TW201314361A - Pigment composition and color filter - Google Patents

Abstract

A pigment composition excellent in transparency and dispersibility is provided. The pigment composition comprises (A) a pigment, (B) a copolymer containing a structural unit represented by general formula (b-1) and a structural unit represented by general formula (b-2), and (C) a solvent.

Description

Pigment composition and color filter

The present invention relates to a pigment composition, a photosensitive composition containing the pigment composition, a color filter produced using the photosensitive composition, a method of producing the color filter, and a liquid crystal display having the color filter Device, and solid-state imaging device.

The color filter contains a pigment composition in which an organic pigment or an inorganic pigment is dispersed, and a polyfunctional monomer, a photopolymerization initiator, an alkali-soluble resin, and other components are used as a photosensitive composition, and are used by a lithography method or the like. It is manufactured by forming a colored pattern.

In recent years, color filters have been used in liquid crystal display devices (LCDs), and their use has not only been extended to monitors but also to televisions (TVs). With the tendency to expand this use, high color characteristics are required in the chromaticity, brightness, contrast, and the like of the color filter. Further, even in a color filter used for an image sensor (solid-state imaging device), a color characteristic is required in the same manner.

Here, in the solvent-based pigment dispersion, generally, a dispersant or a resin having high affinity with a pigment and a solvent is contained in order to disperse the pigment. For example, Japanese Laid-Open Patent Publication No. Hei 11-197485 discloses the use of a dispersing agent having an ethyleneimine group to improve the adsorptivity to a pigment.

In the above-mentioned Japanese Patent Publication No. Hei 11-197485, the inventors of the present invention conducted a review, and as a result, it was found that the imine group (alkali) is easily heat-colored and impairs the color filter. The transparency required for the light sheet. Further, as a method of manufacturing a color filter, a photosensitive resist is generally used. However, in a process using a photoresist, there is a step of removing an unnecessary portion and removing it, and the pair of developing solutions for the resist used for the photoresist The effect is so that even in the dispersion, alkali solubility is required.

In order to solve the above problems, the present invention aims to provide a photosensitive composition having high transparency and excellent alkali developability, and a pigment composition for adjusting the photosensitive composition.

In the above-mentioned problem, the inventors of the present invention conducted a review and found that by introducing a highly flexible polyester chain and a carboxylic acid into the polymer, it is possible to provide the same dispersibility as in the related art while ensuring transparency. Further, the present invention has finally been completed by a pigment composition excellent in solubility in an alkali developing solution.

Specifically, it is achieved by the following <1>. Better achieved by <2>~<13>.

<1> A pigment composition comprising: (A) a pigment, (B) comprising at least one structural unit represented by the following formula (b-1) and at least one of the formula (b-2) a copolymer of structural units, and (C) a solvent; (In the above formula (b-1), R ¹ represents a hydrogen atom or a methyl group; L is a group represented by -XO-, X is a linear or branched alkylene group; and W is a linear or branched chain. Alkyl, n is an integer from 1 to 12); (In the formula (b-2), R ² represents a hydrogen atom or a methyl group).

<2> The pigment composition according to <1>, wherein 70% by weight or more of the copolymer (B) is a structural unit represented by the formula (b-1).

<3> The pigment composition according to <1> or <2> wherein the (B) copolymer has a weight average molecular weight of from 5,000 to 50,000.

The pigment composition according to any one of the above-mentioned general formula (b-1), wherein the X-type linear chain has an alkyl group having 1 to 6 carbon atoms, and the W system A linear alkyl group having 3 to 10 carbon atoms.

<5> The pigment composition according to any one of <1> to <4>, wherein the weight ratio of the structural unit represented by the formula (b-1) to the structural unit represented by the formula (b-2) It is 60~95:40~5.

The pigment composition of any one of <1> to <5>, wherein the (B) copolymer is the following polymer; (In the above formula, R ¹ and R ² each represent a hydrogen atom or a methyl group; a: b is 3 to 25: 97 to 75, and n is an integer of 1 to 6).

The pigment composition according to any one of <1> to <6> wherein the (A) pigment has an average primary particle diameter of 10 to 50 nm.

<8> The pigment composition according to any one of <1> to <7>, It further contains (D) a pigment dispersant.

<9> A photosensitive composition according to any one of <1> to <8>, wherein (E) a photopolymerizable compound and (F) a photopolymerization initiator are contained.

<10> The photosensitive composition according to <9>, which further contains an alkali-soluble resin.

<11> A color filter having a coloring pattern formed using the photosensitive composition as described in <9> or <10>.

<12> A liquid crystal display device or a solid-state image sensor comprising the color filter according to <11>.

<13> A method of producing a color filter comprising: applying a photosensitive composition as described in <9> or <10> to a substrate directly or via another layer to form a photosensitive film of a photosensitive film The forming step and the patterning and developing of the pattern on the formed photosensitive film are sequentially performed to form a colored pattern forming step of the colored pattern.

According to the present invention, a pigment composition excellent in transparency and dispersibility can be provided.

[Formation of the Invention]

Hereinafter, the contents of the present invention will be described in detail. In addition, the "~" in the present specification is used to mean that the numerical values described before and after are used as the lower limit and the upper limit.

The pigment composition of the present invention is characterized by comprising: (A) a pigment, (B) at least one structural unit represented by the following formula (b-1) and at least one a copolymer of a structural unit represented by the formula (b-2), and (C) a solvent. Hereinafter, the pigment composition of the present invention will be described in detail.

(A) pigment

The pigment which can be used for the pigment composition of the present invention is not particularly limited as long as it does not deviate from the gist of the present invention, and any of various inorganic pigments and organic pigments which are conventionally known can be used. It is preferably a pigment having an average primary particle diameter of 10 to 50 nm, more preferably a pigment having an average primary particle diameter of 10 to 40 nm. By using the pigment having an average primary particle diameter in this range, a photosensitive composition for a color filter having excellent dispersibility stability or coloring power and high contrast and high contrast can be obtained.

Hereinafter, representative pigments usable in the present invention will be mentioned.

The red pigment which can be used in the present invention includes the entire red pigment used in the production of a usual color filter, and specific examples thereof include CI Pigment Red (PR) 1, 2, 3, 4, 5, and 6. 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 279, etc., but not particularly limited thereto, various red pigments can be used.

The yellow pigment which can be used in the present invention includes the entire yellow pigment used in the production of a usual color filter, and specific examples thereof include CI Pigment Yellow (PY) 1, 2, 3, 4, 5, and 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, etc., but Not particularly limited by these, various yellow pigments can be used.

