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    • 专利摘要:
    PURPOSE: Provided are a novel photosensitive coloring composition having excellent dispersion stability and fluidity and a color filter using the composition. A color filter has extremely reduced inferiority by using a color resist where the generation of insoluble agglomerate at the terminal part of a dispense nozzle or a slit die and the inside of an air operator or a pipe made of Teflon or polypropylene is remarkably reduced, by using the composition. CONSTITUTION: The photosensitive coloring composition comprises a resin having a copolymer of at least one kind of compound represented by the formula I and another compound having an ethylenically unsaturated double bond; a monomer; and a colorant, wherein R1 is H or CH3; R2 is an alkylene group of C2-C3; R3 is H or an alkyl group of C1-C20 which may contains a benzene ring; and n is an integer of 1-15. Preferably the another compound having an ethylenically unsaturated double bond is at least one selected from the group consisting of (meth)acrylic acid and (meth)acrylate. The composition comprises further at least one selected from the group consisting of a basic group-having pigment derivative, a basic group-having anthraquinone derivative and a basic group-having triazine derivative.
    公开号:KR20040030286A
    申请号:KR1020030061291
    申请日:2003-09-03
    公开日:2004-04-09
    发明作者:조노시타유키요시；다노우에다다시；이토이다케시；다니미즈히로
    申请人:도요 잉키 세이조 가부시끼가이샤；도판 인사츠 가부시키가이샤；
    IPC主号:
    专利说明:

    Photosensitive coloring composition and color filter {PHOTOSENSITIVE COLORED COMPOSITION AND COLOR FILTER}
    [1] The present invention relates to novel photosensitive coloring compositions and color filters. The photosensitive coloring composition of this invention can be used suitably for image forming materials, such as an optical color filter and a soldering resist. In particular, this invention relates to the photosensitive coloring composition and color filter which can be used suitably for manufacture of the color filter used for a color liquid crystal display device, a color imaging tube element, etc.
    [2] The color filter used for a color liquid crystal display device, a color imaging tube element, etc. forms the color image of fine patterns, such as a stripe form or a mosaic form in which 2 or more types of color tones differ on a transparent substrate like a glass substrate. Although pattern width changes with the use of a color filter and each color, it is about 5-700 micrometers. Moreover, the positional accuracy of the overlapping of the patterns is several micrometers to several tens of micrometers, and the color filter is manufactured by the microfabrication technique with high dimensional precision.
    [3] As a manufacturing method of a color filter, various methods, such as a dyeing method, an electrodeposition method, a printing method, and a pigment dispersion method, are known, but if it considers productivity, quality, cost, etc. comprehensively, in the present state, a pigment dispersion method is the best and a color filter is performed. It is widely adopted as a manufacturing method of the. The pigment dispersion method is a method of forming a color image on a substrate by photolithography using a color resist made of a photosensitive resin composition colored by dispersing an organic pigment to produce a color filter.
    [4] However, in the pigment dispersion method, it is difficult to disperse | distribute a pigment stably, and especially the selection of the dispersion resin which has a big influence on the dispersion stability of a pigment was difficult.
    [5] As a method of apply | coating the said color resist on a glass substrate, application | coating by a spin coater is common, but if a fluidity | liquidity of a pigment is insufficient at this time, a uniform coating film will not be obtained.
    [6] In general, the viscosity of the color resist, which is a pigment dispersion, is known to depend on the shear rate. Since the film thickness of the color resist at the time of spin coating is proportional to the viscosity, in order to obtain a uniform coating film, the viscosity of the color resist applied to the center part and the outer peripheral part of a transparent substrate needs to be the same.
    [7] The apparent viscosity of the color resist when dispensing and rotating the color resist on the substrate is close to the viscosity when the shear rate is low because the linear velocity is slow at the center portion. On the other hand, since the linear velocity is high at the outer periphery of the substrate, the apparent viscosity of the color resist is close to the viscosity when the shear rate is high. Therefore, in the thixotropic color resist, the apparent viscosity becomes high at the center of the substrate having a low shear rate, so that the film thickness is thick, and the film thickness becomes thin at the outer peripheral portion having a high shear rate and high apparent viscosity. Since the color filter requires a uniform film thickness in the substrate, the color resist needs to be a fluid having a uniform viscosity, i.e., a Newtonian fluid, regardless of the magnitude of the shear rate.
    [8] Since the color filter requires especially high transparency, the thing which disperse | distributed fairly fine pigment uniformly in the transparent vehicle is used.
    [9] In the case where the fine particles of the pigment are dispersed in the vehicle, it is difficult to obtain a stable dispersion, which causes various problems in the manufacturing operation and in the value of the obtained product. For example, a dispersion containing a pigment composed of fine particles sometimes exhibits high viscosity, making it difficult to take out or transport products from the disperser of the product, and also, in the case of a bad case, may cause gelation during storage, making it difficult to use. . Moreover, there exist some things which generate | occur | produce a state defect, such as a fall of transparency and a leveling defect, about the coating film of color resist. Therefore, in order to produce a high transparency color filter by the pigment dispersion method, the technique which stably disperses finer pigment is required.
