JP2009198868A - Dye-containing negative type curable composition, color filter and method for manufacturing therefor, and solid imaging element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance a residual color rate after developing processing, and to restrain a shape from being changed caused by thermal sagging in accompaniment to heat treatment after patterning. <P>SOLUTION: A dye-containing negative type curable composition contains (A) an organic solvent soluble dye, (B) a photopolymerization initiator, (C) a photopolymerizable compound containing amine structure, (D) a photopolymerizable compound different from (C) the photopolymerizable compound containing the amine structure, and (E) an organic solvent. The amine structure of the photopolymerizable compound is preferably tertiary amine structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dye-containing negative curable composition, a color filter using the same, a method for producing the same, and a solid-state imaging device.

  As a method for producing a color filter used for a liquid crystal display element (LCD or the like) or a solid-state image pickup element (CCD or CMOS), a pigment dispersion method is widely known.

  The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This is a method suitable for producing a color filter with high positional accuracy, a large screen, and high definition because patterning is performed by a photolithography method. When a color filter is produced by a pigment dispersion method, a photosensitive composition is applied on a glass substrate by a spin coater or a roll coater to form a coating film, and a colored pixel is formed by pattern exposure and development of the coating film. The color filter is obtained by repeating this operation for each color.

  In the case of producing a display element such as a liquid crystal display element or a solid-state image sensor using a color filter using a pigment, a pigment having a finer particle size is required from the viewpoint of improving contrast (for example, patents). Reference 1). This is due to a factor that the polarization axis rotates due to light scattering, birefringence, and the like by the pigment. If the pigment is not sufficiently refined, light is scattered and absorbed by the pigment, the light transmittance is lowered, the contrast is lowered, and further, the curing sensitivity at the time of pattern exposure is lowered.

  In particular, in color filters for solid-state image sensors, in recent years, further higher definition has been desired. Therefore, it is difficult to further improve the resolution with a conventional pigment dispersion system. That is, there is a problem that color unevenness occurs due to the influence of coarse pigment particles. Therefore, the pigment dispersion system is not suitable for applications requiring a fine pattern with a pixel size of 1.5 to 3.0 μm square, such as a solid-state imaging device.

  In response to such a situation, techniques for using dyes instead of pigments have been proposed. Further, in recent years, color filters used in solid-state imaging devices have been required to have thin colored patterns (for example, a thickness of 1 μm or less) from the viewpoint of improving image quality due to high light condensing properties and light color separation properties. Therefore, it is necessary to increase the dye density in terms of color density. On the other hand, as the dye concentration is increased, the sensitivity is greatly reduced, and the pattern is easily peeled off in the low exposure area, and the relative amount of components contributing to photolithographic properties is reduced. There is a problem that heat distortion occurs and the shape during pattern formation cannot be maintained, and even if the dye concentration is increased, the dye itself cannot be kept high due to elution into the developer, that is, so-called color loss. .

As one method for solving such a problem, a method of increasing the amount of initiator added has been known.
Further, as a technique related to this problem, a photothermal polymerizable composition containing a polymerizable compound having a triazine skeleton in combination with a heteroalicyclic block isocyanate compound having a triazine skeleton has been disclosed (for example, Patent Document 2). It is said that excellent solvent resistance and peel resistance can be obtained. Furthermore, there is a disclosure relating to a photosensitive resin composition using isocyanuric acid ethylene oxide-modified tri (meth) acrylate as a photopolymerizable compound (see, for example, Patent Document 3).
JP 2000-321863 A JP 2006-119441 A JP-A-8-62841

  However, in the method of increasing the amount of the initiator added as described above, the generation of the residue is remarkably inappropriate, and further, heat sagging occurs in the heating process at a high temperature such as post baking, the pattern shape collapses, and the forward taper The rectangular shape cannot be obtained. This tends to be particularly prominent when a fine pattern having a pattern size of 2 μm square or less (for example, a Bayer pattern having a pattern size of 1.5 μm square or less) is formed.

  In addition, the composition using the above heteroalicyclic blocked isocyanate compound or isocyanuric acid ethylene oxide-modified tri (meth) acrylate having an imide structure containing a carbonyl group in the structure suppresses the effects of color loss and thermal sag. In particular, it is difficult to form a fine pattern having a size of 2 μm square or less in a desired rectangular shape while maintaining a desired color density.

  The present invention has been made in view of the above, and has a high residual color ratio after development processing, a shape change due to thermal sag accompanying heat treatment after patterning is suppressed, and a dye excellent in color density and pattern formability Containing negative curable composition, color filter with suppressed color loss during development processing and deformation due to thermal sag, high color density and good pattern shape (particularly, pattern rectangularity in the case of solid-state imaging device), and method for producing the same An object of the present invention is to provide a solid-state imaging device excellent in color reproducibility and to achieve the object.

  In the present invention, when the polymerizable compound responsible for curing of the composition has basicity and has a structure capable of interacting with an acidic group or ester group in the composition, it is resistant to heat after exposure curing (patterning). Based on the knowledge that the improvement effect is great and that a polymerizable compound containing such a structure is used in combination with another polymerizable compound contributes to the reduction of dye elution into the developer. It has been achieved.

Specific means for achieving the above object are as follows.
<1> (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, (C) a photopolymerizable compound containing an amine structure, (D) a photopolymerizable compound containing an amine structure (C) It is a dye-containing negative curable composition containing a different photopolymerizable compound and (E) an organic solvent.
<2> The dye-containing negative curable composition according to <1>, wherein the amine structure of the photopolymerizable compound including the (C) amine structure is a tertiary amine structure.
<3> The dye-containing negative according to <1> or <2>, wherein the photopolymerizable compound (C) having an amine structure is a compound represented by the following general formula (I): It is a mold curable composition.