The green pigment which can be used in the present invention includes all of the green pigments used in the production of a usual color filter, and specifically, for example, CI Pigment Green (PG) 7, 10, 36, 37, 58, and JP-2008- The zinc halide phthalocyanine pigments and the like described in JP-A-2004-70342, and the like are not particularly limited, and various green pigments can be used.

The blue pigment and the violet pigment which can be used in the present invention include all of the blue pigments used in the production of a usual color filter, and specific examples thereof include CI Pigment Blue (PB) 15, PB 15: 2, and PB 15 . : 3, PB15: 4, B15: 5, PB15: 6, PB16, PB79, CI Pigment Violet (PV) 19, 23, 29, etc., but not particularly limited by these, can use various blue pigments, purple pigment.

Among the above pigments, preferred are PG58, PG36, PY138, PY150, PB15:6, PR254 or PR177. If such a pigment is used, it can be mentioned The color supply is high in purity and high in transparency, and is suitable for a pigment dispersion of a color filter.

Further, in the present invention, the average primary particle diameter is obtained by capturing a particle in a field of view by a transmission electron microscope, and for each of 400 primary particles of a pigment constituting agglomerates on a secondary image. The average of the diameter (long diameter) of the elder and the diameter (short diameter) of the short is the average value.

The method for preparing a pigment having an average primary particle diameter of 10 nm to 50 nm is not particularly limited, and the particle diameter can be adjusted to the above range by microparticles by any method, but the crystal growth can be easily suppressed. Further, in order to obtain a pigment particle having a relatively small primary particle diameter, a method of adjusting the pigment to the average primary particle diameter is preferably a solvent salt milling treatment.

For the solvent salt milling treatment, reference is made to paragraphs 0022 to 0030 of JP-A-2011-145668.

The pigment used in the present invention needs to have an average primary particle diameter of 10 nm or more and 50 nm or less. From the viewpoint of comparison, the average primary particle diameter is more preferably 10 nm or more and 40 nm or less, and particularly preferably 10 nm or more and 35 nm or less.

The content of the pigment in the pigment composition of the present invention can be selected according to the purpose, but it is preferably from 5 to 30% by weight in the pigment composition, and more preferably from the viewpoint of dispersion stability. 20% by weight range.

(B) copolymer

The (B) copolymer used in the present invention contains at least one structural unit represented by the following formula (b-1) and at least one structural unit represented by the formula (b-2); (In the above formula (b-1), R ¹ represents a hydrogen atom or a methyl group; L is a group represented by -XO-, X is a linear or branched alkylene group; and W is a linear or branched chain. Alkyl, n is an integer from 1 to 12); (In the formula (b-2), R ² represents a hydrogen atom or a methyl group).

In the formula (b-1), R ^{1 is} preferably a methyl group.

The L system is bonded to the O atom side in the formula (b-1). That is, it has a structure of a main chain -C(=O)OXO-(CO-WO-) _n H).

X is preferably a linear alkylene group. The carbon number of the alkyl group which X has is preferably from 1 to 6, more preferably from 2 to 4.

In the formula (b-1), W is preferably a linear alkyl group. Further, the carbon number of W is preferably from 3 to 10, more preferably from 4 to 8.

n is an integer from 1 to 12, preferably an integer from 1 to 8, more preferably an integer from 1 to 6. A mixture of these is preferred.

In the formula (b-2), R ^{2 is} preferably a hydrogen atom.

The copolymer (B) used in the present invention is preferably 70% by weight or more of the structural unit of the formula (b-1), and more preferably 80% by weight or more of the structural unit is a formula (b-1). ) The constituent units shown.

In addition, the copolymer (B) may contain only one type of the constituent unit represented by the formula (b-1) and the constituent unit represented by the formula (b-2), and may contain two or more types.

The ratio (weight ratio) of the structural unit represented by the formula (b-1) to the structural unit represented by the formula (b-2) is preferably 60 to 95:40 to 5, more preferably 70 to 95:30. ~5, especially good is 80~93:20~7.

The copolymer (B) used in the present invention may contain other constituent units, but is preferably 20% by weight or less, and more preferably 10% by weight or less based on all the constituent units. As an example of another structural unit, the structural unit represented by the following general formula (b-3) can be illustrated.

(In the formula (b-3), R ³ is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group or an aryl group).

The carbon number of R ⁴ is preferably from 1 to 10.

The weight average molecular weight (Mw) of the (B) copolymer used in the present invention is preferably from 5,000 to 50,000.

The (B) copolymer used in the present invention can be produced by a well-known method.

In the present invention, it is particularly preferred to use the following copolymer (B).

(In the above formula, R ¹ and R ² each represent a hydrogen atom or a methyl group; a: b is 3 to 25: 97 to 75, and n is an integer of 1 to 6).

More preferably, R ¹ is a methyl group and R ² is a hydrogen atom.

The (B) copolymer used in the present invention is preferably contained in the pigment composition of the present invention in an amount of from 1 to 10% by weight, more preferably from 2 to 8% by weight. (B) The copolymer may contain two or more types, and in this case, the total amount of these is preferably in the above range.

Further, the pigment composition of the present invention preferably does not substantially contain a polymer having an imine group. For example, it means that the polymer having an imine group is 1% by weight or less of the pigment composition.

(C) solvent

The pigment composition of the present invention further contains a solvent.

As the solvent (C) usable in the present invention, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and butyl propionate may be mentioned. Ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate Ethyl 3-oxopropionates; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methacrylate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, pyruvic acid Pyruvate, propyl pyruvate, methyl acetyl, acetyl acetate Ester, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; aromatic hydrocarbons Classes such as toluene, xylene, and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether are preferred. , butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl Ether acetate and the like.

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

The content of the solvent (C) in the pigment composition is appropriately selected depending on the use of the pigment composition or the like. When the pigment composition is used in the preparation of a photosensitive composition to be described later, the solid content concentration of the (A) pigment, the (B) polymer, and the desired pigment dispersant can be used from the viewpoint of workability. It is contained in a form of 5 to 50% by weight.

Other ingredients

In the pigment composition of the present invention, in addition to the components (A) to (C) described above, various additives may be used in combination as long as the effects of the present invention are not impaired.

(D) Pigment Dispersant

As the pigment dispersant, a well-known pigment dispersant or a surfactant can be appropriately selected and used.

