JP2009244802A - Photosensitive colored composition and method of manufacturing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive colored composition that minimizes exposure illuminance dependence (in particular, shape irregularities of line width or the like at low illuminance of ≤95% of high illuminance), has high normalized remaining film thickness and little development residue and can stably form a pattern excellent in resolution, to provide a color filter which permits precise and high-quality image display, and to provide a method of manufacturing the color filter. <P>SOLUTION: The photosensitive colored composition includes a dye, a polymerizable monomer, an alkali-soluble resin, a photopolymerization initiator and a compound represented by general formula (I). In the general formula (I), R<SP>1</SP>and R<SP>2</SP>respectively and independently present a hydrogen atom, a 1-20C alkyl group or a 6-20C allyl group, R<SP>1</SP>and R<SP>2</SP>may be equal to each other or different from each other and do not present hydrogen atom at the same time, R<SP>1</SP>and R<SP>2</SP>may form a cyclic amino group together with nitrogen atom and R<SP>3</SP>and R<SP>4</SP>present an electron-absorbing group, respectively and independently. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive coloring composition containing a dye as a colorant, a color filter using the same, and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display element or a solid-state imaging element, 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 of producing a color filter by a photolithographic method using a photosensitive coloring composition in which a pigment is dispersed in various photosensitive compositions. Etc., and has the advantage of being stable. In addition, 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 photosensitive composition is applied on a glass substrate with 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. As the above-mentioned pigment dispersion method, there is a method in which a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, see Patent Document 1). This method is based on the principle that a photopolymerization initiator generates an active radical by irradiation with ultraviolet rays or the like, which attacks a polymerizable group such as a (meth) acryloyl group to induce a polymerization reaction. That is, the polymerization is not started until the presence of active radicals. Until now, in order to obtain excellent resolution and proper line width by the pigment dispersion method, measures such as adjustment of the amount of active radicals generated, that is, adjustment of the type and amount of the photopolymerization initiator, have been taken. It was. For example, when the finally obtained line width is thick, the amount of active radicals is reduced by using a less sensitive initiator or by reducing the amount of the initiator to be used. The method of adjustment is applied.

  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 with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In view of such a problem, a technique using a dye instead of a conventional pigment has been proposed.

  On the other hand, the required product spec width has become stricter as color filters are further refined, and variations in line width, film thickness, spectral spectrum, etc. due to exposure illuminance dependence are reduced. The need to do so has arisen. That is, when exposure is performed at low illuminance, there is a tendency that variations in the shape of the pattern to be formed tend to occur as compared to, for example, pattern formation by exposure at high illuminance. This problem caused by the exposure illuminance dependency is difficult to solve by simply adjusting the type and amount of the photopolymerization initiator as described above, particularly for a color having a high i-line transmittance. In order to improve the exposure illuminance dependence, usually a measure to increase the amount of photopolymerization initiation is taken, but if the amount of photopolymerization initiator is increased, the line width becomes too thick or it is caused by exposure halation. Peripheral residues are likely to occur.

As a method of eliminating the exposure illuminance dependency as described above, a technique for improving the resolution of a pattern and reducing the illuminance of an exposure machine by using an antioxidant is disclosed (for example, see Patent Document 2). . In addition, a technique has been proposed in which exposure dependency is reduced and pattern resolution is improved by using another type of antioxidant (see, for example, Patent Documents 3 to 4).
JP-A-2-181704 Japanese Patent Laid-Open No. 2006-11397 JP 2003-25524 A JP 2003-25525 A

  However, in the technique using the above-mentioned antioxidant, especially when exposed at low illuminance (for example, illuminance of 95% or less of high illuminance), fluctuations in the line width, film thickness, spectral spectrum, etc. of the formed pattern are caused. It cannot be suppressed and it is difficult to stably form a pattern having a good shape.

  The present invention has been made in view of the above, and exposure illuminance dependency (particularly, shape variation such as line width at low illuminance of 95% or less of high illuminance) is suppressed to be small, and the remaining film ratio is high. It is an object of the present invention to provide a photosensitive coloring composition that can stably form a pattern with little development residue and excellent resolution, and a color filter capable of displaying fine and high-quality images and a method for producing the same. It is an object to achieve the object.

  Specific means for achieving the above object are as follows.

〔一般式（Ｉ）中、Ｒ^１及びＲ^２は、各々独立に、水素原子、炭素原子数１〜２０のアルキル基、又は炭素原子数６〜２０のアリール基を表す。Ｒ^１とＲ^２とは互いに同一でも異なっていてもよいが、同時に水素原子を表すことはなく、Ｒ^１及びＲ^２は窒素原子と共に環状アミノ基を形成してもよい。Ｒ^３及びＲ^４は、各々独立に電子吸引基を表す。〕 <1>
A photosensitive coloring composition comprising a dye, a polymerizable monomer, an alkali-soluble resin, a photopolymerization initiator, and a compound represented by the following general formula (I).

