JP4689553B2 - Photocurable coloring composition and color filter using the same - Google Patents

Description

  The present invention relates to a photocurable coloring composition useful for forming a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a color filter obtained using the same.

  In recent years, various displays such as televisions, personal computers, and mobile phones are required to have high image quality and high saturation, and in particular, for televisions, large screens are also required. At present, the mainstream of these displays is a liquid crystal display system, and in order to achieve the above-described high image quality, high saturation, and large screen, the technology of the color filter used therein has become very important. Specifically, it is a technique relating to a process for producing a color filter and a photocurable coloring composition adapted thereto.

With regard to high-definition color filters, it is necessary to form a pattern with high accuracy for pattern exposure and subsequent development in order to make the line width of the color filter pattern formation fine. In addition, in order to increase the saturation, it is essential to adjust the hue of the colorant and increase the density. However, in the curable composition to which the conventional pigment dispersion system is applied, there are problems such as color unevenness due to the pigment being relatively coarse particles, and it is difficult to further improve the resolution. It was not suitable for applications requiring a fine pattern such as a solid-state imaging device. Therefore, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 1).
Whether a dye or a pigment is used as the colorant, it is essential to increase the content of the colorant in the color curable composition for producing a color filter. On the other hand, the color curable composition The content of the photopolymerization initiator and photopolymerizable monomer, which are components necessary for curing the resin, is limited, or the exposure wavelength light for the effect is prevented from reaching the glass support interface. It is necessary to increase the sensitivity of the curable coloring composition and increase the adhesion to the support.

Furthermore, in recent years, with the increase in substrate size, it is indispensable to manufacture large-area color filters. However, if the conventional productivity is maintained without changing the energy cost in the process, the application time, exposure time, etc. Reduction is indispensable. For this reason, it is necessary to improve the wettability of the photocurable coloring composition to the glass support for achieving a high coating speed and to increase the sensitivity to cope with a short exposure time (small exposure amount). Yes.
In addition, when the screen is enlarged, minute defects after the color filter fabrication greatly influences the yield, and as a result, the heat resistance, light resistance, etc. of the curable composition that forms the colored pattern are also higher than before. Stabilization at a high level is required.

  Conventionally, as a curable composition for producing a color filter, for example, a radiation-sensitive composition in which a binder polymer containing a carboxyl group, a polyfunctional acrylate such as pentaerythritol hexaacrylate, and a photopolymerization initiator are combined. 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole as a highly sensitive photopolymerization initiator in such a radiation-sensitive composition, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like have been proposed (for example, see Patent Documents 2 and 3).

  In addition, as a photopolymerization initiator applicable to the curable composition, 2,2′-bis (2-chlorophenyl) is used as a photopolymerization initiator applicable to a radiation-sensitive composition used for a printing plate or a photoresist. ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- Tetra (trialkoxyphenyl) biimidazole has been proposed (see, for example, Patent Documents 4 and 5).

However, the sensitivity of any of the above curable compositions is not yet satisfactory, and it is necessary to irradiate with high energy radiation when curing. When a colored pattern of a color filter is formed using such a curable composition, if the irradiation amount is insufficient, problems such as missing or missing patterns, a remaining film rate or a decrease in pixel strength, etc. are caused. In the coloring pattern of the obtained color filter, there arises a problem that the resolution and the adhesion between the support and the support are lowered.
As described above, even when a colorant is contained in a high concentration, a curable coloring composition that cures with high sensitivity and has a good pattern forming property, and resolution and support obtained using the same Although a color filter having a colored pattern with excellent adhesion to the surface is desired, it has not been provided yet.
JP-A-2-127602 JP-A-6-75372 JP-A-6-75373, etc. Japanese Patent Publication No. 48-38403 JP-A-62-174204

The present invention has been made in view of the above-described problems, and an object thereof is to achieve the following objects.
That is, the object of the present invention is to cure with high sensitivity and form a high-resolution pattern even when the colorant is contained in a high concentration, and has excellent adhesion to a glass substrate. A photocurable coloring composition that can form a colored pattern that is useful for the production of a color filter, and a high-resolution colored pattern that is excellent in adhesion to a support obtained by using the composition. It is to provide a color filter.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by a photocurable coloring composition containing a specific photopolymerization initiator and a specific black pigment, and complete the present invention. It came to. That is, the means for solving the above problems are as follows.

<1> A photopolymerization initiator represented by the following general formula (I), (A) a carbon black having a specific surface area of 110 m ² / g or less and a pH of 2 to 9, (B) silica-coated carbon black, and ( C) A photocurable coloring composition comprising at least one black pigment selected from the group consisting of resin-coated carbon black and a compound having an ethylenically unsaturated group capable of addition polymerization.

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following general formula (IA) or (IB). R ³ represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. W represents a halogen atom. X and Y each independently represent a chlorine atom or a bromine atom. m and n each independently represents 0, 1 or 2.

In general formulas (IA) and (IB), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group.
<2> On a glass support, a laminate comprising the photocurable coloring layer comprising the photocurable coloring composition according to <1> is subjected to pattern exposure to cure the exposed region of the photocurable coloring layer. A color filter comprising a colored pattern obtained by developing an unexposed area.