Specifically, the compound described in paragraphs [0021] to [0089] of JP-A-2009-256572, the organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and (meth)acrylic acid are mentioned. a cationic surfactant such as Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) or W001 (manufactured by Yusei Co., Ltd.); polyoxyethylene Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactant such as distearate or sorbitan fatty acid ester; anionic surfactant such as W004, W005, W017 (manufactured by Yusei Co., Ltd.); EFKA-46, EFKA-47 EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by CIBA SPECIALTY CHEMICALS), Disperseaid 6, Disperseaid 8, Disperseaid 15, Disperseaid 9100 (all SAN NOPCO) Polymer dispersant, etc.; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Solsperse dispersant (made by LUBRIZOL Co., Ltd.); Adekapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P- 123 (Asahi Kasei Co., Ltd.) and Isonet S-20 (Sanyo Chemical 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 (share) system). Further, an oligomer or a polymer having a polar group at a molecular terminal or a side chain such as an acrylic copolymer may be mentioned.

When the pigment composition is used in combination with the pigment dispersant, the amount of the pigment dispersant is preferably 1 to 100 parts by weight, more preferably 3, based on 100 parts by mass of the pigment (A). ~70 copies.

Further, the pigment composition of the present invention may optionally contain a dye derivative. The pigment derivative is a compound in which a part of a structure or a polar group having affinity with a dispersing agent is introduced into a pigment, and the pigment derivative is adsorbed on the surface of the pigment, and the adsorption point of the dispersing agent is used as a pigment to make the pigment fine. The particles are dispersed in the pigment composition to prevent re-agglomeration, and are effective for forming a color filter having high contrast and excellent transparency.

The content of the pigment derivative in the pigment composition is preferably from 1 to 30 parts, more preferably from 3 to 25 parts, per 100 parts by mass of the pigment. When the content is within the above range, the dispersion can be favorably dispersed while reducing the viscosity, and the dispersion stability after dispersion can be improved, and high transmittance and excellent color characteristics can be obtained, and the photosensitive composition of the present invention can be adjusted by using the composition. When a color filter is produced, a color filter having high contrast and good color characteristics can be obtained.

For the method of adjusting the pigment composition, reference is made to paragraphs 0042 to 0044 of JP-A-2011-145668.

Since the pigment composition of the present invention has good dispersibility and contrast of the pigment, it can be used for various applications requiring coloring, and is particularly suitable for use in a photosensitive composition used in the production of a color filter.

<Photosensitive composition>

The photosensitive composition of the present invention contains the pigment composition of the present invention described above The material (E) polymerizable compound, (F) photopolymerization initiator and the desired alkali-soluble resin may contain other components as needed. Hereinafter, each component contained in the photosensitive composition of the present invention will be described in detail.

Pigment composition

The photosensitive composition of the present invention is composed of at least one of the pigment compositions of the present invention.

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

(E) Photopolymerizable compound

The photosensitive composition of the present invention contains at least one of photopolymerizable compounds. The photopolymerizable compound usable in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a compound group is widely known in the industrial field, and the present invention can be used without particular limitation. These include, for example, chemical forms of monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and copolymers thereof. Examples of the monomer and the copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or esters thereof and guanamines. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyvalent alcohol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used. Further, it is also possible to suitably use a nucleophilic substituent having a hydroxyl group, an amine group, a thiol group or the like And an addition reaction of a carboxylate or a guanamine with a monofunctional or polyfunctional isocyanate or an epoxy, and a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid. Further, in order to promote development, a compound having an organic acid group such as an alkylene oxide group or a carboxylic acid group in the structure may be suitably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted carboxylic acid ester having a cleavable substituent such as a halogen group or a tosyloxy group or a guanamine and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable. Further, as another example, a compound group such as an unsaturated phosphonic acid, styrene or vinyl ether may be used instead of the above unsaturated carboxylic acid.

Specific examples of the monomer of the ester of the aliphatic polyvalent alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butylene glycol in the acrylate. Acrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether , trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol IV Acrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene oxy ethoxylate) A heteropolycyanate, a polyester acrylate oligomer, an isocyanuric acid EO modified triacrylate, or the like.

Among the methacrylates, there are tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate. , trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate , pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double [p-(3-Methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethyl Methane, etc.

In itaconate, there are ethylene glycol dicone ester, propylene glycol diconconate, 1,3-butanediol diconcanate, 1,4-butanediol diconcanate, Tetramethylene glycol diconconate, pentaerythritol diconconate, sorbitol tetraconcanate, and the like. Among the crotonic acid esters, there are ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradodetoic acid ester and the like. Among the isocrotonate, there are ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Among the maleate esters, there are ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like.

The details of the photopolymerizable compound, such as the structure, the use alone or in combination, or the amount of addition, can be arbitrarily set in accordance with the performance design of the final photosensitive composition. For example, choose from the following points of view.

In the case of sensitivity, it is preferred to have a structure in which the content of the unsaturated group per molecule is large, and in the case of many, it is preferably a bifunctional or higher. Further, in order to increase the strength of the cured film, it may be a trifunctional or higher functional group, and further, a different functional number may be used in combination. Different polymerization groups (for example, acrylate, methacrylate, styrene compound, vinyl ether compound), and methods for adjusting both sensitivity and strength are also effective.

Moreover, the compatibility with the other components in the photosensitive composition, such as a binder polymer such as an alkali-soluble resin, a photopolymerization initiator, and the like, and the dispersibility of the pigment, the selection of the polymerizable compound. The use of the method is an important factor, and for example, the use of a low-purity compound or a combination of two or more kinds thereof can improve the compatibility.

Further, for the purpose of improving adhesion to a substrate or the like, a specific structure may be selected. (E) The photopolymerizable compound is preferably used in an amount of from 5 to 70% by weight, more preferably from 10 to 60% by weight, based on the nonvolatile component in the photosensitive composition. Further, these may be used alone or in combination of two or more. Further, the method of using the photopolymerizable compound can be arbitrarily selected from the viewpoints of the size of the polymerization inhibition of oxygen, the resolution, the blushing property, the refractive index change, and the surface tackiness, and the like. .

(F) Photopolymerization initiator

The photosensitive composition of the present invention contains at least one of (F) a photopolymerization initiator. The photopolymerization initiator is, for example, a halomethyl group described in JP-A-57-6096. Halomethyl-s-three described in the oxadiazole, Japanese Patent Publication No. Sho 59-133428, and the like An aromatic carbonyl compound such as a ketal, an acetal or a benzoin alkyl ether described in each of the descriptions of the active halogen compound, the US Patent No. 4,381,879, the European Patent Publication No. EP88050A, and the like. An aromatic ketone compound such as a diphenyl ketone or a coumarin or an acridine compound described in the specification of Fr-2456741, or a coumarin or a profenamine described in JP-A-10-62986 A compound such as an alkali dimer or the like, a ruthenium organoboron compound described in JP-A-8-015521, and the like.

