JP2008197285A - Curable composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition for a color filter which cures with high sensitivity to form an excellent cured film, has a good pattern forming property and excels in adhesion to a hard surface being a substrate, even when the composition contains a colorant in high concentration. <P>SOLUTION: The curable composition contains (A) an onium salt having at least two cationic parts, (B) a coloring component and (C) a compound having a nucleophilic group. A binder polymer having a nucleophilic group is suitable for use as the compound having the nucleophilic group (C). This curable composition is useful for forming a colored pattern or a black matrix of a color filter. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition suitable for producing a color filter used for a liquid crystal display element (LCD), a solid-state image sensor (CCD, CMOS, etc.) and the like.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device. In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

  In color filter applications for liquid crystal displays (LCDs), the substrate size is increasing for large TV production, and low energy curing is desired to improve productivity when large substrates are used. In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity. In order to improve the contrast, the curable composition used for the production of the color filter is required to have a finer particle size of the colorant (organic pigment or the like) used. (For example, refer to Patent Document 1.) Along with this, the amount of dispersant added for dispersing the pigment tends to increase. Moreover, the higher thing is calculated | required as content rate of the coloring agent (organic pigment) which occupies in solid content of a curable composition for color purity improvement. Therefore, the content of the photopolymerization initiator and the photopolymerizable monomer in the solid content in the curable composition tends to decrease.

On the other hand, curing with low energy is also desired in color filter applications for solid-state imaging devices. Moreover, the pattern thinning is progressing and the pigment density | concentration in a composition is improving with this. Furthermore, in the pigment-based color filter, the proportion of the pigment dispersant in the composition tends to increase as the pigment becomes finer. In addition, in order to cope with problems such as color unevenness that occurs because the pigment is relatively coarse particles, a technique using an organic solvent-soluble dye instead of the pigment as a colorant has been proposed (for example, Patent Documents). 2). However, in dye-based color filters, with the increase in dye concentration, the problem of the polymerization inhibition effect derived from dyes has become prominent. Due to such factors, the content of the photopolymerization initiator and the photopolymerizable monomer, which are components necessary for curing the curable composition, is limited in both cases for liquid crystal displays and solid-state imaging devices. Furthermore, the colorant concentration is high, and since it is exposed to light and cured in the air, the sensitivity is low and sufficient curing cannot be obtained, the adhesion to the substrate is insufficient, and peeling occurs during development. was there.
JP 2006-30541 A JP-A-2-127602

  The object of the present invention, which has been made in consideration of the problems in the prior art, is to form a cured film excellent in curing with high sensitivity, even when the colorant is contained in a high concentration. An object of the present invention is to provide a curable composition for a color filter which is excellent in adhesion to the surface and useful for forming a color pattern of a color filter.

As a result of intensive studies, the present inventor has found that the above problems can be solved by using a specific polymerizable compound, and has completed the present invention. That is, the means for solving the above problems are as follows.
<1> A curable composition for a color filter comprising (A) an onium salt having at least two cation moieties, (B) a coloring component, and (C) a compound having a nucleophilic group.
<2> The curable composition for a color filter according to <1>, further comprising (D) a radical polymerizable compound.
<3> (C) The curable composition for color filters according to <1> or <2>, wherein the nucleophilic group in the compound having a nucleophilic group is a carboxylic acid group.
<4> (A) The curable composition for a color filter according to any one of <1> to <3>, wherein the onium salt having at least two cation sites is a diazonium salt resin.
<5> (B) The curable composition for color filters according to any one of <1> to <4>, wherein the coloring component is a dye.

Although the operation of the present invention is not clear, it is estimated as follows.
The curable composition of the present invention contains a polyvalent onium salt and a compound having a nucleophilic group, and a curing reaction due to coupling between the polyvalent onium salt and the nucleophilic group occurs upon application of energy. This curing reaction is unlikely to be inhibited by oxygen or a coexisting colorant, so it is considered to cure with high sensitivity and form a cured film with good film properties. In addition, since the polyvalent onium salt has a plurality of reactive partial structures, the initiator itself works in a cross-linking manner, and this is also useful for expressing high sensitivity and excellent curability.
In addition, since a polyvalent onium salt simultaneously generates radicals upon energy application, as in a preferred embodiment of the present invention, by allowing a radical polymerizable compound to coexist in the curable composition, a polyvalent onium salt can have a polyvalent onium salt together with the coupling reaction. It is considered that radical polymerization reaction can be carried out at the same time, and higher sensitivity and improved film quality are achieved.

  According to the present invention, even when a colorant is contained at a high concentration, a color filter that forms an excellent cured film by curing with high sensitivity and has excellent adhesion to a hard surface as a substrate. It is possible to provide a curable composition for a color filter that is useful for forming a colored pattern of the color filter.