    [10] Moreover, in a color resist, since pigment particles tend to aggregate gradually, a viscosity rises, or thixotropy becomes strong over time, when a color resist is apply | coated by a spin coater, immediately after preparation of a color resist After aging, the film thickness and coating uniformity are different.
    [11] From the above, it is important that the color resist is a Newtonian fluid and its physical properties do not change for a long time.
    [12] Moreover, the color resist may be apply | coated also by slit other than a spin coater, a spin coater, a roll coater, a catheter coater. The color resist is supplied from a chemical tank to a nozzle, a slit die, or the like via a pipe such as Teflon, polypropylene, or an air operated valve.
    [13] Conventional photosensitive coloring compositions have low dispersion stability of pigments, so that when the resist is applied with the coater, insoluble aggregates are generated in pipes such as Teflon and polypropylene, inside the air operator valve, the dispense nozzle, or the slit die tip. In addition, this aggregate causes a foreign material defect in the color filter and significantly reduces productivity.
    [14] In order to solve the various problems mentioned above, the method of using the pigment derivative which has an organic pigment as a mother skeleton and has an acidic group and a basic group as a substituent in a side chain as a dispersing agent is proposed (for example, Japanese Patent Application Office 41). -2466, U.S. Patent No. 2855403, Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 1-247468, and Japanese Patent Application Laid-open No. 3-26767.
    [15] Moreover, use of the copolymer which has an alkyleneoxy group is also proposed (for example, refer Unexamined-Japanese-Patent No. 62-25164, Unexamined-Japanese-Patent No. 4-223468, and Unexamined-Japanese-Patent No. 5-39450). ).
    [16] However, even if such a method is used, a satisfactory effect is not obtained except for some things.
    [17] Therefore, an object of this invention is to provide the photosensitive coloring composition excellent in the dispersion stability of a pigment.
    [18] Moreover, an object of this invention is to provide the color filter which used such a photosensitive coloring composition.
    [19] This invention is a photosensitive coloring composition containing resin, a monomer, and a coloring agent, Comprising: A compound (b) in which the said resin has an ethylenically unsaturated double bond different from at least 1 sort (s) of the compound (a) represented by following General formula (I). It provides a photosensitive coloring composition characterized in that the copolymer resin with at least one kind.
    [20] (I)
    [21] In the formula (I), R 1 is H or CH 3, R 2 has a carbon number of 2 or 3 of an alkylene group, R 3 is hydrogen, or benzene may also include a ring alkyl group having a carbon number of 1 ~ 20, n is 1 It is an integer of ~ 15.
    [22] Moreover, this invention provides the color filter which has a transparent substrate and the color material layer formed on the transparent substrate using the photosensitive coloring composition of this invention.
    [23] Hereinafter, the present invention will be described in more detail.
    [24] The photosensitive coloring composition of this invention contains the copolymer resin of the compound (a) represented by the said General formula (I), and the compound (b) which has another ethylenically unsaturated double bond. This resin (copolymer) prevents agglomeration of the colorant (pigment) contained in the photosensitive coloring composition of the present invention and maintains a finely dispersed state of the pigment, and has a high color transmittance and high color purity. It is important for manufacturing filters.
    [25] The compound (a) represented by general formula (I) which is a structural component of the said resin becomes favorable adsorption / orientation to the pigment surface by the effect of (pi) electron of a benzene ring.
    [26] In general formula (I), alkylene group R <2> contains 2-3 carbon atoms. Moreover, although the alkyl group of R <3> has 1-20 carbon atoms, More preferably, it has 1-10 carbon atoms. When the alkyl group of R 3 has 1 to 10 carbon atoms, the alkyl group is impeded to inhibit the access between the resins and promotes adsorption / orientation to the pigment. However, when the carbon number exceeds 10, the steric hindrance effect of the alkyl group is increased. The adsorption / orientation to the pigment of the benzene ring to which the alkyl group couple | bonds also tends to interfere. This tendency becomes remarkable as the carbon chain length of the alkyl group of R 3 becomes longer, and when carbon number exceeds 20, the adsorption / alignment of the benzene ring to which the said alkyl group couple | bonds extremely falls. As an alkyl group containing the benzene ring represented by R <3> , a benzyl group, 2-phenyl (iso) propyl group, etc. are mentioned.
    [27] Examples of the compound (a) include ethylene oxide (EO) -modified (meth) acrylates of phenol, EO or propylene oxide (PO) -modified (meth) acrylates of paracumylphenol, and EO-modified (meth) acrylates of nonylphenol and nonyl PO modified (meth) acrylate of a phenol, etc. are mentioned. Compound (a) can be used individually or in combination of 2 or more types. Among these compounds, EO or PO-modified (meth) acrylates of paracumylphenol not only have an effect of Electrons of the benzene ring, but also have a three-dimensional effect, and can form a better adsorption / alignment surface with respect to the pigment. Therefore, the effect is higher.