  In the general formula (I), X, Y, and Z each independently represent a divalent linking group bonded to a nitrogen atom with an alkylene group, or a single bond. A, B, and C each independently represent a monovalent end group, and at least one of A, B, and C contains an ethylenically unsaturated double bond.

<4> The dye-containing negative curable composition according to any one of <1> to <3>, wherein the organic solvent-soluble dye is an acidic dye.
<5> The dye-containing negative according to any one of <1> to <4>, wherein the content of the organic solvent-soluble dye is 40% by mass or more based on the total solid content. It is a mold curable composition.
<6> The dye-containing negative curable composition according to any one of <1> to <5>, wherein the photopolymerization initiator (C) including an amine structure is an oxime compound. It is a composition.

<7> The dye-containing negative curable composition according to any one of <1> to <6>, which is used for forming a color filter for a solid-state imaging device.
<8> A color filter using the dye-containing negative curable composition according to any one of <1> to <7>.
<9> After coating the dye-containing negative curable composition according to any one of <1> to <7> above on a support, the coating film formed by coating is exposed through a mask and developed. And a method of manufacturing a color filter having a step of forming a pattern.
<10> A solid-state imaging device including the color filter according to <8>.

According to the present invention, a dye-containing negative curable composition having a high residual color ratio after development processing, a shape change due to thermal sag accompanying heat treatment after patterning is suppressed, and excellent in color density and pattern formability Can be provided.
In addition, according to the present invention, a color filter which suppresses deformation due to color loss and thermal sagging during development processing, has a high color density, and has a good pattern shape (particularly, the pattern rectangularity in the case of a solid-state imaging device), and a manufacturing method thereof Can be provided.
Furthermore, according to the present invention, it is possible to provide a solid-state imaging device excellent in color reproducibility.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter using the same, a manufacturing method thereof, and a solid-state imaging device will be described in detail.

<Dye-containing negative curable composition>
The dye-containing negative curable composition of the present invention comprises at least (A) an organic solvent-soluble dye, (B) a photopolymerization initiator, (C) a photopolymerizable compound containing an amine structure, and (D) the above (C) A photopolymerizable compound different from the photopolymerizable compound containing an amine structure (hereinafter sometimes referred to as “other photopolymerizable compound other than (C)”) and (E) an organic solvent. It is comprised and may contain other components, such as an alkali-soluble binder and a crosslinking agent, as needed.
Hereinafter, each component which comprises the dye-containing negative curable composition of this invention is explained in full detail.

(A) Organic solvent-soluble dye The dye-containing negative curable composition of the present invention contains at least one organic solvent-soluble dye. The organic solvent-soluble dye can be used without particular limitation, and can be selected, for example, from conventionally known dyes for color filters.
Examples of the known dyes include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, US Patent. No. 4,808,501, U.S. Pat.No. 5,667,920, U.S. Pat.No. 5,059,500, JP-A-5-333207, JP-A-6-35183, Examples thereof include dyes described in JP-A-6-51115 and JP-A-6-194828.

  The chemical structure of organic solvent soluble dyes is triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrazoleazo, anilinoazo, pyrazolotriazoleazo, pyridoneazo, pyrrolopyrazole azomethine , Xanthene, phthalocyanine, benzopyran, indigo, anthrapyridone, and the like. Particularly preferred organic solvent-soluble dyes are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes, anthraquinone dyes, and anthrapyridone dyes.

  In the case of forming a resist system that can be patterned by development with water or alkali, an acid dye and / or an organic solvent-soluble dye can be removed from the viewpoint of completely removing the binder and / or dye to be removed by development. In some cases, the derivative can be preferably used. In addition, as organic solvent-soluble dyes, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof may be preferably used. it can.

  Among them, as the organic solvent-soluble dye in the present invention, an alkali-soluble organic solvent-soluble dye is preferable in that alkali developability is good and simple pattern formation is possible, and further, patterning in alkali development is good. From the viewpoint of interacting with the later-described “(C) photopolymerizable compound containing an amine structure” and suppressing shape deformation due to thermal sag during heat treatment after exposure curing (particularly post-baking at 200 ° C. or higher). Acid dyes and / or derivatives thereof are preferred.

Hereinafter, the acid dye and / or its derivative will be described.
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 developer used during development, salt-forming with a basic compound, It is selected in consideration of all the required performance such as absorbance, interaction with other components in the curable composition, light resistance, heat resistance and the like.

Specific examples of acid dyes and / or derivatives thereof 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, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 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 acid dyes and / or derivatives thereof,
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;
Dyes such as these 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 they are complementary colors such as yellow, magenta, and cyan. However, when they are primary colors such as red, green, and blue, they are generally 2 in terms of hue. It is preferable to use a combination of two or more kinds of dyes. As the organic solvent-soluble dye, it is preferable to assemble a primary color system by combining two or more kinds of dyes.

  In the present invention, when two or more kinds of organic solvent-soluble dyes are combined, they can be suitably used as a mixed system (mixture) in which at least two kinds of dyes having different absorption characteristics are combined, and the primary color system is suitably configured. can do.