Hereinafter, the curable composition for a color filter of the present invention, and a color filter and a production method using the curable composition will be described in detail.
[Curable composition for color filter]
The curable composition for a color filter of the present invention comprises (A) an onium salt having at least two cationic sites, (B) a coloring component, and (C) a compound having a nucleophilic group, and optionally (D ) It contains a radically polymerizable compound and other additives.
Hereinafter, the components contained in the curable composition of the present invention will be sequentially described.

<(A) Onium salt having at least two cationic sites>
First, (A) an onium salt having at least two cation sites (hereinafter referred to as (A) a specific onium salt as appropriate), which is a characteristic component of the present invention, will be described.
The (A) specific onium salt according to the present invention can be used without particular limitation as long as it is a compound that can be decomposed by light or heat and has a plurality of cationic sites in its structure. As the decomposition mechanism, for example, in the case of a compound that decomposes by light, it is possible to use a compound that directly absorbs and decomposes light, and a sensitizer having absorption at the exposure wavelength coexists. Therefore, it is also possible to apply a mechanism in which (A) the specific onium salt is decomposed by performing electron transfer or energy transfer.

An onium salt having at least two cation sites refers to a compound in which a plurality of cation moieties are linked to one molecule of an onium salt compound by a covalent bond.
The plurality of cation moieties may be introduced directly into the onium salt compound molecule, or can be introduced into the molecule by including a structural unit containing an onium cation structure as a polymerizable component.
Examples of the onium structure that can be used in the present invention include sulfonium salts, iodonium salts, diazonium salts, azinium salts, phosphonium salts, ammonium salts, and the like. From the viewpoint of sensitivity, a sulfonium salt, an iodonium salt, and a diazonium salt are preferable. From the viewpoint of improving sensitivity and adhesion between the curable composition and the substrate, a diazo resin in which the diazonium salt is a resin is preferable. .

(A) The counter anion of the specific onium salt can be used as long as it is a monovalent anion, but preferably PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , sulfonate anion, carboxylate anion, saccharin conjugate base, Represents halogen anion, sulfuric acid monoester anion, phosphate ester anion, phosphate anion, more preferably PF ₆ ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , sulfonate anion, carboxylate anion from the viewpoint of sensitivity and stability Most preferably, sulfonate anion, PF ₆ ^- is preferred.
Further, (A) the two or more counter anions X ⁻ for the specific onium salt may be the same or different from each other, but are preferably the same from the viewpoint of ease of production.

Although the preferable specific example of (A) specific onium salt used suitably for this invention below is shown, this invention is not limited to these.
Examples of the iodonium salt-based specific onium salt compound include the following [Exemplary Compound (I-1) to Exemplary Compound (I-51)].

  Examples of the sulfonium salt compounds include the following [Exemplary Compound (S-1) to Exemplified Compound (S-40)].

  Furthermore, as the specific onium salt (A), the following polyvalent diazonium salts can be used as well. As shown in the following exemplified compounds, the polyvalent diazonium salt is preferably a compound having an electron donating group such as an alkoxy group, amino group, alkyl group, thioalkoxy group, or aryloxy group in the molecule. Specific examples of the polyvalent diazonium salt [Exemplary compounds (N2-1) to (N2-7)] that can be used in the present invention are shown below, but are not limited thereto.

  Further, another preferred (A) specific onium salt diazo resin in the present invention is a polymer compound having a partial structure represented by the following general formula (I), more preferably the general formula (II). preferable. That is, a diazo resin in which a plurality of partial structures represented by the general formula (I) are introduced at arbitrary positions in the main chain structure of the polymer compound, or a structural unit represented by the general formula (II) A diazo resin containing a plurality of copolymer components is preferred. By taking such an embodiment, it is possible to arbitrarily control the number of onium cations introduced into the molecule according to the purpose.

In the general formulas (I) and (II), R ¹ , R ² , and R each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a thioalkoxy group, and n represents an integer of 1 to 3. .
When n is 2 to 3, a plurality of R may be the same or different from each other.
Moreover, Y in general formula (II) represents a bivalent coupling group, Preferably -NH-, -O-, and -S- are represented.
R ³ represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxy ester group, or a carboxyl group.
R ⁴ and R ⁵ each independently represents a hydrogen atom, an alkyl group, a carboxyl group, an aryl group, or an alkoxy group.
X ⁻ represents a monovalent anion. Preferably, tetrafluoroborate anion, hexafluorophosphate anion, perchlorate anion, periodate anion, organic acid anion having carboxylate anion structure, organic acid anion having sulfonate anion structure, sulfonamide anion structure Examples include an organic acid anion, an organic acid anion having a phosphate anion structure, an organic acid anion having a sulfinate anion structure, and an organic acid anion having a monosulfate anion structure.