The photocurable coloring composition of the present invention (hereinafter appropriately referred to as a curable composition) includes a specific photopolymerization initiator having a hetero ring in the molecule, and (A) a specific surface area of 110 m ² / g or less. And at least one black pigment selected from the group consisting of carbon black having a pH of 2 to 9, (B) silica-coated carbon black, and (C) resin-coated carbon black, and addition-polymerizable ethylenic unsaturation Contains compounds with groups.
The mechanism of action of the present invention is not clear, but is estimated as follows.
Carbon black useful as a black pigment has high self-aggregation properties and is difficult to disperse uniformly, and the photopolymerization initiator having a triazine ring structure used in the present invention is also highly sensitive due to its structure. It is known that it is easy to self-aggregate. The specific photopolymerization initiator used in the photocurable coloring composition of the present invention has a very high affinity with the specific carbon black described above, and the presence of the initiator and the carbon black repels each other in the coating state. Without being dispersed uniformly, and as a result, the spatial distance between the photocuring component and the photopolymerization initiator is reduced over the entire area of the formed film, as compared with the case of a non-uniform dispersion state. It is considered that the photocuring efficiency is substantially improved and the sensitivity is increased.
The cured film obtained by exposing and curing the photocurable coloring in a uniform dispersed state is improved in strength of the film itself due to an efficient curing reaction, and is in close contact with the lower layer, It is considered that high adhesion of the cured film has been achieved. On the other hand, in the unexposed area, the developer permeability becomes uniform, so that the coating film dissolves quickly, and excellent developability is developed. The strength of the exposed area and the developability of the unexposed area are both compatible and fine. It is considered that even if it is a simple pattern, good pattern formability is expressed and high resolution is possible.

According to the present invention, even when a colorant is contained in a high concentration, it can be cured with high sensitivity, can form a high resolution pattern, and has excellent adhesion to a glass substrate. A photocurable coloring composition which can form a pattern and is useful for preparation of a color filter can be provided.
Furthermore, by using the photocurable coloring composition of the present invention, it is possible to provide a color filter having a colored pattern with high resolution and excellent adhesion to a support.

Hereinafter, the photocurable coloring composition of the present invention and a color filter obtained using the same will be described in detail.
(Photocurable coloring composition)
The photocurable coloring composition of the present invention comprises (1) a photopolymerization initiator represented by the following general formula (I) (hereinafter referred to as “specific initiator” as appropriate), (2) (A) specific surface area. There 110m ² / g or less and a pH of 2-9 carbon black, (B) silica coated carbon black, and (C) 1 or more black pigments selected from the group consisting of resin-coated carbon black, and, ( 3) It has a photocurable colored layer containing a compound having an ethylenically unsaturated group capable of addition polymerization.
Hereinafter, each component contained in the photocurable coloring composition according to the present invention will be sequentially described.

<(1) Photopolymerization initiator represented by the following general formula (I)>
The curable colored layer of the present invention contains a specific photopolymerization initiator containing a triazine ring structure in the molecule.

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following general formula (IA) or (IB). R ³ represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. W represents a halogen atom. X and Y each independently represent a chlorine atom or a bromine atom. m and n each independently represents 0, 1 or 2.
The alkyl group, aryl group, and alkoxy group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, and a carboaryloxy group. Group, acyl group, nitro group, dialkylamino group, sulfonyl derivative and the like.

In general formulas (IA) and (IB), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group.
The alkyl group and the aryl group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, Examples include an acyl group, a nitro group, a dialkylamino group, and a sulfonyl derivative.

In the general formula (I), R ¹ and R ² may form a heterocycle composed of a nonmetallic atom together with the nitrogen atom bonded thereto, and in this case, examples of the heterocycle include those shown below. It is done.

  Specific examples of the specific initiator represented by the general formula (I) include 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl). -S-triazine, 4- [m-chloro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p -N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s- Lyazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (Trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo -PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl]- 2,6 Di (trichloromethyl) -s-triazine,

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

4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m -Bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- ( -Bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, etc., and two halogen atoms in the phenyl moiety The triazine etc. which were introduced above are mentioned.

  These specific initiators are those having a radical generating site and a triazine skeleton in the molecule, preferably those having two halogen atoms in the central phenyl ring, or those having a bromine atom. It is done.

A specific initiator can be used individually or in combination of 2 or more types.
It is preferable that content of the specific initiator in a photocurable coloring composition is the range of 0.1-15.0 mass% in conversion of solid content, More preferably, it is 0.5-10.0 mass%. In this range, the polymerization reaction proceeds efficiently, and the strength of the obtained cured film is excellent.

(Other photopolymerization initiators)
In addition, in a curable composition, in addition to the said specific initiator, unless the effect of this invention is impaired, photoinitiators other than this can be used together.
The photopolymerization initiator that can be used here is a compound that is decomposed by light and starts and accelerates polymerization of a compound having an ethylenically unsaturated group capable of addition polymerization, which will be described later, and has absorption in a wavelength region of 300 to 500 nm. It is preferable.

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, biimidazoles. Compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
Among these, from the viewpoint of increasing sensitivity, at least one compound selected from the group consisting of trihalomethyltriazine compounds, biimidazole compounds, and oxime compounds is most preferable, and biimidazole compounds are most preferable.

