Classifications

• • 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
• • 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
• • 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
  • C09B25/00—Quinophthalones
• • 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
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
  • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
  • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
  • C09B29/3665—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
• • 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
  • 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
  • C09B67/0085—Non common dispersing agents
  • C09B67/009—Non common dispersing agents polymeric dispersing agent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/206—Filters comprising particles embedded in a solid matrix
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133509—Filters, e.g. light shielding masks
  • G02F1/133514—Colour filters

Definitions

• Color material dispersion colored resin composition, color filter, and liquid crystal display
• the present invention relates to a color material dispersion, a colored resin composition (hereinafter sometimes referred to as “resist”), a color filter, and a liquid crystal display device.
• a pigment dispersion that has excellent depolarization characteristics, can form colored pixels with high contrast, and has excellent storage stability, a colored resin composition containing the pigment dispersion, and the colored resin composition And a liquid crystal display device using the color filter.
• a pigment dispersion method As a method for producing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known. Among them, the pigment dispersion method having excellent properties on average in terms of spectral characteristics, durability, pattern shape, accuracy, etc. is most widely adopted.
• the pigment dispersion method is performed, for example, by the following procedure. That is, on a transparent support such as a glass substrate, a black matrix is formed by a light-shielding film such as carbon black, chromium, and chromium oxide, and then, for example, a resist in which a red pigment is dispersed is coated on the entire surface by spin coating or the like. Then, it is exposed through a mask and developed after exposure to form red pixels. By applying, exposing, and developing blue and green resists in the same procedure, blue and green pixels are formed, and three color pixels are formed.
• the black matrix between the pixels is concave, in many cases the surface where the pixels are formed is covered with a transparent resin such as an epoxy resin or an talic resin for surface smoothness.
• a protective film is formed, but such a protective film may not be provided.
• a transparent conductive film such as an ITO (Indium Tin Oxide) film is formed on the protective film by sputtering or vacuum deposition.
• the depolarization characteristics for color filters that is, the power that is in the situation where the demand for improvement in contrast is increasing more than ever. Such required characteristics are fully satisfied! is the current situation.
• an object of the present invention is to provide a colorant dispersion excellent in depolarization characteristics, capable of forming colored pixels with high contrast, and excellent in storage stability, and the colorant dispersion. It is in providing the colored resin composition containing, the color filter using this colored resin composition, and the liquid crystal display device using this color filter.
• the gist of the present invention is as follows.
• a colored rosin composition comprising the colorant dispersion described in 1 above.
• the color material dispersion of the present invention it is possible to form a colored pixel having excellent depolarization characteristics and high contrast, and as a result, a high-quality color filter and a liquid crystal display device are manufactured. I can do it.
• the colorant dispersion and the colored rosin composition of the present invention are high in quality because of excellent storage stability.
• the colorant dispersion of the present invention is (
• A) a coloring material, (B) a dispersant as an essential component, and if necessary, additives other than the above components may be blended.
• (meth) acryl means “acryl and Z or methacryl”, “attalate and Z or methacrylate” and the like, for example, “(meth) Acrylic acid
• Total solids refers to all components of the colorant dispersion of the present invention other than the solvent components described below.
• the color material means a color material for the color material dispersion of the present invention.
• the colorant is characterized in that it contains a pigment having a crystallite size of 140 A or less in terms of a half-value width force of X-ray diffraction calculated from the Sierra equation.
• the crystallite size of the pigment contained in the colorant is characterized in that it includes a pigment having a value of 140 A or less in terms of the half-width power of X-ray diffraction calculated from the Sierra equation. .
• the crystallite size is preferably 130A or less. It is usually 50A or more.
• the value at which the full width at half maximum of X-ray diffraction is calculated from the Sierra equation is the value calculated from the following equation based on the measured value by X-ray diffraction.
• the following shows an example of the measurement method and analysis method of crystallite size X-ray diffraction of the present invention.
• Measurement is usually performed by using an X-ray diffractometer.
• the X-ray diffractometer is a concentrated X-ray powder X-ray diffractometer using CuKa (CuKa + CuKa) rays as an X-ray source.
• the measurement conditions are set to, for example, scanning range (2 ⁇ ) 3 to 70 °, scan step width 0.05 °, scanning speed 3.0 ° Zmin, diverging slit, scattering slit 1 °, and receiving slit 0.2 mm. You can.
• the half-value width ( ⁇ 0) is obtained by profile fitting of the measured value by the X-ray diffractometer.
• X-ray diffraction pattern analysis software or the like is usually used.
• powder X-ray diffraction pattern analysis software JADE5.0 + manufactured by MDI can be mentioned.
• the profile fitting can be set as follows, for example. That is, using Peason-VII function considering CuKa contribution (calculated
• All the refinement variables are derived from CuKa), and the knock ground is fixed at the ideal position.
• the refinement variables are diffraction angle (2 ⁇ ), peak height, half width (
• the asymmetric variables to be refined are constrained to be the same.
• the crystallite size (D) is calculated using the Schiller equation shown below.
• ⁇ Half width of diffraction line (radian)
• ⁇ Bragg angle of diffraction line (radian)
• the half-value width (j8) derived from the sample used for the calculation is the half-value width curve calculated in advance from each diffraction peak half-value width (derived from CuKa) of standard Si (NIST Si 640b). Using the (regression quadratic curve), calculate the device-derived half-value width (j8 i) for the relevant angle, and use the following half-value correction formula.
• the X-ray diffraction peak derived from CuKa line used for the calculation of crystallite size is 8.5 ° and 9.2 °, for example, CI pigment yellow 150 of the azo pigment. Is the crystallite size of the pigment.
• C.I. Pigment Yellow 138 a quinophthalone-based pigment, use 12.3 ° and 12.9 °.
• C.I. Pigment Yellow 139 an isoindoline pigment, use 9.1 ° and 12.3 °.
• CI pigment yellow 180 a benzimidazolone pigment, use 6.4 °, 6.7 °, and 9.5 °.
• C. I. pigment violet 23 a dioxazine pigment, 5.7 ° and 10.2. Use to calculate.
• the coloring material (A) in the present invention may be composed only of the pigment described in [1-1-1], but other coloring materials can be used in combination with the pigment.
• other coloring materials dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance, and the like.
• pigments used in the [1-11-1] chapter and this chapter pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, black pigment are used. be able to.
• the structure includes azo, phthalocyanine, quinacridone, benzimidazolone, isoindoline, quinophthalone, isoindolinone, dioxa
• Various inorganic pigments can be used in addition to organic pigments such as gin, indanthrene, and perylene. Specific examples of usable pigments are shown by pigment numbers below.
• the following “CI” means the color index (CI).
• red pigments examples include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37 , 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53 : 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81 : 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144 , 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 19
• Blue pigments include C. I. Pigment Benore 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15:
• C.I. pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. pigment blue 15: 6 can be mentioned.
• Green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 1 8, 19, 26, 36, 45, 48, 50, 51, 54, You can raise 55 and have the power S. Among these, CI Pigment Green 7 and 36 are preferable.
• C.I. pigment yellow 83, 117, 129, 138, 139, 150, 154, 15 is preferable.
• CI pigment range 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 22, 24, 34, 36, 38, 39, 43, 46, 48 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 Among these, C.I. Pigment Orange 38 and 71 are preferable.
• Purple pigments include CI pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
• C.I. pigment violet 19, 23 is preferable, and C.I. pigment violet 23 is more preferable.
• the color material dispersion of the present invention is a color material dispersion for a black matrix of a color filter
• a black color material can be used as the color material.
• the black color material may be a single black color material or a mixture of red, green, blue and the like. These coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
• Color materials that can be mixed to prepare a black color material include Victoria Pure Blue (42595), Auramin 0 (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 (50240), Ellioglaucin X (42080), No.
• pigments that can be used in combination are represented by CI numbers.
• black color material examples include carbon black, acetylene black, lamp black, bone black, graphite, iron black, iron black, cyanine black, and titanium black.
• carbon black and titanium black are also preferable in terms of light blocking ratio and image characteristics.
• Examples of carbon black include the following carbon black. Made by Mitsubishi Gakaku: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3 150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OILllB, OIL30B, OIL31
• titanium black examples include the following.
• a method for producing titanium black a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), and obtained by high-temperature hydrolysis of titanium tetrachloride.
• a method of reducing the obtained ultrafine titanium dioxide in a reducing atmosphere containing hydrogen Japanese Patent Laid-Open No. 57-205322
• a method of reducing titanium dioxide dihydrate or titanium dioxide hydroxide at high temperature in the presence of ammonia JP-A-60-65069, JP-A-61-201610)
• a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia. 61—201610) but is not limited to these.
• titanium black examples include Titanium Black 10S, 12S, 13R, 13M, 13M-C, etc. manufactured by Mitsubishi Materials.
• aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.
• barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can be used as the pigment.
• a plurality of the above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
• the other colorants in this chapter are preferably used dispersed in an average particle size of 1 ⁇ m or less, preferably 0.5 m or less, more preferably 0.25 m or less.
• dyes that can be used as coloring materials include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbo dyes, and methine dyes. .
• Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Benolet 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12 , CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Day Sparse Orange 5, CI Disperse Thread 58, CI Dayspur Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7 and the like.
• anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56 , CI Disperse Blue 60 etc.
• phthalocyanine dyes for example, CI pad blue 5 isotropic quinone imine dyes, for example, CI basic blue 3, CI basic blue 9, etc.
