TW201300945A - Colored photosensitive composition, method for manufacturing color filter, color filter, and liquid crystal display device - Google Patents

Abstract

The invention relates to a colored photosensitive composition which comprises (A) a color material having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, (E) a photopolymerization initiator and (F) a polymerizable compound having radical scavenging ability; a color filter using the colored photosensitive composition; and a liquid crystal display device provided with the color filter.

Description

Coloring photosensitive composition, method for producing color filter, color filter, and liquid crystal display device

The present invention relates to a colored photosensitive composition which has high transparency of a color material and which can maintain excellent light resistance and developability and solvent resistance while maintaining the color purity, and color contained in the colored pattern. A filter, a method of manufacturing a color filter, and a liquid crystal display device.

In the past, if it is a small-sized liquid crystal display device such as a mobile phone, a portable game machine, or a PDA (personal digital assistant), it is necessary to use a backlight source having a limited capacitance such as a secondary battery or a dry battery, and the display can be used. The color material of the color filter of the device has always advantageously used a color material which has high transparency and can transmit the bright line of the backlight well to display the color.

In recent years, the enlargement of liquid crystal display devices has progressed in applications such as liquid crystal display monitors for personal computers, liquid crystal televisions, and the like. For such liquid crystal display devices, there is no longer a backlight power supply limitation, and display devices are The RGB color reproduction is taken seriously. Therefore, for the color material of the color filter, in addition to the previous transparency, higher image quality, that is, contrast, and improvement in color purity are required.

In response to the above requirements, a color filter has been developed and put into practical application, which is a pigment composition which refines the particle size of the pigment, together with an alkali-soluble resin, a photopolymerizable compound, and light. The polymerization initiator and other components are used as a coloring composition, and a three-color pattern of red, green, and blue is formed on a transparent substrate such as glass by a photolithography method or the like.

For the green coloring pattern, from the viewpoint of color tone and fastness, it is usually green such as copper chloride phthalocyanine pigment (CI pigment green 7) or copper bromine copper phthalocyanine pigment (CI pigment green 36). pigment. In recent years, in order to improve the chroma (color purity and color density) of pigments, it has been reviewed that the central metal is not copper, but is a polyhalogenated metal such as aluminum, titanium, cobalt, nickel, zinc, tin or lead. Cyanine pigments, in particular, have been proposed for various pigments in the case of poly-halogenated zinc phthalocyanine pigments (CI Pigment Green 58) having a high chroma. For example, the degree of substitution of Br, Cl (see, for example, Patent Document 1 or 2), the pigment treatment method using a betaine type surfactant, various crystal forms, and the like have been progressed, and reports indicate that: In the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2°) of the Cu-Kα line is 26.4° or 25.5°, and the maximum diffractive peak has a large chromatographic copper phthalocyanine system with high chroma (color purity and The color density is useful because it is excellent in stability over time (see, for example, Patent Document 3). Further, it has been revealed that a color filter having high transparency and high color purity can be obtained by using such pigments.

On the other hand, color filters are required to have light resistance to avoid fading and discoloration due to light from the backlight. In order to improve the light resistance, there has been a colored photosensitive composition which has been improved by the color material itself (see, for example, Patent Documents 4 to 6), or a colored photosensitive composition which is added with a compound such as a matting agent or a light stabilizer. (See, for example, Patent Documents 7 and 8). Further, there is also a report of a polymerizable monomer which can improve light resistance (see, for example, Patent Document 9), but there is no report of an example in which a polymerizable monomer is used for a color filter and a coloring photosensitive composition.

In general, when the dye is inferior in light resistance as compared with the pigment, the dye is always actively and repeatedly improved in light resistance. However, it is known that the light resistance is deteriorated in order to improve the brightness of the pigment. Therefore, for the above pigments, it is required to maintain high transparency and high color purity. Improve light resistance.

[Previous Technical Literature] (Patent Literature)

(Patent Document 1) Japanese Patent Laid-Open Publication No. 2003-161823

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2007-284592

(Patent Document 3) Japanese Patent Laid-Open Publication No. 2008-24743

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2008-138037

(Patent Document 5) Japanese Patent Laid-Open Publication No. 2009-149779

(Patent Document 6) Japanese Patent Laid-Open Publication No. 2009-215380

(Patent Document 7) Japanese Patent Laid-Open Publication No. 2000-214580

(Patent Document 8) Japanese Patent Laid-Open Publication No. 2004-139050

(Patent Document 9) Japanese Patent Laid-Open Publication No. 2004-155812

The present invention has been made in view of the above problems, and an object thereof is to provide a coloring photosensitive composition for a color filter which can form a coloring pattern excellent in light resistance. Further, the coloring photosensitive composition is used to provide a color filter excellent in light resistance and excellent in color characteristics, and a method for producing the color filter and a liquid crystal display device are provided.

The inventors of the present invention have intensively studied the results to solve the above problems, and found that by adding a polymerization having a radical scavenging capacity to a colored photosensitive composition using a color material having a phthalocyanine skeleton. The present invention can be finally achieved by a compound which can remarkably improve the above problems.

That is, the present invention is as follows.

<1> A colored photosensitive composition comprising: (A) a color material having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, and (E) light a polymerization initiator and (F) a polymerizable compound having a radical trapping energy.

<2> The colored photosensitive composition of the item <1>, wherein the content of the (F) polymerizable compound having a radical trapping energy is 0.1% by mass or more and 5.0% by mass or less based on the total solid content.

<3> The colored photosensitive composition according to the item <1> or <2>, wherein the (F) polymerizable compound having a radical trapping energy has an amine structure or a phenol structure.

The colored photosensitive composition according to any one of <1> to <3> wherein the (F) polymerizable compound having a radical trapping energy is selected from the group consisting of acrylonitrile and methacrylium. At least one of the groups serves as a polymerizable group.

The colored photosensitive composition according to any one of the items <1> to <4> wherein the (F) polymerizable compound having a radical trapping energy is selected from the following formula (1), ( At least one of 5) and (6):

In the above formulae (1), (5) and (6), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group, a hydroxyl group, and a carbon number of 10 The following alkyl group, an alkoxycarbonyl group having a carbon number of 10 or less, an alkylsulfonylaminocarbonyl group having a carbon number of 10 or less, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group a fluorenylaminosulfonyl group having a carbon number of 10 or less, an alkoxy group having a carbon number of 10 or less, an alkylthio group having a carbon number of 10 or less, an aryloxy group having a carbon number of 10 or less, or a nitro group An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a decyloxy group having a carbon number of 10 or less, a mercapto group having a carbon number of 10 or less, an amine methyl sulfonyl group, an amine sulfonyl group, and a carbon number of 10 or less. An aryl group, a substituted amine group, a substituted ureido group, a substituted phosphonic acid group, or a heterocyclic group; R ⁴ is a hydrogen atom or an alkyl group having a carbon number of 30 or less; R ⁵ and R ⁶ are each Independently represents a branched alkyl group having a carbon number of 30 or less; X is an aliphatic alkyl chain representing a single bond, an ester group, a carbon number of 30 or less, an aromatic chain, a polyethylene glycol chain, or a combination thereof The (m+n) valence linkage; m and n are An integer of from 1 to 3 independently represents.

The colored photosensitive composition according to any one of <1> to <5> wherein at least one of the (A) color materials contains a metal in a chemical structure.

The colored photosensitive composition according to any one of <1> to <6> wherein at least one of the (A) color materials is a green pigment.

The colored photosensitive composition according to any one of the items <1> to <7>, wherein at least one selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 is contained. As the (A) color material.

<9> A method of producing a color filter, comprising the steps of: applying a colored photosensitive composition according to any one of items <1> to <8> to a substrate to form a colored layer; After the colored layer is exposed in a pattern, the uncured portion is removed by the developer to form a colored pattern.

<10> A color filter manufactured according to the manufacturing method of the item <9>.

<11> A liquid crystal display device comprising the color filter of item <10>.

By using the colored photosensitive composition of the present invention, a colored pattern excellent in light resistance can be obtained. Further, a color filter and a liquid crystal display device which are excellent in light resistance and excellent in light resistance can be obtained.

[Best Embodiment of the Invention]

Hereinafter, the colored photosensitive composition of the present invention, a color filter using the colored photosensitive composition, and a liquid crystal display device using the color filter will be described in detail.

<Coloring photosensitive composition>

The colored photosensitive composition of the present invention comprises at least: (A) a color material having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, and (E) photopolymerization initiation. And a color-sensitive photosensitive composition of (F) a polymerizable compound having a radical trapping ability.

Hereinafter, the components constituting the colored photosensitive composition of the present invention will be described.

<(A) Color material having a phthalocyanine skeleton>

In the case of the colored photosensitive composition of the present invention, since the color material is a color material having a phthalocyanine skeleton, a color filter having a high color purity or a high contrast can be obtained.

The color material having a phthalocyanine skeleton may have up to 16 hydrogen atoms by a bromine atom and/or a chlorine atom because it has 16 hydrogen atoms in the phthalocyanine ring. These halogen atoms may all be the same or different.

The number of substitution of the halogen atom is preferably 8 or more and 16 or less, and more preferably 10 or more and 16 or less.

It is preferable that at least one of the (A) color materials is a green pigment, and the phthalocyanine-based green pigment is suitable for use because it is substituted with eight or more bromine atoms to have a yellow color with high luminance. The green pixel pattern of the color filter. In particular, those having a substitution number of bromine atoms of 10 to 16 are suitable for use in the present invention because of their higher brightness.

In the present invention, in particular, from the viewpoint of obtaining a color of high luminance, at least one of the above (A) color materials preferably contains a metal in a chemical structure, and is intended to use a metal flower in the center portion. Phthaakocyanine pigment.

The center metal is not particularly limited as long as it can maintain the stability of the color material, and is preferably copper, aluminum, titanium, cobalt, nickel, zinc, tin, lead, etc., and from the viewpoint of saturation, It is preferably a zinc-containing one.

The phthalocyanine pigment can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method. A more specific production method is disclosed in Japanese Laid-Open Patent Publication No. 2008-19383, JP-A-2007-320986, and JP-A-2004-70342.

Among these, from the viewpoint of cost, a zinc halide phthalocyanine pigment disclosed in Japanese Laid-Open Patent Publication No. 2004-70342 is preferably used. Further, in terms of stability, it is preferably a crystal-converted zinc halide phthalocyanine pigment disclosed in Japanese Laid-Open Patent Publication No. 2008-19383, although it is a combination of other additives or subsequent steps. Further, in order to improve the dispersibility, a preferred mode is a resin-coated zinc halide phthalocyanine pigment disclosed in Japanese Laid-Open Patent Publication No. 2007-320986.

Specific examples of the above (A) color material include C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, and the like.

The average primary particle diameter of the phthalocyanine pigment of the present invention is preferably in the range of 10 nm to 100 nm, more preferably in the range of 10 nm to 70 nm. By using the phthalocyanine pigment having an average primary particle diameter in this range, it is possible to obtain a coloring photosensitive composition for a color filter having excellent dispersibility stability or coloring power and high luminance and high contrast.

Further, in the present invention, the "average primary particle diameter" is obtained by photographing particles in a field of view using a transmission electron microscope, and measuring the primary particles of 100 phthalocyanine pigments constituting agglomerates on a two-dimensional image. The average of the long diameter (long diameter) and the shorter one (short diameter) is averaged and averaged.