The content of the photopolymerization initiator that can be used in combination is preferably 75% by mass or less, more preferably in the range of 0 to 50% by mass with respect to the specific initiator.
Further, the total amount of the specific initiator and the other photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.1 to 30% by mass with respect to the total solid content of the composition. Preferably it is 0.3-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

(Sensitizer)
A sensitizer can be used in combination with these specific initiators.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm (330 nm) to 450 nm.
Specific examples of the sensitizer include, 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 ( For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquino) ), Squalium (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, 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, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

Such sensitizers can be further subjected to various chemical modifications for improving the properties of the curable composition.
For example, by combining a sensitizer and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, the exposure film can be increased in strength or exposed. It is possible to suppress unnecessary precipitation of the specific sensitizer from the subsequent film.
In addition, partial structures having radical generating ability in the sensitizer and the photopolymerization initiator (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, borate, amine) , Trimethylsilylmethyl, carboxymethyl, carbonyl, imine, and other oxidatively cleavable moieties) can significantly increase the photosensitivity particularly in a low concentration of the starting system.

A sensitizer may be used individually by 1 type, or may use 2 or more types together.
The content of the sensitizer is preferably 0.1% by mass to 20% by mass and more preferably 0.2% by mass to 20% by mass in the total solid content of the curable composition.
When the concentration of the colorant in the curable composition is very high and the light transmittance of the formed color pattern (photosensitive layer) becomes extremely low, specifically, these sensitizers are used. By adding it when the light transmittance of 365 nm of the photosensitive layer when not added is 10% or less, the effect is remarkably exhibited.

<(2) (A) 1 selected from the group consisting of carbon black having a specific surface area of 110 m ² / g or less and a pH of 2 to 9, (B) silica-coated carbon black, and (C) resin-coated carbon black More than black pigments>
The colorant used in the present invention is a black pigment selected from specific carbon blacks described in detail below (hereinafter referred to as specific black pigments as appropriate).
[(A) Carbon black having a specific surface area of 110 m ² / g or less and a pH of 2 to 9 (specific black pigment (A))]
Examples of the carbon black suitably used in the present invention include those having a specific surface area of 110 m ² / g or less and a physical property value of pH 2 to 9. When the specific surface area exceeds 110 m ² / g, a large amount of a polymer dispersant necessary for stabilizing the dispersion is required. However, since the polymer dispersant is insoluble in the developer, resolution and developability are deteriorated. It becomes easy to do. Moreover, when the pH value exceeds 9, the polymer dispersant is difficult to adsorb and dispersion stabilization is difficult. Carbon black having a pH of less than 2 is extremely difficult to industrially manufacture and is not practical.
Here, the specific surface area and pH of carbon black can be measured by a conventional method. In the present invention, the specific surface area is determined by the BET method (N ₂ gas adsorption amount), and the pH is determined by the KOH neutralization titration method. The measured value is used.

Carbon black having such physical properties is also available as a commercial product. Specifically, for example, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, #manufactured by Mitsubishi Chemical Corporation are available. 970, # 960, # 950, # 900, # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Rack LI, Diamond Black II, Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R Diamond Black N760M, Diamond Black LR.
Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb.
Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal.
Degussa AG of carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V (both goods And all of these satisfy the above physical properties.

[(B) Silica-coated carbon black (specific black pigment (B))]
Another embodiment of the specific black pigment preferably used in the present invention includes carbon black (specific black pigment (B)) whose surface is coated with silica.
(B) By using silica-coated carbon black, the photocurable coloring composition of the present invention can exhibit excellent image forming properties and high light shielding properties.

Carbon black used for the silica coating is not particularly limited, and furnace black, acetylene black or the like having a specific surface area of 25 to 500 g / m ² is usually used. Specifically, for example, commercially available carbon black as shown below can be mentioned.
Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.
Made by Degussa: Printex95, Printex 90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, SpecialBlack550, SpeckS350
Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS480, etc.
Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1020, Raven1040, etc. (all trade names).

In the case of silica-coated the carbon black, the amount of silica, 0.5 to 50 wt% as a normal SiO _2, preferably about 1 to 40 wt%.
The silica coating amount in the specific black pigment (B) can be measured by TG-DTA differential heat-thermogravimetric change measurement or ESCA method.

The method of coating the carbon black with silica can be performed in a gas phase or a liquid phase, but any method may be used.
When coating by a gas phase method, first, carbon black is put in a sealed container, and the sealed container is deaerated. A silica source such as tetramethoxysilane or tetraethoxysilane is introduced therein, the silane source is adsorbed on the carbon black surface, and the carbon black and the silica source are reacted. After completion of the reaction, excess silica source is removed under reduced pressure, and then alkali such as ammonia is introduced into a sealed container to convert methoxy group and ethoxy group into hydroxy group. By this series of operations, a silica coating layer is formed on the carbon black surface. This operation can be repeated as necessary to control the silica coating amount on the carbon black.

When silica is coated by the liquid phase method, an aqueous dispersion of carbon black is prepared, an alkali such as potassium hydroxide or ammonia is added to the aqueous dispersion of carbon black, and a silica source is added thereto. As the silica source at this time, a silicate solution obtained by dealkalizing a water glass aqueous solution with a cation exchange resin or the like is preferably used.
Further, as another means of the liquid phase method, a sol-gel reaction of a silica source such as tetramethoxysilane or tetraethoxysilane may be used. The method using the sol-gel reaction may be carried out by making the carbon black aqueous dispersion acidic with hydrochloric acid or the like or making it alkaline with ammonia or the like and then adding a silica source such as tetramethoxysilane or tetraethoxysilane for reaction. .

