KR20080014698A - Photocurable coloring composition and color filter using the same - Google Patents

Abstract

A photocurable coloring composition is provided to be cured with high sensitivity, to form a high-resolution pattern, and to form a colored pattern having adhesiveness with a glass substrate. A photocurable coloring composition includes a photopolymerization initiator, a black pigment, and a compound having an addition-polymerizable ethylenic unsaturated group. The photopolymerization initiator has a structure represented by the following formula I. The black pigment contains at least one selected from the group consisting of (A) a carbon black having a specific surface area of 110 m^2/g or less and a pH of 2-9, (B) a silica-coated carbon black, and (C) a resin-coated carbon black.

Description

PHOTOCURABLE COLORING COMPOSITION AND COLOR FILTER USING THE SAME}

The present invention provides a photocurable coloring composition useful for forming a color filter for use in a liquid crystal display device (Liquid Crystal Display (LCD)), a solid-state imaging device (Charge Coupled Device (CCD), Complementary Metal Oxide Semiconductor (CMOS), etc.), and It relates to a color filter obtained using it.

In recent years, the display of various apparatuses, such as a television, a personal computer, and a mobile telephone, is requesting high image quality and high chroma. In particular, large screens are also required for television displays. At present, the mainstream of these displays is a liquid crystal display system, and in order to achieve the high quality, high saturation, and large screen, the technology of the color filter used in the system has become very important. Specifically, the technology regarding the process of manufacturing a color filter, and the photocurable coloring composition suitable for it has become important.

For high precision of the color filter, it is necessary to form the pattern with high precision for pattern exposure and subsequent phenomena in order to make the line width precise in the pattern formation of the color filter. In addition, for high saturation, color adjustment and high concentration of the colorant are essential. However, the curable composition to which the conventional pigment dispersion system is applied has a problem such that color unevenness occurs because the pigment is a relatively rough and coarse particle. Therefore, further improvement of the resolution using the said curable composition is difficult, and therefore the said curable composition was not suitable for the use which requires a micro pattern like a solid-state image sensor. Then, the technique of using the dye of soluble organic solvent instead of a pigment as a coloring agent is proposed (for example, refer Unexamined-Japanese-Patent No. 2-127602).

In the case of using a dye as the colorant or in the case of using a pigment, it is necessary to increase the content of the colorant in the colored curable composition for producing a color filter, but on the other hand, photopolymerization is a component necessary for curing the colored curable composition. Since the content of the initiator and the photopolymerizable monomer is limited or the exposure wavelength light for curing is prevented from reaching the glass support interface, it is likely to occur, so that the high sensitivity of the curable coloring composition and the high adhesion to the support are necessary. Done.

In recent years, with the expansion of the substrate size, the production of large area color filters has become indispensable. However, in the process, when it is going to maintain the conventional productivity without changing an energy cost, reduction of application time, exposure time, etc. becomes a necessity. For this reason, high sensitivity which can cope with the improvement of the wettability with respect to the glass support of a photocurable coloring composition for achieving a quick application | coating speed, and short exposure time (a small exposure amount) is needed.

In addition, when the display is large screened, since the minute defects after the production of the color filter largely influence the yield, stabilization at a level higher than that of the prior art also requires heat resistance, light resistance, and the like of the curable composition forming the colored pattern.

Conventionally, as a curable composition for color filter manufacture, the radiation sensitive composition which combined the polyfunctional acrylate, such as a binder polymer containing a carboxyl group, pentaerythritol hexaacrylate, and a photoinitiator, is used, for example, As a highly sensitive photoinitiator in a composition, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole and 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like have been proposed (see, for example, Japanese Patent Laid-Open No. 6-75372 and Japanese Patent Laid-Open No. 6-75373). .

Moreover, as a photoinitiator which can be applied to a curable composition, the photoinitiator which can be applied to the radiation sensitive composition used for a printing plate and a photoresist is used, As a photoinitiator, 2,2'-bis (2-chlorophenyl) -4 is used. , 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 and the like have been proposed (see, for example, Japanese Patent Application Laid-open No. 48-38403 and Japanese Patent Application Laid-open No. 62-174204).

However, also in any of said curable compositions, a sensitivity is not yet satisfactory and it is necessary to irradiate high energy radiation at the time of hardening. When the colored pattern of the color filter is formed using such a curable composition, if the radiation dose is insufficient, problems such as missing or missing patterns, residual film ratio or lowered pixel intensity may occur, and further, coloring of the obtained color filter. There arises a problem that the adhesion between the resolution and the support is lowered in the pattern.

As mentioned above, even when it contains a coloring agent in high concentration, the color filter provided with the curable coloring composition which hardens with high sensitivity and has a favorable pattern formation property, and the coloring pattern excellent in the adhesiveness of the resolution and support body obtained using it is desired, However, it is currently not provided.

The present invention has been made in view of the above problems in the prior art.

That is, this invention can harden with high sensitivity even if it contains a coloring agent in high concentration, can form a high resolution pattern, can also form the coloring pattern excellent in adhesiveness with a glass base material, A useful photocurable coloring composition and a color filter having a high resolution obtained using the same and a coloring pattern excellent in adhesion with a support are provided.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject can be solved by the photocurable coloring composition containing a specific photoinitiator and a specific black pigment, and came to complete this invention. That is, the structure of this invention is as follows.

As a photocurable coloring composition containing the <1> photoinitiator, a black pigment, and the compound which has an ethylenically unsaturated group which can be addition-polymerized,

The photopolymerization initiator is represented by the following general formula (I); And

The black pigment,

(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) The said photocurable coloring composition characterized by containing at least 1 chosen from the group which consists of resin coating carbon black.

In general formula (I), R <^1> , R <^2> respectively independently represents the group represented by a hydrogen atom, an alkyl group, an aryl group, 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 represent 0, 1 or 2;

In General Formulas (IA) and (IB), R ⁵ , R ⁶ , and R ⁷ each independently represent an alkyl group or an aryl group.

The color filter containing the <2> glass support body and the coloring pattern formed on the said glass support body, Pattern exposure of the laminated body by which the said coloring pattern forms the photocurable colored layer which consists of a photocurable coloring composition as described in <1>. An exposure step of curing the exposure area of the photocurable colored layer; And a developing step of forming the colored pattern by developing the laminated body having completed exposure and removing unexposed regions.

The photocurable coloring composition (henceforth called a curable composition) of this invention is a specific photoinitiator which has a heterocyclic ring in a molecule | numerator, (A) specific surface area is 110 m <2> / g or less, and pH is 2-9 And a compound having at least one black pigment selected from the group consisting of phosphorus carbon black, (B) silica coated carbon black, and (C) resin coated carbon black, and an ethylenically unsaturated group capable of addition polymerization.

The mechanism of action of the present invention is not clear, but is estimated as follows.

Carbon black, which is useful as a black pigment, has high magnetic cohesion and is difficult to uniformly disperse. Moreover, although the photoinitiator which has the triazine ring structure used for this invention is highly sensitive, it is known that it is easy to self-aggregate due to the structure. The specific photoinitiator used in the photocurable coloring composition of this invention has very high affinity with said specific carbon black, and presence of an initiator and carbon black does not repel each other in a coating film state, and it is disperse | distributed uniformly. As a result, since the spatial distance of a photocuring component and a photoinitiator becomes small over the whole area | region in the formed film, compared with the case of a non-uniform dispersion state, it is considered that photocuring efficiency improves and it is highly sensitive.

The cured film (exposure part) obtained by exposing and hardening | curing the photocurable coloring composition of a uniform dispersion state is uniformly in close contact with the lower layer, as well as the intensity | strength of the film itself improves due to an efficient hardening reaction, It is thought that high adhesiveness was also achieved. On the other hand, in the unexposed part, since the coating film melt | dissolves quickly by making developer permeability uniform, the outstanding developability is expressed. Thus, it is thought that the intensity | strength of an exposed part and developability of an unexposed part are compatible, favorable pattern formation property is expressed even if it is a fine pattern, and high resolution was attained.

Hereinafter, the photocurable coloring composition of this invention and the color filter obtained using it are demonstrated in detail.

[Photocurable Coloring Composition]

The photocurable coloring composition of this invention is (1) photoinitiator represented by following General formula (I) (Hereinafter, it calls suitably "a specific initiator"), (2) (A) specific surface area is 110 m <2> / g or less 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 (3) an ethylenically unsaturated group capable of addition polymerization. It has a photocurable colored layer containing the compound, It is characterized by the above-mentioned.

Hereinafter, each component contained in the photocurable coloring composition which concerns on this invention is demonstrated sequentially.

<(1) Photoinitiator represented by the following general formula (I)>

Curable colored layer of this invention contains the specific photoinitiator which contains a triazine ring structure in a molecule | numerator.

