JP4942928B2 - Color filter resin, photosensitive resin composition, and color filter - Google Patents

Description

  The present invention relates to a color filter used in a liquid crystal display, a plasma display, an electroluminescence panel, a color video camera, and the like, a photosensitive resin usable for the color filter, a method for producing the photosensitive resin, and a photosensitive resin composition. About.

  Since the photosensitive resin composition can be polymerized and cured by irradiating with ultraviolet rays or electron beams, it can be used for photocurable ink, photosensitive printing plate, printed wiring board, various photoresists, color filters, and the like. Is used.

  In recent years, there has been a demand for further reduction in weight and thickness of electronic devices. In color filters, a colored layer and a black matrix having a fine pattern are maintained with sufficient aperture ratio and sufficient color purity and contrast. A photosensitive resin composition that can be patterned with high accuracy is desired.

  As such a photosensitive resin composition, for example, there is a technique of using a composition in which a colorant such as a pigment and a dye is blended at a high concentration in an alkali-developable photosensitive resin composition. However, since light is shielded by an increase in the amount of the colorant, there is a problem that the sensitivity of the photosensitive resin composition is lowered, the exposure time necessary for a sufficient effect is lengthened, and the productivity is deteriorated.

Moreover, there exists the method of using the radiation sensitive resin composition which mix | blends a coloring agent with high density | concentration as a photosensitive resin composition, and contains alkali-soluble unsaturated resin (for example, refer patent documents 1 thru | or 5). However, even if these compositions were used, sufficient sensitivity could not be obtained, and fine pattern processing of the colored layer and the black matrix could not be performed.
Japanese Patent No. 3148429 Japanese Patent No. 3509269 JP-A-8-278629 JP-A-8-314131 Japanese Patent Laid-Open No. 11-84126

  An object of the present invention is to apply a colored photosensitive resin composition for a color filter so that a colored layer having sufficient color purity and a black matrix having sufficient light shielding properties are formed with high pattern accuracy. Another object of the present invention is to provide a resin for a color filter capable of miniaturizing a black matrix.

  Further, the object of the present invention is high sensitivity, and when applied to a colored photosensitive resin composition for a color filter, a colored layer having sufficient color purity and a black matrix having sufficient light shielding properties are patterned. It is an object of the present invention to provide a photosensitive resin composition that is formed with high accuracy and is capable of miniaturizing a colored layer and a black matrix.

  Still another object of the present invention is to provide a color filter in which a colored layer having sufficient color purity and a black matrix having sufficient light shielding properties are formed with high pattern accuracy, and the colored layer and the black matrix can be miniaturized. There is to do.

The color filter resin of the present invention is represented by the following formula (1), and is subjected to heat treatment, whereby a part thereof dissociates and volatilizes, and the weight is 85% by weight with respect to the weight before the heat treatment. It is characterized by decreasing to the following.

In the formula, X is a main skeleton portion of a polymer of an ethylenically unsaturated compound represented by the following formula (2) or a main skeleton portion of a condensate of an aromatic compound represented by the following formula (3). ,

n is an integer of 1 to 2, m is an integer of 10 to 1000,
l is an integer from 1 to 50;
R ₁ is hydrogen or a methyl group,
R ₂ is an alkylene group having a straight or branched chain having 2 to 8 carbon atoms R ₃ is an alkylene group having a straight or branched chain having 1 to 18 carbon atoms, an alkylene having an alicyclic skeleton A group selected from the group consisting of a group, an alkylene group having an alicyclic skeleton having one or more unsaturated bonds, and a hydrocarbon group having an aromatic skeleton,
R ₄ is selected from the group consisting of hydrogen, —CH ₂ CH ₂ OR ₆ (R ₆ is an alkyl group having a linear or branched chain having 2 to 8 carbon atoms and a hydroxyalkyl group), and a cyclic ether group. And R ₅ is a group selected from the group consisting of hydrogen, an acryloyloxy group, and a methacryloyloxy group.

  In addition, the photosensitive resin composition of the present invention contains the color filter resin, a photopolymerizable monomer, and a photopolymerization initiator, and is subjected to heat treatment, so that the volume becomes the volume before the heat treatment. On the other hand, it is reduced to 85% by volume or less.

  Furthermore, the color filter of the present invention is a color filter comprising a substrate, a black matrix formed on the substrate, and a colored layer formed on the substrate surface provided with the black matrix. At least one of the layer and the black matrix is formed by patterning a resin composition containing the color filter resin and the colorant according to claim 1 and then performing a heat treatment. .

  According to the present invention, the colorant concentration in the color layer and the black matrix subjected to the heat treatment after pattern processing can be reduced by using the color filter resin whose volume becomes smaller than the volume before the heat treatment. High quality that can make the colored layer and the black matrix finer and thinner without sacrificing the color purity and light shielding layer characteristics, etc. A simple color filter can be obtained easily.