  As carbon black used for coating silica, carbon black not subjected to pretreatment, that is, each of the above-described carbon blacks can be used as it is, but a water vapor plasma treatment is performed to introduce hydroxyl groups on the surface. Alternatively, surface-modified carbon black can be used. Examples of the water vapor plasma treatment include a method in which carbon black is placed in a sealed container, and after degassing, a plasma irradiation is performed while introducing water vapor to introduce hydroxyl groups on the surface of the carbon black.

  As another surface modification method for improving the silica coating efficiency on the surface of carbon black, a method of oxidizing the surface of carbon black can be used. Examples of the oxidation treatment include a high-temperature baking method by heating at 100 to 300 ° C. in an air atmosphere, an acid treatment method in which an acid such as nitric acid and perchloric acid, or hydrogen peroxide is contacted at a temperature of 100 to 250 ° C., ozone There is an ozone oxidation method in which heating is performed at a temperature of 100 to 300 ° C. in an atmosphere.

  The silica coating methods such as the liquid phase method and the gas phase method, and various pretreatment methods such as water vapor plasma treatment and oxidation treatment for carbon black may be performed in any combination. A mode in which silica black is coated on a plasma-treated carbon black by a gas phase method, (b) a mode in which silica coating is performed on a non-treated carbon black by a gas phase method, and (c) a liquid phase method on untreated carbon black. And (c) untreated carbon black, in which (a) carbon black in which a hydroxyl group is introduced to the surface by water vapor plasma treatment is coated with silica by a gas phase method, and (c) untreated carbon black. Further, carbon black coated with silica by the liquid phase method is more preferable.

The specific black pigment (B) may be silica-coated over the entire surface of the carbon black, and the effect of the present invention can be obtained even when a silica coating layer is present on a part of the surface.
The presence of silica on the surface of the specific black pigment (B) can be confirmed by the ESCA method.

[(C) Resin-coated carbon black]
Another embodiment of the specific black pigment preferably used in the present invention includes carbon black (specific black pigment (C)) whose surface is resin-coated.
Examples of the carbon black used for forming the specific black pigment (C) include furnace black, channel black, acetylene black, and lamp black, and furnace black is preferable.
The particle size of carbon black is usually 20 μm or less, preferably 5 μm or less, and more preferably 1 μm or less. From the viewpoint of dispersibility and workability, the particle size is preferably 0.01 μm or more.
By coating the surface of the carbon black with a resin, a specific black pigment (C) suitable for the present invention can be obtained.
Examples of the resin that covers the surface of carbon black include thermosetting resins such as epoxy resins, phenol resins, melamine resins, xylene resins, diallyl phthalate resins, gyptal resins, and alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, and polybutylene. Synthetic resins such as thermoplastic resins such as terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, polyetheretherketone, etc. Preferably, it is an epoxy resin.

Specific examples of the epoxy resin that can be suitably used for forming the resin coating layer include glycylamine epoxy resin, triphenyl glycidimethane epoxy resin, tetraphenyl glycidimethane epoxy resin, and aminophenol epoxy. Examples thereof include polyfunctional epoxy resins such as resins, diamidediphenylmethane type epoxy resins, phenol novolac type epoxy resins, orthocresol type epoxy resins, and bisphenol A novolac type epoxy resins.
Although there is no restriction | limiting in particular in the manufacturing method of resin-coated carbon black, For example, the method of forming a coating layer by applying the resin emulsion to carbon black can be mentioned. That is, when an epoxy resin is used as the resin, a carbon black dispersion is prepared, and a curing agent and an epoxy resin emulsion may be added thereto.
Examples of the curing agent used together with the epoxy resin for forming the coating layer include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl- Examples include 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4diamino-6- [2-methylimidazolyl- (1)]-ethyl S-triazine. The amount of the curing agent used is generally about 1% by mass to 30% by mass with respect to the total amount of the epoxy resin and the curing agent, preferably 5% to 25%, more preferably 10% to 20%. Range.

  To coat carbon black with a resin other than an epoxy resin, for example, a resin emulsion may be added in a state where carbon black is dispersed in a dispersion medium, followed by heating and dispersion. When an epoxy resin is used as the resin and carbon black is coated with a curing agent, the resin emulsion and the curing agent may be added in a state where the carbon black is dispersed in the dispersion medium.

  The ratio of the resin in the resin-coated carbon black thus obtained is usually 5% to 40%, preferably 7% to 20% by mass fraction. If it is less than 5%, the electric resistance of the black matrix tends to be low. If it exceeds 40%, it may be difficult to uniformly disperse the resin-coated carbon black in the black photosensitive resin composition or the black matrix.

The specific black pigment (C) may be resin-coated over the entire surface of the carbon black, and the effect of the present invention can be obtained even when a resin coating layer is present on a part of the surface.
The presence of the resin layer on the surface of the specific black pigment (C) can be confirmed by a TG-DTA or ESCA method.

  In this invention, 1 or more types of black pigments selected from the said specific black pigment (A)-specific black pigment (C) are contained. When these are used in combination, the same type of black pigment may be combined with different physical properties, coating materials, and coating amounts. For example, (B) silica-coated carbon black and (C) resin-coated carbon black, Different types may be combined.

