹拌手段である一対の撹拌羽根 41, 42とを備えてなる。 FIG. 3 is a cross-sectional view schematically showing still another embodiment of the apparatus used in the method for producing an organic particle dispersion composition of the present invention. In the production apparatus of FIG. 3, the stirring device 50 includes two liquid supply ports 32 and 33 for allowing the organic material solution and the poor solvent to flow in, and a liquid discharge port 36 for discharging the mixed liquid after the stirring treatment, respectively. A cylindrical stirring tank 38 provided, and a pair of stirring blades 41 and 42 as stirring means for controlling the stirring state of the liquid in the stirring tank 38 by being driven to rotate in the stirring tank 38. Become.
撹拌槽 38は、上下方向に中心軸を向けた円筒状の槽本体 39と、該槽本体 39の上 下の開口端を塞ぐ槽壁となるシールプレート 40とで構成されている。また、撹拌槽 38 および槽本体 39は、透磁性に優れた非磁性材料で形成されている。 2つの液供給 口 32, 33は槽本体 39の下端寄りの位置に装備されており、液排出口 36は槽本体 3 9の上端寄りの位置に装備されている。 The agitation tank 38 includes a cylindrical tank body 39 whose central axis is directed in the vertical direction, and a seal plate 40 serving as a tank wall that closes the upper and lower opening ends of the tank body 39. Further, the agitation tank 38 and the tank body 39 are made of a nonmagnetic material having excellent magnetic permeability. 2 liquid supply The ports 32 and 33 are provided at a position near the lower end of the tank body 39, and the liquid discharge port 36 is provided at a position near the upper end of the tank body 39.
[0218] そして、一対の撹拌羽根 41, 42は、撹拌槽 38内の相対向する上下端に離間して 配置されて、互いに逆向きに回転駆動される。各撹拌羽根 41, 42は、それぞれの撹 拌羽根 41, 42が近接する槽壁 (シールプレート 40)の外側に配置された外部磁石 4 6と磁気カップリング Cを構成している。即ち、各、撹拌羽根 41, 42は、磁力でそれぞ れの外部磁石 46に連結されており、各外部磁石 46を独立したモーター 48, 49で回 転駆動することで、互いに逆向きに回転操作される。  [0218] Then, the pair of stirring blades 41, 42 are disposed apart from the opposed upper and lower ends in the stirring tank 38, and are driven to rotate in directions opposite to each other. Each stirring blade 41, 42 constitutes an external magnet 46 and a magnetic coupling C arranged outside the tank wall (seal plate 40) where the stirring blade 41, 42 is close. That is, the stirring blades 41 and 42 are coupled to the respective external magnets 46 by magnetic force, and are rotated in opposite directions by being driven by the independent motors 48 and 49. Operated.
[0219] 槽 38内に対向配置された一対の撹拌羽根 41, 42は、図 3中に波線の矢印 (X)及 び実線の矢印 (Y)で示すように、それぞれ向きの異なる撹拌流を槽 38内に形成する 。そして、それぞれの撹拌羽根 41, 42の形成する撹拌流は、流れ方向が異なるため に互 、に衝突して槽 38内における撹拌を促進する高速の乱流を槽 38内に生成して 、槽 38内の流れが定常化することを防止し、撹拌羽根 41, 42の回転を高速ィ匕した 場合にも撹拌羽根 41, 42の回転軸回りに空洞が形成されることを阻止すると同時に 、撹拌作用を十分に受けずに撹拌槽 38の内周面に沿って槽 38内を流れる定常流 が形成されるという不都合の発生を阻止することができる。したがって、撹拌羽根 41, 42の回転の高速ィ匕により、容易に処理速度を向上させることができ、さらに、その際 に、槽 38内の液体の流れが定常化して撹拌混合が不十分の液体が排出されること を阻止して、処理品位の低下を防止することができる。  [0219] The pair of stirring blades 41, 42 arranged opposite to each other in the tank 38 are provided with stirring flows having different directions as indicated by the wavy arrow (X) and the solid arrow (Y) in FIG. Form in tank 38. Since the stirring flows formed by the respective stirring blades 41 and 42 have different flow directions, they collide with each other to generate a high-speed turbulent flow in the tank 38 that promotes stirring in the tank 38, 38 prevents the flow in the steady state and prevents the formation of a cavity around the rotation axis of the stirring blades 41 and 42 even when the stirring blades 41 and 42 are rotated at high speed. It is possible to prevent the inconvenience that a steady flow flowing in the tank 38 along the inner peripheral surface of the stirring tank 38 is formed without being sufficiently affected. Therefore, the processing speed can be easily improved by the high-speed rotation of the stirring blades 41 and 42, and further, the liquid flow in the tank 38 becomes steady and liquid with insufficient stirring and mixing at that time. Can be prevented, and the degradation of the processing quality can be prevented.
また、撹拌槽 38内の各撹拌羽根 41, 42は、磁気カップリング Cによって撹拌槽 38 の外部に配置されたモーター 48, 49に連結されているため、撹拌槽 38の槽壁に回 転軸を揷通させる必要がなくなり、撹拌槽 38を回転軸の挿通部のない密閉容器構造 にすることができるため、撹拌混合した液の槽外への漏出を防止すると同時に、回転 軸用の潤滑液 (シール液)等が不純物として槽 38内の液に混入することによる処理 品位の低下を防止することができる。  Further, since the stirring blades 41 and 42 in the stirring tank 38 are connected to the motors 48 and 49 disposed outside the stirring tank 38 by the magnetic coupling C, the rotating shaft is connected to the tank wall of the stirring tank 38. The stirring tank 38 can be made into a closed container structure without the insertion part of the rotating shaft, preventing leakage of the stirred and mixed liquid to the outside of the tank, and at the same time, lubricating oil for the rotating shaft. It is possible to prevent deterioration in processing quality due to (sealing liquid) or the like being mixed into the liquid in the tank 38 as an impurity.
[0220] 本発明の有機粒子分散組成物の製造方法にお!、て、これらの構成を有する製造 装置を用いて、バッチ方式だけでなく連続フロー方式でも有機顔料粒子の製造をす ることができ、大量生産にも対応できる。また生成した有機粒子分散液が迅速に排出 されることにより、撹拌槽内に供給される有機材料溶液と貧溶媒液の比を常に一定に することが可能になる。このため、製造開始時から製造終了時まで、分散液の有機材 料の溶解度を一定にすることが可能になり、単分散な有機粒子を安定に製造するこ とがでさる。 [0220] In the method for producing an organic particle dispersion composition of the present invention, an organic pigment particle can be produced not only in a batch method but also in a continuous flow method using a production apparatus having these configurations. It can handle mass production. The generated organic particle dispersion is quickly discharged. As a result, the ratio of the organic material solution and the poor solvent solution supplied into the stirring tank can be kept constant. For this reason, it becomes possible to make the solubility of the organic material of the dispersion liquid constant from the start of manufacture to the end of manufacture, and monodisperse organic particles can be stably produced.
さらに槽内の液体の流れが定常化して撹拌混合が不十分の有機粒子分散液が排 出されることを阻止し、また、回転軸用の潤滑液 (シール液)等が不純物として槽内の 液に混入することを防止することで、単分散な有機粒子をさらに安定に製造すること ができる。  Furthermore, the liquid flow in the tank becomes steady, preventing the organic particle dispersion liquid with insufficient stirring and mixing from being discharged, and the lubricating liquid (seal liquid) for the rotating shaft is used as an impurity as the liquid in the tank. By preventing it from being mixed in, monodispersed organic particles can be produced more stably.
[0221] (製造装置例 3)  [0221] (Manufacturing device example 3)
本発明の有機粒子分散組成物の製造に用いられる装置として、さらに別の実施態 様である、剪断力を持つ羽根を用いて攪拌する製造方法について説明する。  As a device used for manufacturing the organic particle dispersion composition of the present invention, a manufacturing method in which stirring is performed using blades having shearing force, which is still another embodiment, will be described.
本発明でいう剪断力とは撹拌羽根が、有機顔料溶液が貧溶媒に混入後に生成す る液滴（ドロップレット）に及ぼすズリカのことである。  The shearing force referred to in the present invention is a shear that the stirring blade exerts on droplets generated after the organic pigment solution is mixed in a poor solvent.
本発明で使用可能な撹拌部の形状は、高剪断力を施し得る形態であれば特に限 定されないが、一般にパドル羽根、タービン羽根、スクリュー羽根、ファウドラー羽根、 等が挙げられ、好ましくはディゾルバー羽根、回転し得るタービン部とその周囲にわ ずかな間隙を置 、て位置する固定化されたステータ部カゝら構成されて ヽる撹拌部の 、撹拌、乳化、分散機が好ましい。  The shape of the stirring unit usable in the present invention is not particularly limited as long as it can be subjected to a high shearing force, but generally includes paddle blades, turbine blades, screw blades, fowler blades, etc. An agitator, an emulsifier, and a disperser are preferably used in the agitating portion that is constituted by a turbine portion that can rotate and a fixed stator portion that is positioned with a small gap around it.
ディゾルバー羽根は、高剪断力形成できる機能を持った特殊な撹拌羽根であり、図 4 1にその 1例を概略的に正面図により示し、その図面代用写真を図 4 2に示す。 また図 5に示すような回転し得るタービン部とその周囲にわずかな間隙を置いて位 置する固定化されたステータ部カゝら構成されている撹拌部を有する装置も好ましく用 いられ、その撹拌、乳化、分散機としては、例えば、マイクロテック' -チオン社製ヒス コトロン、特殊機化工業社製 T. Kホモミクサ一、 IKA社製 ULTRA- TURRAXが挙 げられる。  The dissolver blade is a special stirring blade having a function capable of forming a high shear force. One example is schematically shown in the front view in FIG. 41, and a photograph in place of the drawing is shown in FIG. In addition, a device having a stirring portion constituted by a turbine portion that can rotate as shown in FIG. 5 and a fixed stator portion that is positioned with a slight gap around the turbine portion is also preferably used. Examples of the stirrer, emulsifier, and disperser include, for example, Histotron manufactured by Microtech-Thion Co., Ltd., T. K Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd., and ULTRA-TURRAX manufactured by IKA.
[0222] 本発明の効果が発現し得る撹拌速度は、貧溶媒の粘度、温度、界面活性剤の種 類や添カ卩量によって異なった値をとる力 100〜10000rpm力 S好ましく 150〜8000r pmがより好ましぐ 200〜6000rpm力 S特〖こ好ましい。この範囲未満の回転数であれ ば本発明の効果は充分発揮されず、逆にこの範囲を超えると、貧溶媒中に気泡を卷 き込み、好ましくない。 [0222] The stirring speed at which the effects of the present invention can be manifested is a force that varies depending on the viscosity of the poor solvent, the temperature, the type of surfactant and the amount of additive, and a force of 100 to 10,000 rpm S, preferably 150 to 8000 rpm 200-6000rpm force S is more preferable. If the rotation speed is less than this range In other words, the effect of the present invention is not sufficiently exhibited. On the other hand, if it exceeds this range, bubbles are introduced into the poor solvent, which is not preferable.
[0223] (製造装置例 4)  [0223] (Manufacturing device example 4)
本発明の上記（2)の実施態様の製造方法に用いられる製造装置は、超臨界流体 あるいは亜臨界流体に顔料を溶解した顔料溶解流体と析出用溶媒とを混合し、粒子 を析出することができる装置であれば特に限定されないが、その好ましい実施態様の 一例について図 7により説明する。  The manufacturing apparatus used in the manufacturing method of the embodiment of the above (2) of the present invention is to mix a pigment dissolving fluid obtained by dissolving a pigment in a supercritical fluid or a subcritical fluid and a precipitation solvent to precipitate particles. Although it will not specifically limit if it is an apparatus which can be performed, FIG. 7 demonstrates an example of the preferable embodiment.
超臨界流体または亜臨界流体とする溶媒 101を容器にいれ、これをポンプ 104aで 送液しヒーター 106で加熱し、背圧弁 114で圧力を調整することにより、超臨界流体 または亜臨界流体がハステロィ配管 108を通じてメッシュ 109aを通り抜けて試料管 1 07〖こ注入される。注入された超臨界流体または亜臨界流体に、あらカゝじめ試料管 10 7に仕込んでお 、た顔料等の試料 103が溶解し、顔料溶解流体カ ッシュ 109bを通 り抜けミキサー 111へ送られる。ミキサー部で、ポンプ 104aで送液された顔料溶解流 体とポンプ 104bで送液された析出用溶媒 102の混合が起こり、溶媒組成と溶媒温 度が急激に変化する。この時、試料溶解度が急激に下がり、析出現象によりナノ粒子 が生成する。ミキサー部で生成したナノ粒子分散液を冷却管 112で室温付近まで冷 却し、常温 ·常圧のナノ粒子分散液 115として系外へ取り出すことができる（なお、図 7中の矢印 Bは送液の方向を示す。 )。  The supercritical fluid or subcritical fluid 101 is put in a container, and is pumped by the pump 104a, heated by the heater 106, and the pressure is adjusted by the back pressure valve 114. Through the pipe 108, the sample pipe 1 07 is injected through the mesh 109a. The sample 103 such as the pigment that has been charged into the supercritical fluid or subcritical fluid injected into the supercritical fluid or subcritical fluid is dissolved, passes through the pigment dissolving fluid cache 109b, and is sent to the mixer 111. It is done. In the mixer section, the pigment-dissolved fluid sent by the pump 104a and the precipitation solvent 102 sent by the pump 104b are mixed, and the solvent composition and the solvent temperature change rapidly. At this time, the sample solubility is drastically decreased, and nanoparticles are generated by the precipitation phenomenon. The nanoparticle dispersion produced in the mixer section is cooled to near room temperature with a cooling pipe 112 and can be taken out of the system as a nanoparticle dispersion 115 at normal temperature and normal pressure (note that arrow B in Fig. 7 is sent). Indicates the direction of the liquid).
[0224] [有機粒子分散液の濃縮] [0224] [Concentration of organic particle dispersion]
本発明の有機顔料分散液の製造方法においては、有機粒子分散液を、脱塩濃縮 することによって、カラーフィルター塗布液やインクジェット用インクに適した濃度の有 機粒子分散液を工業的な規模で生産することが可能である。  In the method for producing the organic pigment dispersion of the present invention, the organic particle dispersion is desalted and concentrated to obtain an organic particle dispersion having a concentration suitable for a color filter coating liquid and an inkjet ink on an industrial scale. It is possible to produce.
[0225] 以下に、分散液を濃縮する方法について説明する。 [0225] A method for concentrating the dispersion is described below.
本発明の有機粒子分散組成物の製造方法にぉ 、ては、分散液の濃縮を限外ろ過 により行う。単に有機粒子析出法により形成した粒子含有液を限外ろ過により濃縮し たのでは濃縮過程において粒径分布が大きく変化してしまう。本発明の有機粒子分 散組成物の製造方法は、そのような粒径分布の変化を抑え、し力も不要な塩を効率 的に除去し濃縮することを可能とするものである。また限外ろ過の後、さらに真空凍 結乾燥により溶媒を昇華させて、濃縮、乾燥する方法を組み合わせることも非常に好 ましい。さらには、限外ろ過以外の濃縮方法と組み合わせてもよい。例えば、有機粒 子分散液に、抽出溶媒を添加混合し、有機粒子を該抽出溶媒相に濃縮抽出して、 その濃縮抽出液をフィルターなどによりろ過して濃縮粒子液とする方法、遠心分離に よって有機粒子を沈降させて濃縮する方法、加熱ないし減圧による溶媒を乾燥させ て濃縮する方法等が好まし 、。またはこれらの組合せなどが非常に好ましく用いられ る。 In the method for producing the organic particle dispersion composition of the present invention, the dispersion is concentrated by ultrafiltration. If the particle-containing liquid formed simply by the organic particle precipitation method is concentrated by ultrafiltration, the particle size distribution changes greatly during the concentration process. The method for producing an organic particle dispersion composition of the present invention suppresses such a change in the particle size distribution, and enables efficient removal and concentration of salt that does not require force. Also after ultrafiltration, further vacuum freezing It is also very preferable to combine the methods of sublimating the solvent by freeze drying, concentrating and drying. Furthermore, you may combine with the concentration methods other than ultrafiltration. For example, an extraction solvent is added to and mixed with an organic particle dispersion, the organic particles are concentrated and extracted into the extraction solvent phase, and the concentrated extract is filtered through a filter or the like to obtain a concentrated particle liquid. Therefore, a method of precipitating and concentrating the organic particles, a method of drying and concentrating the solvent by heating or decompression, etc. are preferred. Or a combination of these is very preferably used.
濃縮後の有機粒子濃度に関しては、 1〜100質量％が好ましぐ 5〜： LOO質量％が より好ましぐ 10〜： LOO質量％が特に好ましい。  Regarding the concentration of organic particles after concentration, 1 to 100% by mass is preferable 5 to: LOO% by mass is more preferable 10 to: LOO% by mass is particularly preferable.
[0226] 本発明の有機粒子分散組成物の製造方法にお!、て、具体的な限外ろ過方法は、 例えばハロゲンィ匕銀乳剤の脱塩/濃縮に用いられる方法を適用することができる。リ サーチ ·ディスクロージャー（Research Disclosure) No.10208 (1972)、 No.13122 (1975)および No.16 351 (1977)が知られている。操作条件として重要な圧力差 や流量は、大矢春彦著「膜利用技術ノ、ンドブック」幸書房出版（1978)、 p275に記 載の特性曲線を参考に選定することができるが、目的の有機粒子分散物を処理する 上では、粒子の凝集を抑えるために最適条件を見いだすことが好ましい。また、膜透 過より損失する溶媒を補充する方法にぉ ヽては、連続して溶媒を添加する定容式と 断続的に分けて添加する回分式とがあるが、脱塩処理時間が相対的に短い定容式 が好ましい。こうして補充する溶媒には、イオン交換または蒸留して得られた純水を 用いるが、純水の中に分散剤、分散剤の貧溶媒を混合してもよいし、有機粒子分散 物に直接添加してもよい。  [0226] In the method for producing an organic particle dispersion composition of the present invention, a specific ultrafiltration method can be applied, for example, a method used for desalting / concentrating a silver halide emulsion. Research Disclosure No. 10208 (1972), No. 13122 (1975) and No. 16 351 (1977) are known. The pressure difference and flow rate, which are important as operating conditions, can be selected with reference to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology No. Book” Koshobo Publishing (1978), p275. In treating the dispersion, it is preferable to find an optimum condition in order to suppress the aggregation of particles. In addition, there are two methods of replenishing the solvent that is lost due to the membrane permeation: the constant volume method in which the solvent is continuously added and the batch method in which the solvent is intermittently added. A short constant volume formula is preferred. Pure water obtained by ion exchange or distillation is used as a solvent to be replenished in this way, but a dispersant, a poor solvent for the dispersant may be mixed in pure water, or added directly to the organic particle dispersion. May be.
[0227] 図 6に、限外ろ過を行うための装置の一構成例を示す。図 6に示されるように、この 装置は有機粒子分散物を収納するタンク 81、このタンク 81内の分散物を循環させる 循環用ポンプ 82、および循環用ポンプ 82によって導入された分散物中の副生成無 機塩を透過水として除去する限外ろ過モジュール 83を有する。透過水が分離された 分散物は再度タンク 81内に戻され、同様の操作が、副生成無機塩の除去の所定の 目的が達成されるまで、繰り返し行われる。さらに、この装置には、透過水によって失 われる溶媒を純水として一定量補充するために使用される補充純水計測用流量計 8 4が設置されており、純水補充量を決定するのに用いられる透過水計測用流量計 85 が設置されている。また、透過水を希薄にするための水を導入するための逆方向洗 浄用ポンプ 86が設置されている。 [0227] FIG. 6 shows a configuration example of an apparatus for performing ultrafiltration. As shown in FIG. 6, this apparatus has a tank 81 for storing the organic particle dispersion, a circulation pump 82 for circulating the dispersion in the tank 81, and a secondary liquid in the dispersion introduced by the circulation pump 82. It has an ultrafiltration module 83 that removes generated organic salt as permeate. The dispersion from which the permeated water has been separated is returned to the tank 81 again, and the same operation is repeated until the predetermined purpose of removing the by-product inorganic salt is achieved. In addition, this device has a replenishment pure water measurement flow meter used to replenish a certain amount of solvent lost by permeate as pure water. 4 is installed, and a permeate flow meter 85 used to determine the amount of pure water replenishment is installed. A reverse cleaning pump 86 is installed to introduce water for diluting the permeate.
[0228] 限外ろ過膜は、すでにモジュールとして組み込まれた平板型、スパイラル型、円筒 型、中空糸型、ホロ一ファイバー型などが旭化成 (株）、ダイセルィ匕学 (株）、（株)東レ 、（株）日東電工など力 市販されているが、総膜面積や洗浄性の観点より、スパイラ ル型もしくは中空糸型が好ましい。また、膜を透過することができる成分のしきい値の 指標となる分画分子量は、用いられる分散剤の分子量より決定する必要があるが、 5, 000以上 50,000以下のちの力 S好まし <、 5,000以上 15,000以下のちの力 Sより好まし い。 [0228] As the ultrafiltration membrane, flat plate type, spiral type, cylindrical type, hollow fiber type, holo fiber type, etc., which are already incorporated as modules, include Asahi Kasei Co., Ltd., Daicel Chemical Co., Ltd., Toray Industries, Inc. Nitto Denko Co., Ltd. is commercially available, but a spiral type or hollow fiber type is preferred from the viewpoint of the total membrane area and detergency. In addition, the molecular weight cut-off, which serves as an index for the threshold value of the component that can permeate the membrane, must be determined from the molecular weight of the dispersant used, but the force after 5,000 to 50,000 is preferred. , More than 5,000 and less than 15,000.
[0229] 凍結乾燥の方法は特に限定されず、当業者が利用可能な方法であればいかなるも のを採用してもよい。例えば、冷媒直膨方法、重複冷凍方法、熱媒循環方法、三重 熱交換方法、間接加熱凍結方法が挙げられるが、好ましくは冷媒直膨方法、間接カロ 熱凍結方法、より好ましくは間接加熱凍結方法を用いるのがよい。いずれの方法に おいても、予備凍結を行なった後凍結乾燥を行なうことが好ましい。予備凍結の条件 は特に限定されないが、凍結乾燥を行なう試料がまんべんなく凍結されている必要 がある。  [0229] The freeze-drying method is not particularly limited, and any method that can be used by those skilled in the art may be adopted. For example, a refrigerant direct expansion method, an overlapping freezing method, a heat medium circulation method, a triple heat exchange method, and an indirect heating freezing method can be mentioned, preferably a refrigerant direct expansion method, an indirect calothermal heat freezing method, more preferably an indirect heating freezing method. Should be used. In any method, it is preferable to perform freeze-drying after preliminary freezing. The pre-freezing conditions are not particularly limited, but the sample to be lyophilized needs to be completely frozen.
[0230] 間接加熱凍結方法の装置としては、小型凍結乾燥機、 FTS凍結乾燥機、 LYOVA C凍結乾燥機、実験用凍結乾燥機、研究用凍結乾燥機、三重熱交換真空凍結乾燥 機、モノクーリング式凍結乾燥機、 HULL凍結乾燥機が挙げられるが、好ましくは小 型凍結乾燥機、実験用凍結乾燥機、研究用凍結乾燥機、モノクーリング式凍結乾燥 機、より好ましくは小型凍結乾燥機、モノクーリング式凍結乾燥機を用いるのがよい。  [0230] Indirect heating freezing methods include small freeze dryer, FTS freeze dryer, LYOVA C freeze dryer, experimental freeze dryer, research freeze dryer, triple heat exchange vacuum freeze dryer, monocooling Lyophilizer and HULL lyophilizer are preferable, but preferably a small lyophilizer, a laboratory lyophilizer, a research lyophilizer, a monocooling lyophilizer, more preferably a small lyophilizer, A cooling freeze dryer may be used.
[0231] 凍結乾燥の温度は特に限定されないが、例えば— 190〜― 4°C、好ましくは— 120 〜― 20°C、より好ましくは— 80〜― 60°C程度である。凍結乾燥の圧力も特に限定さ れず、当業者が適宜選択可能である力 例えば、 0. l〜35Pa、好ましくは l〜15Pa 、さらに好ましくは、 5〜： LOPa程度で行なうのがよい。凍結乾燥時間は、例えば 2〜4 8時間、好ましくは 6〜36時間、より好ましくは 16〜26時間程度である。もっとも、これ らの条件は当業者に適宜選択可能である。凍結乾燥方法については、例えば、製剤 機械技術ハンドブック:製剤機械技術研究会編、地人書館、 P.120— 129(2000年 9月） ；真空ハンドブック：日本真空技術株式会社編、オーム社、 p.328— 331(1992年);凍 結及び乾燥研究会会誌:伊藤孝治他、 Νο.15、 p.82(1965)などを参照することができ る。 [0231] The temperature of lyophilization is not particularly limited, but is, for example, -190 to -4 ° C, preferably -120 to -20 ° C, more preferably about -80 to -60 ° C. The pressure of lyophilization is not particularly limited, and can be appropriately selected by those skilled in the art. For example, 0.1 to 35 Pa, preferably 1 to 15 Pa, more preferably 5 to about LOPa. The freeze-drying time is, for example, 2 to 48 hours, preferably 6 to 36 hours, and more preferably about 16 to 26 hours. However, these conditions can be appropriately selected by those skilled in the art. For lyophilization methods, for example, formulations Mechanical Technology Handbook: Formulation Mechanical Technology Study Group, Jinshokan, P.120—129 (September 2000); Vacuum Handbook: Nihon Vacuum Technology Co., Ltd., Ohm, p.328—331 (1992); You can refer to the Journal of the Society of Freezing and Drying: Koji Ito et al., Νο.15, p.82 (1965).
[0232] 以下に、濃縮抽出する方法について説明する。この濃縮抽出に用いられる抽出溶 媒は特に制約されないが、有機粒子分散液の分散溶媒 (例えば、水系溶媒)と実質 的に混じり合わず (本発明において、実質的に混じり合わずとは、相溶性が低いこと をいい、溶解量 50質量％以下が好ましぐ 30質量％以下がより好ましい）、混合後、 静置すると界面を形成する溶媒であることが好ましい。また、この抽出溶媒は、有機 粒子が抽出溶媒中で再分散しうる弱い凝集 (ミリングまたは高速攪拌などの高いせん 断力を加えなくても再分散が可能である）を生ずる溶媒であることが好ましい。このよ うな状態であれば、粒子サイズを変化させる強固な凝集を起こさず、目的の有機粒子 を抽出溶媒で湿潤させる一方、フィルターろ過などにより容易に水などの分散溶媒を 除去することができる点で好ま 、。  [0232] A method for concentration extraction will be described below. The extraction solvent used for this concentration extraction is not particularly limited, but does not substantially mix with the dispersion solvent (for example, aqueous solvent) of the organic particle dispersion (in the present invention, it does not mix substantially) Low solubility means 50% by mass or less is preferable, and 30% by mass or less is more preferable.) After mixing, it is preferably a solvent that forms an interface when allowed to stand. In addition, this extraction solvent must be a solvent that produces weak aggregation (re-dispersion is possible without applying high shearing force such as milling or high-speed stirring) in which organic particles can be re-dispersed in the extraction solvent. preferable. In such a state, the target organic particles are moistened with the extraction solvent without causing strong aggregation that changes the particle size, and the dispersion solvent such as water can be easily removed by filter filtration or the like. Liked in.
抽出溶媒としてはエステル系溶媒、アルコール系溶媒、芳香族系溶媒、脂肪族系 溶媒が好ましぐエステル系溶媒、芳香族系溶媒または脂肪族系溶媒がより好ましく 、エステル系溶媒が特に好ましい。  The extraction solvent is preferably an ester solvent, an alcohol solvent, an aromatic solvent or an aliphatic solvent, more preferably an ester solvent, an aromatic solvent or an aliphatic solvent, and particularly preferably an ester solvent.
エステル系溶媒としては、例えば、 2- (1ーメトキシ）プロピルアセテート、酢酸ェチ ル、乳酸ェチルなどが挙げられる。アルコール系溶媒としては、例えば、 n—ブタノ一 ル、イソブタノールなどが挙げられる。芳香族系溶媒としては、例えば、ベンゼン、トル ェン、キシレンなどが挙げられる。脂肪族系溶媒としては、例えば、 n—へキサン、シ クロへキサンなどが挙げられる。また、抽出溶媒は上記の好ましい溶媒による純溶媒 であっても、複数の溶媒による混合溶媒であってもよい。  Examples of the ester solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol solvent include n-butanol and isobutanol. Examples of the aromatic solvent include benzene, toluene, xylene and the like. Examples of the aliphatic solvent include n-hexane and cyclohexane. Further, the extraction solvent may be a pure solvent based on the above preferred solvent or a mixed solvent composed of a plurality of solvents.