Further, in the primary particles of the phthalocyanine pigment of the present invention, if the aspect ratio of the aspect ratio is in the range of 1 to 3, the viscosity characteristics can be improved in each application field, and the fluidity can be made higher. In order to measure the aspect ratio, the particles in the field of view were photographed using a transmission electron microscope or a scanning electron microscope in the same manner as in the case of measuring the average particle diameter of the primary particles as described above. Further, in the primary particles of the 100 aggregates on the two-dimensional image, the average of the long diameter (long diameter) and the shorter one (short diameter) are measured and calculated from the values. Got it.

If a phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 100 nm is to be obtained, it may be a microparticle obtained by any method, but the crystal growth can be easily suppressed, and an average primary particle can be obtained. From the viewpoint of a smaller diameter pigment particle, it is preferred to use a solvent salt milling treatment.

The solvent salt polishing is a kneading and grinding of a phthalocyanine pigment, an inorganic salt, and an organic solvent. The phthalocyanine pigment having a large particle size can be first subjected to dry grinding and then subjected to solvent salt polishing. Specifically, the phthalocyanine pigment, the inorganic salt, and the organic solvent insoluble therein are fed to a kneader and kneaded and ground therein. At this time, the kneader can be, for example, a kneader or a Mahler mixer or the like.

The inorganic salt is preferably a water-soluble inorganic salt, and an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate is preferably used. Further, it is more preferred to use an inorganic salt having an average particle diameter of 0.5 to 50 μm. Such an inorganic salt can be obtained by finely pulverizing a general inorganic salt.

In order to obtain a phthalocyanine pigment having an average primary particle diameter in the range of 10 nm to 100 nm, it is preferred to increase the ratio of the use amount of the inorganic salt in the solvent salt polishing with respect to the amount of the phthalocyanine pigment used. That is, the amount of the inorganic salt used is preferably from 5 to 20 parts, more preferably from 7 to 15 parts, per part by mass of the phthalocyanine pigment.

The organic solvent is preferably an organic solvent which inhibits crystal growth, and the organic solvent is preferably a water-soluble organic solvent, and for example, diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol can be used. , 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol , dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol and the like.

The amount of the water-soluble organic solvent to be used at this time is not particularly limited, and is 0.01 to 5 parts by weight, preferably 0.8 to 2 parts, per part by mass of the phthalocyanine pigment.

The temperature at which the solvent salt is ground is preferably from 30 to 150 ° C, more preferably from 80 to 100 ° C. The solvent salt milling time is preferably from 5 to 20 hours, more preferably from 8 to 18 hours.

Thereby, a mixture containing a phthalocyanine pigment, an inorganic salt, and an organic solvent as a main component can be obtained by removing an organic solvent and an inorganic salt from the mixture, and if necessary, a solid having a phthalocyanine pigment as a main component By washing, filtering, drying, pulverizing, etc., a finer phthalocyanine pigment powder can be obtained.

Washing can be either water washing or hot water washing. The number of washings can be repeated in the range of 1 to 5 times. In the case where the aforementioned mixture of a water-soluble inorganic salt and a water-soluble organic solvent is used, the organic solvent and the inorganic salt can be easily removed by washing with water.

The above-mentioned filtration separation and washing after washing are, for example, batch or continuous type in which dehydration and/or solvent removal of the pigment is carried out by heating at 80 to 120 ° C in a heating source of the dryer. Drying, etc., the dryer is usually a box dryer, a belt dryer, a spray dryer, and the like. Further, the pulverization after drying is not an operation of increasing the specific surface area or reducing the average particle diameter of the primary particles, but is, for example, a case where the pigment is turned into a lamp or the like in the case of drying using a box dryer or a belt dryer. In the case of powdering for unwinding the pigment, for example, pulverization using a mortar, a hammer mill, a disc mill, a tip-type ball mill, a jet mill, or the like is used.

The toner having the (A) phthalocyanine skeleton of the present invention can be obtained by, for example, the above-described method, but a commercially available general-purpose pigment or pigment dispersion product can also be usually used.

By the coloring agent having the (A) phthalocyanine skeleton obtained as described above, since the aggregation property of the primary particles is weak and the property is more easily unwound, the covering power becomes large, and the colored film having high contrast can be easily produced.

In the present invention, these phthalocyanine pigments may be used singly or in combination of several kinds. In the case of use in combination, other halogenated phthalocyanine pigments having different bromination ratios or chlorination ratios or brominated phthalocyanines having different central metals may be used in combination. By changing the bromination rate and the chlorination rate, or changing the center metal, the color tone of the pigment changes, so that a change in the hue which is more reproducible can be expected.

In the colored photosensitive composition of the present invention, the color material of the (A) phthalocyanine skeleton can be combined with other color materials, and the hue of the coloring photosensitive composition can be adjusted to increase the transmittance.

For example, it is possible to form a green pixel and a phthalocyanine green pigment with a yellow pigment or an orange pigment. Examples of the "yellow pigment" are yellow pigments such as a disazo-based yellow pigment, an isoporphyrin-based yellow pigment, a quinophthalone-based yellow pigment, a benzimidazolone-based yellow pigment, and a nickel azo-based yellow pigment. An orange pigment such as a diketopyrrolopyrrole orange pigment or a purple ringtone orange pigment may be used as needed.

Specific examples thereof are: CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214; and CI Pigment Orange 2, 5, 13, 16, 17:1 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, and the like.

Among these, CI Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154 are preferred. 166, 173, 180, 185, etc., more preferably CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 138, CI Pigment Yellow 139.

In particular, when C.I. Pigment Yellow 150, C.I. Pigment Yellow 138, and C.I. Pigment Yellow 139 are used, it is preferred because of high transmittance and high contrast.

Further, in order to form a blue pixel, a phthalocyanine blue pigment may be used in combination with a purple pigment. Examples of "purple pigments" include: quinacridone violet pigments, It is a purple pigment, an anthraquinone violet pigment, an indigo purple pigment, It is a purple pigment.

Specific examples include: C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, in particular, since C.I. Pigment Violet 23 has high transmittance and high contrast, it is preferred.

When the average primary particle diameter of these pigments is in the range of 10 nm to 40 nm, the transmittance is high and the contrast is high, so that it is preferable. More preferably in the range of 10 nm to 30 nm. In order to make the average primary particle diameter small and fine, the salt milling method similar to phthalocyanine is effective, and salt grinding may be performed together with the phthalocyanine pigment, or salt milling may be performed individually.

The average primary particle diameter was measured by SEM (scanning electron microscope) or TEM (transmission electron microscope), and 100 particle sizes were measured in a portion where the particles were not aggregated, and the average value was calculated.

In the colored photosensitive composition of the present invention, the total amount of the pigment containing the phthalocyanine pigment is a total amount other than the solvent (B) in comparison with the coloring photosensitive composition of the present invention (hereinafter, "coloring photosensitive" The total amount of the constituents other than the solvent (B) is referred to as "total solid content", and is preferably 5 to 60%, more preferably 10 to 50%, and most preferably 15 to 45 in terms of mass. %. By using the added amount in this range, a color filter excellent in color characteristics, high in contrast, and high in luminance can be obtained.

<Pigment Dispersion Composition>

In the preparation of the colored photosensitive composition of the present invention, a preferred mode is to previously (A) a pigment having a phthalocyanine skeleton and other color materials dispersed together or separately to form a pigment dispersion composition.

The pigment dispersion composition is one in which the pigment and the solvent are dispersed, but a dispersant, a resin or the like may be added if necessary. Further, if necessary, it can be further used by using other components such as a pigment derivative.

- Modulation of pigment dispersion composition -

The modulation mode of the pigment dispersion composition of the present invention is not particularly limited. For example, a vertical or horizontal sand grinder, a tip-type ball mill, a roll shear, and an ultrasonic disperser can be used for the pigment, the pigment dispersant and the solvent. Alternatively, it is obtained by subjecting beads composed of glass, zirconium oxide or the like having a particle diameter of 0.01 to 1 mm to a microdispersion treatment.

Two roll type, three roll type, ball mill, drum mill, disperser, kneader, co-kneader, homogenizer, blender, uniaxial or biaxial extrusion can also be used before performing bead dispersion. A press or the like is subjected to a kneading dispersion treatment while imparting a strong shearing force.

Further, detailed details regarding kneading and dispersion are disclosed in "Paint Flow and Pigment Dispersion" by T. C. Patton (published by John Wiley and Sons, 1964) and the like.

- Pigment concentration -

The content of the pigment in the pigment dispersion composition is preferably from 10 to 60% by mass, more preferably from 15 to 50% by mass, based on the total solid content (mass) of the composition. When the content of the pigment is within this range, it is effective in securing a sufficient color density and excellent color characteristics.

-Dispersant-

The pigment dispersion composition preferably contains at least one dispersant. Since the dispersant is contained, the dispersibility of the pigment can be improved.

The dispersant can be suitably used, for example, by a conventional pigment dispersant or surfactant.

Specifically, a wide variety of compounds can be used, and examples thereof include, for example, an organic polyoxyalkylene polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and a (meth)acrylic acid system. (Total) polymer POLYFLOW No. 75, No. 90, No. 95 (Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.) "Cational surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether "Non-ionic surfactant" such as polyethylene dilaurate, ethylene glycol distearate, and sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) "Anionic surfactant"; "amphoteric surfactant" having a carboxylbetaine structure, a guanylamine betaine structure, a sulfobetaine structure, a hydroxybetaine structure, etc.; MEGAFACE F171, F172, F173 (Daichi ink) "Fluorine-based surfactant" manufactured by the chemical industry (Dainippon Ink and Chemicals, Inc.); EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (all manufactured by BASF Japan Ltd. (formerly known as Ciba Specialty Chemicals Co., Ltd.) ), DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (all manufactured by San Nopco Co., Ltd.) and other "polymer dispersants"; SOLSPERSE 3000, 5000, 9000, Various SLOSPERSE dispersants (manufactured by Lubrizol Japan, Ltd.) of 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc.; Adekapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by ADEKA Corporation) and ISONET S-20 (Sanyo Chemical Industries) Co., Ltd.), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (BYK Chemie Corp.). Other examples include an acrylate-based copolymer, an oligomer or a polymer having an N,N-disubstituted amine group or a polar group such as an acidic group at a molecular terminal or a side chain, and a tertiary amine modification. The polyurethane resin of the type, the AB type, ABA type block copolymer, etc. which are described in Unexamined-Japanese-Patent No. 2009-52010.

The content of the dispersant in the pigment dispersion composition is preferably from 1 to 100% by mass, more preferably from 3 to 70% by mass, based on the total mass of the pigment.

-Pigment derivatives -

The pigment dispersion composition is a pigment derivative which can be added as needed. A portion having affinity with a dispersing agent or a pigment derivative introduced into a polar group is adsorbed on the surface of the pigment, and this is used as a absorbing portion of the dispersing agent, whereby the pigment can be dispersed in the coloring photosensitive particle by fine particles. The composition is effective in preventing re-aggregation, which is a color filter excellent in contrast and excellent in transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a matrix and an acidic group or a basic group or an aromatic group is introduced as a substituent in a side chain. Specific examples of the organic pigment include a quinophthalone pigment, a phthalocyanine pigment, an azo pigment, a quinophthalone pigment, an isoporphyrin pigment, an isoindolinone pigment, and a quinoline. Pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, and the like. Generally not called pigment naphthalene, lanthanide, trinitrogen Light yellow aromatic polycyclic compounds such as a system or a quinoline system are also included. A pigment derivative can be used, for example, in Japanese Laid-Open Patent Publication No. H11-49974, JP-A-H11-189732, JP-A No. Hei 10-245501, JP-A-2006-265528, and JP-A No. 8-295810 The above is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The content of the pigment derivative in the pigment dispersion composition is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, based on the mass of the pigment. When the content of the pigment derivative is within this range, although the viscosity of the pigment dispersion composition is lowered, the dispersion can be favorably performed, and the dispersion stability after dispersion can be improved.