  These specific black pigments can also be used in combination with other black inorganic pigments and organic pigments. The other black pigment has a light shielding property lower than that of carbon black contained as a main material of the specific black pigment, and is preferably 50% by weight or less based on the total amount of the black colorant. Examples of other black pigments include titanium black, aniline black, iron oxide black pigments, and black pigments in which organic pigments of three colors of red, green, and blue are mixed.

The specific black pigment in the present invention is preferably used as a light-shielding material. From such a viewpoint, for example, a black matrix having a high light-shielding ratio of 3.0 or more and a light-shielding ratio of 3.5 or more at a film thickness of 1 μm is formed. At that time, it is necessary to add an appropriate amount of the specific black pigment to the photocurable coloring composition with respect to the total solid content in the curable composition.
In the present invention, the content of the black pigment in the photocurable coloring composition of the present invention is selected from the viewpoints of curing sensitivity and color density, including the pigment (including the content when a dispersant is used), and the curable composition. It is preferably 20% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 75% by mass or less, and further preferably 30% by mass or more and 60% by mass or less with respect to the total solid content. preferable.

  When there are too few specific black pigments, when a color filter, especially the black matrix, is produced with the curable composition of the present invention, there is a tendency that an appropriate light-shielding property cannot be obtained. On the other hand, if the amount is too large, photocuring does not proceed sufficiently and the strength as a film is reduced, and the development latitude during alkali development tends to be narrow. However, the specific initiator according to the present invention has light absorption efficiency. High and evenly dispersed in the curable composition due to the interaction with the specific black pigment. Therefore, even when the black pigment is contained in such a high concentration, there is a significant sensitivity improvement effect. It is exhibited and has excellent adhesion to the support of the cured film.

(Color pigment)
In the photocurable coloring composition of the present invention, in addition to the specific black pigment, various conventionally known pigments suitable for color filter applications are selected and used in combination according to the purpose. be able to.
As the pigment that can be used in the photocurable coloring composition according to the present invention, various conventionally known inorganic pigments or organic pigments can be used. In addition, it is preferable to use a pigment having a particle size as small as possible considering that it is preferable that the formed photocurable colored layer has a high light transmittance regardless of whether it is an inorganic pigment or an organic pigment. In consideration of handling properties, the average particle size of the pigment is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm. 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 an organic pigment, for example,
CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CI Pigment Orange 36, 38, 43, 71;
CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CI pigment violet 19, 23, 32, 39;
CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CI Pigment Green 7, 36, 37;
CI Pigment Brown 25, 28;
CI 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 the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CI Pigment Orange 36, 71,
CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CI Pigment Violet 19, 23, 32,
CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CI 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 , Etc. 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. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. 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 pigments other than the specific black pigment, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof are used, and a combination of the specific black pigment and titanium carbon is preferable. The mass ratio of the specific black pigment to titanium carbon is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

The pigment in the present invention preferably has an average particle diameter r (unit: nm) satisfying 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. By using such a pigment having an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

<Pigment dispersant>
In the present invention, since a pigment is used as a colorant, a known pigment dispersant can be used in combination. Examples of the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic. -Based copolymers, naphthalenesulfonic acid formalin condensates], and polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, 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.

Among these, examples of the polymer dispersant used for dispersing the specific black pigment of the present invention include a polyisocyanate compound, a compound having one or more hydroxyl groups in the molecule (number average molecular weight of 300 to 10,000), and the same molecule. Examples thereof include a dispersion resin obtained by reacting an active hydrogen with a compound having a tertiary amino group, and a polymer dispersant having a weight average molecular weight of preferably 1,000 to 200,000.
Hereinafter, the dispersant useful for dispersing the specific black pigment of the present invention will be described.

  Examples of the polyisocyanate compound include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'- Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanate having an aromatic ring such as silylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Examples thereof include triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  The compound having one or more hydroxyl groups in the same molecule (having a number average molecular weight of 300 to 10,000) is preferably a compound having one or two hydroxyl groups, particularly polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc. And those having one end hydroxyl group of these compounds alkoxylated with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting mixtures of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol) Propylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1, 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 Polylactone diol or polylactone monool obtained by using polyhydric alcohol as an initiator, for example, polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms.

  Polycarbonate glycol includes poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. Can be mentioned. The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  In the present invention, a compound having an active hydrogen and a tertiary amino group in the same molecule used to constitute a dispersant suitable for the specific black pigment, particularly the specific black pigment (A) having no surface coating layer will be described. . Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is an N-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, N-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and an NH ₂ group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Further, specific examples of the compound having a triazole ring and an NH ₂ group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H— 1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino- Examples include 1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.
A preferable blending ratio of the dispersion resin raw material used for dispersing the specific black pigment is a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 10 to 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight. The compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0. 3 to 24 parts by weight.

  The weight average molecular weight of the dispersion resin is 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000 in terms of polystyrene measured by GPC. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are inferior. If it exceeds 200,000, the solubility is lowered and the dispersibility is inferior.

  The production of the polymer dispersant for dispersing the specific black pigment is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  A normal urethanization reaction catalyst is used as a catalyst for production. Examples include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron series such as iron acetylacetonate and ferric chloride, and tertiary amine series such as triethylamine and triethylenediamine. It is done.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g by the amine value of the dispersion resin after the reaction. More preferably, it is the range of 5-95 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the dispersion resin has high temporal stability.

