JP2007023262A - Pigment-containing thermosetting composition, and color filter, image recording material, and method for producing the color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting composition rich in pigment with a small amount of a resin used, suitable for etching, excellent in spectroscopic characteristics, pattern form's rectangularity and adhesion to lower and upper layers, and capable of thin-film formation, to provide a color filter and an image recording material each using the composition, and to provide a method for producing the color filter. <P>SOLUTION: The pigment-containing heat-curable composition includes a pigment dispersion obtained by dispersing a composition comprising a thermosetting resin, a solvent, and a pigment, wherein the concentration of the pigment is 65 wt.% or more and less than 100 wt.% with respect to the total solid contents. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pigment-containing thermosetting composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device (LCD), a solid-state imaging device (CCD, CMOS, etc.), and the pigment-containing heat. The present invention relates to a color filter using a curable composition, an image recording material, and a method for producing a color filter for performing pattern formation by a dry etching method.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. Further, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is colored by pattern exposure and development. By performing this operation repeatedly for each color, a color filter can be obtained.

  Examples of the pigment dispersion method include a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin (see, for example, Patent Documents 1 to 4).

  In recent years, there has been a demand for higher definition in color filters for solid-state imaging devices, and a technique using a dye has been proposed (see, for example, Patent Document 5). However, the dye-containing curable composition has a problem that it is generally inferior to the pigment in various performances such as light resistance, heat resistance, solubility, and coating uniformity. Furthermore, in particular, in the case of the use for producing a color filter for a solid-state image sensor, a film thickness of 1.5 μm or less is required, so that a large amount of dye must be added to the curable composition, thereby When the adhesion of the ink becomes insufficient, sufficient curing cannot be obtained, or the dye is lost even in the exposed area, there is a problem that the pattern formation is extremely difficult.

Regardless of pigments and dyes, color filters using the photolithographic method need to contain a considerable amount of components other than the colorant, that is, a binder resin, a photopolymerizable compound, and an initiator. is there. However, there is a strong demand for color filters in recent years in order to improve image quality by reducing shading.
In contrast to the color filter manufacturing method using the photolithographic method, a dry etching method has been known for a long time as a method for forming a fine pattern with a thinner film. The dry etching method has been conventionally employed as a method for forming a pattern on a dye-deposited thin film (see, for example, Patent Document 6), and the film is formed with the same spectral characteristics as that of a photolithographic system. A thin film having a thickness of 1/2 or less can also be formed.
However, in the formation of a thin film by vapor deposition, contamination of the vapor deposition apparatus is unavoidable, and it is a heavy load for the production of a color filter. Further, since the pixel is formed only with the pigment or the dye, the adhesion with the lower planarization film or the upper layer is poor, which is one of the causes of the yield not increasing.

JP-A-2-181704 JP-A-2-199403 Japanese Patent Laid-Open No. 5-273411 JP-A-7-140654 JP-A-6-75375 JP-A-55-146406

  The present invention is suitable for etching, has excellent spectral characteristics, rectangular shape of the pattern shape, and adhesion to the lower layer and the upper layer, can be thinned, and has a low total amount of resin used. It is an object of the present invention to provide a high-concentration pigment-containing thermosetting composition, and a color filter and an image recording material using the same. It is another object of the present invention to provide a method for producing a color filter that simultaneously produces an excellent color filter and is produced by dry etching with high cost performance.

Specific means for solving the above problems are as follows.
<1> A pigment dispersion obtained by dispersing a composition containing a thermosetting resin, a solvent, and a pigment is contained in a range where the pigment concentration in the total solid content is 50% or more and less than 100%. This is a pigment-containing thermosetting composition.

  <2> The pigment-containing thermosetting composition according to <1>, further including a curing catalyst for the thermosetting resin.

  <3> The pigment-containing thermosetting composition according to <1> or <2>, wherein the thermosetting resin has an epoxy group.

  <4> A color filter comprising the pigment-containing thermosetting composition according to any one of <1> to <3>.

  <5> An image obtained by laminating a photosensitive resin layer on a colored layer formed using the pigment-containing thermosetting composition according to any one of <1> to <3>. Recording material.

  <6> A method for producing a color filter using the image recording material according to <5>, wherein at least a pattern image is formed on the photosensitive resin layer of the image recording material, and then dry etching is performed, A color filter manufacturing method, wherein a pattern is formed on a colored layer of a recording material.

  According to the present invention, it is suitable for etching, has excellent spectral characteristics, rectangular shape of the pattern shape, and adhesiveness with the lower layer and the upper layer, and can be thinned. It is possible to provide a thermosetting composition containing a small amount of pigment and a color filter and an image recording material using the same. In addition, an excellent color filter can be manufactured at the same time, and a method for manufacturing a color filter manufactured by dry etching with high cost performance can be provided.

  Hereinafter, the pigment-containing thermosetting composition of the present invention, and the color filter, the image recording material, and the method for producing the color filter using the pigment-containing thermosetting composition of the present invention will be described in detail.

<Pigment-containing thermosetting composition>
The pigment-containing thermosetting composition of the present invention is a pigment dispersion obtained by dispersing a composition containing a thermosetting resin, a solvent, and a pigment, and the pigment concentration in the total solid content is 50% or more and less than 100%. It is included in the range which becomes. That is, the pigment-containing thermosetting composition of the present invention can reduce the content of components other than the pigment by imparting a thermosetting function to the resin used for dispersion, and can be a dispersion with a higher pigment concentration. By making the dispersion liquid with a higher pigment concentration, it is possible to further reduce the thickness. The pigment-containing thermosetting composition of the present invention contains a thermosetting compound and other additives as necessary.

-Pigment dispersion-
The pigment dispersion in the present invention is obtained by dispersing a composition containing a thermosetting resin, a solvent, and a pigment.