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other, but do not represent a hydrogen atom at the same time, and R ¹ and R ² may form a cyclic amino group together with a nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group. ]

<2>
The photosensitive coloring composition as described in <1> whose compound represented by the said general formula (I) is 0.01-10 mass% in solid content in a photosensitive coloring composition.

<3>
The photosensitive coloring composition as described in <1> or <2>, wherein at least one of the photopolymerization initiators is an oxime ester compound.

<4>
<1>-<3> The manufacturing of the color filter which forms a pattern by apply | coating the photosensitive coloring composition of any one of <1>-, exposing the apply | coated coating layer through a photomask, and developing. Method.

<5>
The color filter produced by the manufacturing method of the color filter as described in <4>.

According to the present invention, exposure illuminance dependency (particularly, shape variation such as line width at a low illuminance of 95% or less of high illuminance) is suppressed to be small, the residual film ratio is high, the development residue is small, and the resolution is reduced. The photosensitive coloring composition which can form the pattern excellent in the property stably can be provided.
In addition, according to the present invention, it is possible to provide a color filter capable of displaying a fine and high-quality image, and a method for manufacturing the same, with less drop in transmittance with visible light.

  Hereinafter, the photosensitive coloring composition of this invention, the color filter comprised using this photosensitive coloring composition, and its manufacturing method are demonstrated in detail.

≪Photosensitive coloring composition≫
The photosensitive coloring composition of the present invention is composed of at least a dye, a polymerizable monomer, an alkali-soluble resin, a photopolymerization initiator, and a compound represented by the following general formula (I). A solvent is used. Moreover, the photosensitive coloring composition of this invention can be further comprised using other components, such as a pigment dispersant and / or a pigment derivative, alkali-soluble resin, as needed.

In the present invention, a photocurable composition containing a dye as a colorant is formed using an ultraviolet absorber having a specific structure, so that the illuminance dependency during exposure, particularly low illuminance (for example, 95% or less of high illuminance). The development performance fluctuations when developing with pattern exposure at low illuminance) are reduced, resulting in reduced resolution of the remaining film after development, fluctuations in development residue, variation in shape such as variation in pattern width, and excellent resolution. A pattern can be formed stably.
Hereinafter, each component which comprises the photosensitive coloring composition of this invention is explained in full detail.

[1] Dye The photosensitive coloring composition of the present invention contains at least one dye. The dye can be used without any particular limitation, and can be selected from conventionally known dyes for use in color filters. Of the dyes, organic solvent-soluble dyes that are soluble in organic solvents are preferred.

  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.

Chemical structures include pyrazole azo, anilino azo, aryl azo, pyrazolo triazole azo, pyridone azo, etc., triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolo. Dyes such as pyrazole 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 where the resist system is developed with water or alkali, acidic dyes and / or derivatives thereof are preferable 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.
Hereinafter, the acidic dye and its derivative will be described.

-Acid dyes and their derivatives-
The acidic dye is not particularly limited as long as it is a dye having an acidic group such as a sulfonic acid, a carboxylic acid, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developing solution used at the time of development processing, and forms a salt with a basic compound. It is selected in consideration of all required performances such as properties, absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Specific examples of acid dyes are given below. 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, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,195,308,312,315,316,339,341,345,346 349, 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 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249,289;
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. Acid dyes and derivatives of these dyes can also be preferably used.

  As the derivative of the acidic dye, an inorganic salt of an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, an amide compound such as a sulfonamide of an acidic dye, or the like may be used. The dye-containing negative curable composition is not particularly limited as long as it can be dissolved when it is prepared in solution, and is soluble in the organic solvent and the developer used in the development process, absorbance, and composition. It is selected in consideration of all necessary performances such as interaction with other components, light resistance, heat resistance and the like.

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.
Nitrogen-containing compounds that form salts with acid dyes, and nitrogen-containing compounds that form amide bonds with acid dyes are soluble in salt or amide compounds in organic solvents and developers, salt-forming properties, dye absorbance / color value, It is selected in consideration of all of the interaction with other components in the composition, heat resistance as a colorant, light resistance, and the like. 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 a molecular weight of 300 or less, more preferably a molecular weight of 280 or less, and a molecular weight of 250 or less. Particularly preferred.

  The molar ratio of nitrogen-containing compound / acid dye (hereinafter abbreviated as “n”) in “salt of acid dye and nitrogen-containing compound” will be described. n is a value that determines the molar ratio between the acidic dye molecule and the nitrogen-containing compound (amine compound) forming a counter ion, and can be freely selected according to the salt forming conditions of the acidic 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 acidic dye is an acidic dye due to the introduction of an acidic group in its structure, it can be converted to a non-acidic dye by changing its substituent. In other words, the acid dye may suitably act during alkali development, but on the other hand, it may be over-developed, and a non-acid dye may be preferably used. As the non-acidic dye, those having no acidic group of the above acidic dye can be suitably used.