  Examples of the absorption characteristics include a maximum absorption wavelength. In this case, for example, a combination of dyes having different maximum absorption wavelengths by 50 nm to 250 nm is preferable, and a combination of dyes having different 50 nm to 200 nm is more preferable. Examples of combinations of such preferable organic solvent-soluble dyes include a combination of Varifast Yellow 1101 and Acid Red 57 (mass ratio 2: 3), and a combination of Direct Yellow 33 and Direct Green 27 (mass ratio 2: 3). ), A combination of Modern Violet 40 and Direct Green 69 (mass ratio 1: 2), and the like.

The content of the organic solvent-soluble dye in the dye-containing negative curable composition varies depending on the dye, but is preferably selected within the range of 10 to 90% by mass with respect to the total solid components of the composition. Can do. Among them, the dye-containing negative curable composition of the present invention has a large amount of dye in the composition, that is, a relatively small amount in the composition such as a photopolymerizable compound other than the dye or a photopolymerization initiator. If the amount of the dye in the composition is too large, that is, if the amount of the photopolymerizable compound other than the dye or the amount of the photopolymerization initiator in the composition is too small, the amine structure is reduced. Since the amount of the photopolymerization compound contained in the composition is relatively reduced, the effect of the present invention may not be obtained. From the viewpoint of further suppressing the thermal sag accompanying the heat treatment of the cured pattern after patterning (after exposure / development, etc.), and further improving the effect of improving the adhesion of the cured pattern to the substrate and the residual color rate after the development process, The content of the organic solvent-soluble dye is more preferably in the range of 40 to 90% by mass, still more preferably in the range of 50 to 80% by mass, and particularly preferably in the range of 55 to 70% by mass.
In addition, when mixing two or more organic solvent-soluble dyes to adjust the color, the amount of organic solvent-soluble dye added in the smallest amount is when the total amount of organic solvent-soluble dye is 100% in terms of hue. It is preferable that it is at least 10% or more.

(B) Photopolymerization initiator The dye-containing negative curable composition of the present invention contains at least one photopolymerization initiator. The photopolymerization initiator acts on the photopolymerizable compound (C) containing an amine structure, which will be described later, and (D) a photopolymerizable compound other than the above (C) to cure the composition. The photopolymerization initiator in the present invention is not particularly limited as long as it can polymerize at least (C) a photopolymerizable compound containing an amine structure and (D) another photopolymerizable compound other than (C). However, it is preferably selected from the viewpoints of characteristics, starting efficiency, absorption wavelength, availability, cost, and the like.

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

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

  Examples of the active halogen compound that is a halomethyl-s-triazine compound include a vinyl-halomethyl-s-triazine compound described in JP-B-59-1281 and 2- ( Naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specific examples of the halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 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- (naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-tria 2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-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-pN, 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, and the like.

  In addition to the above, as the photopolymerization initiator, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ) manufactured by Midori Chemical Co., Ltd. -123), T series manufactured by PANCHIM (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, manufactured by Ciba Specialty Chemicals) Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173),

4,4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2-benzyl-2-dimethylamino-4- Morpholinobyrophenone, 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 useful.

  Among these photopolymerization initiators, oxime compounds are preferable in terms of sensitivity. For example, 2- (O-benzoyloxime) -1- [4- (phenylthio) (preferably manufactured by Ciba Specialty Chemicals) is preferable. Phenyl] -1,2-octanedione and 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H (preferably manufactured by Ciba Specialty Chemicals) -Carbazol-3-yl] ethanone is particularly preferred.

A sensitizer and a light stabilizer can be used in combination with the photopolymerization initiator.
Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, and 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-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) ) Phenyl-p-methylstyryl ketone Benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, and the like, 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. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalo disclosed in JP-B 51-48516 And methyl-s-triazine compounds.

  The total content of the photopolymerization initiator (and known initiator) in the dye-containing negative curable composition is (C) a photopolymerizable compound containing an amine structure, which will be described later, and other than the above (C) 0.01-50 mass% is preferable with respect to solid content (mass) of a photopolymerizable compound, 1-30 mass% is more preferable, and 1-20 mass% is especially preferable. When the content of the photopolymerization initiator is 0.01% by mass or more, polymerization and curing can be favorably performed. When the content of the photopolymerization initiator is 50% by mass or less, the polymerization rate increases, but the molecular weight decreases and the film strength decreases. There is no weakening.

(C) Photopolymerizable compound containing amine structure The dye-containing negative curable composition of the present invention contains at least one photopolymerizable compound containing an amine structure. This photopolymerizable compound contains an amine structure in its structure and exhibits basicity, whereby an acid group (for example, a carboxylic acid group) or an ester group present in the composition, for example, an organic solvent-soluble dye (particularly an acid dye) ), The cured pattern after exposure and development is given heat resistance. As a result, even when heat treatment (for example, heat treatment at high temperature (eg, 200 ° C. or higher) such as post-baking) is applied, shape deformation due to thermal sagging of the pattern can be suppressed, and the color filter is highly cured by heat treatment. A pattern image having a good shape can be formed as the pixel pattern. In addition, by using together with other photopolymerizable compounds other than (C) that do not contain an amine structure, which will be described later, the elution of the dye into the developing solution during development processing is suppressed, and the residual color ratio after development processing And a colored pattern having a high color density can be obtained.
Particularly in the case of a color filter for a solid-state imaging device, for example, a pattern image having a good cross-sectional profile close to a rectangle having a high color density even with a thin film having a thickness of 1 μm or less and having little forward taper deformation due to heat is formed. Can do. In addition, the adhesion of the formed pattern to the substrate or the like is improved, and the occurrence of image defects due to peeling can be suppressed.