• quinoline dyes for example, CI solvent yellow 33, CI acid Yellow 3, CI Disperse Yellow 64 Isotropic Nitro dyes include, for example, CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42 and the like.
• the ratio of (A) the color material to the total solid content in the color material dispersion of the present invention is usually 10 to 90. % By weight, preferably 30-90% by weight. If the content ratio of the color material is too small, the coloring power is lowered and the film thickness becomes too thick with respect to the color density, which adversely affects the gap control in the liquid crystal cell. On the other hand, if the content ratio of the coloring material is too large, the dispersion stability deteriorates and there is a risk of problems such as re-aggregation and thickening.
• the colorant dispersion of the present invention must contain (A) a graft copolymer containing a nitrogen atom and Z or an acrylic block copolymer as (B) a dispersant. Further, it is preferable that the polymer further comprises (b) a polymer obtained by polymerizing a monomer component essentially comprising a specific compound, which will be described later.
• the performance of a dispersant is its adsorption behavior on the solid surface.
• the adsorption behavior is excellent in the order of random copolymerization, graft copolymer ⁇ block copolymer. ⁇ . (One row, Jones and Richards, Polymers at surfaces and Interfaces p281). The mechanism is unknown, but the following can be inferred.
• the monomers constituting the copolymer are highly likely to be stably arranged in the copolymer sterically and Z or electrically during the copolymerization. Become.
• the portion (molecule) in which the monomer is stably arranged is sterically and Z or electrically stable, and therefore it may be an obstacle when adsorbed on the pigment.
• a portion that prevents adsorption of the dispersant can be arranged at a position where the adsorption portion force between the pigment and the dispersant is also separated. .
• an optimum portion for adsorption can be arranged in the adsorption portion between the pigment and the dispersant, and a suitable portion can be arranged in a portion requiring solvent affinity.
• the dispersion of the colorant containing a small crystallite size 1 and pigments affects the good dispersibility of this molecular arrangement. It is assumed that
• a graft copolymer containing a nitrogen atom is preferable in that the pigment according to [1 1-1] used in the present invention can be dispersed very efficiently. The reason for this is not clear, but it has a structure that can actively displace the part (molecule) that hinders the adsorption of the pigment and the dispersant around the adsorption part to the pigment. It is guessed that it is.
• the graft copolymer containing a nitrogen atom those having a repeating unit containing a nitrogen atom in the main chain are preferred. Among them, it is preferable to have a repeating unit represented by the formula (I) or a repeating unit represented by Z and the formula ( ⁇ ).
• R represents an alkylene group having 1 to 5 carbon atoms
• A represents a hydrogen atom or the following formulas (III) to (
• V represents one of the following.
• R is a linear or branched carbon such as methylene, ethylene or propylene.
• A represents a hydrogen atom or any one of the following formulas (III) to (V), and is preferably formula (III).
• R and A have the same meanings as R and A in the formula (I).
• W represents a linear or branched alkylene group having 2 to 10 carbon atoms
• alkylene groups having 4 to 7 carbon atoms such as butylene, pentylene and hexylene are preferred.
• p represents an integer of 1 to 20, preferably an integer of 5 to 10.
• Y represents a divalent linking group, and in particular, the number of carbon atoms such as ethylene and propylene.
• An alkylene group having 1 to 4 carbon atoms and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are preferable.
• W is linear or branched such as ethylene, propylene, butylene
• Y is a hydrogen atom or —CO—R (R is ethyl, pro
• q represents an integer of 1 to 20, preferably an integer of 5 to 10.
• W is carbon having 1 to 5 carbon atoms and an alkyl group or hydroxyl group having 1 to 5 carbon atoms.
• an alkyl group having 10 to 20 carbon atoms such as stearyl and a hydroxynolequinole group having 10 to 20 carbon atoms having 1 to 2 hydroxyl groups such as monohydroxystearyl are preferable. .
• the content of the repeating unit represented by the formula (I) or (II) in the graft copolymer of the present invention is usually higher, preferably 50 mol% or more, and preferably 70 mol% or more. There is no particular limitation on the content ratio of the repeating unit represented by the formula (I) and the repeating unit represented by the formula (II). It is preferable to have more repeating units.
• the total number of repeating units represented by formula (I) or formula (II) is usually 1 to 100, preferably 10 to 70, more preferably 20 to 50. Examples of other repeating units that may contain a repeating unit other than those represented by formula (I) and formula (II) include an alkylene group and an alkyleneoxy group.
• the graft copolymer of the present invention is Are preferably —NH and —R—NH (R is as defined above for R).
• the main chain may be a straight chain or may be branched! /.
• the amine value of the graft copolymer of the present invention is usually 5 to: LOOmgKOHZg, preferably 10 to 70 mgKOHZg, and more preferably 15 to 40 mgKOHZg or less. If the amine value is too low, the dispersion stability may decrease and the viscosity may become unstable. Conversely, if the amine value is too high, the residue may increase, and the electrical characteristics after the liquid crystal panel is formed may deteriorate.
• the weight average molecular weight of the above-mentioned dispersant measured by GPC is particularly preferably from 3,000 to 100,000 particles, from 5,000 to 50,000 forces S. If the weight average molecular weight is less than 3000, aggregation of the coloring material cannot be prevented and the viscosity may be increased or gelled. If the weight average molecular weight exceeds 100000, the viscosity of the color material itself becomes high. Not preferred because of lack of solubility.
• a method for synthesizing the dispersant a known method can be employed. For example, a method described in Japanese Patent Publication No. 63-30057 can be used.
• graft copolymer having the same structure as described above can be applied.
• the acrylic block copolymer is preferable in that the pigment described in [1 1-1] used in the present invention can be extremely efficiently dispersed. The reason for this is not clear, but it is presumed that due to the controlled molecular arrangement, there are few structures that hinder the dispersant from adsorbing to the pigment.
• Acrylic block copolymers include A block with quaternary ammonium base and Z or amino group in the side chain, and B block without quaternary ammonium base and Z or amino group.
• An A—B block copolymer and a Z or B—A—B block copolymer are preferred.
• the A block constituting the block copolymer of the acrylic block copolymer has a quaternary ammonium base and a Z or amino group.
• the quaternary ammonium base is preferably N + RRR ⁇ ⁇ — (where R 1, R 2 and R are Each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Or two or more of R 1, R and R are bonded together to form a cyclic structure
• This quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.
• Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring obtained by condensing two of these.
• the nitrogen-containing heterocycle is more preferably a saturated ring that is preferably non-aromatic. Specific examples include the following.
• R represents any group of R 1 to R 5]
• These cyclic structures may further have a substituent.
• R to R in N + R R R may have a substituent la 2a 3a la 3a
• the A block is particularly preferably one containing a partial structure represented by the following general formula (VI).
• R 1, R 2 and R 3 are each independently a hydrogen atom or substituted la 2a 3a
• R is a hydrogen atom or a methyl group
• X represents a divalent linking group
• Y— represents a counterion
• hydrocarbon groups of R 1, R 2, and R 3 are each independently charcoal la 2a 3a
• a substituent having a primary alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms is preferable.
• Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, and a phenyl group.
• a methyl group, an ethyl group, a propyl group, and a benzyl group are preferable.
• examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, one CONH—R—, one COO—R— (where R and R are ,
• COO—R— is preferable.
• the amino group is preferably —NR R (wherein R and R each independently have a substituent, lb 2b lb 2b
• R and R are the same as R and R above, and R is alkylene having 1 or more carbon atoms.
• the group R 1 represents a hydrogen atom or a methyl group.
• R and R are preferably methyl groups.
• R is preferably methylene groups and ethylene groups.
• R is preferably a hydrogen atom.
• the specific quaternary ammonium base and the partial structure containing Z or an amino group as described above may be contained in one A block in two or more kinds.
• two or more kinds of quaternary ammonium bases and / or amino group-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization.
• Examples of the partial structure that may be contained in the partial structural force A block that does not contain the quaternary ammonium base and / or amino group include the (meth) acrylic acid ester monomer described later.
• a partial structure derived from one is mentioned.
• the quaternary ammonium base and the partial structure containing no Z or amino group, the content in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. Most preferably, the quaternary ammonia base and / or the amino group-free partial structure is not contained in the A block.
• examples of the B block constituting the block copolymer of the dispersant include styrene monomers such as styrene and a-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (meta) ) Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylate monomers such as hydroxyethyl (meth) acrylate, glycidyl acrylate, N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylates such as (meth) acrylic chloride Acrylate (Meth) acrylamide
• the B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (VII).
• R represents a hydrogen atom or a methyl group.
• R 1 has a substituent.
• Two or more types of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block.
• the B block may further contain a partial structure other than these. Partial structural strength derived from two or more types of monomers Does not contain quaternary ammonia salt groups.
• each partial structure is random or block copolymerized in the B block. It may be contained in any of the embodiments.
• a partial structure other than the partial structure derived from the (meth) acrylate monomer is used.
• the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably 0 to 99% by weight, more preferably 0 to 85% by weight.
• the acrylic dispersant used in the present invention has such a force as A block and B block.
• Such a block copolymer is prepared, for example, by the living polymerization method shown below.
• the living polymerization method includes a key-on living polymerization method, a cation living polymerization method, and a radical living polymerization method.
• the polymerization active species is eron, and for example, it is shown in the following scheme.
• the polymerization activity I4 species is a radical, and is represented by the following scheme, for example.