The dispersion resin and the pigment are subjected to a dispersion treatment before blending into the resist solution. Dispersion is performed by adding a pigment, a dispersion resin and a solvent, and optionally a binder resin, to form a mill base, which is processed by a method such as a ball mill, a sand mill, a bead mill, a three roll, a paint shaker, an ultrasonic wave, or a bubble homogenizer. Two or more of these processing methods can be combined.
The particle diameter of the preferable pigment obtained by the dispersion treatment is in the range of 0.005 to 0.7 μm, more preferably 0.01 to 0.5 μm. In addition, the specific black pigment in this invention and the carbon black particle size used as its raw material are measured with the laser Doppler type particle size measuring device. When the particle size exceeds the upper limit of the above range, the developability, resolution and stability are lowered. Moreover, in order to make it below the lower limit, it is necessary to make the pigment particles finer than the primary particles of carbon black or higher, so that the production is extremely difficult.

  In the present invention, the content of the other colored pigment in the photocurable coloring composition of the present invention is preferably in the range of 0 to 50% by mass with respect to the specific black pigment, and the total content of both , 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 more preferably 50% by mass or more and 80% by mass with respect to the total solid content constituting the curable composition. More preferably, it is as follows.

<(3) Compound having an ethylenically unsaturated group capable of addition polymerization>
A compound having an addition-polymerizable ethylenically unsaturated group that can be used in the present invention (hereinafter appropriately referred to as a polymerizable compound) is an addition-polymerizable compound having at least one ethylenically unsaturated double bond. , Selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. 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, isocyanuric acid There are EO-modified triacrylate and the like.

  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.

  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 (A) 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 (A)
(In the general formula (A), 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 photocurable coloring composition having an excellent 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.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the compatibility of the addition polymerization compound with other components (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) contained in the curable composition is also improved. The selection / use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

  The photocurable coloring composition of the present invention is used as described above (1) a specific initiator, (2) a specific black pigment, and (3) a compound having an addition-polymerizable ethylenically unsaturated group and if desired. You may further contain the arbitrary component explained in full detail below with a sensitizer as needed. Hereinafter, optional components that can be used in the present invention will be described.

<Binder polymer>
In the photocurable coloring composition of the present invention, a binder polymer can be used in combination as necessary for the purpose of improving the properties of the formed film.
It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. 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.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (13).

(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 acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(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. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

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. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and 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.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 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.
When such other binder polymer is used, the content is preferably 0 to 50% by mass, and more preferably 0 to 30% by mass.

<Co-sensitizer>
The photocurable coloring 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.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
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.

<Adhesion improver>
In the present invention, it is preferable to add an adhesion improver in order to improve adhesion to a hard surface (substrate) as a base material. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.
0.5-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of a contact | adherence improving agent, 0.7-20 mass% is more preferable.

<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 a binder.

<Diluent>
The photocurable coloring composition of the present invention may be used by dissolving it in various organic solvents when it is applied on a support in the production of a color filter.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content in the organic solvent is preferably 2 to 60% by mass.

[Color filter]
Next, the color filter of the present invention will be described.
In the color filter of the present invention, a photocurable colored layer made of a photocurable coloring composition is formed on the surface of a glass support, and pattern exposure is performed by means such as through a mask. It develops and forms by forming a coloring pattern in the glass support surface.
The photocurable coloring layer may be formed by applying a photocurable coloring composition to a glass support and drying it, or by laminating a sheet prepared in advance with the photocurable coloring composition. You may form in close contact on a support body.

<Glass support>
As the support that can be used in the present invention, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and imaging elements and the like used for liquid crystal display elements and the like are used. 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 according to 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. .
The curable composition applied on the support is usually dried at 70 to 110 ° C. for about 2 to 4 minutes to form a layer composed of the photocurable coloring composition.

  As a coating film thickness after drying 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.

  The photocurable coloring composition according to the present invention is cured with high sensitivity by exposure, is excellent in developability of an unexposed portion after exposure, and is high on the surface of a glass support to which the photocurable coloring composition is applied. Shows adhesion.

The color filter of the present invention is characterized by having a colored pattern formed as described above on a glass support.
Specifically, the photocurable colored layer made of the photocurable coloring composition of the present invention is subjected to pattern exposure through a predetermined mask pattern or by scanning exposure, and a coating film portion irradiated with light. By curing only this and developing the uncured area with a developer, a patterned film composed of black pixels can be formed, which is useful as a black matrix for a color filter. Furthermore, the color filter of the present invention is manufactured by forming pixels of other hues by a conventional method as necessary.

<Exposure process>
In the exposure step, the photocurable colored layer is subjected to pattern exposure, for example, by exposure through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, particularly ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferably used. Exposure is preferably ^{5mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

<Development process>
Subsequent to the exposure step, an alkali development treatment is performed to elute the light non-irradiated portion in the exposure step into an aqueous alkali solution. Thereby, only the photocured part 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 alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. 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.

  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.

  Thereafter, a photocurable colored layer of another hue is formed, and a color filter having a desired hue is produced by repeating the exposure process and the development process (and, if necessary, the curing process) for the desired number of hues. .