  The “amine structure” of a photopolymerizable compound containing an amine structure is a structural part in which a nitrogen atom has an unshared electron pair and exhibits basicity, and any structure of primary amine, secondary amine, and tertiary amine Including amide and imide structures in which the carbonyl group is directly linked to the nitrogen atom.

  The photopolymerizable compound containing an amine structure can be selected from compounds containing an amine structure and at least one polymerizable site depending on the purpose. The polymerizable site may be either a polycondensation site or an addition polymerization site (for example, a group), but an addition polymerizable site is preferred, and an ethylenically unsaturated double bond is desirable. The amine structure in the photopolymerizable compound may be a structure derived from any of primary amines, secondary amines, and tertiary amines, but tertiary amines are preferred from the viewpoint of the stability of the compound in the composition. In addition, the number of ethylenically unsaturated double bonds in the photopolymerizable compound may be only one in one molecule or two or more in one molecule. From the viewpoint of curability and adhesion when forming a pattern, it is preferable that two or more ethylenically unsaturated double bonds are contained in one molecule, and further three or more.

  Among photopolymerizable compounds containing an amine structure, it has a tertiary amine structure in that it is stable in the composition and difficult to add to an ethylenically unsaturated double bond, and has high basicity and high interaction. The compound represented by the following general formula (I) is preferable.

  In the general formula (I), X, Y, and Z each independently represent a divalent linking group bonded to a nitrogen atom with an alkylene group, or a single bond.

  The alkylene group of the divalent linking group is not particularly limited, and may be linear or branched, and may be unsubstituted or have a substituent. Examples of the substituent in the case of having a substituent include an alkyl group having 1 to 30 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group). , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group), alkenyl having 2 to 30 carbon atoms Groups (example: ethylenyl group, propenyl group, vinyl group, allyl group, styryl group, butenyl group, hexenyl group), aryl groups having 6 to 30 carbon atoms (phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group) 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, pleadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group Group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthylenyl group, heptaphenyl group, heptacenyl group, pyrantrenyl group, and oberenyl group), for example, halogen groups such as fluorine atom, chlorine atom, bromine atom, iodine atom, for example methoxy group Alkoxy groups such as ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group such as acetoxy group and propionyl Acyloxy groups such as oxy group and benzoyloxy group, for example, acetyl group, benzoyl group, isobutyryl group, methoxalyl group, acrylic group, methacryl group and other acyl groups such as methylsulfanyl group, tert-butylsulfuric group Alkylsulfanyl groups such as nyl groups, for example, arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups, as well as monovalent groups such as hydroxy groups, formyl groups, mercapto groups, nitro groups, cyano groups, and trifluoromethyl groups Or a monovalent terminal group represented by A, B, or C below. These substituents may be further substituted with these substituents.

  Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is particularly preferable from the viewpoint of high reactivity and high developability.

  Examples of the “divalent linking group bonded to the nitrogen atom with an alkylene group” include, for example, an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, a urea bond, a urethane bond, an ester bond, an aryleneoxy group, and the like. The group which connected at least 2 sorts can be mentioned. Among these, an alkylene group, an alkyleneoxy group, a urea bond, an alkyleneoxycarbonyl group, or a group in which at least two of these are linked is preferable in terms of high reactivity and high developability.

  A, B, and C in the general formula (I) each independently represent a monovalent end group, and at least one of A, B, and C includes an ethylenically unsaturated double bond. Since a polymerizable group is present in one or more of the three end groups of A, B, and C, the composition is curable and can form a cured pattern by a polymerization reaction.

  Among the monovalent end groups represented by A, B, and C, the end group that does not contain an ethylenically unsaturated double bond is not particularly limited, and may be an alkyl group, an aryl group, a halogen group, an alkoxy group, Select appropriately from aryloxy group, alkoxycarbonyl group, acyloxy group, acyl group, arylsulfanyl group, hydroxy group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, etc. can do. Among these, an alkyl group having 1 to 30 carbon atoms, an aryl group, and a hydroxy group are preferable. The terminal group containing an ethylenically unsaturated double bond is preferably an unsubstituted or substituted alkenyl group, and examples of the substituent in the case of having a substituent include an alkyl group. As the alkenyl group, an unsubstituted or substituted alkenyl group having 2 to 10 carbon atoms (more preferably 2 to 4 carbon atoms) is preferable, and vinyl and propenyl groups are particularly preferable.

A, B, and C may be end groups containing an ethylenically unsaturated double bond, particularly in terms of polymerization sensitivity, curability, and adhesion at the time of pattern formation. Preferably, all of A, B and C are more preferably end groups containing an ethylenically unsaturated double bond.
Furthermore, the number of ethylenically unsaturated double bonds in one molecule of the compound represented by the general formula (I) is generally preferably in the range of 1 to 10, preferably 2 to 8, for the same reason as described above. Is more preferable, and 3 to 6 is particularly preferable.

  The molecular weight of the photopolymerizable compound containing an amine structure (including the compound represented by the general formula (I)) is preferably 200 to 1500, more preferably 250 to 800, from the viewpoint of coating solution solubility. .

  Hereinafter, specific examples of the photopolymerizable compound containing an amine structure (including the compound represented by the general formula (I)) will be shown. However, the present invention is not limited to these.

