KR102339140B1 - Producing method of photosensitive resin composition for color filter, and photosensitive resin composition for color filter - Google Patents

Abstract

An object of the present invention is to provide a method for producing a photosensitive resin composition for a color filter in which high-quality photolithography is possible after a pigment is finely dispersed at a high concentration, and defects due to the presence of foreign substances are less likely to occur.
(A) a compound obtained by reacting a cyclic acid anhydride with a hydroxyl group-containing compound obtained by reacting a bisphenol fluorene type epoxy compound with an ethylenically unsaturated bond group-containing carboxylic acid, (B) a dispersant, and (Z) a solvent containing In the first step of dispersing (C) the pigment in a dispersion medium so that the average particle diameter thereof is 50 nm or less, (D) a polymerizable monomer having at least one ethylenically unsaturated bond and (E) a photoinitiator in the dispersion obtained in the first step It is a manufacturing method of the photosensitive resin composition for color filters including the 2nd process of mix|blending and the 3rd process of filtering the dispersion liquid obtained at the 2nd process with the filtration precision smaller than the film thickness of the cured film formed using it.

Description

The manufacturing method of the photosensitive resin composition for color filters, and the photosensitive resin composition for color filters TECHNICAL FIELD

The present invention relates to a method for producing a photosensitive resin composition for a color filter and a photosensitive resin composition for a color filter. In particular, it relates to a method for producing a photosensitive resin composition for a color filter for producing pixels such as red, green, blue, and yellow, and a photosensitive resin composition for a color filter manufactured by such a method.

Currently, color filters are widely used for colorization of a liquid crystal display device, a white organic EL device, or a solid-state image sensor. As a material for forming the pixel of a color filter, a photosensitive resin composition in which an organic pigment is dispersed is mainstream, but the trend of improvement of polarization contrast required in liquid crystal display devices and reduction of the pixel size of the color filter as a whole (higher pixel density), It is necessary to perform high-quality photolithography after finely dispersing the atomized organic pigment in the photosensitive resin composition at a high concentration.

The film thickness of the cured film of the photosensitive resin composition which forms a color filter is about 2 micrometers at most, and may be formed to 1 micrometer or less depending on a use. In such a thin film, since it is easy to generate|occur|produce the defect by presence of a foreign material, in order to prevent it, microfiltration of the photosensitive resin composition and use for manufacture of a color filter are performed (for example, refer patent document 1). However, in the photosensitive resin composition in which the atomized organic pigment was finely dispersed at a high concentration, clogging of the filter medium during filtration due to aggregation of the pigment or the like easily occurred, and there was a problem that sufficient productivity could not be obtained. As a countermeasure, it is generally effective to increase the amount of the dispersant of the pigment, but in that case, it is inhibited by the dispersant and it is difficult to perform high-quality photolithography.

Patent document 2 describes the manufacturing method of the photosensitive resin compound for black matrices co-dispersing a specific compound with a dispersing agent.

Japanese Patent Laid-Open No. 2009-210646 Japanese Patent Laid-Open No. 2008-9401

The present invention has been made in view of the problems of the prior art, and high-quality photolithography is possible after finely dispersing pigments, particularly atomized organic pigments at a high concentration, and photosensitivity for color filters that are less prone to defects due to the presence of foreign substances It aims at providing the manufacturing method of a resin composition, and the photosensitive resin composition for color filters manufactured by such a method.

As a result of studying in order to solve the said subject, the present inventors discovered that it was suitable for this objective to disperse|distribute a pigment using the compound which has a specific structure, and completed this invention.

That is, the present invention relates to (A) a compound obtained by reacting a cyclic acid anhydride with a hydroxyl group-containing compound obtained by reacting a bisphenol fluorene-type epoxy compound with an ethylenically unsaturated bond group-containing carboxylic acid, (B) a dispersing agent, and (Z ) a first step of dispersing (C) the pigment so that the average particle diameter thereof is 50 nm or less in a dispersion medium containing a solvent as an essential component;

A second step of blending an additive component comprising (D) a polymerizable monomer having at least one ethylenically unsaturated bond and (E) a photoinitiator as essential components to the dispersion obtained in the first step;

It is the manufacturing method of the photosensitive resin composition for color filters characterized by including the 3rd process of filtering the dispersion liquid obtained at the 2nd process with the filtration precision smaller than the film thickness of the cured film formed using it.

Here, component C is preferably an organic pigment having a specific surface area of 50 m 2 /g or more by the BET method, and component D and component E are preferably selected from compounds having a solubility of 5 wt% or more with respect to component Z.

In addition, the present invention is a photosensitive resin composition for a color filter manufactured by the above manufacturing method.

Hereinafter, the present invention will be described in detail.

The production method of the present invention comprises (A) a compound obtained by reacting a cyclic acid anhydride with a hydroxyl group-containing compound obtained by reacting a bisphenol fluorene type epoxy compound with an ethylenically unsaturated bond group-containing carboxylic acid, (B) a dispersing agent, and ( Z) a first step of dispersing (C) the pigment so that the average particle diameter thereof is 50 nm or less in a dispersion medium containing a solvent as an essential component;

A second step of blending an additive component comprising (D) a polymerizable monomer having at least one ethylenically unsaturated bond and (E) a photoinitiator as essential components to the dispersion obtained in the first step;

The 3rd process of filtering the dispersion liquid obtained at the 2nd process with the filtration precision smaller than the film thickness of the cured film formed using it is included. Although each process needs to be processed in the order of the number, it is not necessarily necessary to carry out continuously, and other processes (for example, a transport process, etc.) may be included in between. In addition, as raw materials used in each process, those manufactured in a process different from the above process may be used.