In general formula (I), R <^1> , R <^2> respectively independently represents the group represented by a hydrogen atom, an alkyl group, an aryl group, 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 represent 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 aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, and sulfonyl derivatives.

In General Formulas (IA) and (IB), R ⁵ , R ⁶ , and R ⁷ each independently represent an alkyl group or an aryl group.

The alkyl group and aryl group may further have a substituent. Examples of the substituent that can be introduced include aryl groups such as phenyl groups, halogen atoms, alkoxy groups, carboalkoxy groups, carboaryloxy groups, acyl groups, nitro groups, dialkylamino groups, and sulfonyl derivatives.

In general formula (I), you may form the heterocyclic ring which consists of a nonmetallic atom with the nitrogen atom which R <^1> and R <^2> couple | bond with them. In that case, what is shown below is mentioned as a heterocyclic ring.

As a specific example of the specific initiator represented by general formula (I), 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro -pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycar Bonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (Trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine , 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o- Luoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) amino Phenyl] -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-ethoxycar Bonylmethylaminophenyl) -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-ethoxycarbonylmethylamino Phenyl) -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 -(o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6- Halogen atom on di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and phenyl moiety Two or more introduced triazines It can be given.

These specific initiators have a radical generating site and a triazine skeleton in the molecule, and preferably those having two halogen atoms or a bromine atom in the centrally located phenyl ring.

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 the range of 0.5-10.0 mass%. In this range, a polymerization reaction advances efficiently and the intensity | strength of the obtained cured film is also excellent.

(Other photopolymerization initiator)

Moreover, in curable composition, in addition to the said specific initiator, photoinitiators other than this can be used together unless the effect of this invention is impaired.

The photoinitiator which can be used here is a compound which decomposes | disassembles by light and starts and accelerates superposition | polymerization of the compound which has the addition-polymerizable ethylenically unsaturated group mentioned later, It is preferable to have absorption in the region of wavelength 300-500 nm. .

As a photoinitiator, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, an azide compound, a metallocene compound, for example And biimidazole-based compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

Especially, at least 1 sort (s) of compound chosen from the group which consists of a trihalomethyl triazine compound, a biimidazole type compound, and an oxime type compound from a viewpoint of high sensitivity is the most preferable, and a biimidazole type compound is the most preferable. Do.

It is preferable that it is 75 mass% or less with respect to the said specific initiator, and, as for content of the photoinitiator which can be used together, it is more preferable that it is the range of 0-50 mass%.

Moreover, it is preferable that the total amount of a specific initiator and another photoinitiator is 0.1-50 mass% with respect to the total solid of a composition, More preferably, it is 0.1-30 mass%, Especially preferably, it is 0.3-20 mass%. In this range, good sensitivity and pattern formability are obtained.

(Sensitizer)

A sensitizer can be used together for these specific initiators.

As a sensitizer which can be used for this invention, it is preferable to sensitize a radical initiator with an electron transfer mechanism or an energy transfer mechanism.

Moreover, as a sensitizer, what belongs to the compounds listed below, and what has an absorption wavelength in the wavelength range of 300 nm-450 nm, Preferably it is 330 nm-450 nm is mentioned.

As a specific example of a sensitizer, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10- dialkoxy anthracene), xanthenes (for example, fluorescein, eosin, erythrosine , Rhodamine B, rose bengal), thioxanthones (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), meroxy Phosphorus (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) Vienna, acriflavin), anthraquinones (eg anthraquinones), squalanes (eg squalane), coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin , Phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane , Distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryl, pyryllium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbi Aromatic ketone compounds, such as a tournic acid derivative, acetophenone, benzophenone, a thioxanthone, Michler's ketone, heterocyclic compounds, such as N-aryl oxazolidinone, etc. are mentioned.

About such a sensitizer, it is also possible to perform various chemical formulas for improving the characteristic of a curable composition.

For example, the sensitizer and the addition-polymerizable compound structure (eg, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. to increase the strength of the exposure film or the film after exposure. Unnecessary precipitation of the specific sensitizer from can be suppressed.

Further, a sensitizer and a partial structure having a radical generating ability in the photopolymerization initiator (e.g., a reductive decomposable moiety such as alkyl halide, onium, peroxide, biimidazole, borate, amine, trimethylsilylmethyl, carboxymethyl, By binding to oxidative cleavage moiety such as carbonyl, imine, etc., the photosensitivity can be remarkably improved especially in a state where the concentration of the initiator is low.

A sensitizer may be used individually by 1 type, or may use 2 or more types together.

0.1 mass%-20 mass% are preferable in the total solid of a curable composition, and, as for content of a sensitizer, 0.2 mass%-20 mass% are more preferable.

When the sensitizer has a very high concentration of the colorant in the curable composition and the light transmittance of the colored pattern (photosensitive layer) formed is extremely low (specifically, for example, when it is formed without adding these sensitizers) When the transmittance of 365 nm light of the photosensitive layer seems to be 10% or less), the effect is remarkably exhibited.

<(2) (1) A species selected from the group consisting of carbon black having a specific surface area of 110 m 2 / g or less and a pH of 2-9, (B) silica coated carbon black, and (C) resin coated carbon black Pigment on Pinterest>

The colorant used in the present invention is a black pigment (hereinafter, appropriately referred to as a specific black pigment) selected from specific carbon blacks described in detail below.

[(A) Carbon black (specific black pigment (A)) having a specific surface area of 110 m 2 / g or less and a pH of 2 to 9]

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 pH of 2 to 9 having a physical property value. When the specific surface area exceeds 110 m 2 / g, a large amount of polymer dispersant necessary for stabilization of dispersion is required. However, since the polymer dispersant is insoluble in a developing solution, resolution and developability of the resulting curable composition tend to decrease. In addition, the pH value exceeding 9 is difficult for the polymer dispersant to adsorb and difficult to stabilize dispersion. Carbon blacks with a pH of less than 2 are not practical due to the considerable difficulty in industrial production.

Here, but can be measured by a specific surface area and pH is the conventional method of carbon black, according to the present invention, the specific surface area is a value measured by pH the BET method (N ₂ gas adsorption amount), are applied to the KOH neutralization titration method I adopt it.

Carbon black having such physical properties can also be obtained as a commercially available product. Specifically, for example, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, manufactured by Mitsubishi Kagaku Corporation # 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 black 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 surmax N990, N991, N907, N908, N990, N991, N908 manufactured by Cancurb;

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;

Degusa 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 ); These etc. are all satisfy | filling the said physical property conditions.

[(B) Silica coating carbon black (specific black pigment (B))]

As another form of the specific black pigment used suitably for this invention, the carbon black (specific black pigment (B)) which coat | covered the surface with silica is mentioned.

By using (B) silica-coated carbon black, the image-forming property and high light-shielding property can be expressed in the photocurable coloring composition of this invention.

There is no restriction | limiting in particular in the carbon black coat | covered with silica, The furnace black, acetylene black, etc. of 25-500 g / m <2> of specific surface areas are used normally. Specifically, the commercially available carbon black shown below is mentioned, for example.

Mitsubishi Kagaku Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900 and the like;

Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, etc.

Kyavbot Co .: Monarch460, Monarch430, Monarch280, Monarch120, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS480, PEARLS130, etc .;

Coron biyan carbon company: RAVEN11, RAVEN15, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, etc. (all brand names).

In the case of silica-coating the carbon black, the silica amount relative to the total amount of silica-coated carbon black is usually 0.5 to 50% by weight, preferably 1 to 40% by weight in terms of SiO ₂ .

The silica coating amount in a specific black pigment (B) can be measured by TG-DTA differential thermal-thermogravimetric change measurement or ESCA method.

The coating of silica on carbon black can be performed in the gas phase or in the liquid phase, but may be performed by any method.

In the case of coating silica by the vapor phase method, first, carbon black is put in a sealed container and the sealed container is degassed. Silica sources, such as tetramethoxysilane and tetraethoxysilane, are introduce | transduced in this, a silane source is made to adsorb | suck on a carbon black surface, and carbon black and a silica source are made to react. After completion of the reaction, the excess silica source is removed under reduced pressure, and then alkali such as ammonia is introduced into the sealed container to convert the methoxy group and the ethoxy group into the hydroxy group. By this series of operations, a silica coating layer is formed on the surface of the carbon black. If necessary, this operation can be repeated to control the coating amount of silica on carbon black.

In the case of coating silica by the liquid phase method, a water dispersion of carbon black is prepared, an alkali such as potassium hydroxide and ammonia is added to the carbon black water dispersion, and a silica source is added thereto. As a silica source at this time, the silicic acid solution etc. which dealkaliated the water glass aqueous solution with the cation exchange resin etc. are used preferably.