<Thermosetting resin>
In the present invention, the thermosetting resin is used to disperse the pigment when preparing the pigment dispersion.
The thermosetting resin that can be used in the present invention is not particularly limited as long as the film can be cured by reaction. Examples thereof include phenol resins such as novolac resins; amino resins such as urea resins, melamine resins, and benzoguanamine resins; Allyl resins such as unsaturated polyester resins and diallyl phthalate resins; Epoxy resins such as alkyd resins, bisphenol A type epoxy resins, novolac type epoxy resins, polyfunctional epoxy resins, alicyclic epoxy resins, epoxy resins; urethane resins; silicon resins, etc. Is mentioned. In addition, a resin having a functional group such as an epoxy group, a methylol group, an alkoxymethyl group, or an acyloxymethyl group can be used as appropriate. Among these, an epoxy group-containing resin having an epoxy group is preferable, and a polyfunctional epoxy group-containing resin is particularly preferable.

  The epoxy group-containing resin may be any resin that has an epoxy group and has crosslinkability, such as bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, Divalent glycidyl group-containing low molecular weight compounds such as hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, and N, N-diglycidyl aniline; similarly, trimethylolpropane triglycidyl ether, trimethylol Trivalent glycidyl group-containing low molecular weight compounds typified by phenol triglycidyl ether, TrisP-PA triglycidyl ether, etc .; similarly, pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether and the like; similarly, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether; And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

  Commercially available products include alicyclic epoxy compound “CEL-2021”, alicyclic solid epoxy resin “EHPE-3150”, epoxidized polybutadiene “PB3600”, flexible alicyclic epoxy compound “CEL-”. 2081 ", lactone-modified epoxy resin" PCL-G ", etc. (all are Daicel Chemical Industries, Ltd.). Other examples include “Celoxide 2000”, “Epolide GT-3000”, and “GT-4000” (all of which are Daicel Chemical Industries, Ltd.). Among these, the alicyclic epoxy resin is most excellent in curability, and “EHPE-3150” is most excellent in curability. These compounds may be used alone or in combination of two or more, and combinations with other types shown below are also possible.

The content of the thermosetting resin in the pigment-containing thermosetting composition of the present invention varies depending on the material, but is preferably 35% by mass or less, more preferably 0.1 to 25% by mass, and particularly preferably. Is 1-20 mass%.
The total content of the thermosetting resin and the thermosetting compound described below in the pigment-containing thermosetting composition of the present invention varies depending on the material, but the total solid content of the thermosetting composition ( 70 mass% or less is preferable with respect to (mass), 0.2-50 mass% is still more preferable, and 1-30 mass% is especially preferable.

  These thermosetting resins can be used as an alternative to the dispersing resin when dispersing the pigment, but some of them have weak holding ability. For this reason, a resin obtained by copolymerizing a functional group having a thermosetting function with the binder that has been originally used as a binder for dispersion described below has a holding ability and is preferably used.

-Binder-
The binder conventionally used for the dispersion is not required to be alkali-soluble and may be soluble in an organic solvent.

  The binder is preferably a linear organic polymer that is soluble in an organic solvent. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, polymers obtained by adding acid anhydrides to polymers having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl Alcohol and the like are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Among these various binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

As the acrylic resin, a copolymer comprising monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, for example, benzyl methacrylate / methacrylic acid, Each copolymer such as benzyl methacrylate / benzylmethacrylamide, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.
By dispersing the colorant in these binders at a high concentration, it is possible to impart adhesion to the lower layer and the like, which also contributes to the coated surface shape during spin coating and slit coating.

As the binder, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to 5 × 10. The polymer of ⁴ is particularly preferred.

  The thermosetting resin in the present invention has not only a pigment dispersion resin but also a function of a thermosetting resin. In other words, the thermosetting resin is not particularly limited as long as it is a thermosetting compound and has a binder function, and the binder described above has a thermosetting function. If there is, it can be used as it is. As described above, as the thermosetting resin in the present invention, those containing an epoxy group in the binder are preferable. Among them, in the above acrylic resin system, a resin such as a copolymer of glycidyl (meth) acrylate is used. preferable.

  Examples of such copolymers include benzyl methacrylate / glycidyl methacrylate copolymer, hydroxyethyl methacrylate / benzyl methacrylate / glycidyl methacrylate copolymer, and benzyl methacrylate / hydroxyethyl methacrylate / glycidyl methacrylate / isobutyl. In addition to the methacrylate copolymer, various monomers can be combined depending on the purpose. Moreover, each copolymerization ratio, molecular weight, etc. can be selected arbitrarily.

  By dispersing the pigment in these thermosetting resins at a high concentration, adhesion to the lower layer and the like can be imparted when a film is formed, which can also contribute to the coating surface shape during spin coating and slit coating. it can.

  As content in the curable composition of the said binder, 0.01-90 mass% is preferable with respect to the total solid (mass) of this composition, 0.1-80 mass% is more preferable, and 0.0. 5-70 mass% is especially preferable.

<Pigment>
As the pigment in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Moreover, it is preferable to use as fine a pigment as possible in the present invention, whether inorganic or organic. Considering handling suitability, the average particle diameter of the pigment particles is preferably 0.001 μm to 0.1 μm, and more preferably 0.005 μm to 0.05 μm. The pigment in the present invention particularly preferably contains 75% by mass or more of pigment particles having a particle diameter in the range of 0.01 ± 0.005 μm with respect to the total mass of the pigment particles. In order to achieve such particle size distribution, it is particularly preferable to disperse the pigment by a dispersion method described later.

  Examples of the inorganic pigment include metal compounds represented by metal oxides and metal complex salts, and specifically, aluminum, iron, cobalt, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the like. Mention may be made of metal oxides and composite oxides of the above metals.

As the organic pigment,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment Orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment Violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Brown 25, 28;
Etc.

  Although the following can be mentioned as an organic pigment which can be preferably used in this invention, This invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;
C. I. Pigment Orange 36, 71;
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;
C. I. Pigment Violet 19, 23, 32;
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

  The organic pigments may be used alone or in various combinations in order to increase color purity. As specific examples, red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone, or at least one of them, disazo yellow pigments, isoindoline yellow pigments, and quinophthalone yellow pigments. A combination with a pigment or a perylene red pigment can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. A combination with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50, more preferably 100: 10 to 100: 30. When the mass ratio is within such a range, the light transmittance can be suppressed and the color purity can be improved, and further, it is possible to prevent the main wavelength from becoming shorter than the NTSC target hue. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a combination thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, more preferably 100: 30 to 100: 120. When the mass ratio is within such a range, the light transmittance of 400 nm to 450 nm can be suppressed, the color purity can be improved, and further, the main wavelength can be prevented from deviating from the NTSC target hue due to the longer wavelength. Can do.