Among them, the photopolymerization initiator is preferably an acetophenone-based, a ketal-based, a diphenylketone-based, a benzoin-based, a benzamidine-based, or a xanthone-based system. Halomethyl A oxadiazole type, an acridine type, a coumarin type, a lovin base dimer type, a bisimidazole type, etc.

As the photopolymerization initiator of the acetophenone type, for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1 can be suitably used. -Phenyl-propan-1-one, p-dimethylaminoacetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, and the like.

The ketal-based photopolymerization initiator may, for example, be a benzyldimethylketal or a benzyl-β-methoxyethylacetal.

The diphenyl ketone-based photopolymerization initiator may, for example, be diphenyl ketone, 4,4'-(bisdimethylamino)diphenyl ketone or 4,4'-(double bis). Ethylamino)diphenyl ketone, 4,4'-dichlorodiphenyl ketone, 1-hydroxy-cyclohexyl-phenyl-one, 2-benzyl-2-dimethylamino-1- 4-morpholinylphenyl)-butanone-1, 2-tolyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-methyl-1 -[4-(Methylthio)phenyl]-2-morpholinylacetone-1 and the like.

As the photopolymerization initiator of the benzoin system or the benzamidine system, for example, benzoin isopropyl ether, benzoin isobutyl ether, and benzene can be suitably used. Alanine methyl ether, methyl phthalyl benzoyl benzoate and the like.

Examples of the xanthone-based photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, and chlorothioxanthone.

As the aforementioned three The photopolymerization initiator is, for example, suitably 2,4-bis(trichloromethyl)-6-p-methoxyphenyl-s-three , 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-three 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-three 2,4-bis(trichloromethyl)-6-biphenyl-s-three , 2,4-bis(trichloromethyl)-6-(p-methylbiphenyl)-s-three P-hydroxyethoxystyryl-2,6-di(trichloromethyl)-s-three Methoxystyryl-2,6-di(trichloromethyl-s-three 3,4-dimethoxystyryl-2,6-di(trichloromethyl)-s-three 4-Benzene Molar-2,6-di(trichloromethyl)-s-three , 4-(o-bromo-pN,N-(diethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)-s-three , 4-(pN,N-(diethoxycarbonylamino)-phenyl)-2,6-di(chloromethyl)-s-three Wait.

As the aforementioned halomethyl The diazole-based photopolymerization initiator may, for example, suitably be 2-trichloromethyl-5-styryl-1,3,4- Diazole, 2-trichloromethyl-5-(cyanostyryl)-1,3,4- Diazole, 2-trichloromethyl-5-(naphthoquinone-1-yl)-1,3,4- Diazole, 2-trichloromethyl-5-(4-styryl)styryl-1,3,4- Diazole and the like.

Examples of the acridine-based photopolymerization initiator include 9-phenyl acridine and 1,7-bis(9-acridinyl)heptane.

As the photopolymerization initiator of the coumarin-based type, for example, 3-methyl-5-amino group-((s-three) can be suitably used. -2-yl)amino)-3-phenylcoumarin, 3-chloro-5-diethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-three) -2-yl)amino)-3-phenylcoumarin.

As the photopolymerization initiator of the above-mentioned lovin base dimer type, for example, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2-(o-methoxy) can be suitably used. Phenylphenyl)-4,5-diphenylimidazolyl dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, and the like.

The diimidazole-based photopolymerization initiator may, for example, be 2-mercaptobenzimidazole or 2,2'-benzothiazole disulfide.

In addition to the above, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, o-benzidine-4'-(benzoxanyl)benzimid-hexyl- Ketone oxime, 2,4,6-trimethylphenylcarbonyl-diphenylphosphonium ruthenium oxide, hexafluorophosphono-trialkylphenyl sulfonium salt and the like.

The photopolymerization initiator usable in the present invention is not limited to the above photopolymerization initiator, and other known ones may be used. For example, a vicinal ketone aldehyde compound described in the specification of U.S. Patent No. 2,367,660, an α-carbonyl compound described in the specification of U.S. Patent Nos. 2,367,661 and 2,367,670, and an even one described in the specification of U.S. Patent No. 2,448,828. And a polynuclear oxime compound described in the specification of U.S. Patent Nos. 3,046,127 and 2,951,758, and the disclosure of the specification of U.S. Patent No. 3,549,367, the disclosure of which is incorporated herein by reference. A combination of a triaryl imidazole dimer/p-aminophenyl ketone, a benzothiazole compound/trihalomethyl-s-three described in Japanese Patent Publication No. Sho 51-48516 A compound or the like.

Further, these photopolymerization initiators may be used in combination.

The content of the photopolymerization initiator in the photosensitive composition is preferably from 0.1 to 15.0% by mass, and more preferably from 0.5 to 10.0% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is within the above range, the polymerization reaction proceeds favorably, and a film having good strength can be formed.

The photosensitive composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator (radical initiator) and increasing the wavelength of the photosensitive wavelength. As the sensitizer usable in the present invention, it is preferred that the sensitizer is made by an electron moving mechanism or an energy moving mechanism for the radical initiator.

The sensitizer which can be used in the present invention includes the following compounds, and has an absorption wavelength in a wavelength range of 300 nm to 450 nm.

Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.

For example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, triphenylene, 9,10-dialkyloxyanthracene) and xanthene (for example, fluorescein, ruthenium, erythrosine, and if Danming B, rose red), thioxanthone (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanine (eg thiocarbonate, Carbon blue), green (such as green, carbon blue), phthalocyanine, thio Classes (such as thioindigo, methylene blue, toluidine blue), acridines (such as acridine orange, chlorferrin, acridine yellow), terpenoids (such as hydrazine), square steroids (such as square 鎓) , acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), keto coumarin, thiophene Class, brown , styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, oxazoles, porphyrins, spiro compounds, quinacridones, indigo, styryl, Pyrylium sulfonium compound, methylene pyrrole compound, pyrazole triazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative, acetophenone, benzophenone, thioxanthone, Aromatic ketone compounds such as Michler's ketone, N-aryl group a heterocyclic compound such as oxazolinedione or the like.

The content of the sensitizer is preferably in the range of 0.1 to 30% by mass, particularly preferably 1 to 20%, based on the mass of all the solid components of the photosensitive composition from the viewpoint of sensitivity and storage stability. The range of % is more preferably in the range of 2 to 15% by mass.