[0233] 抽出溶媒の量は有機粒子を抽出できれば特に制約されないが、濃縮して抽出する ことを考慮して有機粒子分散液より少量であることが好まし 、。これを体積比で示すと 、有機粒子分散液を 100としたとき、添加される抽出溶媒は 1〜： LOOの範囲であること が好ましぐより好ましくは 10〜90の範囲であり、 20〜80の範囲が特に好ましい。多 すぎると濃縮ィ匕に多大な時間を要し、少なすぎると抽出が不十分で分散溶媒中に粒 子が残存する。 [0233] The amount of the extraction solvent is not particularly limited as long as the organic particles can be extracted, but it is preferable that the amount of the extraction solvent is smaller than that of the organic particle dispersion in consideration of concentration and extraction. When this is represented by volume ratio, when the organic particle dispersion is 100, the extraction solvent added is preferably in the range of 1 to: LOO, more preferably in the range of 10 to 90, and 20 to A range of 80 is particularly preferred. If it is too much, it will take a lot of time to concentrate, and if it is too little, extraction will be insufficient and the particles will be dispersed in the dispersion solvent. The child remains.
抽出溶媒を添加した後、分散液と十分に接触するように攪拌混合することが好まし い。攪拌混合は常用の方法を用いることができる。抽出溶媒を添加し混合するときの 温度に特に制約はないが、 1〜100°Cであることが好ましぐ 5〜60°Cであることがより 好ましい。抽出溶媒の添加、混合はそれぞれの工程を好ましく実施できるものであれ ばどのような装置を用いてもよいが、例えば、分液ロート型の装置を用いて実施でき る。  After adding the extraction solvent, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. Conventional methods can be used for stirring and mixing. The temperature at which the extraction solvent is added and mixed is not particularly limited, but is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. Any device may be used for adding and mixing the extraction solvent as long as each step can be preferably performed. For example, a separation funnel type device can be used.
[0234] 有機粒子分散液の分散溶媒と濃縮抽出液を分離するため、フィルターろ過すること が好ましい。フィルターろ過の装置は、例えば、加圧ろ過のような装置を用いることが できる。好ましいフィルタ一としては、ナノフィルター、ウルトラフィルターなどが挙げら れる。フィルターろ過により、残された分散溶媒の除去を行い、濃縮抽出液中の有機 粒子をさらに濃縮して濃縮粒子液とすることが好ましい。  [0234] In order to separate the dispersion solvent of the organic particle dispersion and the concentrated extract, it is preferable to filter. As the filter filtration apparatus, for example, an apparatus such as pressure filtration can be used. Preferred filters include nanofilters and ultrafilters. It is preferable to remove the remaining dispersion solvent by filter filtration and further concentrate the organic particles in the concentrated extract to obtain a concentrated particle solution.
[0235] 以下に遠心分離について説明する。遠心分離による有機粒子の濃縮に用いられる 遠心分離機は有機粒子分散液 (または有機粒子濃縮抽出液）中の有機粒子を沈降 させることができればどのような装置を用いてもよい。遠心分離機としては、例えば、 汎用の装置の他にもスキミング機能（回転中に上澄み層を吸引し、系外に排出する 機能)付きのものや、連続的に固形物を排出する連続遠心分離機などが挙げられる 遠心分離条件は、遠心力（重力加速度の何倍の遠心加速度が力かる力を表す値） で 50〜： LOOOO力好まし <、 100〜8000力より好まし <、 150〜6000カ^特に好まし ヽ 。遠心分離時の温度は、分散液の溶剤種による力 — 10〜80°Cが好ましぐ— 5〜7 0°Cがより好ましぐ 0〜60°Cが特に好ましい。  [0235] Centrifugation will be described below. The centrifuge used for concentration of organic particles by centrifugation may be any device as long as it can precipitate organic particles in an organic particle dispersion (or organic particle concentrated extract). As a centrifuge, for example, in addition to a general-purpose device, one with a skimming function (function of sucking the supernatant layer during rotation and discharging it out of the system) or continuous centrifugation that continuously discharges solid matter. Centrifugation conditions include centrifugal force (a value that represents the force at which centrifugal acceleration is multiplied by the gravitational acceleration) 50 ~: LOOOO force preference <, 100 ~ 8000 force preference <, 150 ~ 6000 is especially preferred 好. The temperature at the time of centrifugation is a force depending on the solvent type of the dispersion liquid—preferably 10 to 80 ° C.—preferably 5 to 70 ° C. Particularly preferably 0 to 60 ° C.
[0236] 以下に乾燥について説明する。減圧乾燥による有機粒子の濃縮に用いられる装置 は有機粒子分散液 (または有機粒子濃縮抽出液)の溶媒を蒸発させることができれ ば特に制限はない。例えば、汎用の真空乾燥器およびロータリーポンプや、液を撹 拌しながら加熱減圧乾燥できる装置、液を加熱減圧した管中に通すことによって連 続的に乾燥ができる装置等が挙げられる。 [0236] Hereinafter, drying will be described. The apparatus used for concentration of organic particles by drying under reduced pressure is not particularly limited as long as the solvent of the organic particle dispersion (or organic particle concentrated extract) can be evaporated. For example, a general-purpose vacuum dryer and a rotary pump, a device capable of drying under heating and heating while stirring the liquid, and a device capable of continuous drying by passing the liquid through a heat-depressurized tube.
加熱減圧乾燥温度は 30〜230°Cが好ましぐ 35〜200°Cがより好ましぐ 40-18 0°C力 S特に好まし ヽ。減圧時の圧力 ίま、 100〜100000Pa力好まし <、 300〜90000 Pa力より好ましく、 500〜80000Pa力特に好まし!/、。 Heating vacuum drying temperature is preferably 30-230 ° C 35-200 ° C is more preferred 40-18 0 ° C force S Especially preferred ヽ. Pressure during decompression ί, 100-100,000 Pa force preferred <, 300-90000 Pa force more preferred, 500-80000 Pa force particularly preferred! / ,.
[0237] 本発明の有機粒子分散組成物の製造において、限外ろ過または上述のような濃縮 方法との組み合わせにより、有機粒子分散液から効率よく有機粒子を濃縮することが できる。濃縮倍率に関しては、例えば、原料となる有機粒子分散液中の粒子の濃度 を 1とすると、濃縮有機粒子ペーストにおける濃度を好ましくは 100〜3000倍程度、 より好ましくは 500〜2000倍程度まで濃縮することができる。  [0237] In the production of the organic particle dispersion composition of the present invention, organic particles can be efficiently concentrated from the organic particle dispersion by combination with ultrafiltration or the above-described concentration method. Regarding the concentration factor, for example, if the concentration of the particles in the organic particle dispersion as the raw material is 1, the concentration in the concentrated organic particle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. be able to.
[0238] 本発明の有機粒子分散組成物の製造方法によれば、有機粒子分散物力 不要な イオンを除去することができる。除去されるイオンは、特に限定されないが、ナトリウム (Na)、カリウム (K)、カルシウム (Ca)、塩素（C1)等の分子量の小さ 、ものを除去す ることが好ましい。例えばカラーフィルター用途においては分子量が小さく動きやす V、イオンが多 、と必要な電圧が保持できず障害となる。除去後のイオンのトータル量 は有機材料に対して、 1質量％以下が好ましぐさらに 0. 1質量％以下がより好ましく 、 0. 01質量％以下が特に好ましい。  [0238] According to the method for producing an organic particle dispersion composition of the present invention, ions unnecessary for the organic particle dispersion force can be removed. The ions to be removed are not particularly limited, but it is preferable to remove ions having a low molecular weight such as sodium (Na), potassium (K), calcium (Ca), chlorine (C1) and the like. For example, in a color filter application, the molecular weight is small and it is easy to move. The total amount of ions after removal is preferably 1% by mass or less, more preferably 0.1% by mass or less, and particularly preferably 0.01% by mass or less, relative to the organic material.
[0239] [有機粒子分散液の再分散]  [0239] [Redispersion of organic particle dispersion]
本発明の有機粒子分散組成物の製造方法にぉ ヽては、濃縮した有機粒子をカラ 一フィルター、インクジェットのインク等の用途に合わせて適当な溶媒中に再び微細 分散化することが好ましい (本発明において、微細分散化とは、分散液中の粒子の凝 集を解き分散度を高めることを ヽぅ)。  For the production method of the organic particle dispersion composition of the present invention, it is preferable to finely disperse the concentrated organic particles again in an appropriate solvent in accordance with the use such as a color filter or an inkjet ink (this book In the invention, fine dispersion means to increase the degree of dispersion by deaggregating particles in a dispersion.
例えばカラーフィルター用途においてはビヒクルに添加して分散させることができる 。前記ビビクルとは、液体状態にあるときに有機粒子を分散させている媒質の部分を いい、液状であって前記有機粒子と作用して固める部分 (バインダー）と、これを溶解 希釈する成分 (有機溶媒)とを含む。  For example, in color filter applications, it can be added to a vehicle and dispersed. The vehicle refers to a portion of a medium in which organic particles are dispersed in a liquid state, a portion that is liquid and hardens by acting with the organic particles (binder), and a component that dissolves and dilutes this (organic) Solvent).
本発明にお 、ては、上述の高分子化合物または酸性基を有する高分子化合物を 含む有機溶媒中で再分散を行うことが好ましい。このとき、該高分子化合物または酸 性基を有する高分子化合物については、有機粒子形成時に用いたもののうち再分 散時に残留して 、るものを利用してもよ 、が、それに加えて有機粒子形成時に用い たものと同種または別種のものを再分散時に添加することが好ましぐ同種のものを 追添加することがより好ま 、。 In the present invention, it is preferable to perform redispersion in an organic solvent containing the above-described polymer compound or a polymer compound having an acidic group. At this time, as for the polymer compound or the polymer compound having an acidic group, a compound remaining at the time of re-dispersion among those used at the time of forming the organic particles may be used, but in addition, an organic compound is used. It is preferable to add the same type or different type used during grain formation during redispersion. More preferred to add.
再分散化後の有機粒子分散組成物の有機粒子濃度は目的に応じて適宜定められ る力 好ましくは分散組成物全量に対して 2〜30質量％であることが好ましぐ 4〜20 質量％であることがより好ましぐ 5〜 15質量％であることが特に好ましい。バインダー および溶解希釈成分の量は有機材料の種類などにより適宜定められるが、有機粒子 分散組成物全量に対して、バインダーは 1〜30質量％であることが好ましぐ 3〜20 質量％であることがより好ましぐ 5〜 15質量％であることが特に好ましい。溶解希釈 成分は 5〜80質量％であることが好ましぐ 10〜70質量％であることがより好ましい。  The organic particle concentration of the organic particle dispersion composition after redispersion is appropriately determined according to the purpose. Preferably, the organic particle concentration is 2 to 30% by mass with respect to the total amount of the dispersion composition. 4 to 20% by mass It is particularly preferable that the content is 5 to 15% by mass. The amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic material, etc., but the binder is preferably 1 to 30% by mass with respect to the total amount of the organic particle dispersion composition, and is 3 to 20% by mass. It is particularly preferable that the content is 5 to 15% by mass. The dissolution dilution component is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
[0240] 上述の濃縮抽出した粒子液において、速やかなフィルターろ過を可能とする状態 では、有機粒子は、通常、濃縮ィ匕により凝集を起こしている。また、遠心分離または 乾燥により濃縮ィ匕した有機粒子も濃縮ィ匕による凝集をおこしている。 [0240] In the above-described concentrated and extracted particle liquid, organic particles are usually agglomerated due to concentration in a state where rapid filter filtration is possible. Organic particles concentrated by centrifugation or drying are also aggregated by the concentration.
このような凝集有機粒子 (本発明において、凝集有機粒子とは、凝集体など粒子が 二次的な力で集まっているものをいう。）を分散する方法として、例えば超音波による 分散方法や物理的なエネルギーを加える方法を用いることができる。  As a method for dispersing such agglomerated organic particles (in the present invention, agglomerated organic particles are particles in which particles such as agglomerates are gathered by a secondary force), for example, a dispersion method using ultrasonic waves or physical It is possible to use a method of adding energy.
超音波照射装置は 10kHz以上の超音波を印加できる機能を有することが好ましく 、例えば、超音波ホモジナイザー、超音波洗浄機などが挙げられる。超音波照射中 に液温が上昇すると、粒子の熱凝集が起こるため (顔料分散技術 表面処理と分散 剤の使い方および分散性評価 技術情報協会 1999参照）、液温を 1〜100°Cと することが好ましぐ 5〜60°Cがより好ましい。温度の制御方法は、分散液温度の制 御、分散液を温度制御する温度調整層の温度制御などによって行うことができる。 物理的なエネルギーを加えて濃縮した有機粒子を分散させる際に使用する分散機 としては、特に制限はなぐ例えば、ニーダー、ロールミル、アトライダー、スーパーミ ル、ディゾルバー、ホモミキサー、サンドミル等の公知の分散機が挙げられる。  The ultrasonic irradiation device preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the particles occurs (see Pigment Dispersion Technology, Surface Treatment and Use of Dispersing Agents and Dispersibility Evaluation Technical Information Association 1999), so the liquid temperature is 1 to 100 ° C. 5-60 ° C is more preferable. The temperature can be controlled by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like. There are no particular restrictions on the dispersing machine used to disperse the concentrated organic particles by applying physical energy. For example, kneaders, roll mills, atriders, super mills, dissolvers, homomixers, sand mills, etc. Examples include a disperser.
再分散時に有機粒子形成時に用いる分散剤として本文中に示した化合物を再度 用 、ることも好まし 、。  It is also preferable to use again the compounds shown in the text as a dispersant used for forming organic particles during redispersion.
[0241] 本発明の有機粒子分散組成物の製造方法によれば、再分散後の有機粒子 (一次 粒子）を微細分散化した粒子とすることができる。特開 2004— 43776号公報では、 再分散後の粒径変化が小さ 、微細な粒子を得る方法が記載されて 、るが、これを詳 細に評価にすると、 0. 50 mを超える粒子が相当量 (例えば 0. 1%程度)観察され 、 CCDのカラーフィルタ一等において性能の低下の原因となりうる。この方法では酸 の添カ卩により貧溶媒中で急激に凝集を生じさせる工程を含むが、このために顔料粒 子の会合が生じるものと推測される。 [0241] According to the method for producing an organic particle dispersion composition of the present invention, finely dispersed particles of redispersed organic particles (primary particles) can be obtained. Japanese Patent Application Laid-Open No. 2004-43776 describes a method for obtaining fine particles with a small change in particle size after redispersion. When evaluated finely, a considerable amount (for example, about 0.1%) of particles exceeding 0.50 m is observed, which may cause a decrease in performance in a CCD color filter or the like. This method includes a step of causing agglomeration rapidly in a poor solvent by adding an acid, and this is presumed to cause association of pigment particles.
一方本願発明の有機粒子分散組成物の製造方法によれば、平均粒径をナノメート ルサイズにすることができ、好ましくは l〜200nmとすることができ、 2〜100nmがよ り好ましく、 5〜50nmが特に好ましい。また、再分散後の粒子の Mv/Mnは、 1.0〜2 .0であることが好ましぐ 1.0〜1.8であることがより好ましぐ 1.0〜1.5であることが特 に好ましい。  On the other hand, according to the method for producing an organic particle dispersion composition of the present invention, the average particle size can be nanometer size, preferably 1 to 200 nm, more preferably 2 to 100 nm, and 5 to 50 nm. Is particularly preferred. Further, the Mv / Mn of the particles after redispersion is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5.
[0242] 本発明の有機粒子分散組成物の製造方法によれば、ナノメートルサイズ (例えば、 10〜： LOOnm)という微小な粒径にもかかわらず、目的とした粒子サイズで有機粒子 を濃縮再分散することができる。このため、インクジェット用のインクとしたとき、光学濃 度が高ぐ画像表面の均一性に優れ、彩度が高く鮮明なインクとすることができる。さ らに、カラーフィルターに用いたときには、光学濃度が高ぐフィルター表面の均一性 に優れ、コントラストが高ぐかつ画像のノイズを少なくすることができる。  [0242] According to the method for producing an organic particle dispersion composition of the present invention, the organic particles are reconcentrated and reconstituted at the intended particle size, despite a nanometer size (for example, 10 to: LOOnm). Can be dispersed. For this reason, when an ink for inkjet is used, it is possible to obtain a clear ink having high optical density, excellent uniformity of the image surface, high saturation, and high clarity. Furthermore, when used in a color filter, the filter surface with high optical density is excellent in uniformity, the contrast is high, and image noise can be reduced.
[0243] [着色感光性榭脂組成物]  [0243] [Colored photosensitive resin composition]
本発明の着色感光性榭脂組成物は、少なくとも、（a)有機ナノ粒子、（b)バインダー 、（c)多官能モノマー（モノマーもしくはオリゴマー）、および (d)光重合開始剤もしく は光重合開始剤系を含む。以下、本発明の着色感光性榭脂組成物の各成分につい て説明する。  The colored photosensitive resin composition of the present invention comprises at least (a) organic nanoparticles, (b) a binder, (c) a polyfunctional monomer (monomer or oligomer), and (d) a photopolymerization initiator or light. Includes a polymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition of the present invention will be described.
[0244] (a)有機ナノ粒子  [0244] (a) Organic nanoparticles
有機ナノ粒子を作製する方法については既に詳細に述べた。有機ナノ粒子の含有 量は、着色感光性榭脂組成物中の全固形分 (本発明において、全固形分とは、有機 溶媒を除く組成物合計をいう。）に対し、 3〜90質量％が好ましぐ 20〜80質量％が より好ましぐ 25〜60質量％がさらに好ましい。この量が多すぎると分散液の粘度が 上昇し製造適性上問題になることがある。少なすぎると着色力が十分でない。着色剤 として機能する有機ナノ粒子 (顔料粒子）としては、粒径 0. 1 μ m以下、特には粒径 0 . 08 m以下であることが好ましい。また、調色のために通常の顔料と組み合わせて 用いてもょ 、。顔料は上記で記述したものを用いることができる。 The method for producing organic nanoparticles has already been described in detail. The content of the organic nanoparticles is 3 to 90% by mass with respect to the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content refers to the total composition excluding the organic solvent). 20 to 80% by mass is more preferable and 25 to 60% by mass is more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, the coloring power is not sufficient. The organic nanoparticles (pigment particles) functioning as a colorant preferably have a particle size of 0.1 μm or less, and particularly preferably a particle size of 0.08 m or less. Also in combination with ordinary pigments for toning Use it. As the pigment, those described above can be used.
[0245] (b)バインダー  [0245] (b) Binder
着色感光性榭脂組成物中のバインダーとしては、先に述べた質量平均分子量 100 0以上の高分子化合物を好ましく用いることができる。ノ インダ一の含有量は、着色 感光性榭脂組成物の全固形分に対して 15〜50質量％が一般的であり、 20〜45質 量％が好ましい。この量が多すぎると組成物の粘度が高くなりすぎ製造適性上問題と なる。少なすぎるど塗布膜の形成上問題がある。  As the binder in the colored photosensitive resin composition, the above-described polymer compound having a mass average molecular weight of 1000 or more can be preferably used. The content of the binder is generally 15 to 50% by mass, preferably 20 to 45% by mass, based on the total solid content of the colored photosensitive resin composition. If this amount is too large, the viscosity of the composition becomes too high, which causes a problem in production suitability. If the amount is too small, there is a problem in forming the coating film.
[0246] (c)多官能モノマー  [0246] (c) Polyfunctional monomer
本発明の着色感光性榭脂組成物に含有させる多官能モノマーとしては、エチレン 性不飽和二重結合を 2個以上有し、光の照射によって付加重合する多官能モノマー であることが好ましい。そのような多官能モノマーとしては、分子中に少なくとも 1個の 付加重合可能なエチレン性不飽和基を有し、沸点が常圧で 100°C以上の化合物を 挙げることができる。その例としては、ジペンタエリスリトールへキサ (メタ）アタリレート 、ポリエチレングリコールモノ（メタ）アタリレート、ポリプロピレングリコールモノ（メタ）ァ タリレート及びフエノキシェチル (メタ）アタリレートなどの単官能アタリレートや単官能メ タクリレート；ポリエチレングリコールジ（メタ）アタリレート、ポリプロピレングリコールジ（ メタ）アタリレート、トリメチロールェタントリアタリレート、トリメチロールプロパントリ（メタ） アタリレート、トリメチロールプロパンジアタリレート、ネオペンチルグリコールジ（メタ）ァ タリレート、ペンタエリスリトールテトラ (メタ）アタリレート、ペンタエリスリトールトリ（メタ） アタリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、ジペンタエリスリトール ペンタ（メタ）アタリレート、へキサンジオールジ (メタ）アタリレート、トリメチロールプロ パントリ（アタリロイルォキシプロピル）エーテル、トリ（アタリロイルォキシェチル)イソシ ァヌレート、トリ（アタリロイルォキシェチル)シァヌレート、グリセリントリ（メタ）アタリレー ト；トリメチロールプロパンやグリセリン等の多官能アルコールにエチレンォキシド又は プロピレンォキシドを付加した後 (メタ)アタリレートイ匕したもの等の多官能アタリレート や多官能メタタリレートを挙げることができる。また、特開平 10— 62986号公報に一 般式（1)および（2)に記載のように、多官能アルコールにエチレンオキサイドやプロ ピレンオキサイドを付加させた後 (メタ）アタリレートイ匕したィ匕合物も好適なものとして挙 げられる。 The polyfunctional monomer to be contained in the colored photosensitive resin composition of the present invention is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such polyfunctional monomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates such as dipentaerythritol hexa (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxychetyl (meth) acrylate, and monofunctional methacrylates. Tacrylate: Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, trimethylol propane diatalate, neopentyl glycol di ( (Meth) atalylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hex (meth) acrylate, dipen Taerythritol Penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylol propantri (atallylooxypropyl) ether, tri (atallylooxychetyl) isocyanurate, tri (atalylooxy) (Cetyl) cyanurate, glycerin tri (meth) atrelate; polyfunctional acrylate such as trimethylolpropane, glycerin and other polyfunctional alcohols after addition of ethylene oxide or propylene oxide. And polyfunctional metatalates. In addition, as described in JP-A-10-62986 in general formulas (1) and (2), after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, (meth) attareitoi was added. Compounds are also listed as suitable. I can get lost.
[0247] 更に特公昭 48— 41708号公報、特公昭 50— 6034号公報及び特開昭 51— 371 93号公報に記載されているウレタンアタリレート類;特開昭 48— 64183号公報、特 公昭 49 -43191号公報及び特公昭 52— 30490号公報に記載されて 、るポリエス テルアタリレート類;エポキシ榭脂と (メタ)アクリル酸の反応生成物であるエポキシァク リレート類等の多官能アタリレー卜やメタタリレートを挙げることができる。  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B 49-43191 and Japanese Patent Publication No. 52-30490, such as polyester acrylates; polyfunctional acrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid; Metatalates can be mentioned.
これらの中で、トリメチロールプロパントリ（メタ）アタリレート、ペンタエリスリトールテト ラ（メタ）アタリレート、ジペンタエリスリトールへキサ (メタ）アタリレート、ジペンタエリスリ トールペンタ (メタ）アタリレートが好まし 、。  Of these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred.
また、この他、特開平 11— 133600号公報に記載の「重合性ィ匕合物 B」も好適なも のとして挙げることができる。  In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
[0248] これらの多官能モノマーは（多官能モノマーとしては、分子量 200〜1000のもの力 S 好ましい。）、単独でも、二種類以上を混合して用いてもよぐ着色感光性榭脂組成 物の全固形分に対する含有量は 5〜50質量％が一般的であり、 10〜40質量％が 好ましい。この量が多すぎると現像性の制御が困難になり製造適性上問題となる。少 なすぎると露光時の硬化力が不足する。  [0248] These polyfunctional monomers (as the polyfunctional monomer, those having a molecular weight of 200 to 1000 are preferable). Colored photosensitive resin compositions that can be used alone or in combination of two or more. The content of the total solid content is generally 5 to 50% by mass, and preferably 10 to 40% by mass. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure will be insufficient.
[0249] (d)光重合開始剤又は光重合開始剤系  [0249] (d) Photopolymerization initiator or photopolymerization initiator system
本発明の着色感光性榭脂組成物に含有させる光重合開始剤又は光重合開始剤 系（本発明において、光重合開始剤系とは複数の化合物の組み合わせで光重合開 始の機能を発現する混合物をいう。）としては、米国特許第 2367660号明細書に開 示されて!/ヽるビシナルポリケタルド-ルイ匕合物、米国特許第 2448828号明細書に記 載されているァシロインエーテルィ匕合物、米国特許第 2722512号明細書に記載の a—炭化水素で置換された芳香族ァシロインィ匕合物、米国特許第 3046127号明細 書及び同第 2951758号明細書に記載の多核キノンィ匕合物、米国特許第 3549367 号明細書に記載のトリアリールイミダゾールニ量体と P—アミノケトンの組み合わせ、 特公昭 51— 48516号公報に記載のベンゾチアゾール化合物とトリハロメチルー s— トリアジンィ匕合物、米国特許第 4239850号明細書に記載されているトリハロメチル— トリアジンィ匕合物、米国特許第 4212976号明細書に記載されているトリハロメチルォ キサジァゾールイ匕合物等を挙げることができる。特に、トリハロメチル一 S トリァジン、 トリハロメチルォキサジァゾール及びトリアリールイミダゾールニ量体が好ましい。 Photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention (in the present invention, the photopolymerization initiator system expresses the function of initiation of photopolymerization by a combination of a plurality of compounds. Vicinal polyketaldo-louis compound disclosed in U.S. Pat. No. 2,367,660, and asylo described in U.S. Pat. No. 2,488,828. In-ether compounds, a-hydrocarbon substituted aromatic acylo-in compounds described in US Pat. No. 2,722,512, polynuclear compounds described in US Pat. Nos. 3,046,127 and 2,951,758 Quinone compounds, combinations of triarylimidazole dimers and P-amino ketones described in US Pat. No. 3,549,367, benzothiazole compounds and trihalomethyl-s-triazine compounds described in JP-B 51-48516 U.S. Patent No. 4239850 No. trihalomethyl described in the specification - Toriajini 匕合 thereof are described in U.S. Pat. No. 4212976 Toriharomechiruo And xadiazol compounds. In particular, trihalomethyl mono-S triazine, trihalomethyl oxadiazole, and triarylimidazole dimer are preferable.
[0250] また、この他、特開平 11— 133600号公報に記載の「重合開始剤 C」や、ォキシム 系として、 1—フエ-ルー 1, 2—プロパンジオン一 2— (o エトキシカルボ-ル）ォキ シム、 O ベンゾィル—4， - (ベンズメルカプト）ベンゾィルーへキシル—ケトキシム、 2, 4, 6 トリメチルフヱ-ルカルポ-ルージフヱ-ルフォスフォ-ルオキサイド、へキ サフルオロフォスフォロ―トリアルキルフエ-ルホスホ-ゥム塩等も好適なものとしてあ げることができる。  [0250] In addition, "polymerization initiator C" described in JP-A-11-133600, or oxime-based 1-Ferru 1, 2-propanedione 1- (o ethoxycarbol) ) Oxim, O Benzyl-4,-(Benzmercapto) Benzyl Hexyl-Ketoxime, 2, 4, 6 Trimethylphenol-Lulphyl-Folphosphate Oxide, Hexafluorophospho-Trialkylphenol Phospho- Umu salt and the like can also be mentioned as suitable.
[0251] これらの光重合開始剤又は光重合開始剤系は、単独でも、 2種類以上を混合して 用いてもよいが、特に 2種類以上を用いることが好ましい。少なくとも 2種の光重合開 始剤を用いると、表示特性、特に表示のムラが少なくできる。  [0251] These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two types of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
着色感光性榭脂組成物の全固形分に対する光重合開始剤又は光重合開始剤系 の含有量は、 0. 5〜20質量％が一般的であり、 1〜15質量％が好ましい。この量が 多すぎると感度が高くなりすぎ制御が困難になる。少なすぎると露光感度が低くなり すぎる。  The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If it is too low, the exposure sensitivity will be too low.