  As the blue pigment, a phthalocyanine pigment alone or a combination thereof with a dioxazine purple pigment can be used. Examples of the combination include C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Furthermore, by using a powdered processed pigment in which the above pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like, a pigment-containing photosensitive material having good dispersibility and dispersion stability. Resin can be obtained.

  As described above, the pigment-containing thermosetting composition of the present invention is preferably a method using a pigment having finely divided pigment particles and a sharp particle size distribution. Specifically, a method using a pigment composed of pigment particles having an average particle diameter of about 0.01 μm and a particle diameter of 75% by mass or more in the range of 0.01 ± 0.005 μm is preferable. In order to adjust the particle size distribution of the pigment within the above range, the pigment dispersion method is particularly important. The method for dispersing the pigment will be described later.

  In the present invention, processed pigments previously treated with an acrylic resin, vinyl chloride-vinyl acetate resin, maleic acid resin, ethyl cellulose resin, nitrocellulose resin or the like can also be suitably used. In the present invention, the processed pigment treated with the various resins is preferably a powder, paste, pellet, or paste in which the resin and the pigment are uniformly dispersed.

<Pigment concentration>
The concentration of the pigment in the pigment dispersion is determined so that the pigment concentration with respect to the total solid content of the pigment-containing thermosetting composition of the present invention is 50% by mass or more and less than 100% by mass. The pigment concentration relative to the total solid content of the pigment-containing thermosetting composition of the present invention is more preferably 60% by mass to 95% by mass, and particularly preferably 65% by mass to 90% by mass. If the content of the pigment is less than 50% by mass, desired spectral characteristics cannot be obtained, color reproduction is poor, and gray balance is also shifted. Moreover, it is preferable at the point which has favorable curability as it is the said range.
The content of the pigment dispersion in the present invention in the pigment-containing thermosetting composition of the present invention is also determined based on the pigment concentration.

The color filter produced with the pigment-containing thermosetting composition of the present invention can be made thin while having spectral characteristics comparable to those of a color filter produced by a photolithography method.
Usually, in order to realize a thin film, it is necessary to increase the solid content concentration with respect to a coating film produced by a photolithography method. On the other hand, in order to obtain desired spectral characteristics, it is necessary to improve the concentration of the pigment.
For this reason, if thinning is performed while obtaining the desired spectral characteristics by the photolithographic method, the content of solids other than the pigment will be reduced. As a result, curing failure and loss of the pattern due to alkali development ( Development and rinsing process). For this reason, there is a limit to the pigment concentration in thinning by the photolithographic method, and almost no pattern was formed when the pigment concentration was 65% by mass or more.

  On the other hand, the color filter of the present invention using the pigment-containing thermosetting composition of the present invention cures the coating film (colored layer) containing the pigment with heat and forms a pattern by dry etching, as will be described later. Therefore, it is not necessary to include a monomer (photopolymerizable compound) or a photopolymerization initiator, which are essential components in the photolithography method, in the layer containing the pigment. For this reason, since the pigment-containing thermosetting composition of the present invention is composed at least of a pigment and a resin cured by heat, the pigment concentration can be set to 65% by mass or more.

The ultimate pigment concentration is 100% by mass by the vapor deposition method, and the film thickness can also be reduced by the vapor deposition method, but (1) there is a problem of equipment contamination, and (2) adhesion with the upper layer and lower layer. As described above, there may be a problem in sex.
The method of applying a curable composition with a high pigment concentration by spin coater or slit coating and producing a thin film by thermosetting is slightly thicker than the vapor deposition method in which thermosetting resin is added, but alkali development. Therefore, it is possible to prepare a curable liquid having a high pigment concentration, which cannot be achieved by the photolithography method.

In the pigment-containing thermosetting composition of the present invention, if the pigment concentration is 65% by mass or more, a preferable target film thickness described later can be obtained. For example, a thermosetting method using an epoxy resin described later is employed. In this case, the pigment concentration can be further set to 70% by mass or more. That is, it is possible to form a film that is thinner than the limit of the photolithography method without changing the spectral characteristics.
In addition, by imparting adhesion to components other than pigments, adhesion performance that could not be obtained by vapor deposition can be realized even with high pigment concentrations.

(dye)
The pigment-containing thermosetting composition of the present invention may use a dye together with the pigment.
The dye can be used without any particular limitation, and includes conventionally known dyes for color filters. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828. From the viewpoint of chemical structure, dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes and anthrapyridone dyes.

  In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be preferably used from the viewpoint of completely removing the binder and / or dye by development. In addition, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.

-Acid dyes-
The acid dye will be described. The acidic dye is not particularly limited as long as it is a dye having an acidic group such as sulfonic acid, carboxylic acid, phenolic hydroxyl group, etc., but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curability. It is selected in consideration of all required performance such as interaction with other components in the composition, light resistance, heat resistance and the like.

Hereinafter, specific examples of the acid dye will be given. However, the present invention is not limited to these. For example,
Acid alizarin violet N;
Acid black 1, 2, 24, 48;
Acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
Acid chroma violet K;
Acid Fuchsin;
Acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
Acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

Acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
Acid violet 6B, 7, 9, 17, 19;
Acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes,
Acid black 24;
Acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
Acid orange 8, 51, 56, 74, 63, 74;
Acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
Acid violet 7;
Acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Acid Green 25;
And the like and derivatives of these dyes are preferred.

  Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; I. Solvent Orange 45; Rhodamine B, Rhodamine 110, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino] -2,7-naphthyl, etc. These acid dyes and derivatives of these dyes can also be suitably used.

  As the derivative of the acid dye, an inorganic salt of an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, etc. can be used, and a curable composition solution Is not particularly limited as long as it can be dissolved, but it requires solubility in organic solvents and developers, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. It is selected considering all of the performance.