  In the present invention, among the “photopolymerizable compounds containing an amine structure”, the compound represented by the general formula (I), and all of X, Y, and Z are alkyleneoxycarbonyl groups. A compound in which two or more of A, B and C are terminal groups containing an ethylenically unsaturated double bond is preferred, and further a compound represented by the above general formula (I), wherein X, Y, And all of Z are alkyleneoxycarbonyl groups, and two or more of A, B and C are unsubstituted or substituted alkenyl groups having 2 to 10 carbon atoms (more preferably 2 to 4 carbon atoms) In particular, the compound is represented by the general formula (I), and all of X, Y, and Z are ethyleneoxycarbonyl groups, and three or more of A, B, and C have 2 carbon atoms. 10 to 10 (or 2 to 4 carbon atoms) unsubstituted or Compound is an alkenyl group having substituent are more preferred.

  (C) The content of the photopolymerizable compound containing an amine structure in the dye-containing negative curable composition is preferably 1 to 60% by mass, and preferably 10 to 50% by mass, based on the total solid content of the composition. Is more preferable, and 20-40 mass% is especially preferable. (C) When the content of the photopolymerizable compound containing an amine structure is 1% by mass or more, the polymerization and curing can be satisfactorily performed, and the color loss and heat caused by the heat treatment of the cured pattern after exposure / development The sagging is suppressed and the adhesion of the pattern can be further improved, and if it is 60% by mass or less, it is advantageous in terms of developability of the unexposed area.

(D) A photopolymerizable compound different from a photopolymerizable compound containing an amine structure The dye-containing negative curable composition of the present invention comprises (C) an amine structure together with the (C) photopolymerizable compound containing an amine structure. It contains at least one of photopolymerizable compounds other than the photopolymerizable compound to be contained (photopolymerizable compounds other than (C)). This photopolymerizable compound can be used by appropriately selecting one or two or more kinds from known photopolymerizable compounds not containing an amine structure.

  In the present invention, in addition to (C) the photopolymerizable compound containing an amine structure, a photopolymerizable compound other than (C) is further used in combination, so that the elution of the dye into the developer particularly during development processing Can be reduced, and the residual color rate after development processing can be increased. As a result, the effect of increasing the dye density is enhanced, and a pattern having a high color density is obtained. Furthermore, the adhesion of the formed pattern to the substrate or the like is further improved, and the effect of preventing the occurrence of image defects due to peeling can be enhanced.

  The photopolymerizable compound other than (C) is not particularly limited as long as it is a photopolymerizable compound that does not contain an amine structure and has a polymerizable group such as an ethylenically unsaturated double bond. Among these, from the viewpoint of solubility in the coating solution, (C) the other photopolymerizable compound used in combination with the photopolymerizable compound containing an amine structure is preferably a monomer compound having a molecular weight of 1500 or less. Examples of the monomer compound include a radical polymerizable monomer.

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. Examples of radically polymerizable monomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 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 (acryloyl) Kishiechiru) isocyanurate, after adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane (meth) those acrylated;
Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193; JP-A-48-64183, JP-B-49-43191, JP-B-52- Examples include polyester acrylates described in each publication No. 30490; polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
Furthermore, what was introduce | transduced as a photocurable monomer and oligomer in the Japan Adhesive Association magazine Vol.20, No.7, 300-308 pages can also be mentioned. As other polymerizable monomer, a polyfunctional (meth) acrylic compound can be preferably used.

  Among the above, as the other photopolymerizable compound used in combination with the photopolymerizable compound (C) containing an amine structure, dipentapentamine is used from the viewpoint of further improving the effect of preventing color loss during development and the adhesion of the pattern. Erythritol hexa (meth) acrylate, tetramethylolmethanetetrakis (acryloyloxyethyl ether) and the like are preferable.

In the dye-containing negative curable composition of the present invention, (D) the content ratio of the photopolymerizable compound different from the photopolymerizable compound containing an amine structure is from the viewpoint of enhancing the effect of improving the residual color after development processing. It is preferable that the content of the photopolymerizable compound containing the (C) amine structure is larger.
Specifically, the content ratio of the photopolymerizable compound containing (C) amine structure is different from (C) photopolymerizable compound containing amine structure and (D) photopolymerizable compound containing amine structure. The range of 10-40 mass% is preferable with respect to the total amount with an ionic compound, The range of 10-30 mass% is more preferable, The range of 15-25 mass% is especially preferable.
Among the photopolymerizable compounds, when the content ratio of the photopolymerizable compound (C) containing an amine structure is 10% by mass or more, the residual color ratio after the development process and the thermal sag caused by the heat treatment after patterning are obtained. The effect of suppressing the shape change due to is increased, and the proportion of 40% by mass or less is advantageous in terms of radical polymerization reaction efficiency.