In a 1st process, a pigment is disperse|distributed. In general, a ball mill, attritor, sand mill, bead mill, dispenser, homogenizer, paint shaker, sambon roll, kneader, ultrasonic disperser, ultra-high pressure disperser, etc. are used to disperse the pigment in the dispersion medium. making is done The disperser is not particularly limited as long as fine dispersion of the pigment is achieved, but dispersion processing by a bead mill using minute beads (such as zirconia beads having a diameter of 0.01 to 0.5 mm) is preferable. The average particle diameter of the dispersed pigment is required to be 50 nm or less, and this aims to cope with the improvement of the polarization contrast required for a liquid crystal display device and reduction of the pixel size (higher pixel density) of the color filter as a whole. It is important that the dispersed state of the pigment is stably maintained even after the completion of the first process, and the conditions of the first process are determined so that the average particle diameter of the dispersed pigment does not change for a certain period of time.

In the present invention, the average particle diameter of the dispersed pigment is obtained by diluting the sampled dispersion with propylene glycol monomethyl ether acetate so that the pigment concentration is 1 wt%, and Otsuka Electronics Co., Ltd. Dynamic light scattering was measured with production FPAR-1000, and the value obtained by calculating the average particle diameter by the cumulant method is used.

A component is a compound obtained by making the cyclic acid anhydride react with respect to the hydroxyl-group containing compound which made the bisphenol fluorene type epoxy compound and the ethylenically unsaturated bond group containing carboxylic acid react. Such compounds are known as photosensitive resins, and examples of such compounds include compounds described in Japanese Unexamined Patent Application Publication No. Hei 5-339356. As a preferable range of the physical properties of component A, the weight average molecular weight (standard polystyrene conversion value in GPC (SEC) measurement) is 1000 to 20,000, more preferably 2000 to 10,000, and the acid value (neutralization titration method) is 50 to 150 KOHmg /g, More preferably, 70-120KOHmg/g can be illustrated.

In the present invention, the weight average molecular weight of component A is a value obtained by dissolving the sampled solution in tetrahydrofuran, measuring the molecular weight distribution using HLC-8220GPC manufactured by Tosoh Corporation, and calculating the weight average molecular weight in terms of standard polystyrene.

In the present invention, the acid value of component A is obtained by dissolving the sampled solution in a mixed solution of tetrahydrofuran and water, neutralizing titration with 0.1 N aqueous potassium hydroxide solution, and calculating the acid value in terms of the solid content of the sample solution from the equivalence point. .

The bisphenol fluorene type epoxy compound used as the synthetic raw material of A component points out the compound represented by following General formula (1), and especially the value of n says what exists in the range of 0-20. Practically, it is preferable that the average value of n is 0-2, and it is more preferable that it is 0.1-1.0.

[However, each R independently represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and m each independently represents a number of 0 to 4. The hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group]

Although the method for synthesizing the bisphenol fluorene type epoxy compound is not particularly limited, the method described in Japanese Unexamined Patent Application Publication No. 9-328534, that is, 9,9-bis(4-hydroxyphenyl)fluorene and epichlorohydrin with alkali The method obtained by condensation in the presence is most generally preferred. 9,9-bis(4-hydroxyphenyl)fluorene may be substituted with m pieces of R as shown in the general formula (1). The value of n is the polymerization degree of the epoxy compound, and since the molar ratio of the raw material compound and the reaction conditions are adjusted by a conventional method during synthesis, it can be set to a desired value.

When an ethylenically unsaturated bond group containing carboxylic acid is made to react with a bisphenol fluorene type epoxy compound, the hydroxyl-group containing compound which is a synthetic intermediate of A component will be obtained. Specific examples of the ethylenically unsaturated bond group-containing carboxylic acid include (meth)acrylic acid, (meth)acrylic acid dimer, half ester of 2-hydroxyethyl (meth)acrylate and succinic anhydride, 2-hydroxyethyl (meth)acrylate, half ester of phthalic anhydride, half ester of 2-hydroxyethyl (meth)acrylate and cyclohexane-1,2-dicarboxylic acid anhydride, 4-vinylbenzoic acid, etc., but (meth)acrylic acid is most preferred do. Here, (meth)acrylic acid refers to acrylic acid or methacrylic acid (the same applies hereafter).

The method of reacting the carboxylic acid containing an ethylenically unsaturated bond group with the bisphenol fluorene type epoxy compound is not particularly limited, but the method described in Japanese Patent Laid-Open No. 3-205417, that is, the method of reacting by heating in the presence of a catalyst is the most Generally preferred. As a catalyst, a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, etc. can be used. Ideally, it is preferable to completely convert the functional group into an ester bond and a hydroxyl group by reacting the epoxy group of the bisphenol fluorene type epoxy compound with the carboxyl group of the carboxylic acid containing an ethylenically unsaturated bond group one-to-one, but the time required for the reaction is limited Alternatively, the reaction may be terminated when a necessary and sufficient reaction rate is reached due to concerns about the progress of side reactions or the like. The reaction rate can be calculated by measuring the epoxy equivalent or acid value, and in general, it is sufficient if the reaction rate reaches 98 mol% or more.