[0252] (その他の添加剤） [0252] (Other additives)
〔溶媒〕  [Solvent]
本発明の着色感光性榭脂組成物においては、上記成分の他に、更に有機溶媒を 用いてもよい。有機溶媒の例としては、特に限定されないが、エステル類、例えば酢 酸ェチル、酢酸 n—ブチル、酢酸イソブチル、ギ酸ァミル、酢酸イソァミル、酢酸ィ ソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸ェチル、酪酸ブチル、アルキ ルエステル類、乳酸メチル、乳酸ェチル、ォキシ酢酸メチル、ォキシ酢酸ェチル、ォ キシ酢酸ブチル、メトキシ酢酸メチル、メトキシ酢酸ェチル、メトキシ酢酸プチル、エト キシ酢酸メチル、エトキシ酢酸ェチル、 3—ォキシプロピオン酸メチル、 3—ォキシプ ロピオン酸ェチルなどの 3—ォキシプロピオン酸アルキルエステル類； 3—メトキシプ 口ピオン酸メチル、 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、 3 エトキシプロピオン酸ェチル、 2 ォキシプロピオン酸メチル、 2 ォキシプロピオ ン酸ェチル、 2—ォキシプロピオン酸プロピル、 2—メトキシプロピオン酸メチル、 2— メトキシプロピオン酸ェチル、 2—メトキシプロピオン酸プロピル、 2—エトキシプロピオ ン酸メチル、 2—エトキシプロピオン酸ェチル、 2—ォキシ 2—メチルプロピオン酸メ チル、 2—ォキシ 2—メチルプロピオン酸ェチル、 2—メトキシー 2—メチルプロピオ ン酸メチル、 2—エトキシ 2—メチルプロピオン酸ェチル、ピルビン酸メチル、ピルビ ン酸ェチル、ピルビン酸プロピル、ァセト酢酸メチル、ァセト酢酸ェチル、 2—ォキソブ タン酸メチル、 2—ォキソブタン酸ェチル等；エーテル類、例えばジエチレングリコー ルジメチノレエーテル、テトラヒドロフラン、エチレングリコーノレモノメチノレエーテル、ェ チレングリコーノレモノェチノレエーテノレ、メチノレセロソノレブアセテート、ェチノレセロソノレ ブアセテート、ジエチレングリコールモノメチルエーテル、プロピレングリコールメチル エーテルアセテート、等；ケトン類、例えばメチルェチルケトン、メチノレイソブチノレケト ン、シクロへキサノン、シクロへキサノール、 2 へプタノン、 3 へプタノン等；芳香族 炭化水素類、例えばトルエン、キシレシ等が挙げられる。これら溶剤のうち、 3—ェトキ シプロピオン酸メチル、 3—エトキシプロピオン酸ェチル、ェチルセ口ソルブァセテー ト、乳酸ェチル、酢酸ブチル、 3—メトキシプロピオン酸メチル、 2 へプタノン、シクロ へキサノン、ェチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレ ングリコールメチルエーテルアセテート等が本発明における溶剤として好ましく用いら れる。これらの溶剤は、単独で用いてもあるいは 2種以上組み合わせて用いてもよい また沸点が 180°C〜250°Cである溶剤を必要によって使用することができる。これら の高沸点溶剤としては、次のものが例示される。ジエチレングリコールモノブチルェ 一テル、ジ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、ジエチレングリコーノレ モノェチルエーテル、 3, 5, 5 トリメチルー 2 シクロへキセン 1 オン、ブチルラ クテート、ジプロピレングリコーノレ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 モノメチルエーテルアセテート、プロピレングリコールジアセテート、プロピレングリコ 一ノレ n プロピノレエーテノレアセテート、ジエチレングリコーノレジェチノレエーテノレ、 2 ェチルへキシルアセテート、 3—メトキシ 3—メチルブチルアセテート、 γブチル ラタトン、トリプロピレングリコールメチルェチルアセテート、ジプロピレングリコール η ブチルアセテート、プロピレングリコールフエ-ルエーテルアセテート、 1, 3 ブタ ンジ才ーノレジアセテート。 In the colored photosensitive resin composition of the present invention, an organic solvent may be used in addition to the above components. Examples of organic solvents include, but are not limited to, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-oxypropion Alkyl 3-alkylpropionates such as methyl 3-ethylpropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxypropionate, 2 Methyl oxypropionate 2 Okishipuropio phosphate Echiru, 2 Okishipuropion propyl, 2-methyl methoxypropionate, 2- Ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethyl ethoxypropionate, 2-oxymethyl 2-methylpropionate, 2-oxyethyl 2-methylpropionate, 2 —Methyl methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propylpyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutane Ethers such as diethylene glycol dimethinole ether, tetrahydrofuran, ethylene glycolenomonomethino ether, ethylenco glycolenomonoenoatenole, methinorecerosorebuacetate, ethinorecerosolebuacetate Jie Tylene glycol monomethyl ether, propylene glycol methyl ether acetate, etc .; Ketones such as methyl ethyl ketone, methinoreisobutinoleketone, cyclohexanone, cyclohexanol, 2 heptanone, 3 heptanone, etc .; aromatic carbonization Hydrogens such as toluene and xyles are exemplified. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, solvate acetate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, 2 heptanone, cyclohexanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent in the present invention. These solvents may be used alone or in combination of two or more. A solvent having a boiling point of 180 ° C. to 250 ° C. may be used as necessary. Examples of these high boiling point solvents are as follows. Diethylene glycol monobutyl ester, diethylene glycol monoethyl enoate acetate, diethylene glycol monoethyl ether, 3, 5, 5 trimethyl-2-cyclohexene 1-one, butyl lactate, dipropylene glycol monomethenoylate Tenoleacetate, Propylene glycol monomethyl ether acetate, Propylene glycol diacetate, Propylene glycol mononole n Propinoleate tenoleacetate, Diethyleneglycolole chinenoreatenore, 2-ethylhexyl acetate, 3-methoxy 3-methylbutyl acetate, γ-butyl Rataton, tripropylene glycol methyl ethyl acetate, dipropylene glycol η butyl acetate, propylene glycol phenol ether acetate 1, 3 pigs Niji-noresi acetate.
溶媒の含有量は、榭脂組成物全量に対して 10〜95質量％が好ましい。  The content of the solvent is preferably 10 to 95% by mass with respect to the total amount of the resin composition.
[0254] 〔界面活性剤〕 [Surfactant]
従来用いられてきたカラーフィルタにお 、ては、高 、色純度を実現するために各画 素の色が濃くなり、画素の膜厚のムラ力 そのまま色ムラとして認識されるという問題 があった。そのため、画素の膜厚に直接影響する、感光性榭脂層の形成 (塗布)時の 、膜厚変動の良化が求められていた。  The color filters that have been used in the past have a problem that the color of each pixel becomes darker in order to achieve high color purity, and the uneven power of the pixel film thickness is recognized as color unevenness as it is. . For this reason, it has been demanded to improve the film thickness fluctuation when forming (coating) the photosensitive resin layer, which directly affects the film thickness of the pixel.
本発明のカラーフィルタ又は本発明の感光性榭脂転写材料においては、均一な膜 厚に制御でき、塗布ムラ (膜厚変動による色ムラ)を効果的に防止するという観点から 、該着色感光性榭脂組成物中に適切な界面活性剤を含有させることが好まし ヽ。 上記界面活性剤としては、特開 2003— 337424号公報、特開平 11— 133600号 公報に開示されている界面活性剤力 好適なものとして挙げられる。界面活性剤の 含有量は、榭脂組成物全量に対して 5質量％以下が好ま ヽ。  The color filter of the present invention or the photosensitive resin transfer material of the present invention can be controlled to have a uniform film thickness, and from the viewpoint of effectively preventing coating unevenness (color unevenness due to film thickness variation), It is preferable to include an appropriate surfactant in the greave composition. Examples of the surfactant include those disclosed in JP-A-2003-337424 and JP-A-11-133600. The content of the surfactant is preferably 5% by mass or less based on the total amount of the resin composition.
[0255] 〔熱重合防止剤〕 [0255] [Thermal polymerization inhibitor]
本発明の着色感光性榭脂組成物は、熱重合防止剤を含むことが好ましい。該熱重 合防止剤の例としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、 p—メトキ シフエノーノレ、ジー tーブチノレー p—クレゾ一ノレ、ピロガローノレ、 tーブチノレ力テコーノレ 、ベンゾキノン、 4, 4'ーチォビス（3—メチルー 6— t—ブチルフエノール）、 2, 2，ーメ チレンビス（4ーメチルー 6— t—ブチルフエノール）、 2—メルカプトべンズイミダゾー ル、フヱノチアジン等が挙げられる。熱重合防止剤の含有量は、榭脂組成物全量に 対して 1質量％以下が好ましい。  The colored photosensitive resin composition of the present invention preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxy fenenore, di-t-butinole p-crezo-monore, pyrogalonore, tert-tinole teconole, benzoquinone, 4, 4'-thiobis (3-methyl-6 — T-Butylphenol), 2,2, -Methylenebis (4-methyl-6-t-butylphenol), 2-Mercaptobens imidazole, and Funothiazine. The content of the thermal polymerization inhibitor is preferably 1% by mass or less based on the total amount of the resin composition.
[0256] 〔補助的に使用する染料、顔料〕 [0256] [Dyes and pigments used auxiliary]
本発明の着色感光性榭脂組成物には、必要に応じ前記着色剤 (顔料）に加えて、 着色剤 (染料、顔料)を添加することができる。着色剤のうち顔料を用いる場合には、 着色感光性榭脂組成物中に均一に分散されていることが望ましぐそのため粒径が 0 . 1 μ m以下、特には 0. 08 μ m以下であることが好ましい。  In addition to the colorant (pigment), a colorant (dye or pigment) can be added to the colored photosensitive resin composition of the present invention as necessary. When using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition, so that the particle size is 0.1 μm or less, particularly 0.0 μm or less. It is preferable that
染料ないし顔料としては、具体的には、前記顔料として、特開 2005— 17716号公 報 [0038]〜 [0040]に記載の色材や、特開 2005 - 361447号公報 [0068]〜 [0 072]に記載の顔料や、特開 2005— 17521号公報 [0080]〜[0088]に記載の着 色剤を好適に用いることができる。補助的に使用する染料もしくは顔料の含有量は、 榭脂組成物全量に対して 5質量％以下が好ま U 、。 Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716, [0038]-[0040], and JP-A-2005-361447 [0068]-[0]. [072] and the colorants described in JP-A-2005-17521, [0080] to [0088] can be suitably used. The auxiliary dye or pigment content is preferably 5% by weight or less, based on the total amount of the resin composition.
[0257] 〔紫外線吸収剤〕  [0257] [Ultraviolet absorber]
本発明の着色感光性榭脂組成物には、必要に応じて紫外線吸収剤を含有すること ができる。紫外線吸収剤としては、特開平 5— 72724号公報記載の化合物のほか、 サリシレート系、ベンゾフエノン系、ベンゾトリアゾール系、シァノアクリレート系、 -ッケ ルキレート系、ヒンダードアミン系などが挙げられる。  The colored photosensitive resin composition of the present invention can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, -chelate-chelated, and hindered amine-based compounds in addition to the compounds described in JP-A-5-72724.
具体的には、フエ-ルサリシレート、 4 t—ブチルフエ-ルサリシレート、 2, 4ージ t ブチルフエ-ルー 3 ' , 5 '—ジ—t—4'ーヒドロキシベンゾエート、 4—tーブチ ルフエ-ルサリシレート、 2, 4ージヒドロキシベンゾフエノン、 2 ヒドロキシー4ーメトキ シベンゾフエノン、 2 ヒドロキシ一 4— n—オタトキシベンゾフエノン、 2— (2'—ヒドロ キシ 5 ' メチルフエニル）ベンゾトリァゾール、 2—（2'—ヒドロキシ 3 ' t ブチ ルー 5，一メチルフエ-ル） 5 クロ口べンゾトリァゾール、ェチル 2 シァノ 3, 3 —ジフエ-ルアタリレート、 2, 2，一ヒドロキシ一 4—メトキシベンゾフエノン、ニッケルジ ブチルジチォカーバメート、ビス（2, 2, 6, 6—テトラメチルー 4 ピリジン） セバケ ート、 4 t—ブチルフエ-ルサリシレート、サルチル酸フエ-ル、 4ーヒドロキシ 2, 2 , 6, 6—テトラメチルピペリジン縮合物、コハク酸一ビス（2, 2, 6, 6—テトラメチルー 4 ピペリデュル）—エステル、 2— [2 ヒドロキシ— 3, 5 ビス（ α , a—ジメチルべ ンジル）フエ-ル]— 2H ベンゾトリァゾール、 7— { [4 クロ口一 6— (ジェチルァミノ )—5 トリァジン— 2—ィル]アミノ} 3 フエ-ルクマリン等が挙げられる。紫外線 吸収剤の含有量は、榭脂組成物全量に対して 5質量％以下が好ま 、。  Specifically, ferric salicylate, 4 t-butyl ferric salicylate, 2,4-di-t-butyl ferrule 3 ', 5'-di-t-4'-hydroxybenzoate, 4-t-butyl fuel Salicylate, 2,4-Dihydroxybenzophenone, 2 Hydroxy-4-methoxybenzophenone, 2 Hydroxy 4-n-Otoxybenzophenone, 2 -— (2′-Hydroxy-5′-methylphenyl) benzotriazole, 2 -— (2 '—Hydroxy 3' t-butyl-5, 1-methylphenol) 5 Chronobenzozoazole, Ethyl 2 Cyan 3, 3—Diphenyl acrylate, 2, 2, 1-hydroxy 4-methoxybenzophenone, Nickel dibutyl Dithiocarbamate, bis (2, 2, 6, 6-tetramethyl-4-pyridine) sebacate, 4 t-butylphenol salicylate, salicylate, 4-hydroxy 2, 2, 6, 6-tetramethylpiperidine condensate, monobis (2, 2, 6, 6-tetramethyl-4-piperidururyl) -ester, 2- [2 hydroxy-3,5 bis (α, a-dimethyl) Benzyl) phenol] —2H benzotriazole, 7 — {[4 black mouth 6- (jetylamino) -5 triazine-2-yl] amino} 3 phenolcoumarin, and the like. The content of the ultraviolet absorber is preferably 5% by mass or less with respect to the total amount of the resin composition.
[0258] また、本発明の着色感光性榭脂組成物においては、上記添加剤の他に、特開平 1 1—133600号公報に記載の「接着助剤」や、その他の添加剤等を含有させることが できる。  [0258] Further, the colored photosensitive resin composition of the present invention contains "adhesion aid" described in JP-A-11-133600, other additives and the like in addition to the above-mentioned additives. It can be made.
[0259] [着色感光性榭脂組成物の塗布膜]  [0259] [Coating film of colored photosensitive resin composition]
本発明の着色感光性榭脂組成物を用いた塗布膜における含有成分については、 既に [着色感光性榭脂組成物]の項において記載したものと同様である。また、本発 明の着色感光性榭脂組成物を用いた塗布膜の厚さは、その用途により適宜定めるこ と力 Sできる力 S、0. 5〜5. O /z mであること力 S好ましく、 1. 0〜3. 0 mであること力 Sより 好ましい。この本発明の着色感光性榭脂組成物を用いた塗布膜においては、そこに 含まれる (c)モノマー又はオリゴマーを重合させて着色感光性榭脂組成物の重合膜 とし、それを有するカラーフィルタを作製することができる（カラーフィルタの作製につ いては後述する。 ) o重合性モノマー又は重合性オリゴマーの重合は、光照射により（ d)光重合開始剤又は光重合開始剤系を作用させて行うことができる。 The components contained in the coating film using the colored photosensitive resin composition of the present invention are the same as those already described in the section of [Colored photosensitive resin composition]. In addition, this departure The thickness of the coating film using the bright colored photosensitive resin composition can be determined as appropriate according to the application force S capable of being S, 0.5-5.O / zm force S, preferably 1. It is more preferably 0 to 3.0 m than force S. In the coating film using the colored photosensitive resin composition of the present invention, (c) a monomer or oligomer contained therein is polymerized to form a colored photosensitive resin composition polymer film, and a color filter having the same (The production of the color filter will be described later.) O Polymerization of the polymerizable monomer or polymerizable oligomer is effected by (d) photopolymerization initiator or photopolymerization initiator system by light irradiation. Can be done.
[0260] (スリット状ノズル） [0260] (Slit nozzle)
尚、上記塗布膜は、着色感光性榭脂組成物を、通常の塗布方法により塗布し乾燥 することによって形成することができるが、本発明においては、液が吐出する部分に スリット状の穴を有するスリット状ノズルによって塗布することが好ましい。具体的には 、特開 2004— 89851号公報、特開 2004— 17043号公報、特開 2003— 170098 号公報、特開 2003— 164787号公報、特開 2003— 10767号公報、特開 2002— 7 9163号公報、特開 2001— 310147号公報等に記載のスリット状ノズル、及びスリツ トコータが好適に用いられる。  The coating film can be formed by applying a colored photosensitive resin composition by a normal coating method and drying, but in the present invention, a slit-like hole is formed in a portion from which the liquid is discharged. It is preferable to apply with a slit-shaped nozzle. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-7 Slit nozzles and slit coaters described in 9163, JP 2001-310147, and the like are preferably used.
[0261] 着色感光性榭脂組成物の基板への塗布方法は、 1〜3 μ mの薄膜を均一に高精 度に塗布できるという点からスピン塗布が優れており、カラーフィルタの作製に広く一 般的に用いることができる。しかし、近年においては、液晶表示装置の大型化および 量産化に伴って、製造効率および製造コストをより高めるために、スピン塗布よりも広 幅で大面積な基板の塗布に適したスリット塗布がカラーフィルタの作製に採用される ようになってきている。尚、省液性という観点力らもスリット塗布はスピン塗布よりも優れ ており、より少ない塗布液量で均一な塗膜を得ることができる。  [0261] The coating method of the colored photosensitive resin composition on the substrate is superior in spin coating because it can uniformly and precisely coat a thin film of 1 to 3 μm, and is widely used for the production of color filters. Can be used generally. However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger than spin coating has been developed in order to increase manufacturing efficiency and manufacturing cost. It has come to be used for the production of filters. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.
[0262] スリット塗布は、先端に幅数十ミクロンのスリット（間隙)を有し且つ矩形基板の塗布 幅に対応する長さの塗布ヘッドを、基板とのクリアランス（間隙）を数 10〜数 100ミクロ ンに保持しながら、基板と塗布ヘッドとに一定の相対速度を持たせて、所定の吐出量 でスリットから供給される塗布液を基板に塗布する塗布方式である。このスリット塗布 は、（1)スピン塗布に比して液ロスが少ない、（2)塗布液の飛びちりがないため洗浄 処理が軽減される、（3)飛び散った液成分の塗布膜への再混入がない、（4)回転の 立ち上げ停止時間がないのでタクトタイムが短縮ィ匕できる、 (5)大型の基板への塗布 が容易である、等の利点を有する。これらの利点から、スリット塗布は大型画面液晶 表示装置用のカラーフィルタの作製に好適であり、塗布液量の削減にとっても有利な 塗布方式として期待されて ヽる。 [0262] For slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is used, and the clearance (gap) with the substrate is several tens to several hundreds. This is a coating method in which the substrate and the coating head are given a constant relative speed while being held in a micron, and the coating liquid supplied from the slit is applied to the substrate with a predetermined discharge amount. This slit coating is (1) less liquid loss than spin coating, (2) no coating liquid jumping, reducing the cleaning process, and (3) respraying scattered liquid components to the coating film. No contamination, (4) rotation Since there is no start-up stop time, the tact time can be shortened, and (5) it is easy to apply to a large substrate. Because of these advantages, slit coating is suitable for producing color filters for large-screen liquid crystal display devices, and is expected to be an advantageous coating method for reducing the amount of coating liquid.
[0263] スリット塗布は、スピン塗布よりも遥かに大面積の塗布膜を形成するため、幅の広い スリット出口力 塗布液を吐出する際、コーターと被塗布物との間にある程度の相対 速度を保つ必要がある。このため、スリット塗布方式に用いる塗布液には良好な流動 性が求められる。また、スリット塗布には、塗布ヘッドのスリットから基板に供給される 塗布液の諸条件を、塗布幅全般に渡って一定に保持することが特に求められる。塗 布液の流動性や粘弾性特性等の液物性が不充分であると、塗布ムラが生じやすぐ 塗布幅方向に塗布厚を一定に保つのが困難になり、均一な塗布膜を得ることができ な!、と!/、う問題が生じてしまう。  [0263] Since slit coating forms a coating film with a much larger area than spin coating, a wide slit exit force When discharging coating liquid, a certain degree of relative speed is applied between the coater and the object to be coated. Need to keep. For this reason, good fluidity is required for the coating solution used in the slit coating method. In addition, the slit coating is particularly required to keep the conditions of the coating solution supplied to the substrate from the slit of the coating head constant over the entire coating width. If the liquid properties such as fluidity and viscoelastic properties of the coating liquid are insufficient, uneven coating will occur and it will be difficult to keep the coating thickness constant in the coating width direction, and a uniform coating film will be obtained. I can't do that!
[0264] これらのことから、ムラがなく均一な塗布膜を得るために塗布液の流動性や粘弾性 特性を改良しょうとする試みが多くなされている。しかし、上述したようにポリマーの分 子量を低下させたり、溶剤への溶解性に優れたポリマーを選択したり、蒸発速度をコ ントロールするために溶剤を種々選択したり、界面活性剤を利用するなどの手段が提 案されているが、いずれも上記の諸問題を改良するには充分ではな力つた。  [0264] For these reasons, many attempts have been made to improve the fluidity and viscoelastic properties of the coating solution in order to obtain a uniform coating film without unevenness. However, as described above, the polymer molecular weight is reduced, a polymer with excellent solubility in the solvent is selected, various solvents are selected to control the evaporation rate, and a surfactant is used. However, all of these measures were not sufficient to improve the above problems.
[0265] [感光性転写材料]  [0265] [Photosensitive transfer material]
次に、本発明の感光性転写材料について説明する。  Next, the photosensitive transfer material of the present invention will be described.
本発明の感光性転写材料は、特開平 5— 72724号公報に記載されている感光性 榭脂転写材料、すなわち一体型となったフィルムを用いて形成することが好ま ヽ。 該ー体型フィルムの構成の例としては、仮支持体 Z熱可塑性榭脂層 Z中間層 Z感 光性榭脂層 Z保護フィルムを、この順に積層した構成が挙げられ、本発明の感光性 転写材料としては、前述の本発明の着色感光性榭脂組成物を用いることによって感 光性榭脂を設けたものである。  The photosensitive transfer material of the present invention is preferably formed using a photosensitive resin transfer material described in JP-A-5-72724, that is, an integrated film. Examples of the constitution of the body-type film include a constitution in which the temporary support Z, the thermoplastic resin layer Z, the intermediate layer Z, the photosensitive resin layer Z, and the protective film are laminated in this order, and the photosensitive transfer of the present invention. As a material, a photosensitive photosensitive resin is provided by using the above-described colored photosensitive resin composition of the present invention.
[0266] (仮支持体） [0266] (Temporary support)
本発明の感光性転写材料において、仮支持体としては、可撓性を有し、加圧、若し くは加圧及び加熱下にお ヽても著し!/、変形、収縮若しくは伸びを生じな ヽものである ことが必要である。そのような仮支持体の例としては、ポリエチレンテレフタレートフィ ルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、ポリカーボネートフィルム等 を挙げることができ、中でも 2軸延伸ポリエチレンテレフタレートフィルムが特に好まし い。 In the photosensitive transfer material of the present invention, the temporary support is flexible and can be marked even under pressure, or even under pressure and heating! /, Deformation, shrinkage or elongation. Does not occur It is necessary. Examples of such a temporary support include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film and the like, and among them, biaxially stretched polyethylene terephthalate film is particularly preferable.
[0267] (熱可塑性榭脂層）  [0267] (Thermoplastic resin layer)
熱可塑性榭脂層に用いる成分としては、特開平 5 - 72724号公報に記載されて ヽ る有機高分子物質が好ましぐヴィカー Vicat法 (具体的にはアメリカ材料試験法ェ 一エステ一エムデ一 ASTMD1235によるポリマー軟ィ匕点測定法）による軟ィ匕点が約 80°C以下の有機高分子物質より選ばれることが特に好ましい。具体的には、ポリエ チレン、ポリプロピレンなどのポリオレフイン、エチレンと酢酸ビュル或いはそのケン化 物の様なエチレン共重合体、エチレンとアクリル酸エステル或いはそのケン化物、ポ リ塩化ビニル、塩ィ匕ビニルと酢酸ビュル及びそのケンィ匕物の様な塩ィ匕ビニル共重合 体、ポリ塩ィ匕ビユリデン、塩化ビ-リデン共重合体、ポリスチレン、スチレンと (メタ）ァク リル酸エステル或いはそのケン化物の様なスチレン共重合体、ポリビュルトルエン、ビ -ルトルエンと（メタ）アクリル酸エステル或いはそのケン化物の様なビュルトルエン共 重合体、ポリ (メタ)アクリル酸エステル、（メタ)アクリル酸ブチルと酢酸ビニル等の (メ タ）アクリル酸エステル共重合体、酢酸ビュル共重合体ナイロン、共重合ナイロン、 N -アルコキシメチルイ匕ナイロン、 N -ジメチルァミノ化ナイロンの様なポリアミド榭脂等 の有機高分子が挙げられる。  As a component used for the thermoplastic resin layer, an organic polymer substance described in JP-A-5-72724 is preferred. The Vicat method (specifically, the American Material Testing Method, Est. It is particularly preferred that the polymer is selected from organic polymer materials having a soft softening point measured by ASTM D1235 of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and butyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, and vinyl chloride. Salt-vinyl copolymer such as butyl acetate and its ken hydrate, poly-salt vinylidene, vinylidene chloride copolymer, polystyrene, styrene and (meth) acrylic acid ester or saponified product thereof Styrene copolymer, polytoluene toluene, vinyl toluene and (meth) acrylic acid ester or saponified butyltoluene copolymer, poly (meth) acrylic acid ester, (meth) acrylic acid butyl and vinyl acetate Such as (meth) acrylic acid ester copolymer, butyl acetate copolymer nylon, copolymer nylon, N-alkoxy Examples thereof include organic polymers such as polyamide resin such as dimethyl methyl nylon and N-dimethylaminolated nylon.
[0268] (中間層）  [0268] (middle layer)
本発明の感光性転写材料においては、複数の塗布層の塗布時、及び塗布後の保 存時における成分の混合を防止する目的から、中間層を設けることが好ましい。該中 間層としては、特開平 5— 72724号公報に「分離層」として記載されている、酸素遮 断機能のある酸素遮断膜を用いることが好ましぐこの場合、露光時感度がアップし、 露光機の時間負荷が減り、生産性が向上する。  In the photosensitive transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function described in JP-A-5-72724 as a “separation layer”. The time load of the exposure machine is reduced and the productivity is improved.
該酸素遮断膜としては、低い酸素透過性を示し、水又はアルカリ水溶液に分散又 は溶解するものが好ましぐ通常のものの中力も適宜選択することができる。これらの 内、特に好ましいのは、ポリビュルアルコールとポリビュルピロリドンとの組み合わせ である。 As the oxygen-blocking membrane, a normal medium force that exhibits low oxygen permeability and is preferably dispersed or dissolved in water or an aqueous alkali solution can be appropriately selected. Of these, the combination of polybulal alcohol and polybulurpyrrolidone is particularly preferred. It is.
[0269] (保護フィルム）  [0269] (Protective film)
感光性榭脂層の上には、貯蔵の際の汚染や損傷力も保護するために薄い保護フ イルムを設けることが好まし ヽ。保護フィルムは仮支持体と同じか又は類似の材料か らなってもよいが、感光性榭脂層から容易に分離されねばならない。保護フィルム材 料としては例えばシリコーン紙、ポリオレフイン若しくはポリテトラフルォロエチレンシ ートが適当である。  It is preferable to provide a thin protective film on the photosensitive resin layer to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin, or polytetrafluoroethylene sheet is suitable as the protective film material.
[0270] (感光性転写材料の作製方法）  [0270] (Method for producing photosensitive transfer material)
本発明の感光性転写材料は、仮支持体上に熱可塑性榭脂層の添加剤を溶解した 塗布液 (熱可塑性榭脂層用塗布液)を塗布し、乾燥することにより熱可塑性榭脂層を 設け、その後熱可塑性榭脂層上に熱可塑性榭脂層を溶解しな 、溶剤力もなる中間 層材料の溶液を塗布、乾燥し、その後感光性榭脂層を、中間層を溶解しない溶剤で 塗布、乾燥して設けることにより作製することができる。  The photosensitive transfer material of the present invention is obtained by applying a coating solution in which an additive for a thermoplastic resin layer is dissolved on a temporary support (a coating solution for a thermoplastic resin layer) and drying the thermoplastic resin layer. After that, a solution of an intermediate layer material that also has solvent power is applied and dried on the thermoplastic resin layer without dissolving the thermoplastic resin layer, and then the photosensitive resin layer is coated with a solvent that does not dissolve the intermediate layer. It can be prepared by coating and drying.
また、前記の仮支持体上に熱可塑性榭脂層及び中間層を設けたシート、及び保護 フィルム上に感光性榭脂層を設けたシートを用意し、中間層と感光性榭脂層が接す るように相互に貼り合わせることによつても、更には、前記の仮支持体上に熱可塑性 榭脂層を設けたシート、及び保護フィルム上に感光性榭脂層及び中間層を設けたシ ートを用意し、熱可塑性榭脂層と中間層が接するように相互に貼り合わせることによ つても、作製することができる。  In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, by bonding together, a sheet provided with a thermoplastic resin layer on the temporary support, and a photosensitive resin layer and an intermediate layer were provided on a protective film. It can also be produced by preparing a sheet and bonding them together so that the thermoplastic resin layer and the intermediate layer are in contact with each other.
[0271] 本発明の感光性転写材料において、感光性榭脂層の膜厚としては、 1. 0〜5. Ο μ m力好ましく、 1. 0〜4. O /z m力より好ましく、 1. 0〜3. 0 m力 ^特に好まし!/ヽ。また、 特に限定されるわけではないが、その他の各層の好ましい膜厚としては、仮支持体 ίま 15〜： LOO /z m 熱可塑'性榭月旨層【ま2〜30 111、中 層 ίま 0. 5〜3. O /z m、保護 フィルムは 4〜40 m力 一般的に好ましい。  In the photosensitive transfer material of the present invention, the thickness of the photosensitive resin layer is preferably 1.0 to 5. μm force, more preferably 1.0 to 4. O / zm force. 0 ~ 3.0 m force ^ Especially preferred! / ヽ. Further, although not particularly limited, the preferred film thickness of each of the other layers is as follows: Temporary support 15 to: LOO / zm Also 0.5-3. O / zm, protective film 4-40 m force is generally preferred.
[0272] 尚、上記作製方法における塗布は、通常の塗布装置等によって行うことができるが [0272] Note that the coating in the above production method can be performed by a normal coating apparatus or the like.