  The above-mentioned dyes can be used as monochromatic dyes when constituting complementary colors such as yellow, magenta, and cyan. However, when constituting primary colors such as red, green, and blue, two or more kinds of dyes are generally used. It can be used in combination. In the present invention, it can be suitably used as a mixed system (mixture) in which at least two kinds of dyes having different absorption characteristics are combined, and a primary color hue can be suitably configured.

  As content in the photosensitive coloring composition of dye, although it changes with dyes, 0.5-80 mass% is preferable with respect to the total solid component of this composition, and 10-60 mass% is more preferable. When mixing two or more kinds of dyes, the amount of the dye to be added in the smallest amount is preferably at least 10% when the total dye amount is 100%.

[2] Ultraviolet Absorber The photosensitive coloring composition of the present invention contains at least one compound represented by the following general formula (I), which is a conjugated diene compound, as an ultraviolet absorber. In the present invention, the use of this conjugated diene compound suppresses subsequent development performance fluctuations particularly when low-illuminance exposure is performed, so it is related to pattern formability such as pattern line width, film thickness, and spectral spectrum. Dependence on exposure illuminance can be suppressed.

In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² May be the same as or different from each other, but do not represent a hydrogen atom at the same time.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, a cyclohexyl group, and n-decyl. Group, n-dodecyl group, n-octadecyl group, eicosyl group, methoxyethyl group, ethoxypropyl group, 2-ethylhexyl group, hydroxyethyl group, chloropropyl group, N, N-diethylaminopropyl group, cyanoethyl group, phenethyl group Group, benzyl group, pt-butylphenethyl group, pt-octylphenoxyethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, ethoxycarbonylmethyl group, 2- (2-hydroxyethoxy) ) Ethyl group, 2-furylethyl group and the like, and methyl group, ethyl group, propyl group, n-butyl group and n-hexyl group are preferred. There.
The alkyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent of the alkyl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, Halogen atom, acylamino group, acyl group, alkylthio group, arylthio group, hydroxy group, cyano group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, An arylsulfonyl group etc. are mentioned.

The aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² may be a single ring or a condensed ring, and is any of a substituted aryl group having a substituent or an unsubstituted aryl group. There may be. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, etc. can be mentioned.
Examples of the substituent of the substituted aryl group having a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, an acyl group, an alkylthio group, an arylthio group, a hydroxy group, and a cyano group. Group, alkyloxycarbonyl group, aryloxycarbonyl group, substituted carbamoyl group, substituted sulfamoyl group, nitro group, substituted amino group, alkylsulfonyl group, arylsulfonyl group and the like. Of these, a substituted or unsubstituted phenyl group, 1-naphthyl group, and 2-naphthyl group are preferable.

R ¹ and R ² may each independently form a cyclic amino group together with a nitrogen atom. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.

Among the above, R ¹ and R ² are each a lower alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl). , 2-ethylhexyl, tert-octyl, etc.) or a substituted or unsubstituted phenyl group (for example, tolyl group, phenyl group, anisyl group, mesityl group, chlorophenyl group, 2,4-di-t-amylphenyl group, etc.) preferable. It is also preferred that R ¹ and R ² are combined to form a ring (for example, a piperidine ring, a pyrrolidine ring, a morpholine ring) containing the nitrogen atom represented by N in the formula.

In the general formula (I), R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less.
Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. . Substituent constants obtained by Hammett's rule include a σ _p value and a σ _m value, and these values are described in many general books. For example, the JA Dean edition “Lange's Handbook of Chemistry” "Twelfth edition, 1979 (Mc Graw-Hill)" and "Chemical domain special issue", 122, 96-103, 1979 (Nanedo), Chemical Reviews, 91, 165-195, 1991 detailed. In the present invention, it does not mean that the values known in the literature described in these documents are limited to only certain substituents, but within the range when measured based on Hammett's law even if the value is unknown. Of course, it is included as long as it is included.

Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, An alkyl group substituted with at least two or more halogen atoms, an alkoxy group substituted with at least two or more halogen atoms, an aryloxy group substituted with at least two or more halogen atoms, or at least two or more halogen atoms Alkyl substituted with Amino group, at least two an alkylthio group substituted with a halogen atom, sigma _p value of 0.20 or more other electron-withdrawing aryl group substituted by group, a heterocyclic group, a chlorine atom, a bromine atom, an azo Group, or selenocyanate group. Of these substituents, the group that can further have a substituent may further have a substituent as described above.

Among the above, in the present invention, R ³ is preferably a group selected from a cyano group, —COOR ⁵ , —CONHR ⁵ , —COR ⁵ , —SO ₂ R ⁵ , and R ⁴ is a cyano group. A group selected from the group, —COOR ⁶ , —CONHR ⁶ , —COR ⁶ , —SO ₂ R ⁶ is preferred. R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms and the aryl group having 6 to 20 carbon atoms represented by R ⁵ and R ^{6 have the same} meanings as those in R ¹ and R ² , and the preferred embodiments are also the same.
Among these, as R ³ and R ⁴ , acyl group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, sulfamoyl group are preferable. In particular, an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, and a sulfamoyl group are preferable.
R ³ and R ⁴ may be bonded to each other to form a ring.