Moreover, in the liquid phase method, you may use the sol-gel reaction of silica sources, such as tetramethoxysilane and tetraethoxysilane, as another means. In the method using a sol-gel reaction, the carbon black water dispersion may be made acidic with hydrochloric acid or the like, or made alkaline with ammonia or the like, followed by addition of a silica source such as tetramethoxysilane and tetraethoxysilane.

As carbon black coated with silica, it is possible to use carbon black without pretreatment, that is, each of the carbon blacks described above. Alternatively, carbon black subjected to surface modification by performing a steam plasma treatment and introducing a hydroxyl group onto the surface may be used. As the water vapor plasma treatment, for example, carbon black is placed in a sealed container, and after degassing, a method of introducing hydroxyl groups on the surface of the carbon black by performing plasma irradiation while introducing water vapor is mentioned.

As another surface modification method for improving the silica coating efficiency of the carbon black surface, the surface of the carbon black may be subjected to oxidation treatment. As an example of an oxidation process, the high temperature baking method by heating at 100-300 degreeC in air atmosphere; An acid treatment method of contacting an acid such as nitric acid or perchloric acid or hydrogen peroxide at a temperature of 100 to 250 ° C; The ozone oxidation method etc. which heat at the temperature of 100-300 degreeC during ozone powder are mentioned.

Although various pretreatment methods, such as the above-mentioned silica coating method, such as a liquid-phase method and a gaseous-phase method, water vapor plasma treatment, and oxidation treatment with respect to carbon black, may be performed in any combination, (a) As a pretreatment, the carbon black which performed the steam plasma treatment as a pretreatment is applied to the gas phase method. Either of the form of silica coating, the form of (b) the silica coating of the untreated carbon black by the gas phase method, and the form of the silica coating of the (c) untreated carbon black by the liquid phase method. Especially, it is more preferable to use the carbon black which carried out silica coating on the carbon black which introduce | transduced the hydroxyl group to the surface by the steam plasma treatment, or the carbon black which silica coated by the liquid method to the untreated carbon black. .

The specific black pigment (B) may be silica-coated over the entire surface of the carbon black surface, or a silica coating layer may be present on a part of the surface. In either case, the effects of the present invention can be obtained.

The presence of silica on the surface of a specific black pigment (B) can be confirmed by the method of ESCA.

[(C) resin coating carbon black]

As another form of the specific black pigment used suitably for this invention, the carbon black (specific black pigment (C)) which resin-coated the surface is mentioned.

As carbon black used for formation of a specific black pigment (C), furnace black, channel black, acetylene black, lamp black, etc. are mentioned, Preferably it is furnace black.

The particle diameter of the carbon black is usually 20 µm or less, preferably 5 µm or less and 1 µm or less, and from the viewpoint of dispersibility and workability, the particle diameter is preferably 0.01 µm or more.

The specific black pigment (C) suitable for this invention can be obtained by resin-coating the surface of the said carbon black.

As resin which coat | covers the surface of carbon black, thermosetting resins, such as an epoxy resin, a phenol resin, a melamine resin, a xylene resin, diallyl phthalate resin, a glyphthal resin, and an alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, for example , Polybutylene terephthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether Synthetic resins, such as thermoplastic resins, such as an ether ketone, etc. are mentioned, Preferably it is an epoxy resin.

As an epoxy resin which can be used suitably for formation of a resin coating layer, Specifically, for example, a glycylamine type epoxy resin, a triphenyl glycidimethane type epoxy resin, a tetraphenyl glycidimethane type epoxy resin, an aminophenol type epoxy Polyfunctional epoxy resins, such as resin, a diamide diphenylmethane type epoxy resin, a phenol novolak-type epoxy resin, an orthocresol type epoxy resin, and a bisphenol A novolak-type epoxy resin, are mentioned.

Although there is no restriction | limiting in particular in the manufacturing method of resin coating carbon black, For example, the method of forming a coating layer by applying the emulsion of resin to carbon black is mentioned. That is, when using an epoxy resin as resin, a carbon black dispersion liquid may be prepared, and the hardening | curing agent and the emulsion of an epoxy resin may be added to it.

As a hardening | curing agent used with an epoxy resin for coating layer formation, it is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2, for example. -Phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4diamino-6- [2-methylimidazolyl- (1)] -Ethyl S-triazine and the like. It is common that the usage-amount of a hardening | curing agent is about 1 mass%-about 30 mass% with respect to the total amount of an epoxy resin and a hardening | curing agent, Preferably it is 5%-25%, More preferably, it is the range of 10%-20%.

In order to coat resin other than an epoxy resin on carbon black, the emulsion of resin may be added, for example, in the state which disperse | distributed carbon black to a dispersion medium, and it may heat and disperse | distribute. When epoxy resin is used as the resin and carbon black is coated with a curing agent, an emulsion of the resin and a curing agent may be added in a state in which carbon black is dispersed in a dispersion medium.

The proportion of the resin in the resin-coated carbon black thus obtained is usually 5% or more and 40% or less, preferably 7% or more and 20% or less in terms of mass fraction. If it is less than 5%, the electrical resistance of the black matrix tends to be low, and 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.

Specific black pigment (C) may be resin-coated over the whole surface of the carbon black surface, and the resin coating layer may exist in a part of the surface. In either case, the effects of the present invention can be obtained.

Presence of the resin layer on the surface of a specific black pigment (C) can be confirmed by the method of TG-DTA or ESCA.

The photocurable coloring composition of this invention contains the 1 or more types of black pigment chosen from the said specific black pigment (A)-specific black pigment (C). When using together these types, you may combine the physical property, coating material, and / or coating amount from a black pigment of the same kind, and different, for example, like (B) silica coating carbon black and (C) resin coating carbon black. You may combine types of things.

Moreover, these specific black pigment can also be used together with another black inorganic pigment and organic pigment. The other black pigment considers that light shielding property is lower than carbon black contained as a main material of a specific black pigment, and it is preferable that the content is 50 weight% or less with respect to the black colorant whole quantity. As an example of another black pigment, the black pigment which mixed titanium black, aniline black, an iron oxide type black pigment, and three organic pigments of red, green, and blue is mentioned.

It is preferable to use the specific black pigment in this invention as a light-shielding material. From such a viewpoint, for example, when forming the black matrix of the high light-shielding rate of 3.0 and 3.5 or more high light-shielding rate in 1 micrometer of film thickness, the addition amount of these specific black pigment to the photocurable coloring composition is in a curable composition. It needs to be an appropriate amount for the total solids.

The content of the black pigment in the photocurable coloring composition of the present invention is 20% by mass relative to the total solid constituting the pigment (including the content when using a dispersant) and the curable composition from the viewpoint of curing sensitivity and color concentration. It is preferable that it is more than 90 mass%, It is more preferable that it is 20 mass% or more and 75 mass% or less, It is further more preferable that it is 30 mass% or more and 60 mass% or less.

When there is too little content of a specific black pigment, when the color filter, especially the black matrix, is produced by the curable composition of this invention, there exists a tendency for suitable light-shielding property to not be obtained. On the other hand, when there is too much content of a specific black pigment, photocuring does not fully advance and the intensity | strength as a film | membrane falls, and the developing latitude at the time of alkali image development tends to become narrow. However, since the specific initiator according to the present invention has high light absorption efficiency and is uniformly dispersed in the curable composition by interaction with a specific black pigment, a significant sensitivity improvement effect is obtained even when the black pigment is contained in such a high concentration. Is exhibited and excellent also in the adhesiveness with the support body of a cured film.

(Coloring pigment)

In addition to the said specific black pigment, 1 type (s) or 2 or more types can be selected and used together in the photocurable coloring composition of this invention according to the objective in addition to the said specific black pigment.

As a pigment which can be used for the photocurable coloring composition which concerns on this invention, various conventionally well-known inorganic pigments or organic pigments can be used. Further, considering that it is preferable that the photocurable colored layer formed of both inorganic pigments and organic pigments has a high light transmittance, it is preferable to use a pigment having a fine particle diameter if possible. In consideration of handling properties, the average particle diameter of the pigment is preferably 0.01 µm to 0.1 µm, more preferably 0.01 µm to 0.05 µm. Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like, and specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And composite oxides of the above metals.

As an organic pigment, for example

C.I. Pigment yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment orange 36, 38, 43, 71;

C.I. Pigment red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment violet 19, 23, 32, 39;

C.I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment green 7, 36, 37;

C.I. Pigment brown 25, 28;

C.I. Pigment black 1, 7;

Carbon black etc. are mentioned.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although the cause is not fully elucidated, it is estimated that the high affinity of the photosensitive polymerization component and a pigment is having an influence.

The following can be mentioned as a pigment which can be used preferably in this invention. However, the present invention is not limited to these.