  The salt of an acid dye and a nitrogen-containing compound will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

The nitrogen-containing compound that forms a salt with the acid dye and the nitrogen-containing compound that forms an amide bond with the acid dye will be described.
Nitrogen-containing compounds are the solubility of salts or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, interaction with other components in the curable composition, and heat resistance as a colorant. In addition, it is selected in consideration of all of light resistance and the like. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.
The molar ratio of nitrogen-containing compound / acid dye (hereinafter referred to as n) in the salt of the acid dye and the nitrogen-containing compound will be described. n is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acid dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

Since the acidic dye shown above is an acidic dye due to the introduction of an acidic group in its structure, it can be made a non-acidic dye by changing its substituent.
In some cases, the acid dye works favorably during alkali development, but on the other hand, it may become over-developed, and a non-acid dye may be preferably used.

<Solvent>
A solvent is used for the pigment dispersion in the present invention (or preparation of the pigment-containing thermosetting composition of the present invention containing the same). As long as the solubility of each component and the applicability of the pigment-containing thermosetting composition are satisfied, the solvent is preferably selected basically in consideration of the solubility, applicability and safety of the dye and binder. In addition, it is preferable that the said organic solvent mixes 2 or more types.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

<Thermosetting compound>
The pigment-containing thermosetting composition of the present invention may contain a thermosetting compound. The thermosetting compound that can be used in the present invention is not particularly limited as long as the film can be cured by heating. For example, a compound having a thermosetting functional group can be used. As the thermosetting compound, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group and an acyloxymethyl group are preferable.

  More preferable thermosetting compounds include (a) the above-mentioned epoxy resin, (b) a melamine compound, a guanamine compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group, A glycoluril compound or a urea compound, and (c) a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups contained in (b) that are substituted for each compound is 2 to 6 for melamine compounds, glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (b).

  The methylol group-containing compound in (b) can be obtained by heating the alkoxymethyl group-containing compound in (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound in (b) can be obtained by mixing and stirring the methylol group-containing compound in (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds in (b) may be used alone or in combination.

  The compound in the above (c), that is, a phenol compound, a naphthol compound or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is a compound in the above (b). As in the case of, the intermixing with the overcoated photoresist is suppressed and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound (containing a methylol group, an alkoxymethyl group or an acyloxymethyl group) in (c).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the compound in (c) above is at least 2 per molecule, and from the viewpoint of thermosetting and storage stability, a phenolic compound that becomes a skeleton A compound in which all of the 2- and 4-positions are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound serving as the skeleton are also preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

As the methylol group-containing compound in (c), a compound in which the phenolic OH group has a hydrogen atom at the 2-position or 4-position is used as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide, etc. Obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound in (c) can be obtained by heating the methylol group-containing compound in (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound in (c) can be obtained by reacting the methylol group-containing compound in (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in (c) include phenolic compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2, 3 -Bisphenols such as xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol A; 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry Co., Ltd. ), Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like.

  Specific examples of (c) include, as a phenol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3- Compound obtained by methoxymethylating one or two methylol groups of cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, tetramethylol Compounds obtained by methoxymethylating 1 to 3 methylol groups of bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishi Roxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound methoxymethylated 1-5 methylol groups, bishydroxymethylnaphthalenediol, etc. Can be mentioned.

  In addition, examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound or Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds in (c) may be used alone or in combination.

  The total content of the thermosetting compound in the pigment-containing thermosetting composition of the present invention is as described above.

<Various additives>
In the pigment-containing thermosetting composition of the present invention, various additives such as a binder, a curing agent, a curing catalyst, a solvent, a filler, and a high amount other than those described above are included in the range that does not impair the effects of the present invention. Molecular compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, dispersants, and the like can be blended.

(Curing agent)
In the present invention, when an epoxy resin is used as the thermosetting resin, it is preferable to add a curing agent. There are many types of curing agents for epoxy resins, and their properties, pot life with resin and curing agent mixture, viscosity, curing temperature, curing time, heat generation, etc. vary greatly depending on the type of curing agent used. An appropriate curing agent must be selected according to the purpose of use, use conditions, working conditions, and the like. The curing agent is described in detail in Chapter 5 of Hiroshi Kakiuchi “Epoxy resin (Shojodo)”. Examples of the curing agent are as follows.
Those that act catalytically include tertiary amines, boron trifluoride-amine complexes, those that react stoichiometrically with functional groups of epoxy resins, polyamines, acid anhydrides, etc .; Examples include diethylenetriamine, polyamide resin, and medium temperature curing examples such as diethylaminopropylamine and tris (dimethylaminomethyl) phenol; examples of high temperature curing include phthalic anhydride and metaphenylenediamine. In terms of chemical structure, amines include diethylenetriamine as an aliphatic polyamine, metaphenylenediamine as an aromatic polyamine, tris (dimethylaminomethyl) phenol as a secondary and tertiary amine, and phthalic anhydride as an acid anhydride. , Polyamide resin, polysulfide resin, boron trifluoride-monoethylamine complex; examples of the synthetic resin initial condensate include phenol resin and other dicyandiamide.

  These curing agents react with an epoxy group by heating and polymerize to increase the crosslinking density and cure. For thinning, both the binder and the curing agent are preferably as small as possible. Particularly, the curing agent is 35% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less with respect to the thermosetting resin. It is preferable that

(Curing catalyst)
A curing catalyst can be used in the pigment-containing thermosetting composition of the present invention. When an epoxy resin is used for the curable resin or the like, useful curing catalysts include imidazole compounds, boron trifluoride complexes (particularly amine complexes), tertiary amines (guanidine, biguanide, titanate, etc.). Among them, an imidazole compound is preferable from the viewpoint of curing speed, and a phosphine derivative, etc. can be used as a curing catalyst, and the addition amount of the curing catalyst is 1 on a mass basis with respect to an epoxy resin having an epoxy equivalent of about 150 to 200. It can be cured in a slight amount of about / 10 to 1/1000, preferably about 1/20 to 1/500, more preferably about 1/30 to 1/250.

  Specific examples of the curing catalyst include those that are commercially available. For example, imidazole silane series “IS-1000”, “IS-1000D”, “IM-1000”, “SP-1000” of Japan Energy Co., Ltd. , “IA-1000A”, “IA-100P”, “IA-100F”, “IA-100AD”, “IA-100FD”, “IM-100F”, “IS-3000”, “IS-4000”, etc. In addition, “1B2PZ” and “SFZ” manufactured by Shikoku Kasei Co., Ltd. are useful, but the present invention is not limited thereto.