The diazo resin having a partial structure represented by the general formula (I) or the general formula (II) is a structural unit containing another alkali-soluble group or a hydrogen bonding property for the purpose of controlling developability and improving stability. It can be copolymerized or polycondensed with a structural unit having a group or a structural unit having different hydrophilicity / hydrophobicity.
Specific examples [Example Compound (NP-1) to Example Compound (NP-16)] of a diazonium salt compound (diazo resin) which is a specific onium salt compound (A) preferable in the present invention are shown in the following. Although it shows with (Mw) (polystyrene conversion), this invention is not restrict | limited to this.

  Examples of the diazo resin include a method for condensing a diazo monomer having a diazo skeleton and a compound having an aldehyde skeleton and / or an acetal skeleton described in JP-A-4-18559, or a double bond group and It can be synthesized by a method in which a monomer having a diazo skeleton is copolymerized with another radical polymerizable monomer, if necessary, or a method in which a compound having a diazo group is introduced into a polymer by a polymer reaction.

Each of the (A) specific onium salts may be used alone in the curable composition of the present invention, or may be used in combination of plural kinds according to the purpose.
(A) It is preferable that specific onium salt content is 0.5 mass%-40 mass% in curable composition solid content of this invention from a viewpoint of a sensitivity and the intensity | strength of a cured film, and 1 mass%-20%. More preferably, it is in the range of 2% by mass to 15% by mass.

<(B) Coloring component>
The curable composition of the present invention contains a coloring component. By using a coloring component (hereinafter, appropriately referred to as (B) a colorant), a colored cured body made of a curable composition can be formed, which is useful for forming a colored pattern of a color filter or a black matrix. is there.
There is no restriction | limiting in particular in the coloring agent added by necessity to the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance, and may be a dye from the viewpoint of hue uniformity and contrast of the formed colored pattern. Preferably, each may be selected according to the purpose.

  As the pigment that can be used in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As the organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  Examples of pigments that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

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

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment A mixture of these can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

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

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

  In the curable composition for a color filter of the present invention, the primary particle diameter of the pigment is preferably from 10 to 100 nm, more preferably from 10 to 70 nm, still more preferably from 10 to 50 nm, from the viewpoint of suppressing uneven color and improving contrast. Most preferred is ˜40 nm.

Moreover, in the formation of the color filter coloring pattern, it is also a preferred aspect to select and use a dye that can be uniformly dissolved in the composition from the viewpoint of suppressing uneven color and improving contrast.
The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

  The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, other in the composition. It is selected in consideration of all the required performances such as interaction with the components, light resistance and heat resistance.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it 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 red1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91 , 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 Yellow3;
And derivatives of these dyes.

Among the acid dyes mentioned above, 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;
acid red1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Dyes such as Acid Green 25 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 and other acid dyes and derivatives of these dyes are also preferably used.

  Among these, (B) colorants include triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo. A colorant selected from pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferable.

The content of the colorant in the curable composition for a color filter is 10 to 80% by mass in the total solid content of the curable composition, considering that the main purpose of use is to form a colored pattern of the color filter. It is preferable that 20-70 mass% is more preferable, and 30-70 mass% is still more preferable.
When the content of the colorant is within the above range, an appropriate chromaticity can be obtained when a color filter is produced, and photocuring is sufficiently advanced to obtain a sufficient strength. The development latitude is also good.

<Dispersant>
When the curable composition of this invention contains a pigment as (B) a coloring agent, it is preferable to add a dispersing agent from a viewpoint of improving the dispersibility of this pigment.
Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the dispersing agent in this invention, it is preferable that it is 1-150 mass% with respect to a pigment, 3-100 mass% is more preferable, and 5-80 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment. In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the present invention, when using a pigment and a dispersant as a colorant, the total content of the colorant and the dispersant is based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less.

<(C) Compound having nucleophilic group>
The curable composition of the present invention is a compound containing a (C) nucleophilic group capable of coupling with a cation that is likely to be generated when the polyfunctional onium salt is decomposed (hereinafter, appropriately referred to as (C) nucleophilicity). Called compound).
(C) Preferable nucleophilic groups in the compound having a nucleophilic group include alcohol groups, phenol groups, sulfonamido groups, carboxyl groups, phosphonic acid groups, thiol groups, amino groups, and the like. The curable composition of the present invention preferably has alkali solubility in order to remove an uncured portion (unexposed portion) by alkali development. In a preferred embodiment of the present invention, the curable composition is used in combination with a radical polymerizable compound. Therefore, the thing with low radical polymerization inhibition is preferable. Therefore, considering these, carboxylic acid is preferable as the kind of nucleophilic group, and a compound having a carboxy group is preferable as (C) the nucleophilic compound.
In addition, the number of nucleophilic groups contained in one molecule of (C) the nucleophilic compound is preferably 2 or more, more preferably in the range of 4 to 1000, from the viewpoint of curability.
The nucleophilic group can be introduced into any compound contained in the curable composition.
For example, from the viewpoint of curability, when a dye is used as the colorant, a nucleophilic group can be directly introduced into the dye skeleton. In this case, the dye having a nucleophilic group has functions of both (B) a colorant and (C) a nucleophilic compound. Moreover, when using a pigment as (B) colorant, it is also possible to introduce into a compound contained in a pigment dispersion liquid, such as a pigment skeleton, a pigment derivative, or a dispersant. When introduced into a pigment or derivative thereof, this pigment (derivative) will have the functions of both (B) a colorant and (C) a nucleophilic compound, and when introduced into a pigment dispersant, The pigment dispersant becomes (C) a nucleophilic compound.