、本発明においては、既に [着色感光性榭脂組成物の塗布膜]の項において説明し た、スリット状ノズルを用いた塗布装置 (スリットコータ）によって行うことが好ましい。ス リツトコータの好ましい具体例等は、前記と同様である。 [0273] [カラーフィルタ] In the present invention, the coating is preferably performed by the coating apparatus (slit coater) using the slit-like nozzle already described in the section of [Coating film of colored photosensitive resin composition]. Preferred specific examples of the slit coater are the same as described above. [0273] [Color filter]
本発明のカラーフィルタは、コントラストに優れたものとして用いることができる。本発 明においてコントラストとは、 2枚の偏光板の間において、偏光軸が平行のときと、垂 直のときとの透過光量の比を表す（「1990年第 7回色彩光学コンファレンス、 512色 表示 10. 4"サイズ TFT— LCD用カラーフィルタ、植木、小関、福永、山中」等参照。  The color filter of the present invention can be used as one having excellent contrast. In the present invention, contrast refers to the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 7th Color Optical Conference, 512 color display 10 See 4 "size TFT — color filters for LCD, Ueki, Koseki, Fukunaga, Yamanaka" etc.
) o  ) o
カラーフィルタのコントラストが高いということは液晶と組み合わせたときの明暗のデ イスクリミネーシヨンが大きくできるということを意味しており、液晶ディスプレイが CRT に置き換わるためには非常に重要な性能である。  The high contrast of the color filter means that the brightness and darkness discrimination when combined with the liquid crystal can be increased. This is a very important performance in order to replace the liquid crystal display with a CRT.
[0274] 本発明のカラーフィルタは、テレビ用として用いる場合は、 F10光源による、レッド（ R)、グリーン (G)、及びブルー（B)のそれぞれ全ての単色の色度力 下表に記載の 値 (以下、本発明にお 、て「目標色度」と 、う。）との差（ Δ E)で 5以内の範囲であるこ と力 子ましく、更に 3以内であることがより好ましぐ 2以内であることが特に好ましい。  [0274] When the color filter of the present invention is used for television, the chromaticity power of each single color of red (R), green (G), and blue (B) by the F10 light source is as described in the table below. The difference (ΔE) from the value (hereinafter referred to as “target chromaticity” in the present invention) is preferably within a range of 5 or less, and more preferably 3 or less. It is particularly preferable that the number is within 2.
[0275] X y Y  [0275] X y Y
R 0. 656 0. 336 21. 4 R 0. 656 0. 336 21. 4
G 0. 293 0. 634 52. 1  G 0. 293 0. 634 52. 1
B 0. 146 0. 088 6. 90  B 0. 146 0. 088 6. 90
[0276] 本発明において色度は、顕微分光光度計 (ォリンパス光学社製; OSP100又は 20 0)により測定し、 F10光源視野 2度の結果として計算して、 xyz表色系の xyY値で表 す。また、 目標色度との差は、 La*b*表色系の色差で表す。 [0276] In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. The The difference from the target chromaticity is expressed by the color difference of the La * b * color system.
[0277] (感光性樹脂層） [0277] (Photosensitive resin layer)
本発明のカラーフィルタは、基板上に感光性榭脂層を形成し、露光して現像するこ とを色の数だけ繰り返す方法などの方法によって製造することができる。尚、必要に 応じて、その境界をブラックマトリックスで区分した構造とすることもできる。  The color filter of the present invention can be produced by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated for the number of colors. If necessary, the boundary may be divided by a black matrix.
上記の製造方法において、基板上に上記感光性榭脂層を形成する方法としては、 (a)上記の各着色感光性榭脂組成物を通常の塗布装置等によって塗布する方法、 及び (b)前述の感光性転写材料を用い、ラミネーターによって貼り付ける方法などが 挙げられる。 In the above production method, as a method of forming the photosensitive resin layer on the substrate, (a) a method of applying each of the above colored photosensitive resin compositions with a normal application device, etc. And (b) a method of using the above-mentioned photosensitive transfer material and affixing with a laminator.
[0278] (a)塗布装置による塗布  [0278] (a) Application by application device
本発明のカラーフィルタを製造する際、着色感光性榭脂組成物の塗布には、通常 の塗布装置を用いることができるが、中でも特に、既に [着色感光性榭脂組成物の塗 布膜]の項において説明した、スリットコータを好適に用いることができる。尚、スリット コータの好ましい具体例等は、前記と同様である。感光性榭脂層を塗布により形成す る場合、その膜厚としては、 1. 0〜3. O /z mが好ましく、 1. 0〜2. 5 /z mがより好まし く、 1. 5〜2. 5 111カ^特に好まし1ヽ0 In the production of the color filter of the present invention, an ordinary coating apparatus can be used for coating the colored photosensitive resin composition, but among others, already [coated film of colored photosensitive resin composition] The slit coater described in the section can be preferably used. Preferred examples of the slit coater are the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3. O / zm, more preferably 1.0 to 2.5 / zm, 1.5 to 2.5 5 111 especially preferred 1 ヽ0
[0279] (b)ラミネーターによる貼り付け  [0279] (b) Pasting with a laminator
本発明の感光性転写材料を用い、フィルム状に形成した感光性榭脂層を、後述す る基板上に、加熱及び Z又は加圧した、ローラー又は平板で、圧着又は加熱圧着す ることによって、貼り付けることができる。具体的には、特開平 7— 110575号公報、特 開平 11— 77942号公報、特開 2000— 334836号公報、特開 2002— 148794号 公報に記載のラミネーター及びラミネート方法が挙げられるが、低異物の観点で、特 開平 7— 110575号公報に記載の方法を用いるのが好ましい。尚、感光性榭脂層を 前記本発明の感光性転写材料により形成する場合の、その好ましい膜厚は、 [感光 性榭脂転写材料]の項にお!ヽて記載した好ま Uヽ膜厚と同様である。  By using a photosensitive transfer material according to the present invention, a photosensitive resin layer formed into a film is pressure-bonded or heat-pressed with a roller or flat plate heated and Z or pressurized on a substrate described later. Can be pasted. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. In the case where the photosensitive resin layer is formed of the photosensitive transfer material of the present invention, the preferable film thickness is the preferred U film thickness described in the section of [Photosensitive resin transfer material]. It is the same.
[0280] (基板）  [0280] (Substrate)
本発明において、カラーフィルタが形成される基板としては、例えば、透明基板が 用いられ、表面に酸ィ匕ケィ素皮膜を有するソーダガラス板、低膨張ガラス、ノンアル力 リガラス、石英ガラス板等の公知のガラス板、或いは、プラスチックフィルム等を挙げる ことができる。  In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known soda glass plate, low expansion glass, non-alkaline glass, quartz glass plate, etc., having an acid silicon film on the surface. Glass plate or plastic film.
また、上記基板は、予めカップリング処理を施しておくことにより、着色感光性榭脂 組成物、又は感光性転写材料との密着を良好にすることができる。該カップリング処 理としては、特開 2000— 39033号公報記載の方法が好適に用いられる。尚、特に 限定されるわけではないが、基板の膜厚としては、 700〜1200 /ζ πιが一般的に好ま しく、 500〜： L 100 m力特に好まし!/ヽ。 [0281] (酸素遮断膜） Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring photosensitive resin composition or a photosensitive transfer material by performing a coupling process previously. As the coupling process, a method described in JP-A-2000-39033 is preferably used. Although not particularly limited, the film thickness of the substrate is generally preferably 700 to 1200 / ζ πι, and 500 to: L 100 m force is particularly preferable! / ヽ. [0281] (Oxygen barrier membrane)
本発明のカラーフィルタは、感光性榭脂層を、着色感光性榭脂組成物の塗布によ つて形成する場合において、該感光性榭脂層上に更に酸素遮断膜を設けることがで き、これにより、露光感度をアップすることができる。該酸素遮断膜としては、既に [感 光性榭脂転写材料]の（中間層）の項において説明したものと同様のものが挙げられ る。尚、特に限定されるわけではないが、酸素遮断膜の膜厚としては、 0. 5〜3. Ο μ mが一般的に好ましい。  In the color filter of the present invention, when the photosensitive resin layer is formed by applying a colored photosensitive resin composition, an oxygen-blocking film can be further provided on the photosensitive resin layer. Thereby, exposure sensitivity can be improved. Examples of the oxygen-blocking film include those already described in the section (intermediate layer) of [Photosensitive resin transfer material]. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3. μm.
[0282] (露光及び現像） [0282] (Exposure and development)
上記基板上に形成された感光性榭脂層の上方に所定のマスクを配置し、その後該 マスク、熱可塑性榭脂層、及び中間層を介してマスク上方力も露光し、次いで現像液 による現像を行う、という工程を色の数だけ繰り返すことにより、本発明のカラーフィル タを得ることがでさる。  A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then the mask upward force is also exposed through the mask, the thermoplastic resin layer, and the intermediate layer, and then development with a developer is performed. It is possible to obtain the color filter of the present invention by repeating the process of performing as many times as the number of colors.
ここで、前記露光の光源としては、感光性榭脂層を硬化しうる波長域の光 (例えば、 365nm、 405nmなど）を照射できるものであれば適宜選定して用いることができる。 具体的には、超高圧水銀灯、高圧水銀灯、メタルハライドランプ等が挙げられる。露 光量としては、通常 5〜200mjZcm2程度であり、好ましくは 10〜： LOOmjZcm2程度 である。 Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The amount of exposure is usually about 5 to 200 mjZcm 2 , preferably 10 to about LOOmjZcm 2 .
[0283] また、前記現像液としては、特に制約はなぐ特開平 5— 72724号公報に記載のも のなど、通常の現像液を使用することができる。尚、現像液は感光性榭脂層が溶解 型の現像挙動をするものが好ましぐ例えば、 1^&= 7〜13のィ匕合物を0. O5〜5mo 1ZLの濃度で含むものが好ま ヽが、更に水と混和性を有する有機溶剤を少量添加 してちよい。  [0283] Further, as the developer, a normal developer such as that described in JP-A-5-72724, which is not particularly limited, can be used. In addition, it is preferable that the developer has a developing behavior in which the photosensitive resin layer is dissolved. For example, a developer containing 1 ^ & = 7 to 13 in a concentration of 0. O5 to 5mo 1ZL. Preferably, a small amount of an organic solvent miscible with water may be added.
水と混和性を有する有機溶剤としては、メタノール、エタノール、 2—プロパノール、 1 プロパノール、ブタノール、ジアセトンアルコール、エチレングリコーノレモノメチノレ エーテノレ、エチレングリコーノレモノェチノレエーテノレ、エチレングリコーノレモノー n—ブ チルエーテル、ベンジルアルコール、アセトン、メチルェチルケトン、シクロへキサノン 、 ε 一力プロラタトン、 Ί ブチロラタトン、ジメチルホルムアミド、ジメチルァセトアミドExamples of organic solvents that are miscible with water include methanol, ethanol, 2-propanol, 1 propanol, butanol, diacetone alcohol, ethylene glycol monomethino ethenole, ethylene glycol monomethino enotenole, and ethylene glycol monomethanol. n- Bed Chirueteru, benzyl alcohol, acetone, methyl E chill ketone, cyclohexanone, epsilon Ichiriki Purorataton, I Buchirorataton, dimethylformamide, dimethyl § Seth amide
、へキサメチルホスホルアミド、乳酸ェチル、乳酸メチル、 ε—力プロラタタム、 Ν—メ チルピロリドン等を挙げることができる。該有機溶剤の濃度は 0. 1質量％〜30質量 %が好ましい。 , Hexamethylphosphoramide, Ethyl lactate, Methyl lactate, ε-force prolatatam, Ν-me Examples include tilpyrrolidone. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
また、上記現像液には、更に通常の界面活性剤を添加することができる。界面活性 剤の濃度は 0. 01質量％〜10質量％が好ましい。  Further, a normal surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
[0284] 現像の方式としては、パドル現像、シャワー現像、シャワー &スピン現像、ディプ現 像等の方法を用いることができる。 [0284] As the development method, methods such as paddle development, shower development, shower & spin development, and dip imaging can be used.
ここで、上記シャワー現像について説明すると、露光後の感光性榭脂層に現像液 をシャワーにより吹き付けることにより、未硬化部分を除去することができる。尚、現像 の前に感光性榭脂層の溶解性が低いアルカリ性の液をシャワーなどにより吹き付け、 熱可塑性榭脂層、中間層などを除去しておくことが好ましい。また、現像の後に、洗 浄剤などをシャワーにより吹き付け、ブラシなどで擦りながら、現像残渣を除去するこ とが好ましい。  Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the photosensitive resin layer after exposure. Prior to development, it is preferable to spray an alkaline solution having a low solubility of the photosensitive resin layer with a shower or the like to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a detergent or the like with a shower and rubbing with a brush or the like.
現像液の液温度は 20°C〜40°Cが好ましぐまた、現像液の pHは 8〜13が好まし い。  The developer temperature is preferably 20 ° C to 40 ° C, and the developer pH is preferably 8 to 13.
[0285] 尚、本発明のカラーフィルタを製造する際、特開平 11— 248921号公報、特許 32 55107号公報に記載のように、カラーフィルタを形成する着色感光性榭脂組成物を 重ねることで土台を形成し、その上に透明電極を形成し、更に分割配向用の突起を 重ねることでスぺーサを形成することが、コストダウンの観点で好ま 、。  [0285] When the color filter of the present invention is produced, as described in JP-A-11-248921 and JP-B-3555107, a colored photosensitive resin composition that forms a color filter is stacked. From the viewpoint of cost reduction, it is preferable to form a base, form a transparent electrode on it, and then form a spacer by overlapping projections for split orientation.
着色感光性榭脂組成物を順次塗布して重ねる場合は、塗布液のレべリングのため 重ねるごとに膜厚が薄くなつてしまう。このため、 K (ブラック） 'R'G'Bの 4色を重ね、 更に分割配向用突起を重ねることが好ましい。一方、熱可塑性榭脂層を有する転写 材料を用いる場合は、厚みが一定に保たれるため、重ねる色は 3又は 2色とすること が好ましい。  When the colored photosensitive resin composition is sequentially applied and stacked, the film thickness becomes thinner each time it is stacked due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors K (black) 'R'G'B, and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, the thickness is kept constant, so that the overlapping color is preferably 3 or 2 colors.
また上記土台のサイズは、転写材料を重ねてラミネートする際の感光性榭脂層の変 形を防止し一定の厚みを保持する観点から、 25 m以上力 子ましく、 30 m以上が 特に好ましい。  In addition, the size of the base is preferably 25 m or more and particularly preferably 30 m or more from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and maintaining a constant thickness. .
[0286] [CCDデバイス] [0286] [CCD device]
本発明の CCDデバイスは、本発明の製造方法により得た顔料ナノ粒子を用いて作 製したカラーフィルタを備えてなる。以下、本発明の CCDデバイスについて詳しく説 明する。 The CCD device of the present invention is manufactured using the pigment nanoparticles obtained by the production method of the present invention. The manufactured color filter is provided. Hereinafter, the CCD device of the present invention will be described in detail.
アルカリ可溶性榭脂  Alkali-soluble rosin
CCDデバイスに用いられるアルカリ可溶性榭脂としては、線状有機高分子重合体 で、有機溶剤に可溶で、弱アルカリ水溶液で現像できるものが好ましい。このような線 状有機高分子重合体としては、側鎖にカルボン酸を有するポリマー、例えば特開昭 5 9— 44615号、特公昭 54— 34327号、特公昭 58— 12577号、特公昭 54— 25957 号、特開昭 59— 53836号、特開昭 59— 71048号明細書に記載されているようなメ タクリル酸共重合体、アクリル酸共重合体、ィタコン酸共重合体、クロトン酸共重合体 、マレイン酸共重合体、部分エステルィヒマレイン酸共重合体等であり、また同様に側 鎖にカルボン酸を有する酸性セルロース誘導体がある。この他に水酸基を有するポリ マーに酸無水物を付加させたものなども有用である。特にこれらのなかでベンジル ( メタ)アタリレート Z (メタ)アクリル酸共重合体やべンジル (メタ）アタリレート Z (メタ)ァ クリル酸/および他のモノマーとの多元共重合体が好適である。この他に水溶性ポリ マーとして、 2—ヒドロキシェチルメタタリレート、ポリビュルピロリドンやポリエチレンォ キサイド、ポリビュルアルコール等も有用である。  The alkali-soluble resin used in the CCD device is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54- Nos. 25957, 59-53836, 59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer Examples of the polymer include maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, a polymer obtained by adding an acid anhydride to a polymer having a hydroxyl group is also useful. Of these, benzyl (meth) atarylate Z (meth) acrylic acid copolymer and benzyl (meth) atarylate Z (meth) acrylic acid / and multi-component copolymers with other monomers are particularly suitable. . Other useful water-soluble polymers include 2-hydroxyethyl methacrylate, polybutyl pyrrolidone, polyethylene oxide, and polybutyl alcohol.
[0287] また、特開平 7— 140654号に記載の 2—ヒドロキシプロピル (メタ）アタリレート Zポ リスチレンマクロモノマー Zベンジルメタタリレート Zメタクリル酸共重合体、 2—ヒドロ キシー3—フエノキシプロピルアタリレート Zポリメチノレメタタリレートマクロモノマー Z ベンジルメタタリレート Zメタクリル酸共重合体、 2—ヒドロキシェチルメタアタリレート Zポリスチレンマクロモノマー Zメチルメタタリレート Zメタクリル酸共重合体、 2—ヒド ロキシェチノレメタアタリレート Zポリスチレンマクロモノマー Zベンジノレメタタリレート Z メタクリル酸共重合体などが挙げられる。上記アルカリ可溶性榭脂の硬化性組成物 中の添加量としては、組成物全質量に対して 5〜90質量％が好ましぐより好ましくは 10〜60質量％である。  [0287] Also, 2-hydroxypropyl (meth) acrylate Z-polystyrene macromonomer Z benzyl metatalylate Z methacrylic acid copolymer described in JP-A-7-140654, 2-hydroxy 3-phenoxy Propyl Atallate Z Polymethylolate Metatalylate Macromonomer Z Benzyl Metatalylate Z Methacrylic Acid Copolymer, 2-Hydroxyethyl Metatalylate Z Polystyrene Macromonomer Z Methyl Metatalylate Z Methacrylic Acid Copolymer, 2-Hydro Examples include roxchettinoremethacrylate, Z-polystyrene macromonomer, Z-benzenoremethacrylate, and methacrylic acid copolymer. As addition amount in the curable composition of the said alkali-soluble rosin, 5-90 mass% is more preferable with respect to the composition total mass, More preferably, it is 10-60 mass%.
[0288] 重合性モノマー  [0288] Polymerizable monomer
重合性モノマーとしては、少なくとも 1個の付加重合可能なエチレン基を有する、常 圧下で 100°C以上の沸点を持つエチレン性不飽和基を持つ化合物であることが好ま しい。 The polymerizable monomer is preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. That's right.
[0289] 少なくとも 1個の付加重合可能なエチレン性不飽和基をもち、沸点が常圧で 100°C 以上の化合物としては、ポリエチレングリコールモノ (メタ）アタリレート、ポリプロピレン グリコールモノ (メタ）アタリレート、フエノキシェチル (メタ）アタリレート、等の単官能の アタリレートやメタアタリレート；ポリエチレングリコールジ (メタ）アタリレート、トリメチロ ールェタントリ（メタ）アタリレート、ネオペンチルグリコールジ（メタ）アタリレート、ペンタ エリスリトールトリ（メタ）アタリレート、ペンタエリスリトールテトラ (メタ）アタリレート、ジぺ ンタエリスリトールへキサ (メタ）アタリレート、へキサンジオール (メタ）アタリレート、トリ メチロールプロパントリ（アタリロイルォキシプロピル）エーテル、トリ（アタリロイ口キシェ チル)イソシァヌレート、グリセリンやトリメチロールェタン等の多官能アルコールにェ チレンオキサイドやプロピレンオキサイドを付加させた後 (メタ)アタリレートイ匕したもの [0289] Compounds having at least one addition-polymerizable ethylenically unsaturated group and a boiling point of 100 ° C or higher at normal pressure include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate. Monofunctional acrylates and meta acrylates such as phenoxychetyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, penta erythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (atalylooxypropyl) ether, toluene (Meth) atelar toy after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as isocyanurate, glycerin and trimethylolethane
、特公昭 48— 41708号、特公昭 50— 6034号、特開昭 51— 37193号各公報に記 載されているようなウレタンアタリレート類、特開昭 48— 64183号、特公昭 49 431Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49 431
91号、特公昭 52— 30490号各公報に記載されているポリエステルアタリレート類、 エポキシ榭脂と (メタ)アクリル酸の反応生成物であるエポキシアタリレート類等の多官 能のアタリレートやメタアタリレートを挙げることが出来る。更に、 日本接着協会誌 VolNo. 91, Japanese Patent Publication No. 52-30490, polyester acrylates, epoxy acrylates which are the reaction products of epoxy resin and (meth) acrylic acid, etc. Atarirate can be mentioned. In addition, Japan Adhesion Association Magazine Vol
. 20、 No. 7、 300〜308頁に光硬ィ匕'性モノマー及び才リゴマーとして紹介されてい るちのち使用でさる。 20, No. 7, pages 300 to 308, introduced as a light-curing monomer and rigomer, later used.
[0290] また、下記一般式 (B— 1)あるいは (B— 2)で示される化合物も使用することができ る。  [0290] A compound represented by the following general formula (B-1) or (B-2) can also be used.
[0291] [化 62] 一般式 (B-1 )  [0291] [Chemical formula 62] General formula (B-1)
CH2-0-(B)n— X CH2-0- (B)n— X CH 2 -0- (B) n — X CH 2 -0- (B) n — X
X-(B)n— OCH2-C-CH2-0-CH2— C-CH2-0- (B)n— X X- (B) n — OCH 2 -C-CH 2 -0-CH 2 — C-CH 2 -0- (B) n — X
CH2-0-(B)n— X CH2-0- (B}n— X CH 2 -0- (B) n — X CH 2 -0- (B} n — X
—般式 (B-2) —General formula (B-2)
CH2-0-{B)m— X CH2-0- (B) m — X
X - (B)m- OCH2- C-CH2- O- (B)m— X X-(B) m -OCH 2 -C-CH 2 -O- (B) m — X
CH2-0-{B) -X [0292] {式（B— 1)、（B— 2)中、 Bは、各々独立に、一（CH CH O)—及び一（CH CH ( CH2-0- (B) -X [0292] {In the formulas (B-1) and (B-2), B is each independently one (CH CH O)-and one (CH CH (
2 2 2 2 2 2
CH ) θ)—のいずれかを表し; Xは、各々独立に、アタリロイル基、メタクリロイル基及CH)) θ) — represents one of the following: X represents each independently an taliloyl group, a methacryloyl group, and
3 Three
び水素原子のいずれかを表し、し力も、式 (B—1)中、アタリロイル基及びメタタリロイ ル基の合計は 5個又は 6個であり、式 (B— 2)中のそれは 3個又は 4個であり； nは，各 々独立に 0〜6の整数を表し、し力も各 nの合計は 3〜24であり； mは、各々独立に 0 〜6の整数を表し、し力も各 mの合計は 2〜 16である。 }  In the formula (B-1), the total of the allyloyl group and the metathalyl group is 5 or 6, and that in the formula (B-2) is 3 or 4 N represents an integer of 0 to 6 each independently, and the sum of each force n is 3 to 24; m represents an integer of 0 to 6 each independently, and the force represents each m The total is 2-16. }
[0293] これらの重合性モノマーは、放射線の照射を得て接着性を有する塗膜を形成し得 るならば、任意の割合で使用できる。使用量は組成物の全固形分に対し通常 5〜90 質量％、好ましくは 10〜50質量％である。  [0293] These polymerizable monomers can be used in any ratio as long as they can form a coating film having adhesiveness upon irradiation with radiation. The amount used is usually 5 to 90% by mass, preferably 10 to 50% by mass, based on the total solid content of the composition.
[0294] 着色剤  [0294] Colorant
着色剤としては、従来公知の種々の染料、無機顔料または有機顔料を一種又は二 種以上混合して用いることができる。  As the colorant, various conventionally known dyes, inorganic pigments or organic pigments can be used singly or in combination.
[0295] 染料は、特に制限はなぐ従来カラーフィルタ用として公知の染料が使用できる。例 えば特開昭 64— 90403号公報、特開昭 64— 91102号公報、特開平 1— 94301号 公報、特開平 6— 11614号公報、特登 2592207号、米国特許 4808501号明細書 、米国特許 5667920号明細書、米国特許 505950号明細書、米国特許 5667920 号明細書、特開平 5— 333207号公報、特開平 6— 35183号公報、特開平 6— 511 15号公報、特開平 6— 194828号公報等に開示されている色素が使用できる。化学 構造としては、ピラゾールァゾ系、ァ-リノァゾ系、トリフエ-ルメタン系、アントラキノン 系、ベンジリデン系、ォキソノール系、ピラゾロトリアゾールァゾ系、ピリドンァゾ系、シ ァニン系、フエノチアジン系、ピロロピラゾールァゾメチン系等の染料が使用できる。 特に、硬化性組成物は比較的低温での硬化が可能なので、顔料に比較して耐熱性 に劣る染料であっても硬化膜に耐久性を付与するためのポスト 'ベータの際の高温度 下にさらされても分解等の問題を軽減することができる。  [0295] As the dye, known dyes for conventional color filters can be used without any particular limitation. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Tokuto 2592207, U.S. Pat. No. 5667920, U.S. Pat.No. 505950, U.S. Pat.No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828 The pigment | dye currently disclosed by the gazette etc. can be used. The chemical structure is pyrazole azo, lino azo, triphenyl methane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. Etc. can be used. In particular, since the curable composition can be cured at a relatively low temperature, even a dye that is inferior in heat resistance compared to a pigment has a high temperature during post-beta to impart durability to the cured film. It is possible to reduce problems such as decomposition even when exposed to water.
[0296] 無機顔料としては、金属酸化物、金属錯塩等で示される金属化合物であり、具体的 には鉄、コノ レト、アルミニウム、カドミウム、鉛、銅、チタン、マグネシウム、クロム、亜 鉛、アンチモン等の金属酸ィ匕物、および前記金属の複合酸ィ匕物を挙げることができ る。 [0296] The inorganic pigment is a metal compound represented by a metal oxide, a metal complex salt, or the like, and specifically iron, conoleto, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony. Metal oxides such as the above, and complex oxides of the above metals The
[0297] 有機顔料としては、 C. I. Pigment Yellow 11, 24, 31, 53, 83, 8 5, 99, 108, 109, 110, 138, 139, 150, 151, 154, 167, 18 5、 C. I. Pigment Orange 36, 38, 43, 71、 C. I. Pigment Red 1 05, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254、 C. I. Pigment Violet 19, 23, 32, 39、 C. I. Pigmen t Blue 1, 2, 15, 16, 22, 60, 66, 15 : 3, 15 : 6、 C. I. Pigmen t Green 7, 36, 37、 C. I. Pigment Brown 25, 28、 C. I. Pigment Black 1, 7、カーボンブラック等を挙げることができる。  [0297] Organic pigments include CI Pigment Yellow 11, 24, 31, 53, 83, 8 5, 99, 108, 109, 110, 138, 139, 150, 151, 154, 167, 18 5, CI Pigment Orange 36, 38, 43, 71, CI Pigment Red 1 05, 122, 149, 150, 155, 171, 175, 176, 177, 209, 224, 242, 254, CI Pigment Violet 19, 23, 32, 39, CI Pigmen t Blue 1, 2, 15, 16, 22, 60, 66, 15: 3, 15: 6, CI Pigmen t Green 7, 36, 37, CI Pigment Brown 25, 28, CI Pigment Black 1, 7, carbon Black etc. can be mentioned.
[0298] これら有機顔料は、単独もしくは色純度を上げるため種々組合せて用いることがで きる。具体例を以下に示す。赤の顔料としては、アントラキノン系顔料、ペリレン系顔 料単独または、それらの少なくとも一種とジスァゾ系黄色顔料またはイソインドリン系 黄色顔料との混合が用いられる。例えばアントラキノン系顔料としては、 C. I.ビグメン トレッド 177、ペリレン系顔料としては、 C. I.ビグメントレッド 155が挙げられ、色再現 性の点で C. I.ビグメントイエロー 83または C. I.ビグメントイエロー 139との混合が良 好である。赤色顔料と黄色顔料の質量比は、 100 : 5から 100 : 50が良好である。この 範囲において、 400nmカゝら 500nmの光透過率を抑え、色純度を上げることができ、 好ましい。  [0298] These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples are shown below. As the red pigment, an anthraquinone pigment, a perylene pigment alone or a mixture of at least one of them with a disazo yellow pigment or an isoindoline yellow pigment is used. For example, CI pigment red 177 is used as an anthraquinone pigment, and CI pigment red 155 is used as a perylene pigment. Mixing with CI pigment yellow 83 or CI pigment yellow 139 is preferable in terms of color reproducibility. It is. The mass ratio of red pigment to yellow pigment is good from 100: 5 to 100: 50. Within this range, it is preferable because the light transmittance of 400 nm to 500 nm can be suppressed and the color purity can be increased.