    [28] Compound (b) is a compound having an ethylenically unsaturated double bond, but is a compound different from compound (a). Specific examples of the compound (b) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, ( Iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl ( Meta) acrylate, isobonyl (meth) acrylate, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, 3-chloro-2-acidphosphooxyethyl (meth) acrylic Elate, acid phospho oxy polyethylene glycol mono (meth) acrylate, etc. Compound (b) can be used individually or in combination of 2 or more types.
    [29] The ratio of the compound (a) in the resin of the present invention is 0.1 to 50% by weight, more preferably 10 to 35% by weight. When the ratio of the compound (a) is less than 10% by weight, the dispersion effect of the pigment is lowered, and when it is less than 0.1% by weight, sufficient pigment dispersion effect cannot be obtained. If the content is more than 35% by weight, the hydrophobicity is increased, the developability of the photosensitive coloring composition may be reduced, or it may cause residue. If the content is more than 50% by weight, the compatibility with other components in the photosensitive coloring composition may be increased. It is remarkably lowered, and precipitation of a monomer and a photoinitiator may arise.
    [30] The weight average molecular weight (Mw) of resin (copolymer) of this invention becomes like this. Preferably it is 5000-100000, More preferably, it is 10000-50000.
    [31] As the compound (b), acid phospho oxyethyl (meth) acrylate, acid phospho oxypropyl (meth) acrylate, 3-chloro-2-acid phospho oxyethyl (meth) acrylate, acid phospho oxypolyethylene When the (meth) acrylic acid ester containing phosphoric acid groups, such as glycol mono (meth) acrylate, is used, a higher pigment dispersion effect may be obtained.
    [32] The ratio of this phosphoric acid group containing (meth) acrylic acid ester is 0.5-5 weight%, More preferably, it is 0.1-5 weight%. When the ratio of the phosphoric acid group-containing (meth) acrylic acid ester is less than 0.05% by weight, sufficient pigment dispersion effect is not obtained. Moreover, when it exceeds 10 weight%, the polarity of resin will increase, a development speed will become remarkably fast, or compatibility with other hydrophobic components will fall, and resin will precipitate.
    [33] Moreover, an ethylenic double bond can be introduce | transduced in the side chain of resin (copolymer) of this invention in order to make monomer or resin react, and to improve the sensitivity of the photosensitive coloring composition. Specifically, when resin has reactive functional groups, such as a hydroxyl group, it has a functional group and ethylenically unsaturated group which react with the said reactive functional groups, such as glycidyl (meth) acrylate and 2- (meth) acryloyloxyisocyanate; By reacting the compound, an ethylenic double bond can be introduced into the side chain.
    [34] The copolymer of this invention can be obtained by radically polymerizing compound (a) and compound (b) in 50-150 degreeC for 2 to 10 hours in presence of a radical initiator and inert gas stream. This polymerization reaction can be performed in presence of a solvent as needed.
    [35] Specific examples of the radical polymerization initiator include organic compounds such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, dit-butyl peroxide and t-butylperoxybenzoate. Azo compounds, such as a peroxide and 2,2'- azobisisobutyronitrile. The radical polymerization initiator is preferably used in a proportion of 1 to 20 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer (that is, the sum of the compound (a) and the compound (b)).
    [36] As a solvent which can be used for the said radical polymerization reaction, For example, Acetic ester, such as water and / or a water miscible organic solvent, ethyl cellosolve acetate, a propylene glycol monomethyl ether acetate; Ketones such as cyclohexanone and methyl isobutyl ketone; Xylene, ethylbenzene and the like. Here, as a water miscible organic solvent, alcohol solvents, such as ethyl alcohol, isopropyl alcohol, and n-propyl alcohol, mono or dialkyl ether of ethylene glycol or diethylene glycol, etc. can be illustrated.
    [37] Since the resin of the present invention exhibits excellent dispersing effect on most of the pigments in most cases, when the color material layer of the color filter is formed using the photosensitive coloring composition of the present invention in which the pigment is dispersed by this resin, a color with little pigment aggregate is present. You can get a layer.
    [38] The (polymerizable) monomers constituting the photosensitive colored composition of the present invention cannot be cured by the active energy ray alone with the resin (copolymer) of the present invention, and thus form a pattern of a color filter by irradiation of the active energy ray. Although not possible, hardening by an active energy ray is enabled by adding the monomer (polymerizable monomer) which has this functional group (ethylenic double bond). The monomer containing only one functional group (ethylenic double bond) in one molecule is a monofunctional monomer, and the monomer containing two or more functional groups (ethylenic double bond) in one molecule is a polyfunctional monomer. The greater the number of functional groups (ethylenic double bonds) in one molecule, the higher the reactivity of the monomer. Examples of such monomers include various acrylic acids such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and tricyclodecanyl (meth) acrylate. Monofunctional monomers, such as ester and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile, polyethyleneglycol di (meth) acryl Elate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanedioldi (meth) acrylate , Diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, trimeth Roll propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylic And polyfunctional monomers such as ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate and pentaerythritol tetra (meth) acrylate.
