JP2006106099A - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-containing negative curable composition suitable for use of a dye, excellent in rectangularity of a pattern shape, ensuring a very small change in the rectangularity by heating after development, and obtaining high hardness, and to provide a color filter using the composition and a method for producing the color filter. <P>SOLUTION: The dye-containing negative curable composition contains (A) an alkali-soluble binder, (B) an organic-solvent-soluble dye, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an organic solvent, (F) a higher fatty acid or at least one derivative thereof, and (G) a surfactant. The color filter is obtained using the composition. The method for producing the color filter is also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device (LCD), a solid-state image pickup device (CCD, CMOS, etc.), and the dye-containing negative. The present invention relates to a color filter using a mold curable composition and a method for producing the same.

  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 photolithographic 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. In addition, since patterning is performed by a photolithography method, it is widely used as a suitable method for producing 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 subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each color.

  As said pigment dispersion method, the thing using the negative photosensitive composition which used together the photopolymerizable monomer and the photoinitiator for alkali-soluble resin is proposed (for example, refer patent documents 1-4). ).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution in the conventional pigment dispersion system, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications requiring a fine pattern such as a solid-state imaging device. Was not suitable.

  In order to solve such a problem, a technique of using a dye instead of a pigment has been conventionally proposed (for example, see 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 the case of the use for producing a color filter for a solid-state imaging device, a film thickness of 1.5 μm or less is particularly required. Therefore, a large amount of dye must be added to the curable composition, thereby When the adhesion is insufficient, sufficient curing cannot be obtained, or the dye is lost even in the exposed area, there is a problem that the rectangularity of the pattern shape is extremely difficult.

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

  INDUSTRIAL APPLICABILITY The present invention is suitable for the use of dyes, is excellent in pattern shape rectangularity, has a very small change in rectangularity due to heating after development processing, and has high hardness and contains a dye-containing negative curable composition. An object of the present invention is to provide a color filter using the. At the same time, an object is to provide a method for producing a color filter that can produce an excellent color filter and has high cost performance.

Specific means for solving the above problems are as follows.
<1> (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an organic solvent, (F) a higher fatty acid or a derivative thereof It is a dye-containing negative curable composition characterized by containing one type and (G) a surfactant.

  <2> The dye-containing negative curable composition according to <1>, wherein the content of the (F) higher fatty acid or derivative thereof is 0.01 to 40% by mass relative to the total solid content.

  <3> The dye-containing negative curable composition according to <1>, wherein the content of the (F) higher fatty acid or derivative thereof is 0.1 to 25% by mass relative to the total solid content.

  <4> The dye-containing negative curable composition according to <1> to <3> above, wherein the (F) higher fatty acid or derivative thereof has 11 or more carbon atoms per molecule.

  <5> The dye according to <1> to <4> above, wherein at least one of the (F) higher fatty acid or a derivative thereof is a saturated fatty acid having 11 or more carbon atoms per molecule or a derivative thereof. It is a negative curable composition.

  <6> The above-mentioned <1> to <4>, wherein at least one of the (F) higher fatty acid or its derivative is an unsaturated fatty acid having 11 or more carbon atoms per molecule or a derivative thereof It is a dye-containing negative curable composition.

  <7> As the (F) higher fatty acid or derivative thereof, a saturated fatty acid having 11 or more carbon atoms per molecule or a derivative thereof, and an unsaturated fatty acid having 11 or more carbon atoms per molecule or a derivative thereof, The dye-containing negative curable composition according to the above <1> to <4>, characterized in that

  <8> (F) At least one of higher fatty acids or derivatives thereof is a compound selected from palmitic acid, stearic acid, behenic acid, arachidic acid, myristic acid, and derivatives thereof. It is a dye-containing negative curable composition of 1> to <7>.

<9> The dye-containing negative curable composition according to the above <1> to <8>, wherein the (G) surfactant is a nonionic surfactant or an anionic surfactant.
<10> A mass ratio ((G) / (F)) of the (F) higher fatty acid or a derivative thereof and the (G) surfactant is 1 or less. 9> A dye-containing negative curable composition.

  <11> A color filter using the dye-containing negative curable composition according to <1> to <10> above.