[0299] 緑の顔料としては、ハロゲンィ匕フタロシアニン系顔料単独又は、ジスァゾ系黄色顔 料、キノフタロン系黄色染料またはイソインドリン系黄色顔料との混合が用いられ、例 免ば、 C. I.ピグメントグリーン 7、 36、 37と C. I.ピグメントイエロー 83、 138、 139との 混合が好ましい。緑顔料と黄色顔料の質量比は、 100 : 5〜： L00 : 100が好ましい。こ の範囲内において、 400nmから 450nmの光透過率を抑え、良好な色純度を得るこ とがでさる。  [0299] As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of a disazo yellow pigment, a quinophthalone yellow dye or an isoindoline yellow pigment is used. For example, CI Pigment Green 7, 36 37 and CI Pigment Yellow 83, 138, 139 are preferred. The mass ratio of the green pigment to the yellow pigment is preferably from 100: 5 to L00: 100. Within this range, the light transmittance from 400 nm to 450 nm can be suppressed and good color purity can be obtained.
[0300] 青の顔料としては、フタロシアニン系顔料単独又は、ジォキサジン系紫色顔料との 混合が用いられ、例えば C. I.ビグメントブルー 15 : 6と C. I.ビグメントバイオレット 23 との混合が好ましい。青色顔料と紫色顔料の質量比は、 100 : 0〜100 : 50が好まし い。この範囲内において、 400nmから 420nmの光透過率を抑え、色純度を上げるこ とがでさる。 [0300] As the blue pigment, a phthalocyanine pigment alone or a mixture with a dioxazine purple pigment is used. For example, CI pigment blue 15: 6 and CI pigment violet 23 are preferably mixed. The mass ratio of blue pigment to purple pigment is preferably 100: 0 to 100: 50. Within this range, the light transmittance from 400 nm to 420 nm can be suppressed and the color purity can be increased. Togashi.
[0301] 更に上記の顔料をアクリル系榭脂、マレイン酸系榭脂、塩ィ匕ビ二ルー酢酸ビニルコ ポリマー及びェチルセルロース樹脂等に微分散させた粉末状加工顔料を用いること により分散性及び分散安定性の良好な顔料含有感光榭脂を得ることが出来る。  [0301] Furthermore, by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic resin, a vinyl chloride vinyl acetate copolymer and an ethyl cellulose resin, the dispersibility and A pigment-containing photosensitive resin having good dispersion stability can be obtained.
[0302] また、ブラックマトリックス用の顔料としては、カーボン、酸化チタン、酸化鉄、単独又 は、混合が用いられカーボンと酸ィ匕チタンの場合が好ましい。質量比は、 100 : 5から[0302] Further, as the pigment for the black matrix, carbon, titanium oxide, iron oxide, alone or a mixture thereof is used, and carbon and titanium oxide are preferable. Mass ratio from 100: 5
100 :40の範囲が好ましい。この範囲内において長波長の光透過率が小さぐまた分 散安定性も良好である。 A range of 100: 40 is preferred. Within this range, the light transmittance at long wavelengths is small and the dispersion stability is also good.
[0303] 溶剤 [0303] Solvent
溶剤としては、エステル類、例えば酢酸ェチル、酢酸—n—ブチル、酢酸イソブチ ル、ギ酸ァミル、酢酸イソァミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロ ピル、酪酸ェチル、酪酸ブチル、アルキルエステル類、乳酸メチル、乳酸ェチル、ォ キシ酢酸メチル、ォキシ酢酸ェチル、ォキシ酢酸ブチル、メトキシ酢酸メチル、メトキ シ酢酸ェチル、メトキシ酢酸プチル、エトキシ酢酸メチル、エトキシ酢酸ェチル、 3— ォキシプロピオン酸メチル、 3—ォキシプロピオン酸ェチルなどの 3—ォキシプロピオ ン酸アルキルエステル類； 3—メトキシプロピオン酸メチル、 3—メトキシプロピオン酸 ェチル、 3 エトキシプロピオン酸メチル、 3 エトキシプロピオン酸ェチル、 2—ォキ シプロピオン酸メチル、 2—ォキシプロピオン酸ェチル、 2—ォキシプロピオン酸プロ ピル、 2—メトキシプロピオン酸メチル、 2—メトキシプロピオン酸ェチル、 2—メトキシ プロピオン酸プロピル、 2—エトキシプロピオン酸メチル、 2—エトキシプロピオン酸ェ チル、 2—ォキシ 2—メチルプロピオン酸メチル、 2—ォキシ 2—メチルプロピオン 酸ェチル、 2—メトキシ 2—メチルプロピオン酸メチル、 2—エトキシ 2—メチルプ 口ピオン酸ェチル、ピルビン酸メチル、ピルビン酸ェチル、ピルビン酸プロピル、ァセ ト酢酸メチル、ァセト酢酸ェチル、 2—ォキソブタン酸メチル、 2—ォキソブタン酸ェチ ル等：エーテル類、例えばジエチレングリコールジメチルエーテル、テトラヒドロフラン 、エチレングリコーノレモノメチノレエーテノレ、エチレングリコーノレモノェチノレエーテノレ、メ チノレセロソルブアセテート、ェチノレセロソルブアセテート、ジエチレングリコーノレモノメ チノレエーテノレ、ジエチレングリコーノレモノェチノレエーテノレ、ジエチレングリコーノレモノ ブチノレエーテノレ、プロピレングリコールメチルエーテルアセテート、プロピレングリコー ルェチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート等； ケトン類、例えばメチルェチルケトン、シクロへキサノン、 2 へプタノン、 3 ヘプタノ ン等;芳香族炭化水素類、例えばトルエン、キシレン等が挙げられる。 Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxy Alkyl esters of 3-oxypropionic acid such as ethyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, methyl 2-oxypropionate, 2 —Oxypropionate 2-propylpropionate, 2-methoxymethyl propionate, 2-methoxypropionate, 2-methoxypropylpropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-oxypropionate 2-methyl methyl propionate, 2-oxy-2-ethyl propionate, 2-methoxy 2-methyl methyl propionate, 2-ethoxy 2-methyl ethyl pionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetate acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .: ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glyconolemonomethinoatenole, ethyleneglycolenolemonoethylenore Etenore Main Chino Les cellosolve acetate, E Chino Les cellosolve acetate, diethylene glycol Honoré monomethyl Chinoreetenore, diethylene glycol Honoré monomethyl E Chino les ether Honoré, diethylene glycol Honoré mono Butinoleethenole, propylene glycol methyl ether acetate, propylene glycol ether ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2 heptanone, 3 heptanone; aromatic carbonization Examples of the hydrogen include toluene and xylene.
[0304] これらのうち、 3 エトキシプロピオン酸メチル、 3 エトキシプロピオン酸ェチル、ェ チルセ口ソルブアセテート、乳酸ェチル、ジエチレングリコールジメチルエーテル、酢 酸ブチル、 3—メトキシプロピオン酸メチル、 2 へプタノン、シクロへキサノン、ェチル カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチル エーテルアセテート等が好ましく用いられる。溶剤の添加量は、組成物中通常 60〜9 0質量％、好ましくは 70〜90質量％である。  [0304] Among these, 3 methyl ethoxypropionate, 3 ethyl ethoxypropionate, ethyl solvate sorb acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 heptanone, cyclohexanone, Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferably used. The amount of the solvent added is usually 60 to 90% by mass, preferably 70 to 90% by mass in the composition.
[0305] これら溶剤は、単独で用いてもあるいは 2種以上組み合わせて用いてもよい。  [0305] These solvents may be used alone or in combination of two or more.
[0306] 更に増感剤を併用することができる。その具体例として、 9 フルォレノン、 2 クロ 口一 9 フルォレノン、 2—メチル 9 フルォレノン、 9 アントロン、 2 ブロモ 9 —アントロン、 2 ェチル 9 アントロン、 9, 10 アントラキノン、 2 ェチル 9, 1 0 アントラキノン、 2—t—ブチルー 9, 10 アントラキノン、 2, 6 ジクロロー 9, 10 —アントラキノン、ベンジル、ジベンザルアセトン、 p— (ジメチルァミノ）フエ-ルスチリ ルケトン、 P— (ジメチルァミノ）フエ-ルー ρ—メチルスチリルケトン、ベンゾアントロン 等ゃ特公昭 51— 48516号公報記載のベンゾチアゾール系化合物が挙げられる。  [0306] Further, a sensitizer can be used in combination. Specific examples include 9 fluorenone, 2 chloro 9 fluorenone, 2-methyl 9 fluorenone, 9 anthrone, 2 bromo 9 —anthrone, 2 ethyl 9 anthrone, 9, 10 anthraquinone, 2 ethyl 9, 10 anthraquinone, 2— t-butyl-9,10 anthraquinone, 2,6 dichloro-9,10-anthraquinone, benzyl, dibenzalacetone, p- (dimethylamino) phenol ketol, P- (dimethylamino) phenol ρ-methylstyryl ketone, benzo Anthrone and the like include benzothiazole compounds described in JP-B 51-48516.
[0307] 上記主要成分、さらに必要に応じて用いられるその他の添加剤を各種の混合機、 分散機を使用して混合分散することによって調製することができる。  [0307] It can be prepared by mixing and dispersing the above main components and other additives used as necessary using various mixers and dispersers.
[0308] CCDデバイスに用いられるカラーフィルタの一般的な製造法は次の通りである。本 発明の組成物 (カラーレジスト液)を基板上に塗布 ·乾燥する工程、得られた乾燥塗 布膜に i線ステッパー等でパターン露光する工程、露光後にアルカリ現像する工程、 次に加熱処理する工程を順次行い、各色（3色あるいは 4色）に前記工程を順次繰り 返して硬化皮膜を作製することによりカラーフィルタが得られる。  [0308] A general manufacturing method of a color filter used in a CCD device is as follows. A step of applying and drying the composition (color resist solution) of the present invention on a substrate, a step of pattern exposure of the obtained dry coating film with an i-line stepper, a step of alkali development after exposure, and a heat treatment A color filter is obtained by sequentially performing the steps and repeating the above steps for each color (three or four colors) to produce a cured film.
[0309] より具体的には、上記の硬化性組成物を、スピンナ一等により、適当な基板上に乾 燥時の膜厚が一般的に 0. 1〜5 111、好ましくは0. 2〜2 mになるように塗布し、 8 5°Cのオーブンに 2分間放置し平滑な塗膜を得る。 [0310] 基板としては、特に限定されな 、が、ガラス板、プラスチックス板、アルミ板、撮像素 子用シリコンウェハ等の電子部品の基材、さらには透明榭脂板、榭脂フィルム、ブラ ゥン管表示面、撮像感の受光面、 CCD, BBD、 CID、 BASIS等の固体撮像素子が 形成されたウェハー、薄膜半導体を用いた密着型イメージセンサー、液晶ディスプレ ィ面、カラー電子写真用感光体、エレクト口クロミィー (EC)表示装置の基板等が挙げ られる。また、基板にカラーフィルタ層との接着性を向上させるために高密着処理を 施すことが好ましい。具体的には、基板上に予めシランカップリング剤等で薄く塗布し た後に硬化性組成物のパターンを形成するか、ある ヽは予め硬化性組成物中にシラ ンカップリング剤を含有させてもよ!、。 [0309] More specifically, the curable composition is generally dried on a suitable substrate with a spinner or the like so that the film thickness when dried is generally 0.1 to 5111, preferably 0.2 to Apply to 2 m and leave in oven at 85 ° C for 2 minutes to obtain a smooth coating. [0310] The substrate is not particularly limited, but it is a substrate for electronic parts such as a glass plate, a plastic plate, an aluminum plate, a silicon wafer for an imaging element, and further a transparent resin plate, a resin film, a brush. Duct tube display surface, light-sensitive surface for image sensing, wafers with solid-state image sensors such as CCD, BBD, CID, BASIS, contact image sensor using thin film semiconductors, liquid crystal display surface, color electrophotographic photosensitive Body, Electrum Chromy (EC) display substrate. In addition, it is preferable to perform a high adhesion treatment on the substrate in order to improve adhesion with the color filter layer. Specifically, a pattern of the curable composition is formed after thinly coating with a silane coupling agent or the like on the substrate in advance, or in some cases, a silane coupling agent is previously contained in the curable composition. Moyo!
[0311] 尚、基板上に段差がある場合は、その段差を解消し塗設面を平滑にするための平 坦化膜を基板上に塗設した後、本発明の硬化性組成物を塗布することができる。例 えば、 CCDなどのイメージセンサーはシリコン基板上に受光量に応じて電子を発生 させる光電子変換部 (フォトダイオード）とその発生した電子を出力する為の読み出し ゲート部とで構成されている力 読み出しゲート部に光が当たるとノイズの原因となり 正確なデータが出力されないため、読み出しゲート部の上部には遮光膜層が形成さ れており、遮光膜層を持たないフォトダイオード部との間で段差が生じている場合が ある。このような段差上にカラーレジストを塗布し、直接カラーフィルタを形成すると光 路長が長くなるため画像が暗ぐまた集光性も劣るようになる。これを改善する為、そ の段差を埋める目的で透明な平坦ィ匕膜を CCDとカラーフィルタとの間に形成するこ とが好ましい。この平坦ィ匕膜の材料としては、本発明におけるような光硬化性レジスト 液、アクリル系、エポキシ系等の熱硬化性榭脂等が挙げられる。  [0311] If there is a step on the substrate, a flattening film for eliminating the step and smoothing the coating surface is applied on the substrate, and then the curable composition of the present invention is applied. can do. For example, an image sensor such as a CCD is composed of a photoelectric conversion unit (photodiode) that generates electrons on a silicon substrate according to the amount of light received, and a readout gate unit that outputs the generated electrons. If the gate is exposed to light, it will cause noise and accurate data will not be output.Therefore, a light-shielding film layer is formed on the top of the readout gate, and there is a step between the photodiode part without the light-shielding film layer. May have occurred. When a color resist is applied on such a step and a color filter is directly formed, the optical path length becomes long, so that the image becomes dark and the light condensing property becomes poor. In order to improve this, it is preferable to form a transparent flat film between the CCD and the color filter in order to fill the step. Examples of the material for the flat film include a photo-curable resist solution as in the present invention, thermosetting resins such as acrylic and epoxy resins, and the like.
[0312] 光硬化性組成物を塗布した後、溶媒を蒸発させ乾燥塗布膜を得るため通常プリべ ークを行う。このプリベータの方法としては、減圧乾燥、高温の空気などによる間接カロ 熱乾燥、ホットプレート等による直接加熱乾燥 (約 80〜140°C、 50〜200秒)等があ る。また、現像後に得られたパターンを、十分硬化させて機械強度を高め永久膜とす るためにポストベータが行われる。例えば、 3色のカラーフィルタの製造に際しては、 最初に形成されたパターンは、その後、他色のレジスト液の塗布、露光、現像を 2度 受ける。この際に、塗布されたレジスト液との混色、露光、現像によるパターンの欠落 が生じないようにポストベータを行うものである。このポストベータはプリベータ同様の 方法が用いられるが、プリベータの条件よりも、高温、長時間で行われる。例えば、ォ ーブンによる間接加熱の場合、約 180〜250°C、約 0. 5〜2時間、ホットプレートによ る直接加熱の場合、約 180〜250°C、約 2〜10分間行われる。 [0312] After the photocurable composition is applied, the solvent is evaporated and a normal baking is performed to obtain a dry coating film. This prebeta method includes drying under reduced pressure, indirect hot heat drying with high-temperature air, etc., and direct heat drying (about 80 to 140 ° C, 50 to 200 seconds) with a hot plate. Further, post-beta is performed in order to sufficiently cure the pattern obtained after development to increase the mechanical strength and form a permanent film. For example, in the production of a three-color filter, the first formed pattern is then subjected to application, exposure and development of another color resist solution twice. In this case, pattern loss due to color mixing, exposure, and development with the applied resist solution Post-beta is performed so as not to occur. This post-beta is used in the same way as pre-beta, but at a higher temperature and longer time than pre-beta conditions. For example, indirect heating by oven is performed at about 180 to 250 ° C. for about 0.5 to 2 hours, and direct heating by hot plate is performed at about 180 to 250 ° C. for about 2 to 10 minutes.
[0313] 露光のための光源は特に限定されないが、パターン形成性に関して顕著な効果が もたらされる光源として水銀灯の i線を挙げることができる。本発明の特徴は工程の適 正の面力 水銀灯の線スペクトルの一つである i線が使用されるイメージセンサー用 カラーフィルタの製造において、特にその特徴が顕著となるが、 LCD用においても使 用できることは勿論である。  [0313] Although the light source for exposure is not particularly limited, i-line of a mercury lamp can be cited as a light source that has a significant effect on pattern formation. The feature of the present invention is an appropriate surface power of the process. The feature is particularly remarkable in the production of a color filter for an image sensor using i-line, which is one of the line spectrum of a mercury lamp, but it is also used for an LCD. Of course, it can be used.
[0314] 硬化性組成物の現像に使用する現像液は特に制限はなぐ従来公知の現像液を 使用することができる。中でも、テトラメチルアンモ -ゥムハイドロキサイド (TMAH)な どの 4級アンモ-ゥム塩類の有機アルカリ系の現像液が本発明の目的を達成する上 で好ましい。  [0314] The developer used for the development of the curable composition is not particularly limited, and a conventionally known developer can be used. Among them, an organic alkaline developer of a quaternary ammonium salt such as tetramethyl ammonium hydroxide (TMAH) is preferable for achieving the object of the present invention.
[0315] 重合開始剤  [0315] Polymerization initiator
重合開始剤としては、通常の光重合開始剤を用いることができる。具体的には、米 国特許第 2, 367, 660号明細書に記載のビシナールポリケトルアルド二ルイ匕合物、 米国特許第 2, 367, 661号及び第 2, 367, 670号明細書に記載のひ カルボ-ル 化合物、米国特許第 2, 448, 828号明細書に記載のァシロインエーテル、米国特許 第 2, 722, 512号明細書に記載の α—炭化水素で置換された芳香族ァシロインィ匕 合物、米国特許第 3, 046, 127号及び第 2, 951, 758号明細書に記載の多核キノ ン化合物、米国特許第 3, 549, 367号明細書に記載のトリアリルイミダゾールダイマ 一 Ζρ ァミノフエ-ルケトンの組合せ、特公昭 51— 48516号公報に記載のベンゾ チアゾール系化合物 Ζトリハロメチール s—トリアジン系化合物、等を挙げることが できる。  As the polymerization initiator, a normal photopolymerization initiator can be used. Specifically, the vicinal polykettle aldo two Louis compound described in US Pat. No. 2,367,660, US Pat. Nos. 2,367,661 and 2,367,670 Substituted with the α-hydrocarbon described in US Pat. No. 2,722,512, the acylo ether described in US Pat. No. 2,448,828. Aromatic acyloin compounds, polynuclear quinone compounds described in U.S. Pat.Nos. 3,046,127 and 2,951,758, triallyl described in U.S. Pat.No. 3,549,367 Examples thereof include a combination of imidazole dimer and αaminophenol ketone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, trihalomethyl s-triazine compounds, and the like.
[0316] 光重合開始剤 (前記の通常の光重合開始剤を含む)の染料含有ネガ型硬化性組 成物中における含有量は、ラジカル重合性モノマーの固形分 (質量）に対して、 0. 0 1〜50質量％が好ましぐ 1〜30質量％がより好ましぐ 1〜20質量％が特に好まし い。該含有量が上記範囲にあると、充分な重合硬化が行なえ、重合が進み難くなつ たり、重合率は大きくなるが分子量が低くなつて膜強度が弱くなつたりすることもない。 [0316] The content of the photopolymerization initiator (including the above-mentioned ordinary photopolymerization initiator) in the dye-containing negative curable composition is 0 with respect to the solid content (mass) of the radical polymerizable monomer. 0 1 to 50% by weight is preferred 1 to 30% by weight is more preferred 1 to 20% by weight is particularly preferred. When the content is in the above range, sufficient polymerization and curing can be performed, and polymerization is difficult to proceed. In addition, the polymerization rate increases but the molecular weight does not decrease and the film strength does not decrease.
[0317] また、上記の光重合開始剤には増感剤ゃ光安定剤を併用することができる。  [0317] Further, a sensitizer or a light stabilizer can be used in combination with the photopolymerization initiator.
その具体例として、ベンゾイン、ベンゾインメチルエーテル、 9 フルォレノン、 2 ク ロロ一 9 フルォレノン、 2—メチル 9 フルォレノン、 9 アントロン、 2 ブロモ 9 —アントロン、 2 ェチル 9 アントロン、 9, 10 アントラキノン、 2 ェチル 9, 1 0 アントラキノン、 2—t—ブチルー 9, 10 アントラキノン、 2, 6 ジクロロー 9, 10 アントラキノン、キサントン、 2—メチルキサントン、 2—メトキシキサントン、 2—ェトキ シキサントン、チォキサントン、 2, 4 ジェチルチオキサントン、アタリドン、 10 ブチ ルー 2—クロロアタリドン、ベンジル、ジベンザルアセトン、 p— (ジメチルァミノ）フエ- ルスチリルケトン、 p— (ジメチルァミノ）フエ-ルー p—メチルスチリルケトン、ベンゾフ ェノン、 p— (ジメチルァミノ）ベンゾフエノン（又はミヒラーケトン）、 p— (ジェチルァミノ） ベンゾフエノン、ベンゾアントロン等や、特公昭 51—48516号公報に記載のベンゾチ ァゾール系化合物等、チヌビン 1130、同 400等が挙げられる。  Specific examples include benzoin, benzoin methyl ether, 9 fluorenone, 2 chloro 9 fluorenone, 2—methyl 9 fluorenone, 9 anthrone, 2 bromo 9 —anthrone, 2 ethyl 9 anthrone, 9, 10 anthraquinone, 2 ethyl 9, 1 0 Anthraquinone, 2-t-butyl-9, 10 Anthraquinone, 2, 6 Dichloro-9, 10 Anthraquinone, Xanthone, 2-Methylxanthone, 2-Methoxyxanthone, 2-Ethoxyxanthone, Thioxanthone, 2, 4 Jetylthioxanthone, Atalidone 10 butyl 2 -chloroataridon, benzyl, dibenzalacetone, p- (dimethylamino) phenol styryl ketone, p- (dimethylamino) phenol-p-methylstyryl ketone, benzophenone, p- (dimethylamino) Benzophenone (or Michler) Ketone), p- (jetylamino) benzophenone, benzoanthrone, and the like, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, and the like.
[0318] 本発明の液晶表示装置は、コントラストに優れる本発明のカラーフィルタを用い、黒 のしまり等の描写力に優れる。なかでも、本発明のカラーフィルタは VA方式であるこ とが好ましい。ノートパソコン用ディスプレイやテレビモニター等の大画面の液晶表示 装置等としても好適に用いることができる。また、本発明のカラーフィルタは CCDデ バイスに用いることができ、優れた性能を発揮する。  [0318] The liquid crystal display device of the present invention uses the color filter of the present invention having excellent contrast and is excellent in descriptive power such as black spots. Of these, the color filter of the present invention is preferably a VA system. It can also be suitably used as a large screen liquid crystal display device such as a notebook personal computer display or a television monitor. In addition, the color filter of the present invention can be used for a CCD device and exhibits excellent performance.
[0319] 本発明の別の好ましい実施態様としては、以下の例が挙げられる。  [0319] Another preferred embodiment of the present invention includes the following examples.
(A)酸性基をもつ高分子化合物存在下にお!/ヽて、良溶媒に溶解した有機材料の溶 液と、該溶媒と相溶する前記有機材料の貧溶媒とを混合し、該有機材料を有機粒子 として生成させ、これを濃縮するにあたり、前記有機粒子を含む分散液を限外ろ過に よって濃縮することを特徴とする有機粒子分散組成物の製造方法。  (A) In the presence of a high molecular compound having an acidic group, the organic material solution dissolved in a good solvent is mixed with the poor solvent of the organic material compatible with the solvent, and the organic material is mixed. A method for producing an organic particle dispersion composition, comprising producing a material as organic particles and concentrating the material, by concentrating the dispersion containing the organic particles by ultrafiltration.
(B)前記有機粒子の数平均粒径が 1 μ m以下であることを特徴とする (A)に記載の 有機粒子分散組成物の製造方法。  (B) The method for producing an organic particle dispersion composition according to (A), wherein the number average particle diameter of the organic particles is 1 μm or less.
(C)前記限外ろ過の後さらに凍結乾燥を行うことを特徴とする (A)または (B)に記載 の有機粒子分散組成物の製造方法。  (C) The method for producing an organic particle dispersion composition according to (A) or (B), wherein freeze drying is further performed after the ultrafiltration.
(D)前記有機材料が、有機顔料であることを特徴とする (A)〜 (C)の 、ずれか 1項に 記載の有機粒子分散組成物の製造方法。 (D) The organic material is an organic pigment, wherein (A) to (C) The manufacturing method of the organic-particle dispersion composition of description.
(E)酸性基を有する高分子化合物を含む有機溶媒中で再分散化することを特徴と する (A)〜 (D)の 、ずれか 1項に記載の有機粒子分散組成物の製造方法。  (E) The method for producing an organic particle-dispersed composition according to any one of (A) to (D), wherein re-dispersion is performed in an organic solvent containing a polymer compound having an acidic group.
[0320] 以下に本発明を実施例に基づき更に詳細に説明するが、本発明はこれらに限定さ れるものではない。 [0320] Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited thereto.
実施例  Example
[0321] (実施例 1) [0321] (Example 1)
顔料（ビグメントレッド 254) 0. 6gを、 1ーメチルー 2—ピロリドンと ImolZL-水酸化 ナトリウム水溶液を 6 : 1で混合した溶液に、 15mmol,Lとなるよう溶解した顔料溶液 を調製した。また、メタクリル酸/メタクリル酸ベンジル共重合体 0. 75g (モル比 28/ 72、質量平均分子量： 3万、 40% 1-メトキシ -2-プロピルアセテート溶液）、顔料分散 剤 A 0.3g、分散剤ポリビュルピロリドン 0. 6g (和光純薬 (株)製、 K30、分子量 40 , 000)を上記の溶液に溶解させた。これとは別に、貧溶媒として水を準備した。  A pigment solution was prepared by dissolving 0.6 g of Pigment (Vigment Red 254) in a solution prepared by mixing 1-methyl-2-pyrrolidone and ImolZL-sodium hydroxide aqueous solution 6: 1 to 15 mmol, L. Also, methacrylic acid / benzyl methacrylate copolymer 0.75 g (molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution), pigment dispersant A 0.3 g, dispersant Polybulpyrrolidone 0.6 g (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) was dissolved in the above solution. Separately from this, water was prepared as a poor solvent.
[0322] ここで、 25°Cに温度コントロールし、藤沢薬品工業社製 GK— 0222— 10型ラモン ドスターラーにより 500rpmで攪拌した貧溶媒の水 1000mlに、顔料溶液を、日本精 密化学社製 NP— KX— 500型大容量無脈流ポンプを用いて流速 50mlZminで 22 Oml注入することにより、有機顔料粒子分散液を調製した。 [0322] Here, the temperature of the solution was controlled at 25 ° C, and the pigment solution was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type ramond stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd., manufactured by Nippon Seimitsu Chemical Co., Ltd. An organic pigment particle dispersion was prepared by injecting 22 Oml at a flow rate of 50 mlZmin using an NP-KX-500 large capacity non-pulsating pump.
調製した有機粒子分散液を、日機装社製ナノトラック UPA— EX150を用いて測定 し、粒径、単分散度を評価したところ、数平均粒径 32nm、 MvZMnl.35であった。 調製した有機顔料粒子分散液 (顔料粒子濃度約 0. 05質量％)を日東電工の限外ろ 過機 CIO— TZRUM— 2を用いることにより脱塩、濃縮を行った。条件は、送液流量 lL/min,送液圧 0. 2MPa、限外ろ過フィルターの分画分子量 50万で行った。そ の結果、 400mlの有機顔料粒子分散液 (顔料粒子濃度約 1. 5質量％)を得た。これ に 500mlの 2—（1—メトキシ）プロピルアセテートをカ卩えて 25°Cで 10分間、 500rpm で攪拌した後 1時間静置し、有機顔料粒子を 2— (1—メトキシ)プロピルアセテート相 に抽出し、濃縮抽出液とした。  The prepared organic particle dispersion was measured using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated. The number average particle size was 32 nm and MvZMnl.35. The prepared organic pigment particle dispersion (pigment particle concentration of about 0.05% by mass) was desalted and concentrated using CIO-TZRUM-2, an ultrafiltration machine manufactured by Nitto Denko. The conditions were as follows: liquid flow rate lL / min, liquid feed pressure 0.2 MPa, ultrafiltration filter molecular weight cut off 500,000. As a result, 400 ml of an organic pigment particle dispersion (pigment particle concentration: about 1.5% by mass) was obtained. To this, 500 ml of 2- (1-methoxy) propyl acetate was added and stirred at 25 ° C for 10 minutes at 500 rpm and then allowed to stand for 1 hour to transfer the organic pigment particles to the 2- (1-methoxy) propyl acetate phase. Extracted into a concentrated extract.
有機顔料粒子を抽出した濃縮抽出液を、住友電工ファインポリマ社製 FP— 010型 フィルタを用いて、ろ過することにより、ペースト状の濃縮顔料液 (顔料粒子濃度 35質 量0 /0)を得た。このとき、ナトリウム (Na)イオン濃度は対顔料で 0. 01質量％であった The concentrated extract from which organic pigment particles have been extracted is filtered using a FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co., Ltd. The amount 0/0) was obtained. At this time, the sodium (Na) ion concentration was 0.01% by mass with respect to the pigment.