• the amount of secondary ammonia base is usually from 0.1 to: LOmmol. Outside this range, good heat resistance and dispersibility may not be combined! / ⁇ .
• Such a block copolymer usually contains an amino group produced in the production process. Its amine value is about 1 to: LOOmg-KOHZg. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralization titration of the basic amino group with an acid.
• the acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably less than lOOmg-KOHZg, which is generally lower.
• the amount is a polystyrene-converted weight average molecular weight (Mw) measured by GPC and is usually in the range of 1000 or more and 100,000 or less. If the molecular weight of the block copolymer is too small, the dispersion stability decreases, and if it is too large, the developability and resolution tend to decrease.
• the dispersant used in the color material dispersion of the present invention preferably further contains (b) an acrylic dispersion resin.
• the acrylic dispersion resin refers to a polymer obtained by polymerizing acrylic acid and Z or acrylic acid ester as monomer components.
• Preferred acrylic dispersion resins include, for example, a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate, and the following general formulas (1) and Z or (2) And a polymer obtained by polymerizing a monomer component essentially comprising a compound represented by
• R la and R 2a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
• R lb represents a hydrogen atom or an alkyl group which may have a substituent, or a divalent linking group or a direct bond
• X represents the following formula (3): Or a substituted adamantyl group which may be substituted.
• R 2b , R 3b , and R 4b represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, and an organic group
• L 2 represents a divalent linking group
• two or more of L 2 and L 3 are bonded to each other to form a ring.
• a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is preferably used because of its high affinity with the pigment.
• the ratio of the (meth) acrylic acid and benzyl (meth) acrylate in the monomer component when obtaining the acrylic dispersed resin (b) is not particularly limited, but (meth) acrylic acid is all monomer component 10-90% by weight, preferably 15 to 80 wt%, more preferably is good is 2 0-70 weight 0/0. Furthermore, benzyl (meth) Atari rate, the total monomer component 5-90 weight 0/0, preferably from 15 to 80 weight 0/0, more preferably may be from 20 to 70 wt%. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be rough during development, and if it is too small, development becomes impossible. Also, if the amount of benzyl (meth) acrylate is too much or too little, it cannot be dispersed.
• the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R la and R 2a is not particularly limited.
• Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tamyl, stearyl, lauryl, 2-ethylhexyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentagel, tricyclohexyl, isobornyl, adamantyl, 2-methyl-2-adamantyl, etc .; alkoxy such as 1-methoxyethyl, 1 ethoxyethyl, etc.
• R la and R 2a may be the same type of substituent or different substituents.
• ether dimer examples include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-probenoate, jetyl-2,2 ′-[oxybis (methylene)] bis-1-probenoate, Di (n-propyl) 2,2 '-[oxybis (methylene)] bis-2-probenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis 2 —Probenoate, di ( n —butyl) —2, 2 ′ [oxybis (methylene)] bis 2—propenoate, di (isobutyl) -2, 2 ′ [oxybis (methylene)] bis 2—probenoe , Di (t-butyl) -2,2 '[oxybis (methylene)] bis 2-probenoate, di (tamyl) 2, 2' — [oxybis (methylene)] bis 2-probenoate, di (Stearyl)
• dimethyl-2,2 '-[oxybis (methylene)] bis-2-probenoate dimethyl-2,2'-[oxybis (methylene)] bis-2-probenoate, dicyclohexyl- ure 2 , 2 ′ — [Oxybis (methylene)] bis-2-probenoate, dibenzyl-1,2,2 ′ — [oxybis (methylene)] bis-2-probenoate are preferred.
• These ether monomers may be used alone or in combination of two or more.
• the proportion of the ether dimer in the monomer component in obtaining the acrylic dispersed resin (b) is not particularly limited, but is 2 to 60% by weight, preferably 5 to 55% by weight in the total monomer component. %, More preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or the gel may easily gel. On the other hand, if the amount is too small, the transparency, heat resistance, etc. Coating Performance may be insufficient.
• R lb is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group.
• the organic groups represented by R 2b , R 3b , and R 4b are, for example, an alkyl group, a cycloalkyl group, an alkyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, And a carboxyl group, an acyloxy group, etc., preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkyl group having 2 to 18 carbon atoms, and a cycloalkenyl having 3 to 18 carbon atoms.
• an alkyl group having 1 to 15 carbon atoms an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom, and an acyloxy group having 1 to 15 carbon atoms, More preferably, they are a C1-C10 alkyl group and a C3-C15 cycloalkyl group.
• R 2b , R 3b , and R 4b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
• ⁇ L 2 is a divalent linking group
• L 3 is a direct bond, alkylene having 1 to 5 carbon atoms, a ring formed by bonding with R 3b or R 4b
• L 2 is alkylene having 1 to 5 carbon atoms.
• preferred examples of the general formula (3) include compounds represented by the following general formula (4).
• R 2b , R 3b , R 4b , ⁇ L 2 are synonymous with R 2b , R 3b , R 4b , L 1 , L 2 in formula (3), R 5b , R 6b represents a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group.
• examples of the organic group represented by R 5b and R 6b include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, and an acyloxy group.
• an alkyl group having 1 to 18 carbon atoms a cycloalkyl group having 3 to 18 carbon atoms, an alkyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, carbon
• R 5b and R 6b are a hydrogen atom, a hydroxyl group, and an alkynole group having 1 to 10 carbon atoms.
• alkyl group of R lb each organic group of R 2b to R 4b , the divalent linking group of 1 ⁇ to, and the adamantyl group of X may each independently have a substituent.
• Halogen atom hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, t butyl group, amyl group, tamyl group, n monohexyl Group, n-heptyl group, n-octyl group, t-octyl group, etc.
• a linear or branched alkyl group of 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a beryl group, a probe group,
• a linear or branched alkenyl group having 2 to 18 carbon atoms such as a xel group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentyl group or a cyclohexyl group; a methoxy group or an ethoxy group Group, n propoxy group, isopropoxy group, n butoxy group, s-butoxy group, t -butoxy group, amyloxy group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, t-octy
• Steal group saturated or unsaturated heterocycles such as 2-chenyl, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, morpholino, pyrrolidinyl, tetrahydrothiophene dioxide Groups, trialkylsilyl groups such as trimethylsilyl groups.
• R ′′ to R 28 are each a hydrogen atom, an alkyl group which may have a substituent, an alkyl group which may have a substituent, or an aryl which may have a substituent. It may have a group or a substituent, and may represent an aralkyl group.
• the positional relationship of the above substituents is not particularly limited.
• the seeds may be different.
• the ratio of the general formula (2) in the monomer component in obtaining the acrylic dispersion resin (b) according to the present invention is not particularly limited, but is 0.5 to It is 60% by weight, preferably 1 to 55% by weight, more preferably 5 to 50% by weight. Too much When used as a dispersant, the dispersion stability of the dispersion may be reduced. On the other hand, if the amount is too small, the soil stain aptitude may be reduced.
• the acrylic dispersed resin (b) preferably has an acid group.
• the resulting curable resin composition has a curable resin capable of undergoing a crosslinking reaction (hereinafter referred to as acid-epoxy curing) utilizing the fact that an ester bond is formed by the reaction of an acid group and an epoxy group.
• a composition or a composition in which an uncured part can be visualized with an alkali developer can be used.
• the acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a strong carboxylic acid anhydride group. These acid groups may be used alone or in combination of two or more.
• a monomer having an acid group and Z or a monomer capable of imparting an acid group after polymerization (hereinafter referred to as "single amount for introducing an acid group”) May be referred to as “body”.)
• body a monomer capable of imparting an acid group after polymerization
• a treatment for imparting an acid group as described later is required after the polymerization.
• Examples of the monomer having an acid group include, for example, a monomer having a strong ruboxyl group such as (meth) acrylic acid tataconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenol maleimide, maleic anhydride, and anhydride. Power that includes monomers having a carboxylic anhydride group such as itaconic acid Among these, (meth) acrylic acid is particularly preferred.
• Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, And monomers having an isocyanate group such as isocyanatoethyl (meth) acrylate.
• These monomers for introducing an acid group may be only one kind or two or more kinds.
• the content ratio is not particularly limited, 5-70 by weight 0/0, is good is preferably 10 to 60 wt%.
• the acrylic dispersed resin may have a radical polymerizable double bond.
• a radical polymerizable double bond for example, a monomer capable of imparting a radical polymerizable double bond after polymerization (hereinafter referred to as “introducing a radical polymerizable double bond”).
• introducing a radical polymerizable double bond After the polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later is performed.
• Examples of the monomer capable of imparting a radical polymerizable double bond after the polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; and a carboxylic acid anhydride such as maleic anhydride and anhydrous itaconic acid A monomer having a group; a monomer having an epoxy group such as glycidyl (meth) atalylate, 3,4-epoxycyclohexylmethyl (meth) atalylate, 0-(or m-, or p) butylbenzylglycidyl ether; Can be mentioned.
• the monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.
• the content ratio is not particularly limited, The content of the monomer component is 5 to 70% by weight, preferably 10 to 60% by weight.
• the acrylic dispersion resin (b) preferably has an epoxy group.
• a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) is used as a monomer component. What is necessary is just to superpose
• Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 0- (or m-, or p-) benzylbenzyl glycidyl ether. Etc. These monomers for introducing an epoxy group may be only one kind or two or more kinds.
• the monomer component for obtaining the acrylic dispersed resin (b) also includes a monomer for introducing the epoxy group
• the content ratio is not particularly limited. 5-70 0/0, it is good is preferably 10 to 60 wt%.