  <12> A color filter comprising the steps of applying the dye-containing negative curable composition of the above <1> to <10> on a support, exposing through a mask, and developing to form a pattern It is a manufacturing method.

  According to the present invention, by adding a higher fatty acid and / or derivative and a surfactant to a dye-containing negative curable composition, it is suitable for use of a dye, has excellent rectangular shape of a pattern shape, and A change in rectangularity due to heating after development processing is very small, and a dye-containing negative curable composition having high hardness, a color filter using the same, and a method for producing the same can be provided.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter constituted using the dye-containing negative curable composition, and a method for producing the same will be described in detail.

  The dye-containing negative curable composition of the present invention comprises (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an organic solvent, (F) at least one of higher fatty acids and derivatives thereof (hereinafter sometimes simply referred to as “higher fatty acids in the present invention”), (G) at least a surfactant and further containing other components such as a crosslinking agent. May be included.

  According to the present invention, it is possible to improve the rectangularity of the pattern shape of the dye-containing negative curable composition by using the higher fatty acid and the surfactant in the present invention in combination and using them in a system using a dye. In addition, the change in rectangularity due to heating after development is very small, and a pattern with high hardness can be formed.

-(A) Alkali-soluble binder-
The alkali-soluble binder will be described. The alkali-soluble binder in the present invention is not particularly limited as long as it is water-soluble or alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. 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-. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer , Maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Similarly, an acidic cellulose derivative having a carboxylic acid in the side chain is useful as the linear organic polymer.

In addition to the above, examples of the linear organic polymer include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meta) ) Acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful.
The linear organic polymer may be a copolymer of hydrophilic monomers, and examples thereof include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol ( (Meth) acrylate, (meth) acrylamide, N-methylolacrylamide, secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, Vinyl triazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) Acrylate, and the like.

  In addition, monomers having a tetrahydrofurfuryl group, phosphoric acid, phosphate ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group, etc. as the above-mentioned hydrophilic monomers Etc. are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and is a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain. Etc. are also useful. Examples of the polymer containing the polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful as the alkali-soluble binder in the present invention.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106. (Osaka Organic Chemical Co., Ltd.), Cyclomer P series (Daicel Chemical Industries, Ltd.) and the like are preferable.

As the alkali-soluble 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 is preferable. A polymer of × 10 ⁴ is particularly preferred.

  As content of the said alkali-soluble binder in the dye-containing negative curable composition of this invention, 10-90 mass% is preferable with respect to the total solid (mass) of a composition, and 20-80 mass% is further. 30 to 70% by mass is preferable.

-(B) Organic solvent soluble dye-
The organic solvent-soluble dye in the present invention can be used without particular limitation as long as it is a dye soluble in an organic solvent, and examples thereof include conventionally known dyes for color filters. Specifically, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 4,808. No. 5,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6- Examples thereof include dyes described in Japanese Patent No. 51115, Japanese Patent Laid-Open No. 6-194828, and the like. From the viewpoint of chemical structure, use dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, etc. be able to. Particularly preferable as the organic solvent-soluble dye 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, acidic dyes and / or derivatives thereof may be preferably used from the viewpoint of completely removing the alkali-soluble 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 dye ~
The acid dye will be described. The acid dye is not particularly limited as long as it is a dye having an acid group such as sulfonic acid, carboxylic acid, or phenolic hydroxyl group, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, curing. It is preferably selected in consideration of all the required performances 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. As the acid dye, 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, 163, 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 above 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, C.I. I. Solvent Orange 45, Rhodamine B, Rhodamine 110, 2,7-Naphthalenedisulphonic acid, 3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5- [minyl] (3-[(5-chloro-2-phenoxyphenyl) hydrazono] -3,4-dihydro-4-oxo-5-[(phenylsulfonyl) amino]), and the like, and of these dyes Derivatives can also be preferably used, and azo, xanthene and phthalocyanine acid dyes other than those mentioned above are also preferred, and CI Solvent Blue 44 is particularly preferred.

  Examples of the acid dye derivatives include inorganic salts of acid dyes having an acid group such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, and sulfonamides of acid dyes (depending on acid dyes and nitrogen-containing compounds). The compound having an amide bond formed) can be used and is not particularly limited as long as it can be dissolved as a curable composition solution. However, solubility in organic solvents and developers, absorbance, and curable composition It is selected in consideration of all the required performance such as interaction with other components, light resistance, heat resistance and the like.