    [39] The pigment as a colorant constituting the photosensitive coloring composition of the present invention is not particularly limited as long as it is usually used. Examples of such pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo and polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal phthalocyanine, amino anthraquinones and diamino dianes. Anthraquinone pigments such as traquinone, anthrapyrimidine, flavantron, anthrone, indanthrone, pyrantrone, and violatron, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, and thioindigo pigments Organic pigments such as isoindolin-based pigments, isoindolinone-based pigments, quinophtharon-based pigments, srenne-based pigments and metal complex pigments, or titanium oxides, zinc oxides, zinc sulfides, lead whites, calcium carbonates and precipitated barium sulfate White Carbon, Alumina White, Kaolin Clay, Talc, Bentonite, Black Iron Oxide, Cadmium Red, Bengala, Molybdenum Red, Molybdate Oren , Chromium Vermilion, Brimstone, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Chromium Oxide, Viridian, Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victorian Green, Ultramarine, Royal Blue, Cobalt Blue, Cerulean Blue, Cobalt Silica Inorganic pigments such as blue, cobalt zinc silica blue, manganese violet and cobalt violet, or carbon black such as acetylene black, channel black and furnace black. It is preferable that these pigments have an average particle diameter of 0.01 micrometer-1 micrometer.
    [40] It is preferable that the photosensitive coloring composition of this invention contains copolymer resin, a monomer, and a coloring agent (pigment) in the ratio of 1-50: 1-10: 1-15 by weight ratio.
    [41] In the photosensitive coloring composition of this invention, at least 1 sort (s) chosen from the pigment derivative which has a basic group, the anthraquinone derivative which has a basic group, or the triazine derivative which has a basic group for the purpose of further improving the effect | action of the copolymer resin of this invention. It is preferable to contain it.
    [42] A pigment derivative is a compound in which a sulfonic acid, an amine, a sulfonamide, or the like is bonded to a mother skeleton of an organic pigment, that is, a group obtained by appropriately removing hydrogen atoms from an organic pigment skeleton, and adsorbed onto the surface of the pigment to prevent the pigment in the photosensitive coloring composition. Dispersion stability can be improved.
    [43] The pigment derivative, anthraquinone derivative or triazine derivative which has a basic group used for this invention has at least 1 substituent which consists of a group represented by following formula (1), (2), (3), and (4). To have.
    [44]
    [45] In the formulas (1) to (4),
    [46] X represents -SO 2- , -CO-, -CH 2 NHCOCH 2- , -CH 2 -or a direct bond.
    [47] m represents the integer of 1-10.
    [48] R 4 and R 5 are each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, or a phenyl group which may be substituted, or are integral with R 4 and R 5 to further form nitrogen, oxygen or sulfur atoms. The heterocyclic ring which may be substituted is shown. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
    [49] R <6> represents the alkyl group which may be substituted, the alkenyl group which may be substituted, or the phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
    [50] R 7 , R 8 , R 9 , and R 10 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
    [51] Y represents -NR 11 -Z-NR 12 -or a direct bond.
    [52] R 11 and R 12 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
    [53] Z represents an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted. As for carbon number of an alkylene group and an alkenylene group, 1-8 are preferable.
    [54] P represents the substituent represented by Formula (5) or the substituent represented by following formula (6).
    [55] Q represents a hydroxyl group, an alkoxyl group, the substituent represented by following formula (5), or the substituent represented by following formula (6).
    [56]
    [57] In Formulas (5) and (6), R 4 to R 10 and m are as defined above.
    [58] The amine component used to form the substituents represented by formulas (1) to (6) is, for example, dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine , N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec -Butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamamine, dihexylamine, di (2- Ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, diddecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleyl Amine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethyl amine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylamino Ethylamine, N, N-diethylaminopropylamine, N, N-diethyl Minohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutyl Aminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2 , 4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecortic acid, isonipecorticate methyl, isonipecortiate ethyl , 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpi Ferridine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methyl homopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine .
    [59] Examples of the organic pigment constituting the pigment derivative having a basic group include azo dyes such as diketopyrrolopyrrole dyes, azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, Anthraquinone pigments such as flavanthrone, ananthrone, indanthrone, pyrantrone, and violatron, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, Isoindolinone pigments, quinophtharone pigments, styrene dyes, and metal complex dyes.