[Binder polymer having a nucleophilic group]
In the present invention, from the viewpoint of improving curability, it is possible to introduce the nucleophilic group into the binder polymer, and using such a binder polymer is also a preferred embodiment. In this case, the binder polymer having a nucleophilic group functions as the (C) nucleophilic compound.
Here, it is preferable to use a linear organic polymer as a binder polymer into which a nucleophilic group can be introduced. As such a “linear organic polymer”, a known one can be arbitrarily used. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

Moreover, the following are illustrated as a monomer which has a functional group which has nucleophilic groups other than carboxylic acid.
(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
These carboxylic acid group-containing monomers and hydroxyl group-containing monomers can be copolymerized with the following monomers (which do not have a nucleophilic group) and have a nucleophilic group in the molecule. A copolymer containing a structural unit can be used as the (C) nucleophilic compound of the present invention.

[(C) Other monomer that can be used in combination when preparing a nucleophilic compound (polymer compound)]
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. The alkali-soluble resin having a bond is particularly effective in terms of sensitivity when used in combination with a radical polymerizable polyfunctional monomer. Moreover, the alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 is excellent in the balance of film strength, sensitivity, and developability, and can be suitably used.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. No. 271741, Patent Application No. 10-116232, etc., urethane group binder polymer containing a carboxylic acid group, particularly a carboxylic acid group, and acid groups and double bonds described in JP-A No. 2002-107918 in the side chain Since the urethane-based binder polymer has excellent strength, it is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.

The weight average molecular weight of the binder polymer having a nucleophilic group that can be used in the present invention is preferably 5,000 or more, more preferably in the range of 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

The amount of the nucleophilic group introduced into the binder polymer having such a nucleophilic group (C) is, from the viewpoint of effect, (A) the mole of onium introduced into the curable composition with respect to the specific onium salt. It is preferred that the molar content of the nucleophilic group is equal to or greater than the amount.
The content of the (C) nucleophilic compound in the curable composition of the present invention is appropriately selected depending on the compound into which the nucleophilic group is introduced. For example, the (B) nucleophilic group as the colorant In the case of using pigments, dyes, and pigment dispersants having the same content as the pigments, dyes, and pigment dispersants, it may be the same as the original preferred content, but the amount of the nucleophilic group contained therein is within the above preferred range. The amount of introduction should be controlled so that
Moreover, it is preferable that content of the binder polymer which has (C) nucleophilic group is 1-50 mass% in conversion of solid content in the curable composition of this invention, and is in the range of 5-40 mass%. More preferably.

<(D) Radical polymerizable compound>
The curable composition of the present invention preferably contains (D) a radical polymerizable compound from the viewpoint of improving sensitivity and curability. By allowing the compound (D) to coexist, a radical polymerization reaction is initiated with a radical generated by the decomposition of the onium cation as well as a cross-linking reaction between the (A) specific onium salt and the (C) nucleophilic compound. Occurs and progresses, and an improvement in sensitivity and film property is achieved.
As a general (D) radical polymerizable compound that can be used in the present invention, a compound widely known as a compound having an ethylenically unsaturated double bond in the industrial field can be used without any particular limitation.
These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. . Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (D) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (D)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  In the present invention, when (D) a radical polymerizable compound is added, it is preferable to select a compound having two or more ethylenically unsaturated bonds from the viewpoint of curing sensitivity, and the compound containing three or more is further included. preferable. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoints, (D) radical polymerizable compounds include bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate. , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol penta Acrylate, sorbitol hexaac Preferred examples include rate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate modified EO, dipentaerythritol hexaacrylate EO modified and the like, and commercially available products include urethane oligomer UAS-10, UAB- 140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha) are preferred.

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 are commercially available products. (Manufactured by Kyoeisha) is more preferred.

  As content of the (D) radically polymerizable compound in the curable composition of this invention, it is preferable that it is 3-50 mass% from a viewpoint of an effect, and it is more preferable that it is the range of 5-40 mass%. preferable.