Moreover, at least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer. In the case of the copolymer, other monomers include acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, esters derived from acrylic acids such as methacrylic acid, preferably lower alkyl esters and amides such as Acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate , And lauryl methacrylate, methylene bisacrylamide, etc.), vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, methacrylonitrile Tolyl, aromatic vinyl compounds (for example, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl acetophenone, sulfostyrene, and styrene sulfinic acid), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether ( For example, vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine, and the like.
Of these, acrylic acid esters, methacrylic acid esters, and aromatic vinyl compounds are particularly preferable.
Two or more of the above comonomer compounds can also be used together. For example, n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, methyl acrylate and methacrylate acid, or the like can be used.

  Hereinafter, preferable specific examples [Exemplary compounds (1) to (14)] of the compound represented by the general formula (I) are shown. However, the present invention is not limited to these.

  The compounds represented by the general formula (1) used in the present invention are disclosed in JP-B 44-29620, JP-A 53-128333, JP-A 61-169831, JP-A 63-53543, JP-A 63-53544. And the method described in JP-A-63-56651.

  Hereinafter, specific methods for synthesizing representative compounds of the present invention will be described.

—Synthesis Method of Compound (1) —
3-Anilinoacrolein anil (13.3 g) and ethylphenylsulfonylacetate (14.3 g) are heated in acetic anhydride (40 ml) to 85-90 ° C. for 2 hours. Acetic anhydride is removed under reduced pressure, ethanol (40 ml) and gen-hexylamine (24.1 g) are added, and the mixture is refluxed for 2 hours. Ethanol is removed, the residue is subjected to column chromatography, purified, and recrystallized from ethanol to obtain the desired product. Mp 95-96 ° C.

  As content in the photosensitive coloring composition of this invention of the compound (conjugated diene type compound) represented by the said general formula (I), 0.01 mass%-10 mass with respect to the total solid of a composition. % Is preferable, 0.01% by mass to 7.5% by mass is more preferable, and 0.01% by mass to 5% by mass is particularly preferable. When the content of the conjugated diene compound (ultraviolet absorber) is 0.01% by mass or more, the light shielding ability at the time of exposure is good and the pattern line width is prevented from being increased due to excessive progress of polymerization. It is easy to obtain the line width and the generation of peripheral residues is further suppressed. On the other hand, when it is 10% by mass or less, the light shielding ability at the time of exposure is not too strong, and the polymerization proceeds better.

  The change in the pattern line width as described above is remarkable in the photosensitive coloring composition of magenta or red with little light absorption with respect to ultraviolet rays such as g-line, h-line and i-line as the exposure light source. It becomes. Therefore, the compound represented by the general formula (I) (conjugated diene compound) is particularly effective when constituting a photocurable coloring composition.

[3] Photopolymerization initiator Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, JP-B-59-1281, JP-A-53-133428, and the like. Active halogen compounds such as halomethyl-s-triazine as described, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers as described in US Pat. No. 4,318,871, European Patent Publication EP-88050A, etc., US patents Aromatic ketone compounds such as benzophenones described in USP-4199420, (thio) xanthones or acridine compounds described in Fr-2456541, coumarins or lophine dimers described in JP-A-10-62986 And other compounds such as JP-A-8-015521. And the like, and the like.

  Examples of the photopolymerization initiator include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarins, lophine dimers, biphenyl Imidazole type, oxime ester type and the like are preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, Preferable examples include 4′-isopropyl-2-hydroxy-2-methyl-propiophenone.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy-cyclohexyl. -Phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl- s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl- 2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-to Azine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (Chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine and the like can be preferably exemplified.

  Examples of the halomethyloxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3. , 4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3 A preferred example is 4-oxodiazole.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the coumarin-based photopolymerization initiator include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s Preferred examples include -triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the lophine dimer-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer and 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  Preferable examples of the biimidazole photopolymerization initiator include 2-mercaptobenzimidazole, 2,2′-benzothiazolyl disulfide and the like.

  Examples of the oxime ester photopolymerization initiator include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1. -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl- Preferable examples include 4 ′-(benzmercapto) benzoyl-hexyl-ketoxime.

  In addition to the above, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylphosphonium salt and the like can be mentioned.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

Among the above photopolymerization initiators, an oxime ester compound is preferable in that when used in combination with the conjugated diene compound represented by the general formula (I), the sensitivity can be increased by adding a small amount. O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethanone is most preferred.
As content in the photosensitive coloring composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By mass. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

  In addition to the above components, it is preferable to add a thermal polymerization inhibitor to the photosensitive coloring 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-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

[4] Polymerizable monomer The photosensitive coloring composition of the present invention contains at least one polymerizable monomer.
As the polymerizable monomer, a compound having at least one addition-polymerizable ethylenic double bond and having a boiling point of 100 ° C. or higher under normal pressure is preferable. By containing the polymerizable monomer together with the photopolymerization initiator and the like, the photosensitive coloring composition of the present invention can be constituted in a negative type.