  The salt of the said acid dye and a nitrogen-containing compound is demonstrated. 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.
The above 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. Selected in consideration of all of light resistance and light resistance. When selecting only from the viewpoint 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. The above 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 above-mentioned acidic dye has become an acidic dye by introducing an acidic group on its structure, it can be made a non-acidic dye by changing its substituent.
The acidic dye may act suitably during alkali development, but may sometimes be overdeveloped. For this reason, a non-acidic dye may be preferably used when overdevelopment occurs during alkali development.

  The content concentration of the organic solvent-soluble dye will be described. The content concentration of the organic solvent-soluble dye in the total solid components of the dye-containing negative curable composition of the present invention varies depending on the dye, but from the viewpoint of balancing the color reproducibility and the film hardening property, it is preferably set to 0. 5-80 mass% is preferable, 0.5-60 mass% is still more preferable, 0.5-50 mass% is especially preferable.

-(C) Photopolymerizable compound-
Next, the photopolymerizable compound in the present invention will be described. The photopolymerizable compound in the present invention is not particularly limited as long as it is a compound polymerized by a photopolymerization initiator, but a radical polymerizable monomer can be preferably used. The radical polymerizable monomer is preferably a compound having at least one addition polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure. The dye-containing negative curable composition of the present invention is formed into a negative type by containing the photopolymerizable compound according to the present invention together with a photopolymerization initiator described later.

  Examples of the radical polymerizable monomer include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate , Trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, hexanediol (meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate; one obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane; Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, Polyester acrylates described in JP-B-52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof be able to. Furthermore, as said radically polymerizable monomer, Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  As content of the said photopolymerizable compound in the dye-containing negative curable composition of this invention, from a viewpoint of improving the hardness and rectangularity of a coating film, it is set to the total solid content (mass) of this composition. On the other hand, 0.1-90 mass% is preferable, 1.0-80 mass% is still more preferable, and 2.0-70 mass% is especially preferable.

-(D) Photopolymerization initiator-
Next, the photopolymerization initiator in the present invention will be described. The said photoinitiator is contained with the said photopolymerizable compound in order to comprise a dye containing negative curable composition in a negative type. The photopolymerization initiator is not particularly limited as long as it can polymerize the photopolymerizable compound, but is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds; 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenones Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of the active halogen compound that is the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl, and the like. -5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxy) Styryl) -1,3,4-oxadiazole, and the like.

  Examples of the active halogen compound which is the halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in Japanese Patent Publication No. 59-1281 and 2- (naphtho) described in JP-A-53-133428. -1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples of the photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,6-bis (trichloromethyl) -4- (3,4- Methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy) -Naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, as the above photopolymerization initiator, commercially available TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, manufactured by Midori Chemical Co., Ltd.) TAZ-113, TAZ-123), T series made by PANCHIM (for example, T-OMS, T-BMP, T-R, TB), Irgacure series made by Ciba Specialty Chemicals (for example, , Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyl) Oxime) -1- [4- (phenylthio) E) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Can be mentioned.

In addition to the above-mentioned photopolymerization initiator, other known photopolymerization initiators can be used in the dye-containing negative curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triaryl imidazole dimer / p-aminophenyl ketone combination, benzothiazole compounds / trines disclosed in Japanese Patent Publication No. 51-48516 And halomethyl-s-triazine compounds.

  The total amount of the photopolymerization initiator used is preferably 0.01% by mass to 50% by mass with respect to the solid content (mass) of the photopolymerizable compound (radical polymerizable monomer), and 1% by mass to 30% by mass. Is more preferable, and 1% by mass to 20% by mass is particularly preferable. When the use amount is in the range of 0.01 to 50% by mass, the polymerization can easily proceed, and the molecular weight can be prevented from being lowered and the film strength can be prevented from being weakened.

-(E) Organic solvent-
The dye-containing negative curable composition of the present invention contains at least one organic solvent. The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the applicability of the dye-containing negative curable composition of the present invention, in particular, the solubility of the dye and binder, applicability, and It is preferable to select in consideration of safety. Moreover, when preparing the dye-containing negative curable composition of this invention, it is preferable that this composition contains an at least 2 type of organic solvent.