Thus, the compound of A component is obtained by making a cyclic acid anhydride react with respect to the obtained hydroxyl-group containing compound. Here, the cyclic acid anhydride means an intramolecular acid anhydride of polyhydric carboxylic acid, for example, succinic anhydride, maleic anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, cyclohexene-1,2-dicarboxylic acid Acid anhydride, cyclohexene-4,5-dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, phthalic anhydride, benzene-1,2,4-tricarboxylic acid-1,2 -Anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, benzene-1,2,4,5-tetracarboxylic dianhydride, cyclohexane-1,2,4,5 -tetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3, 3',4,4'-tetracarboxylic dianhydride, diphenyl sulfone-3,3',4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4 '-[1,1,1,3,3,3-hexafluoropropane-2,2-diyl]diphthalic dianhydride etc. are mentioned. Moreover, a 6-membered ring acid anhydride like glutaric anhydride can also be used.

The method for reacting the cyclic acid anhydride with the hydroxyl group-containing compound is not particularly limited, but the method described in Japanese Patent Laid-Open No. 5-339356, that is, the method of reacting by heating in the presence of a catalyst is most generally preferred. As a catalyst, a tertiary amine, a quaternary ammonium salt, a tertiary phosphine, a quaternary phosphonium salt, etc. can be used. Cyclic acid anhydride half-esterifies a hydroxyl group and converts it to a carboxyl group, so it has an effect of imparting an acid value to the compound. However, when an acid dianhydride is selected, it becomes a crosslinking point and simultaneously increases molecular weight, so it is useful. Among them, the method of controlling the acid value and molecular weight together by using the acid dianhydride and the acid monhydride in combination is particularly advantageous, and it is preferable to use the acid dianhydride in combination in the range of 0.01 to 10 moles with respect to 1 mole of the acid dianhydride. do. What is necessary is just to set the addition amount of the cyclic acid anhydride with respect to a hydroxyl group according to the target acid value, It is preferable that it is 0.5-1.0 mol with respect to 1 mol of hydroxyl groups. To confirm the progress of the reaction, it is sufficient to observe the characteristic absorption spectrum of the acid anhydride group by infrared spectroscopy.

Component A combines heat resistance and optical properties (high transparency, high refractive index, low birefringence) derived from a bisphenol fluorene skeleton, polymerizability derived from an ethylenically unsaturated bond group-containing carboxylic acid, and alkali solubility derived from a cyclic acid anhydride. It is a compound which can be used suitably for the photosensitive resin composition for filters. In the present invention, by using component A in the first step, high-quality photolithography is possible after finely dispersing pigments, particularly atomized organic pigments at a high concentration, and the color that is difficult to generate defects due to the presence of foreign substances by microfiltration It becomes possible to obtain the photosensitive resin composition for filters. Component A is considered to have a function of physically preventing re-aggregation of the dispersed pigment by having a bulky bisphenol fluorene skeleton, and it is estimated that this also acts on improvement of photolithography performance and suppression of foreign substances. In addition, although dispersion of a pigment using component A is disclosed in patent document 2, the manufacturing method of the photosensitive resin composition for color filters for producing pixels, such as red, green, blue, yellow, is not described at all. Moreover, when manufacturing the necessity of microfiltration or the photosensitive resin composition for color filters, the subject that clogging of a filter medium occurs easily is not mentioned at all either. In order to improve the color characteristics of the color filter (the characteristics of the spectral transmittance of the pixel), it is necessary to minimize the surface treatment of the organic pigment, and therefore the dispersion of the organic pigment is more difficult compared to carbon black etc. When the manufacturing method of

Component B is a dispersing agent, and known compounds conventionally used for dispersing pigments and the like, for example, compounds commercially available under the names of dispersants, dispersion stabilizers, dispersion wetting agents, and dispersion accelerators, etc. can be used without particular limitation. Examples of dispersants effective for dispersion stabilization of pigments include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative dispersants (dispersion aids), and the like. A cationic polymer dispersant having a cationic functional group such as a pyrrolyl group, a pyridyl group, a primary, secondary or tertiary amino group, an amine value of 1 to 100 KOH mg/g, and a number average molecular weight in the range of 1,000 to 100,000 is preferable. do. An example of such a cationic polymer dispersant is disclosed in Japanese Patent Laid-Open No. 9-169821. As for B component, only one type of compound may be used and it may use it combining plurality. Examples of commercial products of component B include "BYK" series manufactured by BYK Additive & Instruments, BASF Japan Ltd. Manufactured "EFKA" series, Lubrizol Corporation "SOLSPERSE" series, Ajinomoto Fine-Techno Co., Inc. Production "AJISPER" series is mentioned. In addition, although high-viscosity substances such as resins generally also have an action of stabilizing dispersion, those having no dispersion promoting ability are not treated as dispersants. However, the present invention is not limited to the use of high-viscosity materials such as resins for the purpose of stabilizing dispersion.