In the present invention, the preferred forms of the above-described components (A) to (D) increase the residual color ratio after the development process, and are deformed due to thermal sag accompanying the heat treatment after patterning (after exposure / development). The combination aspect shown to the following [1]-[6] is preferable at the point to suppress.
[1] (A) At least one organic solvent-soluble dye is an acidic dye and / or a derivative thereof, and (C) a photopolymerizable compound containing an amine structure is represented by the general formula (I) A form that is a compound (more preferably two or three of A, B, and C contain an ethylenically unsaturated double bond).
[2] (A) At least one organic solvent-soluble dye is an acid dye and / or a derivative thereof, (B) a photopolymerization initiator is an oxime compound, and (C) a light containing an amine structure The form in which the polymerizable compound is a compound represented by the general formula (I) (more preferably, two or three of A, B, and C contain an ethylenically unsaturated double bond).
[3] (A) At least one organic solvent-soluble dye is an acid dye and / or a derivative thereof, and the content of the organic solvent-soluble dye is 40 to 90% by mass with respect to the total solid content of the composition. And (C) the photopolymerizable compound containing an amine structure is a compound represented by the general formula (I) (more preferably, two or three of A, B, and C are ethylenically unsaturated A form that includes a double bond).
[4] (A) At least one of the organic solvent-soluble dyes is an acid dye and / or a derivative thereof, and the content of the organic solvent-soluble dye is 40 to 90% by mass with respect to the total solid content of the composition. And (B) the photopolymerization initiator is an oxime compound, and (C) the photopolymerizable compound containing an amine structure is a compound represented by the general formula (I) (more preferably, A, A form in which two or three of B and C contain an ethylenically unsaturated double bond).
[5] (A) At least one organic solvent-soluble dye is an acid dye and / or a derivative thereof, and the content of the organic solvent-soluble dye is 40 to 90% by mass with respect to the total solid content of the composition. And (B) the photopolymerization initiator is an oxime compound, and (C) the photopolymerizable compound containing an amine structure is a compound represented by the general formula (I) (X, Y, and Z). Are all alkyleneoxycarbonyl groups, and two or more of A, B and C are terminal groups containing an ethylenically unsaturated double bond).
[6] In the above [1], [2], [3], [4], or [5], “(D) a photopolymerizable compound different from a photopolymerizable compound containing an amine structure” is dipenta A form that is erythritol hexa (meth) acrylate or tetramethylolmethanetetrakis (acryloyloxyethyl ether).

(E) Organic solvent The dye-containing negative curable composition of the present invention contains at least one organic solvent. The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each component and the applicability of the dye-containing negative curable composition, and particularly the solubility, applicability, and safety of the dye and binder. It is preferable to select in consideration of the properties.

  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 lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate and the like;

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, 2-ethyl-oxobutanoic acid, and the like;

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.

  When these organic solvents contain the solubility of a dye and an alkali-soluble binder, it is also preferable to mix 2 or more types from a viewpoint of the solubility, the improvement of a coating surface shape, etc. 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 A mixed solution composed of two or more selected from carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferably used.

  The amount of the organic solvent used is preferably such that the total solid content concentration of the dye-containing negative curable 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.

(E) Other components The dye-containing negative curable composition of the present invention contains, in addition to the above components, other components such as an alkali-soluble binder and a crosslinking agent, as long as the effects of the present invention are not impaired. You may go out.

-Alkali-soluble binder-
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be 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-58-12777, 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, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group and an acid anhydride added thereto, a polyhydroxystyrene resin, a polysiloxane resin, and poly (2-hydroxyethyl (meth) acrylate). ), Polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like 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 examples of the hydrophilic monomer include a tetrahydrofurfuryl group, a phosphoric acid group, a phosphoric ester group, a quaternary ammonium base, an ethyleneoxy chain, a propyleneoxy chain, a sulfonic acid group and a salt-derived group, a morpholinoethyl group, and the like. Also useful are monomers comprising

  In addition, the alkali-soluble binder in the present invention may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. Polymers contained in are also useful. Examples of the polymer containing the above-described 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 addition, 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 binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

Alkali-soluble binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

-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 is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (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, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) 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 diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

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

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

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

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

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated 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 according to (b) may be used alone or in combination.

  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, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are 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.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (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 according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 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, as a phenol compound or a naphthol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of cymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

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 according to (c) may be used alone or in combination.

  In the present invention, it is not always necessary to contain a crosslinking agent. When it contains a crosslinking agent, the total content of the crosslinking agent (a) to (c) in the dye-containing negative curable composition varies depending on the material, but the solid content (mass) of the curable composition is different. On the other hand, 1-70 mass% is preferable, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable.

-Thermal polymerization inhibitor-
In addition to the above components, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. For example, 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, etc. are useful.

-Other additives-
In the dye-containing negative curable composition of the present invention, various additives such as a filler, a polymer compound other than the alkali-soluble binder, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet ray are optionally added. Absorbers, anti-aggregation agents and the like 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; 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; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility in the non-exposed 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.

The dye-containing negative curable composition of the present invention can be suitably used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs), solid-state imaging devices (eg, CCDs, CMOSs, etc.) and the like. .
The dye-containing negative curable composition of the present invention is particularly suitable for forming a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required. Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the effect of coarse particles in the pigment In the case of dyes, color loss may occur due to elution of the dye itself into the developer, or when the amount of dye increases, the relative amount of components that contribute to photolithographic properties decreases and post baking after patterning, etc. It is easy to cause thermal sag by heat treatment. This is particularly noticeable when the pixel pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm). In addition, in the case of a thin film having a thickness of 1 μm or less, the amount of components that contribute to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by the increase in the amount of colorant. Sensitivity is increased, and the pattern is easily peeled off in the low exposure region, and heat sag is easily caused by heat treatment such as post-baking after patterning as described above. This is particularly noticeable when the film thickness is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm).
When forming such a color filter for a solid-state imaging device, in particular, by using the dye-containing negative curable composition of the present invention, forward taper due to thermal sag can be effectively suppressed and close to a rectangle. A pattern is obtained. Furthermore, high sensitivity can be obtained, and the adhesion of the formed pattern to the substrate or the like can be improved, thereby preventing the occurrence of peeling and hence the occurrence of image defects.