• the monomer component for obtaining the acrylic dispersed resin includes the essential component compound and In addition to the monomers, other copolymerizable monomers may be included as required.
• the other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n- Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylate 2-ethylhexyl, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meta ) (Meth) acrylic acid esters such as 2-hydroxyethyl acrylate; aromatic bur compounds such as styrene, butyltoluene and a- methylstyrene
• acrylic dispersion resin (b) when acrylic dispersion resin (b) is used as a dispersant, it is preferable to use benzyl (meth) acrylate. In that case, 1 to 70% by weight of the total monomer component is preferable. Should be 5-60% by weight! / ,.
• the content ratio is not particularly limited, but 95% by weight or less is preferable 85% % Or less is more preferable.
• the polymerization reaction method of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but a solution polymerization method is particularly preferable.
• the polymerization temperature varies depending on the ratio and the molecular weight of the target polymer.
• the polymerization temperature is 40 to 150 ° C, and the polymerization concentration is 5 to 50%. More preferably, the polymerization temperature is 60 to 130 ° C and the polymerization concentration. It should be 10-40%.
• a solvent used for the polymerization
• the solvent used may be used.
• ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
• ethyl acetate, butyl acetate Esters such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate
• Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethinoate ethere, propylene glycol monomethyl ether
• Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; black mouth form; dimethyl sulfoxide; and the like
• a commonly used polymerization initiator may be added, if necessary.
• the polymerization initiator is not particularly limited, and examples thereof include tamenoid oxide monooxide, diisopropylbenzene hydride peroxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxide isopropyl carbonate, t-amyl peroxide.
• Organic peroxides such as oxy 2-ethylhexanoate and t-butylperoxy 2-ethyl hexanoate; 2, 2'-azobis (isobutyor-tolyl), 1, 1'-azobis (cyclohexanecarbo-tolyl), 2 , 2′-azobis (2,4 dimethylvale-tolyl), azo 2, such as dimethyl 2,2′-azobis (2 methylpropionate);
• These polymerization initiators may be used alone or in combination of two or more.
• the amount of initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers used, the reaction conditions, the molecular weight of the target polymer, etc., but the weight average molecular weight without gelation. Is from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight, based on the total monomer components, from the viewpoint that a polymer of several thousand to several tens of thousands can be obtained.
• a commonly used chain transfer agent may be added as necessary to adjust the molecular weight.
• the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercabtan, mercaptoacetic acid and methyl mercaptoacetate, and a-methylstyrene dimer.
• the residual monomer has a high chain transfer effect. N-dodecyl mercaptan and mercaptoacetic acid are available. Yes.
• the amount used is not particularly limited as long as it is appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc. 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on the total monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained. Is preferred.
• the cyclization reaction of the ether dimer proceeds simultaneously in the polymerization reaction.
• the cyclization rate of the ether dimer need not necessarily be 100 mol%.
• an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride or the like may be added
• a monomer having an epoxy group such as glycidyl (meth) acrylate
• the ability to add a compound having an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol, or after adding an acid such as (meth) acrylic acid
• an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride or the like may be added to the generated hydroxyl group.
• a monomer having a Isoshianeto group such isocyanato Echiru (meth) Atari rate
• Re be such an addition compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid.
• the monomer capable of imparting the radical polymerizable double bond described above is used as the monomer component, and thereby the radical polymerizable double bond is introduced.
• the treatment for imparting the radical polymerizable double bond has different forces depending on the type of monomer that can impart the radical polymerizable double bond to be used.
• a monomer having a carboxyl group such as (meth) acrylic acid taconic acid is used.
• Carboxylic anhydride groups such as maleic anhydride and itaconic anhydride can be added by adding a compound having an epoxy group such as vinylbenzyl glycidyl ether and a radically polymerizable double bond.
• a compound having a hydroxyl group and a radically polymerizable double bond such as 2-hydroxychetyl (meth) atalylate may be added.
• the weight average molecular weight of the acrylic dispersed resin (b) is not particularly limited, but is preferably 2000 to 200,000, more preferably ⁇ 5000 to 100,000. When the weight average molecular weight force exceeds 00000, the viscosity becomes too high to form a coating film, whereas when it is less than 2000, sufficient heat resistance tends to be exhibited.
• the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g. If the acid value of the acrylic dispersed resin (b) is less than 30 mg KOHZg, it will be difficult to apply to alkali development, and if it exceeds 500 mg KOHZg, the viscosity will be too high to form a coating film. .
• a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by the general formula (1) is a compound known per se, for example, And compounds described in JP-A-2004-300203 and JP-A-2004-300204.
• component (b) is added to, or in place of, a polymer obtained by polymerizing a monomer component essentially comprising the compound represented by general formula (1) and Z or (2) [2-1] , “(W): Epoxy group-containing (meth) atarylate 5 to 90 mol%, (X): Other radical polymerizable compound 10 to 95 mol that can be copolymerized with component (W)” %, And (Y) unsaturated monobasic acid was added to 10 mol: L 00 mol% of the epoxy group contained in the obtained copolymer, and the (Y) It is also possible to use 10 to 10% of the hydroxyl group produced when the fraction is added: (Z) rosin obtained by carrotizing polybasic acid anhydride.
• the dispersant used in the color material dispersion of the present invention may contain other dispersants as required in addition to the dispersant and the acrylic dispersion resin.
• Other dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. And the like, and the like.
• dispersants are trade names such as EFKA (manufactured by Efka Chemicals Beebuy (EFK A)), Disperbyk (manufactured by Big Chemi Co., Ltd.), Disparon (manufactured by Enomoto Kasei Co., Ltd.), SOLS PERSE (General power company), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants can be used alone or in admixture of two or more.
• EFKA manufactured by Efka Chemicals Beebuy (EFK A)
• Disperbyk manufactured by Big Chemi Co., Ltd.
• Disparon manufactured by Enomoto Kasei Co., Ltd.
• SOLS PERSE General power company
• KP manufactured by Shin-Etsu Chemical Co.,
• the content of the (B) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight, based on the (A) colorant. % Or less. If the content of the dispersant is too small, the dispersion stability deteriorates and problems such as reaggregation and thickening occur. On the other hand, if the amount is too large, the ratio of the pigment is relatively reduced, so the coloring power is low, and the film thickness is too thick for the color density. Poor control may occur.
• the content of (a) the graft copolymer containing nitrogen atoms and Z or acrylic block copolymer described in [1-2-1] is usually 40% of the amount of (A) the colorant. It is not more than wt%, preferably not more than 30 wt%, more preferably not more than 20 wt%, and usually not less than 0.1 wt%.
• the content of the polymer obtained by polymerizing the monomer component (b) that contains the specific compound as described in [1-2-2] is usually 55% by weight or less based on (A) the colorant. It is preferably 35% by weight or less, more preferably 30% by weight or less, and usually 0.1% by weight or more. (B) If the content of the dispersant is too small, the dispersion is unstable. The image formability is reduced.
• the content of other dispersants described in [1 2-3] is usually 40% by weight or less, preferably 30% by weight or less, more preferably 20% by weight or less, based on (A) the colorant. Usually, it is 0% by weight or more, preferably 0.1% by weight or more.
• the colorant dispersion of the present invention is generally prepared by dissolving or dispersing the above-described solid content in the solvent (C).
• the solvent dissolves or disperses (A) the color material, (B) the dispersant, and other components blended as necessary in the color material dispersion of the present invention. Has the function of adjusting the viscosity.
• Solvents include, for example, diisopropyl ether, mineral spirit, n-pentane, aminoreatenore, ethinorecaprylate, n-hexane, getinoreatenore, isoprene, ethyl isobutyl ether, butyl stearate, n-octane , Norsol # 2, Apco # 18 Sonorvent, Diisobutylene, Aminoreacetate, Butinoreacetate, Apcocinner, Butyl Ether, Diisoptyl Ketone, Methyl Cyclohexene, Methyl Nonyl Ketone, Phyl Ether, Dodecane, Soal Solvent No. 1 and No.
• the content of the solvent in the entire colorant dispersion of the present invention is not particularly limited, but is usually 99% by weight or less, usually 70% by weight or more, preferably 75% by weight or more, and more preferably. It is preferably 80% by weight or more. If the proportion of the solvent is too large, it is inappropriate to form a color material dispersion because the solid content of the color material, dispersant, etc. is too small. On the other hand, if the proportion of the solvent is too small, the viscosity increases and it is not suitable for coating.
• the colorant dispersion liquid of the present invention may contain a part of the below-described noinda rosin. By containing rosin, the dispersion stability when producing the colorant dispersion of the present invention can be enhanced.
• the amount of the binder resin added is preferably 5 to: LOO% by weight, particularly 10 to 80% by weight, based on the (A) color material in the color material dispersion. If the amount of binder resin added is less than 5% by weight, the effect of increasing the dispersion stability is insufficient, and if it exceeds 100% by weight, the colorant density decreases, so that a sufficient color density cannot be obtained. [0107] [1 4 2] Dispersing aid
• Examples of the dispersion aid include pigment derivatives.
• Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, di-xazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, And derivatives such as dioxazine pigments.
• substituents of pigment derivatives sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc.
• pigment skeleton or alkyl groups, aryl groups, complex groups examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group.
• substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions.
• pigment derivatives include azo acid sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigments. And sulfonic acid derivatives of dioxazine pigments.