<(E) Photopolymerization initiator>
When (D) the radical polymerizable compound is used in combination with the curable composition of the present invention, it contains (E) a photopolymerization initiator other than the (A) specific onium salt as long as the effects of the present invention are not impaired. can do.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates the polymerization of the (D) specific radical polymerizable compound, and preferably has an absorption in a wavelength region of 300 to 500 nm. . Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryls. Examples thereof include a rubiimidazole compound, an organic boric acid compound, a disulfonic acid compound, an oxime ester compound, an acylphosphine (oxide) compound, and an onium salt compound having only one cationic site in the molecule.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188865, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  Examples of the onium salt compound include compounds having only one cation site in the molecule selected from the compound group exemplified below. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  In the present invention, (E) an iodonium salt that can be suitably used as another photopolymerization initiator is a diaryl iodonium salt, and from the viewpoint of stability, an electron-donating group such as an alkyl group, an alkoxy group, and an aryloxy group. A diaryl iodonium salt substituted with 2 or more by is preferable. In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As other photopolymerization initiator (E) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, Phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, monofunctional onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof And a compound selected from the group consisting of a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  The content of (E) another photopolymerization initiator as an optional component contained in the curable composition of the present invention is 0.1 to 50% by mass with respect to the total solid content of the curable composition. More preferably, it is 0.5-30 mass%, Most preferably, it is 1-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

<Compound having an adhesive group>
In the present invention, if necessary, a compound having an adhesive group capable of ensuring adhesion to the substrate can be used in combination in the curable composition.
The adhesive group can be used as long as it has adhesiveness to the substrate used in the color filter, but a compound having adsorptivity to a glass substrate or a silicon substrate is particularly preferable.
Preferred adhesive groups include acid groups such as sulfonic acid groups, phosphonic acid groups, and carboxyl groups; ester groups of these acids; metal salts of these acids; onium salts of these metals; onium groups such as ammonium groups and pyridinium groups; It is preferably a group selected from a substituent that generates a silanol group by hydrolysis such as an alkoxysilyl group; a zwitterionic group such as a phenolic hydroxyl group and an N-oxide group; and a chelating group such as iminodiacetic acid.
From the viewpoint of adhesion, an alkoxysilyl group and / or a hydrolyzed group thereof is preferable.
If necessary, in addition to the adhesive group, a compound having a group that improves sensitivity such as a group that improves developability, a carbon-carbon double bond group, or a cyclic alkoxy group in the molecule may be selected and used. Is possible.
As a group for improving developability, a functional group having a hetero atom is preferable, and it has an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group, an amino group, a urethane group, an amide group, a thiol group, a sulfo group, a urea group, and the like. Can do.
The group for improving the sensitivity preferably has a methacryl group, an acryl group, a styryl group, a vinyl ether group, an allyl group, a cyclic alkenyl group, a furyl group, an oxetane group, an epoxy group, or a tetrahydrofuran group. It is preferable to have a methacryl group, an acryl group, and a styryl group from the viewpoint of sensitivity.

Specific examples of the compound having such an adhesive group include the following compounds.
Moreover, preferable content is the range of 0.1-15 mass%.

<(F) Sensitizer>
The curable composition of the present invention contains (F) a sensitizer for the purpose of (A) improving the decomposability of the specific onium salt, improving the decomposition efficiency of the coinitiator, and increasing the photosensitive wavelength. Also good. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11- And the compounds described in Japanese Patent No. 271969.

  More preferable examples of the sensitizer include compounds represented by the following general formulas (I) to (V).

In the general formula (I), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with the adjacent A ¹ and the adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. May be. W represents an oxygen atom or a sulfur atom.

In the general formula (II), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W has the same meaning as that shown in formula (I).

In the general formula (III), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a group of a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In the general formula (IV), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group, Represents a substituted or unsubstituted aryl group, L ⁵ and L ⁶ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and adjacent carbon atoms; R ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.

In the general formula (V), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

  Preferable specific examples of the compounds represented by the general formulas (I) to (V) include those shown below.

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer in the curable composition of the present invention is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency, and is 0. More preferably, the content is 5 to 15% by mass.

<(H) Co-sensitizer>
The curable composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

<(I) Polymerization inhibitor>
In the present invention, when a compound (D) having a polymerizable ethylenically unsaturated double bond is used as an optional component during production or storage of the curable composition, unnecessary thermal polymerization of the compound is performed. It is desirable to add a small amount of thermal polymerization inhibitor to prevent it.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>
Furthermore, in the present invention, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and binder.

  As described above, the curable composition of the present invention cures with high sensitivity and has good storage stability even when it contains a large amount of the color component (B). In addition, since it exhibits high adhesion to the surface of a hard material such as a substrate to which the curable composition is applied, it is useful for forming a color filter coloring pattern or a black matrix.