  The color filter resin of the present invention is represented by the above formula (1) and is subjected to heat treatment, whereby the weight thereof is reduced to 85% by weight or less with respect to the weight before the heat treatment.

  In addition, the photosensitive resin composition of the present invention contains the color filter resin, a photopolymerizable monomer, and a photopolymerization initiator, and is subjected to heat treatment, so that the volume becomes the volume before the heat treatment. However, it is reduced to 85% by volume or less.

  Furthermore, the color filter of the present invention uses the above photosensitive resin composition, and the substrate, the black matrix formed on the substrate, and the coloring formed on the substrate surface provided with the black matrix. The colored layer is formed by patterning by exposing and developing the colored photosensitive resin composition containing the photosensitive resin composition and the colorant, and then performing a heat treatment. .

  Preferably, the black matrix can be formed, for example, by photolithography or printing using the color filter resin. Examples of the printing method include reverse printing.

  According to the present invention, when the heat treatment is performed, the resin layer is formed using the composition containing the color filter resin whose weight is reduced to 85% by weight or less with respect to the weight before the heat treatment. The weight and volume of the obtained resin layer are reduced.

  Moreover, when this resin for color filters is mix | blended with the photosensitive resin composition, the photosensitive resin layer is formed and it heat-processes, the weight and volume of the obtained resin layer will reduce.

  Furthermore, when a colorant is blended in this photosensitive resin composition to form a colored photosensitive resin layer and subjected to heat treatment, the weight and volume of the resulting photosensitive resin layer are reduced, and as a result The agent concentration becomes higher than the colorant concentration before the heat treatment. Using this, the colorant concentration in the colored photosensitive resin composition at the time of pattern processing is adjusted to a concentration that is highly sensitive to exposure light, and the colorant concentration after heat treatment is colored with sufficient color purity The concentration can be adjusted to obtain a layer, or to obtain a black matrix having sufficient light shielding properties.

  Further, according to the present invention, a composition containing, for example, an ink composition containing a resin for a color filter whose weight is reduced to 85% by weight or less with respect to the weight before the heat treatment is obtained by heat treatment. The matrix can be patterned and then heat treated. As a result, the colorant concentration after the heat treatment can be made higher than the colorant concentration in the ink composition during pattern processing by printing, and a black matrix having sufficient light shielding properties can be obtained.

  As described above, by using the present invention, it is possible to easily obtain a color filter having good pattern accuracy and capable of miniaturizing the colored layer and the black matrix without impairing the color purity and characteristics of the light shielding layer. it can.

  Moreover, in the photosensitive resin composition of this invention, the volume reduction after a heating is 85 volume% or less with respect to the volume before a heating, Preferably it is 85 volume%-65 volume%. If it exceeds 85% by volume, there is a disadvantage that the pigment concentration in the colored layer cannot be increased. If it is less than 65% by volume, the chemical resistance, light resistance and heat resistance of the colored layer film tend to deteriorate.

  Furthermore, the temperature for heating the color filter resin used in the present invention and the composition containing the same is preferably 100 ° C. to 300 ° C. If the temperature is lower than 100 ° C, the decomposition of the resin does not proceed sufficiently, and the light shielding property tends to be insufficient. If the temperature exceeds 300 ° C, the residual resin decomposes more than the setting, and the chemical resistance of the film, light resistance, There is a tendency for heat resistance to deteriorate.

In this color filter resin, the weight ratio of the acid anhydride in the solid content is preferably 10 to 50% by weight, more preferably 15 to 30% by weight. When the weight ratio of the acid anhydride in the solid content of the photosensitive resin is less than 10% by weight, the volume of the resin after heating tends to exceed 85% by volume with respect to the volume of the resin before heat treatment. When it becomes larger, the acid anhydride addition reaction tends to become difficult.

In the color filter resin according to the present invention, the acid value is preferably 1 to 150, more preferably 5 to 50, in terms of solid content.

  When the acid value exceeds 150, developability becomes too high in alkali development, and the development speed is too high, and problems such as the surface of the exposed portion being eroded by the developer tend to occur.

  In order to obtain the color filter resin of the present invention, for example, an acrylic resin or a novolac resin can be used.

  As the novolac resin, for example, phenol novolac epoxy resin, cresol novolac epoxy resin, or the like can be used.

  By adding a carboxylic acid having an ethylenically unsaturated group such as (meth) acrylic acid as a carboxyl group-containing compound to these novolac epoxy resins, a photosensitive polyvalent hydroxyl group-containing resin can be obtained.

  The material of the acrylic resin is, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) as a monomer. Alkyl (meth) acrylates such as acrylate pendyl (meth) acrylate, lauryl (meth) acrylate, hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, Use ether group-containing (meth) acrylates such as glycidyl (meth) acrylate and alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. The polymer and the like. In addition, these monomers can be used individually or in combination of 2 or more types. Furthermore, compounds such as styrene, cyclohexylmaleimide, and phenylmaleimide that can be copolymerized with these acrylates can be copolymerized.