Examples of polymerizable monomers 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, Methylolethane 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 (acryloyloxy) (Methyl) acrylate after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as chill) isocyanurate, glycerin and trimethylolethane; JP-B-48-41708, JP-B-50-6034, JP Urethane acrylates as described in JP-A-51-37193; polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be mentioned. Among these, as the polymerizable monomer, a polyfunctional (meth) acrylic compound is preferable.

  10-80 mass% is preferable with respect to the total solid of a composition, and, as for content in the photosensitive coloring composition of a polymerizable monomer, 10-40 mass% is more preferable. When the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the unexposed area, maintain a sufficient degree of cure of the exposed area, and significantly reduce the elution of the unexposed area. Can be prevented.

[5] Alkali-soluble resin The photosensitive coloring composition of the present invention can be constituted using an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

  The alkali-soluble resin is preferably a linear organic high molecular polymer and 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-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Similarly, acidic cellulose derivatives having a carboxylic acid in the side chain are useful.

  In addition to the above, alkali-soluble resins include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinyl Pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful.

  Further, the linear organic polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, 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 straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric acid ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and groups derived from salts thereof, morpholinoethyl group, etc. Including monomers are also useful.

  Further, the alkali-soluble resin may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful.

  Examples of the polymer having a polymerizable group include commercially available 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, and the like are also useful.

  Among these various alkali-soluble resins, 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 a copolymer obtained by polymerization of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, and (meth) acrylamide, and a commercially available product. 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.

The alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoints of developability, liquid viscosity, and the like, and is preferably 2000 to 1 × 10 ⁵ . A polymer is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

  The content of the alkali-soluble resin in the photosensitive coloring composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, more preferably 30 to 30% by mass with respect to the total solid content of the composition from the viewpoint of developability and the like. 70% by mass is particularly preferred.

[6] Organic Solvent The photosensitive coloring composition of the present invention can generally be constituted using an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the photosensitive coloring composition are satisfied, but in particular, the solubility, coating property, and safety of dyes, ultraviolet absorbers, and binders. It is preferable to select in consideration. Moreover, when preparing the photosensitive coloring composition of this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of the organic 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.

  As described above, these organic solvents may be used in combination of two or more from the viewpoints of the solubility of the ultraviolet absorber and the alkali-soluble resin, the improvement of the coated surface, and the like, in particular, methyl 3-ethoxypropionate, Ethyl 3-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 A mixed solution composed of two or more selected from glycol methyl ether acetate is preferably used.

  The content of the organic solvent in the photosensitive coloring composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.

[7] Other additives In the photosensitive coloring composition of the present invention, various additives, for example, a filler, a polymer compound other than those described above, a surfactant, an adhesion promoter, an antioxidant, are included as necessary. Further, an aggregation preventing agent or the like can be blended.

  Specific examples of these 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; nonionic, 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) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; and anti-aggregation agents such as sodium polyacrylate.

The photosensitive coloring composition of the present invention is an organic carboxylic acid, preferably a molecular weight of 1000, in order to promote alkali solubility in the UV-irradiated part of the photosensitive coloring composition and to further improve developability. The following low molecular weight organic carboxylic acids can be contained.
Specific examples of the organic carboxylic acid include 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 acid, 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 Acid; Aliphatic tricarboxylic acid such as tricarballylic acid, aconitic acid, and camphoronic acid; Aromatic monocarboxylic acid such as benzoic acid, toluic acid, cumic acid, hemellitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellito Aromatic polycarboxylic acids such as acids, trimesic acid, merophanoic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid It is done.

≪Color filter and its manufacturing method≫
The color filter of the present invention is formed by arranging a plurality of colored or non-colored patterns on a substrate, and is produced using the above-described photosensitive colored composition of the present invention. The color filter of the present invention can be most preferably produced by the method for producing the color filter of the present invention using the photosensitive coloring composition of the present invention. It was applied directly or via another layer (preferably after drying) to form a coating layer (hereinafter, this may be referred to as “coating film forming step”), and the coating was formed. The coating layer is exposed imagewise at least with ultraviolet rays (for example, through a predetermined mask pattern) (hereinafter, this may be referred to as “exposure process”), and the exposed coating layer is developed with a developer (for example, alkali development). The pattern can be formed by developing with a liquid (hereinafter sometimes referred to as “development process”). In the present invention, if necessary, a coating layer after the development treatment, that is, a step of applying heat treatment to the pattern (hereinafter sometimes referred to as “post-baking step”) can be further provided.
Moreover, in the manufacturing method of the color filter of this invention, the hardening process hardened by further heating and / or exposing the pattern after exposure and image development as needed can further be provided.

  In the coating film forming step, the photosensitive coloring composition is applied on a substrate by a coating method such as spin coating, casting coating, roll coating, slit coating, etc. (preferably dried afterwards). A colored composition layer (coating layer) is formed.