[0323] 前記ペーストを使!ヽ、下記組成の顔料分散組成物を調製した。 [0323] Using the paste, a pigment dispersion composition having the following composition was prepared.
前記ペースト 21. 3g  Paste 21.3 g
顔料分散剤 A 0.6g  Pigment dispersant A 0.6g
メタクリル酸 Zメタクリル酸ベンジル共重合体 * 15. 8g  Methacrylic acid Z benzyl methacrylate copolymer * 15.8 g
1ーメトキシ- 2-プロピルアセテート 42. 3g  1-Methoxy-2-propyl acetate 42.3 g
*モル比 28/72、質量平均分子量： 3万、 40% 1-メトキシ- 2-プロピルアセテート溶 液  * Molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution
[0324] [化 63]  [0324] [Chemical 63]
顔粉散剤 A  Facial powder A
Figure imgf000115_0001
Figure imgf000115_0001
[0325] 上記組成の顔料組成物をモーターミル M-50 (アイガー社製）で、直径 0.65mmの ジルコユアビーズを用い、周速 9m/sで分散した。  [0325] The pigment composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger) at a peripheral speed of 9 m / s using Zirco Your beads having a diameter of 0.65 mm.
このようにして作製した顔料組成物を、顔料分散組成物 Aとして日機装社製ナノトラ ック UPA— EX150を用いて測定し、粒径、単分散度を評価した。  The pigment composition thus prepared was measured as a pigment dispersion composition A using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated.
[0326] (実施例 2) [0326] (Example 2)
顔料分散組成物 Aにお 、て、ペーストを用いて顔料分散組成物 Aを調製する際に 用いたメタクリル酸/メタクリル酸ベンジル共重合体をメタクリル酸/メタクリル酸べンジ ル /スチレン共重合体 15. 8g (モル比 27 : 60 : 13、質量平均分子量： 2万 8千、 40 %1-メトキシ -2-プロピルアセテート溶液）とした以外は、顔料分散組成物 Aと同様に して顔料分散組成物 Bを作製した。  In Pigment Dispersion Composition A, the methacrylic acid / benzyl methacrylate copolymer used for preparing Pigment Dispersion Composition A using the paste was replaced with methacrylic acid / benzyl methacrylate / styrene copolymer 15 Pigment dispersion composition as in Pigment dispersion composition A, except that 8 g (molar ratio 27:60:13, mass average molecular weight: 28,000, 40% 1-methoxy-2-propyl acetate solution) was used. Object B was made.
[0327] (実施例 3) [Example 3]
顔料分散組成物 Aにお 、て、ペーストを用いて顔料分散組成物 Aを調製する際に 用いたメタクリル酸/メタクリル酸ベンジル共重合体をポリアクリル酸 15. 8g (質量平 均分子量： 3万 3千、 40% 1-メトキシ -2-プロピルアセテート溶液）とした以外は、顔料 分散組成物 Aと同様にして顔料分散組成物 Cを作製した。 In Pigment Dispersion Composition A, 15.8 g (weight average) of the methacrylic acid / benzyl methacrylate copolymer used in preparing Pigment Dispersion Composition A using the paste was used. Pigment Dispersion Composition C was prepared in the same manner as Pigment Dispersion Composition A, except that the average molecular weight was 33,000 and a 40% 1-methoxy-2-propyl acetate solution was used.
[0328] (実施例 4) [Example 4]
顔料分散組成物 Bにお ヽて、有機顔料粒子分散液調製時に用いたメタクリル酸/メ タクリル酸ベンジル共重合体を用いな力つた以外は、顔料分散組成物 Bと同様にして 顔料分散組成物 Dを作製した。  Pigment dispersion composition B was the same as pigment dispersion composition B except that the methacrylic acid / benzyl methacrylate copolymer used in preparing the organic pigment particle dispersion was used. D was produced.
[0329] (実施例 5) [0329] (Example 5)
顔料分散組成物 Bにお ヽて、有機顔料粒子分散液調製時に用いたメタクリル酸/メ タクリル酸ベンジル共重合体を用いず、 0. 75gのメタクリル酸/メタクリル酸べンジル 共重合体を顔料分散組成物調製時に追加した以外は、顔料分散組成物 Bと同様に して顔料分散組成物 Eを作製した。  In Pigment Dispersion Composition B, instead of using the methacrylic acid / benzyl methacrylate copolymer used in preparing the organic pigment particle dispersion, 0.75 g of methacrylic acid / benzyl methacrylate copolymer was dispersed in the pigment. Pigment dispersion composition E was prepared in the same manner as pigment dispersion composition B, except that it was added during preparation of the composition.
(比較例 1)  (Comparative Example 1)
実施例 1と同様にして有機顔料粒子分散液を調液した。  An organic pigment particle dispersion was prepared in the same manner as in Example 1.
ついでこの水性分散液に 10%塩酸を滴下して pHを 4. 0に調製し、顔料粒子を凝 集させた。その後、この凝集物を住友電工ファインポリマ社製 FP— 010型フィルター を用いて減圧濾過し、 500mlのメタノールで 5回洗いして、脱塩および脱水されたぺ 一スト状の濃縮顔料液 (顔料粒子濃度 30質量0 /0)を得た。このとき、ナトリウム (Na)ィ オン濃度は対顔料で 0. 02質量％であった。 Subsequently, 10% hydrochloric acid was added dropwise to the aqueous dispersion to adjust the pH to 4.0, and the pigment particles were aggregated. The aggregate is then filtered under reduced pressure using a FP-010 filter manufactured by Sumitomo Electric Fine Polymer Co., Ltd., washed 5 times with 500 ml of methanol, and desalted and dehydrated in the form of a concentrated concentrated pigment solution (pigment). particle concentration 30 mass 0/0) was obtained. At this time, the sodium (Na) ion concentration was 0.02 mass% with respect to the pigment.
このペーストを用いて実施例 1と同様に顔料分散物を調製し，顔料分散組成物 Fを 作製した。  Using this paste, a pigment dispersion was prepared in the same manner as in Example 1 to prepare Pigment Dispersion Composition F.
[0330] 得られた顔料分散組成物 A〜Fを、それぞれガラス基板上に厚みが 2 μ mになるよ うに塗布し、サンプルを作製した。このサンプルを光学顕微鏡により観察し、 1mm2に おける直径が 0. 5 μ m以上の粒子の個数 (粗大粒子数)を評価し、粒子サイズ及び 粒子サイズ分布 MvZMnとともに表 1に示す。 [0330] The obtained pigment dispersion compositions A to F were each applied onto a glass substrate so as to have a thickness of 2 µm, thereby preparing samples. This sample was observed with an optical microscope, and the number of particles with a diameter of 0.5 μm or more (coarse particle number) at 1 mm 2 was evaluated. The particle size and particle size distribution MvZMn are shown in Table 1.
[0331] [表 1] 試料 ( n m ) M v /M n 粗大粒子数 備考 顔料分散組成物 A 3 3 1 . 4 0 2 本発明 顔料分散組成物 B 3 4 1 . 4 5 3 本発明 顔料分散組成物 C 3 3 1 . 4 5 3 本発明 顔料分散組成物 D 4 2 1 . 5 5 5 本発明 顔料分散組成物 E 4 0 1 . 5 3 4 本発明 顔料分散組成物 F 3 3 1 . 5 0 2 3 比較例 [0331] [Table 1] Sample (nm) M v / M n Coarse particle number Remarks Pigment dispersion composition A 3 3 1.4 0 2 Inventive pigment dispersion composition B 3 4 1.4 5 3 Invented pigment dispersion composition C 3 3 1. 4 5 3 Inventive pigment dispersion composition D 4 2 1.5 5 5 Invented pigment dispersion composition E 4 0 1.5 5 3 4 Invented pigment dispersion composition F 3 3 1.5 5 0 2 3 Comparative example
[0332] 上記の結果より、塩を除去する目的で限外ろ過を行った後再分散した粒子サイズ 分布は、本発明の酸性基をもつ高分子化合物存在下で有機粒子を調製した場合 ( 顔料分散組成物 A〜E)はほとんど変化しなカゝつた。有機粒子を調製時に酸性基をも つ高分子化合物が存在する場合 (顔料分散組成物 A〜C)は特に、粒子サイズおよ び粒子サイズ分布の変化が小さく好ましい。一方、濃縮時に酸による凝集を行った場 合は (顔料分散組成物 F)粒子サイズはほとんど本発明と同じであつたが粗大粒子数 が多く実用上問題であることが分力つた。 [0332] From the above results, the particle size distribution re-dispersed after ultrafiltration for the purpose of removing salt is obtained when organic particles are prepared in the presence of the polymer compound having an acidic group of the present invention (pigment). The dispersion compositions A to E) were almost unchanged. In the case where a polymer compound having an acidic group is present when preparing organic particles (pigment dispersion compositions A to C), the change in particle size and particle size distribution is particularly small. On the other hand, when agglomeration with an acid was performed during concentration, (Pigment Dispersion Composition F) the particle size was almost the same as that of the present invention, but the number of coarse particles was large and this was a practical problem.
[0333] (実施例 6)  [0333] (Example 6)
顔料（ビグメントレッド 254) 0. 6gを、 1ーメチルー 2—ピロリドンと ImolZL-水酸化 ナトリウム水溶液を 6 : 1で混合した溶液に、 15mmol,Lとなるよう溶解した顔料溶液 を調製した。また、メタクリル酸/メタクリル酸ベンジル共重合体 0. 75g (モル比 28/ 72、質量平均分子量： 3万、 40% 1-メトキシ -2-プロピルアセテート溶液）、顔料分散 剤 A 0.3g、分散剤ポリビュルピロリドン 0. 6g (和光純薬 (株)製、 K30、分子量 40 , 000)を上記の溶液に溶解させた。これとは別に、貧溶媒として水を準備した。  A pigment solution was prepared by dissolving 0.6 g of Pigment (Vigment Red 254) in a solution prepared by mixing 1-methyl-2-pyrrolidone and ImolZL-sodium hydroxide aqueous solution 6: 1 to 15 mmol, L. Also, methacrylic acid / benzyl methacrylate copolymer 0.75 g (molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution), pigment dispersant A 0.3 g, dispersant Polybulpyrrolidone 0.6 g (manufactured by Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) was dissolved in the above solution. Separately from this, water was prepared as a poor solvent.
[0334] ここで、 25°Cに温度コントロールし、藤沢薬品工業社製 GK— 0222— 10型ラモン ドスターラーにより 500rpmで攪拌した貧溶媒の水 1000mlに、顔料溶液を、日本精 密化学社製 NP— KX— 500型大容量無脈流ポンプを用いて流速 50mlZminで 22 Oml注入することにより、有機顔料粒子分散液を調製した。 [0334] Here, the temperature was controlled at 25 ° C, and the pigment solution was added to 1000 ml of poor solvent water stirred at 500 rpm with a GK-0222-10 type ramond stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd., manufactured by Nippon Seimitsu Chemical Co., Ltd. An organic pigment particle dispersion was prepared by injecting 22 Oml at a flow rate of 50 mlZmin using an NP-KX-500 large capacity non-pulsating pump.
調製した有機粒子分散液を、日機装社製ナノトラック UPA— EX150を用いて測定 し、粒径、単分散度を評価したところ、数平均粒径 32nm、 MvZMnl.35であった。 調製した有機顔料粒子分散液 (顔料粒子濃度約 0. 05質量％)を限外ろ過機を用い ることにより、濃縮顔料液 (顔料粒子濃度 10質量％)を得た。このとき、ナトリウム (Na) イオン濃度は 0. 02質量％であった。 The prepared organic particle dispersion was measured using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd., and the particle size and monodispersity were evaluated. The number average particle size was 32 nm and MvZMnl.35. The prepared organic pigment particle dispersion (pigment particle concentration: about 0.05 mass%) was used with an ultrafilter to obtain a concentrated pigment liquid (pigment particle concentration: 10 mass%). At this time, sodium (Na) The ion concentration was 0.02% by mass.
さらに、アドバンテック東洋株式会社社製 VF35を用い、— 35°Cで凍結させた後、 6 X lOtorrで 16時間、凍結乾燥を行い、顆粒状の顔料にした。  Further, using VF35 manufactured by Advantech Toyo Co., Ltd., it was frozen at −35 ° C., and then freeze-dried with 6 × 10 torr for 16 hours to obtain a granular pigment.
[0335] 前記顆粒状の顔料を使!ヽ、下記組成の顔料分散組成物を調製した。 [0335] Using the granular pigment, a pigment dispersion composition having the following composition was prepared.
前記顔料 6. 3g  Pigment 6.3g
顔料分散剤 A 0. 6g  Pigment dispersant A 0.6 g
メタクリル酸 Zメタクリル酸ベンジル共重合体 * 15. 8g  Methacrylic acid Z benzyl methacrylate copolymer * 15.8 g
1ーメトキシ- 2-プロピルアセテート 42. 3g  1-Methoxy-2-propyl acetate 42.3 g
*モル比 28/72、質量平均分子量： 3万、 40% 1-メトキシ- 2-プロピルアセテート溶 液  * Molar ratio 28/72, mass average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution
[0336] 上記組成の顔料組成物をモーターミル M-50 (アイガー社製）で、直径 0.65mmの ジルコユアビーズを用い、周速 9m/sで分散した。  [0336] The pigment composition having the above composition was dispersed with a motor mill M-50 (manufactured by Eiger) at a peripheral speed of 9 m / s using Zircoyu beads having a diameter of 0.65 mm.
このようにして作製した顔料組成物を、顔料分散組成物 A1として日機装社製ナノト ラック UPA— EX150を用いて測定し、粒径、単分散度を評価した。  The pigment composition thus prepared was measured using a nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. as a pigment dispersion composition A1, and the particle size and monodispersity were evaluated.
[0337] (実施例 7) [Example 7]
顔料分散組成物 A1にお 、て、ペーストを用いて顔料分散組成物 A1を調製する際 に用 、たメタクリル酸/メタクリル酸ベンジル共重合体をメタクリル酸/メタクリル酸ベン ジル /スチレン共重合体 15. 8g (モル比 27 : 60 : 13、質量平均分子量： 2万 8千、 4 0%1-メトキシ -2-プロピルアセテート溶液）とした以外は、顔料分散組成物 A1と同様 にして顔料分散組成物 B1を作製した。  In the pigment dispersion composition A1, a methacrylic acid / benzyl methacrylate copolymer was used to prepare the pigment dispersion composition A1 by using a paste, and a methacrylic acid / benzyl methacrylate / styrene copolymer 15 Pigment dispersion composition as in Pigment dispersion composition A1, except that 8 g (molar ratio 27:60:13, weight average molecular weight: 28,000, 40% 1-methoxy-2-propyl acetate solution) was used. Material B1 was produced.
[0338] (実施例 8) [0338] (Example 8)
顔料分散組成物 A1にお 、て、ペーストを用いて顔料分散組成物 A1を調製する際 に用いたメタクリル酸/メタクリル酸ベンジル共重合体をポリアクリル酸 15. 8g (質量 平均分子量： 3万 3千、 40% 1-メトキシ -2-プロピルアセテート溶液）とした以外は、顔 料分散組成物 A1と同様にして顔料分散組成物 C1を作製した。  In the pigment dispersion composition A1, methacrylic acid / benzyl methacrylate copolymer used for preparing the pigment dispersion composition A1 using a paste was added with 15.8 g of polyacrylic acid (mass average molecular weight: 33,3) A pigment dispersion composition C1 was prepared in the same manner as the pigment dispersion composition A1, except that the solution was 1,000, 40% 1-methoxy-2-propyl acetate solution.
[0339] (実施例 9) [Example 9]
顔料分散組成物 B1にお ヽて、有機顔料粒子分散液調製時にもち 、たメタクリル酸 /メタクリル酸ベンジル共重合体を用いな力つた以外は、顔料分散組成物 A1と同様 にして顔料分散組成物 Dlを作製した。 Pigment dispersion composition B1 was the same as pigment dispersion composition A1 except that when the organic pigment particle dispersion was prepared, a methacrylic acid / benzyl methacrylate copolymer was used. Thus, a pigment dispersion composition Dl was prepared.
[0340] (実施例 10) [Example 10]
顔料分散組成物 B1にお ヽて、有機顔料粒子分散液調製時に用いたメタクリル酸/ メタクリル酸ベンジル共重合体を用いず、 0. 75gのメタクリル酸/メタクリル酸べンジル 共重合体を顔料分散組成物調製時に追加した以外は、顔料分散組成物 A1と同様 にして顔料分散組成物 E1を作製した。  In the pigment dispersion composition B1, 0.75 g of methacrylic acid / benzyl methacrylate copolymer was used instead of the methacrylic acid / benzyl methacrylate copolymer used in preparing the organic pigment particle dispersion. A pigment dispersion composition E1 was produced in the same manner as the pigment dispersion composition A1, except that it was added during preparation of the product.
[0341] 顔料分散組成物 A1〜E1の粒子サイズ分布 MvZMnを表 2に示す。 [0341] Table 2 shows the particle size distributions MvZMn of the pigment dispersion compositions A1 to E1.
[0342] [表 2] [0342] [Table 2]
Figure imgf000119_0001
Figure imgf000119_0001
[0343] 上記の結果より、塩を除去する目的で限外ろ過を行いさらに凍結乾燥を行った後 に再分散した粒子サイズ分布は、本発明の酸性基をもつ高分子化合物存在下で有 機粒子を調製した場合 (顔料分散組成物 A1〜C1)はほとんど変化しなカゝつた。有機 粒子を調製時に酸性基をもつ高分子化合物が存在しな 、場合 (顔料分散組成物 D1 )、あるいは有機粒子を調製時に酸性基をもつ高分子化合物が存在せず、かつ顔料 分散組成物調製時にその分の酸性基をもつ高分子化合物追加した場合 (顔料分散 組成物 E1)において粒子サイズ分布 Mv/Mnの変化は若干見られたものの、実用 上は殆ど問題の無いレベルであるといえる。  [0343] From the above results, the particle size distribution re-dispersed after ultrafiltration and lyophilization for the purpose of removing salt is organic in the presence of the polymer compound having an acidic group of the present invention. When the particles were prepared (pigment dispersion compositions A1 to C1), there was almost no change. When there is no polymer compound having an acidic group when preparing organic particles (pigment dispersion composition D1), or when there is no polymer compound having an acidic group when preparing organic particles, and preparing a pigment dispersion composition When a polymer compound having an acidic group corresponding to that amount is sometimes added (pigment dispersion composition E1), the particle size distribution Mv / Mn is slightly changed, but it can be said that there is almost no problem in practical use.
[0344] なお、用いた試薬の詳細は下記のとおりである。 [0344] The details of the reagents used are as follows.
試薬 製造元 ビグメントレッド 254 (ィルガフォアレッド） チバ'スペシャルティ '  Reagent Manufacturer Pigment Red 254 (Ilga Fore Red) Ciba 'Specialty'
ケミカルズ社製  Made by Chemicals
1ーメチルー 2—ピロリドン 和光純薬社製  1-Methyl-2-pyrrolidone Wako Pure Chemical Industries, Ltd.
2— (1ーメトキシ)プロピルアセテート 和光純薬社製 lmol/1 水酸化ナトリウム水溶液 和光純薬社製 2-— (1-Methoxy) propyl acetate Wako Pure Chemical Industries, Ltd. lmol / 1 Sodium hydroxide aqueous solution Wako Pure Chemical Industries, Ltd.
lmol/1 塩酸水溶液 和光純薬社製  lmol / 1 Hydrochloric acid aqueous solution Wako Pure Chemical Industries
[0345] (実施例 11) [0345] (Example 11)
ジォキサジン構造を有する有機顔料 (C. I. Pigment Violet 23、大日精化 (株） 社製、商品名 ノィォレット RE) lgを図 7の構成を有する装置の試料管 107に仕込 んだ。超臨界流体とする溶媒 1として準備したアセトンを試料管 107に供給して、顔 料溶解流体としてミキサー 111に供給した。これとは別に 1質量％のポリビニルピロリ ドン (和光純薬社製、商品名 ポリビュルピロリドン K— 30、質量平均分子量 40, 000 )を含有する水を析出溶媒 2として準備し、ミキサー 111に供給した。ミキサーで上記 顔料溶解流体と析出溶媒とを混合することによって顔料ナノ粒子分散液 115を調製 し収集した。  An organic pigment having a dioxazine structure (C.I. Pigment Violet 23, manufactured by Dainichi Seika Co., Ltd., trade name: NOOLET RE) lg was charged into a sample tube 107 of an apparatus having the configuration shown in FIG. Acetone prepared as solvent 1 to be used as a supercritical fluid was supplied to the sample tube 107 and supplied to the mixer 111 as a pigment-dissolving fluid. Separately, water containing 1% by weight of polyvinyl pyrrolidone (trade name: Polybulol pyrrolidone K-30, mass average molecular weight 40, 000, manufactured by Wako Pure Chemical Industries, Ltd.) is prepared as precipitation solvent 2 and supplied to mixer 111. did. The pigment nanoparticle dispersion liquid 115 was prepared and collected by mixing the pigment-dissolving fluid and the precipitation solvent with a mixer.
このとき、アセトンと析出溶媒との質量比が 1 : 1となるようにして供給した。顔料溶解 用アセトンの温度 (試料管 107内の温度）を 245°Cとし、圧力は 15MPaとなるようにし た。析出溶媒と混合した後の温度は 90°Cであった (ミキサー 111の出口温度)。 調製した顔料粒子分散液を実施例 1同様に評価したところ顔料粒子濃度約 0. 05 質量％であった。調製した顔料粒子を実施例 1同様に観察したところ、数平均粒径 は約 36nm、 Mv/Mnは 1. 40であった。  At this time, it supplied so that mass ratio of acetone and a precipitation solvent might be set to 1: 1. The temperature of acetone for dissolving pigment (the temperature in sample tube 107) was 245 ° C, and the pressure was 15 MPa. The temperature after mixing with the precipitation solvent was 90 ° C. (outlet temperature of mixer 111). The prepared pigment particle dispersion was evaluated in the same manner as in Example 1. As a result, the pigment particle concentration was about 0.05% by mass. The prepared pigment particles were observed in the same manner as in Example 1. As a result, the number average particle diameter was about 36 nm and Mv / Mn was 1.40.
[0346] 調製した有機顔料粒子分散液から実施例 1と同様の方法により、ペースト状の濃縮 顔料分散液 (顔料粒子濃度 33質量％)を得た。このペーストを用いて、下記組成の 顔料分散組成物を調製した。このときナトリウム (Na)イオン濃度は対顔料で 0. 01質 量％であった。 [0346] From the prepared organic pigment particle dispersion, a paste-like concentrated pigment dispersion (pigment particle concentration 33% by mass) was obtained in the same manner as in Example 1. Using this paste, a pigment dispersion composition having the following composition was prepared. At this time, the sodium (Na) ion concentration was 0.01 mass% with respect to the pigment.
ペース卜 22. 6g  Pace 卜 22. 6g
顔料分散剤 A 0. 8g  Pigment dispersant A 0.8 g
質量平均分子量 13, 000の高分子化合物 18. 0g  High molecular weight compound with a weight average molecular weight of 13,000 18.0g
(例示化合物 C 1)  (Exemplary compound C 1)
1ーメトキシ 2 プロピルアセテート 41. 0g  1-Methoxy 2-propyl acetate 41.0 g
上記組成の顔料分散組成物から実施例 1と同様にモーターミルを用いて顔料分散 組成物 Gを作製した。 Pigment dispersion from the pigment dispersion composition of the above composition using a motor mill in the same manner as in Example 1. Composition G was made.
[0347] (実施例 12) [0347] (Example 12)
実施例 11にお 、て一般式（1)で表される高分子化合物 C 1に代えてメタクリル酸 'メタクリル酸ベンジル共重合体（モル比 28Z72、質量平均分子量 30000、 40% 1 ーメトキシ 2—プロピルアセテート溶液)を用いた他は、顔料分散組成物 Gと同様に 顔料分散組成物 Hを作製した。  In Example 11, instead of the polymer compound C 1 represented by the general formula (1), methacrylic acid 'benzyl methacrylate copolymer (molar ratio 28Z72, mass average molecular weight 30000, 40% 1-methoxy 2-propyl A pigment dispersion composition H was prepared in the same manner as the pigment dispersion composition G except that the acetate solution was used.
[0348] (比較例 2) [0348] (Comparative Example 2)
実施例 11と同様にして有機顔料粒子分散液を調製した。  An organic pigment particle dispersion was prepared in the same manner as in Example 11.
っ ヽでこの水性分散液を比較例 1と同様の方法で凝集および洗浄、濾過を行!、、 脱塩および脱水されたペースト状の濃縮顔料液 (顔料粒子濃度 31質量％)を得た。 このときナトリウム (Na)イオン濃度は対顔料で 0. 03質量0 /。であった。 The aqueous dispersion was then agglomerated, washed and filtered in the same manner as in Comparative Example 1 to obtain a desalted and dehydrated paste-like concentrated pigment liquid (pigment particle concentration 31% by mass). At this time, the sodium (Na) ion concentration was 0.03 mass 0 / with respect to the pigment. Met.
このペーストを用いて実施例 11と同様に顔料分散物を調製し、顔料分散組成物 Iを 作製した。  Using this paste, a pigment dispersion was prepared in the same manner as in Example 11 to prepare Pigment Dispersion Composition I.
[0349] 実施例 1他と同様に測定した、顔料分散組成物 G〜Iの粒子サイズ、粒子サイズ分 布および粗大粒子数、さらにコントラストを表 3に示す。  Example 1 Table 3 shows the particle size, the particle size distribution and the number of coarse particles, and the contrast of the pigment dispersion compositions G to I measured in the same manner as in others.
[0350] (コントラストの測定方法）  [0350] (Contrast measurement method)
得られた顔料分散組成物 G〜Iを、それぞれガラス基板上に厚みが 2 mになるよう に塗布し、サンプルを作製した。ノ ックライトユニットとして 3波長冷陰極管光源 (東芝 ライテック (株)社製 FWL18EX— N)に拡散板を設置したものを用い、 2枚の偏光板 ( (株)サンリツ社製の偏光板 HLC2— 2518)の間にこのサンプルを置き、偏光軸が 平行のときと、垂直のときとの透過光量を測定し、その比をコントラストとした（「1990 年第 7回色彩光学コンファレンス、 512色表示 10. 4"サイズ TFT— LCD用カラーフ ィルタ、植木、小関、福永、山中」等参照。 ) o  The obtained pigment dispersion compositions G to I were each coated on a glass substrate so as to have a thickness of 2 m, thereby preparing samples. As a knocklight unit, a three-wavelength cold-cathode tube light source (FWL18EX—N manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed was used, and two polarizing plates (polarizing plate manufactured by Sanritsu Co., Ltd. HLC2— 2518), and measured the amount of transmitted light when the polarization axis was parallel and vertical, and the ratio was taken as the contrast (“1990 7th Color Optical Conference, 512 color display 10 See 4 "size TFT—LCD color filters, plants, Koseki, Fukunaga, Yamanaka" etc.) o
[0351] [表 3] 粒径 (nm) M v /Mn コントラス ト 粗大粒子数 備考 顔ネ粉散組成物 G 3 7 1 . 4 5 1 5 8 0 0 7 本発明 顔粉散誠物 H 3 9 1 . 4 5 1 3 5 0 0 1 2 本発明 顔 散組成物 I 4 8 1 . 6 2 9 8 0 0 4 6 比較例 [0352] 上記のように、超臨界流体を用いて粒子を形成し、限外濾過を行った本発明の組 成物では粒子サイズ、サイズ分布とも粒子形成時からの変化が小さく好ましい。また 限外濾過を行った後、一般式 (1)の化合物の存在下で再分散した本発明の顔料分 散組成物は特に高いコントラスト値を示し、更に好ましい結果となっているが、比較例 では粒子形成時力 の変化が大きぐ特に粗大粒子が多くなつておりコントラスト値も 低ぐ実用上本発明のものに大きく劣ることは明らかである。 [0351] [Table 3] Particle size (nm) M v / Mn Contrast Number of coarse particles Remarks Face dust powder composition G 3 7 1. 4 5 1 5 8 0 0 7 The present invention face powder powder H 3 9 1 .4 5 1 3 5 0 0 1 2 Oxidous Composition of the Present Invention I 4 8 1.6 6 2 9 8 0 0 4 6 Comparative Example [0352] As described above, the composition of the present invention in which particles are formed using a supercritical fluid and subjected to ultrafiltration is preferable because both the particle size and size distribution are small in change from the time of particle formation. In addition, the pigment dispersion composition of the present invention redispersed in the presence of the compound of the general formula (1) after performing ultrafiltration exhibits a particularly high contrast value, which is a more preferable result. However, it is clear that the change in the force at the time of particle formation is large, especially the number of coarse particles is large, and the contrast value is low.