• the addition amount of the pigment derivative is usually 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to LO based on the total solid content of the colorant dispersion of the present invention. % By weight. If the amount of the pigment derivative is small, dispersion stability deteriorates and problems such as re-aggregation and thickening occur. On the other hand, if the amount is too large, the contribution to dispersion stability is saturated, and on the contrary, the color purity may be lowered.
• a predetermined amount of each of the color material, the solvent, and the dispersant is weighed, and the color material is dispersed in a dispersion treatment step to obtain a liquid color material dispersion.
• a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used. Since the coloring material is atomized by this dispersion treatment, the colored resin composition using the coloring material dispersion of the present invention has improved coating characteristics. In addition, the transmittance of the product color filter substrate is improved.
• the binder resin or the dispersion aid may be used in combination as appropriate.
• the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several millimeters or zircoyu beads.
• the temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C.
• the dispersion time varies depending on the composition of the color material dispersion (color material, solvent, dispersant, etc.) and the size of the sand grinder apparatus, and therefore needs to be adjusted as appropriate.
• the above-described color material dispersion of the present invention is suitably used as a colored resin composition for the purpose of forming a pixel image of a color filter, among other powers that can be used for various applications.
• a colored resin composition a noda resin, a monomer, a photopolymerization initiator, and other solid components may be blended together with the pigment dispersion of the present invention.
• total solid content refers to all components of the colored resin composition of the present invention other than the solvent components described later.
• binder resin examples include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11 140144, JP-A-11-174224, JP-A-11-174224, Known polymer compounds described in 2000-56118, JP2003-233179, JP2004-224894, JP2004-300203, JP2004-300204, etc. are used.
• acrylic dispersion resin described in [1 2-2] can also be used as a binder resin.
• a polymer compound containing no nitrogen atom is preferred, and the acrylic dispersion resin described in [1-2-2] and (W): (meth) acrylate having an epoxy group and 5 to 90 mol 0 / 0 , (X): 10 to 95 mol% of another radical polymerizable compound that can be copolymerized with the (W) component is copolymerized, and 10 to 10 of the epoxy group contained in the copolymer is obtained.
• (Y) Unsaturated monobasic acid is added to 100 mol%, and (Y) component is added. Preferred is rosin obtained by adding basic acid anhydride.
• (W) examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3, 4 epoxy butyl (meth) acrylate, (3, 4 epoxy cyclohexyl) methyl Among the forces that can be exemplified by (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl (meth) acrylate is preferable. These (W) components may be used alone or as a mixture of two or more.
• the copolymerization ratio of the other radical polymerizable compound that can be copolymerized with the component (X): (W) is 10 to 95 mol% as described above, preferably 20 to 80 mol. %, More preferably 30 to 70 mol%. If this ratio is too large, the amount of the (W) component is reduced, so that the addition amount of the polymerizable component and the alkali-soluble component is insufficient, and if it is too small, the heat resistance and strength are lowered, which is not preferable.
• radical polymerizable compounds that can be copolymerized with the component (X): (W) include mono (meth) acrylates having a structure represented by the following general formula (5). It is preferable to use seeds or two or more kinds.
• R 4e to R 9e each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc.
• R 1Qe and R Ue each represent a hydrogen atom or a methyl group, E methyl group
• a force represents an alkyl group having 1 to 3 carbon atoms, such as propyl or linked to may form a ring.
• R 1Qe and R Ue is connected
• the ring formed is preferably an aliphatic ring and may be either saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
• mono (meth) acrylate having a structure represented by the following general formula (6), (7), or (8) is preferable.
• these structures By introducing these structures into the binder resin, heat resistance and strength can be increased.
• these mono (meth) acrylates may be used alone or in admixture of two or more.
• R 12 represents a hydrogen atom or a methyl group
• R 13 represents the chemical formula (5).
• Containing Yuryou mono (meth) Atari rate having a structure of the formula in copolymerized monomer (5) is usually 5 to 90 mol 0/0, preferably from 10 to 70 mole 0/0, more preferably is a 15 to 5 0 mole 0/0.
• radical polymerizable compound other than the above is not particularly limited, but specific examples thereof include:
• (Meth) acrylic acid amide (meth) acrylic acid N, N dimethylamide, (meth) acrylic acid N, N jetylamide, (meth) acrylic acid N, N dipropylamide, (meth) acrylic acid N, N — (Meth) acrylic acid amides such as di-iso-propylamide and (meth) acrylic acid anthraceramide;
• Unsaturated dicarboxylic acid diesters such as cetyl citrate, cetyl maleate, cetyl fumarate, itaconate;
• Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide;
• component (X) In order to impart superior heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as component (X).
• the copolymerization ratio of at least one kind selected from styrene, benzyl (meth) acrylate and monomaleimide is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
• a known solution polymerization method is applied to the copolymerization reaction between the component (W) and the component (X).
• the solvent to be used is not particularly limited as long as it is inert to radical polymerization, and ordinary organic solvents such as organic solvents can be used.
• ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butylacetate sorb acetate
• diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyral carbitol acetate.
• Acetates propylene glycol monoalkyl ether acetates;
• Acetates such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers;
• Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl ethers;
• 1, 4 ethers such as dioxane and tetrahydrofuran
• Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
• Hydrocarbons such as benzene, toluene, xylene, octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactic esters such as methyl lactate, ethyl lactate and butyl lactate;
• Examples include dimethylformamide and N-methylpyrrolidone.
• These solvents may be used alone or in combination of two or more.
• the amount of these solvents used is 30 to L000 parts by weight, preferably 50 to 800 parts by weight, with respect to 100 parts by weight of the copolymer obtained. If the amount of solvent used is outside this range, it will be difficult to control the molecular weight of the copolymer.
• the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and it is possible to use a commonly used organic peroxide catalyst catalyst compound. it can.
• Organic peroxide catalysts are classified into known ketone peroxides, peroxyketals, hard mouth peroxides, diallyl peroxides, disilver oxides, peroxyesters, and peroxydicarbonates. Can be mentioned.
• radical polymerization initiator examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexylperoxybenzoate, and t-butinolepero Xi-2-ethinorehexanoate, t-hexenoleperoxy 2-ethinorehexanoate, 1,1-bis (t-butylperoxy) -1,3,3,5 trimethylcyclohexane, 2,5 dimethyl-2,5 bis (T-Butylperoxy) hexyl 3,3 isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl chloride, bis (4 t-butylcyclohexyl) per Oxydicarbonate, diisopropylperoxydicarbonate,
• the amount of the radical polymerization initiator used is 0.5 to 20 parts by weight, preferably 100 parts by weight of the monomer used in the copolymerization reaction, that is, the total of (W) component and (X) component, preferably 1 to: L0 parts by weight.
• the copolymerization reaction can be carried out by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and heating while stirring.
• the monomer added with the radical polymerization initiator is heated, You may carry out by dripping in the stirred solvent.
• a monomer may be dropped while a radical polymerization initiator is added to the solvent and the temperature is raised.
• the reaction conditions can be changed freely according to the target molecular weight.
• the component (Y) to be added to the epoxy group contained in the copolymer of the component (W) and the component (X) is an unsaturated monobasic acid.
• the component (Y) known compounds can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples thereof include alicyclic acid, methacrylic acid, crotonic acid, o Examples thereof include monocarboxylic acids such as —, m—, p-bulubenzoic acid, ⁇ -haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano substitution. Of these, acrylic acid and cocoon or methacrylic acid are preferred.
• These ( ⁇ ) ingredients can be used alone or in combination of two or more.
• glycidyl (meth) acrylate or polymerizable unsaturated group is added to a part of the generated carboxyl group.
• (Z) Glycidyl ether having no polymerizable unsaturated group in part of the carboxyl group produced after addition of polybasic acid anhydride to add developable glycidyl ether compound It is also possible to add a compound, or to add both.
• glycidyl ether compounds having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group and an alkyl group (trade name: Denacol EX, manufactured by Nagase Chemical Industries, Ltd.) — 111, Denacol EX—121, Denacol EX—141, Denacol EX—145, Denacol EX—146, Denacol EX—171, Denacol EX—192), etc.
• the polystyrene-reduced weight average molecular weight (Mw) of such binder resin measured by GPC is preferably 300,000 to 100,000, more preferably 5,000 to 50,000! This molecule If the amount is less than 3000, the heat resistance and film strength are inferior, and if it exceeds 100000, the solubility in the developer is insufficient, which is not preferable.
• the molecular weight distribution (weight average molecular weight (Mw) Z number average molecular weight (Mn)) is preferably 2.0 to 5.0.
• Such binder resin may be used alone or in combination of two or more.
• Such a binder resin is particularly excellent in adhesion to a substrate in which undissolved matter remains on the non-image area on the substrate, in combination with a urethane dispersant and an acrylic dispersant described later.
• the effect that a high density color pixel can be formed is preferable.
• Such binders ⁇ during the total solid content of the colored ⁇ composition of the present invention usually 0.1 to 80 weight 0/0, preferably be contained in an amount of 1 to 60 weight 0/0.
• the content of the Norder resin is less than this range, the film becomes brittle and the adhesion to the substrate may be reduced.
• the amount is larger than this range, the permeability of the developer into the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.
• the photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator and a calorifying agent such as a sensitizing dye added as necessary.
• the photopolymerization initiator system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.