    [60] The anthraquinone derivative which has a basic group may have substituents, such as alkyl groups, such as a methyl group and an ethyl group, an amino group, a nitro group, a hydroxyl group, or an alkoxy group, such as a methoxy group and an ethoxy group, or halogen, such as chlorine.
    [61] The triazine derivative having a basic group may be an alkyl group such as methyl group or ethyl group or an alkyl group such as amino group or dimethylamino group, diethylamino group or dibutylamino group or alkoxy group such as nitro group or hydroxyl group or methoxy group, ethoxy group or butoxy group or Substituted by a phenyl group or methyl group, ethyl group, methoxy group, ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, hydroxyl group, etc. which may be substituted by halogen such as chlorine or methyl group, methoxy group, amino group, dimethylamino group or hydroxyl group It is 1,3,5-triazine which may have substituents, such as the phenylamino group which may be used.
    [62] The pigment derivative or anthraquinone derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, after introducing the substituent represented by following formula (7)-formula (10) to an organic pigment | dye or anthraquinone, the amine component which reacts with the said substituent, and forms Formula (1)-Formula (4), Example For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5- It is obtained by making triazin-2-ylamino] aniline etc. react.
    [63]
    [64]
    [65] Moreover, when an organic pigment | dye is an azo pigment | dye, the azo pigment by introduce | transducing the substituent represented by Formula (1)-Formula (4) beforehand into a diazo component or a coupling component, and performing a coupling reaction after that. It is also possible to prepare derivatives.
    [66] The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, the amine component which uses a cyanuric chloride as a starting material and forms the substituent represented by Formula (1)-Formula (4) in at least 1 chlorine of cyanuric chloride, for example, N, N-dimethyl It is obtained by reacting aminopropylamine or N-methylpiperazine or the like followed by reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.
    [67] The pigment derivative which has the said basic group, the anthraquinone derivative which has a basic group, and / or the triazine derivative which has a basic group can be used in the ratio of 1-30 weight part with respect to 100 weight part of pigments.
    [68] It is also possible to contain pigment dispersants, such as an alkylene oxide polymer, in addition to the said pigment derivative in the photosensitive coloring composition of this invention.
    [69] An alkylene oxide polymer is a polymer which contains an ethylene oxide and / or a propylene oxide unit in a molecule | numerator, and is obtained by adsorb | sucking on the surface of a pigment and / or a pigment dispersant by the amphiphilic property resulting from a hydrophilic group and a hydrophobic group. It improves the dispersion stability of the pigment in the photosensitive coloring composition and at the same time improves the flow characteristics. Pigment dispersants, such as an alkylene oxide polymer, can be used in the ratio of 1-50 weight part with respect to 100 weight part of pigments.
    [70] Moreover, in order to provide the photosensitive coloring composition of this invention with the characteristics, such as alkali developability, adhesiveness, solvent resistance, and heat resistance, in addition to the said resin, general acrylic resin, (alpha) -olefin / (anhydride) maleic acid copolymer, and styrene Resin, such as / (maleic anhydride) copolymer, isobutylene / (maleic anhydride), styrene / styrene sulfonic acid copolymer, and ethylene / (meth) acrylic acid copolymer, can be added suitably. These general resins can be used in the photosensitive coloring composition by the ratio of 1-50 weight%.
    [71] In addition, the photosensitive coloring composition of this invention contains a photoinitiator, when hardening this composition with an ultraviolet-ray.
    [72] Examples of this photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane Acetophenone photoinitiators, such as -1-one, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzo Benzoin photoinitiators such as phosphorus methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, Benzophenone series photoinitiators, such as 4-benzoyl-4'-methyldiphenyl sulfide, a thioxanthone, 2-chlorothioxone, 2-methyl thioxane, an isopropyl thioxane, and 2, 4- diiso Thioxane-based photoinitiators such as propyl thioxane, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trickle) Rommethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloro Rhomethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-tri Azine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-tri Triazine photoinitiators such as azine, carbazole photoinitiators, imidazole series photoinitiators and the like. These photoinitiators can be used individually or in mixture of 2 or more types. A photoinitiator can be used in the ratio of 0.5-80 weight part with respect to 100 weight part of monomers.
    [73] A sensitizer can be used with the said photoinitiator. Examples of the sensitizer include α-acyloxyester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone, canpaquinone, ethylanthraquinone, 4,4'-diethylisophthalo Phenone, 3,3'4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, and the like. A sensitizer can be used in the ratio of 0.1-50 weight part with respect to 100 weight part of photoinitiators.
    [74] Moreover, water, an organic solvent, etc. can be added to the photosensitive coloring composition of this invention, in order to fully disperse a pigment and to apply | coat uniformly thinly on a transparent substrate. An organic solvent can be used individually or in mixture.
    [75] The photosensitive coloring composition of this invention can be manufactured, for example by the following methods 1-4.