(Dispersant)
The dispersant can be added to improve the dispersibility of the pigment. As the dispersant, known ones can be appropriately selected and used, and examples thereof include a cationic surfactant, a fluorosurfactant, and a polymer dispersant.

  Furthermore, the graft copolymer having a specific acid amide group-containing monomer and a quaternary ammonium salt monomer residue in the main chain described in JP-A-10-254133 has an excellent effect of finely dispersing the pigment. Therefore, it can be used as the dispersant. By using the graft copolymer, it is possible to finely disperse the pigment while reducing energy and time consumption, and the dispersed pigment may aggregate or settle even over time. Long-term dispersion stability can be maintained.

  The dispersants may be used alone or in combination of two or more. The amount of the dispersant added to the pigment-containing thermosetting composition of the present invention is usually preferably about 0.1 to 50 parts by mass with respect to 100 parts by mass of the pigment.

(Other additives)
Specific examples of the above-mentioned various other additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; , Cationic and anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyl Adhesion promoters such as limethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4- Antioxidants such as methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxy UV absorbers such as benzophenone; and anti-aggregation agents such as sodium polyacrylate.

<Method for preparing pigment-containing thermosetting composition>
A method for preparing the pigment-containing thermosetting composition of the present invention that is preferable in the present invention will be described. However, the present invention is not limited to this.

As described above, the pigment-containing thermosetting composition of the present invention is characterized by using a pigment dispersion in which a pigment is dispersed together with a solvent in the presence of a thermosetting resin. As a method for dispersing the pigment, a method using a pigment having finely divided pigment particles and a sharp particle size distribution is suitable. Specifically, a method using a pigment composed of 75% by mass or more of pigment particles having an average particle size of about 0.01 μm and a particle size in the range of 0.01 ± 0.005 μm is preferable.
In order to adjust the particle size distribution of the pigment within the above range, the pigment dispersion method is particularly important. As such a dispersion method, for example, dry dispersion (kneading dispersion treatment) in which a high-viscosity state is dispersed using a roll mill such as a kneader or two-roll, and a relatively low-viscosity state using a three-roll or bead mill is used. Examples of the dispersion method include a combination of wet dispersion (fine dispersion treatment) for dispersion. In the dispersion method, it is also preferable to co-disperse two or more kinds of pigments or not to use a solvent or to minimize the amount used during the kneading dispersion treatment. In order to relieve the solvent shock, it is preferable to add the thermosetting resin component separately during the kneading dispersion treatment and during the fine dispersion treatment (use in two divisions), and shift from the kneading dispersion treatment to the fine dispersion treatment. In order to prevent re-aggregation of the pigment particles, it is preferable to use a thermosetting resin component having excellent solubility. Furthermore, it is also effective to use high hardness ceramics or beads with a small particle diameter for the beads of the bead mill used during the fine dispersion treatment.

In the present invention, in particular, two or more pigments are used, and two or more pigments are further dispersed in a high viscosity state of 50000 mPa · s or more, and then further dispersed in a low viscosity state of 1000 mPa · s or less. It is preferable to use a pigment.
Generally, these pigments are supplied after drying by various methods after synthesis. Usually, it is dried from an aqueous medium and supplied as a powder. However, since water requires a large latent heat of vaporization for drying, a large amount of heat energy is given to dry it to form a powder. Therefore, the pigment usually forms an aggregate (secondary particle) in which primary particles are aggregated.

In the method for preparing a pigment-containing thermosetting composition of the present invention, first, a pigment dispersion in which a pigment is dispersed together with a solvent in a thermosetting resin is prepared.
Specifically, the kneading and dispersing treatment is performed so that the viscosity after kneading and dispersing the thermosetting resin to the pigment is 50,000 mPa · s or more (preferably 50,000 to 100,000 mPa · s). It is preferable to apply. Here, the kneading dispersion treatment may be high viscosity dispersion or dry dispersion.

  Then, if necessary, a thermosetting resin or other dispersant is additionally added to the pigment dispersion after the kneading dispersion treatment, and the viscosity after the fine dispersion treatment is 1000 mPa · s or less (preferably 100 mPa · s or less). It is preferable to perform a fine dispersion treatment so that the viscosity is relatively low. The fine dispersion treatment may be low viscosity dispersion or wet dispersion.

  In the kneading and dispersing treatment, the solvent ratio is preferably 0 to 20% by mass with respect to the dispersion. Thus, when the dispersion is performed without using much solvent, the surface of the pigment particles can promote the wetting with the constituent component mainly composed of the resin component of the vehicle. The solid / gas interface between the pigment particles and air can be converted to a solid / solution interface between the pigment particles and the vehicle solution. When the interface formed by the surfaces of the pigment particles is converted from air to a solution and mixed and stirred, the pigment can be dispersed to a fine state close to the primary particles.

  Thus, in order to highly disperse the pigment, it is effective to convert the interface formed by the pigment particle surface from air to a solution. Such conversion requires a strong shearing force or compressive force. For this reason, in the said kneading | mixing dispersion | distribution process, it is preferable to use the thing of high viscosity as a to-be-kneaded material using the kneader which can exhibit strong shearing force and compressive force.

  In the fine dispersion treatment, it is preferable to mix and stir together with fine dispersion media such as glass or ceramic. Furthermore, it is preferable that the ratio of the solvent at the time of a fine dispersion process is 20-90 mass% of to-be-dispersed material. At the time of the fine dispersion treatment, since it is necessary to distribute the pigment particles uniformly and stably to a fine state, a disperser capable of imparting impact force and shear force to the agglomerated pigment particles; It is preferable to use a low-viscosity material.

  The thermosetting compound of the present invention is added to the pigment dispersion thus obtained by adding a curing catalyst or a curing agent or a thermosetting compound as necessary, and further adding a solvent as necessary. Can be prepared.

<Image recording material>
A colored layer is produced using the pigment-containing thermosetting composition of the present invention, and a photosensitive resin layer using the photosensitive resin composition is further laminated to be used as the image recording material of the present invention.

<Colored layer>
The coloring layer is, for example, a coating method such as spin coating, slit coating, cast coating, roll coating, etc., on the support directly or via another layer with the pigment-containing thermosetting composition of the present invention containing a solvent. Can be formed by coating.
The specific thickness of the colored layer is preferably 0.005 μm to 0.9 μm, preferably 0.01 μm to 0.65 μm, and more preferably 0.02 μm to 0.6 μm.