The photosensitive composition of the present invention preferably further contains a co-sensitizer. In the present invention, the co-sensitizer has an effect of further increasing the sensitivity of the sensitizing dye or the initiator to the actinic radiation, or suppressing polymerization failure of the photopolymerizable compound by oxygen.

Examples of such a co-sensitizer include amines. For example, MRSander et al., "Journal of Polymer Society", Vol. 10, p. 3173 (1972), Japanese Patent Publication No. 44-20189, and JP-A-51- Japanese Unexamined Patent Publication No. Publication No. No. No. No. No. No. No. Nos. Nos. Nos. Nos. Nos. Nos. Nos. Nos. Nos. Nos. s. Specific examples of the compound and the like described in Disclosure No. 33,825 include triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-nonyldimethylaniline, p-methylthiodimethylaniline, and the like.

The sulfur sulphate and the sulphate of the sensitizing agent are exemplified by the sulphuric acid and the sulphide, and the sulphur is described in JP-A-53-702806, JP-A-55-500806, and JP-A-5-142772. The alcohol compound, the disulfide compound of JP-A-56-75643, and the like, specifically, 2-mercaptobenzothiazole and 2-mercaptobenzoene Oxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, β-mercaptophthalene, and the like.

Further examples of the co-sensitizer include an amino acid compound (for example, N-phenylglycine), an organometallic compound (for example, tributyltin acetate) described in Japanese Patent Publication No. 48-42965, and the like. A hydrogen compound (for example, trithiane or the like) described in JP-A-H05-344727, and the like.

The content of the total sensitizer is preferably from 0.1 to 30 by mass based on the mass of all the solid components of the photosensitive composition from the viewpoint of the improvement of the curing speed due to the polymerization growth rate and the balance of chain transfer. The range of % is particularly preferably in the range of 1 to 25% by mass, more preferably in the range of 0.5 to 20% by mass.

Sensitized pigment

In the photosensitive composition used in the present invention, it is preferred to add a sensitizing dye from the viewpoint of improving sensitivity. The radical reaction of the polymerization initiator component or the polymerization reaction of the polymerizable compound by the polymerization reaction of the polymerization initiator component is promoted by exposure of the wavelength absorbable by the sensitizing dye.

Examples of such a sensitizing dye include a well-known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

As the sensitizing dye usable in the present invention, preferred spectral sensitizing dyes or dyes are, for example, polynuclear aromatics (e.g., ruthenium, osmium, triphenylene), xanthene (e.g., luciferin, blush, red) Blush, rhodamine B, rose red), cyanine (such as thiocarbonate, Carbonic cyanine), phthalocyanines (eg, phthalocyanine, carbonyl phthalocyanine), thiophene Class (eg thiophene , methylene blue, toluidine blue), acridine (such as acridine orange, chloroflavon, acridine yellow), phthalocyanine (such as phthalocyanine, metal phthalocyanine), porphyrins (such as tetraphenyl) Porphyrins, central metal-substituted porphyrins, chlorophylls (eg, chlorophyll, chlorophyllin, central metal-substituted chlorophyll), metal complexes, terpenoids (eg, quinones), square quinones (eg, square quinones), and the like.

Other preferable aspects of the sensitizing dye include a compound group belonging to the following group and a dye having a maximum absorption wavelength at 350 to 450 nm.

For example, polynuclear aromatics (for example, ruthenium, osmium, tri-ortylene), xanthene (for example, luciferin, ruthenium, erythrosine, rhodamine B, rose red), cyanine (for example) Such as thiocarbonate, Carbonic cyanine), phthalocyanines (eg, phthalocyanine, carbonyl phthalocyanine), thiophene Class (eg thiophene , methylene blue, toluidine blue), acridine (such as acridine orange, chlorferrin, acridine yellow), terpenoids (such as hydrazine), square steroids (such as square 鎓).

Thiol compound

The thiol compound acts as a co-sensitizer and also has an effect of improving the adhesion to the substrate. The co-sensitizer further enhances the sensitivity of the sensitizing dye or the photopolymerization initiator to the active radiation, or suppresses the polymerization failure of the ethylenically unsaturated compound due to oxygen. The details of the thiol compound can be referred to in paragraphs 0123 to 0141 of JP-A-2011-122125.

The content of the thiol compound in the photosensitive composition is preferably from 0.1 to 5.0% by weight, more preferably from 0.2 to 4% by weight, based on the total solid content of the composition. Within this range, it is preferred because it does not impair the polymerizability.

Alkali soluble resin

In the photosensitive composition of the present invention, it is preferred to contain at least one of alkali-soluble resins. The alkali-soluble resin may be contained in the adjustment stage of the pigment composition, or may be added separately in two steps of the adjustment of the pigment composition and the adjustment stage of the photosensitive composition.

The alkali-soluble resin-based linear organic high molecular polymer may have at least one base which promotes alkali solubility (for example, a carboxyl group, from a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Among the alkali-soluble resins of a phosphate group, a sulfonic acid group or the like, it is suitably selected. Among them, those which are soluble in an organic solvent and which can be visualized by a weak aqueous alkali solution are more preferred.

In the production of the alkali-soluble resin, for example, a method by a well-known radical polymerization method can be employed. When the alkali-soluble resin is produced by a radical polymerization method, the polymerization conditions of the temperature, the pressure, the type and amount of the radical initiator, the kind of the solvent, and the like can be easily set by the industry, and the conditions can be experimentally determined. .

The linear organic high molecular polymer is preferably a polymer having a carboxylic acid in a side chain. For example, Japanese Patent Publication No. 59-44615, Special Public Show No. 54-34327, Special Public Show No. 58-12577, Special Public Show No. 54-25957, Special Open No. 59-53836, Special Open No. 59-71048 The methacrylic acid copolymer, the acrylic acid copolymer, the itaconic acid copolymer, the crotonic acid copolymer, the maleic acid copolymer, the partially esterified maleic acid copolymer, etc. described in each of the publications, and the carboxylic acid in the side chain An acidic polymer derivative, a polymer having a hydroxyl group, an acid anhydride additive or the like, and a polymer having an unsaturated bonding site such as a (meth) acryl fluorenyl group or an allyl group in the side chain, Also better.

Among these, a benzyl (meth)acrylate/(meth)acrylic copolymer or a multicomponent copolymer composed of benzyl (meth)acrylate/(meth)acrylic acid/other monomer is particularly suitable. Further, those in which 2-hydroxyethyl methacrylate is copolymerized or the like 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 copolymer and acrylic acid 2 described in JP-A-7-140654 -Hydroxy-3-phenoxypropyl ester / polymethyl methacrylate macromer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / Methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer.