<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. By using the dye-containing negative curable composition of the present invention, a high residual color rate is obtained after development processing, and heat resistance is provided after patterning, so a high color density is obtained even in a thin film, and heat during heat treatment A color filter composed of a fine pattern with good shape and high resolution that is less affected by sagging and can be manufactured. Furthermore, a cured pattern can be formed with high sensitivity, adhesion with a support and the like can be improved, and a color filter with reduced occurrence of peeling (pixel defects) can be obtained.

  The method for producing a color filter of the present invention comprises the steps of applying the dye-containing negative curable composition of the present invention on a support, exposing the applied coating film through a mask, and developing to form a pattern. It is provided and configured. Specifically, the radiation-sensitive composition layer is formed by coating the dye-containing negative curable composition of the present invention on a support by a coating method such as spin coating, cast coating, roll coating, and the like. Is exposed to light through a predetermined mask pattern and developed with a developing solution to form a negative colored pattern (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.

The exposure may be performed by any of a proximity method, a mirror projection method, and a stepper method. In particular, the exposure is performed by a stepper method (reduction projection exposure method using a reduction projection exposure machine). preferable. In the stepper method, a pattern is formed by performing exposure while varying the exposure amount stepwise, and the rectangularity of the pattern can be particularly improved when performing stepper exposure.
Moreover, as an exposure apparatus used for stepper exposure, for example, an i-line stepper (trade name: FPA-3000i5 +, manufactured by Canon Inc.) can be 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 substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.

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

The color filter of the present invention can obtain a colored pattern having excellent rectangularity by using the dye-containing negative curable composition of the present invention, and the solid-state imaging device provided with this color filter has excellent color reproducibility. Have
The configuration of the solid-state imaging device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.
A support body has a plurality of photodiodes constituting a light receiving area of a CCD image sensor (solid-state imaging device) and a transfer electrode made of polysilicon or the like, and only the light receiving portion of the photodiode is placed on the photodiode and the transfer electrode. It has a light shielding film made of tungsten or the like having an opening, and has a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light shielding film and the photodiode light receiving portion on the light shielding film, on the device protective film, This is a configuration having the color filter of the present invention.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

  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.

Example 1
1) Preparation of dye-containing negative curable composition Each compound having the following composition was mixed and dissolved to prepare a dye-containing negative curable composition of the present invention.
〔composition〕
・ Cyclohexanone (organic solvent) ・ ・ ・ 26g
・ Resin A (alkali-soluble binder) ... 2.0g
(Benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio]))
・ Amine-containing monomer A having the following structure: 1.0 g
((C) Photopolymerizable compound containing amine structure)
・ Monomer a with the following structure: 2.0 g
((D) Other photopolymerizable compound other than (C) not containing an amine structure)
・ The following oxime A (photopolymerization initiator): 1.0 g
・ Valifast yellow 1101 (organic solvent soluble dye) ... 4.0 g

2) Production of silicon substrate with undercoat layer Resist CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied onto a silicon substrate (wafer) using a spin coater so as to have a film thickness of 2 μm. Heat-dried at 1 degreeC for 1 hour, and the cured film (undercoat layer) was formed.

3) Exposure and development of dye-containing negative curable composition (image forming process)
Apply the dye-containing negative curable composition obtained in 1) above to the undercoat layer of the silicon substrate with the undercoat layer obtained in 2) above using a spin coater so that the film thickness becomes 1 μm. The sample was pre-baked at 100 ° C. for 120 seconds to prepare a sample in which a colored resist layer was formed on a silicon substrate.

(Examples 2-15, Comparative Examples 1-8)
In Example 1, except that each composition included in the dye-containing negative curable composition was changed to the composition shown in Table 1 below, the dye-containing negative curable composition was changed in the same manner as in Example 1. Prepared and made a sample.

(Examples 16-18, Comparative Examples 9-11)
In Example 1, an organic solvent-soluble dye (Valifast yellow 1101) was used in the same manner as in Example 1 except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 2 below. A dye-containing negative curable composition having a weight increased to 5.0 g was prepared to prepare a sample.

(Examples 19 to 21, Comparative Examples 12 to 14)
In Example 1, an organic solvent-soluble dye (Valifast yellow 1101) was prepared in the same manner as in Example 1 except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 3 below. A dye-containing negative curable composition having a weight increased to 6.0 g was prepared to prepare a sample.

(Examples 22-24, Comparative Examples 15-17)
In Example 1, except that each composition contained in the dye-containing negative curable composition was changed to the composition shown in Table 4 below, in the same manner as in Example 1, two organic solvent-soluble dyes were used. A dye-containing negative curable composition having a total dye amount increased to 6.0 g was prepared to prepare a sample.

(Examples 25-27)
In Examples 22-24, except having changed each composition contained in a dye containing negative curable composition into the composition shown in following Table 5, respectively, it carried out similarly to Examples 22-24, and organic-solvent soluble dye was used. Using two kinds, a dye-containing negative curable composition having a total dye amount increased to 6.0 g was prepared, and a sample was prepared.

(Evaluation)
The following evaluation was performed about the sample produced in said Example and comparative example. The evaluation results are shown in Tables 1 to 5 below.
-1. Sensitivity
The colored resist layer of each sample thus obtained was irradiated at a wavelength of 365 nm using an i-line reduced projection exposure apparatus while changing the exposure amount through a mask of 2 μm length × 2 μm width. After irradiation, development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Electronics Materials Co., Ltd.). Subsequently, after rinsing with running water for 20 seconds, a pattern image was formed by spray drying. The formed pattern image was confirmed by an ordinary method by observation with an optical microscope and SEM photograph.
At this time, an exposure amount at which the width of the pixel pattern of 2 μm in length × 2 μm in width and the width of the space between the pixel patterns was 1: 1 was set as an appropriate exposure amount, and the exposure amount was set as sensitivity. The sensitivity indicates that the smaller the exposure value, the higher the sensitivity.