• Examples of the photopolymerization initiator constituting the photopolymerization initiator component include metallocenes containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197. Compounds, hexaarylbiimidazole derivatives described in JP-A-10-39503, halomethyl-striazine derivatives, N-arylglycine such as N-phenolglycine, a-amino acids, N-aryl-a-amino acid salts, N Radical activators such as aryl-a-amino acid esters, triaminoalkylphenone compounds, oxime ester initiators described in JP-A-2000-80068, JP-A-2006-36750, etc. Is mentioned.
• 2-(4-Methoxyphenyl) 4, 6-bis (trichloromethyl) s triazine 2— (4-Methyl Toxinaphthyl) -4,6-bis (trichloromethyl) s triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s triazine, 2- (4-ethoxycarbonaphthyl) 4, 6-bis (trichloromethyl) s halomethylated triazine derivatives such as triazine;
• Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethyl anthraquinone, 2-t butyl anthraquinone, and 1-mouth anthraquinone;
• Benzophenones such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methinolebenzophenone, 2-clobenbenzophenone, 4-bromobenzophenone, 2-force ruboxybenzophenone Derivatives;
• Benzoic acid ester derivatives such as dimethylaminobenzoyl ethyl, P-jetylaminobenzoic acid ethyl; 9-phenolacridine, 9- (P-methoxyphenyl) atridine and other alkidine derivatives; 9, 10-dimethylbenzphena Phenazine derivatives such as gin;
• Anthrone derivatives such as benzanthrone
• Dicyclopentagenyl Ti-dimonochloride dicyclopentagenyl Ti bis-phenyl, di-cyclopentagenyl Ti-bis-1, 2, 4, 4, 5, 6-pentafluorophenyl Dicyclopentadienyl Ti-bis 2, 3, 5, 6-tetrafluoro 1-yl phenyl dicyclopentadienyl Ti-bis 2, 4, 6 Trifluorophenyl 1 Dicyclopentadiene Ti — 2, 6—Ziploropheny 1 yl, Dicyclopentadiene Ti, 2, 4-Difluoropheny 1 il, Sicyclopentagel 1 Ti —Bis-1, 2, 4, 4, 6, 6 Pentafluorophenol-1-yl, Dimethylcyclopentagel-Ti—Bis-1,2,6 Difluorofluoro-1-yl Cyclopentadiene Ti— 2, 6 Difluoro 1——Pil 1—Fil Etanoyl derivatives such as 2-yl;
• the following compounds can be preferably used.
• Examples of the accelerator constituting the photopolymerization initiator component include N, N dialkylaminobenzoic acid alkyl esters such as N, N dimethylaminobenzoic acid ethyl ester, 2 mercaptobenzothiazole, 2-mercaptobenzoxazole, 2- Mercaptobe A mercapto compound having a heterocyclic ring such as nzoimidazole or an aliphatic polyfunctional mercapto compound is used.
• photopolymerization initiators and accelerators may be used alone or in combination of two or more.
• photopolymerization initiator component examples include dialkylacetophos described in pages 16 to 26 of “Fine Chemical” (March 1, 1991, vol. 20, No. 4).
• benzoin, thixanthone derivatives, etc. as described in JP-A-58-403023 and JP-B-45-37377, hexarylbiimidazole, S-trihalomethyltriazine, JP-A-4-221958, JP-A-4-219756, and the like, which contain an ethylenic saturated double bond containing titanocene and a xanthene dye, an amino group or a urethane group and capable of addition polymerization.
• Examples include systems that combine compounds.
• the blending ratio of the photopolymerization initiator component is generally 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the total solid content of the colored resin composition of the present invention. If the blending ratio is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed part in the developer may be lowered, leading to poor development. If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity.
• sensitizing dyes examples include xanthene dyes described in JP-A-4 221958 and JP-A-4-219756, and coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335.
• amino group-containing sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenol group in the same molecule.
• amino group-containing sensitizing dyes preferred are compounds having an amino group and a phenol group in the same molecule.
• amino group-containing sensitizing dyes preferred are compounds having an amino group and a phenol group in the same molecule.
• the blending ratio of the sensitizing dye in the colored composition for a color filter of the present invention is usually 0 to 20% by weight, preferably 0.1 to 15% by weight, based on the total solid content of the colored resin composition. More preferably, it is 0.2 to 10% by weight.
• the monomer is not particularly limited as long as it contains a photopolymerizable low molecular weight compound that can be polymerized, but at least an ethylenic double bond that is preferably a polyfunctional monomer having a functional group is preferable.
• ethylenic compound One addition-polymerizable compound (hereinafter referred to as “ethylenic compound”) is more preferred.
• the monomer may have an acid group.
• An ethylenic compound refers to an element that undergoes addition polymerization and curing by the action of a photopolymerization initiator described later when the coloring composition for a color filter of the present invention is irradiated with actinic rays. It is a compound having a tylene double bond.
• the term “monomer” in the present invention means a concept opposite to a so-called polymer substance, and in addition to “monomer” in the narrow sense, It means a concept including "mer”, “trimer”, and "oligomer”.
• Examples of the ethylenic compound having an acid group include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, aliphatic polyhydroxy compounds and unsaturated rubonic acids. Esters, aromatic polyhydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and the like. Ethylene compounds having a urethane skeleton obtained by reacting an ester or polyisocyanate compound obtained by an ester reaction with a polyvalent hydroxy compound and a (meth) atallyloyl-containing hydroxy compound Thing etc. are mentioned.
• Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.
• ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid examples include ethylene gallium ditalylate, triethylene glycol ditalylate, trimethylol propane tritalylate, trimethylol ethane tritalylate, pentaerythritol diester.
• acrylic acid esters such as attalylate, pentaerythritol triatalylate, pentaerythritol tetraatalylate, dipentaerythritol tetraatalylate, dipentaerythritol pentaatalylate, dipentaerythritol hexaatalylate, and glycerol acrylate.
• acrylic acid part of these acrylates was replaced with a methacrylic acid ester substituted for the methacrylic acid part, an itaconic acid ester substituted for the itaconic acid part, a crotonic acid ester substituted for the crotonic acid part, or a maleic acid part.
• maleic acid esters were replaced with a methacrylic acid ester substituted for the methacrylic acid part, an itaconic acid ester substituted for the itaconic acid part, a crotonic acid ester substituted for the crotonic acid part, or a maleic acid part.
• maleic acid esters maleic acid esters.
• esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include: Hyde Mouth Quinone Diatalylate, Hyde Mouth Quinone Dimetatalylate, Resorcin Ditalitalate, Resorcin Dimetatalylate, Pyrogallol Tritalylate Etc.
• the ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may not necessarily be a single substance but a mixture.
• Typical examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and Glycerin condensate Etc.
• Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) atallyloyl group-containing hydroxy compound include hexamethylene diisocyanate and trimethylhexamethyate.
• Aliphatic diisocyanates such as diisocyanate; cycloaliphatic diisocyanates such as cyclohexane diisocyanate, isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, etc.
• ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allylic esters such as diaryl phthalate; and bull group-containing compounds such as dibule phthalate. Etc. are also useful.
• the monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, the above-described ethylenic property is required in order to be able to use this as it is. It is also possible to introduce an acid group by reacting the hydroxyl group of the compound with a non-aromatic carboxylic anhydride.
• non-aromatic carboxylic acid anhydride examples include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, and succinic anhydride.
• examples include acid and maleic anhydride.
• the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound.
• a polyfunctional monomer having an acid group by reacting a non-aromatic carboxylic acid anhydride with a sil group is particularly preferred.
• the aliphatic polyhydroxy compound is pentaerythritol and Z or Dipentaerythritol.
• One of these monomers may be used alone, but since it is difficult to use a single compound for production, two or more of these monomers may be used in combination. Also, if necessary, monomer A polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.
• a preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOHZg, and particularly preferably 5 to 30 mg-KOHZg. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties will be lowered, and if it is too high, the production and handling will be difficult, the photopolymerization performance will be lowered, and the curability such as the surface smoothness of the pixels will be poor. Therefore, when two or more types of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used, the acid groups as the entire polyfunctional monomer fall within the above range. It is essential to make such adjustments.
• more preferred polyfunctional monomers having an acid group are dipentaerythritol hexaatalylate, dipentaerythritol pentaatalylate, and dipentaerythritol pentamer, commercially available as T 01382 manufactured by Toagosei Co., Ltd. It is a mixture mainly composed of acrylate succinate. A combination of other polyfunctional monomers with this polyfunctional monomer can also be used.
• the blending ratio of these polyfunctional monomers is usually 5 to 80% by weight, preferably 10 to 70% by weight, based on the total solid content of the colored resin composition of the present invention. % By weight, preferably 10 to: L00% by weight, more preferably 20 to 80% by weight.
• the blending ratio of the multifunctional monomer is appropriately adjusted according to the type of the coloring material of the coloring composition and the acid value of the multifunctional monomer used.
• the coloring composition for a color filter of the present invention may further contain an organic carboxylic acid and Z or an organic carboxylic acid anhydride in addition to the above components.
• Organic carboxylic acids include aliphatic carboxylic acids and Z or aromatic carboxylic acids.
• Specific examples of aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, jetyl acetic acid, enanthic acid, strong prillic acid, glycolic acid, acrylic acid, and methacrylic acid.
• aromatic carboxylic acids include benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid, phthalic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and melophane.
• Acid pyromellitic acid, phenacetic acid, hydroacetropic acid, hydrocacinic acid, mandelic acid, succinic acid, atropic acid, kaynic acid, methyl kainate, benzyl cinnamate, cinnamylidene acetic acid, tamalic acid
• carboxylic acids in which a carboxyl group is directly bonded to a phenol group such as umbelic acid, and carboxylic acids in which a carboxyl group is bonded via a carbon atom having a phenyl group.