  Examples of the organic solvent include esters (for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate);

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl 2-propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy -2-methylpropi Methyl pyrate, ethyl 2-ethoxy-2-methylpropionate, etc.); methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. ;

Ethers (for example, 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 (for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.); aromatic hydrocarbons (for example, toluene, xylene, etc.) are preferred.

  As described above, these organic solvents may be used in admixture of two or more kinds from the viewpoints of solubility of dyes and alkali-soluble resins, improvement of the coated surface, and the like. In particular, the above-mentioned methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl A mixed solution composed of two or more selected from ether acetate is preferably used.

-(F) Higher fatty acids and their derivatives-
The higher fatty acid and its derivative (higher fatty acid in the present invention) will be described. The higher fatty acid is a chain monocarboxylic acid represented by “R—COOH (R: CH ₃ (CH ₂ ) _m )” and means a compound having a total carbon number of 10 or more in one molecule. When the number of the chain monocarboxylic acid is less than 10, the effect of the present invention cannot be sufficiently exerted because the film is not sufficiently cured. Those having 11 or more are preferred, and those having 13 or more are more particularly effective when the total carbon number is 11 or more in promoting the hardening of the film. The “carbon number” does not include the carbon number of the derivative portion.

  As the higher fatty acid in the present invention, any higher fatty acid or derivative thereof that satisfies the above-mentioned conditions can be used without particular limitation. Specifically, undecyl acid, lauric acid, tridecylic acid, myristic acid, tridecylic acid, Saturated fatty acids such as pentadecylic acid, heptadecylic acid, palmitic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacoic acid, montanic acid, melicic acid, and lactelic acid, and their derivatives; undecylene Acid, oleic acid, elaidic acid, celetic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, and stearolic acid, palmitoleic acid, lindelic acid, cis-6-hexadecenoic acid Unsaturated fatty acids and their derivatives ; And the like. With respect to the above derivatives, any known esters, amides, acyl halides, ketene dimers, amines, etc., as well as derivatives described in books and dictionaries related to general fatty acids can be used without particular limitation. Among the above, the higher fatty acid in the present invention is preferably a compound selected from palmitic acid, stearic acid, behenic acid, arachidic acid, myristic acid, and derivatives thereof.

As the higher fatty acid in the present invention, from the viewpoint of promoting the hardening of the film and improving the rectangularity, in particular, a saturated fatty acid having 11 or more carbon atoms per molecule or a derivative thereof, and the total number of carbon atoms per molecule. Are preferably 11 or more unsaturated fatty acids or derivatives thereof. These may be used singly or in combination of two or more. From the viewpoint of further film curing and adhesion to the substrate, saturated fatty acids having 11 or more total carbon atoms per molecule or derivatives thereof It is preferable to use an unsaturated fatty acid having 11 or more carbon atoms per molecule or a derivative thereof in combination.
Specific examples of such combinations include behenamide and stearamide, palmitic acid and palmitoleic acid, stearic acid and oleic acid, lauric acid and Linderic acid, parimitin Examples include a combination of an acid, methyl palmitate and cis-6-hexadecenoic acid.
In this case, the molar ratio (x / y) between the saturated fatty acid (x) and the unsaturated fatty acid (y) is 95 from the viewpoint of improving the curability of the film, adhesion to the substrate, and compatibility with the resist. / 5 to 10/90 is preferable, and 80/20 to 50/50 is more preferable.

  In the dye-containing negative curable composition of the present invention, the content of the higher fatty acid in the present invention is 0.01 to 40% by mass with respect to the total solid content from the viewpoint of improving the curability of the film. Further, from the viewpoint of adhesion to a substrate and compatibility with a resist, the content is preferably 0.1 to 25% by mass, and particularly preferably 0.15 to 15% by mass.

-(G) Surfactant-
The dye-containing negative curable composition of the present invention contains a surfactant together with the higher fatty acid. As the surfactant, any surfactant other than a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can be used. Moreover, the said surfactant may use 2 or more types together.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative oxyethylene, oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene Ethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, sugar, or commercially available “Troysol S366” (manufactured by Troy Chemical), as well as “Emulgen 103” and “Emulgen 220” Oxyethylene alkyl ethers (manufactured by Kao Corporation); sorbitan fatty acid esters such as “Reodol SP-L10” and “Emazole O-10V” (Kao Corporation) Etsu Chemical Co., Ltd.); "New Call 1205" (manufactured by Nippon emulsifier Co., Ltd.), and the like.