  Further, for example, it is possible to obtain a non-photosensitive resin having a plurality of hydroxyl groups by homopolymerization of (meth) acrylate having a hydroxyl group such as hydroxyethyl acrylate or copolymerization thereof with other (meth) acrylates. .

  In addition, for example, carboxylic acid having an ethylenically unsaturated group such as (meth) acrylic acid is monopolymerized or copolymerized, and the resulting resin is reacted with an epoxy group-containing compound such as glycidyl methacrylate, and is photosensitive. A resin having a plurality of hydroxyl groups can be obtained.

  Furthermore, for example, by adding a carboxylic acid-containing compound such as (meth) acrylic acid to a resin of homopolymerization of epoxy-containing (meth) acrylate such as glycidyl methacrylate or copolymerization of these with other (meth) acrylate, Yes, a resin having a plurality of hydroxyl groups can be obtained.

  The polymerization of each acrylic resin can be carried out with a compound such as styrene, cyclohexylmaleimide, phenylmaleimide and the like. An ethylenically unsaturated group can be introduced into the acrylic polymer to form a photosensitive resin.

  Further, for example, a resin having a hydroxyl group containing, for example, hydroxymethacrylate as a monomer is reacted with an isocyanate group such as methacryloyloxyethyl isocyanate and a compound having an ethylenically unsaturated group so as to leave an unreacted hydroxyl group. A resin having a hydroxyl group can be obtained.

  The hydroxyl group of the resin having a plurality of hydroxyl groups thus prepared can be reacted with a polybasic acid anhydride to introduce a carboxyl group into the resin to obtain a resin having a carboxyl group. The method is not limited to the method described above.

  Examples of acid anhydrides used in the above reaction include, for example, malonic acid anhydride, succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride , Methyltetrahydrophthalic anhydride, trimellitic anhydride and the like.

  The acid group is adjusted by reacting the carboxyl group of the resin with a compound that reacts reversibly, and the color filter resin of the present invention is obtained. For example, the compound that reacts reversibly with the carboxylic acid can be dissociated from the skeleton of the color filter resin by heat treatment and evaporated to reduce the volume of the resin.

Examples of compounds which reversibly reacts with a carboxylic acid, isobutyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, diethylene glycol monomethyl ether, dihydropyran, and tetrahydrofuranyl chloride, and the like.

  The photosensitive resin composition according to the present invention contains at least a photopolymerizable monomer and a photopolymerization initiator in addition to the color filter resin described above.

  The addition amount of the photopolymerizable monomer is preferably 300 to 3 parts by weight with respect to 100 parts by weight of the color filter resin. When the amount is less than 3 parts by weight, there is a tendency that sufficient sensitivity cannot be obtained. When the amount exceeds 300 parts by weight, a change of 85% by volume or less tends not to be obtained.

  The addition amount of the photopolymerization initiator is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the color filter resin. If the amount is less than 0.1 parts by weight, the photopolymerization rate tends to be low and the sensitivity tends to decrease. If the amount is more than 30 parts by weight, the adhesion to the substrate or the like tends to decrease.

  Examples of the photopolymerizable monomer include monomers containing a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, such as ethylene glycol di (meth) acrylate and diethylene glycol. Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include (meth) acrylic acid esters such as rutetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate, and these can be used alone or in admixture of two or more. .

  Examples of the photopolymerization initiator include acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone. Benzophenones, for example, benzophenones such as 2-chlorobenzophenone, p, p-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, such as benzyldimethyl ketal , Teoxaneson, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Anthraquinones such as 2-ethylanthraquinone octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, such as 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine, 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine Triazines such as azopisisobutyronitrile, organic peroxides such as benzoyl peroxide, cumene peroxide, and thiols such as 2-mercaptobenzimidazole, 2-mercaptopentazoxazole, 2-mercaptopentazothiazole, etc. Compounds, etc. These alone or may be used in combination of two or more.

  In addition, a compound that does not function as a photopolymerization initiator alone but increases the ability of the photopolymerization initiator when used in combination with the above compound can be added as necessary. Examples of such compounds include tertiary amines such as triethanolamine that are effective when used in combination with benzophenone.

  A colorant can be added to the photosensitive resin composition according to the present invention and used for a colored layer constituting a pixel portion of a color filter. In addition, a black colorant can be added to the photosensitive resin composition and used for a black matrix provided between the pixel portions. Examples of the colorant include pigments and dyes. A pigment can be preferably used from the viewpoint of heat resistance and light resistance. As the pigment, red (Red), C.I. I. No. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, etc. I. Pig. 7, 36, C. blue as blue. I. No. 15, 22, 60, 64, etc., yellow as C.I. I. No. Violet such as 20, 24, 83, 86, 93, 109, 117, 139, and 153 includes C.I. I. No. 19, 23, 29, 30, 40, 50, etc. I. No. 7 or the like is generally used.