[0353] (実施例 13)  [Example 13]
〔感光性転写材料の作製〕  [Production of photosensitive transfer material]
厚さ 75 μ mのポリエチレンテレフタレートフィルム仮支持体の上に、スリット状ノズル を用いて、下記処方 HIからなる熱可塑性榭脂層用塗布液を塗布、乾燥させた。次 に、下記処方 P1から成る中間層用塗布液を塗布、乾燥させた。更に、下記表 4に記 載の組成よりなる遮光性を有する榭脂組成物 K1を塗布、乾燥させ、該仮支持体の 上に乾燥膜厚が 15 mの熱可塑性榭脂層と、乾燥膜厚が 1. 6 mの中間層と、乾 燥膜厚が 2. 4 mの遮光性を有する榭脂層を設け、保護フィルム (厚さ 12 mポリ プロピレンフイノレム）を圧着した。  On a 75 μm-thick polyethylene terephthalate film temporary support, using a slit nozzle, a coating solution for a thermoplastic resin layer having the following formulation HI was applied and dried. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, a light-shielding resin composition K1 having the composition described in Table 4 below was applied and dried, and a thermoplastic resin layer having a dry film thickness of 15 m on the temporary support and a dry film. An intermediate layer with a thickness of 1.6 m and a light-shielding resin layer with a dry film thickness of 2.4 m were provided, and a protective film (polypropylene phenol with a thickness of 12 m) was pressure-bonded.
こうして仮支持体と熱可塑性榭脂層と中間層 (酸素遮断膜)と遮光性を有する榭脂 層とがー体となった感光性榭脂転写材料を作製し、サンプル名を感光性榭脂転写材 料 K1とした。  In this way, a photosensitive resin transfer material comprising a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a light-shielding resin layer was prepared, and the sample name was photosensitive resin. The transfer material was K1.
[0354] *熱可塑性榭脂層用塗布液:処方 HI  [0354] * Coating solution for thermoplastic resin layer: Formulation HI
'メタノール 11. 1質量部  'Methanol 11.1 parts by mass
•プロピレングリコールモノメチルエーテルアセテート 6. 4質量部 • Propylene glycol monomethyl ether acetate 6.4 parts by mass
•メチルェチルケトン 52. 4質量部 • Methyl ethyl ketone 52.4 parts by mass
'メチルメタタリレート /2—ェチルへキシルアタリレート/ベンジル  'Methylmetatalylate / 2-ethylhexyl talylate / benzyl
メタタリレート Zメタクリル酸共重合体 (共重合組成比（モル比）  Metatalylate Z Methacrylic Acid Copolymer (Copolymerization composition ratio (molar ratio)
= 55/11. 7/4. 5/28. 8、分子量 = 10万、 Tg 70。  = 55/11. 7/4. 5/28. 8, Molecular weight = 100,000, Tg 70.
5. 83質量部  5.83 parts by mass
•スチレン Zアクリル酸共重合体 (共重合組成比（モル比）  • Styrene Z acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63Z37、分子量 = 1万、 Tg 100。C) 3. 6質量部 •2, 2—ビス [4— (メタクリロキシポリエトキシ）フエ-ル] = 63Z37, molecular weight = 10,000, Tg 100. C) 3.6 parts by mass • 2, 2—Bis [4— (Methacryloxypolyethoxy) phenol]
プロパン (新中村化学工業 (株)社製） 9. 1質量部  Propane (made by Shin-Nakamura Chemical Co., Ltd.) 9. 1 part by mass
•界面活性剤 1 0. 54質量部  • Surfactant 1 0.54 parts by mass
[0355] *界面活性剤 1 (メガファック F— 780— F (大日本インキ化学工業 (株)社製)）の組 成は、  [0355] * The composition of Surfactant 1 (Megafac F—780—F (Dainippon Ink Chemical Co., Ltd.))
•C F CH CH OCOCH = CH :40質量部と  • C F CH CH OCOCH = CH: 40 parts by mass
6 13 2 2 2  6 13 2 2 2
H (OCH (CH ) CH ) OCOCH = CH : 55質量部と  H (OCH (CH) CH) OCOCH = CH: 55 parts by mass
3 2 7 2  3 2 7 2
H (OCH CH ) OCOCH = CH : 5質量部との  H (OCH CH) OCOCH = CH: 5 parts by mass
2 2 7 2  2 2 7 2
共重合体 (分子量 3万） 30質量部  Copolymer (Molecular weight 30,000) 30 parts by mass
•メチルェチルケトン 70質量部  • 70 parts by weight of methyl ethyl ketone
[0356] *中間層（酸素遮断層）用塗布液処方: P1 [0356] * Coating solution formulation for intermediate layer (oxygen barrier layer): P1
'ポリビュルアルコール 32. 2質量  'Polybulol alcohol 32. 2 mass
(PVA205 (鹼ィ匕率 =88%)； (株)クラレネ土製）  (PVA205 (Niety rate = 88%); Kurarene clay)
'ポリビュルピロリドン 14. 9質量咅  'Polybulol pyrrolidone 14. 9 mass
(PVP、 K— 30；アイエスピー ·ジャパン株式会社製）  (PVP, K-30; made by IPS Japan Ltd.)
•メタノーノレ 429質量言  • Methanore 429 mass statements
'蒸留水 524質量部  '524 parts by weight of distilled water
[表 4]  [Table 4]
Figure imgf000123_0001
Figure imgf000123_0001
[0358] ここで、上記表 4に記載の遮光性を有する榭脂組成物 K1の調製について説明する 遮光性を有する榭脂組成物 Klは、まず表 4に記載の量の K顔料分散物 1、プロピ レンダリコールモノメチルエーテルアセテートをは力り取り、温度 24°C (± 2°C)で混合 して 150rpmlO分間攪拌し、次いで、表 4に記載の量のシクロへキサノン、バインダ 一 1、ハイドロキノンモノメチルエーテル、 DPHA液、 2, 4 ビス（トリクロロメチル） 6 — [4，— (N, N ビスエトキシカルボ-ルメチル）アミノー 3，—ブロモフエ-ル]— s— トリアジン、界面活性剤 1をは力り取り、温度 25°C (± 2°C)でこの順に添加して、温度 40°C (± 2°C)で 150rpm30分間攪拌することによって得られた。 [0358] Here, the preparation of the light-blocking composition K1 having the light-shielding properties described in Table 4 above will be described. The resin composition Kl having a light-shielding property is obtained by first removing the amount of K pigment dispersion 1 and polypropylene alcohol monomethyl ether acetate in the amounts shown in Table 4 and mixing them at a temperature of 24 ° C (± 2 ° C). The amount of cyclohexanone, binder 1-1, hydroquinone monomethyl ether, DPHA solution, 2, 4 bis (trichloromethyl) 6 — [4,-(N, N bisethoxy] Carbomethyl) amino-3, —bromophenol] — s— triazine, surfactant 1 was removed and added in this order at a temperature of 25 ° C (± 2 ° C) to give a temperature of 40 ° C (± It was obtained by stirring at 150 rpm for 30 minutes at 2 ° C).
[0359] 尚、表 4に記載の組成物の内、 [0359] Of the compositions listed in Table 4,
*K顔料分散物 1の組成は、  * The composition of K Pigment Dispersion 1 is
•カーボンブラック  •Carbon black
(デグッサ社製、商品名 Special Black250) 13. 1質量部  (Product name: Special Black 250, manufactured by Degussa) 13.1 parts by mass
•前記顔料分散剤 A 0. 65質量部  • Pigment dispersant A 0.65 parts by mass
'ポリマー（ベンジルメタタリレート/メタクリル酸 = 72/28モル比  'Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
のランダム共重合物、分子量 3. 7万） 6. 72質量部 Random copolymer, molecular weight 37,000) 6. 72 parts by mass
•プロピレングリコールモノメチルエーテルアセテート 79. 53質量部 Propylene glycol monomethyl ether acetate 79.53 parts by mass
[0360] *バインダー 1の組成は、 [0360] * The composition of Binder 1 is
'ポリマー（ベンジルメタタリレート/メタクリル酸 = 78/22モル比  'Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
のランダム共重合物、分子量 4万） 27質量部  Random copolymer, molecular weight 40,000) 27 parts by weight
•プロピレングリコールモノメチルエーテルアセテート 73質量部  • 73 parts by mass of propylene glycol monomethyl ether acetate
[0361] * DPHA液の組成は、  [0361] * The composition of DPHA solution is
'ジペンタエリスリトールへキサアタリレート（重合禁止剤 MEHQ 500ppm含有、 日本化薬 (株)社製、商品名： KAYARAD DPHA) 76質量部 •プロピレングリコールモノメチルエーテルアセテート 24質量部  'Dipentaerythritol hexaatalylate (containing polymerization inhibitor MEHQ 500ppm, Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass • Propylene glycol monomethyl ether acetate 24 parts by mass
[0362] 尚、界面活性剤 1は、前記熱可塑性榭脂層用塗布液 HIに用いた界面活性剤 1と 同様である。  [0362] The surfactant 1 is the same as the surfactant 1 used in the coating solution HI for thermoplastic resin layer.
[0363] 〔遮光性を有する隔壁の形成〕 [Formation of light-blocking partition walls]
無アルカリガラス基板を、 25°Cに調整したガラス洗浄剤液をシャワーにより 20秒間 吹き付けながらナイロン毛を有する回転ブラシで洗浄し、純水シャワー洗浄後、シラ ンカップリング液 (N— β (アミノエチル） y—ァミノプロピルトリメトキシシラン 0. 3質量Glass cleaning solution adjusted to 25 ° C on an alkali-free glass substrate for 20 seconds by shower Wash with a rotating brush with nylon bristles while spraying, wash with pure water shower, then silane coupling liquid (N-β (aminoethyl) y-aminopropyltrimethoxysilane 0.3 mass
%水溶液、商品名： KBM603、信越ィ匕学工業 (株)社製)をシャワーにより 20秒間吹 き付け、純水シャワー洗浄した。この基板を基板予備加熱装置で 100°C2分加熱した % Aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 100 ° C for 2 minutes with a substrate preheating device.
[0364] 前記感光性榭脂転写材料 K1の保護フィルムを剥離後、ラミネータ (株式会社日立 インダストリィズ社製 (LamicII型)）を用い、前記 100°Cで 2分間加熱した基板に、ゴ ムローラー温度 130°C、線圧 100NZcm、搬送速度 2. 2mZ分でラミネートした。 仮支持体を剥離後、超高圧水銀灯を有するプロキシミティ型露光機（日立ハイテク 電子エンジニアリング株式会社製)で、基板とマスク (画像パターンを有す石英露光 マスク）を垂直に立てた状態で、露光マスク面と該熱可塑性樹脂層の間の距離を 20 O /z mに設定し、露光量 lOOmjZcm2でパターン露光した。マスク形状は格子状で、 画素と遮光性を有する隔壁との境界線に該当する部分における、遮光性を有する隔 壁側に凸な角の曲率半径は 0. 6 mとした。 [0364] After the protective film of the photosensitive resin transfer material K1 is peeled off, a rubber roller temperature is applied to the substrate heated at 100 ° C for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)). Lamination was performed at 130 ° C, linear pressure 100 NZcm, conveyance speed 2. 2 mZ min. After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. the distance between the mask surface and the thermoplastic resin layer is set to 20 O / zm, and an exposure energy of lOOmjZcm 2. The mask shape is a lattice shape, and the radius of curvature of the corner that protrudes toward the light-shielding partition wall at the boundary line between the pixel and the light-shielding barrier is 0.6 m.
[0365] 次に、トリエタノールアミン系現像液（2. 5%のトリエタノールァミン含有、ノ-オン性 界面活性剤含有、ポリプロピレン系消泡剤含有、商品名： T PD1、富士写真フィル ム株式会社製）にて 30°C50秒、フラットノズル圧力 0. 04MPaでシャワー現像し熱可 塑性榭脂層と中間層 (酸素遮断層）を除去した。  [0365] Next, a triethanolamine developer (containing 2.5% triethanolamine, containing a non-ionic surfactant, containing a polypropylene antifoaming agent, trade name: TPD1, Fuji Photo Film) Made by showering at 30 ° C for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
引き続き炭酸ナトリウム系現像液 (0. 06モル Zリットルの炭酸水素ナトリウム、同濃 度の炭酸ナトリウム、 1%のジブチルナフタレンスルホン酸ナトリウム、ァ-オン性界面 活性剤、消泡剤、安定剤含有、商品名： T CD1、富士写真フィルム株式会社製)を 用い、 29°C30秒、コーン型ノズル圧力 0. 15MPaでシャワー現像し遮光性を有する 榭脂層を現像しパターユング離画壁 (遮光性を有する隔壁パターン)を得た。  Subsequently, a sodium carbonate developer (0.06 mol Z liters of sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, ionic surfactant, antifoaming agent, stabilizer, Product name: TCD1, manufactured by Fuji Photo Film Co., Ltd., shower developed at 29 ° C for 30 seconds, cone type nozzle pressure 0.15 MPa, developing a light-shielding resin layer, and patterning separation wall (light-shielding property) Partition wall pattern).
[0366] 弓 Iき続き洗浄剤 (燐酸塩 ·珪酸塩 ·ノ-オン性界面活性剤 ·消泡剤 ·安定剤含有、商 品名「T— SD1 (富士写真フィルム株式会社製)」）を用い、 33°C20秒、コーン型ノズ ル圧力 0. 02MPaでシャワーとナイロン毛を有す回転ブラシにより残渣除去を行い、 遮光性を有する隔壁を得た。その後更に、該基板に対して該榭脂層の側から超高圧 水銀灯で 500miZcm2の光でポスト露光後、 240°C、 50分熱処理した。 [0367] 〔プラズマ撥水化処理〕 [0366] Using a bow I-continuous detergent (phosphate, silicate, non-ionic surfactant, antifoam, stabilizer, trade name “T-SD1 (Fuji Photo Film Co., Ltd.)”) Residue removal was performed with a rotating brush having a shower and nylon bristles at 33 ° C for 20 seconds and a cone type nozzle pressure of 0.02 MPa to obtain a light-shielding partition wall. Thereafter, the substrate was further post-exposed with light of 500 miZcm 2 with an ultra-high pressure mercury lamp from the side of the resin layer and then heat-treated at 240 ° C. for 50 minutes. [Plasma water repellency treatment]
その後、下記方法によりプラズマ撥水化処理を行った。  Thereafter, plasma water repellency treatment was performed by the following method.
遮光性を有する隔壁を形成した前記基板に、力ソードカップリング方式平行平板型 プラズマ処理装置を用いて、以下の条件にてプラズマ撥水化処理を行った。  Plasma water repellency treatment was performed on the substrate on which the light-shielding partition walls were formed using a force sword coupling parallel plate type plasma processing apparatus under the following conditions.
使用ガス ： CF4 ガス流量 ：80sccm  Gas used: CF4 Gas flow rate: 80sccm
圧力 : 40Pa  Pressure: 40Pa
RFパワー ：50W  RF power: 50W
処理時間 ：30sec  Processing time: 30sec
[0368] 〔カラーフィルタ用インクジェットインクの調製〕 [Preparation of inkjet ink for color filter]
特開 2002— 201387号公報の実施例 1を参考に以下の処方でインクを調製した。  An ink was prepared according to the following formulation with reference to Example 1 of JP-A-2002-201387.
[表 5] [Table 5]
組成成分含有量 (質量部） Bインク 1 Bインク 2 Bインク 3 Rインク 1 Gインク 1 顔料分散組成物 G(C. I. P. V. 23) 8 顔料分散組成物 H(C. I. P. V. 23) 8 顔料分散組成物 I(C. I. P. V. 23) 8 顔料分散組成物 J (C. L P. R. 254) 75 顔料分散組成物 K(C. I. P. G. 36) 75 顔料分散組成物し (C. I. P. B. 15:6) 20 20 20 Composition component content (parts by mass) B ink 1 B ink 2 B ink 3 R ink 1 G ink 1 Pigment dispersion composition G (CIPV 23) 8 Pigment dispersion composition H (CIPV 23) 8 Pigment dispersion composition I (CIPV 23) 8 Pigment dispersion composition J (C. L PR 254) 75 Pigment dispersion composition K (CIPG 36) 75 Pigment dispersion composition (CIPB 15: 6) 20 20 20
高分子分散剤 (AVECIA社製ソルノ一  Polymer dispersant (Sornoichi manufactured by AVECIA)
1.5 1.5 1.5 1.5 1.5 ス 24000)  1.5 1.5 1.5 1.5 1.5 24000)
'ヽ 'インダ一(ベンジルメタクリ b "トメタク  'ヽ' Indah (benzyl methacrylate b)
3.0 3.0 3.0 3.0 3.0 リル酸共重合体）  3.0 3.0 3.0 3.0 3.0 Rylic acid copolymer)
ジペンタエリスリト_ 1^ンタァクリレート 2.0 2.0 2.0 2.0 2.0 トリプロピレングリコールジァクリレート 5.0 5.0 5.0 5.0 5.0 Dipentaerythritol_ 1 ^ tantalate 2.0 2.0 2.0 2.0 2.0 Tripropylene glycol diacrylate 5.0 5.0 5.0 5.0 5.0
2—メチル一1—〔4— (メチルチオ)フエ 2-Methyl-1-1- (4- (methylthio) phenol
二ル〕一 2—モンフォリノプロパン）一 1 - 2.0 2.0 2.0 2.0 2.0 オン  2) 1 2-Monfolinopropane) 1-2.0 2.0 2.0 2.0 2.0 ON
ジエチレングリコールモノブチルェ~^  Diethylene glycol monobutyle ~ ^
75 75 75 40 40 ルァセテ一ト、 29. 9dyn/cm  75 75 75 40 40 Lucate, 29.9 dyn / cm
[0369] 上記表 5の各成分の混合につ ヽては、先ず、顔料及び高分子分散剤を溶剤の一 部に投入、混合し、 3本ロールとビーズミルを用いて攪拌して顔料分散液を得た。一 方、他の配合成分を溶剤の残部に投入、攪拌して溶解分散し、バインダー溶液を得 た。そして、顔料分散液を少量ずつバインダー溶液中に添加しながらディソルバーで 十分に攪拌し、カラーフィルタ用インクジェットインクを調製した。 [0369] For mixing the respective components in Table 5, the pigment and the polymer dispersant were first charged and mixed in a part of the solvent, and the mixture was stirred using a three-roll and bead mill, and then the pigment dispersion liquid was mixed. Got. On the other hand, other compounding ingredients were added to the remainder of the solvent, and dissolved and dispersed by stirring to obtain a binder solution. Then, the pigment dispersion was added little by little to the binder solution and sufficiently stirred with a dissolver to prepare an ink-jet ink for a color filter.
[0370] ビグメントバイオレット 23に代えて、ビグメントレッド 254、ビグメントグリーン 36、又は ビグメントブルー 15 : 6を用いた以外実施例 11と同様にして、顔料分散組成物 J、 Kお よび L、をそれぞれ作製した。  [0370] Pigment dispersion compositions J, K and L in the same manner as in Example 11 except that Pigment Red 254, Pigment Green 36, or Pigment Blue 15: 6 was used instead of Pigment Violet 23. , Respectively.
調製した顔料分散組成物 J、 K、 Lを用いて表 5に示す組成で調製し、 Rl、 Gl、 Bl 〜3インクを作製した。 [0371] [カラーフィルタ及び液晶表示装置の作製] Using the prepared pigment dispersion compositions J, K, and L, the inks were prepared with the compositions shown in Table 5 to prepare Rl, Gl, and Bl-3 inks. [0371] [Production of color filter and liquid crystal display device]
〔画素形成〕  [Pixel formation]
上記で得られた Rインク 1、 Gインク 1、 Bインク 1をピエゾ方式のヘッドを用いて、まず 以下のようにして遮光性隔壁に囲まれた凹部にインクを打滴した。そして下記のよう にして、本発明のカラーフィルタ 1を得た。  The R ink 1, G ink 1, and B ink 1 obtained above were first ejected into a recess surrounded by a light-shielding partition as follows using a piezo-type head. And the color filter 1 of this invention was obtained as follows.
ヘッドは 25. 4mmあたり 150のノズル密度で、 318ノズルを有しており、これを 2個 ノズル列方向にノズル間隔の 1 Z2ずらして固定することにより、基板上にはノズル配 列方向に 25. 4mmあたり 300滴打滴される。  The head has 2 nozzles with a nozzle density of 25.4 mm and 318 nozzles. Two of these are fixed in the nozzle row direction by shifting the nozzle spacing by 1 Z2 and 25 on the substrate in the nozzle row direction. 300 drops per 4mm.
ヘッドおよびインクは、ヘッド内に温水を循環させることにより吐出部分近辺が 50士 0. 5°Cとなるように制御されている。  The head and the ink are controlled so that the vicinity of the discharge portion is 50 ° C 0.5 ° C by circulating hot water in the head.
ヘッド力 のインク吐出は、ヘッドに付与されるピエゾ駆動信号により制御され、一 滴あたり 6〜42plの吐出が可能であって、本実施例ではヘッドの下 lmmの位置でガ ラス基板が搬送されながらヘッドより打滴される。搬送速度は 50〜200mmZsの範 囲で設定可能である。またピエゾ駆動周波数は最大 4. 6KHzまでが可能であって、 これらの設定により打滴量を制御することができる。  The ink ejection of the head force is controlled by a piezo drive signal applied to the head, and it is possible to eject 6 to 42 pl per drop. In this embodiment, the glass substrate is conveyed at a position lmm below the head. However, it is ejected from the head. The conveyance speed can be set in the range of 50 to 200 mmZs. The piezo drive frequency can be up to 4.6 KHz, and the droplet ejection volume can be controlled by these settings.
[0372] R、 G、 Bそれぞれ、顔料の塗設量が、 1. 1、 1. 8、 0. 75gZm2になるように、搬送 速度、駆動周波数を制御し、所望する R、 G、 Bに対応する凹部に R、 G、 Bのインクを 打滴した。 [0372] The transport speed and drive frequency are controlled so that the amount of pigment applied is 1.1, 1.8, and 0.75gZm 2 for each of R, G, and B. The desired R, G, and B R, G, and B inks were ejected into the recesses corresponding to.
打滴されたインクは、露光部に搬送され、紫外発光ダイオード (UV— LED)により 露光される。 UV— LEDは日亜化学社製 NCCU033を用いた。本 LEDは 1チップか ら波長 365nmの紫外光を出力するものであって、約 500mAの電流を通電すること により、チップ力ゝら約 lOOmWの光が発光される。これを 7mm間隔に複数個配列し、 表面で 0. 3WZcm2のパワーが得られる。打滴後露光されるまでの時間、および露 光時間はメディアの搬送速度およびヘッドと LEDの搬送方向の距離により変更可能 である。着弾後、 100度で 10分間乾燥させ、その後露光した。 The ejected ink is transported to the exposure section and exposed by an ultraviolet light emitting diode (UV—LED). As the UV LED, NCCU033 manufactured by Nichia Corporation was used. This LED outputs ultraviolet light with a wavelength of 365 nm from a single chip. When a current of about 500 mA is applied, about lOOmW of light is emitted from the chip. A plurality of these are arranged at intervals of 7 mm, and a power of 0.3 WZcm 2 can be obtained on the surface. The exposure time after droplet ejection and the exposure time can be changed according to the transport speed of the media and the distance between the head and the LED transport direction. After landing, it was dried at 100 degrees for 10 minutes and then exposed.
距離および搬送速度の設定に応じて、メディア上の露光エネルギーを 0. 01〜15J Zcm2の間で調整することができる。搬送速度により露光エネルギーを調整した。 これら露光パワー、露光エネルギーの測定にはゥシォ電機製スぺクトロラディオメ一 タ URS— 40Dを用い、波長 220nmから 400nmの間を積分した値を用いた。 Depending on the distance and transport speed settings, the exposure energy on the media can be adjusted between 0.01 and 15 J Zcm 2 . The exposure energy was adjusted according to the conveyance speed. For measurement of these exposure power and exposure energy, Spectroradiome A value obtained by integrating the wavelength between 220 nm and 400 nm using URS-40D was used.
打滴後のガラス基板を 230°Cオーブン中で 30分ベータすることで、遮光性隔壁、 各画素共に完全に硬化させた。  The glass substrate after droplet ejection was beta-cured in an oven at 230 ° C for 30 minutes, so that both the light-shielding partition and each pixel were completely cured.
[0373] (ITO電極の形成） [0373] (Formation of ITO electrode)
カラーフィルタが形成されたガラス基板をスパッタ装置に入れて、 100°Cで 1300A 厚さの ITO (インヂゥム錫酸ィ匕物）を全面真空蒸着した後、 240°Cで 90分間ァニール して ITOを結晶化し、 ITO透明電極を形成した。  A glass substrate with a color filter is placed in a sputtering system, and 1300A thick ITO (indium stannate) is vacuum-deposited at 100 ° C on the entire surface, and then annealed at 240 ° C for 90 minutes. Crystallization formed an ITO transparent electrode.
[0374] (スぺーサの形成） [0374] (Formation of spacers)
特開 2004— 240335号公報の [実施例 1]に記載のスぺーサ形成方法と同様の方 法で、上記で作製した ITO透明電極上にスぺーサを形成した。  A spacer was formed on the ITO transparent electrode produced in the same manner as the spacer forming method described in [Example 1] of JP-A-2004-240335.
[0375] (液晶配向制御用突起の形成） [0375] (Formation of protrusions for controlling liquid crystal alignment)
下記のポジ型感光性榭脂層用塗布液を用いて、前記スぺーサを形成した ITO透 明電極上に液晶配向制御用突起を形成した。  A liquid crystal alignment control protrusion was formed on the ITO transparent electrode on which the spacer was formed, using the following positive photosensitive resin layer coating solution.
但し、露光、現像、及び、ベータ工程は、以下の方法を用いた。  However, the following methods were used for exposure, development, and beta process.
所定のフォトマスクが感光性榭脂層の表面から 100 mの距離となるようにプロキシ ミティ露光機 (日立ハイテク電子エンジニアリング株式会社製)を配置し、該フォトマス クを介して超高圧水銀灯により照射エネルギー 150miZcm2でプロキシミティ露光し た。 Proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the prescribed photomask is at a distance of 100 m from the surface of the photosensitive resin layer, and irradiated with an ultrahigh pressure mercury lamp through the photomask. and proximity exposure in the energy 150miZcm 2.
続いて、 2. 38%テトラメチルアンモ-ゥムヒドロキシド水溶液を、シャワー式現像装 置にて 33°Cで 30秒間基板に噴霧しながら現像した。こうして、感光性榭脂層の不要 部 (露光部）を現像除去することにより、カラーフィルタ側基板上に、所望の形状にパ ターニングされた感光性榭脂層よりなる液晶配向制御用突起が形成された液晶表示 装置用基板を得た。  Subsequently, 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying the substrate at 33 ° C. for 30 seconds with a shower type developing device. In this manner, by developing and removing unnecessary portions (exposed portions) of the photosensitive resin layer, liquid crystal alignment control protrusions composed of the photosensitive resin layer patterned in a desired shape are formed on the color filter side substrate. A liquid crystal display device substrate was obtained.
次いで、該液晶配向制御用突起が形成された液晶表示装置用基板を 230°C下で 30分ベータすることにより、液晶表示装置用基板上に硬化された液晶配向制御用突 起を形成した。  Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusion was formed was beta-treated at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display device substrate.
[0376] <ポジ型感光性榭脂層用塗布液処方 > [0376] <Coating liquid formulation for positive photosensitive resin layer>
'ポジ型レジスト液（富士フィルムエレクトロニクス マテリアルズ (株)社製 FH— 2413F) ： 53. 3質量部 'Positive resist solution (Fuji Film Electronics Materials Co., Ltd. FH— 2413F): 53.3 parts by mass
•メチルェチルケトン ： 46. 7質量部  • Methyl ethyl ketone: 46.7 parts by mass
•メガファック F— 780F (大日本インキ化学工業 (株)社製） : 0. 04質量部  • Megafuck F—780F (Dainippon Ink Chemical Co., Ltd.): 0.04 parts by mass
[0377] (液晶表示装置の作成） [0377] (Creation of liquid crystal display device)
上記で得られた液晶表示装置用基板上に更にポリイミドよりなる配向膜を設けた。 その後、カラーフィルタの画素群を取り囲むように周囲に設けられた遮光性を有す る隔壁の外枠に相当する位置にエポキシ榭脂のシール剤を印刷すると共に、 MVA モード用液晶を滴下し、対向基板と貼り合わせた後、貼り合わされた基板を熱処理し てシール剤を硬化させた。このようにして得た液晶セルの両面に、（株)サンリツ社製 の偏光板 HLC2— 2518を貼り付けた。次いで、 3波長冷陰極管光源 (東芝ライテック (株)社製 FWL18EX— N)のバックライトを構成し、前記偏光板が設けられた液晶セ ルの背面となる側に配置し、本発明の液晶表示装置 1とした。  An alignment film made of polyimide was further provided on the liquid crystal display substrate obtained above. After that, an epoxy resin sealant is printed at a position corresponding to the outer frame of the light-shielding partition wall that is provided around the color filter pixel group, and MVA mode liquid crystal is dropped. After being bonded to the counter substrate, the bonded substrate was heat-treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a three-wavelength cold-cathode tube light source (FWL18EX-N manufactured by Toshiba Lighting & Technology Co., Ltd.) was constructed and placed on the side of the liquid crystal cell provided with the polarizing plate, and the liquid crystal of the present invention Display device 1 was used.
[0378] カラーフィルタ 1の B1インクを B2〜3インクに変える以外は全く同様にして、カラー フィルタ 2〜3をそれぞれ作製した。次いで、カラーフィルタ 1に代え、カラーフィルタ 2 〜3をそれぞれ用いて MVA方式の液晶表示装置 2〜3を作製した。 [0378] Color filters 2 to 3 were produced in the same manner except that the B1 ink of the color filter 1 was changed to the B2 to 3 inks. Next, in place of the color filter 1, color filters 2 to 3 were used, respectively, to fabricate MVA liquid crystal display devices 2 to 3.