C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C.I. Pigment Orange 36, 71,

C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C.I. Pigment violet 19, 23, 32,

C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C.I. Pigment Black 1

These organic pigments can be used individually or in combination in order to raise color purity. The specific example of the said combination is shown below. For example, as a red pigment, you may use the red pigment which consists of one selected from the group which consists of an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment, or a plurality containing at least 1 sort (s) of these, You may use the red pigment and the mixture of the yellow pigment which consists of a disazo yellow pigment, an iso indorine yellow pigment, or the plural yellow pigment containing one or more selected from the group which consists of a quinophthalone type yellow pigment. For example, as an anthraquinone pigment, C.I. Pigment red 177. As a perylene pigment, C.I. Pigment Red 155, C.I. Pigment thread 224. As diketopyrrolopyrrole pigments, C.I. Pigment red 254 is mentioned. In terms of color reproducibility, the red pigment is C.I. It is preferably used in combination with Pigment Yellow 139. Moreover, as for content ratio (mass ratio) of the red pigment and a yellow pigment in the mixture of organic pigments, 100: 5-100: 50 are preferable. If it is 100: 4 or less, since it is difficult to suppress the light transmittance from 400 nm to 500 nm, color purity may not be improved. In addition, since the dominant wavelength of the absorption wavelength of a pigment becomes near short wavelength in 100: 51 or more, the deviation from NTSC target color may become large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, content ratio (mass ratio) can be adjusted according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used alone, or a mixture of the green pigment and the disazo yellow pigment, the quinophthalone yellow pigment, the azomethine yellow pigment or the isoindolin yellow pigment may be used. do. Examples of such mixing include C.I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Mixing with Pigment Yellow 185 is preferred. As for content ratio (mass ratio) of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable. When the said mass ratio is less than 100: 5, since it becomes difficult to suppress the light transmittance of 400 nm-450 nm, color purity may not be improved. If the wavelength exceeds 100: 150, the dominant wavelength of the absorption wavelength of the pigment becomes near the long wavelength, which may cause a large deviation from the NTSC target color. It is especially preferable that the said mass ratio exists in the range of 100: 30-100: 120.

As the blue pigment, a phthalocyanine-based pigment may be used alone, or a mixture of the blue pigment and the dioxazine-based purple pigment may be used. For example, C.I. Pigment Blue 15: 6 and C.I. Mixing of pigment violet 23 is preferred. As for content ratio (mass ratio) of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 0-100: 10.

Moreover, as a pigment for black matrices, carbon pigments other than the said specific black pigment, titanium carbon, iron oxide, titanium oxide, etc. can be used individually or in mixture. The combination of the said specific black pigment and titanium carbon is preferable. Moreover, it is preferable that content ratio (mass ratio) of a specific black pigment and titanium carbon exists in the range of 100: 0-100: 60. Above 100: 61, dispersion stability may fall.

The average particle diameter r (unit: nm) of the pigment in the present invention preferably satisfies 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, and particularly preferably 30 ≦ r ≦ 200. By using the pigment of such average particle diameter r, red and green pixels of high contrast ratio and high light transmittance can be obtained. The "average particle diameter" here means the average particle diameter with respect to the secondary particle which the primary particle (single microcrystal) of a pigment aggregated.

In addition, the pigment which can be used in this invention is that the secondary particle which has a particle diameter of (average particle diameter +/- 100) nm has the particle diameter distribution of the secondary particle which is 70 mass% or more of the whole, Preferably it is 80 mass% or more. desirable.

Pigment Dispersant

In this invention, since the pigment is used as a coloring agent, a well-known pigment dispersant can be used together. As a pigment dispersant, a polymeric dispersant [For example, a polyamide amine and its salt, a polycarboxylic acid and its salt, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly (meth) acrylate, (meth) acrylic-type Copolymers, naphthalenesulfonic acid formalin condensates], and polyoxyethylene alkyl phosphate esters, polyoxyethylene alkylamines, alkanolamines, pigment derivatives, and the like.

Polymeric dispersants can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers from the structure thereof.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. Therefore, as the polymer dispersant having a preferred structure, terminal modified polymers, graft polymers, and block polymers having anchor sites on the pigment surface can be proposed. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

As a specific example of the pigment dispersant which can be used for this invention, BYK Chemie Corporation made "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) , 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)," EFKA4047, 4050, 4010, 4165 (poly Urethane), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative) ), 6750 (Azo Pigment Derivative), "Aji Spa PB821, PB822" by Ajinomoto Fan Techno Co., Ltd. "Florene TG-710 (urethane oligomer)" by Kyoeisha Kagaku Corporation, "Polyflow No. 50E, No. 300 (acrylic copolymer) "," disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA by Kusumoto Kasei Co., Ltd. -705, DA-725, "Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)" by Chaos Corporation, "Homogenol L-18 (Polymeric Polycarbide) Acid) "," Emalgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether) "," acetamine 86 (steallylamine acetate) "," Solpersper 5000 (phthalocyanine derivative) made by Lubrizol, " 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (grafted polymer), Nikko T106 (manufactured by Nikko Chemical Co., Ltd.) Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), etc. are mentioned.

Especially, as an example of the polymeric dispersing agent used for disperse | distributing the specific black pigment of this invention, a polyisocyanate compound, the compound which has one or more hydroxyl groups in a molecule (number average molecular weight 300-10,000), and active hydrogen in the same molecule And a dispersing resin obtained by reacting a compound having a tertiary amino group, and a weight average molecular weight thereof is preferably 1,000 to 200,000.

Hereinafter, the dispersing agent useful for dispersion of the specific black pigment of this invention is described.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate Aliphatic diisocyanates such as aromatic diisocyanates, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylene Aromatic rings, such as alicyclic diisocyanate, such as bis (cyclohexyl isocyanate) and (omega), (omega)-diisocyanate dimethyl cyclohexane, xylylene diisocyanate, (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl xylylene diisocyanate; Aliphatic diisocyanate having, lysine ester triisocyanate, 1,6,11- cloud Such as decane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate Triisocyanate, these trimers, a water addition product, these polyol addition products, etc. are mentioned. Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate, and these may be used alone or in combination.

As a method for producing a trimer of isocyanate, the polyisocyanate is partially used in the isocyanate group by using a suitable trimerization catalyst (for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc.). The method of trimerization is carried out, the trimerization is stopped by addition of a catalyst poison, and unreacted polyisocyanate is removed by solvent extraction and thin film distillation, and the desired isocyanurate group containing polyisocyanate is mentioned. have.

As a compound which has one or more hydroxyl groups in the same molecule (number average molecular weight 300-10,000), the compound which has one or two hydroxyl groups is preferable. Particularly preferred examples include polyether glycols, polyester glycols, polycarbonate glycols, polyolefin glycols, and the like, in which a single terminal hydroxyl group of these compounds is alkoxylated to an alkyl group having 1 to 25 carbon atoms, and a mixture of two or more thereof.

As polyether glycol, polyether diol, polyether ester diol, and these two or more types of mixtures are mentioned. As polyetherdiol, what is obtained by making alkylene oxide single or copolymerizes, for example, polyethyleneglycol, polypropylene glycol, polyethylene-propylene glycol, polyoxy tetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and those 2 or more types of mixtures are mentioned. Polyether ester diols obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides or by reacting alkylene oxides with polyester glycols, for example poly (polyoxytetra) Methylene) adipate, and the like. Most preferred as the polyether glycol are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which a single terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

As polyester glycol, dicarboxylic acid (succinic acid, glutaric acid, azipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, di Propylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 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-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol Aliphatic glycols such as 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylylene glycol, bis Aromatic glycols such as hydroxyethoxybenzene, N Obtained by polycondensing N-alkyldialkanolamine such as -methyldiethanolamine, for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, or the like. And polylactone diols or polylactone monools obtained by using diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, for example, polycaprolactone glycol, polymethylvalerolactone and mixtures of two or more thereof. . The most preferable as polyester glycol is polycaprolactone glycol or polycaprolactone which used the C1-C25 alcohol as an initiator.

Examples of polycarbonate glycols include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. Can be mentioned.

The number average molecular weight of the compound which has one or two hydroxyl groups in the same molecule is 300-10,000, Preferably it is 500-6,000, More preferably, it is 1,000-4,000.

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

Examples of the compound 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 etc. are mentioned.

Examples of the compound in which the tertiary amino group is an N-containing hetero ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring and benzoxazole ring N-containing hetero 6-membered ring such as N-containing hetero 5-membered ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, such as benzothiazole ring and benzothiadiazole ring Can be mentioned. Preferred as these N-containing hetero rings are imidazole rings or triazole rings.

Specific examples of the compound having an imidazole ring and those already NH _2, and the like can be mentioned 1- (3-aminopropyl) imidazole, histidine, 2-amino-imidazole, 1- (2-aminoethyl) imidazole. Further specifically exemplifying a compound having a triazole ring and an NH ₂ group, 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- 1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. are mentioned.

Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4- Triazoles are preferred.

The preferred blending ratio of the raw material of the dispersing resin used for the dispersion of the specific black pigment is 10 to 200 weights of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule relative to 100 parts by weight of the polyisocyanate compound. 20 parts by weight, preferably 20 parts by weight to 190 parts by weight, more preferably 30 parts by weight to 180 parts by weight, and 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight of the compound having active hydrogen and a tertiary amino group in the same molecule.

The weight average molecular weight of the dispersion resin is in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000 in polystyrene conversion as measured by GPC. If the molecular weight is less than 1,000, the dispersibility and the dispersion stability are inferior, and if it exceeds 200,000, the solubility is reduced, the dispersibility is inferior, the gelation is likely to occur, and the reaction is difficult to control.

The manufacturing of the polymer dispersing agent which disperse | distributes a specific black pigment is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent at the time of manufacture, Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters, such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene , Hydrocarbons such as xylene and hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol and third butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, and dimethylform Aprotic polar solvents such as amide, N-methylpyrrolidone and dimethyl sulfoxide are used.

As a catalyst at the time of manufacture, a normal urethanation reaction catalyst is used. For example, tin type, such as dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dioctoate, stanas octoate, iron type, such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine Tertiary amines, such as these, etc. are mentioned.

It is preferable that the introduction amount of the compound which has active hydrogen and a tertiary amino group in the same molecule is controlled in the range of 1-100 mgKOH / g by the amine value of the dispersion resin after reaction. More preferably, it is the range of 5-95 mgKOH / g. If the amine value is less than or equal to the above range, the dispersibility tends to be lowered, and if it exceeds the above range, developability tends to decrease. Moreover, when an isocyanate group remains in dispersion resin in the above reaction, when an isocyanate group does not remain by making an alcohol or an amino compound react, it is preferable because time-lapse stability of a dispersion resin becomes high.

The dispersion resin and the pigment are subjected to dispersion treatment before blending into the resist liquid. Specifically, for example, a pigment, a dispersing resin and a solvent, and optionally a binder resin are added to form a mill base, which is a ball mill, a sand mill, a bead mill, three rolls, a paint shaker, an ultrasonic wave, a bubble homogenizer, or the like. Disperse treatment by the method. These treatment methods can also be combined 2 or more.

The particle diameter of the preferable pigment obtained by a dispersion process is 0.005-0.7 micrometer, More preferably, it is the range of 0.01-0.5 micrometer. In addition, the particle size of the specific black pigment in this invention and the carbon black used as a raw material is measured by the laser Doppler type particle size measuring machine. When the particle diameter exceeds the upper limit of the above range, deterioration of developability, resolution, and stability occurs. In addition, in order to make below a lower limit, although the pigment particle must be made into the primary particle or more of carbon black, manufacture of such a pigment particle is remarkably difficult.

In this invention, it is preferable that content of the other colored pigment in the photocurable coloring composition of this invention is 0-50 mass% with respect to content of the said specific black pigment. It is preferable that the sum total of content of the said specific black pigment and another coloring pigment is 30 mass% or more and 90 mass% or less with respect to the total solid which comprises a curable composition, It is more preferable that it is 40 mass% or more and 85 mass% or less, 50 It is more preferable that it is 80 mass% or less by mass% or more.

<(3) Compound having an ethylenically unsaturated group capable of addition polymerization>

The compound which has an addition polymerizable ethylenically unsaturated group which can be used for this invention (henceforth called a polymeric compound suitably) is an addition polymeric compound which has at least 1 ethylenically unsaturated double bond, and has a terminal ethylenically unsaturated bond. It is selected from compounds having at least one, preferably two or more. Such compound groups are widely known in the industrial field, and in the present invention, these can be used without particular limitation. These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its ester, and amide are mentioned, Preferably The ester of unsaturated carboxylic acid and aliphatic polyhydric alcohol compound, and the amides of unsaturated carboxylic acid and aliphatic polyamine compound are used. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxys, and monofunctional or polyfunctional carboxyl groups Dehydration condensation reactions with acids are also suitably used. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and desorption of halogen groups or tosyloxy groups Substitution reaction products of unsaturated carboxylic acid esters or amides having a substituent with monofunctional or polyfunctional alcohols, amines and thiols are also preferable. As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the above unsaturated carboxylic acid.

In the monomer of the ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, as an example of acrylic acid ester, ethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3- butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, neopentyl glycol diacrylate, trimetholpropane triacrylate, trimetholpropane tri (acryloyloxypropyl) ether, trimethol ethane triacrylate, hexanediol diacrylate, 1 , 4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol Triacrylate, Sor And the like toll tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate.

Specific examples of the methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimetholpropane trimethacrylate, trimetholethane trimethacrylate, Ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate Acrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p -(Methacryloxy ethoxy) phenyl] dimethylmethane and the like.

Specific examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, Sorbitol tetrataconate and the like. Specific examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, and the like. Specific examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like. Specific examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate, and the like.

Examples of other esters include, for example, aliphatic alcohol esters described in Japanese Patent Publication No. 51-47334, Japanese Patent Publication No. 57-196231, Japanese Patent Publication No. 59-5240, Japanese Patent Publication No. 59-5241, Japan Those having an aromatic skeleton described in Japanese Patent Application Laid-Open No. 2-226149, those containing an amino group described in Japanese Patent Application Laid-Open No. 1-165613, and the like are also preferably used. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydramine compound and unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis- Methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and hydroxyl group is also preferable. As the specific example, the vinyl monomer which contains the hydroxyl group represented by following General formula (A) in the polyisocyanate compound which has two or more isocyanate groups in 1 molecule as described in Unexamined-Japanese-Patent No. 48-41708, for example is used. And a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule added.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)

(However, in general formula (A), R ⁴ and R ⁵ represent H or CH _3. )

Furthermore, urethane acrylates such as those described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293 and Japanese Patent Laid-Open No. 2-16765, and Japanese Patent Laid-Open No. 58-49860, and Japanese Patent Publication Also preferred are urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Application Laid-Open No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Furthermore, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecules described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238, The photocurable coloring composition excellent in the photosensitive speed can be obtained.

As other examples, the polyester acrylates, epoxy resins, and (meth) described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-30490, and each publication Polyfunctional acrylates and methacrylates, such as epoxy acrylate which made acrylic acid react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, Unexamined-Japanese-Patent No. 1-40336, the vinylphosphonic-acid type compound of Unexamined-Japanese-Patent No. 2-25493, etc. are also mentioned. Can be mentioned. Moreover, in some cases, the structure containing the perpooluroalkyl group of Unexamined-Japanese-Patent No. 61-22048 is used preferably. Japan Adhesives Association vol. 20, No. 7, 300 to 308 pages (1984) can also be used as photocurable monomers and oligomers.

About these addition polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, addition amount, etc. can be arbitrarily set according to the final performance design of a curable composition. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in many cases, bifunctional or more is preferable. Moreover, in order to raise the intensity | strength of a cured film, what is more than trifunctional is good, and also it uses sensitivity and other polymerizable groups (for example, acrylic ester, methacrylic ester, styrene type compound, and vinyl ether type compound) together. The method of adjusting both strengths is also effective.

The addition and use of the addition polymer compound are also important factors for compatibility and dispersibility with other components (e.g., photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) contained in the curable composition. For example, compatibility can be improved by using a low purity compound and using 2 or more types together. Moreover, a specific structure can also be selected for the purpose of improving adhesiveness with a board | substrate.

The photocurable coloring composition of the present invention is used together with the (1) specific initiator, (2) specific black pigment, and (3) a compound having an ethylenically unsaturated group capable of addition polymerization, as described above, and a sensitizer used as desired. As needed, you may further contain the optional component demonstrated in detail below. Hereinafter, the arbitrary components which can be used for this invention are demonstrated.

Binder Polymer

In the photocurable coloring composition of this invention, a binder polymer can be used together as needed for the purpose of the improvement of the film characteristics formed, and the like.

It is preferable to use linear organic polymer as a binder. As such a "linear organic polymer", a well-known thing can be used arbitrarily. Preferably, in order to enable water development or weakly alkaline water development, a linear organic polymer soluble or swellable in water or weakly alkaline water is selected. The linear organic polymer is selected and used not only as a film forming agent but also as a water, a weak alkaline water or an organic solvent developer. For example, the use of water-soluble organic polymers makes water development possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain (for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Application Publication 54-25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, Japanese Patent Laid-Open No. 59-71048, that is, a resin obtained by copolymerizing a monomer having a carboxyl group alone or in copolymerization, Resins obtained by hydrolyzing or half-esterifying or half-amidating an monomer having an acid anhydride alone or copolymerizing an epoxy anhydride, an epoxy acrylate modified with an unsaturated monocarboxylic acid and an acid anhydride, and the like). Can be. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxy styrene, and the like, and maleic anhydride and the like as the monomer having an acid anhydride.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group is useful.