[Color filter and manufacturing method thereof]
Next, a color filter using the curable composition for a color filter of the present invention and a manufacturing method thereof will be described.
The color filter is characterized by having a colored pattern formed on the support using the curable composition for color filters of the present invention.
Hereinafter, the color filter will be described in detail along with its manufacturing method.

The color filter is formed by applying the curable composition of the present invention on a support to form a curable composition layer (hereinafter, abbreviated as “curable composition layer forming step” as appropriate), and the above. A step of exposing the curable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate) and a step of developing the curable composition layer after exposure to form a colored pattern (hereinafter referred to as “exposure step”). And abbreviated as “development process” as appropriate).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Curable composition layer forming step>
In the curable composition layer forming step, the curable composition of the present invention is applied on the support to form a curable composition layer.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, an image sensor, etc. Examples of the photoelectric conversion element substrate 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 to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

As a coating film thickness of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further more preferable.
When used as an LCD, it is particularly preferably 1 to 2 μm, and when used for a CCD, CMOS, etc., 0.4 to 1 μm.
Drying (prebaking) of the photocurable composition layer applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.

<Exposure process>
In the exposure step, the curable composition layer formed in the curable composition layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
In the case of using a color filter for the liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

<Development process>
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and an alkaline aqueous solution obtained by diluting these alkaline agents with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. Is preferably used as a developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Moreover, inorganic alkali salts, such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, can also be used.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured.
Thereby, a color filter is obtained.
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  In the production method of the present invention, after performing the above-described curable composition layer forming step, exposure step, and development step, if necessary, the formed colored pattern is cured by heating and / or exposure. A process may be included.

  By repeating the curable composition layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

  The application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is patterned exposure and alkaline development in the same manner as the above pixel manufacturing method except that a black colorant such as carbon black or titanium black is added to the curable composition of the present invention as a colorant. Further, after that, post-baking can be performed to promote the curing of the film.

  Since the color filter uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is excellent in development resistance, so exposure sensitivity is improved. A high-resolution pattern can be formed that is excellent, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, the present invention will be 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, “%” and “part” are based on mass.

<Example 1>
[1. Preparation of curable composition]
Here, an example in which a curable composition containing a colorant (pigment) is prepared for forming a color filter for use in a liquid crystal display element will be described.
1-1. First, the following components were kneaded and dispersed with two rolls.
・ C. I. Pigment Red 254 [(B) coloring component] 22 parts by mass C.I. I. Pigment Yellow 139 [(B) coloring component] 8 parts by mass Resin solution (benzyl methacrylate / methacrylic acid /
Hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10,
Mw: 10000, solvent: 60% propylene glycol methyl ether acetate,
Resin solid content concentration: 40%) 40 parts by mass Solvent: 20 parts by mass of propylene glycol methyl ether acetate Dispersant: (trade name: BY-161, BYK) 2 parts by mass

Furthermore, the following component (solvent) was further added to the dispersion obtained above, and the mixture was finely dispersed overnight with a sand mill.
・ Solvent: 200 parts by mass of propylene glycol methyl ether acetate (PGMEA)

1-2. Preparation of curable composition (coating liquid) The following components were further added to the dispersion-treated pigment, followed by stirring and mixing to prepare a curable composition solution.
[Curable composition formulation 1]
Specific onium salt [(A): Exemplified compound (NP-1)] 1 part by mass DPHA (manufactured by Nippon Kayaku Co., Ltd.) [(D) radical polymerizable compound] 8 parts by mass benzyl methacrylate / hydroxyethyl methacrylate /
Methacrylic acid (60/10/30) Mw = 50,000 [(C)] 5 parts by mass -Compound having substrate adhesive group [(D-1): structure below] 0.1 part by mass -Surfactant ( Product name: Tetranic 150R1, BASF) 0.2 parts by mass Solvent: PGMEA 100 parts by mass

[2. (Production of color filter)
2-1. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).
(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and development After that, the photocurable coating film was exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kw ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film was developed by Fuji Film Electronics. It was covered with a 1% aqueous solution of Alkali developer CDK-1, manufactured by Materials, and allowed to stand for 40 seconds.

2-3. Heat treatment After standing still, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the photocuring treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). Thereby, a colored resin film (color filter) was formed on the glass substrate.

[3. (Performance evaluation)
Storage stability of the colored curable composition coating solution prepared above, exposure sensitivity of the curable composition coating film (colored layer) formed on the glass substrate using the colored curable composition, and substrate adhesion Property, developability, and pattern cross-sectional shape were evaluated as follows. The results are shown in Table 1.