Thereby, since a colored photosensitive composition having high transmittance and excellent color characteristics can be obtained, when the colored photosensitive composition is applied to, for example, a color filter manufacturing use, good color characteristics can be obtained. Contrast to a high color filter.

In addition, a polymer compound such as an alkali-soluble resin to be described later may be added to the pigment dispersion composition. It can be said that the polar group such as an acid group contained in the alkali-soluble resin is also effective for the dispersion of the pigment, and is most effective for the dispersion stability of the pigment dispersion liquid.

- solvent -

The solvent in the pigment dispersion composition is not particularly limited as long as it is an organic solvent generally used for the pigment-dispersible composition. Examples thereof include, for example, 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, and acetic acid. Ester, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, The solvent such as toluene or xylene may be used in combination with the melting point, the viscosity, and the dispersibility of the pigment.

The content of the solvent in the pigment dispersion composition is appropriately selected depending on the use of the pigment dispersion composition and the like. When the pigment dispersion composition is used to prepare a colored photosensitive composition to be described later, it may contain a solid component concentration (in a pigment dispersion composition) from the viewpoint of handling properties. The total amount excluding the solvent is regarded as a solid component) to be 5 to 50% by mass.

In the coloring composition of the coloring photosensitive composition of the present invention, the content of the pigment is preferably in the range of 5 to 70% by mass based on the total solid content (mass) of the coloring photosensitive composition. The amount, more preferably, will be in the range of 15 to 60% by mass. When the content of the pigment dispersion composition is within this range, it is effective in ensuring sufficient color density and excellent color characteristics.

<(B) Solvent>

The colored photosensitive composition of the present invention is usually prepared by using a solvent together with the above components.

The solvent may, for example, be an "ester" such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate or isopropyl butyrate. Ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxy Ethyl acetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-oxyl 3-methylpropionate and ethyl 3-oxypropionate Alkyl propionates (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxopropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate) , ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2-methyl Methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2-methylpropionic acid Ester), as well as methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate, methyl 2-oxobutanoate, 2-oxobutoxybutyric acid Ethyl esters, etc.; "ethers" such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl sulphate acetate, ethyl celecoxib acetate Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, etc.; Examples of the "ketone" include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; and "aromatic hydrocarbons" such as toluene and xylene.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl sarbutazone acetate, ethyl lactate, diethylene glycol dimethyl ether, and acetic acid are preferred. Butyl ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and the like.

The solvent may be used singly or in combination of two or more.

<(C) Polymerizable monomer>

In the present invention, the curing component of the colored photosensitive composition is a polymerizable monomer.

The polymerizable monomer of the present invention is not particularly limited as long as it is polymerizable, and a low molecular compound, a dimer, a trimer, an oligomer or the like having at least one ethylenic double bond can be used. A polymerizable compound can be added.

Examples of the "ethylenic compound" include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monovalent hydroxy compound, an ester of an aliphatic polyvalent hydroxy compound and an unsaturated carboxylic acid, an aromatic polyvalent hydroxy compound and an unsaturated carboxylic acid. An ester, an ester obtained from an esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid, a polyvalent hydroxy compound such as a fatty acid polyvalent hydroxy compound or an aromatic polyvalent hydroxy compound, a polyisocyanate compound, and a (meth) propylene hydride containing An olefinic compound having a urethane skeleton and the like which are reacted with a hydroxy compound.

The specific polymerizable compound can be classified according to the number of polymerizable groups in one molecule as shown below, but is not limited thereto.

[Compound having a polymerizable group in one molecule]

Examples thereof include hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and 4-n-butyl (meth)acrylate. Cyclohexyl ester, borneol (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyl diglycol (meth)acrylate, (methyl) Butoxyethyl acrylate, 2-chloroethyl (meth)acrylate, cyanoethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-(meth)acrylate Methoxyethoxy)ethyl ester, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-perfluorodecyl methacrylate, benzyl (meth)acrylate Ester, 2,3,4,5-tetramethylphenyl (meth)acrylate, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, (meth)acrylic epoxy Propyl ester, glycidoxybutyl (meth)acrylate, glycidoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (methyl) propyl 3-hydroxypropyl enoate, poly(meth)acrylic acid oxirane monomethyl ether ester, (meth)acrylic acid oligo-oxirane monomethyl ether ester, poly(meth)acrylic acid ethylene oxide Ester, (meth)acrylic acid oligo-oxirane ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, EO-modified (meth)acrylic acid phenolate, EO modified ( Methyl) cresyl acrylate, EO modified (meth) methacrylate, PO modified methacrylate (meth) acrylate, EO modified - (meth) acrylate 2 -ethylhexyl ester and the like.

[Compounds having two polymerizable groups in one molecule]

Examples of the compound having two (meth)acryl fluorenyl groups in the same molecule as a polymerizable group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and di(methyl). ) Triethylene glycol acrylate, polyethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, two 1,6-hexanediol (meth)acrylate, neopentyl glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, di(methyl) Propylene triacrylate propylene glycol, propylene glycol di(meth)acrylate, 2-hydroxy-1,3-dipropoxypropane, 2,2-bis[4-(acryloxyethoxy)phenyl] Propane, 2,2-bis[4-(propyleneoxydiethoxy)phenyl]propane, bis(acryloxyethyl)ether of bisphenol A, bisphenol A type epoxy resin (methyl Acrylic acid modified product, 3-methyl pentyl glycol di(meth)acrylate, 2-hydroxy-3-propenyl propyl methacrylate, dimethylol-tricyclomethyl bis(meth)acrylate An alkyl ester or the like; preferably dimethylol-tricyclodecyl di(meth)acrylate, di(methyl) Neopentyl glycol acrylate, ethoxylated di(meth)acrylic acid bisphenol A ester, bisphenol A type epoxy resin (meth)acrylic acid modified product, and the like.

[Compound having three polymerizable groups in one molecule]

For example, trimethylolpropane tris(meth)acrylate, trimethylolethane tris(meth)acrylate, trimethylolpropane tris(meth)acrylate modified with alkylene oxide , pentaerythritol tri(meth)acrylate, dineopentyl tris(meth)acrylate, trimethylolpropane tris((meth)acryloxypropyl)ether, alkylene oxide Modified tris(meth)acrylic acid isocyanurate, trispentaerythritol propionate, and tris(meth)propenyloxyethyl ester Trimethylolpropane tris(meth)acrylate modified with hydroxytrimethylacetaldehyde, sorbitan tris(meth)acrylate, trimethylolpropane tris(propyl)acrylate , ethoxylated glyceryl triacrylate, and the like.

[Compound having four or more polymerizable groups in one molecule]

Examples of the "compound having four or more polymerizable groups in one molecule" include, for example, neopentyl glycol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, and tetrakis(tetra)(meth)acrylate. Hydroxymethylpropane ester, dipivalaerythritol tetra(meth)acrylate, neopentyl glycol ethoxylate (meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, sorbitan penta(meth)acrylate, sorbitol hexa(meth)acrylate, hexamethylene (meth) acrylate phosphate creatinine modified with alkylene oxide Ester, hexamethylene hexa(meth) acrylate modified by caprolactone, urethane acrylate of UA-306H, UA-306T, UA-306I, etc., manufactured by Kyoeisha Chemical Co., Ltd. ester.

When the total solid content of the colored photosensitive composition of the present invention is 100% by mass, the mixing amount of the polymerizable monomer is 5 to 80% by mass, preferably 10 to 60% by mass, more preferably 15 to 50% by mass. The range of %.

Among these, from the viewpoint of maintaining appropriate solvent resistance or ITO sputtering suitability in the subsequent step, it is preferred to have two or more (meth) acrylonitrile groups in the same molecule. The acrylate monomer is more preferably one having three or more polymerizable groups. In particular, it is advantageous to have four or more polymerizable bases, such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or a mixture thereof (mixed ratio of mass ratio of dipentane pentoxide The tetraol ester: dipentaerythritol hexaacrylate = 2 to 4: 8 to 6) is suitably used from the viewpoint of solvent resistance or ITO sputtering suitability.

Further, from the viewpoint of development latitude, it is advantageous to have one to three hydrophilic groups in the same molecule, and in particular, a compound having a hydroxyl group or a carboxyl group in the molecule contributes greatly to improvement in developability. From this point of view, a compound having an acid group such as a carboxyl group at the terminal of the acrylate monomer is preferred. Specific examples thereof include an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic acid, or an acid group-modified compound obtained by introducing an acid group such as a carboxyl group at the terminal of the polyfunctional acrylate compound. (For example, ARONIX M-510, ARONIX M-520, and ARONIX TO-2349, manufactured by Toagosei Co., Ltd.), in particular, ARONIX M-520 and ARONIX TO-2349 are suitably used.

In order to coexist with solvent resistance or ITO sputtering suitability and development latitude, in addition to using a compound containing three or more polymerizable groups and acid groups in the same molecule, it is also possible to have three or more polymerizations in one molecule. The compound of the nature is used in combination with a compound containing an acid group. When used in combination, it is assumed that the polymerizable compound is 100 parts by mass, and the acid group-containing compound is used in the range of 1 to 50% by mass, preferably in the range of 1 to 40% by mass, more preferably 5 to 5%. 20% by mass range.

<(D) Binder Resin>

The (D) binder resin of the present invention can be used as long as it is a polymer compound soluble in a solvent, and a preferred binder is considered in consideration of the alkali developability by photolithography. The resin is an alkali soluble resin.

The alkali-soluble resin may be contained at the stage of preparing the pigment dispersion composition, or may be added at the stage of preparing the pigment dispersion composition and preparing the coloring photosensitive composition.

The alkali-soluble resin is a linear organic high molecular polymer and is an alkali-soluble polymer having at least one alkali-soluble group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) therein, and is further preferably soluble in an organic solvent. And can be developed with a weak aqueous solution.

For the production of the alkali-soluble resin, for example, a method according to a conventional radical polymerization method can be used. The polymerization conditions in the case of producing an alkali-soluble resin by a radical polymerization method, such as the temperature, the pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like, can be easily set by those skilled in the art, or can be set according to experiments. condition.

The above linear organic high molecular polymer is preferably a polymer having a carboxylic acid in a side chain. For example, it is exemplified in Japanese Patent Laid-Open No. 59-44615, Japanese Special Public Show No. 54-34327, Japanese Special Public Show No. 58-12577, Japanese Special Public Show No. 54-25957, Japanese Special Open No. 59-53836, and Japanese Special The methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid disclosed in each of the publications of the Japanese Patent Publication No. 59-71048 An acid copolymer or the like, an acidic cellulose derivative having a carboxylic acid in a side chain, a polymer addition anhydride having a hydroxyl group, and the like, and a polymer having a (meth)acryl fluorenyl group in a side chain It can also be cited as a preferred one.

Among these, particularly suitable are benzyl (meth)acrylate/(meth)acrylic acid copolymer or benzyl (meth)acrylate/(meth)acrylic acid/dimers composed of other monomers. Copolymer. Other than this, those which copolymerize 2-hydroxyethyl methacrylate etc. are also useful. The polymer can be used in any combination.

In addition to the above, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 7-14065. Copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polyphenylene Ethylene macromonomer/methyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like.

Other alkali-soluble adhesive resin can be used. Japanese Laid-Open Patent Publication No. Hei 7-207211, Japanese Patent Publication No. Hei 8-259876, Japanese Patent Application Laid-Open No. Hei No. Hei 10-300922 A conventional polymer compound disclosed in JP-A-H07-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020.

With respect to the specific structural unit of the alkali-soluble resin, in particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith can be easily obtained, and adjustment of alkali solubility and the like is easy, and therefore it is suitable for use. .