  In order to further improve the workability during dispersion, the photosensitive resin composition of the present invention can be diluted by adding a solvent.

  Solvents include methanol, ethanol, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve, methyl cellosolve acetate, diglyme, cyclohexanone, ethylbenzene, xylene, isoamyl acetate, n amyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, ethylene glycol monobutyl Ether acetate, triethylene glycol, triethylin glycol monomethyl ether, triethylin glycol monomethyl ether acetate, triethylene glycol monoethyl ether, triethylene glycol monoethyl ether acetate, liquid polyethylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate , Dipropylene glycol monoethyl ether, dipropylene glycol monoethyl ether acetate, lactic acid ester, and ethyl ethoxypropionate. These can be used alone or in admixture of two or more. Moreover, various additives etc. can be mix | blended within the range which does not impair the effect of this invention.

  In order to apply the photosensitive resin composition and the colorant on the substrate, a dispersion liquid containing them can be prepared. These materials described above can be kneaded using a disperser such as a two-roll mill, a three-roll mill, a sand mill, and a paint conditioner.

  FIG. 1 is a cross-sectional view illustrating a configuration of an example of the color filter of the present invention.

  The color filter 10 of the present invention includes a substrate 1 and a plurality of colors composed of a plurality of colored layers 2 arranged on the substrate 1 in a predetermined pattern, for example, a red colored layer 2R, a green colored layer 2G, and a blue colored layer 2B. And a black matrix 3 that shields light between adjacent colored layers 2, and at least a part of the colored layer 2 and the black matrix 3 is formed using the color filter resin of the present invention. .

  On these pixel portions and the black matrix, an overcoat layer 4 can be optionally formed to protect them.

  The substrate that can be used in the color filter of the present invention preferably has a certain degree of rigidity and smoothness, and when the color filter is used as a transmission type, a substrate having further transparency is selected. .

  Examples of the substrate include a substrate having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, a polyimide substrate, an Al substrate, and a GaAs substrate.

  These substrates can be subjected to pretreatment such as chemical treatment with a chemical such as a silane coupling agent, plasma treatment, ion plating treatment, sputtering treatment, gas phase reaction treatment, and vacuum deposition treatment.

  When a silicon substrate is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT), or the like can be formed on the surface of the silicon substrate or the like.

  The black matrix is printed by using the ink containing the color filter resin of the present invention, or by photolithography using the photosensitive resin composition containing the color filter resin of the present invention, or other photosensitive resin. The composition or a metal such as chromium can be formed on the substrate.

  Hereinafter, an example of a method for producing a color filter of the present invention using photolithography will be described with reference to FIGS.

  First, as shown in FIG. 2, a transparent substrate 5 such as glass on which the black matrix 3 is formed is prepared.

  Next, a colored photosensitive resin composition containing a colorant of each color and the photosensitive resin composition of the present invention is prepared according to the colored layers of, for example, red, green, and blue, and among them, for example, as shown in FIG. Then, after applying the green photosensitive resin composition by spin coating, heating is performed, for example, at 100 ° C. for 3 minutes to dry volatile components such as a solvent (prebaking), and the green photosensitive resin layer 6 Form.

  As a method for applying the colored photosensitive resin composition, for example, a known method such as a spray coating method, a spin coating method, a roll coating method, or a curtain coating method can be used.

  Next, after cooling, as shown in FIG. 4, the green photosensitive resin layer 6 is exposed to active energy rays through a photomask 9 having a predetermined pattern using, for example, an ultrahigh pressure mercury lamp as a light source.

  Thereafter, the unexposed area is developed with an alkaline developer such as a 2, 5% aqueous sodium carbonate solution, washed thoroughly with water, and further washed with water and dried. In this way, as shown in FIG. 5, a patterned green colored layer 11G is obtained on the transparent substrate 5 on which the black matrix 3 is formed. An antifoaming agent or a surfactant can be added to the developer as necessary. After the development, for example, heat treatment is performed at 230 ° C. for 60 minutes to perform main curing (post-bake). By repeating this until the pixel portion having the desired number of colors is formed, the colored layer is patterned, for example, the blue colored layer patterned using the blue photosensitive resin composition is converted into the red photosensitive resin composition. A red colored layer patterned with the object is obtained. In this way, the color filter of the present invention can be obtained.

  As an alkali component of the alkali developer, for example, sodium hydroxide, sodium carbonate, or the like can be used.

  FIG. 6 is a cross-sectional view illustrating the configuration of the color filter obtained.

  As shown in the figure, the color filter 20 is composed of a transparent substrate 5 and a colored layer 2 arranged in a predetermined pattern, for example, a plurality of color pixel portions composed of a red colored layer 11R, a green colored layer 11G, and a blue colored layer 11B. The black matrix 3 that shields light between the adjacent colored layers 11R, 11G, and 11B.

  This method can be applied not only when the pixel portion is formed but also when a black matrix is provided.