Component C is a pigment, and known compounds (organic pigments, inorganic pigments, carbon black, titanium black, etc.) known as colorants for color filters can be used without particular limitation, but organic pigments are preferable, and among them, an average particle diameter of 50 nm or less In order to achieve the fine dispersion of , it is particularly preferable to have an atomization process (specific surface area by BET method of 50 m 2 /g or more). Specifically, azo pigment, condensed azo pigment, azomethine pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline pigment, dioxadine pigment, trene pigment, perylene pigment, perinone pigment, qui Although a nophthalone pigment, a diketopyrrolopyrrole pigment, a thioindigo pigment etc. are mentioned, As a color index name, Pigment red 2, copper 3, copper 4, copper 5, copper 9, copper 12, copper 14, copper 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179 , 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, dong 254, 255, 256, 257, 262, 264, 266, 272, 279, Pigment Orange 5, 13, 16, 34, 36, 38, 43, Building 61, Building 62, Building 64, Building 67, Building 68, Building 71, Building 72, Building 73, Building 74, Building 81, Pigment Yellow 1, Building 3, Building 12, Building 13, Building 14, Building 16 , 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, dong 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, East 183, East 185, East 191, East 194, East 199, East 213, East 214, Pigment Green 7, East 36, East 58, Pigment Blue 15, East 15:1, East 15:2, East 15:3, 15:4, 15:6, dong 16, Copper 60, Copper 80, Pigment Violet 19, Copper 23, Copper 37, and the like can be exemplified. Among them, in particular, organic pigments having three or more aromatic rings (including heterocycles) in one molecule, for example, phthalocyanine pigments, are generally difficult to disperse, so that the effect of applying the manufacturing method of the present invention is high. It is preferable to carry out As for C component, only one type of compound may be used and it may use it combining plurality. It is widely practiced to select and use a plurality of organic pigments in a predetermined ratio because of the control of the color characteristics of the color filter. The manufacturing method can be used suitably also in such a case.

As a method of atomizing an organic pigment, a well-known method can be used, For example, the dry milling method, the solvent milling method, the salt milling method, the solvent salt milling method, the acid pasting method, the acid slurry method, etc. are mentioned. In atomization, it is important to make a particle size small and to arrange a particle size uniformly.

The manufacturing method of this invention shows the highest effect, when C component manufactures the photosensitive resin composition for color filters which occupies 40 weight% or more of the total of A-E components. Increasing the content of component C is important because it improves color purity by thinning the color filter, but according to the manufacturing method of the present invention, even under such high dye concentration conditions, microfiltration of the photosensitive resin composition or productivity of high-quality photolithography is not reduced. It becomes possible to manufacture a color filter without it.

Component D and component E are components added in the second step, and specific examples thereof will be described later.

Component Z is a solvent, for example, ester solvents (butyl acetate, cyclohexyl acetate, etc.), ketone solvents (methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (diethylene glycol dimethyl ether, diethylene glycol) ethyl methyl ether, etc.), alcohol solvents (3-methoxybutanol, ethylene glycol mono-t-butyl ether, etc.), aromatic solvents (toluene, xylene, etc.), aliphatic solvents, amine solvents, amide solvents, etc. A well-known solvent can be used especially without restriction|limiting. From the viewpoint of safety, ester or ether solvents having a propylene glycol skeleton, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and the like are preferably used. In addition, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 1,3-butylene glycol diacetate and the like having a similar structure are also preferable. As the Z component, only one type of compound may be used, or a plurality of them may be used in combination. Among these solvents, propylene glycol monomethyl ether acetate is the most preferable from the viewpoints of dispersion stability of the organic pigment, surface tension of the solvent, and drying properties.

The weight ratio of each component in the first step is preferably A:B:C:Z=(1-10):(1-10):(1-20):(60-97), (1-5) ):(1-5):(10-15):(75-88) is more preferable. In addition, when the B component is used within 30% by weight, preferably within 25% by weight with respect to the C component, it is more advantageous because high-quality photolithography can be easily performed. Moreover, you may add other necessary components (For example, fillers, such as silica and talc, organic dye, etc.) with respect to the total of A component, B component, C component, and Z component within 10 weight%.

In a 2nd process, an additive component is mix|blended. Blending may be performed with a mixer or the like, and an additive component comprising as essential components (D) a polymerizable monomer having at least one ethylenically unsaturated bond and (E) a photoinitiator may be mixed with the dispersion obtained in the first step. In the second step different from the first step, the purpose is to mix and dissolve the blended additive components without performing active dispersion processing. Although component D and component E may be added in the first step, since they have high reactivity, stability may be impaired during dispersion processing. Therefore, it is advantageous to provide the second process separately from the first process.

Component D is a polymerizable monomer having at least one ethylenically unsaturated bond, and known compounds conventionally used for photosensitive materials can be used without particular limitation. Specifically, diethylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol hexa (meth) (meth)acrylic acid ester derivatives such as acrylate, bisphenol A-type epoxydi(meth)acrylate, bisphenol F-type epoxydi(meth)acrylate, bisphenol fluorene type epoxydi(meth)acrylate, phenol novolac type (meth)acrylic acid epoxy ester derivatives, such as epoxy poly(meth)acrylate and cresol novolak-type epoxy poly(meth)acrylate, etc. can be illustrated. Further, a reaction product of the above (meth)acrylic acid derivative and a compound having (preferably a plurality of) isocyanate groups or acid anhydride groups in the structure is also suitable (however, the compound corresponding to component A is excluded). In addition to (meth)acrylic acid derivatives, maleic acid derivatives, maleimide derivatives, crotonic acid derivatives, itaconic acid derivatives, cinnamic acid derivatives, vinyl derivatives, vinyl alcohol derivatives, vinyl ketone derivatives, vinyl aromatic derivatives, and the like can be mentioned. The compound having these ethylenically unsaturated bonds may further have a thermally reactive functional group such as an epoxy group or an alkali-soluble functional group such as a carboxyl group, and may be compound-functionalized. D component may use only one type of compound, and may use it combining plurality.