Examples of the substrate include soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, 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). In some cases, a black matrix for isolating each pixel pattern constituting the color filter is formed on these substrates.
Further, an undercoat layer may be provided on these substrates, if necessary, in order to improve adhesion with a layer provided on the substrate, prevent diffusion of substances, or planarize the substrate surface.

  In the exposure step, the coating layer formed in the coating film forming step is exposed by irradiating actinic rays or radiation in an image-like manner with a specific pattern through a mask or the like, for example. Examples of the actinic ray or radiation include infrared rays, visible rays, ultraviolet rays, far-ultraviolet rays, X-rays, electron beams, etc., but at least ultraviolet rays are preferred, and in particular, g rays, h rays, i rays, etc. Ultraviolet rays are preferably used. For color filters for liquid crystal display devices, exposure using mainly h-line and i-line is preferable for proximity exposure machines and mirror projection exposure machines, and for color filters for solid-state image sensors, i-type is mainly used for stepper exposure machines. Exposure using lines is preferred.

The exposure illuminance is preferably 10 mJ / cm ² or more, more preferably 20 mJ / cm ² or more, more preferably 30 mJ from the viewpoint of throughput in the proximity exposure machine and mirror projection exposure machine used for the production of color filters for liquid crystal display devices. / Cm ² or more is particularly preferable. In the stepper exposure machine used for the production of the color filter for the solid-state imaging device, 300 mJ / cm ² or more is preferable, 500 mJ / cm ² or more is more preferable, and 1000 mJ / cm ² or more is particularly preferable from the viewpoint of throughput. Further, the exposure amount is generally preferably 1000 mJ / cm ² or less, more preferably 500 mJ / cm ² or less, and particularly preferably 300 mJ or less from the viewpoint of throughput.

In the developing step, the exposed coating layer is developed with a developer to reveal a pattern.
Any developer can be used as long as it dissolves the unexposed portion of the photosensitive coloring composition and hardly dissolves the exposed portion (radiation irradiated portion). Specifically, various organic solvents and combinations thereof, and alkaline aqueous solutions can be used.

  As said organic solvent, the above-mentioned solvent which can be used when preparing a photosensitive coloring composition can be 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, And choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the like.

  As the developer, it is preferable to use an alkaline aqueous solution adjusted so that the alkali concentration is preferably pH 11 to 13, more preferably pH 11.5 to 12.5. When the alkali concentration is pH 13 or less, pattern roughness, peeling, and reduction in the remaining film ratio can be avoided, and when the alkali concentration is pH 11 or more, the development speed is good and the generation of residues can be prevented.

  In the development process, development is performed using a developer such as an alkaline aqueous solution. Examples of the development method include a dipping method, a spray method, and a paddle method. The development temperature is preferably 15 to 40 ° C. Further, after development, washing is generally performed with running water.

  Furthermore, in the method for producing a color filter of the present invention, it is preferable that a heat treatment is performed by providing a post-baking step in order to sufficiently cure the coated layer after development. 100-300 degreeC is preferable and the heating temperature in a post-baking process has more preferable 150-250 degreeC. The heating time is preferably about 10 minutes to 1 hour, more preferably about 5 minutes to 30 minutes.

  The color filter of the present invention can have a plurality of patterns on a substrate, for example, a pattern in which colored pixels, a black matrix, and the like are regularly arranged. The colored pixels constituting the color filter are generally formed in a quadrilateral shape, and in this case, one side (maximum side) is generally formed in a range of 1.5 to 200 μm. Among these, 5 μm or less is preferable, 4 μm or less is more preferable, and 3 μm or less is particularly preferable from the viewpoint of effective use of a substrate such as a silicon wafer, miniaturization of a device using a solid-state image sensor, and high-speed operation of the solid-state image sensor.

  The thickness of the colored pixel in the color filter is not particularly limited, but it tends to be thin from the viewpoint of effective use of a substrate such as a silicon wafer and shading of a device using a solid-state image sensor. It is preferably 2 μm or less, more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less.

  The content of the dye in the colored pixels constituting the color filter is not particularly limited, but is preferably 25% by mass or more based on the total solid content of the composition from the viewpoint of color separation. More preferably, it is 30 mass% or more, and 40 mass% or more is especially preferable.

  The color filter of the present invention can be used as a color filter for a liquid crystal display device (LCD). However, it can be used for an image sensor such as a CCD or CMOS, particularly for a high-resolution CCD element or CMOS element exceeding 1 million pixels. It is preferable to use it. The color filter of the present invention is optimally used, for example, as a color filter disposed between a light receiving portion and a microlens for condensing light in each colored pixel constituting the CCD.

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. Unless otherwise specified, “part” is based on mass.

-Preparation of resist solution for planarization film-
The following components were mixed and stirred with a homogenizer stirrer to prepare a flattening film resist solution.