  Further, the colored photosensitive resin composition can be once applied onto a transfer support member such as a transfer cylinder (so-called blanket) or a transfer film to perform the above pattern processing, and then transferred to a substrate.

  As an active light source used for exposure, light having a wavelength of 300 to 450 nm such as an ultraviolet electron beam can be used. For example, light irradiated from ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, or the like is used. be able to.

  The color filter using the colored photosensitive resin composition of the present invention has different components depending on the application, and there is no limitation on the configuration, but in general, the color filter is patterned on the transparent substrate and the transparent plate. The plurality of color pixel portions are arranged in such a manner that white light incident on the pixel portions is colored in the color of the pixel portions. In liquid crystal displays, plasma displays, electroluminescence panels, etc., light from a light source built in the display or sunlight incident on the screen of the display is used as incident light. Enables display of the screen. Moreover, in a color video camera, a digital camera, etc., it is provided as a component part of a solid-state image sensor, and can play a role of splitting light incident from an imaging target. Here, the dispersed light is converted into an electric signal by a light receiving element, and recording this enables recording of a color image.

  Examples of the black colorant used in the black matrix include carbon black, graphite, iron black, aniline black cyanine black, and titanium black. Carbon black is preferred from the standpoints of light-shielding properties and image characteristics. Specifically, for example, trade names “MA7”, “MA8”, “MA11”, “MA100”, “MA220”, “MA230”, “# 52”, “# 50”, “# 47” manufactured by Mitsubishi Chemical Corporation ”,“ # 45 ”,“ # 2700 ”,“ # 2650 ”,“ # 2200 ”,“ # 1000 ”,“ # 990 ”,“ # 900 ”, etc., trade names“ Printex95 ”,“ Printex90 ”manufactured by Tegusa "," Printex85 "," Printex75 "," Printex55 "," Printex45 "," Printex40 "," Printex30 "," Printex3 "," PrintexA "," PrintexG "," SpecialBlackP "," 250Bc " And "Spe Product names “Monarch460”, “Monarch430”, “Monarch280”, “Monarch120”, “Monarch800”, “Monarch4630”, “REGAL99”, “REGAL99R”, “REGAL415”, “REGAL415”, “CialBlack100” “REGAL250”, “REGAL250R”, “REGAL330”, “BLACK PEARLS480”, “BLACK PEARLS130”, etc., manufactured by Columbian Carbon Co., Ltd. "RAVEN410", "RAVEN420", "RAVEN450", "RAVEN500", "RA EN780 "," RAVEN850 "," RAVEN890H "," RAVEN1000 "," RAVENl020 "," RAVEN1040 ", and the like.

  Hereinafter, the present invention will be specifically described with reference to examples.

Example 1
Synthesis of a resin having a plurality of carboxyl groups A five-necked reaction vessel having an internal volume of 2 liters was prepared. In this vessel, 486 g of propylene glycol monomethyl ether acetate (PGMAc) as a solvent and cresol novolac epoxy as a novolac-based epoxy resin 264 g of resin (“YDCN-704” epoxy equivalent: 205 manufactured by Tohto Kasei Co., Ltd.), acrylic acid 969, methoquinone (MQ) 0.07 g, and triphenylphosphine (TPP) 1.8 g as a carboxyl group-containing compound, air The mixture was heated at 100 ° C. for 35 hours while blowing, to obtain an acrylic acid adduct solution of a polyhydric alcohol compound and photosensitivity.

  Furthermore, 136 g of tetrahydrophthalic anhydride was added as a polybasic carboxylic acid anhydride to the resulting acrylic acid adduct solution of the novolak resin and heated at 70 ° C. for 24 hours to obtain an acid anhydride adduct solution. .

Furthermore, 69 g of isobutyl vinyl ether is added as a compound that reacts reversibly with a carboxylic acid that reacts reversibly, and heated at 70 ° C. for 15 hours, and has the same structure as the above formula (1), provided that the formula (1 ), N is 1, x is represented by the above formula (3), l is an integer of 5 to 40, R ₁ is a methyl group, R ₂ is a propylene group, R ₃ is a cyclohexene ring, and R ₄ is —CH _2. A photosensitive resin in which CH ₂ OR ₆ was used, R ₅ was an acryloyloxy group, and R ₆ was an isobutyl group was obtained.

  When 10 mg of the obtained photosensitive resin was heated at 230 ° C. for 60 minutes and its weight change measurement (under a nitrogen gas atmosphere) was performed, the weight change was reduced by 30% by weight with respect to the photosensitive resin before heating. .

Preparation of photosensitive resin composition To 6.5 g of the obtained photosensitive resin, 2.5 g of dipentaerythritol hexaacrylate as a photopolymerizable monomer and 1.8 g of benzophenone as a photopolymerization initiator were added. A functional resin composition was obtained.

Preparation of colored photosensitive resin composition To the obtained photosensitive resin composition, 48 g of carbon black dispersion (EX-2777 manufactured by Mikuni Dye Co., Ltd.) as a colorant and 27 g of ethyl cellosolve as a solvent were added and stirred well. A black colored photosensitive resin composition was obtained.