Component E is a photoinitiator, and known compounds conventionally used for photosensitive materials can be used without particular limitation. Specifically, acetophenone compounds such as acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and benzyl dimethyl ketal, benzophenone, 2,4,6-trimethylbenzophenone, 4,4' -benzophenone compounds such as bis(N,N-diethylamino)benzophenone; benzoin ether compounds such as benzoin ethyl ether and benzoin-tert-butyl ether; 2-methyl-1-[4-(methylsulfur) α- such as panyl)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one aminoalkylphenone compounds, thioxanthone compounds such as thioxanthone and 2,4-diethylthioxanthone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, etc. Biimidazole compounds such as organic peroxides, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole, bis(η ₅ -cyclopenta titanocene compounds such as dienyl)bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]titanium, 2,4,6-tris(trichloromethyl)-1,3,5-tri Triazine compounds such as azine, 2-[3,4-(methylenedioxy)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, (2,4,6-trimethyl Acyl phosphine oxide compounds such as benzoyl)diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, quinone compounds such as camphorquinone, 1-[4-(phenylsulfanyl)phenyl] Octane-1,2-dione=2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone=O-acetyloxime, (9-ethyl- Oxime ester compounds, such as 6-nitrocarbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone =O-acetyloxime, etc. are mentioned. E component may use only 1 type of compound, and may use it combining plurality.

In the second step, since the purpose of dissolving the additive component is to dissolve the additive component, the component D and component E are preferably selected from compounds having a solubility of 5% by weight or more with respect to the solvent of component Z, and more preferably 10% by weight or more. . When the solubility of component D and component E is lower than this, the solubility is poor, and not only is it easy to cause clogging of the filter medium during microfiltration, but also re-agglomeration after filtration may cause foreign matter to be generated. In the present invention, solubility refers to the weight of a solute soluble in 100 g of a solvent at room temperature expressed as a percentage.

In the second step, in addition to component D and component E, other necessary components can be added, for example, epoxy resin, vinyl resin, polyester resin, polyamide resin, polyimide resin, polyurethane resin, polyether resin, melamine. Resins such as resins, crosslinking agents, surfactants, silane coupling agents, viscosity modifiers, wetting agents, defoamers, antioxidants, ultraviolet absorbers, and additives such as chain transfer agents, known compounds applied to the photosensitive resin composition for color filters It can be used without particular limitation. More specifically, as resins, epoxy resins (bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol fluorene type epoxy compound, tetramethylbiphenyl type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound) , glycidyl ether of polyhydric alcohol, glycidyl ester of polyhydric carboxylic acid, polymer comprising glycidyl (meth)acrylic acid as a unit, 3,4-epoxycyclohexanecarboxylic acid (3,4-epoxycyclo 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, an alicyclic epoxy compound represented by hexyl)methyl (e.g. Daicel Corporation manufactured "EHPE3150"), epoxidized polybutadiene (for example, "NISSO-PB/JP-100" manufactured by Nippon Soda Co., Ltd.), epoxy compound having a silicone skeleton, etc.), surfactant as additives (Fluorine-based surfactants (eg, “Megafac” series manufactured by DIC Corporation), silicone-based surfactants (eg, “FZ” series manufactured by Dow Corning Toray Co., Ltd.), etc.), and silane coupling agents (3- It is advantageous to use (glycidyloxy)propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, etc.) It is preferable to use within 10% by weight of the For the purpose, such as adjustment of a pigment density|concentration, you may add A component suitably in a 2nd process. In addition, in a 2nd process, it may further add a solvent to adjust to a desired solid content concentration, and what is necessary is just to select this solvent similarly to Z component.

In a 3rd process, the photosensitive resin composition is filtered. In the present invention, filtration is performed with a filtration accuracy smaller than the film thickness of the cured film formed using the filtered photosensitive resin composition, and filtration is performed with a filtration accuracy smaller than two-thirds of the film thickness of the cured film to be formed. more preferably. What is necessary is just to perform filtration by a well-known method, but pressure filtration is common. A solvent-resistant depth filter, a surface filter, or a membrane filter is preferable for the filter medium to be used, and polypropylene, nylon, PTFE, etc. are mentioned as a specific material. These filters are manufactured by Pall Corporation, Sumitomo 3M Ltd., Roki Techno Co., Ltd. It is marketed from etc., and it can select and use it suitably with reference to the filtration precision set by a filter manufacturer. Filtration accuracy generally does not guarantee that foreign matter of a size larger than that is completely captured, and always includes the possibility of a slight capture leakage (passage), but the dispersion obtained in the first and second steps of the present invention is Since the pigment is finely dispersed, the risk of entrapment leakage is relatively small, which is advantageous. Moreover, when the filtration precision smaller than two-thirds of the film thickness of the cured film to form is selected, it will become possible to acquire the very high foreign material removal effect.