The other monomer copolymerizable with the above (meth)acrylic acid may, for example, be an alkyl (meth)acrylate, an aryl (meth)acrylate, a vinyl compound or the like. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Specific examples of the above "alkyl (meth)acrylate and aryl (meth)acrylate" include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , (butyl) (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, Benzyl acrylate, toluene acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.

Examples of the "vinyl compound" include styrene, α-methylstyrene, vinyltoluene, glycidyl (meth)acrylate, acrylonitrile, vinyl acetate, and N-vinylpyrrolidone. Tetrahydrofuran methyl (meth)acrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ =CR ³¹ R ³² [here, R ³¹ represents a hydrogen atom or has a carbon number of 1 to 5 An alkyl group, R ³² is an aromatic hydrocarbon ring having a carbon number of 6 to 10, and CH ₂ = C(R ³¹ )(COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or a carbon number of 1 to 5 The alkyl group, R ³³ is an alkyl group having a carbon number of 1 to 8 or an aralkyl group having a carbon number of 6 to 12, and the like.

These other monomers which can be copolymerized may be used alone or in combination of two or more. Preferred other copolymerizable monomers are selected from the group consisting of CH ₂ =CR ³¹ R ³² , CH ₂ =C(R ³¹ )(COOR ³³ ), phenyl (meth)acrylate, benzyl (meth)acrylate And at least one of styrene, particularly preferably CH ₂ =CR ³¹ R ³² and/or CH ₂ =C(R ³¹ )(COOR ³³ ). These R ³¹ , R ³² and R ³³ are each synonymous with the former.

In the present invention, the (D) binder resin may be used alone or in combination of several compounds. The content of the binder resin of the alkali-soluble resin or the like in the coloring photosensitive composition is preferably from 1 to 20% by mass, more preferably from 2 to 15% by mass, based on the total solid content of the composition. It is 3 to 12% by mass.

Further, the mixing of the (C) polymerizable monomer / (D) binder resin is preferably in the range of 0.1 to 10, more preferably in the range of 0.4 to 8, and still more preferably in the range of 0.5 to 5 by mass ratio. range.

<(E) Photopolymerization initiator>

The (E) photopolymerization initiator in the present invention is widely used without any particular limitation as long as it is a conventional compound having an ability to initiate polymerization by light irradiation.

Conventional "photopolymerization initiators" which are generally used are: for example, camphorquinone, benzophenone, benzophenone derivative, mercaptophosphine, mercaptophosphine derivative, acetophenone, acetophenone Derivatives such as α-hydroxycycloalkylphenyl ketones or 2-hydroxy-2-methyl-1-phenyl-acetone, dialkoxyacetophenones, α-hydroxy- or 4-arylfluorenyl -1,3-two Alkane, benzoin alkyl ethers and benzyl ketals, such as benzyl dimethyl ketal, phenyl glyoxylate and its derivatives, dimer glyoxylate, peracid Esters such as benzophenone tetracarboxylic acid peresters (for example as disclosed in EP 1 126,541), halomethyltrinitrogens Classes such as 2-[2-(4-methoxy-phenyl)-vinyl]-4,6-bis-trichloromethyl[1,3,5]triazole , 2-(4-methoxy-phenyl)-4,6-bis-trichloromethyl[1,3,5]triazole , 2-(3,4-dimethoxy-phenyl)-4,6-bis-trichloromethyl[1,3,5]triazole 2-methyl-4,6-bis-trichloromethyl[1,3,5]triazole a hexaarylbisimidazole/coinitiator, such as o-chlorohexaphenyl-biimidazole in combination with 2-hydrothiobenzothiazole; a ferrocenium compound or a titanocenes, such as a bicyclic ring Pentadienyl-bis(2,6-difluoro-3-pyrrolo-phenyl)titanium; for example, a mixture with an O-mercapto oxime ester compound as disclosed in GB 2,339,571. A co-initiator is a boric acid compound.

The content of the photopolymerization initiator in the composition of the present invention is preferably from about 0.05 to 30% by mass, more preferably from 0.1 to 20% by mass, still more preferably from 0.2 to 10% by mass based on the total solid content.

It is also preferred that the colored photosensitive composition of the present invention contains a co-sensitizer. The co-sensitizer in the present invention has an effect of further improving the sensitivity of the sensitizing dye or the initiator to the actinic radiation or suppressing the polymerization inhibition of the photopolymerizable compound caused by oxygen.

Examples of such a total sensitizer include, for example, "Journal of Polymer Society" by MR Sander et al., Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-20189, and Japanese Unexamined Co., Ltd. Japanese Laid-Open Patent Publication No. Sho. No. Sho. No. Sho. Sho. Sho. Sho. Sho. Sho. Sho. Sho. Sho. Sho. Sho. The compound or the like as disclosed in JP-A-64-33104, Research Disclosure No. 33825, specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-nonyldimethylaniline, and the like Methylthiodimethylaniline and the like.

Other examples of the co-sensitizers include mercaptans and sulfides, and are disclosed in, for example, JP-A-53-702, JP-A-55-500806, and JP-A-5-142772. The thiol compound, the disulfide compound in JP-A-56-75643, and the like, specifically, 2-hydrothiobenzothiazole and 2-hydrothiobenzophenone Oxazole, 2-hydrothiobenzimidazole, 2-hydrothio-4(3H)-quinazoline, β-hydrothionaphthalene, and the like.

In addition, other examples include an amino acid compound (for example, N-phenylglycine), an organometallic compound (for example, tributyltin acetate, etc.) disclosed in Japanese Patent Publication No. Sho 48-42965, A hydrogen donor body as disclosed in Japanese Laid-Open Patent Publication No. H-55-34414, or a sulfur compound (for example, trithiane or the like) disclosed in Japanese Laid-Open Patent Publication No. Hei 6-308727.

The content of the co-sensitizer is preferably in the range of 0.1 to 30% by mass, based on the total solid content of the photosensitive composition, from the viewpoint of increasing the curing rate by the equilibrium between the polymerization growth rate and the chain transfer. It is preferably in the range of 1 to 25% by mass, and more preferably in the range of 0.5 to 20% by mass.

<(F) Polymerizable compound having radical trapping energy>

The colored photosensitive composition of the present invention contains (F) a polymerizable compound having a radical capturing energy (hereinafter, sometimes referred to as "additive").

The coloring photosensitive composition of the present invention is subjected to heat treatment (post-baking) at a temperature of 100 to 250 ° C in the formation process of the color filter coloring pattern as will be described later. The general additive with free radical trapping energy is reported by many compounds, but it is required that the free radical trapping energy is not deactivated after heat treatment. Since the polymerizable compound is less likely to be volatilized or decomposed by heat, it is particularly excellent in heat resistance and can exert remarkable effects in the mode of the present invention.

The colored photosensitive composition of the present invention is characterized in that (F) a polymerizable compound having a radical capturing energy is used, whereby the ITO can be sputtered without impairing the transparency and color purity inherent to the toner. Light resistance, developability, and solvent resistance.

Although it is not clear that the light-resistance improving effect by the polymerizable compound having a radical trapping property is improved, it is presumed that the coloring radical formed by the excitation of the phthalocyanine-based coloring material by light irradiation is recognized. The discoloration at the time of the light resistance test was suppressed. In particular, a polymerizable compound having a radical scavenging energy is most effective in volatilization by heating compared with other non-polymerizable radical scavengers, and it is estimated that the light is irradiated after post-baking. Capture free radicals.

The additive of the present invention is composed of a polymerizable moiety and a radical scavenging site, and the polymerizable site and the radical scavenging site may be directly bonded or introduced into a linking site for bonding. It is also possible to use two or more additives in combination. Second, explain the respective parts.

The radical scavenging site exhibits an effect of suppressing deterioration of radical formation caused by light irradiation. The (F) polymerizable compound having a radical trapping property is preferably a compound having an amine structure or a phenol structure, and conventionally, a hindered type amine group, a hindered type phenol type, a sulfur type, and a phosphorus are mentioned. The structure of the department. Among them, from the viewpoint of radical scavenging energy, a hindered amine structure or a hindered phenol structure is preferred. Specifically, the hindered amine is (1,2,2,6,6-pentamethyl-4-piperidinyl), (2,2,6,6-tetramethyl-4-piperidine) The thiol group is a 3,5-tributyl-4-hydroxyphenyl group or the like.

Here, the term "steric type" means steric hindrance. Owing to the steric hindrance, the reaction rate of the radical scavenging site is lowered, and only highly active radicals can be efficiently captured, and thus it is suitable for use as a radical scavenger.

The polymerizable portion is responsible for preventing volatilization and decomposition of the radical scavenging site. When the polymerizable portion of the additive of the present invention has a structure in which polymerization can be carried out by heat or light irradiation, a conventionally known polymerizable group can be used without particular limitation. Specific examples of the "polymerizable group" include (meth)acrylonitrile, (meth)acryloxy group, (meth)acrylamide group, vinyl group, vinyloxy group, and maleimide. Base, epoxy group, epoxy propyl group, and the like. These polymerizable groups may further be partially substituted. In particular, the polymerizable group preferably has at least one selected from the group consisting of an acryloyl group and a methacryl fluorenyl group. Specifically, the polymerizable portion is preferably a (meth) acrylonitrile group due to ease of synthesis. (Meth) propylene oxime.

The linking site is not particularly limited as long as it is a general organic group, and a cyclic aliphatic group, a chain aliphatic group, an aromatic group or the like can be widely used, and in particular, an alkyl group or a polyethylene group is preferable. Glycol chain. The organic group may have a branch, and if it has a branch, it may have a plurality of polymerizable sites or radical scavenging sites at the respective ends. The alkyl group may, for example, be methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, cyclohexyl, cyclopentyl, neopentyl, isopropyl , isobutyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms. With regard to the polyethylene glycol chain, the preferred range of the number of carbon atoms is the same as in the case of the alkyl group.

In the present invention, the content of the (F) polymerizable compound having a radical trapping property is preferably from about 0.1 to 5.0% by mass, more preferably from 0.2 to 4.0% by mass based on the total solid content of the colored photosensitive composition. More preferably, it is 0.5 to 2.0% by mass.

When the amount is less than 0.1%, the radical trapping effect may not be sufficiently exhibited. When the amount exceeds 5.0%, the sensitivity to exposure is reduced, so that when it is useful as a color filter, it may not be formed. To pattern, or to have a rough or notched surface.

Hereinafter, the sterically hindered amine type polymerizable compound and the sterically hindered phenol type polymerizable compound will be specifically described.

<Hindered amine type polymerizable compound>

The radical scavenging site in the hindered amine type polymerizable compound is preferably piperidine, pyridine or pyrene from the viewpoint of radical scavenging energy. Trinitrogen Or pyrimidine, pyrrole, pyrrolidone, pyrrolidine, anthracene, imidazole, triazole, hydrazine, hydrazine, or pyrazole, more preferably piperidine, pyrrole or pyrrolidine, still more preferably piperidine.

The sterically hindered piperidine preferably has a hydrogen atom adjacent to the nitrogen atom of the piperidine (positions 2 and 6) and has no hydrogen atom, and the hydrogen atom is preferably substituted with an alkyl group. The nitrogen atom of piperidine preferably has a hydrogen atom or is substituted with an alkyl group.

The substitution position at the polymerizable portion of piperidine is preferably 3 or 4, more preferably 4.

The polymerizable portion of the hindered amine type polymerizable compound is preferably a (meth)acrylonitrile group or a (meth)acryloxy group, more preferably a (meth)acryloxy group.