As the specific constituent unit of the alkali-soluble resin, a copolymer of (meth)acrylic acid and a monomer copolymerizable therewith is particularly suitable.

Examples of the other monomer copolymerizable with the (meth)acrylic acid include an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted by a substituent.

Specific examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. Butyl acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl acrylate , toluene acrylate, naphthalene acrylate, cyclohexyl acrylate, and the like.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, and methacrylic acid. Tetrahydrofurfuryl ester, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH ₂ =CR ³¹ R ³² [here, R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms], and CH ₂ = C(R ³¹ )(COOR ³³ ) [wherein R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³³ represents carbon. A number of 1 to 8 alkyl groups or a carbon number of 6 to 12 aralkyl groups].

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

The content of the alkali-soluble resin in the photosensitive composition is preferably from 1 to 20% by weight, more preferably from 2 to 15% by weight, particularly preferably from 3 to 12% by weight, based on the total solid content of the composition. .

Solvent

The photosensitive composition of the present invention can be suitably suitably prepared using the above components together with a solvent.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyl. Ethyl acetate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetic acid Ethyl ester , butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxylate, and alkyl 3-oxopropionate such as methyl 3-oxypropionate and ethyl 3-oxypropionate Classes (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropane 2-oxopropionic acid alkyl esters such as methyl ester, ethyl 2-oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, 2-methoxypropane) Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2- Ethyl oxy-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, and methyl pyruvate, acetone Ethyl acetate, propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc.; ethers, such as diethylene glycol Ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, two Glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone , 3-heptanone, etc.; aromatic hydrocarbons such as toluene, xylene, and the like.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether are preferred. , butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl Ether acetate and the like.

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

In the photosensitive composition of the present invention, the solvent is preferably contained in a proportion of 70 to 90% by weight, more preferably 75 to 85% by weight.

Other ingredients

In the photosensitive composition of the present invention, a fluorine-based organic compound, a thermal polymerization inhibitor, a colorant, another filler, a polymer compound other than an alkali-soluble resin, a surfactant, a adhesion promoter, and an antioxidant may be contained as necessary. Various additives such as an ultraviolet absorber and a coagulation inhibitor. For example, paragraph numbers 0146 to 0163 of JP-A-2011-122125 can be referred to.

<Color filter and method of manufacturing the same>

The method for producing a color filter according to the present invention is characterized in that the photosensitive composition of the present invention is applied to a substrate directly or via another layer to form a photosensitive film forming step of the photosensitive film, and On the formed photosensitive film, pattern exposure and development are sequentially performed to form a colored pattern forming step of the colored pattern, and by the manufacturing method, the photosensitive composition of the present invention is obtained, and the contrast is excellent. A color filter of the present invention having a modified colored pattern.

In the color filter of the present invention, by using the photosensitive composition of the present invention, a colored film is formed on a substrate such as glass directly or via an undercoat layer or a adhesion enhancing layer. Made with colored patterns). Hereinafter, a method of manufacturing the color filter of the present invention will be described in order of steps.

(Formation of photosensitive composition layer)

For example, the photosensitive composition of the present invention is applied to the substrate directly or via another layer to form a photosensitive composition layer.

The coating of the photosensitive composition can be carried out by a usual method, and is preferably applied by a coating method such as spin coating, slit coating, cast coating, or roll coating.

The drying (prebaking) of the film formed by the photosensitive composition of the present invention (preferably coated) on the substrate can be carried out using a hot plate, an oven or the like at a temperature ranging from 50 to 140 ° C, 10 It is carried out under conditions of ~300 seconds.

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

(pattern exposure)

Next, pattern exposure is performed on the formed photosensitive composition layer by a method such as a specified mask pattern. By exposure to this pattern, the exposed areas are hardened.

Here, as the radiation used for the exposure, ultraviolet rays such as g-line, h-line, i-line, and j-line are particularly preferable.

(development)

After the pattern is exposed, the uncured portion is removed by development with a developing liquid to form a colored pattern (for example, a colored pixel). As will be described later, the colored patterns are formed in order of respective colors (for example, three colors or four colors), and a color filter having colored pixels of three colors or four colors is obtained.

In the development, the unhardened portion after the exposure is eluted in the developing liquid, and only the hardened portion remains. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

As the developing solution, any film which dissolves the photosensitive composition in the uncured portion, but which does not dissolve the hardened portion, may be used. specific Alternatively, a combination of various organic solvents or an aqueous alkaline solution can be used.

The organic solvent may be exemplified as the solvent which can be used when preparing the pigment composition or the photosensitive composition of the present invention.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, and dimethylethanolamine. Basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene An alkaline aqueous solution dissolved in a range of 0.001 to 10% by weight, preferably 0.01 to 1% by weight.

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

After the development, the remaining developer liquid is removed by washing, and after being dried, it is usually subjected to heat treatment (post-baking) at a temperature of 100 to 250 °C.

The post-baking is usually performed by heating at a temperature of about 200 ° C to 250 ° C (hard baking) in order to heat the film after curing. Thereafter, the baking treatment can be carried out in a continuous or batch manner on the coated film after development under the above conditions using a heating means such as a hot plate or a convection oven (hot air circulation dryer) or a high frequency heating machine. .

The above operation can be carried out in accordance with the desired number of hue, and each color is repeatedly repeated in order to produce a color filter formed by forming a cured film of a plurality of colored colors. By the above steps, the color filter can be most suitably produced.

By using the photosensitive composition of the present invention, it is produced by the above steps, and it is less difficult in the process, and liquid crystal is produced with high quality and low cost. A color filter used in a display element or solid-state imaging element.

Examples of the substrate on which the coloring pattern is formed include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, and a transparent conductive film attached thereto, or a solid-state image sensor. A photoelectric conversion element substrate used in the like, for example, a germanium substrate or the like, and a plastic substrate. On these substrates, black stripes that separate the pixels are usually formed.

In the plastic substrate, at least one layer selected from the group consisting of a self-barrier gas layer and a solvent-resistant layer is preferably used.

When the photosensitive composition is applied to the substrate via another layer, examples of the other layer include a gas barrier layer and a solvent resistant layer.

The color filter of the present invention has a coloring pattern formed by using the photosensitive composition of the present invention, and the dispersibility and contrast of the (A) pigment contained in the photosensitive composition are good, and can be formed due to improved brightness. A color scheme with excellent hue.