3-1. Exposure sensitivity of coating film (colored layer),
The exposure dose was changed to various exposure doses of 10 to 100 mJ / cm ² to perform exposure and development, and the exposure dose at which the pattern line width after post-baking was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

3-2. Exposure to developer solution 75 mJ / cm ² , immersion in 2% aqueous solution of alkaline developer CDK-1 manufactured by Fuji Film Electronics Materials, and time (seconds) until the image is peeled off and eluted It was measured.
The longer the time (seconds), the better.

<Examples 2 to 5>
In the curable composition of Example 1, (A) Exemplified compound (NP-1) and (C) nucleophilic compound, which are specific polymerizable compounds, were replaced with the exemplified compounds shown in Table 1 below, and sensitizers. As shown in Table 1, and in Example 4, in place of 100 parts by mass of PEGMA as a solvent, a mixture of 80 parts by mass of PGMEA and 20 parts by mass of 1-methoxy-2-propanol was used. All were performed in the same manner as in Example 1 to obtain a colored pattern, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.
In addition, the sensitizer in the following Table 1

<Comparative Example 1>
In the curable composition of Example 1, (A) Except having replaced the exemplary compound (NP-1) which is a specific polymerizable compound with the comparative polymerizable compound shown by following Table 1, all is the same as Example 1. went. The results are shown in Table 1.
<Comparative example 2>
In the curable composition of Example 2, (A) Except having replaced the exemplary compound (NP-1) which is a specific polymerizable compound with the comparative compound shown in the following Table 1, all was performed similarly to Example 1. A colored pattern was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.

The addition amount of the sensitizer is 0.4 parts by mass, and the description “−” in the table indicates that no sensitizer is included.
The (C) nucleophilic compound (binder polymer having a nucleophilic group) shown in Table 1 is as follows.
B-1: benzyl methacrylate / hydroxyethyl methacrylate / methacrylic acid
(60/10/30) Mw = 50.000
B-2: benzyl methacrylate / methyl methacrylate / methacrylic acid
(60/10/30) Mw = 50.000
The structures of sensitizers (Z-1), (Z-2), (Z-3) and comparative onium salt compounds (H-1), (H-2) in Table 1 are shown below.

  The said Examples 1-5 are the aspects which formed the coloring pattern for color filter formation for a liquid crystal display element use. From the results of Table 1, the curable composition for a color filter of the present invention has excellent curing sensitivity and improved developer resistance of the formed colored pattern, and thus has excellent adhesion to the substrate and film strength. It can be seen that a cured film is formed.

Hereinafter, an example in which a curable composition containing a colorant (dye) is prepared for forming a color filter for use in a solid-state imaging device will be described.
<Example 6>
[1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<composition>
Propylene glycol monomethyl ether acetate ... 19.20 parts (PGMEA: solvent)
-Ethyl lactate ... 36.67 parts-Binder polymer ... 30.51 parts [Benzyl methacrylate / methacrylic acid / methacrylic acid-2-
40% PGMEA solution of hydroxyethyl copolymer (molar ratio = 60/22/18)]
-Dipentaerythritol hexaacrylate ... 12.20 parts-Polymerization inhibitor (p-methoxyphenol) ... 0.0061 parts-Fluorosurfactant ... 0.83 parts (F-475, Dainippon Ink & Chemicals, Inc.) Made)
Specific onium salt [(A): compounds described in Table 2] 0.586 parts

[2. Production of silicon substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

[3. Preparation of colorant-containing curable composition (dye system)]
A compound of the following composition A-1 was mixed and dissolved to prepare a colored curable composition A-1.
<Composition A-1>
・ Cyclohexanone (solvent) 80 parts ・ Valifast Yellow 1101 [dye (B)] 5.0 parts ・ Acid Red 57 [dye (B)] 5.0 parts ・ Dipentaerythritol hexaacrylate (DPHA) [(D )] ... 3.5 parts (C) Compound having a nucleophilic group (B-3) 2.5 parts B-3: Benzyl methacrylate / methacrylic acid / methacrylic acid-2-
Hydroxyethyl copolymer (molar ratio = 60/22/18)
-Onium salt having at least two cationic sites [(A)] ... 1.0 part [Exemplary Compound (NP-3)]
Sensitizer [compound described in Table 2] 0 part or 0.5 part Glycerol propoxylate 0.5 part

[5. Preparation and evaluation of color filter using colored curable composition]
-Pattern formation and sensitivity evaluation-
3 above. The colored curable composition A-1 prepared in the above 2. The curable composition layer (coating film) was formed by coating on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1). Then, a heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.9 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.), exposure was performed at various exposure doses of 100 to 1600 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  A silicon wafer substrate on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The results of measurement evaluation are shown in Table 2 below.

<Developer resistance>
It is exposed at 900 mJ / cm ² and is immersed in an alkali developer CD-2000 (produced by Fuji Film Electronics Materials Co., Ltd., manufactured by FUJIFILM Electronics Materials) until the image is peeled off or eluted. Time (seconds) was measured.
The longer the time (seconds), the better.