In the hindered amine type polymerizable compound, the radical scavenging site and the polymerizable moiety may be directly bonded or bonded at the linking site.

Among the hindered amine type polymerizable compounds, a compound having a structure of the following formula (1) is preferred from the viewpoint of stability of the compound and ease of handling.

In the above formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group, a hydroxyl group, an alkyl group having a carbon number of 10 or less, and a carbon number of An alkoxycarbonyl group of 10 or less, an alkylsulfonylaminocarbonyl group having a carbon number of 10 or less, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a carbon number of 10 or less a mercaptoaminosulfonyl group, an alkoxy group having a carbon number of 10 or less, an alkylthio group having a carbon number of 10 or less, an aryloxy group having a carbon number of 10 or less, a nitro group, an alkoxycarbonyloxy group, An aryloxycarbonyloxy group, a fluorenyl group having 10 or less carbon atoms, a decyloxy group having 10 or less carbon atoms, an amine methyl sulfonyl group, an amine sulfonyl group, an aryl group having 10 or less carbon atoms, a substituted amino group a substituted ureido group, a substituted phosphonic acid group, or a heterocyclic group; R ⁴ represents a hydrogen atom or an alkyl group having a carbon number of 30 or less; X represents a single bond, an ester group, and has a carbon number of 30 or less. An aliphatic alkyl chain, an aromatic chain, a polyethylene glycol chain, or a combination of (m+n) valent linking groups; m and n each independently represent an integer of 1 or more and 3 or less.

R ¹ , R ² and R ³ in the formula (1) are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, and a carbon number. The alkoxycarbonyl group having 10 or less, the aryloxy group having 10 or less carbon atoms, the fluorenyl group having 10 or less carbon atoms, and the decyloxy group having 10 or less carbon atoms are further preferably a hydrogen atom or a carbon number of 10 The alkyl group below is more preferably a hydrogen atom or an alkyl group having 5 or less carbon atoms, still more preferably a hydrogen atom or a methyl group. In particular, R ¹ and R ^{2 are} preferably a hydrogen atom.

R ⁴ in the formula (1) is further preferably a hydrogen atom or an alkyl group having a carbon number of 30 or less, more preferably a hydrogen atom or an alkyl group having a carbon number of 10 or less, a hydrogen atom or a methyl group. X in the formula (1) is preferably a single bond or a linking group represented by the following. In the following linking group, * represents a position of attachment to a radical scavenging site or a polymerizable site. n is an integer representing 30 or less independently, preferably an integer of 3 or more and 15 or less, and more preferably an integer of 3 or more and 10 or less.

m and n in the formula (1) are each independently preferably 1 or 2. Specific examples of the compound represented by the formula (1) are as follows, but are not limited to the compounds.

Among the compounds represented by the formula (1), particularly, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (formula (3) below), methyl group is suitably used. 2,2,6,6-tetramethyl-4-piperidinyl acrylate (formula (4)), and the like. (Formula (3))

(Formula (4))

The sterically hindered phenol type polymerizable compound is a phenolic hydroxyl group at the radical scavenging site of the sterically hindered phenol type polymerizable compound, and preferably a carbon atom (position 2 and position 6) adjacent to the hydroxyl group of the phenol is not There is a hydrogen atom, and the hydrogen atom is preferably substituted with an alkyl group, and the alkyl group is further preferably a branched alkyl group, and more preferably a branched alkyl group having a carbon number of 30 or less.

The substitution position at the polymerizable portion of the phenol is preferably 2 or 4 positions. The polymerizable site in the sterically hindered phenol type polymerizable compound is preferably a (meth)acryl fluorenyl group or a (meth) propylene fluorenyloxy group, and more preferably a (meth) acryloxy group. In the sterically hindered phenol type polymerizable compound, the radical scavenging site and the polymerizable moiety may be directly bonded or bonded at the linking site. Among the sterically hindered phenol type polymerizable compounds, from the viewpoint of stability of the compound and ease of handling, a compound having a structure of the following formula (5) or (6) is preferred.

In the above formula (5) and formula (6), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group or a hydroxyl group, and have a carbon number of 10 or less. An alkyl group, an alkoxycarbonyl group having a carbon number of 10 or less, an alkylsulfonylaminocarbonyl group having a carbon number of 10 or less, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a mercaptoaminosulfonyl group having a carbon number of 10 or less, an alkoxy group having a carbon number of 10 or less, an alkylthio group having a carbon number of 10 or less, an aryloxy group having a carbon number of 10 or less, a nitro group or an alkane An oxycarbonyloxy group, an aryloxycarbonyloxy group, a decyloxy group having 10 or less carbon atoms, an anthracenyl group having 10 or less carbon atoms, an amine carbaryl group, an amine sulfonyl group, and an aryl group having 10 or less carbon atoms a substituted amino group, a substituted ureido group, a substituted phosphonic acid group, or a heterocyclic group; R ⁵ and R ⁶ each independently represent a branched alkyl group having a carbon number of 30 or less; X is a representative single a bond, an ester group, an aliphatic alkyl chain having a carbon number of 30 or less, an aromatic chain, a polyethylene glycol chain, or a combination of (m+n) valent linking groups; m and n are each independently Represents an integer of 1 or more and 3 or less.

R ¹ , R ² and R ³ in the general formulae (5) and (6) are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 10 or less, and an alkoxy group having a carbon number of 10 or less. a group having an alkoxycarbonyl group having 10 or less carbon atoms, an aryloxy group having 10 or less carbon atoms, a mercapto group having 10 or less carbon atoms, a mercapto group having 10 or less carbon atoms, more preferably a hydrogen atom or The alkyl group having a carbon number of 10 or less is more preferably a hydrogen atom or an alkyl group having 5 or less carbon atoms, still more preferably a hydrogen atom or a methyl group. In particular, R ¹ and R ^{2 are} preferably a hydrogen atom. R ⁵ and R ⁶ in the general formulae (5) and (6) are each independently preferably a branched alkyl group having a carbon number of 15 or less, and more preferably a branched alkyl group having a carbon number of 10 or less. More preferably, it is a tertiary butyl group, a 2-dimethylpropyl group, a 2-dimethylbutyl group, a 2,3-dimethylbutyl group, or a substituted phenyl group, or may be substituted. More preferably, the benzyl group is a tertiary butyl group or a 2-dimethylpropyl group.

X in the general formulae (5) and (6) is preferably a linking group represented by the following. Further, in the following linking group, * represents a position of attachment to a radical capturing site or a polymerizable site. n is an integer representing 30 or less independently, preferably an integer of 3 or more and 15 or less, more preferably an integer of 3 or more and 10 or less. Further, in the following linking group, R is a hydrogen atom or an alkyl group having a carbon number of 10 or less.

m and n in the general formulae (5) and (6) are each independently preferably 1 or 2. Specific examples of the compounds represented by the general formulae (5) and (6) are as follows, but are not limited thereto.

Among the compounds represented by the general formulae (5) and (6), a compound represented by the following general formula (7) is preferred.

R ⁷ in the formula (7) is a hydrogen atom or an alkyl group having a carbon number of 5 or less, R ⁸ is a branched alkyl group or an aryl group having a carbon number of 15 or less, and R ⁹ represents a carbon number of 15 or less. The following alkyl groups. R ⁸ in the formula (7) is preferably a branched alkyl group or an aryl group having a carbon number of 10 or less, more preferably a tertiary butyl group, a 2,2-dimethylpropyl group or a 2,2-di group. Methyl butyl, 2,3-dimethylbutyl, (which may also be substituted) phenyl, or (also may be substituted) benzyl, further more preferably tertiary butyl, or 2,2 - dimethyl propyl. R ⁹ in the formula (7) is preferably an alkyl group having a carbon number of 10 or less, more preferably an alkyl group having a carbon number of 5 or less. Among the compounds represented by the formula (7), the following compound I (Sumilizer GM manufactured by Sumitomo Chemical Co., Ltd.) and the following compound II (with Sumilizer GS) are particularly suitably used. )Wait.

(Compound I)

(Compound II)

<Other Additives> In the colored photosensitive composition of the present invention, an ultraviolet absorber, a thermal polymerization initiator, a surfactant, a development accelerator, a thermal polymerization inhibitor, a filler, a dispersant, and an anticoagulation may be contained as needed. Various additives such as collectors.

<Ultraviolet absorber> The polymerizable compound having a radical scavenging energy in the above (F) can be added to a general ultraviolet absorber which does not contain a polymerizable group, insofar as it does not cause a problem. In this case, when an organic ultraviolet absorber having good compatibility with the polymerizable compound having a radical scavenging energy (F) is used, a synergistic effect can be expected, and it is preferable. In particular, it is preferred that the main skeleton is a hydroxybenzophenone type, a benzotriazole type, a cyanoacrylate type, or a trinitrogen a compound derivative. Further, it may be a polymer such as a vinyl polymer containing such an ultraviolet absorber in a side chain.

Specifically, it may, for example, be 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone , 2-hydroxy-4-n-phenylmethyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4, 4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxy Benzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxy Benzophenone, 2,3,4-trihydroxybenzophenone, 2-(2-hydroxy-5-trimethylphenyl)benzotriazole, 2-(2-hydroxy-5-three Grade octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tertiary butylphenyl)benzotriazole, ethyl-2-cyano-3,3-diacrylate Phenyl ester, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyltriazole (co)polymer of 2-hydroxy-4-(2-propenyloxyethoxy)benzophenone, 2-(2'-hydroxy-5'-methylpropenyloxyethylphenyl) a (co)polymer of -2H-benzotriazole. These organic ultraviolet absorbers may be used in combination of two or more.

<Thermal Polymerization Initiator> It is also effective to contain a thermal polymerization initiator in the colored photosensitive composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compound include an azobis compound, and examples of the "peroxide compound" include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, and dioxane. A base peroxide, a peroxy ester, a peroxydicarbonate, and the like.

<Interfacial Agent> The colored photosensitive composition of the present invention is preferably formed using various surfactants from the viewpoint of improving coatability. By the surfactant, the liquid properties (especially fluidity) as a coating liquid can be improved, and the uniformity of the coating thickness or the liquid-saving property can be improved. That is, since the interfacial tension between the substrate and the coating liquid is lowered to improve the wettability of the substrate and the coating property to the substrate is improved, uneven thickness can be formed even in the case where a film of about several μm is formed with a small amount of liquid. A film having a small uniform thickness is effective. In addition, it is effective in slit coating which is prone to liquid breakage.

As the surfactant, various surfactants of a nonionic, cationic or anionic system can be used. Among them, a fluorine-based surfactant which is a nonionic surfactant and has a perfluoroalkyl group is preferable. The fluorine content of the fluorine-based surfactant is suitably from 3 to 40% by mass, more preferably from 5 to 30% by mass, particularly preferably from 7 to 25% by mass. When the fluorine content is within the above range, it is effective in coating thickness uniformity or liquid-repellent property, and is also good in solubility in the composition.

Examples of the "fluorine-based surfactant" include MEGAFACE F171, the same F172, the same F173, the same F177, the same F141, the same F142, the same F143, the same F144, the same R30, and the same F437 (the above is the Dainippon Ink Chemical Industry ( Shares), FLUORAD FC430, FC431, FC171 (above is Sumitomo 3M Co., Ltd.), SURFLON S-382, SC-101, SC-103, SC -104, the same SC-105, the same SC1068, the same SC-381, the same SC-383, the same S393, the same KH-40 (the above is manufactured by Asahi Glass Co., Ltd.) and the like.