Pattern processing using colored photosensitive resin composition After spin-coating r-glycidoxypropyl methylethoxysilane on a substrate and spin-drying it, the colored photosensitive resin composition was spin-coated (800 rpm, 40 Seconds) and allowed to dry. After heating at 100 ° C. for 3 minutes, exposure was performed using a mask having a pixel size of 30 μm × 100 μm and an ultrahigh pressure mercury lamp as a light source. Next, after developing with a 2.5% aqueous sodium carbonate solution, wash well with water, and after drying, heat treatment is performed at 230 ° C. for 60 minutes to fix the pattern, and the black colored layer thus patterned is formed on the substrate as a black matrix. Formed.

Test and Evaluation The following tests and evaluations were performed using the obtained colored photosensitive resin composition.

Measurement of light-shielding property Light-shielding property is an OD value, and the approximate OD value is a value representing the extent to which a substance absorbs light. When the optical path length is constant, the larger the OD value, the higher the concentration of the colorant. . A film having a thickness of about 1 μm is formed on a glass plate having a thickness of 1.1 mm using the above colored photosensitive resin composition, and the coated film is then coated with a Macbeth (registered trademark) densitometer (TR-927 orthomatic type). Was used to determine the OD value. The results are shown in Table 1 below.

Measurement of sensitivity The obtained colored photosensitive resin composition is exposed to light at an exposure amount of 100 mJ / cm ² for about 3 seconds using an ultra-high pressure mercury lamp, and developed with a 2.5% aqueous sodium carbonate solution. It was confirmed whether it was cured. In this case, the effect was evaluated as a. Moreover, photocuring was insufficient at 100 mJ / cm ² , exposure was performed for about 6 seconds at an exposure amount of 200 mJ / cm ² , and development with a 2.5% aqueous sodium carbonate solution was evaluated as b. . The results are shown in Table 1 below.

Measurement and Evaluation of Remaining Film Ratio After the colored photosensitive resin composition was spin-coated on a substrate and spin-dried, the film thickness A of the applied colored photosensitive resin layer was measured. Further, an ultrahigh pressure mercury lamp was used as a light source, and exposure was performed at an exposure amount of 200 mJ / cm ² . Next, after developing with a 2.5% aqueous sodium carbonate solution, washing thoroughly with water and further drying, baking was performed at 230 ° C. for 1 hour to fix the pattern, and the thickness B of the resulting colored layer was measured. The case where the rate of change of the film thicknesses A and B (A ÷ B × 100) was 85% or less was rated as “◯”, and the case where it was 85% or more was rated as “X”.

Adhesion test during development A colored photosensitive resin composition having a film thickness of 1.2 μm was applied on a substrate, a mask having a line width of 6.0 μm was used for the obtained coating film, and an ultrahigh pressure mercury lamp was used as a light source. The exposure was performed at an exposure amount of 200 mJ / cm ² . Next, a 2.5% sodium carbonate aqueous solution was developed and washed thoroughly with water. About the obtained colored photosensitive resin layer, the peeling condition of the pattern was investigated. When the development time was changed to +10 seconds, +20 seconds, +30 seconds, and +40 seconds, the case that was in close contact for 20 seconds or more was marked with ◯, and the one that was less than that was marked with X.

Example 2
Synthesis of a resin having a plurality of carboxyl groups A five-neck reaction vessel having an internal volume of 2 liters was prepared. As a solvent, 686 g of cyclohexanone, 332 g of glycidyl methacrylate (GMA) as an epoxy group-containing compound, azobisisobutyronitrile ( AIBN) 6.6 g was added and heated at 80 ° C. for 6 hours while blowing nitrogen to obtain a polymer solution of GMA.

  Next, 172 g of acrylic acid (AA), 0.05 g of methoquinone (MQ), and 0.5 g of triphenylphosphine (TPP) are added to the resulting GMA polymer solution as a carboxylic acid-containing compound, and 100 g The mixture was heated at 24 ° C. for 24 hours to obtain a GMA resin acrylic acid adduct solution which is a polyhydric alcohol compound and has photosensitivity.

  Further, 186 g of tetrahydrophthalic anhydride was added as a polybasic carboxylic acid anhydride to the resulting acrylic acid adduct solution of GMA resin and heated at 70 ° C. for 10 hours to obtain an acid anhydride adduct solution.

Subsequently, as a compound that reacts reversibly with carboxylic acid, 75 g of hydroxyethyl vinyl ether is added and heated at 70 ° C. for 15 hours to have the same structure as the above formula (1), where n is 1 , X is represented by the formula (2), m is an integer of 10 to 100, R ₁ is a methyl group, R ₂ is a propylene group, R ₃ is a cyclohexene ring, R ₄ is —CH ₂ CH ₂ OR ₆ , R ₅ acryloyloxy group, R ₆ is to obtain a photosensitive resin is a hydroxyethyl group.