When alkali-soluble resin is used as a copolymer, monomers other than the monomer previously mentioned can also be used as a compound to copolymerize. As an example of another monomer, the compound of following (1)-(13) is mentioned.

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl meth Acrylic acid esters having aliphatic hydroxyl groups such as acrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, and methacrylic acid esters.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, Alkyl acryl, such as 3, 4- epoxycyclohexyl methyl acrylate, vinyl acrylate, 2-phenyl vinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-acryloxy ethyl acrylate, and propargyl acrylate. Rate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Cyclohexyl, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1 Alkyl methacrylates such as propenyl methacrylate, allyl methacrylate, 2-aryloxyethyl methacrylate and propargyl methacrylate.

(4) acrylamide, methacrylamide, N-methyrolacrylamide, N-ethylacrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide , N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N- diallyl acrylamide, N, N- diallyl methacrylamide, allyl acrylamide, Acrylamide or methacrylamide, such as allyl methacrylamide.

(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 chloro acetate, vinyl butyrate, and vinyl benzoate.

(7) Styrene, such as styrene, (alpha) -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxy styrene.

(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-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid monomer in which a hetero atom is bonded to an α position. For example, the compound described in JP 2001-115595 specification, JP 2001-115598 specification, etc. are mentioned.

Among these, alkali-soluble resins having double bonds in the side chains described in (meth) acrylic resins having allyl groups, vinyl ester groups and carboxyl groups in the side chains and Japanese Patent Application Laid-Open Nos. 2000-187322 and 2002-62698; Alkali-soluble resin which has an amide group in the side chain described in Unexamined-Japanese-Patent No. 2001-242612 is preferable because it is excellent in the balance of film strength, a sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication A urethane-based binder polymer containing an acid group described in 63-287947, Japanese Patent Application Laid-Open No. 1-271741, Japanese Patent Application Laid-open No. Hei 10-116232, or the acid group and a double bond described in Japanese Patent Application Laid-Open No. 2002-107918. Since a urethane type binder polymer is very excellent in strength, it is advantageous at the point of chain resistance and low exposure suitability.

In addition, the acetal modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Laid-Open No. 2001-318463 and the like is preferred because of its excellent balance between film strength and developability.

Moreover, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as water-soluble linear organic polymer. Moreover, alcohol-soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane, and epichlorohydrin etc. are also useful in order to raise the intensity | strength of a hardened film.

Preferably the weight average molecular weight of the binder polymer which can be used by this invention is 5,000 or more, More preferably, it is the range of 10,000-300,000, The number average molecular weight becomes like this. Preferably it is 1,000 or more, More preferably, it is 2,000- It is in the range of 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably one or more, more preferably in the range of 1.1 to 10.

These binder polymers may be any of random polymers, block polymers and graft polymers.

The binder polymer which can be used by this invention can be synthesize | combined by a conventionally well-known method. As a solvent used at the time of synthesis, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy Ethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, lactic acid Methyl, ethyl lactate, dimethyl sulfoxide, water, etc. are mentioned. These solvent can be used individually or in mixture of 2 or more types.

As a radical polymerization initiator used when synthesize | combining the binder polymer which can be used in this invention, well-known compounds, such as an azo initiator and a peroxide initiator, are mentioned.

When using such a binder polymer, it is preferable that content is 0-50 mass% with respect to the mass of the total solid of a curable composition, More preferably, it is the range of 0-30 mass%.

Notary sensitizer

It is also preferable that the photocurable coloring composition of this invention contains a co-sensitizer. In the present invention, the sensitizer has an action of further improving the sensitivity of the sensitizing dye and the initiator to the active radiation, or inhibiting the polymerization inhibition of the polymerizable compound by oxygen.

Examples of such a sensitizer include amines such as MR Sanders, Vol. 10, pp. 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, The compound of Research Disclosure 33825, etc. are mentioned, Specifically, a triethanolamine, p-dimethylamino benzoic acid ethyl ester, p-formyldimethyl aniline, p-methylthio dimethyl aniline, etc. are mentioned.

As another example of a sensitizer, thiols and sulfides, for example, a thiol compound disclosed in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, Japan The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto- 4 (3H) -quinazolin, (beta) -mercaptonaphthalene, etc. are mentioned.

Other examples of the sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds described in JP-A-48-42965 (e.g., tributyltin acetate, etc.), JP-A-55-34414 Hydrogen donors described in Japanese Patent Application Laid-Open and sulfur compounds described in Japanese Patent Application Laid-open No. Hei 6-308727 (for example, trithiane).

As for content of these co-sensitizers, the range of 0.1-30 mass% is preferable with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the hardening rate by the balance of a polymerization growth rate and chain transfer, and is 1-25 mass% The range of is more preferable, and the range of 0.5-20 mass% is further more preferable.

<No Polymerization System>

It is preferable to add a small amount of thermal polymerization inhibitor to the photocurable coloring composition of the present invention in order to prevent unnecessary thermal polymerization of the compound having an ethylenically unsaturated double bond which can be polymerized during production or storage of the curable composition.

Examples of the thermal polymerization inhibitor which can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t-butylcatechol, benzoquinone, 4,4'-thio Bis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine first cerium salt, etc. are mentioned. have.

As for the addition amount of a thermal polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of the whole composition. Moreover, in order to prevent the inhibition of polymerization by oxygen, you may add higher fatty acid derivatives, such as behenic acid and behenic acid amide, etc., and may make it localize on the surface of the photosensitive layer in the drying process after application | 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 enhancer>

In order to improve adhesiveness with the hard surface (substrate) which is a base material, it is preferable to add an adhesion promoter to the photocurable coloring composition of this invention. As an adhesion promoter, a silane coupling agent, a titanium coupling agent, etc. are mentioned.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyl Trimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrier Methoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxy Ethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, Trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryl Oxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane, etc. are mentioned. Can be.

Especially, (gamma) -methacryloxypropyl trimethoxysilane, (gamma) -methacryloxypropyl triethoxysilane, (gamma) -acryloxypropyl trimethoxysilane, (gamma) -acryloxypropyl triethoxysilane, (gamma) -mercaptopropyl Trimethoxysilane, (gamma) -aminopropyl triethoxysilane, and phenyl trimethoxysilane are preferable, and (gamma) -methacryloxypropyl trimethoxysilane is the most preferable.

0.5-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of an adhesion improving agent, 0.7-20 mass% is more preferable.

<Other additives>

Moreover, in order to improve the physical property of a cured film, you may add well-known additives, such as an inorganic filler, a plasticizer, and a sensing agent which can improve the ink buildability of the photosensitive layer surface, to the photocurable coloring composition of this invention.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerine, and the like. In the case, 10 mass% or less can be added with respect to the total mass of a compound and an binder which have an ethylenically unsaturated double bond.

<Diluent>

When apply | coating the photocurable coloring composition of this invention on the support body at the time of manufacture of a color filter, you may be provided for use in the state melt | dissolved in various organic solvents.

As an organic solvent used here, 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 mono Methyl 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-meth 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 , And the like 3-methoxypropyl acetate, N, N- dimethylformamide, dimethyl sulfoxide, butyric γ- lactone, lactic acid, methyl, ethyl lactate.

These solvents can be used individually or in mixture. It is preferable that the density | concentration of solid content in the coating liquid formed by melt | dissolving the photocurable coloring composition of this invention in an organic solvent is 2-60 mass%.

[Color Filter]

Next, the color filter of this invention is demonstrated.

The color filter of this invention forms the photocurable colored layer which consists of a photocurable coloring composition on the surface of a glass support body, and pattern-exposes by means, such as through a mask, and develops the photocurable colored layer after exposure, and surface of a glass support body. It is obtained by forming a coloring pattern in.

Formation of a photocurable colored layer may apply | coat and dry a photocurable coloring composition to a glass support body, and may be formed, and also may form the sheet previously prepared by the photocurable coloring composition on the glass support body by the laminating method.

<Glass support>

As a support body which can be used for this invention, the soda glass used for a liquid crystal display element etc., Pyrex (trademark) glass, quartz glass, and the thing which adhered the transparent conductive film to these, or the photoelectric conversion element substrate used for an imaging element etc. For example, a silicon substrate, a complementary metal oxide film semiconductor (CMOS), etc. are mentioned. These substrates may be provided with black stripes separating the pixels.

Moreover, you may form a primer layer on these support bodies in order to improve adhesion with an upper layer, to prevent the spread of a substance, or to planarize the surface of a board | substrate as needed.