各液晶表示装置の表示性能の評価を行った結果、液晶表示装置 3 (比較例）に対 して本発明のカラーフィルタを有する液晶表示装置 1〜2は黒のしまりと青の描写力 に優れることを確認した。  As a result of the evaluation of the display performance of each liquid crystal display device, the liquid crystal display devices 1 and 2 having the color filter of the present invention have excellent blackness and blue descriptive power as compared with the liquid crystal display device 3 (comparative example). It was confirmed.
[0379] [IPSモード、 PVAモードの液晶表示装置の作製] [0379] [Preparation of IPS mode, PVA mode LCD]
上記のカラーフィルタ 1〜 3を用 、て以下の方式の、液晶表示装置を作製した。  Using the above color filters 1 to 3, a liquid crystal display device of the following method was produced.
[0380] 'PVAモード用液晶表示装置の作製 [0380] 'Preparation of liquid crystal display for PVA mode
カラーフィルタ 1〜3について、それぞれ、 R画素、 G画素、及び Β画素並びにブラッ クマトリクスの上に更に、 ITO (Indium Tin Oxide)の透明電極をスパッタリングに より形成した。次いで、特開 2006— 64921号公報の実施例 1に従い、前記で形成し た ITO膜上のブラックマトリクス上部に相当する部分にスぺーサを形成した。  For the color filters 1 to 3, transparent electrodes of ITO (Indium Tin Oxide) were further formed by sputtering on the R pixel, the G pixel, the blue pixel, and the black matrix, respectively. Next, according to Example 1 of Japanese Patent Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the black matrix on the ITO film formed as described above.
別途、対向基板としてガラス基板を用意し、カラーフィルタ基板の透明電極上及び 対向基板上にそれぞれ PVAモード用にパターニングを施し、その上に更にポリイミド よりなる配向膜を設けた。 その後、カラーフィルタの画素群を取り囲むように周囲に設けられたブラックマトリク ス外枠に相当する位置に紫外線硬化樹脂のシール剤をデイスペンサ方式により塗布 し、 PVAモード用液晶を滴下し、対向基板と貼り合わせた後、貼り合わされた基板を UV照射した後、熱処理してシール剤を硬化させた。このようにして得た液晶セルの 両面に、（株)サンリツ社製の偏光板 HLC2— 2518を貼り付けた。次いで、赤色 (R) LEDとして FR1112H (スタンレー（株）社製のチップ型 LED)、緑色（G) LEDとして DG1112H (スタンレー（株）社製のチップ型 LED)、青色（B) LEDとして DB1112H (スタンレー (株)社製のチップ型 LED)を用いてサイドライト方式のバックライトを構成 し、前記偏光板が設けられた液晶セルの背面となる側に配置し、液晶表示装置とし た。 Separately, a glass substrate was prepared as a counter substrate, patterned on the transparent electrode and the counter substrate of the color filter substrate for the PVA mode, respectively, and an alignment film made of polyimide was further provided thereon. After that, a UV curable resin sealant is applied to the position corresponding to the outer periphery of the black matrix surrounding the pixel group of the color filter by the dispenser method, and the PVA mode liquid crystal is dropped to the opposite substrate. After bonding, the bonded substrate was irradiated with UV, and then heat treated to cure the sealant. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as the red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as the green (G) LED, and DB1112H ( A side-light type backlight was constructed using a chip-type LED (manufactured by Stanley Co., Ltd.) and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.
これらの表示装置を用いて表示性能の評価を行ったところ、比較例の液晶表示装 置 3に対して、本発明の液晶表示装置 1〜2は優れた表示性能を発揮した。  When the display performance was evaluated using these display devices, the liquid crystal display devices 1 and 2 of the present invention exhibited excellent display performance with respect to the liquid crystal display device 3 of the comparative example.
•IPSモード用液晶表示装置の作製 • Manufacture of IPS mode LCD
カラーフィルタ 1〜3について、それぞれ、 R画素、 G画素、及び B画素並びにブラッ クマトリクスの上に更に、 ITO (Indium Tin Oxide)の透明電極をスパッタリングに より形成した。次いで、特開 2006— 64921号公報の実施例 1に従い、前記で形成し た ITO膜上のブラックマトリクス上部に相当する部分にスぺーサを形成した。  For the color filters 1 to 3, transparent electrodes of ITO (Indium Tin Oxide) were further formed on the R pixel, G pixel, B pixel, and black matrix by sputtering. Next, according to Example 1 of Japanese Patent Laid-Open No. 2006-64921, a spacer was formed in a portion corresponding to the upper part of the black matrix on the ITO film formed as described above.
上記で得られたスぺーサ付カラーフィルタ基板に、ポリイミドを塗布し、ラビング処理 し、配向膜を形成した。  Polyimide was applied to the color filter substrate with spacers obtained above, and rubbed to form an alignment film.
更に、前記より得られたカラーフィルタ基板に対して、駆動側基板及び液晶材料を 組合せることによって液晶表示素子を作製した。即ち、駆動側基板として、 TFTとくし 型の画素電極 (導電層）とが配列形成された IPS用 TFT基板を準備し、該 TFT基板 の画素電極等が設けられた側の表面と、前記より得た、カラーフィルタ基板の着色画 素層が形成された側の表面とが対向するように配置し、前記で形成したスぺーサによ る間隙を有して固定した。この間隙に液晶材料を封入し、画像表示を担う液晶層を設 けた。このようにして得た液晶セルの両面に、（株)サンリツ社製の偏光板 HLC2— 2 518を貼り付けた。次いで、冷陰極管のバックライトを構成し、前記偏光板が設けられ た液晶セルの背面となる側に配置し、液晶表示装置とした。 これらの表示装置を用いて表示性能の評価を行ったところ、 PVAモードのときよりも 程度は小さくなるものの、比較例の液晶表示装置 3に対して、本発明の液晶表示装 置 1〜2は優れた表示性能を発揮した。 Further, a liquid crystal display element was produced by combining a drive side substrate and a liquid crystal material with the color filter substrate obtained above. That is, an IPS TFT substrate in which TFTs and comb-shaped pixel electrodes (conductive layers) are arrayed is prepared as a drive-side substrate, and the surface of the TFT substrate on which the pixel electrodes and the like are provided is obtained from the above. Further, the color filter substrate was disposed so as to face the surface on the side where the colored pixel layer was formed, and fixed with a gap by the spacer formed as described above. Liquid crystal material was sealed in this gap, and a liquid crystal layer responsible for image display was provided. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, a backlight of a cold cathode tube was constructed and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device. When the display performance was evaluated using these display devices, the liquid crystal display devices 1 and 2 of the present invention were compared with the liquid crystal display device 3 of the comparative example, although the degree was smaller than that in the PVA mode. Excellent display performance.
[0382] (実施例 14) [Example 14]
[1] CCDデバイスの作製  [1] Fabrication of CCD device
以下のような処方で顔料分散液（1)〜（3)を作製した。  Pigment dispersions (1) to (3) were prepared according to the following formulation.
[0383] 顔料分散液（1) · · ·緑色 G [0383] Pigment dispersion (1) · · · Green G
•C. I. P. G. 36 90質量部  • C. I. P. G. 36 90 parts by mass
•C. I. P. G. 7 25質量部  • C. I. P. G. 7 25 parts by mass
•C. I. P. Y. 139 40質量部  • C. I. P. Y. 139 40 parts by mass
•PLAAD ED151 20質量部  • PLAAD ED151 20 parts by mass
(楠本化成 (株)社製）  (Made by Enomoto Kasei Co., Ltd.)
•ベンジルメタクリレート Zメタクリル酸共重合体 25質量部  • Benzyl methacrylate Z methacrylic acid copolymer 25 parts by mass
(共重合モル比 70 : 30、質量平均分子量 3万）  (Copolymerization molar ratio 70:30, weight average molecular weight 30,000)
'プロピレングリコールモノメチルエーテルアセテート 625質量部  'Propylene glycol monomethyl ether acetate 625 parts by mass
[0384] 顔料分散液 (2) · · ·青色 B [0384] Pigment dispersion (2) · · · Blue B
•C. I. P. B. 15 : 6 125質量部  • C. I. P. B. 15: 6 125 parts by mass
，顔料分散組成物 G 90質量部  , Pigment dispersion composition G 90 parts by mass
•PLAAD ED211 (楠本化成 (株)製） 45質量部  • PLAAD ED211 (Enomoto Kasei Co., Ltd.) 45 parts by mass
•ベンジルメタクリレート Zメタクリル酸共重合体 25質量部  • Benzyl methacrylate Z methacrylic acid copolymer 25 parts by mass
(共重合モル比 70 : 30、質量平均分子量 3万）  (Copolymerization molar ratio 70:30, weight average molecular weight 30,000)
'プロピレングリコールモノメチルエーテルアセテート 730質量部  'Propylene glycol monomethyl ether acetate 730 parts by mass
[0385] 顔料分散液 (3) · · ·赤色 R [0385] Pigment dispersion (3) · · · Red R
•C. I. P. R. 254 80質量部  • C. I. P. R. 254 80 parts by mass
•C. I. P. Y. 139 20質量部  • C. I. P. Y. 139 20 parts by mass
•PLAAD ED472 45質量部  PLAAD ED472 45 parts by mass
•ベンジルメタクリレート Zメタクリル酸共重合体 25質量部  • Benzyl methacrylate Z methacrylic acid copolymer 25 parts by mass
(共重合モル比 70 : 30、質量平均分子量 3万） 'プロピレングリコールモノメチルエーテルアセテート 720質量部 (Copolymerization molar ratio 70:30, weight average molecular weight 30,000) 'Propylene glycol monomethyl ether acetate 720 parts by mass
[0386] (着色榭脂組成物の調製） [0386] (Preparation of colored rosin composition)
上記から得られた各色の顔料分散液の各々 200質量部当たりにつき、下記組成物を それぞれ攪拌機にて均一に混合し、各色用のカラーフィルター用着色榭脂組成物を 調製した。  The following composition was uniformly mixed with a stirrer for each 200 parts by mass of the pigment dispersion of each color obtained from the above to prepare a colored resin composition for a color filter for each color.
<組成>  <Composition>
•ベンジルアタリレート Zメタクリル酸共重合体 35質量部 • Benzyl acrylate / Z methacrylic acid copolymer 35 parts by mass
(共重合モル比 = 70730、質量平均分子量 3万） (Copolymerization molar ratio = 70730, weight average molecular weight 30,000)
.ジペンタエリスリトールペンタアタリレート 38質量部 'プロピレングリコーノレモノメチノレエーテノレアセテート 120質量部 .ェチノレ 3 エトキシプロピオネート 40質量部 'ハロメチルトリアジン系開始剤 4質量部  Dipentaerythritol pentaatalylate 38 parts by mass 'Propylene glycolanol monomethinoleateolate acetate 120 parts by mass Ethinore 3 Ethoxypropionate 40 parts by mass' Halomethyltriazine initiator 4 parts by mass
(光重合開始剤 製品名 TAZ107 みどり化学 (株)製）  (Photopolymerization initiator, product name: TAZ107 Midori Chemical Co., Ltd.)
[0387] (カラーフィルタおよび CCDデバイスの作製） [0387] (Production of color filters and CCD devices)
下記組成物を攪拌機で混合し、平坦化膜用レジスト液を調製した  The following composition was mixed with a stirrer to prepare a resist solution for a planarization film.
し鶴  Shizuru
•ベンジルアタリレート Zメタクリル酸共重合体 165質量部  • 165 parts by weight of benzyl acrylate / methacrylic acid copolymer
(共重合モル比 = 70730、質量平均分子量 3万）  (Copolymerization molar ratio = 70730, weight average molecular weight 30,000)
.ジペンタエリスリトールペンタアタリレート 65質量部  Dipentaerythritol pentaatalylate 65 parts by mass
'プロピレングリコーノレモノメチノレエーテノレアセテート 138質量部  '' 138 parts by mass of propylene glycol monomethino ethenore acetate
.ェチノレ 3 エトキシプロピオネート 123質量部  .Ethinole 3 123 parts by mass of ethoxypropionate
'ハロメチルトリアジン系開始剤 t部  'Halomethyltriazine initiator t
(光重合開始剤 製品名 TAZ107 みどり化学 (株)社製）  (Photopolymerization initiator, product name: TAZ107 Midori Chemical Co., Ltd.)
[0388] 得られた平坦ィ匕用レジスト液を、フォトダイオードを形成した 6インチシリコンウェハ 上にスピンコートで均一に塗布した。尚、スピンコートは、塗布後に塗布膜の表面温 度を 100°C X 120秒の条件でホットプレートを用いて加熱処理した際に膜厚が約 1. 5 μ mになるように塗布回転数を調節した。 [0388] The obtained flat resist solution was uniformly applied by spin coating onto a 6-inch silicon wafer on which photodiodes were formed. In spin coating, the coating rotation speed is adjusted so that the film thickness is about 1.5 μm when the surface temperature of the coating film is heated using a hot plate under conditions of 100 ° CX 120 seconds after coating. Adjusted.
その後 220°Cで 1時間オーブン中に置いて、塗布膜を硬化させ、シリコ： に形成されたフォトダイオード表面を一様に覆うように平坦ィ匕膜を形成した。 Then put it in an oven at 220 ° C for 1 hour to cure the coating film, A flat film was formed so as to uniformly cover the surface of the photodiode formed.
[0389] 次 、で、各色にっ 、て G、 R、 Bの順に、平坦ィ匕膜上に上述のカラーフィルタ用着 色榭脂組成物を、上記平坦化膜用レジスト液調整処方に対し 100質量部を塗布、乾 燥 (プリベータ）、パターン露光、アルカリ現像、リンス、硬化乾燥 (ポストベータ）を行 つて着色榭脂被膜を形成し、フォトダイオード付シリコンウェハ上にカラーフィルタを 作製した。  [0389] Next, in the order of G, R, and B for each color, the above-described colored resin composition for a color filter is applied to the flattened film on the flattened film resist formulation. 100 parts by mass were applied, dried (pre-beta), pattern exposure, alkali development, rinsing, and curing-drying (post-beta) to form a colored resin film, and a color filter was produced on a silicon wafer with a photodiode.
[0390] 尚、パターン露光は 2 mマスクパターンを介して、 i線ステッパー（商品名： FPA— 300015 +、キャノン (株）社製）を用いて 500mjZcm2で行った。 [0390] Pattern exposure was performed at 500 mjZcm 2 using an i-line stepper (trade name: FPA-300015 +, manufactured by Canon Inc.) through a 2 m mask pattern.
また、アルカリ現像には、有機アルカリ性現像液 (商品名： CD— 2000、富士フィル ムエレクト口-クスマテリアルズ (株)社製）の 40質量0 /0水溶液を用いて、室温にて 60 秒間パドル現像を行った後、 20秒スピンシャワーにて純水でリンスを行い、更に純水 で水洗を行った。その後、水滴を高温のエアーで飛ばし、基板を自然乾燥させてパ ターンを得た後、ホットプレート上で表面温度 200°C · 5分間の条件でポストべーク処 理を施した。以上のようにして本発明の CCDデバイスを作製した。 Further, the alkali developer, an organic alkaline developer: - using a 40 mass 0/0 aqueous solution (trade name CD- 2000, Fuji fill Muerekuto port box Materials Co., Ltd.), 60 seconds paddle at room temperature After the development, rinsing with pure water was performed in a spin shower for 20 seconds, followed by washing with pure water. After that, water droplets were blown with high-temperature air, the substrate was naturally dried to obtain a pattern, and then post-baked on a hot plate at a surface temperature of 200 ° C for 5 minutes. The CCD device of the present invention was manufactured as described above.
[0391] 上記 CCDデバイスに対して、顔料分散液（2)につ 、て、顔料分散組成物 Gを顔料 分散組成物 H〜I〖こ代えた以外同様にして、 CCDデバイスを作製した。  [0391] A CCD device was produced in the same manner as the above-mentioned CCD device, except that the pigment dispersion composition G was replaced with the pigment dispersion composition H to I for the pigment dispersion liquid (2).
[0392] 得られた各 CCDデバイスをデジタルカメラに搭載し、同一光源下で Kodak社製グ レースケール付きカラ一チャートを撮影した画像をモニター上で観察した。その結果 、本発明の製造方法で得た顔料ナノ粒子を用いて作製した CCDデバイスは、なめら カゝで均一性の高い再現画像が得られ、優れた撮像特性を発揮した。一方、比較例の 顔料分散組成物を用いたものは、ややざらつき感があり色ムラがみられた。  [0392] Each CCD device obtained was mounted on a digital camera, and an image of a color chart with a gray scale made by Kodak was observed on the monitor under the same light source. As a result, the CCD device produced using the pigment nanoparticles obtained by the production method of the present invention produced a smooth and highly uniform reproduced image, and exhibited excellent imaging characteristics. On the other hand, those using the pigment dispersion composition of the comparative example had a slightly rough feeling and color unevenness.
産業上の利用の可能性  Industrial applicability
[0393] 本発明の有機ナノ粒子分散組成物の製造方法は、有機粒子作製時、貧溶媒に対 する良溶媒の量を増やした際や、製造スケールを上げた際にも、粒子サイズの増加 、単分散性の悪ィ匕を実質的に生じることなく濃縮脱塩することができ、また濃縮により 凝集させた有機粒子を容易に再分散することができ、高効率な有機粒子の作製が可 能である。 [0393] The method for producing the organic nanoparticle dispersion composition of the present invention increases the particle size even when the amount of good solvent relative to the poor solvent is increased or the production scale is increased during the preparation of organic particles. Therefore, it is possible to concentrate and desalinate without substantially causing monodispersity, and it is possible to easily re-disperse the organic particles aggregated by concentration, and to produce highly efficient organic particles. Noh.
本発明の有機ナノ粒子分散組成物の製造方法で製造された濃縮有機粒子ペース トおよびそこカゝら得られる有機粒子は、好適なインクジェットインクもしくはその原料微 粒子、またはカラーフィルター塗布液もしくはその原料微粒子として好適に利用可能 である。 Concentrated organic particle pace produced by the method for producing an organic nanoparticle dispersion composition of the present invention The organic particles obtained from them and the like can be suitably used as a suitable inkjet ink or its raw material fine particles, or a color filter coating liquid or its raw material fine particles.
本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明 を説明のどの細部においても限定しょうとするものではなぐ添付の請求の範囲に示 した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。  While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.

Claims

請求の範囲 The scope of the claims
[1] 良溶媒に溶解した有機材料の溶液と、該溶媒と相溶する前記有機材料の貧溶媒と を混合し、該有機材料をナノサイズの有機粒子として生成させ、これを濃縮するにあ たり、前記有機粒子を含む分散液を限外ろ過によって濃縮することを特徴とする有機 ナノ粒子分散組成物の製造方法。  [1] A solution of an organic material dissolved in a good solvent and a poor solvent of the organic material compatible with the solvent are mixed to produce the organic material as nano-sized organic particles, which are concentrated. Or a method of producing an organic nanoparticle dispersion composition, wherein the dispersion containing the organic particles is concentrated by ultrafiltration.
[2] 前記有機材料溶液が、有機顔料を超臨界流体もしくは亜臨界流体に溶解した顔料 含有流体であることを特徴とする、請求項 1に記載の有機ナノ粒子分散組成物の製 造方法。  [2] The method for producing an organic nanoparticle dispersion composition according to [1], wherein the organic material solution is a pigment-containing fluid in which an organic pigment is dissolved in a supercritical fluid or a subcritical fluid.
[3] 酸性基を持つ高分子化合物を含有する事を特徴とする請求項 1又は 2に記載の有 機ナノ粒子分散組成物の製造方法。  [3] The method for producing an organic nanoparticle dispersion composition according to [1] or [2], comprising a polymer compound having an acidic group.
[4] 酸性基を持つ高分子化合物の存在下、前記有機材料液と貧溶媒の混合を行うこと を特徴とする請求項 1〜3のいずれかに記載の有機ナノ粒子分散組成物の製造方法 [4] The method for producing an organic nanoparticle dispersion composition according to any one of claims 1 to 3, wherein the organic material liquid and a poor solvent are mixed in the presence of a polymer compound having an acidic group.
[5] 前記有機粒子の数平均粒径が 1 m以下であることを特徴とする請求項 1〜4のい ずれ力 1項に記載の有機ナノ粒子分散組成物の製造方法。 [5] The method for producing an organic nanoparticle dispersion composition according to any one of [1] to [4], wherein the number average particle diameter of the organic particles is 1 m or less.
[6] 前記限外ろ過の後さらに凍結乾燥を行うことを特徴とする請求項 1〜5のいずれか 1 項に記載の有機ナノ粒子分散組成物の製造方法。 [6] The method for producing an organic nanoparticle dispersion composition according to any one of [1] to [5], wherein freeze drying is further performed after the ultrafiltration.
[7] 前記有機材料が、有機顔料であることを特徴とする請求項 1〜6のいずれか 1項に 記載の有機ナノ粒子分散組成物の製造方法。 [7] The method for producing an organic nanoparticle dispersion composition according to any one of [1] to [6], wherein the organic material is an organic pigment.
[8] 酸性基を有する高分子化合物を含む有機溶媒中で再分散化することを特徴とする 請求項 1〜7のいずれか 1項に記載の有機ナノ粒子分散組成物の製造方法。 [8] The method for producing an organic nanoparticle dispersion composition according to any one of claims 1 to 7, wherein the organic nanoparticle dispersion composition is redispersed in an organic solvent containing a polymer compound having an acidic group.
[9] 一般式（1)で表される高分子化合物を含有することを特徴とする請求項 1〜8のい ずれ力に記載の有機ナノ粒子分散組成物の製造方法。 [9] The method for producing an organic nanoparticle dispersion composition according to any one of [1] to [8], comprising a polymer compound represented by the general formula (1).
[化 1]  [Chemical 1]
( A-R^— R1 P1 ) —般式 （1 ) (AR ^ — R 1 P 1 ) — General formula (1)
〔式中、 R1は、（m+n)価の連結基を表し、 R2は単結合あるいは 2価の連結基を表す 。 A1は、酸性基、塩基性窒素原子を有する基、ウレァ基、ウレタン基、配位性酸素原 子を有する基、炭素数 4以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシ ァネート基、および水酸基からなる群より選ばれる基を有する 1価の有機基、または 置換基を有してもよ!ヽ有機色素構造もしくは複素環を含有する 1価の有機基を表す。 ただし、 n個の A1は互いに同一であっても、異なっていてもよい。 mは 1〜8の数を表 し、 nは 2〜9の数を表し、 m+nは 3〜： LOを満たす。 P1は高分子骨格を表す。〕 [Wherein R 1 represents a (m + n) -valent linking group, and R 2 represents a single bond or a divalent linking group. . A 1 is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, or an isocyanate group. And a monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group which may have a substituent, or an organic dye structure or a heterocyclic ring. However, n A 1 s may be the same or different. m represents a number from 1 to 8, n represents a number from 2 to 9, and m + n satisfies 3 to: LO. P 1 represents a polymer skeleton. ]
[10] 前記一般式（1)で表される高分子化合物を有機ナノ粒子の形成時、抽出または濃 縮時、濃縮後の凝集有機粒子の分散時、これらの工程が終了したのちのいずれかの 工程において含有させることを特徴とする請求項 9に記載の有機ナノ粒子分散組成 物の製造方法。 [10] When the polymer compound represented by the general formula (1) is formed during the formation of organic nanoparticles, at the time of extraction or concentration, or when the aggregated organic particles are dispersed after concentration, any one of these steps is completed. 10. The method for producing an organic nanoparticle dispersion composition according to claim 9, wherein the organic nanoparticle dispersion composition is contained in the step.
[11] 請求項 1〜10のいずれか 1項に記載の製造方法で製造された有機ナノ粒子分散 組成物よりカラーフィルタ用インクジェットインクを調製することを特徴とするカラーフィ ルタ用インクジェットインクの製造方法。  [11] A method for producing an inkjet ink for a color filter, comprising preparing an inkjet ink for a color filter from an organic nanoparticle dispersion composition produced by the production method according to any one of claims 1 to 10. .
[12] 請求項 1〜10のいずれか 1項に記載の製造方法で製造された有機ナノ粒子分散 組成物中の有機粒子と、バインダーと、多官能モノマーと、光重合開始剤または光重 合開始剤系とを少なくとも含むことを特徴とする着色感光性榭脂組成物。  [12] Organic nanoparticle dispersion produced by the production method according to any one of claims 1 to 10, organic particles in the composition, binder, polyfunctional monomer, photopolymerization initiator or photopolymerization. A colored photosensitive resin composition comprising at least an initiator system.
[13] 仮支持体上に、少なくとも、請求項 12に記載の着色感光性榭脂組成物を含む感光 性榭脂層を設けたことを特徴とする感光性転写材料。  [13] A photosensitive transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 12 is provided on a temporary support.
[14] 請求項 12記載の着色感光性榭脂組成物または請求項 13記載の感光性転写材料 を用いて作製したことを特徴とするカラーフィルタ。  [14] A color filter produced using the colored photosensitive resin composition according to claim 12 or the photosensitive transfer material according to claim 13.
[15] 基板上に遮光性を有する隔壁を形成し、該隔壁により区切られた複数の凹部を設 け、インクジェット方式により R (赤)インク、 G (緑)インク、および B (青)インクのそれぞ れを前記凹部に吹き付けて堆積させ、各凹部に各色の着色榭脂層を形成するカラ 一フィルタの製造方法であって、前記 Rインク、 Gインク、および Bインクの少なくとも 1 種に請求項 11に記載の製造方法で得られるインクジェットインクを用いることを特徴 とするカラーフィルタ。  [15] A partition wall having a light-shielding property is formed on the substrate, and a plurality of recesses separated by the partition wall are provided, and R (red) ink, G (green) ink, and B (blue) ink are formed by an inkjet method. A color filter manufacturing method in which each of the concave portions is sprayed and deposited, and a colored resin layer of each color is formed in each concave portion, and charged to at least one of the R ink, G ink, and B ink. Item 14. A color filter using an ink-jet ink obtained by the production method according to Item 11.
[16] 請求項 14または請求項 15に記載のカラーフィルタを備えたことを特徴とする液晶 表示装置。 前記液晶表示装置が、 VA方式であることを特徴とする請求項 16に記載の液晶表 請求項 14または請求項 15に記載のカラーフィルタを備えたことを特徴とする CCD [16] A liquid crystal display device comprising the color filter according to claim 14 or 15. The liquid crystal display according to claim 16, wherein the liquid crystal display device is a VA method. The CCD comprising the color filter according to claim 14 or claim 15.
PCT/JP2006/314700 2005-07-25 2006-07-25 Process for production of composition having organic particles dispersed therein WO2007013475A1 (en)

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CN102146229A (en) * 2011-01-11 2011-08-10 上海驰怀新材料科技有限公司 UV (Ultra Voilet) light curing transfer printing coating sizing agent and transfer printing coating
CN104557612A (en) * 2013-10-18 2015-04-29 中国科学院苏州纳米技术与纳米仿生研究所 Preparation method for organic micrometer or nanometer material
JP6249785B2 (en) 2014-01-16 2017-12-20 理想科学工業株式会社 Colored resin particle dispersion and inkjet ink
JP6148626B2 (en) * 2014-01-16 2017-06-14 理想科学工業株式会社 Colored resin particle dispersion and inkjet ink
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JP6185849B2 (en) 2014-01-16 2017-08-23 理想科学工業株式会社 Colored resin particle dispersion and inkjet ink

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002194244A (en) * 2000-12-25 2002-07-10 Fuji Photo Film Co Ltd Pigment dispersion composition, coloring photosensitive composition obtained by using the same and color filter
JP2003286427A (en) * 2002-03-28 2003-10-10 Fuji Photo Film Co Ltd Organic pigment ink and method for manufacturing aqueous dispersion of organic pigment
JP2004043776A (en) * 2002-05-21 2004-02-12 Canon Inc Particle containing water-insoluble color material, its dispersion, method of manufacturing them and ink containing the particle or dispersion
JP2004091560A (en) * 2002-08-30 2004-03-25 Japan Science & Technology Corp New method for producing pigment nanoparticle
JP2004315656A (en) * 2003-04-16 2004-11-11 Konica Minolta Holdings Inc Method for producing colored microparticle dispersion and inkjet recording ink

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4718770B2 (en) * 2003-10-02 2011-07-06 セイコーエプソン株式会社 Ink composition for inkjet recording

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002194244A (en) * 2000-12-25 2002-07-10 Fuji Photo Film Co Ltd Pigment dispersion composition, coloring photosensitive composition obtained by using the same and color filter
JP2003286427A (en) * 2002-03-28 2003-10-10 Fuji Photo Film Co Ltd Organic pigment ink and method for manufacturing aqueous dispersion of organic pigment
JP2004043776A (en) * 2002-05-21 2004-02-12 Canon Inc Particle containing water-insoluble color material, its dispersion, method of manufacturing them and ink containing the particle or dispersion
JP2004091560A (en) * 2002-08-30 2004-03-25 Japan Science & Technology Corp New method for producing pigment nanoparticle
JP2004315656A (en) * 2003-04-16 2004-11-11 Konica Minolta Holdings Inc Method for producing colored microparticle dispersion and inkjet recording ink

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US8343709B2 (en) 2007-09-06 2013-01-01 Fujifilm Corporation Processed pigment, pigment-dispersed composition, colored photosensitive composition, color filter, liquid crystal display element, and solid image pickup element
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