<Liquid crystal display element>

The liquid crystal display element of the present invention includes the color filter of the present invention.

More specifically, an alignment film is formed on the inner surface side of the color filter, and the liquid crystal display element panel of the present invention is obtained by facing the electrode substrate and filling the gap portion with liquid crystal and sealing.

According to the aspect of the present invention, the occurrence of color unevenness caused by aggregation of the pigment is suppressed, and a color filter having a good contrast, improved brightness, a color unevenness, and a high contrast color filter can be provided. By using this color filter, it is possible to provide a high-quality coloring liquid. Crystal display element.

<Solid image sensor>

The solid-state imaging device of the present invention includes the color filter of the present invention. According to the present invention, a solid-state imaging element excellent in color characteristics can be provided.

The configuration of the solid-state image sensor is not particularly limited as long as it has a color filter and functions as a solid-state image sensor. For example, the following configuration is exemplified. a plurality of photodiodes constituting a light receiving region of a CCD image sensor (solid-state imaging device) and a transfer electrode formed of a polycrystalline silicon or the like on the support, and the photodiode and the transfer electrode have only The light-receiving portion of the photodiode has a light-shielding film made of tungsten or the like, and has a protective film made of tantalum nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the photodiode light-receiving portion. A color filter is provided on the protective film of the device.

Furthermore, it may be configured to have a light collecting means (for example, a microlens or the like, the same applies hereinafter) on the protective layer of the device and under the color filter (near the side of the support), or may have a color filter. The composition of the concentrating means, and the like.

Example

The invention will now be described more specifically by way of examples. The materials, the amounts used, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention is not limited by the specific examples shown below.

(Synthesis of Polymer 1)

Acrylic acid (10.0g), ε-caprolactone of hydroxyethyl methacrylate 5 Ear addition product (Placcel FM-5: manufactured by DAICEL Chemical Industry Co., Ltd.) (90.0 g) and methoxypropanediol (233 g) were introduced into a three-necked flask substituted with nitrogen, and a stirrer (Xindong Science Co., Ltd.: III) A motor was stirred while allowing nitrogen to flow into the flask while heating to raise the temperature to 85 °C. 2,2-Azobis(dimethyl 2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) (1.8 g) was added thereto, and the mixture was stirred under heating at 85 ° C for 3 hours. Then, V-601 (0.4 g) was further added, and the mixture was stirred under heat for 3 hours, and then cooled to obtain a 30% solution of the polymer 1. The weight average molecular weight of the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard material, and it was 1,45,000. Further, the composition ratio (mass ratio) of the constituent units obtained by 1H-NMR was 10/90.

(Synthesis of Polymer 2)

In a 1 liter flask equipped with a nitrogen gas introduction tube, a stirring device, and a condenser, 15 g of 2-hydroxyethyl methacrylate, 150 g of δ-octanolactone, and 5 g of titanium tetrabutoxide (IV) were added while blowing nitrogen gas. Heating at 140 ° C for 3 hours gave Intermediate 1 with repeating unit n = 9. Polymer 2 was obtained in the same manner except that the ε-caprolactone 5 molar addition product of the synthesis example of the polymer 1 was changed to the intermediate 1 .

(Synthesis of Polymer 3)

In a 1 liter flask equipped with a nitrogen gas introduction tube, a stirring device, and a condenser, 15 g of 2-hydroxypropyl methacrylate, 140 g of ε-caprolactone, and 5 g of titanium tetrabutoxide (IV) were added while blowing nitrogen gas. Heating at 140 ° C for 3 hours gave Intermediate 2 with repeating unit n = 12. The polymer 3 was obtained in the same manner except that the ε-caprolactone 5 molar addition product of the synthesis example of the polymer 1 was changed to the intermediate 2 .

(Synthesis of Polymers 4~16)

In addition to the amount of the ε-caprolactone 5 molar addition product (Placcel FM-5: manufactured by DAICEL Chemical Industry Co., Ltd.) of the synthetic acrylic acid (AA) of the polymer 1 and the hydroxyethyl methacrylate, The same procedure was carried out to obtain polymers 4 to 16.

(Synthesis of Polymer 17)

22.4 g of a polyethyleneimine having a molecular weight of 1800 (trade name: Epomin SP-018, manufactured by Nippon Shokubai Co., Ltd.) was added with 12.0 g of 12-hydroxystearic acid, and the reaction was stirred at 140 ° C for 5 hours under a nitrogen atmosphere. . Thereto, a mixture of 578.9 g of ε-caprolactone and 0.25 g of tetrabutyl titanate was stirred and reacted at 150 ° C for 2 hours in a nitrogen atmosphere to obtain a polymer 17 (a waxy substance having a molecular weight of 20,000).

In the above table, MAA means methacrylic acid, BzMA means benzyl methacrylate, iBuMA means isobutyl methacrylate, MMA means methyl methacrylate, AA-6: terminal methacryl oxime polymethacrylate Methyl ester (AA-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), AB-6: terminal methacryl oxime polybutyl acrylate (AB-6, manufactured by East Asia Synthetic Chemical Industry Co., Ltd.), AS-6 : Terminal methacryl oxime polystyrene (AS-6, manufactured by Toagosei Chemicals Co., Ltd.).

<Preparation of Pigment Composition>

The components of the following composition (1) were mixed, and the mixture was stirred and mixed for 1 hour at a number of revolutions of 3,000 rpm using a homogenizer to prepare a mixed solution containing a pigment.

[Composition (1)]

Next, the mixed solution obtained above is further used by using 0.1 mm. A bead disperser of zirconia beads, Apecsmill (manufactured by Shou Industrial Co., Ltd.), was subjected to dispersion treatment for 2 hours to obtain a yellow pigment dispersion liquid.

<Evaluation of Pigment Composition>

The following evaluation was performed about the obtained pigment composition.

(1) Determination and evaluation of viscosity

For the obtained pigment composition, the viscosity η1 of the pigment composition immediately after dispersion and the viscosity η2 of the pigment composition after one week of dispersion (at room temperature) were measured using an E-type viscometer, and (η2-η1) /η1 is 0.3 or less When it is regarded as A, it is regarded as B when it exceeds 0.3, and the dispersion stability is evaluated. The evaluation results are shown in the table below. Here, the low viscosity means that the dispersibility is good.

In the above, each of the polymers 1 was changed to the polymer described in the above table, and the pigment was changed as follows, and the same procedure was carried out. The results are shown in the table below.

As is apparent from the above table, the pigment composition of the present invention is excellent in dispersibility and dispersion stability.