As a coating method of the curable composition concerning this invention on a support body, various coating methods, such as a slit application | coating, an inkjet method, a rotary application | coating, cast | coating application | coating, roll coating, and screen printing, can be applied.

The curable composition applied on the support is usually dried at 70 to 110 ° C. under a condition of about 2 to 4 minutes to form a layer made of the photocurable coloring composition.

0.1-10 micrometers is preferable, as for the coating film thickness after drying of a curable composition, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is more preferable.

The photocurable coloring composition of this invention hardens with high sensitivity by exposure, is excellent in the developability of the unexposed part after exposure, and shows high adhesiveness to the glass support surface to which a photocurable coloring composition is applied.

The color filter of this invention has a coloring pattern formed on the glass support body as mentioned above, It is characterized by the above-mentioned.

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. In the subsequent development step, only the coating film portion irradiated with light in the exposure step is cured, and the uncured region is developed with a developer. As a result, a patterned film made of black pixels can be formed. The patterned film is useful as a black matrix of a color filter. If necessary, pixels of different colors are formed by conventional methods. It is possible to manufacture the color filter of this invention by the above process.

The said developing process and an exposure process are demonstrated below.

Exposure process

In an exposure process, pattern exposure is performed by exposing the said photocurable colored layer through a mask, etc., and only the coating film part irradiated with light is hardened.

It is preferable to perform exposure by irradiation of a radiation. As radiation which can be used at the time of exposure, especially ultraviolet rays, such as g line | wire and i line | wire, are used preferably, and a high pressure mercury lamp is used more preferably. 5mJ / cm <2> -1500mJ / cm <2> is preferable, 10mJ / cm <2> -1000mJ / cm <2> is more preferable, and 10mJ / cm <2> -800mJ / cm <2> is the most preferable.

Development Process

Alkali image development is performed after an exposure process, and the tailings irradiation part in an exposure process is eluted to an alkali aqueous solution. As a result, only the photocured portion remains on the support.

As a developing solution, the organic alkali developing solution which does not cause damage to an underlying circuit etc. is preferable. Developing temperature is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

As an alkali used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dia The alkaline aqueous solution which diluted the organic alkaline compounds, such as xacyclo- [5,4,0] -7-undecene, with pure water so that a density | concentration may be 0.001-10 mass%, Preferably 0.01-1 mass% is used. Moreover, when using the developing solution which consists of such alkaline aqueous solution, generally the coloring pattern formed after image development is rinsed with pure water.

Moreover, in the manufacturing method of this invention, even after performing the curable composition layer formation process, exposure process, and image development process mentioned above, the hardening process of hardening the coloring pattern formed as needed by heating and / or exposure is included. do.

Thereafter, a photocurable colored layer having a different color is formed, and a series of processes of performing an exposure step and a developing step (and a curing step, if necessary) are repeated by a desired number of colors, thereby producing a color filter having a desired color.

In this invention, a color filter can be manufactured using the laminated body which has a layer which consists of a photocurable coloring composition which can form interaction with glass on a glass support body. Therefore, it is excellent in pattern formation property, and the formed coloring pattern shows high adhesiveness with a support substrate. Moreover, in the unexposed part, the film structure which consists of curable compositions has the outstanding uniformity, and it does not worry about generation | occurrence | production of the pigment which suppresses the permeability of a developing solution, and the aggregate of a photoinitiator, penetration of a developing solution is uniform, and it progresses rapidly and is high developability Indicates. Therefore, it is excellent in exposure sensitivity, the adhesiveness with the board | substrate of an exposure part is favorable, and the high resolution pattern without a residual film can be formed. Therefore, the said pattern can be used suitably as a black matrix of solid-state image sensors, such as a liquid crystal display element and CCD, and is especially preferable for a CCD element, CMOS, etc. of high resolution exceeding 1 million pixels. The color filter of this invention can be used as a color filter arrange | positioned, for example between the light receiving part of each pixel which comprises CCD, and the microlens for condensing.

EXAMPLE

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. In addition, unless otherwise indicated, "%" and "part" represent a "mass%" and a "mass part", respectively.

Example 1

Here, the example which prepares the photocurable coloring composition (alpha-1) containing a coloring agent (pigment), and manufactures the color filter for liquid crystal display element uses using the said curable composition (alpha-1) is demonstrated.

[1.Preparation of Photocurable Coloring Composition α-1]

1-1. Preparation of pigment dispersion (Q1): Black

As a pigment, 27 parts by mass of carbon black MA-220 (manufactured by Mitsubishi Kagaku Corporation, specific black pigment (A)) and a benzyl methacrylate / methacrylic acid copolymer (copolymer ratio 70/30 molar ratio, weight average molecular weight 30000) 8 The mixture liquid which consists of a mass part and 65 mass parts of propylene glycol monomethyl ether acetates was mixed and disperse | distributed by the bead mill for 20 hours, and pigment dispersion (Q1) was prepared.

It was 100 nm as a result of measuring the average particle diameter of the pigment about the obtained pigment dispersion (Q1) by the dynamic light scattering method.

1-2.Preparation of photocurable coloring composition (alpha) -1 (coating liquid)

<Composition α-1>

600 parts by mass of pigment dispersion (Q1)

Alkali Soluble Resin

(Benzyl methacrylate / methacrylic acid copolymer, mol ratio: 70/30,

 Mw: 10000) 190 parts by mass

40 parts by mass of dipentaerythritol hexaacrylate [polymerizable compound]

20 parts by mass of pentaerythritol triacrylate

80 parts by mass of compound 1 (following structure) [specific photopolymerization initiator]

Sympathetic agent: 30 parts by mass of N-phenyl-2-mercaptobenzoimidazole

Surfactant: 1 part by mass (trade name: Tetranic 150R1, BASF)

Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate

10 parts by mass of γ-methacryloxypropyltriethoxysilane

[2.Production of color filter]

2-1.Formation of Curable Composition Layer

After using the photocurable coloring composition (alpha) -1 containing the pigment obtained by making it into a resist solution and apply | coating a slit to the glass substrate of 550 mm x 650 mm on the following conditions, it was made to stand for 10 minutes, and it vacuum-dried and prebaking. (prebake) (100 degreeC 80 second) was performed, and the photocurable colored layer was formed.

(Slit application condition)

Gap between the openings of the dispensing head tip: 50 μm

Dispense Speed: 100mm / sec

Clearance of substrate and coating head: 150 μm

Coating thickness (dry thickness): 2 μm

Application temperature: 23 ℃

2-2 Exposure, phenomenon

Thereafter, the surface of the photocurable colored layer was exposed in a pattern through a mask using a 2.5 kW ultra-high pressure mercury lamp, and after exposure, the entire surface of the coating film was made of an organic developer (trade name: CD, manufactured by Fujifilm Arch Co., Ltd.). Covered with 10% aqueous solution and stopped for 60 seconds.

2-3.Heat Treatment

After stopping, the pure water was sprayed in the shower phase, the developer was wash | cleaned, and the coating film which performed the said photocuring process and image development process was heated in the oven of 220 degreeC for 1 hour (post bake). Thereby, the coloring pattern was formed on the glass substrate, and the color filter (black matrix) was obtained.

[3.Performance Evaluation]

Exposure pattern formability in the photocurable colored layer of the color filter laminated body formed on the glass substrate using the photocurable coloring composition (alpha) -1 (coating liquid) prepared above, and the coloring pattern in a color filter Substrate adhesiveness was evaluated as follows. The results are shown in Table 1.

3-1.Pattern formation of coating film (colored layer)

The photocurable coloring composition (alpha) -1 (coating liquid) was apply | coated on a glass substrate, and it dried and set it as 1.0 micrometer in film thickness. Spin coat conditions were made into 20 seconds at 800 rpm after 5 second at 300 rpm, and drying conditions were 80 seconds at 100 degreeC. Next, it exposed by 100 mJ / cm <2> exposure amount using the photomask for a test of 20 micrometers of line widths. Next, using a 60% CD-2000 (manufactured by FUJIFILM Electronics) developer, it developed at 25 degreeC until the residual film of an unexposed part completely disappeared. (The disappearance of a residual film shows the remaining state of a pigment component. Was done by checking with the dark field of). After rinsing with running water for 20 seconds, spray drying was completed to complete the pattern formation. The film thickness after image development of the area | region to which light was irradiated in the exposure process was measured, and the film | membrane reduction with respect to the film thickness 100% before exposure was evaluated by the following references | standards. The smaller the film reduction, the higher the exposure sensitivity, and the shorter the development time until reaching the state where no residual film is present (excellent developability), which indicates that the pattern formability is good.