  The colored layer is preferably formed by applying the pigment-containing thermosetting composition of the present invention to form a coating film, and then thermally curing the coating film by a heating process. The heating step may be performed at the same time as drying after coating, or a separate thermosetting step may be provided after coating and drying. In the heating step, a known heating means such as an oven or a hot plate is used, preferably 130 ° C. to 300 ° C., more preferably 150 ° C. to 280 ° C., particularly preferably 170 ° C. to 260 ° C., preferably 10 ° C. Second to 3 hours, more preferably 30 seconds to 2 hours, particularly preferably 60 seconds to 60 minutes. However, considering the production, the time required for curing is preferably as short as possible.

<Photosensitive resin layer>
As described above, after forming a colored layer using the pigment-containing thermosetting composition of the present invention and curing it by heating, a positive or negative photosensitive resin composition is formed on the layer. The used photosensitive resin layer can be provided.
The positive photosensitive resin composition is used for positive photoresists that are sensitive to radiation such as ultraviolet rays (g rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams, and X rays. Any suitable positive resist composition can be used. Of the radiation, the one that exposes the photosensitive resin layer is preferably g-line or i-line for the purpose of the present invention, and i-line exposure is particularly preferable.

  Specifically, the positive photosensitive resin composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive-type photosensitive resin composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by light irradiation with a wavelength of 500 nm or less to generate a carboxyl group, and as a result, the alkali-insoluble state becomes alkali-soluble. It is used as a positive photoresist. Since this positive photoresist has remarkably excellent resolution, it is used for manufacturing integrated circuits such as ICs and LSIs. Examples of the quinonediazide compound include naphthoquinonediazide compounds.

  In recent years, with respect to integrated circuits, the width of wiring has become finer as the degree of integration has improved, and for this reason, dry etching has become the mainstream in place of conventional wet etching. In this dry etching, the shape of the resist is directly reflected in the shape of the layer to be etched. Therefore, if the shape of the resist is poor, etching is performed up to a portion that does not require etching, which may cause defective integrated circuits and poor yield. For this reason, a resist having a good profile with little development residue (scum) or the like is required more than ever. Further, in dry etching, the temperature of the substrate rises, and the resist pattern may be thermally deformed to reduce the dimensional accuracy. For this reason, the heat resistance of a resist is requested | required more than before. Looking at positive photoresists currently used from this point of view, many products that satisfy various performances such as profile, scum, resolution and heat resistance are commercially available. For example, Fuji Film Electronics Materials ( FH-6000 series, for example, “FH-6400L”, “FH-6800L”, etc., and FHi-3000 series, for example, “FHi-3200”, “FHi-3950”, etc. Series such as “FHi-644”, “FHi-645”, and Fi-SP series manufactured by the same company such as “Fi-SP2” can be mentioned. However, the present invention is not limited to this, and it can be used as a positive-type photosensitive resin composition regardless of whether it is commercially available as long as it has a mask shape preferable for pattern formation.

  Examples of the negative photosensitive resin composition include negative photoresists sensitive to radiation rays such as ultraviolet rays (g rays, i rays), far ultraviolet rays, X rays, electron rays, molecular rays, γ rays, and synchrotron radiation. A composition. More specifically, a negative photoresist composition that is excellent in resolving power and sensitivity and that does not substantially cause microdefects due to undeveloped residues is preferable. The negative photoresist according to the present invention is applied on the colored layer to a thickness of, for example, 0.5 μm to 3 μm by spin coating or roller coating. Thereafter, it is heated and dried, a circuit pattern or the like is printed by ultraviolet irradiation through an exposure mask, and if necessary, after a post-exposure heating step (PEB), development is performed to obtain a negative image. Further, patterning can be applied to the thermosetting resin layer by etching using this image as a mask. Typical application fields are semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, and other photof application processes. Moreover, it can also be applied to a lithographic printing plate by utilizing the difference in affinity between the image and the support substrate for ink. With higher integration of semiconductor substrate processing, higher resolution of the photoresist is required.

  The negative photosensitive resin layer preferably contains a photopolymerization initiator and a polymerizable compound having an ethylenically unsaturated bond. The following prior art is known about the negative photosensitive resin composition used for formation of such a photosensitive resin layer. For example, Japanese Patent Publication No. 54-23574 discloses a technique for photocuring a novolak resin in combination with a photoacid generator composed of an organic halide. Also, West German Patent Publication No. 2057473 discloses that a phenol resin such as novolak can be applied as a binder between a photoacid generator composed of a diazo compound and a photocurable composition composed of methylolated melamine. Further, JP-A-60-263143 discloses a composition comprising a photoacid generator, an acid curable amino blast resin such as a melamine resin, and a general novolac resin, and is aqueous developable and heat stable. High negative image is obtained. JP-A-62-164045 discloses that an organic halide having light absorption in the far ultraviolet region can be advantageously used as a photoacid generator for such a composition. Similarly, Japanese Patent Application Laid-Open No. 2-52348 states that an organic halide having a pKa value in a specific region is advantageous as a similar photoacid generator. Furthermore, Japanese Patent Application Laid-Open No. 2-154266 shows that oxime sulfonic acid esters are effective as a photoacid generator for a similar photocurable composition. As another example, JP-A-2-146444 discloses a composition in which a photoacid generator having a specific trichlorotriazine group and a novolak resin containing 30% or more of m-cresol in alkoxylated melamine are combined. It is useful for high energy beam exposure. Further, European Patent No. 396460A discloses that a novolak resin having a high degree of branching is used in a similar composition. These negative photosensitive resin compositions are commercially available, for example, SC series manufactured by Fujifilm Electronics Materials, Inc., such as “SC-60”, “SC-450”, etc. HR series, for example, “HR-100”, “HR-200”, HNR series manufactured by the same company, for example, “HNR-80”, “HNR-120”, and the like. However, the present invention is not limited to these, and any mask having a preferable shape for pattern formation can be used regardless of whether it is commercially available.