    [76] 1. A pigment composition obtained by mixing a pigment and a pigment dispersant (pigment derivative and other pigment dispersant) beforehand into a monomer and copolymer resin or its organic solvent solution or aqueous solution is added, and is disperse | distributed. Even if the pigment composition only mixes and prepares the powder of a pigment powder and a pigment dispersant, the target effect can fully be acquired. However, a solution containing a pigment dispersant is added to a dispersion obtained by mechanically mixing by various mills such as kneader, attritor, roll, super mill, or by dispersing the pigment in water or an organic solvent, and dispersing the pigment on the surface of the pigment. By adsorbing or adhering a pigment and a pigment dispersant to a solvent having a strong dissolving power such as sulfuric acid and co-precipitating with a poor solvent such as water, better results can be obtained.
    [77] 2. A pigment and a pigment dispersant (pigment derivative or other pigment dispersant) added as necessary to a monomer and copolymer resin or its organic solvent solution or aqueous solution are respectively disperse | distributed.
    [78] 3. A pigment and a pigment dispersant (pigment derivative and other pigment dispersant) are previously disperse | distributed to monomer and copolymer resin or its organic solvent solution, or aqueous solution, respectively, and then they are mixed. In this case, you may disperse a pigment dispersant only with a solvent.
    [79] 4. After disperse | distributing a pigment to monomer and copolymer resin or its organic solvent solution, or aqueous solution, a pigment dispersant is added.
    [80] The dispersion of the pigment and the pigment dispersant into the monomer and copolymer resin or the organic solvent solution or the aqueous solution is three roll mill, two roll mill, sand mill, kneader, dissolver, high speed mixer, homo mixer, attritor, etc. This can be performed using various dispersion apparatuses. Moreover, at the time of dispersion, in order to perform dispersion | distribution favorable, various surfactant can be added.
    [81] The photosensitive colored composition of the present invention can remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more of coarse particles and mixed dust by means of centrifugation, sintering filter, membrane filter, or the like. Is done.
    [82] In the production of a color filter using the photosensitive coloring composition of the present invention, after uniformly applying the photosensitive coloring composition of the present invention on a transparent substrate, pattern exposure is performed with active energy rays such as ultraviolet rays and electron beams through a photomask, It is performed by what is called photolithography which wash | cleans a miner part with a solvent or aqueous alkali solution, and obtains a desired pattern.
    [83] The photosensitive coloring composition of this invention is apply | coated by a coating method, such as spray coating, spin coating, roll coating, on a transparent substrate.
    [84] As a transparent substrate, resin, such as a glass plate, a polycarbonate, polymethyl methacrylate, a polyethylene terephthalate, is used.
    [85] At present, due to environmental problems, most solvents are not used for development, and alkali development is becoming mainstream. As the alkaline developer, aqueous solutions of inorganic alkalis such as sodium carbonate and sodium hydroxide, and organic alkalis such as dimethylbenzylamine and triethanolamine are used. It is also possible to add an antifoamer and surfactant to this alkaline developing solution.
    [86] Further, in order to increase the exposure sensitivity, after the photosensitive coloring composition of the present invention is applied and dried, an aqueous solution or an alkali water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film which prevents polymerization inhibition by oxygen. It is also possible to perform exposure after that.
    [87] Hereinafter, the present invention will be described in more detail with reference to Examples. Here, the manufacture example of the copolymer concerning this invention, the manufacture example of the pigment derivative which has a basic group, and the Example of this invention are shown. In addition, the following "%" represents the "weight%." In addition, "part" shows a "weight part." The molecular weight of a copolymer is the weight average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography).
    [88] <Production Example of Copolymer>
    [89] Preparation Example 1
    [90] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the inside of the flask was nitrogen-substituted, followed by n-butyl from the dropping tube. 13.3 parts of methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.) and 2,2'-azobisiso A mixture of 0.4 part of butyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (1) having a solid content of 30%. The weight average molecular weight of this copolymer (1) was 2600.
    [91] Preparation Example 2
    [92] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the inside of the flask was nitrogen-substituted, followed by n-butyl from the dropping tube. 13.3 parts of methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of nonylpheninoxy polyethylene glycol acrylate (Aronix M111 manufactured by Toagosei Co., Ltd.) and 2,2'-azobisiso A mixture of 0.4 part of butyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (2) having a solid content of 30%. The weight average molecular weight of this copolymer (2) was 28000.
    [93] Preparation Example 3
    [94] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80 ° C. -Butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, nonylphenoxy polypropylene glycol acrylate (Aronix M117 by Toagosei Co., Ltd.) 7.4 parts, 2,2'- azo The mixed solution of 0.4 part of bisisobutyronitrile was dripped over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (3) having a solid content of 30%. The weight average molecular weight of this copolymer (3) was 22000.