  Since the color filter of the present invention is produced using a laminate having a layer made of a photocurable coloring composition capable of forming an interaction with glass on a glass support, it is excellent in pattern formability and formed. The colored pattern shows high adhesion to the support substrate, and in the unexposed area, the film structure made of the curable composition has excellent uniformity and suppresses the developer permeability. In addition, there is no concern about the occurrence of agglomerates of photopolymerization initiators, and the penetration of the developer is uniform and promptly progresses to show high developability. Therefore, the exposure sensitivity is excellent and the adhesion between the exposed portion and the substrate is good. It is possible to form a high-resolution pattern that has no residual film. Therefore, it can be suitably used as a black matrix of 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, CMOS, or the like exceeding 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, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.
[Example 1]
Here, an example in which a photocurable coloring composition α-1 containing a colorant (pigment) is prepared and a color filter for use in a liquid crystal display element is produced using the curable composition α-1 will be described. .

[1. Preparation of photocurable coloring composition α-1]
1-1. Preparation of pigment dispersion (Q1): Black pigment As a pigment, 27 parts by mass of carbon black MA-220 [manufactured by Mitsubishi Chemical Corporation, specific black pigment (A)], benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio 70) (30 molar ratio, weight average molecular weight 30000) 8 parts by mass and propylene glycol monomethyl ether acetate 65 parts by mass were mixed and dispersed by a bead mill for 20 hours to prepare a pigment dispersion (Q1).
With respect to the obtained pigment dispersion (Q1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 100 nm.

1-2. Preparation of Photocurable Coloring Composition α-1 (Coating Liquid) <Composition α-1>
Pigment dispersion (Q1) 600 parts by mass Alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer, molar ratio: 70/30,
Mw: 10000) 190 parts by mass • Dipentaerythritol hexaacrylate [polymerizable compound] 40 parts by mass • 20 parts by mass of pentaerythritol triacrylate • Compound 1 (the following structure) [specific photopolymerization initiator] 80 parts by mass • Co-sensitization Agent: N-phenyl-2-mercaptobenzimidazole 30 parts by mass Surfactant: (trade name: Tetranic 150R1, BASF) 1 part by mass Solvent: Propylene glycol monomethyl ether acetate 1000 parts by mass Gamma-methacryloxypropyl 10 parts by mass of triethoxysilane

[2. (Production of color filter)
2-1. Formation of the curable composition layer The photocurable coloring composition α-1 containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then left as it was for 10 minutes. Then, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a photocurable colored 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 Thereafter, the surface of the photocurable colored layer is exposed in a pattern through a mask using a 2.5 kW ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film is an organic developer (trade name: CD The film was covered with a 10% aqueous solution of Fuji Film Arch Co., Ltd. and allowed to stand for 60 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 pattern was formed on the glass substrate to obtain a color filter (black matrix).

[3. (Performance evaluation)
Exposure pattern formability in the photocurable coloring layer of the color filter laminate formed on the glass substrate using the photocurable coloring composition α-1 (coating liquid) prepared above, and further coloring in the color filter The substrate adhesion of the pattern was evaluated as follows. The results are shown in Table 1.

3-1. Pattern Formability of Coating Film (Colored Layer) The photocurable coloring composition α-1 (coating liquid) was coated on a glass substrate and dried to a film thickness of 1.0 μm. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, using a test photomask having a line width of 20 μm, exposure was performed at an exposure amount of 100 mJ / cm ² . Next, development was performed using a 60% CD-2000 (produced by Fuji Film Electronics Materials) at 25 ° C. until the remaining film in the unexposed area disappeared completely. This was done by checking the remaining condition in the dark field of an optical microscope). Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning. The film thickness after development of the area irradiated with light in the exposure process was measured, and the film reduction with respect to 100% of the film thickness before exposure was evaluated according to the following criteria. The smaller the film loss, the higher the exposure sensitivity and the shorter the development time required to reach a state where there is no residual film (excellent developability), indicating that the pattern forming properties are better due to these compatibility.
○: 95% or more Δ: less than 95 to 85% or more ×: less than 85%

3-2. Coating film (colored layer) pattern formation 2 (thin line reproducibility)
At the time of the exposure of 3-1, the exposure was performed at an exposure amount of 80 mJ / cm ² using a test photomask having a line width of 5 μm to 20 μm. Next, development was performed using a 60% CD-2000 (produced by Fuji Film Electronics Materials) at 25 ° C. until the remaining film in the unexposed area disappeared completely. This was done by checking the remaining condition in the dark field of an optical microscope). Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning. A line width in which the film thickness after development of the region irradiated with light in the exposure process maintained 95% or more with respect to 100% of the film thickness before exposure was confirmed and used as an evaluation index. It shows that a thin line width image formed with little film loss due to development is excellent in fine line reproducibility.
○: 10 μm or less Δ: 10-15 μm
×: 15-20 μm

3-3. Substrate adhesion The substrate adhesion was evaluated by confirming the coloring pattern in the color filter after post-baking by an ordinary method using an optical microscope and SEM photograph observation. Details of the evaluation method are as follows.