• malonic acid is particularly preferred, with monocarboxylic acid and dicarboxylic acid being preferred, and malonic acid, glutaric acid, and glycolic acid being more preferred.
• the molecular weight of the organic carboxylic acid is 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving the soiling is insufficient.
• organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and Z or aromatic carboxylic acid anhydrides.
• aliphatic carboxylic acid anhydrides include acetic anhydride, anhydrous trichlorodiacetic acid, anhydrous Trifluoroacetic acid, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, glutaric anhydride, 1,2-cyclohexenedicarboxylic anhydride, n-octadecyl succinic anhydride, 5 —An aliphatic carboxylic acid anhydride such as norbornene-2,3-dicarboxylic acid.
• aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride, and the like.
• organic carboxylic acid anhydrides maleic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are more preferable.
• the molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less. Is preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid anhydride is too large, the effect of improving the soiling is insufficient, and if it is too small, there is a risk of reducing the amount of additive and process contamination due to sublimation and volatilization.
• organic carboxylic acids and organic carboxylic acid anhydrides may be used singly or in combination of two or more.
• the amount of addition of these organic carboxylic acid and organic carboxylic anhydride is usually 0.01% by weight or more, preferably 0.03% by weight, based on the total solid content of the colored resin composition of the present invention. Above, more preferably 0.05% by weight or more, usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. If the amount added is too small, a sufficient calorie effect cannot be obtained, while if it is too large, surface smoothness and sensitivity may be deteriorated and undissolved peeling pieces may be generated.
• the colored coffin composition of the present invention may further contain a solid content other than the above components as necessary.
• a solid content other than the above components include surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, and development improvers.
• surfactants such as ionic, cationic, nonionic, and amphoteric surfactants can be used. However, nonionic surfactants are unlikely to adversely affect various properties. It is preferable to use a surfactant.
• the addition amount of the surfactant is usually 0 to the total solids in the coloring ⁇ composition of the present invention. 001-10 weight 0/0, preferably from 0.005 to 1 weight 0/0, more preferably 0.01 to 0.5% by weight, most preferably 0.03-0.3% by weight. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed, and if it is more, the smoothness and uniformity of the coating film cannot be expressed, and other characteristics are poor. There is a case to hesitate.
• thermal polymerization inhibitor for example, no, iduloquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, ⁇ -naphthol and the like are used.
• the addition amount of the thermal polymerization inhibitor is 0 to 3% by weight based on the total solid content of the colored composition of the present invention. Preferred to be in the range.
• plasticizer examples include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl dallicol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin.
• the amount of these plasticizers added is preferably 10% by weight or less based on the total solid content of the colored composition of the present invention.
• a storage stabilizer a surface protective agent, an adhesion improver, a development improver and the like can be added as necessary.
• the amount of these components added is preferably 20% by weight or less based on the total solid content of the colored composition of the present invention.
• the colorant dispersion obtained by the dispersion treatment or the like described in [15] is mixed with a solvent, a binder resin, a polyfunctional monomer, a photopolymerization initiator system component, and if necessary. Mix other ingredients to make a uniform dispersion. In each of the dispersion treatment step and the mixing step, fine dust may be mixed. Therefore, it is preferable to filter the obtained colored resin composition with a filter or the like.
• a color filter is usually manufactured by forming a black matrix on a transparent substrate and then sequentially forming red, green, and blue pixel images.
• the coloring composition for a color filter of the present invention is used as at least one kind of pixel image forming coating liquid among black, red, green and blue.
• black resists use a red, green, or blue color resist on a transparent substrate, or a resin black matrix forming surface formed on a transparent substrate, or use a chromium compound or other light shielding metal material.
• a pixel image of each color is formed on the formed metal black matrix forming surface by performing respective processes of coating, heat drying, image exposure, development and thermosetting.
• the transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength.
• Materials include, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resin, Examples include unsaturated polyester resin, thermosetting resin sheets such as poly (meth) acrylic resin, and various glasses. Among these, from the viewpoint of heat resistance, glass and heat resistant resin are preferable.
• the transparent substrate and the black matrix forming substrate described later have corona discharge treatment, ozone treatment, silane coupling agent, urethane-based resin, etc. as necessary.
• a thin film forming process of various resins may be performed.
• the thickness of the transparent substrate is usually in the range of 0.05 to LOmm, preferably 0.1 to 7 mm.
• the film thickness is usually in the range of 0.01 to 10 m, preferably 0.05 to 5 m.
• the black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive black composition for black matrix.
• a light-shielding metal thin film or a photosensitive black composition for black matrix As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.
• These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape by a positive type photoresist, cerium nitrate nitrate and perchlorine are applied to chromium. Etching solution mixed with acid and Z or nitric acid is used. For other materials, etching is performed using an etching solution according to the material, and finally the positive photoresist is removed with a special release agent. A black matrix can be formed.
• a thin film of these metals or metal 'metal oxide is formed on the transparent substrate by vapor deposition or sputtering.
• a film having a repeating pattern such as a stripe, a mosaic, or a triangle is formed.
• the coating film is exposed and developed to form a resist image.
• the coating film can be etched to form a black matrix.
• a black matrix is formed using a coloring composition containing a black color material.
• a black color material such as carbon black, black lead, iron black, iron black, cyanine black, titanium black, or a red color appropriately selected from inorganic or organic pigments and dyes
• a black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a coloring composition containing a black color material by mixing green and blue.
• a photomask is overlaid on the formed coating film.
• a pixel image is formed by performing image exposure, development, and heat curing or photocuring as necessary through the above, to create a colored layer of the pixel image.
• a color filter image can be formed by performing this operation for each of the three colored compositions of red, green, and blue.
• the coloring composition for the color filter can be applied by a spinner method, a wire bar method, a flow coat method, a die coating method, a roll coating method, a spray coating method, or the like.
• the die coating method significantly reduces the amount of coating solution used and suppresses the generation of foreign substances that are completely free from the effects of mist adhering to the spin coating method. I like it.
• the thickness of the coating film is usually in the range of 0.2 to 20 111 as the film thickness after drying, more preferably in the range of 0.5 to 10 / ⁇ ⁇ , and more Preference is given to a range of 0.8 to 5 m.
• Drying of coating film Drying of the coating film formed by applying the coloring composition to the transparent substrate is preferably performed by a drying method using a hot plate, an IR oven, or a competition oven. Usually, pre-drying is followed by two-stage drying that is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the kind of the solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 40 to 80 ° C and 15 seconds to 5 minutes, preferably 50 to 70 ° C, depending on the type of solvent component and the performance of the dryer used. In the range of 30 seconds to 3 minutes.
• the temperature condition for reheat drying is 50 to 200 ° C higher than the predrying temperature, and preferably 70 to 160 ° C, particularly 70 to 130 ° C.
• the drying time is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes, depending on the heating temperature. The higher the drying temperature is, the better the adhesion to the transparent substrate is. However, if the drying temperature is too high, the binder resin is decomposed and thermal polymerization may be induced to cause development failure.
• the coating film may be dried by a reduced pressure drying method in which the temperature is not increased and drying is performed in a reduced pressure chamber.
• Image exposure is carried out by applying a negative matrix pattern on the dried coating film of the colored composition, and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the colored composition film in order to prevent a decrease in sensitivity of the colored composition film due to oxygen.
• an oxygen blocking layer such as a polyvinyl alcohol layer
• the light source used for image exposure is not particularly limited.
• a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp examples include lamp light sources such as carbon arc and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers.
• An optical filter can also be used when irradiating light of a specific wavelength.
• Development can be performed after the image exposure using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound.
• This aqueous solution further includes an organic solvent, a buffer, Complexing agents, dyes or pigments can be included.
• alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, phosphorus Inorganic alkaline compounds such as sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or tri- Ethanolamine, mono'di- or trimethylami, mono'di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenedimine, tetramethyl Organic alcohol such as ammonia hydroxide (TMAH) and choline Li property I ⁇ thereof.
• TMAH ammonia hydroxide
• TMAH ammonia hydroxide
• TMAH ammonia hydroxide
• surfactant examples include non-ionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters.
• Amphoteric surfactants such as surfactants, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, etc. These may be used, and these may be used alone or in combination of two or more.
• Examples of the organic solvent include one or more of isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butylcetosolve, phencelesolve, propylene glycol, diacetone alcohol and the like.
• the organic solvent may be used alone or in combination with an aqueous solution.
• the development processing conditions are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, particularly 15 to 45 ° C, particularly preferably 20 to 40 ° C.
• the development method is immersion development or spray development. , Brush developing method, ultrasonic developing method and the like.
• the developed color filter substrate is usually subjected to a heat curing treatment or a light curing treatment, preferably a heat curing treatment.
• a heat curing treatment or a light curing treatment preferably a heat curing treatment.
• the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.
• the patterning image formation for one color is completed. This process is repeated in sequence to pattern (black,) red, green, and blue to form a color filter. Note that the order of the three-color patterning of red, green, and blue is not limited to the order described above.
• the color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of a component such as a color display or a liquid crystal display device.
• a transparent electrode such as ITO
• the surface smoothness and durability are improved.
• a top coat layer such as polyamide or polyimide can be provided on the image as necessary.
• the transparent electrode may not be formed in applications such as the planar alignment type drive system (IPS mode).