○: 95% or more

△: less than 95 to 85% or more

×: Less than 85%

3-2. Pattern Formability 2 (Fine Line Reproducibility) of Coating Film (Coloring Layer)

The exposure amount of 80 mJ / cm <2> was exposed using the test photomask of 5 micrometers-20 micrometers of line | wire widths at the time of said exposure of 3-1. Next, 60% CD-2000 (manufactured by FUJIFILM Electronics Materials) developer was used, and developed at 25 ° C until the residual film of the unexposed part disappeared completely (disappearance of the residual film was determined by the optical microscope. In the dark field of the field). After rinsing with running water for 20 seconds, spray drying was completed to complete the pattern formation. In the exposure process, the film thickness after image development of the area | region to which light was irradiated confirmed the line | wire width holding 95% or more with respect to the film thickness 100% before exposure, and made it into the index of evaluation. The formation of a thin line width image in a state where the film reduction due to the phenomenon is small indicates that the fine line reproducibility is excellent.

○ 10 μm or less

Δ: 10-15 μm

X: 15-20 micrometers

3-3.Board Adhesion

Substrate adhesiveness was evaluated by confirming the coloring pattern in the color filter after post-baking by a conventional method by an optical microscope and SEM photograph observation. The detail of an evaluation method is as follows.

<Substrate adhesiveness>

As evaluation of board | substrate adhesiveness, it was observed whether the pattern defect and the clearance gap with a board | substrate generate | occur | produce. 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.

(Circle): A pattern defect and the gap with a board | substrate were not observed at all.

(Triangle | delta): Although a pattern defect was not observed and there exists an area | region where some clearance gap is seen between a board | substrate, it was a level which is satisfactory practically.

X: Pattern defect was observed clearly and it was the level which cannot be used practically.

EXAMPLES 2-12

In Example 1, at least 1 of the black pigment used for the specific initiator (compound 1) in the composition (alpha) -1 used for preparation of the photocurable coloring composition (alpha) -1, and the pigment dispersion (Q1) is shown in following Table 1 Except having replaced by losing, all the photocurable coloring compositions (alpha) -2-(alpha) -12 were prepared by the method similar to Example 1. Using these, the color filter which has a coloring pattern was obtained by the method similar to Example 1, respectively. Moreover, evaluation similar to Example 1 was performed. The results are shown in Table 1.

In addition, the structure of the specific initiator (compound 2-compound 4) used here is shown below.

The detail of the black pigment (for this invention product and comparison) of Table 1 is as follows.

[Specific Black Pigment (A): Uncoated Type] Specific Surface Area (m 2 / g) pH

           CB-1 24 8.8

              (Brand name: Asahi thermal, product of Asahi carbon company)

           CB-2 31 3.0

              (Brand name: MA-220, product of Mitsubishi Kagaku Corporation)

           CB-3 65 3.5

              (Brand name: SpecialBlack 350, product made in Degusa)

           CB-4 104 3.5

              (Brand name: MA-11, Mitsubishi Kagaku Corporation)

[Comparative black pigment: uncoated type] Specific surface area (m 2 / g) pH

           CBX-1 24 10.0

           (The CB-1 was immersed in 1N ammonia water for 24 hours and then pressurized.

           Filtration, dry)

           CBX-2 31 1.8

           (Pressure filtration after the CB-20 was immersed in 1N hydrochloric acid for 24 hours.

           After, dry)

           CBX-3 300 3.5

           (The CB-4 was mixed with pure water and a bead mill with a particle diameter of 1 mm at 10 o'clock.

           After liver treatment, filtered under pressure, and dried)

[Specific Black Pigment (B): Silica Covered Type]

CB-5: 10 g of carbon black (Mitsubishi Kagaku Co., Ltd. make, MA100), 200 ml of pure waters, and 1 g of concentrated hydrochloric acid were added, and it stirred, and the water dispersion was prepared. Tetraethoxysilane 1.0g was put into the water dispersion, and it heated at 60 degreeC for 3 hours. After the reaction, the mixture was filtered under pressure and dried to obtain silica coated carbon black CB-5.

[Specific Black Pigment (C): Resin Coating Type]

CB-6: To 100 parts by mass of carbon black (CI pigment black 7), an emulsion of an epoxy resin (12 parts by mass) and 2-ethyl-4-methylimidazole (2 parts by mass) are added to the epoxy resin. To form a coating layer to obtain a resin-coated carbon black CB-6.

Comparative Examples 1 to 12

In Example 1, at least 1 of the black pigment used for the specific initiator (compound 1) in the composition (alpha) -1 used for preparation of the photocurable coloring composition (alpha) -1, and the pigment dispersion (Q1) is shown in following Table 1 Except having replaced with the comparative initiator or the comparative black pigment, all the photocurable coloring compositions (beta)-(beta) -12 were prepared by the method similar to Example 1. Using these, the color filter which has a coloring pattern was obtained by the method similar to Example 1, respectively. Moreover, evaluation similar to Example 1 was performed. The results are shown in Table 1.

Moreover, the structure of the comparative photoinitiator [comparative compound 1-the comparative compound 4] used for the comparative example is shown below.

From the result of Table 1, the color filters of Examples 1-12 produced using the photocurable coloring composition containing a specific initiator and a specific black pigment are excellent in pattern formation property, especially fine wire reproducibility, and the board | substrate adhesiveness of the formed coloring pattern is excellent. By using this photocurable coloring composition of this invention, it is favorable that it has high exposure sensitivity, is excellent in developability, the formation of a high precision pattern, and it turns out that the color filter excellent in the board | substrate adhesiveness of the formed coloring pattern is obtained.

On the other hand, Comparative Examples 1-4 which used carbon black outside the range of this invention as a black pigment, or Comparative Examples 5-8, an initiator, and a black pigment which used the comparative compound outside the range of this invention as a photoinitiator are both in this invention. All of Comparative Examples 9-12 which are compounds outside the range are inferior in pattern formation property, fine wire reproducibility, and adhesiveness with a board | substrate compared with an Example.

As mentioned above, it turns out that the outstanding effect of this invention is acquired only by using the photocurable coloring composition of this invention containing both a specific initiator and a specific black pigment.

Claims (9)

As a photocurable coloring composition containing a photoinitiator, a black pigment, and the compound which has a polymerizable ethylenically unsaturated group: The photopolymerization initiator is represented by the following general formula (I); And The black pigment, (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) At least one selected from the group consisting of resin-coated carbon black, wherein the photocurable coloring composition.

In the formula, each of R ¹ and R ² independently represents a hydrogen atom, an alkyl group, an aryl group, 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, n each independently represent 0, 1 or 2:

In formula, R <^5> , R <^6> , R <^7> respectively independently represents an alkyl group or an aryl group. The photopolymerization initiator according to claim 1, wherein the photopolymerization initiator is 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine , 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl ) Aminophenyl] -2,6-di (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-ethoxycar Bonylmethylaminophenyl) -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-ethoxycarbonylmethylamino Phenyl) -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 -(o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6- Halogen atom on di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, and phenyl moiety Two or more triazines introduced It contains at least one selected from the group consisting of a photocurable coloring composition. The photocurable colored composition according to claim 1, wherein the black pigment contains the carbon black (A) having a specific surface area of 24 to 104 m 2 / g and a pH of 3.0 to 8.8. The photocurable coloring composition according to claim 2, wherein the black pigment contains (A) carbon black having a specific surface area of 24 to 104 m 2 / g and a pH of 3.0 to 8.8. 2. The black pigment according to claim 1, wherein the black pigment contains (B) silica-coated carbon black having a silica amount of 1 to 40% by weight in terms of SiO _{2 relative} to the total amount of (B) silica-coated carbon black. Photocurable coloring composition. 3. The black pigment according to claim 2, wherein the black pigment contains (B) silica-coated carbon black in which the silica amount relative to the total amount of (B) silica-coated carbon black is in the range of 1 to 40% by weight in terms of SiO _2. Photocurable coloring composition. The black pigment of claim 1, wherein the black pigment is an epoxy resin, a phenol resin, a melamine resin, a xylene resin, a diallyl phthalate resin, a glyphtal resin, an alkylbenzene resin, a polystyrene, a polycarbonate, a polyethylene terephthalate or a polybutylene terephthalate. , Modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, and polyether ether ketone A photocurable coloring composition comprising (C) resin coated carbon black coated with a resin containing one or more selected from. The method of claim 2, wherein the black pigment is epoxy resin, phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate , Modified polyphenylene oxide, polysulfone, polyparaphenylene telephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, and polyether ether ketone (C) resin coating carbon black coated with resin containing one or more selected from the group, The photocurable coloring composition characterized by the above-mentioned. A color filter comprising a glass support and a coloring pattern formed on the glass support: The coloring pattern, An exposure step of pattern-exposing the laminate having the photocurable colored layer made of the photocurable colored composition according to any one of claims 1 to 8, and curing the exposure region of the photocurable colored layer; And A color filter formed by a method including a developing step of forming the colored pattern by developing the laminated body having completed exposure and removing unexposed regions.