The photosensitive resin composition for color filters manufactured by the manufacturing method of this invention can produce a cured film by apply|coating to a board|substrate etc. and hardening by light irradiation, heat baking, etc. As a method of apply|coating the photosensitive resin composition, a well-known method can be used, For example, application|coating by a spin coater, a bar coater, a slit coater, etc. is mentioned. In addition, after application|coating, it is preferable to dry the photosensitive resin composition using a hot plate, a reduced pressure dryer, etc. However, the method of application|coating and drying in particular is not restrict|limited.

A known method can be used for curing by light irradiation, for example, ultraviolet light using a xenon lamp, a halogen lamp, a tungsten lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc. as a light source. investigation can be taken. When performing such light irradiation, image exposure is performed using a photomask or the like, and an image can be formed on the substrate by further processing with a developing solution. The developer is not particularly limited as long as it dissolves the unexposed portion and does not dissolve the exposed portion, but it is preferably an aqueous alkali solution containing various additives. Here, examples of the alkali component of the developer include alkali metal carbonates, alkali metal hydroxides, and quaternary ammonium hydroxides, and examples of the additives include organic solvents, surfactants, antifoaming agents, and antifungal agents. A well-known method can be used also about the image development method, For example, immersion image development, spray image development, brush image development, ultrasonic image development etc. are mentioned. The method of light irradiation and development is also not particularly limited.

Moreover, in order to raise the intensity|strength of a cured film, it is preferable to heat-fire after light irradiation. A known method can be used also for the method of heating and baking, For example, although processing by a hot plate, a hot-air oven, etc. is mentioned, it does not restrict|limit in particular. Although there is no restriction|limiting in particular about the curing conditions of a cured film, It is preferable to perform 10-1000 mJ/cm<2> ultraviolet light irradiation for photocuring, and to perform heat baking at 200-250 degreeC for 20-60 minutes about thermosetting. In addition, a well-known method can be used as a method of producing a color filter using such a cured film.

(Effects of the Invention)

The photosensitive resin composition for a color filter prepared by the manufacturing method of the present invention enables high-quality photolithography after finely dispersing a pigment, particularly an atomized organic pigment at a high concentration, and also makes it difficult to generate defects due to the presence of foreign substances. It is very useful by increasing the productivity of

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these. Incidentally, parts and percentages (%) indicate parts by weight and percentages by weight (% by weight) unless otherwise specified.

Analysis was performed as follows.

Acid value: The sampled solution was dissolved in a mixed solution of tetrahydrofuran and water, neutralized and titrated with a 0.1 N aqueous potassium hydroxide solution, and the acid value in terms of solid content of the sample solution was calculated from the equivalence point.

Weight average molecular weight: The sampled solution was dissolved in tetrahydrofuran, molecular weight distribution was measured by HLC-8220 GPC manufactured by Tosoh Corporation, and the weight average molecular weight in terms of standard polystyrene was calculated.

Average particle size: The sampled dispersion was diluted with propylene glycol monomethyl ether acetate so that the pigment concentration was 1%, and Otsuka Electronics Co., Ltd. Dynamic light scattering was measured by production FPAR-1000, and the average particle size by the Qumland method was calculated.

The components used by the Example and the comparative example are shown below.

A-1 to 3: Components synthesized in Reference Examples 1 to 3 (solid content of 50% solution)

AX-1: Component synthesized in Reference Example 4 (solid content of 50% solution)

B-1: Ajinomoto Fine-Techno Co., Inc. Production "AJISPER PB822"

C-1: Atomized Pigment Red 177 (specific surface area 70 m 2 /g by BET method)

C-2: Atomized Pigment Red 254 (specific surface area 85 m 2 /g by BET method)

C-3: Atomized Pigment Green 36 (specific surface area 65 m 2 /g by BET method)

C-4: Atomized Pigment Green 58 (specific surface area 75 m 2 /g by BET method)

C-5: Atomized Pigment Yellow 138 (specific surface area 70 m 2 /g by BET method)

C-6: Atomized Pigment Blue 15:6 (specific surface area 90 m 2 /g by BET method)

C-7: Atomized Pigment Violet 23 (specific surface area 50 m 2 /g by BET method)

CX-1: Pigment Red 177 (specific surface area 35 m 2 /g by BET method)

D-1: dipentaerythritol hexaacrylate (solubility in Z-1: 10 wt% or more)

E-1: 1-[4-(phenylsulfanyl)phenyl]octane-1,2-dione=2-O-benzoyloxime (solubility in Z-1: 10% by weight or more)

E-2: 1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone=O-acetyloxime (solubility in Z-1: 5-10 wt%)

S-1: Daicel Corporation "EHPE3150"

S-2: Dow Corning Toray Co., Ltd. Production "FZ-2122"

Z-1: propylene glycol monomethyl ether acetate

Z-2: propylene glycol diacetate

Here, "A-" "B-" "C-" "D-" "E-" "Z-" represents that each corresponds to the A, B, C, D, E, Z component of the present invention, and " S-" represents other components used as needed. In addition, "AX-" shows that it does not have the structure of A component of this invention, and "CX-" shows that the specific surface area by BET method is less than 50 m<2>/g.