<Resist liquid composition for flattening film>
Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (45%, weight average molecular weight 30000, manufactured by Fujikura Kasei Co., Ltd., product name Acrybase FF- 187) ... 22 parts, dipentaerythritol pentaacrylate ... 6.5 parts (manufactured by Nippon Kayaku Co., Ltd., product name KAYARAD DPHA)
Propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries, Ltd., product name MMPGAC) 13.8 parts Ethyl-3-ethoxypropionate (manufactured by Nagase Sangyo Co., Ltd., product name ethyl-3 ethoxypropio) Nate) ... 12.3 parts · Halomethyltriazine compound (Compound I below) (manufactured by PANCHIM, product name Triazine PP) ... 0.3 parts

The halomethyltriazine compound (I) is the following compound.

-Fabrication of planarization film-
This flattening film resist solution was applied onto a 6-inch silicon wafer by spin coating. Subsequently, heat treatment was performed on a hot plate at a surface temperature of 120 ° C. for 120 seconds to obtain a uniform coating film having a thickness of about 2 μm on the silicon wafer. Next, the coating film was cured in an oven at 220 ° C. for 1 hour to obtain a flattened film.

-Preparation of photosensitive coloring composition-
A compound having the following composition was mixed and dissolved to prepare a photosensitive coloring composition.

<Composition of photosensitive coloring composition>
-Resin A (benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer propylene glycol monomethyl ether acetate solution (30%, weight average molecular weight 30000, manufactured by Fujikura Kasei Co., Ltd., product name Acrylic) Base FF-187) 30.48 parts monomer A 1.46 parts (dipentaerythritol pentaacrylate; manufactured by Nippon Kayaku Co., Ltd., product name KAYARAD DPHA)
・ C. I. Acid Red289 ... 6.69 parts · Solvent A (organic solvent) ... 60.00 parts (propylene glycol monomethyl ether acetate; manufactured by Daicel Chemical Industries, Ltd., product name MMPGAC)
・ Initiator A (compound II below; manufactured by Ciba Specialty Chemicals Co., Ltd., product name IRGACURE OXE01) 0.314 parts ・ compound (III) (ultraviolet absorber) 0.576 parts ・ interface Activator A: 0.36 part (fluorine-based surfactant; manufactured by Dainippon Ink & Chemicals, Inc., product name MegaFuck F-144)
・ Polymerization inhibitor A (p-methoxyphenol, manufactured by Kanto Chemical Co., Ltd., product name p-methoxyphenol): 0.001 part

-Production of coating film-
After applying the photosensitive coloring composition obtained above by spin coating on the flattened film of the silicon wafer, the surface temperature of the coating film surface is 100 ° C. for 120 seconds, and then heated and dried on a hot plate, A coating film having a thickness of about 1.0 μm after drying was formed.

−Preparation of color filter pixel pattern−
Next, an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) is passed through a mask pattern in which 2.0 μm square pixels are arranged in a 4 mm × 3 mm region on the substrate with respect to the dried coating film. ) At an exposure amount of 100 mJ / cm ² , exposure was performed at two levels of illuminance of 1200 mW / cm ² (high illuminance) and 600 mW / cm ² (low illuminance).

The pattern-exposed coating film was subjected to paddle development for 60 seconds at room temperature using a 60% aqueous solution of an organic alkaline developer CD-2000 (Fuji Film Electronics Materials Co., Ltd.), and then spin showered for another 20 seconds. And rinsed with pure water. Thereafter, it was further washed with pure water. Thereafter, water droplets were blown off with high-pressure air, the substrate was naturally dried, and post-baked with a hot plate at 220 ° C. for 300 seconds to form a colored pattern (colored resin film) on the silicon wafer.
As described above, a color filter for a solid-state imaging device was produced.

-Evaluation-
The following evaluation and measurement were performed on the color filter for a solid-state imaging device obtained from the above. The results of evaluation and measurement are shown in Table 2 below.

(1) Pixel pattern shape The 2.0 μm square pixel pattern shape of the obtained color filter is further measured using a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.), for the color filter on the silicon wafer. Observation was performed at a magnification of 30,000 from above, and the shape of the corner was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2 below. A rounded corner is different from the pattern shape of other colors adjacent to each other at the time of device manufacture, and is measured as a color mixture and noise at the time of image recognition, thereby deteriorating the performance of the device.
<Evaluation criteria>
◯: Corners were not round and a good rectangle was obtained.
Δ: Corners were rounded, but were practically acceptable.
X: The corner was rounded like a fan, and a rectangle was not obtained.

(2) Peripheral residue The pixel pattern of the color filter after post-baking is observed from the upper side of the color filter on the silicon wafer by 30,000 times using a length measuring SEM (S-7800H, manufactured by Hitachi, Ltd.). Then, the presence or absence of residues was visually evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: There was no development residue.
Δ: A slight amount of development residue was observed, but was practically acceptable.
X: The generation | occurrence | production of the residue was remarkable.

(3) Residual film ratio Thickness D ¹ of the pixel pattern of the color filter after post-baking and the film thickness D ² after exposure and before development are measured with a stylus type surface shape measuring instrument (Dektak8, manufactured by Beiko Japan). The remaining film ratio (%; = D ¹ / D ² × 100) is obtained by dividing the obtained film thickness D ¹ by the film thickness D ² and evaluated according to the following evaluation criteria using this as an index. did. It is desirable that the remaining film rate is high from the viewpoint of exposure sensitivity. The results are shown in Table 2 below.
<Evaluation criteria>
A: The exposure sensitivity was good and the remaining film ratio was 70% or more.
X: The exposure sensitivity was insufficient, and the remaining film rate was also less than 70%.