  When the weight change of the obtained photosensitive resin was measured in the same manner as in Example 1, the weight change was reduced by 28% by weight.

Preparation of photosensitive resin composition To 10.5 g of the obtained photosensitive resin, 0,8 g of trimethylolpropane triacrylate as a photopolymerizable monomer and 1.4 g of benzophenone as a photopolymerization initiator were added. A composition was obtained.

Preparation of colored photosensitive resin composition To the obtained photosensitive resin composition, 48 g of carbon black dispersion (EX-2901 manufactured by Mikuni Dye Co., Ltd.) as a colorant and 27 g of ethyl cellosolve as a solvent were added and stirred well. As a result, a black colored photosensitive resin composition was obtained.

  Using the obtained colored photosensitive resin composition, a black colored layer patterned in the same manner as in Example 1 was formed on the substrate.

Test and Evaluation Tests and evaluations were conducted in the same manner as in Example 1 using the obtained black colored photosensitive resin composition. The results obtained are shown in Table 1 below. Example 3
Synthesis of a resin having a plurality of carboxyl groups A five-neck reaction vessel with an internal volume of 2 liters is prepared, 800 g of propylene glycol monomethyl ether acetate (PGMAc) as a solvent, and 30 g of methyl methacrylate (MMA) as a monomer of an acrylic polymer. In addition, 140 g of butyl methacrylate (BMA) as another monomer of the acrylic polymer, 60 g of hydroxyethyl methacrylate (HEMA) and 4 g of azobisisobutyronitrile (AIBN) as a hydroxyl group-containing monomer were added, and 8 at 80 ° C. while blowing nitrogen. Heating for a period of time gave an acrylic resin polymer solution that was a polyhydric alcohol compound and had no photosensitivity.

  Furthermore, 74 g of phthalic anhydride as a polybasic carboxylic acid anhydride was added to the obtained polymer solution and heated at 70 ° C. for 10 hours to obtain an acid anhydride adduct solution.

Furthermore, as a compound that reacts reversibly with carboxylic acid, 52 g of diethylene glycol monovinyl ether is added and heated at 70 ° C. for 10 hours to have the same structure as the above formula (1), provided that in formula (1) , N is 1, x is represented by the above formula (2), m is 20 to 1000, R ₁ is a methyl group, R ₂ is an ethylene group, R ₃ is a benzene ring, and R ₄ is —CH ₂ CH ₂ OR _6. R ₅ is hydrogen and R ₆ is a hydroxyethoxyethyl group.

A solution containing a photosensitive resin was obtained.

  When the weight change of the obtained photosensitive resin was measured in the same manner as in Example 1, the weight change was reduced by 25% by weight with respect to the photosensitive resin before heating.

Preparation of photosensitive resin composition To 21 g of the obtained photosensitive resin, 0, 8 g of trimethylolpropane triacrylate as a photopolymerizable monomer, and 2.0 g of 2,2′-diethoxyacetophenone as a photopolymerization initiator. In addition, a photosensitive resin composition was obtained.

Preparation of colored photosensitive resin composition To the obtained photosensitive resin composition, 48.3 g of carbon black dispersion (EX-2901 manufactured by Mikuni Dye Co., Ltd.) as a colorant and 27 g of ethyl cellosolve as a solvent were added and stirred well. As a result, a black colored photosensitive resin composition was obtained.

  Using the obtained colored photosensitive resin composition, a black colored layer patterned in the same manner as in Example 1 was formed on the substrate.

Test and Evaluation Tests and evaluations were conducted in the same manner as in Example 1 using the obtained black colored photosensitive resin composition. The obtained results are shown in Table 1 below. Comparative Example 1
In the same manner as in Example 1, a novolak resin acrylic acid adduct solution was obtained. Unlike Example 1, a polybasic carboxylic acid anhydride and a compound that reversibly reacts with carboxylic acid were not added.

  When the weight change of the obtained photosensitive resin was measured in the same manner as in Example 1, the weight change was reduced by 4.6% by weight.

  A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that the acrylic acid adduct solution of the novolak resin was used instead of the photosensitive resin of Example 1.

Test and Evaluation Tests and evaluations were conducted in the same manner as in Example 1 using the obtained black colored photosensitive resin composition. The obtained results are shown in Table 1 below. Comparative Example 2
A colored photosensitive resin composition was prepared in the same manner as in Example 2 except that the acrylic acid adduct solution of the novolak resin was used in place of the photosensitive resin of Example 2.

Test and Evaluation Tests and evaluations were conducted in the same manner as in Example 1 using the obtained black colored photosensitive resin composition. The obtained results are shown in Table 1 below. Comparative Example 3
A colored photosensitive resin composition was prepared in the same manner as in Example 3 except that the acrylic acid adduct solution of the novolak resin was used instead of the photosensitive resin of Example 3.