[Reference Example 1]

510 g of a bisphenol fluorene type epoxy compound represented by the general formula (1) (epoxy equivalent 255), 2.0 mol of acrylic acid (carboxylic acid containing an ethylenically unsaturated bond group), 0.10 mol of triphenylphosphine (catalyst), BHT (polymerization inhibitor) ) 0.05 mol was dissolved in 255 g of propylene glycol monomethyl ether acetate, and reacted at 100° C. while bubbling dry air. When the reaction rate of the epoxy group and the carboxyl group reaches 99 mol%, 0.50 mol of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) and cyclohexene-4,5-dicarboxyl 0.50 mol of an acid anhydride (cyclic acid anhydride) was added, and it was made to react further. After confirming the consumption of the acid anhydride group by infrared spectroscopy, it was diluted with propylene glycol monomethyl ether acetate and cooled at room temperature to obtain a 50% solution with a solid content concentration of component A-1. The acid value of component A-1 was 96KOHmg/g, and the weight average molecular weight was 40 thousand.

[Reference Example 2]

630 g of bisphenol fluorene type epoxy compound represented by the general formula (1) (epoxy equivalent 315), 2.0 mol of acrylic acid (carboxylic acid containing an ethylenically unsaturated bond group), 0.10 mol of triphenylphosphine (catalyst), BHT (polymerization inhibitor) ) was dissolved in 315 g of propylene glycol monomethyl ether acetate, and reacted at 100° C. while bubbling dry air. When the reaction rate of the epoxy group and the carboxyl group reaches 99 mol%, 0.50 mol of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) and cyclohexene-4,5-dicarboxyl 0.50 mol of an acid anhydride (cyclic acid anhydride) was added, and it was made to react further. After confirming the consumption of the acid anhydride group by infrared spectroscopy, the mixture was diluted with propylene glycol monomethyl ether acetate and cooled at room temperature to obtain a 50% solution with a solid content concentration of component A-2. The acid value of component A-2 was 84KOHmg/g, and the weight average molecular weight was 6,000.

[Reference Example 3]

510 g of a bisphenol fluorene type epoxy compound represented by the general formula (1) (epoxy equivalent 255), 2.0 mol of acrylic acid (carboxylic acid containing an ethylenically unsaturated bond group), 0.10 mol of triphenylphosphine (catalyst), BHT (polymerization inhibitor) ) 0.05 mol was dissolved in 255 g of propylene glycol monomethyl ether acetate, and reacted at 100° C. while bubbling dry air. When the reaction rate of the epoxy group and the carboxyl group reaches 99 mol%, 0.65 mol of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) and cyclohexene-4,5-dicarboxyl 0.02 mol of an acid anhydride (cyclic acid anhydride) was added, and it was made to react further. After confirming the consumption of the acid anhydride group by infrared spectroscopy, it was diluted with propylene glycol monomethyl ether acetate and cooled at room temperature to obtain a 50% solution with a solid content concentration of component A-3. The acid value of component A-3 was 87KOHmg/g, and the weight average molecular weight was 9,000.

[Reference Example 4]

370 g of bisphenol A epoxy compound (epoxy equivalent weight 185), 2.0 mol of acrylic acid (carboxylic acid containing an ethylenically unsaturated bond group), 0.10 mol of triphenylphosphine (catalyst), and 0.05 mol of BHT (polymerization inhibitor) propylene glycol monomethyl ether It was dissolved in 185 g of acetate and reacted at 100° C. while bubbling dry air. When the reaction rate of the epoxy group and the carboxyl group reaches 99 mol%, 0.50 mol of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (cyclic acid anhydride) and cyclohexene-4,5-dicarboxyl 0.50 mol of an acid anhydride (cyclic acid anhydride) was added, and it was made to react further. After confirming the consumption of the acid anhydride group by infrared spectroscopy, it was diluted with propylene glycol monomethyl ether acetate and cooled at room temperature to obtain a 50% solid concentration solution of the component AX-1. The AX-1 component had an acid value of 114 KOH mg/g and a weight average molecular weight of 3,000.

[Example 1]

(Preparation of the photosensitive resin composition for color filters)

10.0 parts of a 50% solids concentration solution of component A-1 (solution obtained in Reference Example 1), 3.0 parts of component B-1, 12.0 parts of component C-1, and 75.0 parts of component Z-1 are mixed, and heated to 30° C. or lower in cooling water A dispersion was obtained by dispersing at a circumferential speed of 8.5 m/s until a stable state was achieved with a bead mill with an internal volume of 600 mL filled with zirconia beads of 0.3 mm in diameter while maintaining the state of 80%. The average particle diameter of the pigment of this dispersion liquid was 45 nm (1st process). Then, 3.0 parts of component D-1, 0.4 parts of component E-1, 0.5 parts of component S-1, 0.1 part of component S-2, and 16.0 parts of component Z-2 are blended into the dispersion, and 3 parts at room temperature using a mixer It stirred and mixed for time (2nd process). Finally, pressure filtration was performed at a pressure of 0.05 MPa using a membrane filter having a filtration accuracy of 0.6 µm to obtain a red photosensitive resin composition for color filters (third step).