Examples of the surfactant other than the fluorine-based compound include a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Industries Co., Ltd.)), an organic polyoxyalkylene polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer POLYFLOW No. 75, No. 90, No. 95 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd. )), W001 (made by Yusho Co., Ltd.), etc. "Cation-based surfactant; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether , polyoxyethylene nonylphenyl ether, polyethylene dilaurate, ethylene glycol distearate, sorbitan fatty acid ester (BASF Corporation, PLURONIC L10, L31, L61 "Lion-free surfactant" such as L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904, and 150R1; "anionic interface activity of W004, W005, and W017 (made by Yusei Co., Ltd.)" Agent."

The amount of the surfactant added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the pigment dispersion composition or the coloring photosensitive composition.

<Developing accelerator> When the alkali solubility of the uncured portion is promoted and the developability of the coloring photosensitive composition is further improved, the organic carboxylic acid may be added to the colored photosensitive composition, and the molecular weight is preferably 1,000. The following low molecular weight organic carboxylic acids. Specific examples thereof include "fatty acid" (formic acid), acetic acid, propionic acid, butyric acid, valeric acid (shikimic acid), trimethylacetic acid, caproic acid, diethyl acetic acid, heptanoic acid, octanoic acid, and the like. Group of monocarboxylic acids; oxalic acid (oxalic acid), malonic acid, succinic acid (succinic acid), glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Fatty acid), bran diacid (tridecanedioic acid), methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid, etc. "aliphatic dicarboxylic acid"; "aliphatic tricarboxylic acid" such as 1,2,3-propane tricarboxylic acid, aconitic acid, and capric acid; benzoic acid, o-toluic acid, and decanoic acid (different "Aromatic monocarboxylic acid" such as propyl benzoic acid), 2,3-dimethylbenzoic acid or 3,5-dimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, Trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), pyromellitic acid (1,2,3,5-benzenetetracarboxylic acid), "Aromatic polycarboxylic acid" such as pyromic acid (1,2,4,5-benzenetetracarboxylic acid); phenylacetic acid, hydrogen ato acid Hydrogen cinnamic acid, bitter almond acid (phenylglycolic acid), phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnaminoacetic acid, coumaric acid, umbrella acid, etc. Other carboxylic acids.

<Thermal polymerization inhibitor>

In the coloring photosensitive composition of the present invention, it is further preferred to add a thermal polymerization preventing agent such as hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, three Butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6- Tertiary butyl phenol), 2-hydrothiobenzimidazole, and the like are useful.

<dispersant, filler, anti-aggregating agent>

In addition to the above, specific examples of the additive in the coloring photosensitive composition include EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (above) It is a polymer dispersant such as Sensei Industrial Co., Ltd., DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSE AID 9100 (manufactured by San Nopco Co., Ltd.); SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, Various SOLSPERSE dispersing agents such as 24000, 26000, and 28000 (manufactured by Zeneca Co., Ltd.); fillers such as glass and alumina; and anti-aggregating agents such as sodium polyacrylate.

The colored photosensitive composition of the present invention may contain (C) a polymerizable monomer and (D) a binder in a solution or dispersion of the (A) color material containing the solvent (B) of the present invention. a resin, (E) a photopolymerization initiator, (F) a polymerizable compound having a radical trapping ability (preferably together with the solvent (B)), and if necessary, mixed with other additives such as a surfactant .

<Color filter and method of manufacturing the same>

The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass by using the colored photosensitive composition of the present invention described above, for example, by coloring the color of the present invention. The composition is applied directly or via another layer (preferably coated by a coating method such as spin coating, slit coating, cast coating, roll coating, etc.) to form a photosensitive film, and is formed. The photosensitive film (colored layer) is exposed through a predetermined mask pattern, exposed, and then developed with a developer to remove the uncured portion to form a colored pattern (for example, a color pixel) of each color (for example, three colors or four colors). The color filter can be optimally manufactured.

Thereby, the color filter used for the liquid crystal display device or the solid-state image sensor can be manufactured with high quality and low cost due to the difficulty in the process.

At this time, it is particularly preferable to use ultraviolet rays such as g-rays, h-rays, i-rays, and j-rays for the radiation to be exposed.

Further, in addition to the general proximity exposure method, an exposure method using a laser light source is also suitable. In the case of laser exposure, the source is an ultraviolet laser. LASER is an abbreviation formed by the first word of the English Light Amplification by Stimulated Emission of Radiation (magnification of light generated by stimulated emission). It includes a phenomenon of stimulated emission occurring in a substance having an inverted population, and an oscillator and amplifier for monochromatic light having stronger interference and directivity through amplification and oscillation of light waves. The excitation medium includes: crystal, glass, liquid, pigment, gas, etc., and the medium can be oscillated by conventional ultraviolet light, liquid laser, gas laser, semiconductor laser, etc. in conventional ultraviolet light. Wavelength of the laser. Among them, from the viewpoint of the output power of the laser and the oscillation wavelength, a solid laser or a gas laser is preferable.

The ultraviolet light which can be used in the wavelength range of 300 nm to 380 nm in the wavelength range of 300 nm to 380 nm in the present invention is more preferably a wavelength in the range of 300 nm to 360 nm due to the photosensitive wavelength in accordance with the resist. Light laser.

Specifically, it is particularly suitable for using a third-order high-order wave (355 nm) or an excimer of a Nd:YAG laser (钕: yttrium aluminum garnet laser) having a large output power and being relatively inexpensive. XeCl (308 nm) and XeF (353 nm) of laser light.

The exposure amount of the exposed object (pattern) is in the range of 1 mJ/cm ² to 100 mJ/cm ² , and more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² . When the amount of exposure is in this range, it is preferable from the viewpoint of productivity of pattern formation.

The exposure apparatus to be used in the present invention is not particularly limited, and a commercially available Callisto (manufactured by V Technology Co., Ltd.), EGIS (manufactured by V Technology Co., Ltd.), or DF2200G (Daily Screen Co., Ltd.) can be used. (made by Dainippon Screen Mfg. Co., Ltd.) and the like. Further, it is also suitable to use a device other than the above.

Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, if an ultraviolet source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has launched a purple LED with a wavelength between 365 nm and 420 nm. Further, when a shorter wavelength is required, an active radiation LED having an emission center between 300 nm and 370 nm has been disclosed in the specification of U.S. Patent No. 6,084,250. In addition, other UV LEDs are also available, so that radiation from different UV domains can be illuminated. A particularly preferred source of active radiation in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength of 340 to 370 m.

Since the ultraviolet laser is excellent in parallelism, pattern exposure can be performed even when no mask is used during exposure. However, when the mask is used to expose the pattern, the linearity of the pattern will be higher, which is preferable.

The drying (prebaking) of the film composed of the colored photosensitive composition of the present invention imparted to the substrate (preferably coated) may be a hot plate, an oven or the like, and is in a temperature range of 50 to 140 ° C and It is carried out under conditions of 10 to 300 seconds.

At the time of development, the unhardened portion after the exposure is eluted to the developer to leave only the cured portion. The development temperature is usually 20 to 30 ° C and the development time is 20 to 90 seconds.

The developer may be used as long as it is a film of a color-sensitive photosensitive composition that can be dissolved in an uncured portion and does not dissolve the hardened portion. Specifically, a combination of various organic solvents or an aqueous alkaline solution can be used.

The organic solvent may be a solvent which can be used in the preparation of the pigment dispersion composition of the present invention or the coloring photosensitive composition.

Examples of the "aqueous alkaline solution" include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, and dimethylethanolamine. Alkaline compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene The aqueous solution is made to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.

Moreover, when an alkaline aqueous solution is used as a developing solution, it is usually washed (washed) with water after development.

After the development, after the excess developer is removed by washing and dried, the heat treatment (post-baking) is usually carried out at a temperature of 100 to 250 °C.

The post-baking is heating after development which is performed to make the hardening complete, and heating (hard baking) is usually performed at about 200 ° C to 250 ° C. The baking treatment is a heating method using a hot plate or a convection oven (hot air circulation dryer), a high frequency heating machine, or the like after the development of the coating film, so that it can be implemented in a continuous or batch manner in accordance with the above conditions. .

By repeating the above operations in accordance with the desired number of chromatic phases and repeating each color sequentially, a color filter formed by forming a cured film of a plurality of colors can be produced.

When the colored photosensitive composition of the present invention is applied to a substrate to form a film, the film has a dry thickness of usually 0.3 μm to 5.0 μm, preferably 0.5 μm to 3.5 μm, and most preferably 1.0 μm to 2.5 μm.

The "substrate" is, for example, an alkali-free glass, a soda-lime glass, a Pyrex (registered trademark) glass, a quartz glass, or the like, which is used for a liquid crystal display device, or the like, or a transparent conductive film attached thereto, or A photoelectric conversion element substrate such as a solid-state image sensor or the like, for example, a germanium substrate or the like, and a plastic substrate. On such substrates, a black strip for isolating each pixel is typically formed.

The plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface.

When the coloring photosensitive composition is provided on the substrate via another layer, the other layer may be a gas barrier layer or a solvent resistant layer.

[Liquid Crystal Display Device]

The color filter of the present invention is particularly suitable for use as a color filter for a liquid crystal display device. A liquid crystal display device having such a color filter can display a high quality image.

The definition of the display device or the description of each display device is disclosed, for example, in "Electronic display device (Kogyo Chosakai Publishing Co., Ltd., published in 1990)", Display device (Sangyo Tosho Publishing Co., Ltd., published in the first year of the year). Further, the liquid crystal display device has been disclosed, for example, in "Second Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Industrial Investigations, Inc., published in 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the "Second Generation Liquid Crystal Display Technology".

Among them, the color filter of the present invention is effective particularly for a liquid crystal display device of a color TFT (color thin film transistor) type. A liquid crystal display device of a color TFT type is disclosed, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Shuppan Co., Ltd., published in 1996)". Further, the present invention is also applicable to a horizontal electric field driving method such as IPS (In-Plane Switching) or a pixel division method such as MVA (Multi-domain Vertical Alignment). Liquid crystal display device with expanded viewing angle, or STN (Super Twisted Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (Optical Compensation Bending) Type: Optically Compensated Bend), FFS (Boundary Field Switching Wide Angle Viewing Technology Type: Fringe Field Switching), and R-OCB (Reflective Optically Compensated Bend).

In addition, the color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) method. In the COA liquid crystal display device, the required characteristics of the color filter layer sometimes require the usual characteristics as described above, plus the required characteristics of the interlayer insulating film, that is, low dielectric constant and peeling resistance. The case of removing liquid resistance. The color filter of the present invention can be considered to increase the transmission of ultraviolet laser light as exposure light by the exposure method using ultraviolet laser, and by selecting the hue or film thickness of the pixel specified by the present invention. Sex. Thereby, the hardenability of the colored pixel is improved, and a pixel having no nick or peeling or skew can be formed. Therefore, the peeling liquid resistance of the colored layer directly or indirectly provided on the TFT substrate is improved, and the COA is improved. A liquid crystal display device of the type is useful. In order to satisfy the required characteristics of the low dielectric constant, a resin film may be provided on the color filter layer.

Further, in order to electrically connect the ITO electrode disposed on the colored layer and the terminal of the driving substrate below the colored layer, in the coloring layer formed by the COA method, it is necessary to form a rectangular through hole having a length of about 1 to 15 μm. Hole) or an electrically-conducting path, and preferably the size of the via (ie, the length of one side) is made to be 5 μm or less, but by using the present invention, It is also possible to form a conduction path of 5 μm or less.

The image display methods for such images are described in, for example, "EL (Electro-Excise), PDP (Plastic Display), LCD Display - Technology and Market Trends - (Research Study Division, Toray Research Center) Of Toray Research Center, Inc., published in 2001), page 43 et al.