(4) The shape of the color filter pixel pattern after development and post-baking after exposure at a line width of 600 mW / cm ² (low illuminance) is a length measurement SEM (S-7800H, manufactured by Hitachi, Ltd.) Was observed at a magnification of 30,000 from above the color filter on the silicon wafer. The line width was evaluated according to the following evaluation criteria from the viewpoint of the appropriate dimension compared with the square pixel of 2.0 μm of the mask pattern. The evaluation results are shown in Table 2 below.
<Evaluation criteria>
A: The line width was 1.80 μm or more and less than 2.20 μm.
X: The line width was less than 1.80 μm or greater than 2.20 μm.

(5) Exposure illuminance dependence-A. Line width | ab |
As described above, each pixel pattern obtained by exposure at the two levels (high illuminance: 1200 mW / cm ² , low illuminance: 600 mW / cm ² ) was obtained by the evaluation of “(4) line width”. The line width a (μm) at low illuminance is compared with the line width b (μm) at high illuminance, the line width difference (= | ab−) is obtained as an index, and evaluated according to the following evaluation criteria did. In the color filter for a solid-state image sensor, since the uniformity of the line width of the obtained pattern is important, 0.05 μm was evaluated as a threshold value. The notation “||” represents an absolute value.
<Evaluation criteria>
○: The line width difference was less than 0.05 μm.
X: The line width difference was 0.05 μm or more.
~ B. Residual film ratio | cd |
As described above, for each of the pixel patterns obtained by exposure at the two levels (high illuminance: 1200 mW / cm ² , low illuminance: 600 mW / cm ² ), the evaluation of the “(1-3) remaining film ratio” is performed. The remaining film ratio c (%) at low illuminance obtained in step 1 and the remaining film ratio d (%) at high illuminance are compared, and the difference in the remaining film ratio (= | c−d |) is obtained as an index. And evaluated according to the following evaluation criteria. In the color filter for a solid-state image sensor, since the uniformity of the film thickness of the pattern obtained is important, 1.0% was evaluated as a threshold value. The notation “||” represents an absolute value.
<Evaluation criteria>
A: The difference in the remaining film ratio was less than 1.0%.
X: The difference in the remaining film ratio was 1.0% or more.

(Examples 2 to 12): Production of color filter for solid-state imaging device In Example 1, except that the composition of the photosensitive coloring composition was changed as shown in Table 1 below, in the same manner as in Example 1, A photosensitive coloring composition was prepared to produce a color filter. The same evaluation as in Example 1 was performed. The results of evaluation and measurement are shown in Table 2 below.

(Comparative Examples 1 to 6): Preparation of color filter for solid-state imaging device In Example 1, except that the composition of the photosensitive coloring composition was changed as shown in Table 1 below, the same as in Example 1, A photosensitive coloring composition was prepared to produce a color filter. The same evaluation as in Example 1 was performed. The results of evaluation and measurement are shown in Table 2 below.

Hereafter, the structure of the compound as described in the column of the ultraviolet absorber etc. of the said Table 1 is shown.

  Compound XII (antioxidant): pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Ciba Geigy, “IRGANOX1010”)

As shown in Table 2, in the example using the ultraviolet absorber represented by the general formula (1), the pattern shape was good, the residue was suppressed, and the exposure illuminance dependency was small.
On the other hand, in comparative examples using triazine-based and benzotriazole-based ultraviolet absorbers (compound X, compound XI), which are other types of ultraviolet absorbers, the line width and the remaining film ratio particularly in low-light exposure. The fluctuation of the exposure illuminance was large and the exposure illuminance dependence could not be suppressed. Moreover, in the comparative example using the compound XII which is an antioxidant, although the exposure illuminance dependence was small, the generation of the development residue could not be suppressed.

Claims (5)

A photosensitive coloring composition comprising at least a dye, a polymerizable monomer, an alkali-soluble resin, a photopolymerization initiator, and a compound represented by the following general formula (I).

[In General Formula (I), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other, but do not represent a hydrogen atom at the same time, and R ¹ and R ² may form a cyclic amino group together with a nitrogen atom. R ³ and R ⁴ each independently represents an electron withdrawing group. ]   The photosensitive coloring composition of Claim 1 whose compound represented by the said general formula (I) is 0.01-10 mass% in solid content in a photosensitive coloring composition.   The photosensitive coloring composition according to claim 1, wherein at least one of the photopolymerization initiators is an oxime ester compound.   The manufacturing of the color filter which forms the pattern by apply | coating the photosensitive coloring composition of any one of Claims 1-3, exposing the apply | coated coating layer through a photomask, and developing. Method.   A color filter produced by the method for producing a color filter according to claim 4.