  Examples of the anionic surfactants include oleyl alcohol sulfates such as sodium lauryl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkyls such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate Examples include aryl sulfonates; sodium dodecylbenzene sulfonate; sulfosuccinic acid di-2-ethylhexyl ester sodium salt and the following surfactant 1.

  Examples of the commercially available anionic surfactants include alkyl sulfates such as “Emar 0”, “Emar 10 Powder”, and “Emar TD” (manufactured by Kao Corporation); “Emar 20C”, “Latherm E” -118B "and" Emar 20T "polyoxyethylene alkyl ether sulfates (manufactured by Kao Corporation); alkylbenzene sulfonates such as" Neopelex GS "and" Neopelex G-25 "(Kao Corporation) In addition, “Demol EP”, “Demol MS”, “Homogenol L-100” (manufactured by Kao), “New Coal 293” (manufactured by Nippon Emulsifier Co., Ltd.) and the like can be mentioned.

Examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride. Examples of commercially available cationic surfactants include “Acetamine 24” (manufactured by Kao Corporation), “Cotamine 86W” (manufactured by Kao Corporation), and the like. Furthermore, examples of amphoteric surfactants include stearyl dimethyl betaine and sodium laurylaminopropionate. Examples of amphoteric surfactants that are commercially available include “Amphitor 24B” (manufactured by Kao Corporation), “Amphitor 24N” (manufactured by Kao Corporation), and the like.
If the surfactant contained in the dye-containing negative curable composition of the present invention is a surfactant, the effects of the present invention can be obtained, but nonionic and anionic surfactants and amphoteric surfactants are preferred, and Most preferred are nonionic and anionic surfactants. The surfactant used in the present invention may be used in combination of two or more depending on the purpose. These can also be selected from those commercially available. The amount of the surfactant used is not particularly limited and can be used within a range that does not affect the surface shape, sensitivity, and rectangularity, but is 2 or less in terms of mass ratio (surfactant / higher fatty acid) to higher fatty acids. Preferably, it is preferably 1 or less.

-Crosslinking agent-
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent usable in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one selected substituent. In addition, a phenol compound, a naphthol compound, or a hydroxyanthracene compound can be used. Especially, as a crosslinking agent used in this invention, a polyfunctional epoxy resin is preferable.

  The (a) epoxy resin may be any epoxy resin as long as it has an epoxy group and has crosslinkability. For example, bisphenol-A-diglycidyl ether, ethylene glycol diglycidyl ether, butanediol di Divalent glycidyl group-containing low molecular weight compounds such as glycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, and N, N-diglycidyl aniline; similarly, trimethylolpropane triglycidyl ether , Trivalent glycidyl group-containing low molecular weight compounds represented by trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether and the like; similarly, pentaerythritol tetraglycidyl ether, tetramethylo Tetravalent glycidyl group-containing low molecular weight compounds represented by bisphenol A tetraglycidyl ether and the like; similarly, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether; Polyglycidyl (meth) acrylate, glycidyl group-containing polymer represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, etc. Is mentioned.

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, and in the case of glycoluril compounds, guanamine compounds, and urea compounds. Is 2 to 4, preferably 5 to 6 in the case of a melamine compound, and 3 to 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 the above (b) may be collectively referred to as a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound in (b), respectively. is there.

  The methylol group-containing compound in (b) above can be obtained by heating the alkoxymethyl group-containing compound in (b) in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like in alcohol. 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 above-described 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, hexa Examples thereof include compounds in which 1 to 5 methylol groups of methylolmelamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetra Examples thereof include a compound obtained by acyloxymethylating 1 to 3 methylol groups of methylolguanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethyl glycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol glycoluril, or a mixture thereof, or a methylol group of tetramethylol glycoluril. 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 of two or more.

  The crosslinking agent (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 the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a methylol group-containing compound, an alkoxymethyl group-containing compound, and an acyloxymethyl group-containing compound in (c), respectively.