Table 1 shows the production conditions of the photosensitive resin composition for color filters of Example 1. In this table, only the solid content is described as the component A-1, and the solvent content of the 50% solution is included in the component Z-1 (hereinafter, the same method is used for components A-2, A-3, and AX-1).

(Evaluation of the photosensitive resin composition for color filters)

The photosensitive resin composition for color filters obtained above was spin-coated on the silicon wafer of 5 inches at rotation speed so that the film thickness after hardening might be set to 1.0 micrometer, and the test piece was produced. The test piece was dried on a hot plate at 90°C for 2 minutes to remove the solvent, and the coated surface was visually observed under a microscope to count the number of foreign substances having a diameter of 1 µm or more. Next, through a photomask having the shape of the test pattern of the pixel of the color filter, an ultra-high pressure mercury lamp with an illuminance of 30 mW/cm 2 was irradiated with ultraviolet rays at 100 mJ/cm 2 (the numerical value is based on the i-line), and image exposure was performed. Thereafter, the test piece was treated with a potassium hydroxide-based alkali developer at 25° C. (100-fold dilution of “NSID” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) for 1 minute, and further washed with water to develop an image. Finally, the test piece was baked in 230 degreeC hot-air oven for 30 minutes, and the cured film of the photosensitive resin composition for color filters was obtained.

The evaluation result of the photosensitive resin composition for color filters of Example 1 is shown in Table 2. There were no foreign substances on the coated surface of the photosensitive resin composition for color filters of Example 1 (0), and the image formation was also good (having a resolution of 1 µm, and no developing residue was seen on the wafer surface). In addition, the resolving ability showed the minimum line width in which image formation was possible among the test patterns having stepwise line widths every 1 µm, and the development residue was determined by visually observing the wafer surface under a microscope.

[Examples 2 to 8]

As the preparation conditions of Example 1 were respectively changed as Table 1 was shown, the other produced and evaluated the photosensitive resin composition for color filters of Examples 2-8 by the method similar to Example 1. Table 2 shows the evaluation result of the photosensitive resin composition for color filters of Examples 2-8. All of these had the favorable characteristics equivalent to Example 1.

[Comparative Examples 1 to 6]

As the production conditions of Example 1 were respectively changed as shown in Table 3, the other were produced and evaluated by the method similar to Example 1 of the photosensitive resin compositions for color filters of Comparative Examples 1-6. The evaluation result of the photosensitive resin composition for color filters of Comparative Examples 1-6 is shown in Table 4. When the A-1 component of Example 1 was changed to the AX-1 component (Comparative Example 1), the fine dispersion was insufficient and the average particle size was large, and the result was inferior to that of Example 1 in all respects of foreign substances, resolution ability, and development residue. became When the B component was used instead of the A component of Example 1 in an increased amount (Comparative Example 2), the dispersion was good, but photolithography could not be performed. Here, by simply excluding component A without increasing component B, it became impossible to obtain a fluid dispersion. When the filtration accuracy of Example 1 is changed to 1.0 µm equal to the film thickness of the cured film (Comparative Example 3), the foreign matter increases significantly, and the film thickness after curing the photosensitive resin composition for color filters under the production conditions of Example 1 Similarly, an increase in foreign matter was observed even when spin-coated at a rotational speed so that α was 0.6 μm and evaluated (Comparative Example 4). When the organic pigment is not atomized, the average particle diameter becomes large, filtration with a filtration accuracy of 0.6 µm (Comparative Example 5) is impossible due to clogging of the filter medium, and filtration with a filtration accuracy of 1.0 µm (Comparative Example 6) is possible, but foreign substances or sea The ability was an insufficient result.

The photosensitive resin composition for a color filter manufactured by the manufacturing method of the present invention can be used not only for the production of a color filter, but also as a coloring component for paints, printing inks, writing instrument inks, plastics, and the like.

Claims (5)

(A) a compound obtained by reacting a cyclic acid anhydride with a hydroxyl group-containing compound obtained by reacting a bisphenol fluorene type epoxy compound with an ethylenically unsaturated bond group-containing carboxylic acid, (B) a dispersant, and (Z) a solvent as essential components (C) a first step of dispersing a pigment having a specific surface area of 50 m 2 /g or more by the BET method in a dispersion medium to
a second step of blending (D) a polymerizable monomer having at least one ethylenically unsaturated bond into the dispersion obtained in the first step, and (E) an additive component containing a photoinitiator as essential components;
The manufacturing method of the photosensitive resin composition for color filters characterized by including the 3rd process of filtering the dispersion liquid obtained at the 2nd process with the filtration precision smaller than the film thickness of the cured film formed using it. The method of claim 1,
The manufacturing method of the photosensitive resin composition for color filters characterized by dispersing component C so that the average particle diameter may become 50 nm or less in the said 1st process. 3. The method of claim 1 or 2,
The addition amount of B component in said 1st process is less than 25 weight% with respect to C component, The manufacturing method of the photosensitive resin composition for color filters characterized by the above-mentioned. 3. The method of claim 1 or 2,
A method for producing a photosensitive resin composition for a color filter, wherein component D and component E are selected from compounds having a solubility of 5% by weight or more with respect to component Z. The photosensitive resin composition for color filters manufactured by the manufacturing method of Claim 1 or 2.