-2. Profile
The pattern image formed with the appropriate exposure amount in the “1. sensitivity” is post-baked at 200 ° C. for 300 seconds, and then the post-baked pattern is observed with a scanning electron microscope (SEM) image. The shape of the cross section (cut surface when cut along a plane parallel to the normal direction of the silicon substrate and parallel to one side of the pattern) was evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: The pattern profile of the cross section was a good rectangle as shown in FIG.
Δ: The cross-sectional pattern profile was in a practically acceptable range, although the substrate non-contact corner was slightly rounded as shown in FIG.
X: The cross-sectional pattern profile had a round top (rounded head) shape as shown in FIG.
XX: The cross-sectional pattern profile was completely round top as shown in FIG.

-3. Adhesion sensitivity
As in the case of “1. Sensitivity”, after changing the exposure amount and performing irradiation, development, etc. to obtain a pattern image, the pattern image after rinsing with running water and then spray drying is peeled off. The lowest minimum exposure was evaluated as adhesion sensitivity. The adhesion sensitivity indicates that the smaller the exposure value, the better.

-4. Residual color-
MCPD shows the yellow density (y ¹ ) of the colored resist layer before exposure / development of each of the obtained samples and the yellow density (y ² ) in the pattern image formed at an appropriate exposure amount in the “1. Sensitivity”. -3000 (manufactured by Otsuka Electronics Co., Ltd.), and the density residual rate D after development was calculated from the following formula using the obtained density value. This density residual rate was used as an index for evaluating the persistence of the dye remaining after development.
^{D [%] = y 2 /} y 1 × 100

  As shown in Table 1 to Table 5, in the examples in which a photopolymerizable compound containing an amine structure and another second photopolymerizable compound not containing an amine structure were used in combination, color loss and heat during development processing Deformation due to sagging was suppressed, and a color filter with high color density and good pattern rectangularity could be formed.

The detail of each component in the said Table 1-Table 5 is as follows.
* Alkali-soluble resin / resin A: benzyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])

* Photopolymerizable compound

* Photopolymerization initiator / oxime A: 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (manufactured by Ciba Specialty Chemicals)
Oxime B: 1- (O-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone (manufactured by Ciba Specialty Chemicals)

In each of the above embodiments, the case where a yellow color filter is formed on a silicon substrate has been mainly described. However, for example, R, G, and B three-color dye-containing negative curability prepared by changing the dye species as desired. By repeating the same operation for the hue using the composition, for example, a color filter composed of three colors of RGB can be obtained.
In the case of producing a solid-state imaging device, the silicon substrate can be produced by replacing the silicon substrate with a substrate for a solid-state imaging device on which a photodiode, a light shielding film, a device protection film, and the like are formed. Specifically, for example, a light shielding film made of tungsten having an opening only in the light receiving portion of the photodiode is formed on a silicon substrate on which the photodiode and the transfer electrode are formed, and the entire surface of the light shielding film and the photodiode light receiving are formed on the light shielding film. A device protective layer made of silicon nitride is formed so as to cover the portion, and a color filter is formed on the formed device protective layer by the same method as in Examples 1 to 17, and is collected on the formed color filter. By forming a microlens that is an optical means, a solid-state imaging device with good color reproducibility can be manufactured.

It is a figure illustrating the evaluation criteria of a profile, (A) is a figure which shows a favorable rectangle, (B) It is a figure with a rounded corner (cadence), (C) shows a round top shape. It is a figure and (D) is a figure which shows perfect round top shape.

Claims (10)

  (A) Organic solvent soluble dye, (B) Photopolymerization initiator, (C) Photopolymerizable compound containing amine structure, (D) Photopolymerization different from photopolymerizable compound containing (C) amine structure A dye-containing negative curable composition comprising a functional compound and (E) an organic solvent.   2. The dye-containing negative curable composition according to claim 1, wherein the amine structure of the photopolymerizable compound containing the amine structure (C) is a tertiary amine structure. The dye-containing negative curable composition according to claim 1 or 2, wherein the (C) photopolymerizable compound containing an amine structure is a compound represented by the following general formula (I): .

[Wherein, X, Y and Z each independently represent a divalent linking group bonded to a nitrogen atom by an alkylene group or a single bond. A, B, and C each independently represent a monovalent end group, and at least one of A, B, and C contains an ethylenically unsaturated double bond. ]   The dye-containing negative curable composition according to any one of claims 1 to 3, wherein the organic solvent-soluble dye is an acid dye.   The dye-containing negative curable composition according to any one of claims 1 to 4, wherein the content of the organic solvent-soluble dye is 40% by mass or more based on the total solid content. .   The dye-containing negative curable composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (C) containing an amine structure is an oxime compound.   It is used for formation of the color filter for solid-state image sensors, The dye containing negative curable composition of any one of Claims 1-6 characterized by the above-mentioned.   The color filter which uses the dye-containing negative curable composition of any one of Claims 1-7.   After applying the dye-containing negative curable composition according to any one of claims 1 to 7 on a support, the applied coating film is exposed through a mask and developed to form a pattern. A method for producing a color filter having a process.   A solid-state imaging device comprising the color filter according to claim 8.

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