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether a pattern defect or a gap with the substrate occurred. These evaluation items were evaluated based on the following criteria. If it is (circle) and (triangle | delta), it is a level which is satisfactory practically.
○: No pattern defect and no gap with the substrate were observed.
(Triangle | delta): Although a pattern defect | defect is not observed and there exists an area | region where a clearance gap is seen with a board | substrate, it was a level which is satisfactory practically.
X: A pattern defect was clearly observed, and it was a practically unusable level.

[Examples 2 to 12]
In Example 1, at least one of the specific initiator (compound 1) in the composition α-1 used for the preparation of the photocurable coloring composition α-1 and the black pigment used in the pigment dispersion (Q1). Photocurable coloring compositions [alpha] -2 to [alpha] -12 were prepared in the same manner as in Example 1 except that one was changed to that shown in Table 1 below. Using these, color filters having a colored pattern were obtained in the same manner as in Example 1. Furthermore, the same evaluation as in Example 1 was performed. The results are shown in Table 1.
Moreover, the structure of the specific initiator (compound 2-compound 4) used here is shown below.

The details of the black pigments listed in Table 1 (for the present invention and for comparison) are as follows.
[Specific black pigment (A): Uncoated type]
Specific surface area (m ² / g) pH
CB-1: Asahi Thermal 24 8.8
(Asahi Carbon Co., Ltd.)
CB-2: MA-220 31 3.0
(Mitsubishi Chemical Corporation)
CB-3: SB 350 65 3.5
(Special Black 350 Degussa)
CB-4: MA-11 104 3.5
(Mitsubishi Chemical Corporation)
[Comparison black pigment: uncoated type]
CBX-1 24 10.0
(CB-1: Asahi Thermal was immersed in 1N ammonia water for 24 hours, filtered under pressure and dried)
CBX-2 31 1.8
(CB-2: MA-220 immersed in 1N hydrochloric acid for 24 hours, pressure filtered and dried)
CBX-3 300 3.5
(CB-4: MA-11 treated with pure water and beads having a particle diameter of 1 mm for 10 hours in a bead mill, pressure filtered, and dried)

[Specific black pigment (B): Silica-coated type]
CB-5: 10 g of carbon black (manufactured by Mitsubishi Chemical Corporation, MA100), 200 ml of pure water, and 1 g of concentrated hydrochloric acid are placed in a flask and stirred to prepare an aqueous dispersion. Tetraethoxysilane 1.0g was put into the water dispersion, and it heated at 60 degreeC for 3 hours. After the reaction, the solution was filtered under pressure and further dried to obtain silica-coated carbon black CB-5.

[Specific black pigment (C): Resin-coated type]
CB-6: An emulsion of epoxy resin (12 parts by mass) and 2-ethyl-4-methylimidazole (2 parts by mass) are added to 100 parts by mass of carbon black (CI pigment black 7), and epoxy resin is added. A coating layer was formed by using a resin coated carbon black CB-6.

[Comparative Examples 1 to 12]
In Example 1, at least one of the specific initiator (compound 1) in the composition α-1 used for the preparation of the photocurable coloring composition α-1 and the black pigment used in the pigment dispersion (Q1). Photocurable coloring compositions [beta] -1 to [beta] -12 were prepared in the same manner as in Example 1 except that one was replaced with the comparative initiator or comparative black pigment shown in Table 1 below. Using these, color filters having a colored pattern were obtained in the same manner as in Example 1. Furthermore, the same evaluation as in Example 1 was performed. The results are shown in Table 1.
In addition, the structure of the photoinitiator for a comparison [comparative compound 1-comparative compound 4] used for the comparative example is shown below.

From the results of Table 1, the color filters of Examples 1 to 12 produced using a photocurable coloring composition containing a specific initiator and a specific black pigment are excellent in pattern formability, particularly fine line reproducibility, The formed colored pattern has good substrate adhesion, and by using the photocurable coloring composition of the present invention, the exposure sensitivity is high, the developability and the high-definition pattern formability are excellent, and the formed pattern is formed. It turns out that the color filter excellent in the board | substrate adhesiveness of a coloring pattern is obtained.
On the other hand, Comparative Examples 1 to 4 using carbon black outside the scope of the present invention as a black pigment, or Comparative Examples 5 to 8 using comparative compounds outside the scope of the present invention as a photopolymerization initiator, initiator, black Both Comparative Examples 9-12, which are both compounds outside the scope of the present invention, are inferior in pattern formation, fine line reproducibility, and adhesion to the substrate as compared with the Examples. It turns out that the outstanding effect of this invention is acquired for the first time by using the photocurable coloring composition of this invention containing both specific black pigments.

Claims (2)

Photopolymerization initiator represented by the following general formula (I), (A) carbon black having a specific surface area of 110 m ² / g or less and pH of 2 to 9, (B) silica-coated carbon black, and (C) resin A photocurable coloring composition comprising at least one black pigment selected from the group consisting of coated carbon black and a compound having an ethylenically unsaturated group capable of addition polymerization.

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following general formula (IA) or (IB). R ³ represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. W represents a halogen atom. X and Y each independently represent a chlorine atom or a bromine atom. m and n each independently represents 0, 1 or 2.

In general formulas (IA) and (IB), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group.   A laminated body having a photocurable colored layer made of the photocurable coloring composition according to claim 1 on a glass support is subjected to pattern exposure, pattern exposure is performed to cure an exposed region of the photocurable colored layer, and A color filter comprising a colored pattern obtained by developing an unexposed area.