  The specific thickness of the photosensitive resin layer is preferably 0.01 μm to 3 μm, preferably 0.1 μm to 2.5 μm, and more preferably 0.15 μm to 2.0 μm. It can be set arbitrarily and is not limited to this.

<Support>
In the image recording material of the present invention, a colored layer is usually formed on a support.
Examples of the support include soda glass, Pyrex (registered trademark) glass, and quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, and photoelectric conversion element substrates used for imaging elements and the like. Examples thereof include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These supports may be formed with black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

<< Color filter and manufacturing method thereof >>
The image recording material of the present invention described above can be effectively used as a color filter material. The manufacturing method will be described in detail below. In the color filter manufacturing method of the present invention, as already described, pattern formation is performed by dry etching.

  In a preferred embodiment of the method for producing a color filter of the present invention, an etching mask (pattern image) is formed on the photosensitive resin layer by a photolithography method, and a pattern is formed on the colored layer by a dry etching method.

First, the photosensitive resin layer described above is exposed to g-line, h-line, i-line, etc. through a predetermined mask pattern, particularly preferably i-line, and developed with a developer. A pattern is formed in the resin composition. In the method for producing a color filter of the present invention, the pattern of the photosensitive resin layer formed here is used as a pattern mask, and dry etching is performed using a gas such as oxygen, CF ₄ , or CO ₂ . By this step, the colored layer is etched into the pattern of the pattern mask, and a color pattern can be formed.

  After the etching is completed, the mask resist (photosensitive resin layer after exposure) is removed with a special stripping solution or solvent. The removal of the resist may be performed after all steps are completed. Next, a pattern is produced by the same method for the second and subsequent colors. For the pattern formation of the last color, only thermosetting is performed, the excess pigment thermosetting composition remaining in the upper layer is removed, planarization is performed by CMP (Chemical mechanical polishing), and all color patterns are formed. Fabrication may be performed.

  Any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer containing the pigment. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

<Dry etching>
The color filter manufacturing method of the present invention forms a pattern by a dry etching method. Representative examples of the dry etching method include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102. As described in the above publications, there is a method of depositing a colorant, applying a mask resist, patterning, and etching.
Examples of the gas used for the dry etching process include O ₂ and CF ₄ .

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

The method for producing a color filter of the present invention is to apply a uniform coating to a spin coater or slit coat at a high pigment concentration that has never been achieved so as to realize a film thickness and adhesion close to vapor deposition, from photolitho method to thermosetting method. By reducing the solid content other than the colorant to the utmost by changing the process, the formation of a rectangular pattern while maintaining the pattern anisotropy by dry etching, and the combination of these, It was possible to realize pattern rectangularity and adhesion with a thin film thickness that could not be achieved. Thus, by using the method for producing a color filter of the present invention, a color filter having a very high pattern rectangularity can be obtained by anisotropically etching a thin film containing a thermoset pigment with a gas such as oxygen or CF _4. Can be made and is very useful.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.

[Example 1]
<< Preparation of pigment-containing thermosetting composition for color filter >>
<Preparation of pigment dispersion>
For each color of green (G), blue (B), and red (R), each material shown in Table 1 below is uniformly kneaded with a kneader, and the kneaded product is then subjected to dry dispersion treatment (kneading dispersion treatment) with two rolls. did.
Next, 785 parts by mass of propylene glycol monomethyl ethyl acetate as a solvent component was added to the dispersion subjected to the dry dispersion treatment. Thereafter, the mixture was stirred with a homogenizer at 2000 rpm for 30 minutes to prepare a dispersion composition of each color of green (G), blue (B), and red (R) in which the pigment was uniformly dispersed. The obtained dispersion composition was finely dispersed with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads.

  Then, it filtered with a 2.5 micrometer filter, and obtained the pigment dispersion liquid (1)-(3) of each color in which the pigment was disperse | distributed uniformly. For each pigment dispersion, the viscosity of the kneaded product (dispersion) at the time of the kneading dispersion treatment and the fine dispersion treatment, and the average particle diameter and the particle diameter of 0.01 ± 0.005 μm in each pigment dispersion liquid Table 1 shows the ratio of the pigment particles. In addition, the particle diameter of the pigment was measured by using MICROTRAC UPA 150 manufactured by Nikkiso Co., Ltd. and using each of the colored resin compositions diluted with propylene glycol monomethyl ethyl acetate as a sample.

<Preparation of pigment-containing thermosetting composition>
For the pigment dispersion of each color, 0.4 parts by mass for the pigment dispersion (1), 0.2 parts by mass for the pigment dispersion (2), and for the pigment dispersion (3) 0.3 parts by mass of a curing catalyst (“1B2PZ manufactured by Shikoku Kasei Co., Ltd.) was added. After confirmation of dissolution, pigment was added with propylene glycol monomethyl ethyl acetate so that the solid content in the composition was 15% by mass. Dilution was made with care so as not to cause a shock.By the above procedure, the pigment dispersion (1) was 79.3% by mass, the pigment dispersion (2) was 73.0% by mass, and the pigment dispersion (3) was A pigment-containing thermosetting composition having a high pigment concentration of 79.8% by mass was prepared.

《Pattern formation》
About each pigment-containing thermosetting composition obtained as described above, a spin coater on a silicon wafer substrate having an undercoat layer using “CT-2000L” manufactured by FUJIFILM Electronics Materials, After coating each so as to form a coating film having a thickness of 0.5 μm, heat treatment was performed at 100 ° C. for 2 minutes on a hot plate to dry the coating film. Next, using a hot plate, the coating film was cured by heating at 220 ° C. for 7 minutes.

Next, “FHi-3950” manufactured by FUJIFILM Electronics Materials Co., Ltd. was applied to the upper layer of each color-cured application sample with a spin coater so that the film thickness was 1.5 μm. Subsequently, after heat-processing at 100 degreeC for 2 minutes and drying a sample, 200 mJ pattern exposure was performed with the i line | wire stepper.
Next, each color sample was developed with “FHD-5” manufactured by FUJIFILM Electronics Materials for 1 minute to form a 1.5 μm × 1.5 μm size mask. These samples, subjected to dry etching unmasked portions at _{CF 4 / O 2 / Ar =} 2/2/1 ratio mixed gas was subjected to patterning. Thereafter, the resist was stripped using a stripping solution “MS-230” manufactured by FUJIFILM Electromaterials, Inc., and a 1.5 μm square pattern with high rectangularity was completed for each color.