Test and Evaluation Tests and evaluations were conducted in the same manner as in Example 1 using the obtained black colored photosensitive resin composition. The obtained results are shown in Table 1 below.

  As shown in Table 1, it was found that the photosensitive resin compositions of Examples 1 to 3 had high sensitivity, high light shielding properties, and good development adhesion. On the other hand, it was found that the photosensitive resin compositions of Comparative Examples 1 to 3 were inferior in light-shielding property and development adhesion, although the sensitivity was high.

  The present invention can be used to make color filters such as liquid crystal displays, plasma displays, electroluminescent panels, and color video cameras.

Sectional drawing showing the structure of an example of the color filter of this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention The figure for demonstrating an example of the manufacturing method of the color filter which concerns on this invention

Explanation of symbols

    DESCRIPTION OF SYMBOLS 1,5 ... Board | substrate, 2, 2R, 2G, 2B, 11R, 11G, 11B ... Colored layer, 3 ... Black matrix, 4 ... Protective layer, 6 ... Colored photosensitive resin layer, 9 ... Mask, 10, 20 ... Color filter

Claims (5)

A resin for a color filter whose weight is reduced to 85% by weight or less with respect to the weight before the heat treatment by performing a heat treatment at a temperature of 100 to 300 ° C. in a nitrogen atmosphere,
The resin for a color filter is obtained by reacting (A) a hydroxyl group of a resin having a plurality of hydroxyl groups and (B) a polybasic acid anhydride to introduce a carboxyl group into the resin, (C) It was obtained by reacting a compound that reacts reversibly with a carboxylic acid to adjust the acid value,
The resin (A) having a plurality of hydroxyl groups is
(A1) A photosensitive polyvalent hydroxyl group-containing resin obtained by adding a carboxylic acid having an ethylenically unsaturated group to a novolac epoxy resin,
(A2) a non-photosensitive resin having a plurality of hydroxyl groups, obtained by homopolymerization of (meth) acrylates having hydroxyl groups or copolymerization thereof with other (meth) acrylates,
(A3) (meth) acrylic acid is homopolymerized or copolymerized, obtained by reacting the resulting resin with an epoxy group-containing compound, a photosensitive resin having a plurality of hydroxyl groups,
(A4) A photosensitive, plural hydroxyl group obtained by adding (meth) acrylic acid to a resin of homopolymerization of epoxy-containing (meth) acrylate or copolymerization of these with other (meth) acrylates Having resin,
(A5) the (A2) in the polymerization of any acrylic resin ~ (A4), styrene, cyclohexyl maleimide, a resin obtained by copolymerizing a compound selected from the group consisting of phenyl maleimide,
(A6) a resin having a plurality of hydroxyl groups obtained by introducing ethylenically unsaturated groups into an acrylic polymer, and
(A7) A photosensitive resin obtained by reacting a compound having an isocyanate group and an ethylenically unsaturated group with a hydroxyl group-containing resin obtained by polymerization using a hydroxyl group-containing methacrylate as a monomer, leaving an unreacted hydroxyl group. A resin having a plurality of hydroxyl groups,
Selected from the group consisting of
The (B) polybasic acid anhydride is malonic acid anhydride, maleic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride. And selected from the group consisting of trimellitic anhydride,
(C) The compound that reacts reversibly with a carboxylic acid is selected from the group consisting of isobutyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.
A resin for a color filter whose weight is reduced to 85% by weight or less with respect to the weight before the heat treatment by performing a heat treatment at a temperature of 100 to 300 ° C. in a nitrogen atmosphere,
A photosensitive resin obtained by reacting a novolak epoxy resin acrylic acid adduct solution and a polybasic carboxylic acid anhydride acid adduct solution with isobutyl vinyl ether,
Acrylic acid adduct of polyglycidyl methacrylate solution and a polybasic carboxylic acid photosensitive resin acid anhydride adduct solution hydroxyethyl vinyl ether with an anhydride obtained by reacting, and methyl methacrylate and butyl methacrylate and hydroxyethyl methacrylate A resin for a color filter selected from the group consisting of a photosensitive resin obtained by reacting a copolymer of the above and an acid anhydride adduct solution of polybasic carboxylic acid anhydride with diethylene glycol monovinyl ether.   The color filter resin according to claim 1 or 2, wherein the weight of the color filter resin is reduced to 65 to 85% by weight with respect to the weight before the heat treatment. The color filter resin according to claim 1, a photopolymerizable monomer, and a photopolymerization initiator are contained, and the volume thereof is increased by performing a heat treatment at a temperature of 100 to 300 ° C. in a nitrogen atmosphere. The photosensitive resin composition, which is reduced to 85% by volume or less with respect to the volume before the heat treatment.   In a color filter comprising a substrate, a black matrix formed on the substrate, and a colored layer formed on a substrate surface provided with the black matrix, at least one of the colored layer and the black matrix A color filter formed by patterning a resin composition comprising the color filter resin and the colorant according to claim 1 and then subjecting to a heat treatment.

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