• IPS mode planar alignment type drive system
• the liquid crystal display device of the present invention is generally formed by forming an alignment film on the color filter of the present invention, spraying a spacer on the alignment film, and then bonding to a counter substrate to form a liquid crystal cell.
• the liquid crystal cell is manufactured by injecting liquid crystal and connecting to the counter electrode.
• the alignment film a resin film such as polyimide is suitable.
• the gravure printing method and the Z or flexographic printing method are usually employed, and the thickness of the alignment film is usually several lOnm.
• the alignment film is cured by heat baking, and then subjected to surface treatment by treatment with a rubbing cloth, which is irradiated with ultraviolet rays, to be processed into a surface state capable of adjusting the tilt of the liquid crystal.
• a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 m is usually preferable.
• a transparent resin film photospacer (PS) is formed on the color filter substrate by photolithography, and this is used in place of the spacer.
• an array substrate is usually used, especially a TFT (thin film transistor) substrate. Is preferred.
• the gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 m.
• the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin.
• the sealing material is cured by ultraviolet (UV) irradiation and Z or heating, and the periphery of the liquid crystal cell is sealed.
• the liquid crystal cell whose periphery is sealed is cut into panels, and then the pressure is reduced in the vacuum chamber. After the liquid crystal inlet is immersed in the liquid crystal, the inside of the chamber leaks. Liquid crystal is injected into the liquid crystal cell.
• the vacuum degree in the liquid crystal cell typically a 1 X 10- 2 ⁇ 1 X 1 0 "Pa, the preferably 1 X 10- 3 ⁇ 1 X 10- 6 Pa.
• the heating temperature that is preferably heated is usually 30 to 100 ° C, more preferably 50 to 90 ° C. Heating during decompression is usually in the range of 10 to 60 minutes and then immersed in the liquid crystal.
• a liquid crystal cell filled with liquid crystal is completed by sealing the liquid crystal injection port with a UV curable resin, thereby completing the liquid crystal display (panel).
• liquid crystals such as aromatic, aliphatic and polycyclic compounds are not particularly limited in the type of liquid crystal, and any of lyotropic liquid crystal, thermotropic liquid crystal and the like may be used.
• Nematic liquid crystal, smectic liquid crystal, and cholesteric liquid crystal are known as thermo-mouth pick liquid crystal, but they may be misaligned.
• the temperature was stabilized at 90 ° C, and the power of the monomer tank and chain transfer agent tank was dropped, and polymerization was started. While maintaining the temperature at 90 ° C, dropping was carried out over 135 minutes each, and 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a 30 wt% polymer solution having a weight average molecular weight of 17 000 and an oxidation of 103 mg KOH / g.
• Propylene glycol monomethyl ether acetate 220.73 parts, V-59 (Wako Pure Chemical Industries, Ltd., azo polymerization initiator) 10 parts were charged in a reaction vessel, heated to 80 ° C under nitrogen atmosphere, 32.13 parts of propylene glycol monomethyl ether acetate 40% solution of a compound represented by the formula (hereinafter referred to as “Compound B”), 57.76 parts of benzyl metatalate, methyl metatalylate 21 88 parts and 44.21 parts of methacrylic acid were added dropwise over 2 hours, followed by further stirring for 4 hours to obtain a polymerization reaction solution.
• Compound B a compound represented by the formula
• Propylene glycol monomethyl ether acetate 35 parts, 1-methoxy-2-propanol 8.8 parts, V-59 (Wako Pure Chemical Industries, Ltd., azo polymerization initiator) 1. Charge 5 parts into a reaction vessel under nitrogen atmosphere The temperature was raised to 80 ° C, 9.5 parts of benzyl methacrylate, 6.5 parts of methyl methacrylate, 5.5 ⁇ ⁇ 2 hydroxyethylenomethacrylate, 3.5 ⁇ ⁇ methacrylolic acid, 10.7 ⁇ was added dropwise over 2 hours. The mixture was further stirred for 4 hours to obtain a polymerization reaction solution.
• the synthesized rosin has an acid value of 176 and a weight-average molecular weight of 15,000 and 7 pieces.
• Examples 1-6, Comparative Examples 1-3 CI Pigment Green 36 and CI Pigment Yellow 150 with different crystallite sizes shown in Table 1 are used as coloring materials. 4.29 parts by weight, propylene glycol monomethyl ether acetate as a solvent, 60.00 parts by weight, as a dispersant 2. Dispersant (a) described in Table 1 in total in terms of solid content 2.14 parts by weight, 4.29 parts by weight of Dispersant (b) described in Table 1 and diameter 0.5 mm Zircon Your Beads 225 Part by weight was filled in a stainless steel container, and dispersed in a paint shaker for 6 hours to prepare a green pigment dispersion.
• the crystallite size of C. I. Pigment Yellow 150 was measured as follows.
• the measuring device is powder X-ray of concentrated optical system using CuK o; (CuK o; + CuK a) ray as X-ray source.
• a diffractometer PW1700 manufactured by PANalytical was used.
• Measurement conditions are scanning range (2 ⁇ ) 3 ⁇ 70 °, scan step width 0.05 °, scanning speed 3.0. Zmin, divergence slit 1 °, scattering slit 1 °, light receiving slit 0.2 mm.
• the crystallite size (D) was calculated by using the following Shirare equation.
• the Shirrer constant (K) 0.9
• the X-ray (CuKa) wavelength ( ⁇ ) 1. 54056 mm.
• the half-value width (j8) derived from the sample used in the above was calculated from the half-value width curve (regression 2) of the standard Si (NIST Si 640b). Next-order curve) was used to calculate the device-derived half-value width () for the relevant angle, and the following half-value width correction formula was used.
• the X-ray diffraction peak derived from CuK ⁇ -ray used for calculation of the crystallite size was 8.5 ° and 9.2 °, and the average value of the obtained crystallite sizes was used as the crystallite size of the pigment.
• a green pigment dispersion was prepared in the same manner as in Example 1 except that 4.29 parts by weight of CI pigment yellow 138 having the crystallite size shown in the table was used instead of CI pigment yellow 150 as the coloring material. was prepared.
• the X-ray diffraction peaks derived from CuK ⁇ rays used to calculate the crystallite size of CI pigment yellow 138 use 12.3 ° and 12.9 °, and the average value of the obtained crystallite size is the crystallite size of the pigment. It was.
• the X-ray diffraction peaks derived from the CuKa line used to calculate the crystallite size of CI Pigment Blue 15: 6 use 5.7 ° and 10.2 °, and the average value of the obtained crystallite size is the pigment crystal. Child size.
• the viscosity (20 rpm) immediately after production of the pigment dispersion and after standing in a thermostat at 23 ° C. for 7 days was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd.
• the viscosity of the pigment dispersions in each Example and Comparative Example was compared with the rate of change in viscosity over 7 days. 1. What was 7% or more was ⁇ , 1.7% or more but less than 5% ⁇ was assigned, and X was given 5% or more. The results are shown in Tables 1 and 2.
• Dispersant C is a urethane-based dispersant“ Disperbykl61 ”manufactured by Big Chemi.
• Y150_a and Y150-b used two kinds of forces with the same crystallite size but different size distributions.
• the pigment dispersion is mixed with other components, and colored soots shown in Table 3 (Examples 1 to 6, Comparative Examples 1 to 4) and Table 4 (Examples 7 and 8, Comparative Examples 5 to 8) are mixed.
• a fat composition was prepared.
• the sample was exposed at 60 mjZcm 2 through a mask pattern with a high-pressure mercury lamp, and then developed using a 0.04 wt% aqueous potassium hydroxide solution at a developer temperature of 23 ° C. After the image formation, it was rinsed with sufficient water and then dried with clean air. After that, post-beta was performed in an oven at 230 ° C for 30 minutes. The film thickness after drying was about 1.8 m.
• This color resist was spin-coated on a glass substrate so that the film thickness after drying was 2 ⁇ m, and dried at 80 ° C. for 10 minutes. Then, after UV irradiation was performed to cure the resin, heat crosslinking was performed at 230 ° C for 30 minutes to obtain a green pixel (Examples 1 to 6, Comparative Examples 1 to 4) and a blue pixel (Example 7, 8, Comparative Examples 5 to 8) were formed.
• the chromaticity of the transmitted light in the C light source was measured using a spectrophotometer (“U4100” manufactured by Hitachi, Ltd.).
• this substrate is placed in close contact between two polarizing plates without any gap, and a light intensity when the polarizing plates are orthogonal A (cd / cm) using a color luminance meter ("BM-5AJ" manufactured by Topcon) 2 )
• the contrast was calculated from the ratio of the amount of light B (cdZcm 2 ) in parallel with the following formula (1), and the results are shown in Tables 1 and 2.
• C B / A (1)
• C 1200 or higher was evaluated as “good” for contrast, and less than 1200 was evaluated as “X” for poor contrast.
• the colorant dispersion of the present invention has good storage stability (no viscosity change!), And the contrast of pixels formed using this is as follows. It was confirmed that it was extremely excellent!
• the color material dispersion of the present invention it is possible to form colored pixels having excellent depolarization characteristics and high contrast, and as a result, a high-quality color filter and a liquid crystal display device are manufactured. I can do it.
• the colorant dispersion and the colored rosin composition of the present invention are high in quality because of excellent storage stability. Therefore, industrial applicability is extremely high in the fields of colorant dispersions, photosensitive coloring compositions, color filters, and liquid crystal display devices.

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