[Example 2]
First, according to Example 1, a blue (B) pattern was formed. Next, for this sample, a second color (green (G)) and third color (red (R)) pattern was formed as follows.
First, the green (G) pigment-containing thermosetting composition of Example 1 was applied on a silicon wafer substrate on which a blue (B) pattern was formed so that the film thickness was 0.5 μm, and 100 ° C. Heat treatment for 2 minutes was performed.

  Next, in the same manner as in Example 1, a photoresist “FHi-3950” was applied on the cured sample, and the blue (B) pattern and the green (G) 0.5 μm pattern formed by the i-line stepper. The film was exposed with a pattern capable of covering the film, and then developed with the “FHD-5” for 1 minute. Here, the upper surface of the blue (B) pattern formed above and the layer of the green pigment-containing thermosetting composition is coated with a photoresist on the portions to be the blue (B) pattern and the green (G) pattern. It was in a state. Next, dry etching was performed in the same manner as in Example 1 to form a green (G) pattern. The remaining mask resist was removed with the same remover as in Example 1 to complete the second color.

The sample was further coated with a red (R) pigment-containing thermosetting composition of the third color, and then heat-treated at 220 ° C. for 7 minutes after heat treatment at 100 ° C. for 2 minutes. Next, this sample is etched with O ₂ gas to remove the red (R) film on the first and second color patterns, and further flattened to produce RGB three-color color filters. did. Further, the color filter of the present invention had no peeling during the process up to the formation of the third color, and was excellent in adhesion.

[Example 3]
In the same manner as in Example 2, RGB color filters were produced. However, for the green (G) pigment dispersion, the yellow pigment is changed from PY-139 to PY-150, and the etching gas used for etching the green (G) coating film is CO / O ₂ = 1 / 1 gas mixture.

[Comparative Example 1]
<Preparation of pigment dispersion>
Each pigment dispersion having the composition shown in Table 2 below was prepared.

<Preparation of colored resinous composition>
Each of the pigment dispersions (4) to (6) obtained from the above and the following composition were uniformly mixed with a mixer to prepare a colored resin composition for a color filter for each color.
1. Green (G) (for pigment dispersion (4) 808 parts by mass)
<Composition>
Dipentaerythritol pentaacrylate (monomer) 10 parts by mass Propylene glycol monomethyl ethyl acetate (solvent) 120 parts by mass Ethyl-3-ethoxypropionate (solvent) 50 parts by mass Halogenated triazine initiator 2 parts by mass

2. Blue (B) (for pigment dispersion (5) 981 parts by mass)
<Composition>
Dipentaerythritol pentaacrylate (monomer) 7 parts by weight Propylene glycol monomethyl ethyl acetate (solvent) 100 parts by weight Ethyl-3-ethoxypropionate (solvent) 40 parts by weight Halogen triazine initiator 2 parts by weight

3. Red (R) (about 634 parts by mass of pigment dispersion (6))
<Composition>
-Dipentaerythritol pentaacrylate (monomer) 5 parts by mass-Propylene glycol monomethyl ethyl acetate (solvent) 70 parts by mass-Ethyl-3-ethoxypropionate (solvent) 30 parts by mass-Halomethyltriazine-based initiator 1 part by mass

  As described above, a colored resin composition to which a photolitho function was imparted at the same pigment concentration as in Example 1 of each color was prepared. With respect to these colored resin compositions, in order to produce a color filter, each of the colored resin compositions on a silicon wafer primed with “CT-2000L” manufactured by FUJIFILM Electronics Materials Co., Ltd., as in Example 1. Was applied with a spin coater to a film thickness of 0.5 μm, and heat treatment was performed at 100 ° C. for 2 minutes on a hot plate to dry the coating film. This sample was exposed to a pattern of 1.5 μm with an i-line stepper and developed with a “CD-2000” alkaline developer manufactured by FUJIFILM Electronics Materials Co., Ltd. The pattern could not be formed. From this result, it is clear that, in the high pigment concentration region as in the present invention, the pattern formation by dry etching by the thermosetting method is optimal as in the color filter manufacturing method of the present invention. It was proved again that this is an essential technology for thinning.

<Evaluation>
The following evaluation was performed for Examples 1 to 3 and Comparative Example 1. The results are shown in Table 3 below.
<Evaluation criteria>
1. Observing the SEM photograph of the cross section of the obtained pattern, the one with a rectangular cross section is “O”,
A taper-like cross-sectional shape that was not rectangular was designated as “x”.

2. Developability The degree of dissolution of the colored film before and after the development of the mask resist was observed, and “◯” indicates that there was no dissolution and development defect, and “X” indicates that the dissolution and development defect was observed.

3. Surface state SEM photograph of the cross section of the obtained pattern is observed, the cross section is rectangular, relative evaluation is made, “○” indicates that the surface and side surfaces have almost no unevenness, and “△” indicates that clear unevenness can be confirmed. ”, Those having clear irregularities and having holes and defects were evaluated as“ x ”.

4). Adhesion Polishing resistance was evaluated using CMP (Chemical mechanical polishing). At this time, the case where there was no peeling was evaluated as “◯”, the case where peeling was less than 20% was evaluated as “Δ”, and the case where peeling was 20% or more was evaluated as “x”.

  As is apparent from the results in Table 3, Examples 1 to 3 were satisfactory for all evaluations. From these results, it can be seen that the method for producing a color filter of the present invention is excellent.

Claims (4)

  A pigment containing liquid dispersion comprising a pigment dispersion obtained by dispersing a composition containing a thermosetting resin, a solvent, and a pigment in a range where the pigment concentration in the total solid content is 50% or more and less than 100%. Thermosetting composition.   A color filter comprising the pigment-containing thermosetting composition according to claim 1.   An image recording material comprising a photosensitive resin layer laminated on a colored layer formed using the pigment-containing thermosetting composition according to claim 1.   A method for producing a color filter using the image recording material according to claim 3, wherein a pattern image is formed at least on the photosensitive resin layer in the image recording material, and then dry etching treatment is performed to color the image recording material. A method for producing a color filter, wherein a pattern is formed on a layer.