The liquid crystal display device liquid of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a view angle compensation film, and the like in addition to the color filter of the present invention. It is composed of various components. The color filter of the present invention is a liquid crystal display device which can be applied to such a conventional member.

The components relating to such are described in, for example, "'94 Liquid Crystal Display Peripherals ‧Chemicals Markets (Japan Citizen, CMC (CMC) Co., Ltd., published in 1994); "2003 LCD Current status and future prospects of related markets (Volume 2) (Fuji Chimera Research Institute, Inc., published in 2003).

The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et al.); or Display Monthly (Monthly DISPLAY), December 2005, pages 18 to 24 (Island Kang Yu), with the 25th To 30 pages (Yamamu Longming) and so on.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a conventional three-wavelength tube of a cold cathode tube, but further by using red, green, and blue LEDs When the light source (RGB-LED) is used as a backlight, it is possible to provide a liquid crystal display device having high luminance and high color reproducibility.

"Embodiment"

Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited to the following examples. In addition, unless otherwise stated, "%" and "parts" are based on quality.

- Synthesis of phthalocyanine pigments -

Zinc phthalocyanine is produced by using phthalonitrile or zinc chloride as a raw material.

The halogenation was carried out by mixing 3.1 parts of thiopurine chloride, 3.7 parts of anhydrous aluminum chloride, 0.46 parts of sodium chloride, and 1 part of zinc phthalocyanine at 40 ° C, and adding 2.2 parts of bromine dropwise. After reacting at 80 ° C for 15 hours, the reaction mixture was poured into water to precipitate a partially brominated zinc phthalocyanine crude pigment. The aqueous slurry was filtered, washed with hot water at 80 ° C, and dried at 90 ° C to obtain 2.6 parts of a purified partially brominated zinc phthalocyanine crude pigment.

1 part of the partially brominated zinc phthalocyanine crude pigment, 7 parts of pulverized sodium chloride, 1.6 parts of diethylene glycol, and 0.09 parts of xylene are fed into a double wrist type kneader (dual arm- Type kneader), kneaded at 100 ° C for 6 hours. After kneading, it was taken out in 100 parts of water at 80 ° C, stirred for 1 hour, and then filtered, washed with hot water, dried, and pulverized to obtain a partially brominated zinc phthalocyanine pigment.

The obtained partially brominated zinc phthalocyanine pigment was found to have an average composition of ZnPcBr ₁₀ Cl ₄ H ₂ (Pc; phthalocyanine) from the halogen content analysis by mass analysis, and contained an average of 10 molecules in one molecule. Bromine and 4 chlorine.

Further, the average value of the primary particle diameters measured by a transmission electron microscope (JE-2010, manufactured by JEOL Ltd.) was 0.065 μm.

- Synthesis of quinophthalone compounds -

Quinone pigment (4,5,6,7-tetrachloro-2-[2-(4,5,6,7-tetrachloro-2,3-dihydro-1,3-di- oxy-1H) -Indol-2-yl)-8-quinolinyl]-1H-isoindole-1,3(2H)-dione) (Paliotol "Yellow K0961HD" manufactured by BASF Corporation) 10 g of 130 g while stirring In 15 ° C of fuming sulfuric acid (25% SO ₃ ). After stirring for 3 hours, it was added to 250 g of ice. After standing for 30 minutes, the resulting suspension was filtered, and the obtained product was washed with water (50 ml).

The above product was charged in 330 ml of water and neutralized with an aqueous ammonia solution (the aqueous ammonia solution was added until the pH became 7). 75 g of ammonium chloride was added and stirred at 80 ° C for 30 minutes, and the precipitate precipitated was filtered at 60 ° C. The obtained wet crystals were washed with water, and then dried at 80 ° C to obtain 17 g of an ammonium salt (3) of a quinone derivative sulfonate.

The ammonium salt (3) of the quinone derivative sulfonate was heat-treated at 180 ° C for 3 hours to obtain 16 g of the quinone derivative sulfonate (4) of the removed ammonium salt (yield 94%).

In 10 g of the sulfonate (4), 2.2 g of oxalyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 ml of N,N-dimethylform were added under ice cooling in chloroform. The guanamine (manufactured by Wako Pure Chemical Industries, Ltd.) was stirred at 50 ° C for 2 hours. The reaction mixture was added to 150 ml of water in an ice bath, and the precipitated crystals were filtered to give 7.4 g of sulfonyl chloride compound (5) (yield: 72%).

To 5.0 g of the compound (5), 0.9 g of 6-chloro-1-hexylamine (manufactured by Rare Chemicals Co., Ltd.) was added to chloroform under ice cooling, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was added to 150 ml of water, and the precipitated crystals were filtered and washed with water, and dried under reduced pressure to obtain 4.3 g of sulfonamide alkyl chloride compound (6) (yield 76%).

To 4.3 g of the compound (6), excess water and anhydrous sodium sulfite (manufactured by Kanto Chemical Co., Inc.) were added, and the mixture was heated at 180 ° C for 12 hours in an autoclave. After naturally cooling, the crystals were filtered to give 3.7 g of the sulfonamide sulfonic acid compound (7) (yield 82%).

- Synthesis of resin (J-1) - (1) Synthesis of resin (i-1)

6.4 g of n-octanoic acid, 200 g of ε-caprolactone, and 5 g of tetrabutyl titanate (IV) were mixed, heated at 160 ° C for 8 hours, and then cooled to room temperature to obtain a polyester resin (i-1).

The composition process is as follows:

(2) Synthesis of resin (J-1)

10 g of polyethylenimine (SP-018, number average molecular weight 1,800, Nippon Shokubai Co., Ltd.) and 100 g of polyester resin (i-1) were mixed. The intermediate (J-1B) was obtained by heating at 120 ° C for 3 hours. Thereafter, it was naturally cooled to 65 ° C, and 200 g of 2-acetic acid propylene glycol 1-methyl ether ester (hereinafter, referred to as PGMEA) containing 3.8 g of succinic anhydride was slowly added and stirred for 2 hours. Thereafter, PGMEA was added to obtain a PGMEA 10 mass% solution of the resin (J-1). The resin (J-1) is one having a side chain derived from the polyester resin (i-1) and a carboxyl group derived from succinic anhydride.

The composition process is as follows:

- Modulation of phthalocyanine pigment dispersion PG58 -

11.9 parts of the above-mentioned partially brominated zinc phthalocyanine pigment (referred to as PG58), 3.1 parts of the compound (7) as a quinophthalone compound, and 9.0 parts of SOLSPERSE 24000GR as a dispersing agent (Lubrizol, Japan (The A mixture of 76 parts of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was mixed, and then dispersed in a sand mill for 3 hours to obtain a phthalocyanine pigment dispersion PG58. The obtained pigment dispersion composition PG58 was found to have a viscosity of 9.2 mPa·s by an E-type viscosity meter and was very stable, so that it was confirmed that good dispersion stability was obtained.

- Modulation of pigment dispersion PY150 containing yellow pigment PY150 -

40 parts of CI Pigment Yellow 150 (PY150) (average particle diameter: 60 nm) as a pigment, and 223 parts of a PGMEA 10 mass% solution (solid content: 22.3 parts) of the above resin (J-1), The pigment dispersion liquid PY150 containing the yellow pigment PY150 was prepared by mixing with a bead ball mill (zirconia beads 0.3 mm) and dispersing for 3 hours.

- Modulation of pigment dispersion PY138 containing yellow pigment PY138 -

40 parts of CI Pigment Yellow 138 (PY138) (average particle diameter: 60 nm) as a pigment, and 223 parts of a PGMEA 10 mass% solution (solid content: 22.3 parts) of the above resin (J-1), The pigment dispersion liquid PY138 containing the yellow pigment PY138 was prepared by mixing with a bead ball mill (zirconia beads 0.3 mm) and dispersing for 3 hours.

- Modulation of pigment dispersion PB15:6 containing blue pigment PB15:6 -

40 parts of CI Pigment Blue 15:6 (PB15:6) (average particle diameter of 60 nm) and 223 parts of PGMEA 10 mass% solution of the above resin (J-1) as a pigment (solid content converted to 22.3 parts) The mixed solution was mixed with a bead ball mill (zirconia beads 0.3 mm) and dispersed for 3 hours to prepare a pigment dispersion liquid PB15:6 containing a blue pigment PB15:6.

- Modulation of pigment dispersion PG36 containing green pigment PG36 -

a mixture of 40 parts of CI Pigment Green 36 (PG36) (average particle diameter of 60 nm) and 200 parts of PGMEA 10% by mass of a resin (J-1) (solid content converted to 20 parts) The liquid was mixed with a bead ball mill (zirconia beads 0.3 mm) and dispersed for 3 hours to prepare a pigment dispersion liquid PG36 containing green pigment PG36.

The average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) to obtain a dispersion of 25 nm.

- Synthesis of Compound 1 as a photopolymerization initiator - (1) Synthesis of Compound A

First, Compound A was synthesized by the following procedure.

Ethylcarbazole (100.0 g, 0.512 mol) was dissolved in 260 ml of chlorobenzene, and after cooling to 0 ° C, aluminum chloride (70.3 g, 0.527 mol) was added. Next, o-tolylmethyl chloride (81.5 g, 0.527 mol) was added dropwise over 40 minutes, warmed to room temperature and stirred for 3 hours. Next, after cooling to 0 ° C, aluminum chloride (75.1 g, 0.563 mol) was added. 4-Chlorobutyryl chloride (79.4 g, 0.563 mol) was added dropwise over 40 minutes, warmed to room temperature and stirred for 3 h. A mixed solution of 156 ml of a 35 mass% aqueous hydrochloric acid solution and 392 ml of distilled water was cooled to 0 ° C, and the reaction solution was added dropwise. The precipitated solid was suction filtered, washed with distilled water and methanol, and recrystallized from acetonitrile to obtain Compound A (yield: 164.4 g, yield: 77%).

(2) Synthesis of Compound B

Next, Compound B was synthesized using Compound A in the following procedure.

Compound A (20.0 g, 47.9 mmol) was dissolved in 64 mL of THF and 4-chlorobenzenethiol (7.27 g, 50.2 mmol) and sodium iodide (0.7 g, 4.79 mmol). Next, sodium hydroxide (2.0 g, 50.2 mmol) was added to the reaction liquid, and refluxed for 2 hours. Next, after cooling to 0 ° C, sodium methoxide 28% methanol solution (manufactured by Nippon Shokubai Co., Ltd.: SM-28) (11.1 g, 57.4 mmol) was added dropwise for 20 minutes, and the temperature was raised to room temperature and stirred. hour. Next, after cooling to 0 ° C, isoamyl nitrite (6.73 g, 57.4 mmol) was added dropwise for 20 minutes, and the mixture was warmed to room temperature and stirred for 3 hours. The reaction solution was diluted with 120 ml of acetone, and a 0.1 N aqueous solution of hydrochloric acid cooled to 0 ° C was added dropwise. The precipitated solid was suction filtered, and washed with distilled water. Then, it was recrystallized from acetonitrile to obtain a compound B of the following structure (yield: 17.0 g, yield: 64%).

(3) Synthesis of Compound 1

Next, the initiator 1 was synthesized using the compound B in the following procedure.

Compound B (18.0 g, 32.4 mmol) was dissolved in 90 mL of N-methylpyrrolidone and triethylamine (3.94 g, 38.9 mmol) was added. Second. After cooling to 0 ° C, ethyl ruthenium chloride (3.05 g, 38.9 mmol) was added dropwise over 20 minutes, then warmed to room temperature and stirred for 2 hours. The reaction solution was added dropwise to 150 ml of distilled water cooled to 0 ° C, and the precipitated solid was suction filtered, washed with 200 ml of isopropyl alcohol cooled to 0 ° C, and dried to obtain the following. Compound 1 of structure (yield 19.5 g, yield 99%).