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) above is required to be at least 2 per molecule, and it becomes a skeleton from the viewpoint of thermal crosslinkability and storage stability. A compound in which all of the 2-position and 4-position of the phenol compound are substituted is preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are 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.
Also in the said naphthol compound, except the ortho position of OH group, it may be unsubstituted or may have a substituent.

The methylol group-containing compound in the above (c) uses, as a raw material, a compound in which the 2-position or 4-position of the phenolic OH group is a hydrogen atom, 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) is 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 the crosslinking agent (c) include phenolic compounds, naphthols, hydroxyanthracene compounds in which the ortho-position or para-position of the phenolic OH group is unsubstituted, and examples thereof include phenol and cresol isomers, 2 , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol- Compounds obtained by methoxymethylating one or two methylol groups of 3-cresol, tri (methoxymethyl) -3-cresol, trimethylol-3-cresol, dimethylol cresol such as 2,6-dimethylol-4-cresol, Compounds obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4 ′ − Suhydroxybiphenyl, TrisP-PA hexamethylol, TrisP-PA hexamethoxymethyl, TrisP-PA hexamethylol compound methoxymethylated from 1 to 5 methylol groups, Bishydroxymethylnaphthalenediol, etc. Is mentioned.

  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 crosslinking agent in the dye-containing negative curable composition varies depending on the material, but from the viewpoint of improving the curability of the coating film, the total solid content (mass) of the composition is 1 to 70 mass% is preferable, 5-50 mass% is still more preferable, 7-30 mass% is especially preferable.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful.

-Various additives-
In the dye-containing negative curable composition of the present invention, various additives, for example, fillers, polymer compounds other than those described above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc., if necessary Can be blended.

  Specific examples of the various 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; 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) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane Adhesion promoters such as 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6 -Antioxidants such as di-t-butylphenol; ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

Further, when the alkali solubility of the non-image area is promoted and the developability of the dye-containing negative curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used.
The dye-containing negative curable composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation-sensitive composition layer, and the layer is formed into a predetermined mask pattern. And a negative coloring pattern is formed by developing with a developer (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  In the production of a color filter, a color filter having a desired hue can be produced by repeating the image forming step (and curing step if necessary) by the desired number of hues. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

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.
In addition, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  Any developer can be used as long as it has a composition that dissolves the uncured part of the dye-containing negative curable composition of the present invention but does not dissolve the irradiated part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

  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.

  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.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

[Example 1]
1) Preparation of dye-containing negative curable composition Each compound was mixed and dissolved in the composition shown below to prepare the dye-containing negative curable composition of the present invention.
〔composition〕
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
-Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts-Palmitic acid 4.0 parts (higher fatty acids in the present invention)
・ Nonionic surfactant 2 parts (trade name: Troisol S366, manufactured by Troy Chemical)

2) Production of silicon wafer with undercoat layer A 6-inch silicon wafer was coated with a resist solution (trade name: CT-2000, manufactured by Fuji Film Arch Co., Ltd.) using a spin coater so as to have a film thickness of 2 μm. After coating, the silicon wafer was heat-dried at 220 ° C. for 1 hour to form a cured film (undercoat layer) on the wafer.

3) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable composition A obtained in 1) above is applied onto the silicon wafer with an undercoat layer obtained in 2) above using a spin coater so that the film thickness becomes 1 μm. Pre-baked at 120 ° C. for 120 seconds.
Next, using an i-line stepper exposure apparatus, the coating film was subjected to pattern exposure of 2 μm at a wavelength of 365 nm. After the exposure, development processing was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, manufactured by Fuji Film Arch Co., Ltd.). Next, the silicon wafer was rinsed with running water for 20 seconds and then spray-dried to obtain a pattern image A on the wafer. Thereafter, the wafer was heated at 200 ° C. for 10 minutes to obtain a final image B (color filter).

[Example 2]
In Example 1, an image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition B” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.

〔composition〕
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts Dodecyl stearate 2.0 parts (higher fatty acids in the present invention)
・ 1.0 parts of sodium dodecylbenzenesulfonate (anionic surfactant)

[Example 3]
In Example 1, an image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition C” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.