<Examples 7 to 10>
Table 2 below shows (A) an onium salt having at least two cation sites and (C) a compound having a nucleophilic group used in the preparation of the colored curable composition A-1 of Example 6. A colored pattern was obtained in the same manner as in Example 6 except that 0.5 part of a sensitizer was added to the formulation shown in Table 2 in place of the compound, and the same evaluation as in Example 6 was performed. . The results are shown in Table 2.
<Comparative Example 3>
Except that the specific onium salt compound (A) used in the preparation of the colored curable composition A-1 of Example 6 was replaced with the comparative onium salt compound shown in Table 2 below, all were the same as in Example 6. went. The results are shown in Table 2.
<Comparative Example 4>
Except that the specific onium salt compound (A) used in the preparation of the colored curable composition A-1 of Example 6 was replaced with the comparative onium salt compound shown in Table 2 below, all were the same as in Example 6. went. The results are shown in Table 2.

In Table 2, “-” indicates that no sensitizer is included.
The (C) nucleophilic compound (binder polymer having a nucleophilic group) shown in Table 2 is as follows. B-3 is the same as the compound used in Example 6.
B-4: benzyl methacrylate / hydroxyethyl methacrylate / methacrylic acid
Polymerized at a molar ratio of 30/20/50, 50% of methacrylic acid
Polymer added with glycidyl methacrylate (Mw = 80,000)
B-5: polymerized at a molar ratio of benzyl methacrylate / methacrylic acid 50/50,
Added 50% glycidyl methacrylate of methacrylic acid
Polymer (Mw = 70,000)
The structures of the comparative onium salt compounds (H-3) and (H-4) shown in Table 2 are shown below.

  From the results in Table 2, the curable composition for a color filter of the present invention was excellent in curing sensitivity even when a colored pattern for a solid-state imaging device was formed. Moreover, since the developing solution tolerance of the formed colored pattern is improved, it can be seen that a cured film having excellent adhesion to the substrate and film strength is formed.

<Example 11>
1. Adjustment of curable composition (pigment type) for color filter for solid-state imaging device 1-1. First, the following components were kneaded and dispersed with two rolls.
・ C. I. Pigment Red 254 22 parts by mass C.I. I. Pigment Yellow 139 8 parts by mass Resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10000, solvent: 60% propylene glycol methyl ether acetate, resin solids concentration : 40%)
40 parts by mass-Solvent: 20 parts by mass of propylene glycol methyl ether acetate-Dispersant: (trade name: BY-161, BYK) 2 parts by mass

Furthermore, the following components were added to the dispersion obtained above and finely dispersed in a sand mill for a whole day and night.
・ Solvent: Propylene glycol methyl ether acetate (PGMEA)
200 parts by mass

1-2. Preparation of curable composition (coating liquid) The following components were further added to the dispersion-treated pigment, followed by stirring and mixing to prepare a curable composition solution.
Pentaerythritol triacrylate 10 parts by mass (A) Specific onium salt [Exemplary compound (NP-10)] 0.5 part by mass (C) Compound having a nucleophilic group (B-4) 4 parts by mass Surfactant (trade name: Tetranic 150R1, BASF) 0.2 parts by mass Solvent: PGMEA 100 parts by mass

<Comparative Example 5>
Similarly, the curable composition of Comparative Example 5 was used except that (A) the specific onium salt (N-3) used in Example 11 was changed to a comparative onium salt [(H-4): the structure]. I got a thing.
(Performance evaluation)
Example 6 of the curable composition in the section of “Preparation of curable composition for color filter (dye system) for use in solid-state imaging device” using the curable composition coating liquid of Example 11 and Comparative Example 5 The coating / exposure / development and performance evaluation performed in the above were carried out. The results are summarized in Table 3.

  From the results of Table 3, the curable composition for a color filter of the present invention has a curing sensitivity even when a pigment is used as a colorant as a coloring pattern for a solid-state imaging device, as in the case where a dye is used. It was excellent. Moreover, since the developing solution tolerance of the formed colored pattern is improved, it can be seen that a cured film having excellent adhesion to the substrate and film strength is formed.

Claims (5)

  A curable composition for a color filter comprising (A) an onium salt having at least two cationic sites, (B) a coloring component, and (C) a compound having a nucleophilic group.   The curable composition for a color filter according to claim 1, further comprising (D) a radical polymerizable compound.   (C) The curable composition for a color filter according to claim 1 or 2, wherein the nucleophilic group in the compound having a nucleophilic group is a carboxylic acid group.   The curable composition for a color filter according to any one of claims 1, 2, and 3, wherein (A) the onium salt having at least two cation sites is a diazonium salt resin. .   (B) The curable composition for a color filter according to any one of claims 1, 2, 3, and 4, wherein the coloring component is a dye.