(Example 1) <Preparation of Colored Photosensitive Composition>

The coloring photosensitive composition of Example 1 was prepared by stirring and mixing the components shown in the following composition 1.

(composition 1)

The abbreviation of the above solvent is as follows:

PGMEA=propylene glycol acetate monomethyl ether ester

EEP=3-ethoxyethyl propionate

(Compound III)

<Coloring pattern formation using a coloring photosensitive composition>

Using the colored photosensitive composition obtained as described above, a colored pattern was formed on the glass substrate as follows.

- Formation of a coloring photosensitive composition layer -

The obtained coloring photosensitive composition was applied to a glass substrate (Morning, manufactured by Corning Incorporated, 0.7 mm thickness). Specifically, the interval between the slit nozzle and the substrate and the discharge amount were adjusted so that the film thickness of the colored composition layer after post-baking was about 2.4 μm, and the coating was applied at a coating speed of 120 mm/sec.

- pre-baking step -

Next, the colored photosensitive composition layer was dried using a vacuum drying apparatus until the degree of vacuum reached 66 Pa, and then heated at 90 ° C for 120 seconds using a hot plate (prebaking treatment).

- Exposure step (near exposure) -

After the prebaking treatment, exposure was carried out at 40 mJ/cm ² using a proximity exposure machine (manufactured by Hitachi High-Technologies Corp., LE5565A).

- development step, baking (post baking) step -

Then, using a developing device (manufactured by Hitachi High-Technologies Corporation), a 1.0% developer solution of potassium hydroxide-based developer CDK-1 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) The CDK-1 is 1 part by mass, the diluted solution of 99 parts by mass of pure water, 25 ° C), the spray pressure is set to 0.2 MPa, and developed for 60 seconds, and then washed with pure water.

After sufficiently drying, it was baked after being applied in an oven at 230 ° C for 40 minutes.

(Examples 2 to 37, Comparative Examples 1 to 18)

In the composition 1 of the first embodiment, the type of the pigment dispersion liquid, the type of the photopolymerization initiator 1, the type and amount of the additive, and the addition amount are as described in Tables 1 to 3, and the examples are the same as the examples. 1 Each of the colored photosensitive compositions of Examples 2 to 37 and Comparative Examples 1 to 18 was prepared in the same manner. Further, the colored pattern was produced in the same manner as in Example 1 except that the exposure method in the exposure step was changed to the ones as described in Tables 1 to 3, respectively.

In Tables 1 to 3, the details of the exposure mode marked as the proximity are the exposure modes (close-up exposure) to which the exposure step of Embodiment 1 is applied. Further, in Tables 1 to 3, the details of the exposure method marked as laser are as follows.

- Exposure step (laser exposure) -

After the prebaking treatment, the laser exposure device uses EGIS (V Technology, YAG laser third higher order wave, wavelength 355 nm, pulse width 6 nsec), and a photosensitive resin composition layer The surface was subjected to 20 times of pulse irradiation of about 1 mJ/cm ² through the mask.

In the table, - is representative of not added, G is representative of green, and B is representative of blue.

Compound I: Sumilizer GM (Sumitomo Chemical)

Compound II: Sumilizer GS (Sumitomo Chemical)

Compound 2: the following structure

Compound 3: the following structure

Compound 4: the following structure

Karenz MTBD-1: Butanediol bis(3-hydrothiobutyrate)

<evaluation>

Each of the colored patterns obtained was evaluated for each item of linearity, shape, chip, solvent resistance, and light resistance. The evaluation methods and evaluation criteria are as follows.

1. Evaluation of the linearity of the coloring pattern -

The evaluation of the linearity of the coloring pattern was performed by using an optical microscope to reflect 200 times, a photograph of the edge portion of the photographic coloring pattern, and the pixel edge portion was observed in a 5 cm × 5 cm photograph and evaluated according to the following criteria.

- Evaluation benchmark -

○: The edge portion of the coloring pattern looks straight

△: One part of the coloring pattern (1/4 or less of the entire length) is zigzag (zigzag)

╳: The edge portion of the coloring pattern is jagged more than 1/4 of the total length

The edge portion of the colored pattern preferably appears to be a straight line.

That is, when the edge portion of the colored pattern becomes jagged due to a residual film, undercut or the like, a colored pattern (pixel pattern) for forming a color filter using the colored photosensitive composition of the present invention is used. In the case of a large black matrix, it is necessary to reduce the aperture ratio due to the expansion of the width of the black matrix. Further, if a large overlap with the black matrix is not taken, there is a possibility that a portion where white light is leaked due to no coloring pattern occurs in the vicinity of the edge of the black matrix. Further, when the edge portion of the colored pattern is in a zigzag shape, there is a problem in practical application in which the transparent electrode formed thereon is broken and the resistance value is increased.

2. Evaluation of the shape, brightness and gap of the colored pattern

The shape and the notch of the coloring pattern were measured by using an optical microscope to reflect a photograph of the edge portion of the 200-times coloring pattern by each of the color filters obtained above, and the shape and the notch were evaluated according to the following criteria.

Here, as for the notch, although (A) the edge portion is lost in the shape of a half moon, and (B) is more elongated than (A), it is considered that the line width is discontinuously thinner than the circumference, Any of the notched shapes is observed even if one is observed. In this assessment, the gap is considered to be a gap even if one is observed.

When a gap occurs, it is not good for practical applications because some of it leaks white light.

Further, the luminance was measured using OSP-SP100 (manufactured by Olympus Corporation).

- Evaluation benchmark -

○: (2-1) The shape of the colored pattern is a forward tapered shape or a rectangular shape, (2-2) no gap, and (2-3) a high luminance

╳: In the above items (2-1) to (2-3), at least one item does not match

3. Evaluation of solvent resistance

The glass substrate on which the colored pattern was formed after the completion of the development step was baked at 230 ° C for 30 minutes using a convection oven. The chromaticity of the obtained baked substrate was measured using OSP-SP100 (manufactured by Olympus Co., Ltd.) in N-methyl-2-pyrrolidone (hereinafter, abbreviated as "NMP") at 23 After immersing for 30 minutes at ° C, ΔE*ab was determined from the chromaticity of the colored pattern before and after the immersion. The chromaticity was measured using OSP-SP100 (manufactured by Olympus Co., Ltd.).

When the ΔE*ab is 3 or more, various types of solvent resistance used in the panel processing are insufficient in the manufacture of a liquid crystal display device, and the like.

Further, the change in the shape of the coloring pattern before and after the immersion of NMP was observed using an optical microscope.

Based on the results obtained, the evaluation was carried out according to the evaluation criteria described below.

- Evaluation benchmark -

○: (3-1) ΔE*ab is 3.0 or less, and (3-2) no change is observed in the shape of the colored pattern.

╳: At least one of the items (3-1) and (3-2) above does not match

4. Evaluation of lightfastness

The glass substrate having the colored pattern after post-baking was subjected to the same evaluation as the solvent resistance described above, and ITO sputtering was performed under the conditions shown in Table 4 below.

The substrate after the ITO sputtering was placed in a xenon weather meter "SX-75" (manufactured by Suga Test Instruments Co., Ltd.) at a temperature of 30 ° C. The temperature was 50%, and the black panel temperature was 63 ° C. 180 W for 120 hours was irradiated from the ITO side.

Thereafter, the chromaticity of the substrate was measured using OSP-SP100 (manufactured by Olympus Co., Ltd.), and ΔE*ab was measured from the chromaticity of the coloring pattern before and after the irradiation.

In the evaluation, those having a ΔE*ab of 3.0 or less were evaluated as excellent in light resistance.

The above evaluation results are shown in Table 5 below.

As shown in Table 5, each of the colored patterns (colored films) obtained by using the colored photosensitive composition of the examples was excellent in linearity, good in shape, and free from chipping, and was also excellent in light resistance and solvent resistance. On the other hand, each of the colored patterns obtained by using the colored photosensitive compositions of Comparative Examples 1 to 18 had a light resistance of ΔE*ab before and after the irradiation exceeding 3.0 and was inferior in light resistance.

As can be seen from Comparative Examples 3, 4, 8, and 9, the non-polymerizable radical scavenger has a light-resistance improving effect, but the (F) polymerizable compound having a radical trapping energy in the present invention is improved. The effect is more significant and long-term reliability can be achieved.

In addition, according to the comparison between Embodiment 2 and Embodiment 1, the same good results can be obtained in any of the embodiments, and therefore, it is known that even in the case of applying the pattern exposure via the laser exposure machine, it is also possible to pass through the high pressure mercury lamp. The exposure is equally obtained to obtain the excellent effects of the present invention.

Claims (11)

A colored photosensitive composition comprising: (A) a color material having a phthalocyanine skeleton, (B) a solvent, (C) a polymerizable monomer, (D) a binder resin, and (E) a photopolymerization initiator And (F) a polymerizable compound having a radical trapping energy. The colored photosensitive composition of the first aspect of the invention, wherein the content of the (F) polymerizable compound having a radical trapping energy is 0.1% by mass or more and 5.0% by mass or less based on the total solid content. The colored photosensitive composition of claim 1, wherein the (F) polymerizable compound having a radical trapping energy has an amine structure or a phenol structure. The colored photosensitive composition according to the first aspect of the invention, wherein the (F) polymerizable compound having a radical trapping energy has at least one selected from the group consisting of an acryloyl group and a methacryl group as a polymerizable group. . The colored photosensitive composition of the first aspect of the invention, wherein the (F) polymerizable compound having a radical trapping energy is at least one selected from the group consisting of the following general formulae (1), (5), and (6); : [In the above formulae (1), (5) and (6), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a cyano group, a hydroxyl group, and a carbon number; An alkyl group of 10 or less, an alkoxycarbonyl group having a carbon number of 10 or less, an alkylsulfonylaminocarbonyl group having a carbon number of 10 or less, an arylsulfonylaminocarbonyl group, an alkylsulfonyl group, an arylsulfonyl group a mercapto group, a mercaptoaminosulfonyl group having a carbon number of 10 or less, an alkoxy group having a carbon number of 10 or less, an alkylthio group having a carbon number of 10 or less, an aryloxy group having a carbon number of 10 or less, and a nitrate a group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a decyloxy group having a carbon number of 10 or less, a mercapto group having a carbon number of 10 or less, an amine methyl sulfonyl group, an amine sulfonyl group, and a carbon number of 10 or less An aryl group, a substituted amine group, a substituted ureido group, a substituted phosphonic acid group, or a heterocyclic group; R ⁴ is a hydrogen atom or an alkyl group having a carbon number of 30 or less; R ⁵ and R ⁶ are Each independently represents a branched alkyl group having a carbon number of 30 or less; X is an aliphatic alkyl chain representing a single bond, an ester group, a carbon number of 30 or less, an aromatic chain, a polyethylene glycol chain, or a combination thereof. The (m+n) valence linkage; m and n are Since independently represents an integer of 1 to 3]. The colored photosensitive composition of claim 1, wherein at least one of the (A) color materials contains a metal in a chemical structure. The colored photosensitive composition of claim 1, wherein at least one of the (A) color materials is a green pigment. The colored photosensitive composition of claim 1, wherein at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58 is contained as the (A) color material. A method of producing a color filter, comprising the steps of: applying a colored photosensitive composition according to any one of claims 1 to 8 to a substrate to form a colored layer; and exposing the colored layer After the pattern is formed, the uncured portion is removed by the developer to form a colored pattern. A color filter manufactured by the manufacturing method of claim 9 of the patent application. A liquid crystal display device comprising the color filter of claim 10 of the patent application.