    [95] Preparation Example 4
    [96] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the nitrogen inside the reaction vessel was replaced with n- from the dropping tube. Butyl methacrylate 13.3 parts, 2-hydroxyethyl methacrylate 4.6 parts, methacrylic acid 4.3 parts, phenoxydiethylene glycol acrylate (Aronix M101 manufactured by Toagosei Co., Ltd.) 7.4 parts, 2,2'-azobis isobuty The mixed solution of 0.4 part of ronitrile was dripped over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (4) having a solid content of 30%. The weight average molecular weight of this copolymer (4) was 26000.
    [97] Preparation Example 5
    [98] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the nitrogen inside the reaction vessel was replaced with n- from the dropping tube. Butyl methacrylate 14.1 parts, 2-hydroxyethyl methacrylate 4.0 parts, methacrylic acid 3.9 parts, paracumyl phenol ethylene oxide modified acrylate (Aronix M110 by Toagosei Co., Ltd.) 7.4 parts, acid phosphooxy ethyl methacrylate A mixed solution of 0.3 part of late (Homer M made by Nihon Kayaku Co., Ltd.) and 0.3 part of 2,2'-azobisisobutyronitrile was dripped over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (5) having a solid content of 30%. The weight average molecular weight of this copolymer (5) was 30000.
    [99] Preparation Example 6 (Comparative Example 1)
    [100] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the nitrogen inside the reaction vessel was replaced with n- from the dropping tube. A mixed solution of 17.7 parts of butyl methacrylate, 6.1 parts of 2-hydroxyethyl methacrylate, 5.8 parts of methacrylic acid and 0.4 part of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain a solution of the desired copolymer (6) having a solid content of 30%. The weight average molecular weight of this copolymer (6) was 27000.
    [101] Preparation Example 7 (Comparative Example 2)
    [102] 70.0 parts of cyclohexanone was put into a separate four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80 ° C, and the inside of the flask was nitrogen-substituted. 21.5 parts of butyl methacrylates, 4.0 parts of 2-hydroxyethyl methacrylates, 3.9 parts of methacrylic acid, 0.3 parts of 2,2'- of acid phosphooxy ethyl methacrylate (Hommer-M by Nippon Kayaku Co., Ltd.) The mixed solution of 0.3 part of azobis isobutyronitrile was dripped over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of the desired copolymer (7) having a solid content of 30%. The weight average molecular weight of this copolymer (7) was 31000.
    [103] <Production of Pigment Derivatives Having Basic Groups>
    [104] Preparation Example 8
    [105] After chlorosulfonation of 50 parts of copper phthalocyanine as a pigment component, the reaction was carried out with 14 parts of N, N-dimethylaminopropylamine as an amine component to obtain 62 parts of a pigment derivative (1) having the following structure.
    [106] Pigment Derivatives (1):
    [107]
    [108] In said formula, CuPc represents a copper phthalocyanine residue.
    [109] Preparation Example 9
    [110] After chloromethylating 50 parts of copper phthalocyanine which is a pigment | dye component, it was made to react with 40 parts of dibutylamine which is an amine component, and 95 parts of pigment derivatives (2) of the following structure were obtained.
    [111] Pigment derivative (2):
    [112]
    [113] In said formula, CuPc represents a copper phthalocyanine residue.
    [114] Preparation Example 10
    [115] The pigment derivative (3) of the following structure was obtained by the method similar to the manufacture example 8 using diphenyl diketopyrrolopyrrole as a pigment component and N-aminopropyl morpholine as an amine component.
    [116] Pigment derivatives (3):
    [117]
    [118] Preparation Example 11
    [119] The pigment derivative (4) of the following structure was obtained by the method similar to the manufacture example 8 using the compound represented by following formula (11) as a amine component using dioxazine violet (Pigment Violet 23) as a pigment component.
    [120]
    [121] Pigment Derivatives (4):
    [122]
    [123] Preparation Example 12
    [124] Pigment derivative (5) having the following structure was reacted by reacting 50 parts of diaminodianthraquinone (Pigment Red 177) serving as a pigment component with 42 parts of cyanuric chloride and 28 parts of N, N-dimethylaminopropylamine forming an amine component. Got wealth.
    [125] Pigment Derivatives (5):
    [126]
    [127] Preparation Example 13
    [128] Pigment derivative (6) of the following structure by diazo-coupling 50 parts of a diazo component which has an amine component represented by following formula (12), and 30 parts of coupler component 5-acetoacetylaminobenzimidazolone (6) 79 Got wealth.
    [129]
    [130] Pigment derivative (6):
    [131]
    [132] In the same manner as in Production Examples 8-13, the dye component, anthraquinone or triazine and the amine component are reacted or the compound having an amine component is subjected to a coupling reaction to synthesize the dye, which is used in the present invention. Various pigment derivatives can be prepared.