〔composition〕
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts Behenamide 1.0 part (higher fatty acid in the present invention)
Stearic acid 1.0 part (higher fatty acid in the present invention)
-1.0 part of the following surfactant 1 (anionic surfactant)

[Example 4]
In Example 1, an image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition D” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.
〔composition〕
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts Methyl stearate 2.0 parts (higher fatty acids in the present invention)
・ Sulfosuccinic acid di-2-ethylhexyl ester sodium salt 1.0 part (anionic surfactant)

[Example 5]
An image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition E” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.

・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
-Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts-Ethyl palmitate 2.0 parts (higher fatty acids in the present invention)
・ 1.0 parts of sodium dodecylbenzenesulfonate (anionic surfactant)

[Example 6]
In Example 1, an image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition F” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts Ethyl behenate 2.0 parts (higher fatty acids in the present invention)
・ Anionic surfactant 0.8 parts (Brand name: Demol EP, manufactured by Kao Corporation)

[Comparative Example 1]
In Example 1, an image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition G” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.
・ 36.9 parts of ethyl lactate ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.8 parts, dipentaerythritol hexaacrylate 7.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts

[Comparative Example 2]
In Example 1, an image (color filter) was prepared in the same manner as in Example 1 except that “dye-containing negative curable composition H” having the following composition was used instead of “dye-containing negative curable composition A”. ) Was formed.
・ Ethyl lactate 43.5 parts ・ Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) 4.1 parts, dipentaerythritol hexaacrylate 6.1 parts, polymerization inhibitor (p-methoxyphenol) 0.0061 parts, photopolymerization initiator 1.0 part (trade name: TAZ-107, (Midori Chemical Co., Ltd.)
-Organic solvent soluble dye (Valifast yellow 1101) 7.0 parts-Butyric acid 2.0 parts

4) Evaluation (1) Rectangularity of pattern With respect to the obtained image (pattern), the rectangularity of the pattern between image A after development and image B after further heat treatment was compared by SEM photograph observation. The rectangularity of the pattern was determined by quantifying the rectangularity by the distance from the center of the cross-sectional photograph to the apex of the upper part of the film with respect to the obtained pattern of 1 μm in length and 2 μm in width in the cross-sectional SEM. When the pattern is an ideal rectangle, there is no rounded corner and the distance from the center to the corner is √ ((0.5) ² + (1.0) ² ) = 1.12. Therefore, it can be seen that the closer to 1.12, the better the rectangularity of the pattern.
Further, in each Example and Comparative Example, the rectangularity of the image C obtained by adding the development time for 30 seconds (total 90 seconds) was similarly compared by SEM photograph observation.

(2) Sensitivity The minimum exposure amount at which the pattern becomes rectangular was measured and used as an index for sensitivity evaluation. The results are shown in Table 1 below.

  As shown in Table 1 above, it can be seen that when a surfactant and a higher fatty acid are used in combination, the rectangularity of the pattern is very high, and further, the change due to heating after development is very small and preferable. It can also be seen that the shape stability when developing up to 90 seconds is high, and the latitude with respect to the development time is also widened.

  The other compounds listed in the text were evaluated in the same manner as in Example 1. However, the rectangularity was improved with respect to Comparative Example 1, and the latitude with respect to the development time was increased.

Claims (7)

  (A) an alkali-soluble binder, (B) an organic solvent-soluble dye, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) an organic solvent, (F) at least one of higher fatty acids or derivatives thereof, and (G) Dye containing negative curable composition characterized by including surfactant.   2. The dye-containing negative curable composition according to claim 1, wherein the (F) higher fatty acid or derivative thereof has a total carbon number of 11 or more per molecule.   The at least one of the (F) higher fatty acid or a derivative thereof is a compound selected from palmitic acid, stearic acid, behenic acid, arachidic acid, myristic acid, and derivatives thereof. The dye-containing negative curable composition according to 2,   The dye-containing negative curable composition according to any one of claims 1 to 3, wherein the (G) surfactant is a nonionic surfactant or an anionic surfactant.   5. The mass ratio ((G) / (F)) of the (F) higher fatty acid or derivative thereof and the (G) surfactant is 1 or less. The dye-containing negative curable composition according to Item.   A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 5.   A color comprising a step of applying a dye-containing negative curable composition according to any one of claims 1 to 5 on a support, exposing through a mask, and developing to form a pattern. The manufacturing method of the filter.