    [133] Examples 1-10, Comparative Examples 1-6
    [134] <Preparation and evaluation of pigment resist (photosensitive coloring composition)>
    [135] Using zirconia beads, the dispersion 1 and the dispersion 2 of the composition shown in Table 1 were prepared with the planetary ball mill. In the example (Examples 1-7, Example 10, Comparative Examples 1-4, and Comparative Example 6) which used the dispersion 1 and the dispersion 2, after mixing both dispersions, it disperse | distributed the other to the mixture. In the example using only the sieve 1 (Examples 8-9 and Comparative Example 5), the mixed solvent (cyclohexanone / propylene glycol monoethyl ether acetate (weight ratio 6/4) in the proportion shown in Table 1 in the dispersion (1) )), Copolymers, polyfunctional monomers (dipentaerythritol hexaacrylate), photoinitiators (2-methyl-1-[(4-methylthio) phenyl-2-morpholinopropan-1-one) and sensitizers ( 4,4'-bis (diethylamino) benzophenone) was mix | blended, and it filtered with the filter of 1 micrometer, and prepared the pigment resist.
    [136] The viscosity of the obtained pigment resist was measured by EL type viscometer (temperature 25 degreeC). In order to examine the occurrence of aggregates, the obtained pigment resist was circulated in a Teflon tube for 72 hours, and then spin-coated to a glass substrate of 100 × 100 mm, dried, followed by exposure, development, and post-baking. Created. The number of aggregates of this color filter was counted. The results are shown in Table 1.
    [137]
    [138]
    [139] From the results shown in Table 1, it was found that the photosensitive colored composition of the present invention has extremely low generation of aggregates in piping and the like and is excellent in dispersion stability of the pigment.
    [140] As mentioned above, this invention provides the photosensitive coloring composition which is excellent in the dispersion stability of a pigment and excellent in fluidity | liquidity. Moreover, by using this photosensitive coloring composition, the color resist which remarkably reduced generation | occurrence | production of insoluble aggregate in piping, such as Teflon and polypropylene, an air operator valve, a dispensing nozzle, or a slit die tip part, can be obtained. . In addition, by using such a color resist, it is possible to obtain a color filter with extremely low foreign material defects.
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] As a photosensitive coloring composition containing a resin, a monomer and a coloring agent, the resin is represented by the following general formula (I):
    (I)
    (Wherein R 1 is H or CH 3 , R 2 is an alkylene group having 2 or 3 carbon atoms, R 3 is hydrogen or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 15 Photosensitive coloring composition characterized by the above-mentioned. It is a copolymer resin with at least 1 sort (s) of the compound (a) and at least 1 sort (s) of the compound (b) which has another ethylenically unsaturated double bond.
    [2" claim-type="Currently amended] The photosensitive coloring composition according to claim 1, wherein the compound (b) is at least one compound selected from the group consisting of (meth) acrylic acid and (meth) acrylic acid ester.
    [3" claim-type="Currently amended] The photosensitive colored composition according to claim 2, wherein the resin is a copolymer resin of the compound (a), (meth) acrylic acid and (meth) acrylic acid ester.
    [4" claim-type="Currently amended] The said resin is a copolymerization resin of 10-35 weight% of a compound (a), 10-55 weight% of (meth) acrylic acid, and 10-80 weight% of (meth) acrylic acid ester, The said resin is characterized by the above-mentioned. Photosensitive coloring composition.
    [5" claim-type="Currently amended] The photosensitive coloring composition according to claim 1, wherein the compound (a) is ethylene oxide or propylene oxide modified (meth) acrylate of paracumylphenol.
    [6" claim-type="Currently amended] The photosensitive colored composition according to claim 1, wherein the compound (b) is a (meth) acrylic acid ester containing a phosphoric acid group.
    [7" claim-type="Currently amended] The photosensitive coloring composition according to claim 1, wherein the resin has an ethylenic double bond in the side chain.
    [8" claim-type="Currently amended] The photosensitive coloring composition according to claim 1, further comprising at least one selected from a pigment derivative having a basic group, an anthraquinone derivative having a basic group or a triazine derivative having a basic group.
    [9" claim-type="Currently amended] A color filter provided with a transparent substrate and the color material layer formed on the transparent substrate using the photosensitive coloring composition of Claim 1.
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    同族专利:
    公开号 | 公开日
    CN100517066C|2009-07-22|
    KR100889301B1|2009-03-18|
    TWI280458B|2007-05-01|
    JP2004101728A|2004-04-02|
    CN1492283A|2004-04-28|
    JP4133137B2|2008-08-13|
    TW200413487A|2004-08-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-09-06|Priority to JPJP-P-2002-00261674
    2002-09-06|Priority to JP2002261674A
    2003-09-03|Application filed by 도요 잉키 세이조 가부시끼가이샤, 도판 인사츠 가부시키가이샤
    2004-04-09|Publication of KR20040030286A
    2009-03-18|Application granted
    2009-03-18|Publication of KR100889301B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2002-00261674|2002-09-06|
    JP2002261674A|JP4133137B2|2002-09-06|2002-09-06|Photosensitive coloring composition|
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