<Modulation of photosensitive composition>

In the dispersion 1 obtained in the first embodiment, each component described in the following composition (2) was further added, and the mixture was stirred and mixed to prepare a photosensitive composition (color resist liquid).

[Composition (2)]

. Photopolymerizable compound: dipentaerythritol hexaacrylate 80 parts

. Photopolymerization initiator: Irgacure OXE01 (manufactured by BASF JAPAN Co., Ltd.) 15 parts

. Alkali-soluble resin: benzyl methacrylate/methacrylic acid (=70/30 [mole ratio]) copolymer (weight average molecular weight: 10,000) 2-ethoxycarbonyl-1-methoxypropane solution (D -1, solid content 40%) 20 parts

. Solvent: 2-Ethyloxy-1-methoxypropane 685 parts

<Evaluation of alkali developability, brightness, and contrast of photosensitive composition> (alkaline imaging)

The obtained photosensitive composition (color resist liquid) was applied onto a 100 mm × 100 mm glass substrate (EAGLE 2000 XG, manufactured by Corning Co., Ltd.) so that the coating film thickness after drying became 2.0 μm, and was allowed to stand in an oven at 90 ° C. Dry for 60 seconds (prebaking). Then, the mask was exposed to light at 100 mJ/cm ² (illuminance: 20 mW/cm ² ), and the exposed coating film was covered with a 1% aqueous solution of an alkali developing solution CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). After the development time has elapsed, the pure water is sprayed to wash away the developing liquid to form a pattern. The development time when there is no defect or peeling and the same pattern as that of the exposure mask is 30 seconds or less is regarded as A, when it is more than 30 and 60 seconds or less, it is regarded as B, and when it is more than 60 seconds, it is regarded as C.

(Brightness: Y value)

For each of the colored substrates to be formed, the Y value (Yd) of the luminance was measured using the MCPD-2000 manufactured by Otsuka Electronics Co., Ltd. on the colored substrate after the development. Next, the Y value (Yb) of the colored substrate which was heat-treated (post-baked) in an oven at 220 ° C for 1 hour was measured. When Yb/Yd is 0.97 or more, it is regarded as A, and when it is less than 0.97, it is regarded as B. The measurement results are shown in the table below.

(Compared)

BM-5 manufactured by TOPCON was used to measure the brightness when the polarizing plates were parallel and the brightness at the time of the orthogonal, and the brightness at the time of parallelism was divided by the brightness at the time of the orthogonal (= brightness in parallel/orthogonality) The brightness of the time is taken as an indicator for evaluating the comparison. For two polarizing plates, a coloring substrate is placed on the opposite side of the brightness measuring device (BM-5), and the contrast is measured as CRi. When the coloring substrate is placed between two polarizing plates, the contrast is taken as CRc. When the ratio of contrast (CRc/CRi) is 0.7 or more, it is regarded as A, and when it is less than 0.7, it is regarded as B.

In the above, each of the dispersions 1 was changed to the dispersion described in the above table, and the dispersion was carried out in the same manner. The results are shown in the table below.

As is apparent from the above table, the photosensitive composition obtained from the pigment composition of the present invention is excellent in image developability, and a color filter excellent in brightness and contrast is obtained. In contrast, it was found that the coloring composition of the comparative example was poor in developability, and the obtained color filter was inferior in brightness and contrast.

Claims (18)

A pigment composition comprising: (A) a pigment, (B) a structural unit represented by at least one of the following formula (b-1) and at least one structural unit represented by the formula (b-2) Copolymer, and (C) solvent; (In the formula (b-1), R ¹ represents a hydrogen atom or a methyl group; L is a group represented by -XO-, X is a linear or branched alkylene group; and W is a linear or branched extension. Alkyl, n is an integer from 1 to 12); (In the formula (b-2), R ² represents a hydrogen atom or a methyl group). The pigment composition of the first aspect of the invention, wherein 70% by weight or more of the (B) copolymer is a constituent unit represented by the formula (b-1). The pigment composition of claim 1, wherein the (B) copolymer has a weight average molecular weight of from 5,000 to 50,000. The pigment composition of claim 1, wherein in the formula (b-1), the X-type linear chain has a C 1 to 6 alkyl group, and the W system has a linear carbon number of 3 to 10 alkyl. The pigment composition of the first aspect of the invention, wherein the weight ratio of the constituent unit represented by the formula (b-1) to the constituent unit represented by the formula (b-2) is from 60 to 95:40 to 5. The pigment composition of claim 1, wherein the (B) copolymer is the following polymer; (wherein R ¹ and R ² each represent a hydrogen atom or a methyl group; a: b is 3 to 25: 97 to 75, and n is an integer of 1 to 6). The pigment composition of claim 1, wherein the (A) pigment has an average primary particle diameter of 10 to 50 nm. The pigment composition of claim 1, which further contains (D) a pigment dispersant. The pigment composition of claim 1, wherein 70% by weight or more of the (B) copolymer is a constituent unit represented by the formula (b-1), and the weight average molecular weight of the (B) copolymer is from 5,000 to 50,000. . The pigment composition of claim 1, wherein 70% by weight or more of the (B) copolymer is a constituent unit represented by the formula (b-1), and the weight average molecular weight of the (B) copolymer is from 5,000 to 50,000. In the formula (b-1), the X-type linear chain has an alkylene group having 1 to 6 carbon atoms, and the W is a linear alkyl group having 3 to 10 carbon atoms. The pigment composition of claim 1, wherein in the formula (b-1), the LX is a linear alkyl group having 1 to 6 carbon atoms, and the W is a linear alkyl group having 3 to 10 carbon atoms. The weight average molecular weight of the (B) copolymer is from 5,000 to 50,000. The pigment composition of claim 1, wherein the (B) copolymer has a weight average molecular weight of from 5,000 to 50,000, and (B) the copolymer is a polymer; (wherein R ¹ and R ² each represent a hydrogen atom or a methyl group; a: b is 3 to 25: 97 to 75, and n is an integer of 1 to 6). The pigment composition of claim 1, wherein 70% by weight or more of the (B) copolymer is a constituent unit represented by the formula (b-1), and the weight average molecular weight of the (B) copolymer is from 5,000 to 50,000. (B) copolymer is the following polymer; (wherein R ¹ and R ² each represent a hydrogen atom or a methyl group; a: b is 3 to 25: 97 to 75, and n is an integer of 1 to 6). A photosensitive composition comprising the pigment composition according to any one of claims 1 to 14 and (E) a photopolymerizable compound and (F) a photopolymerization initiator. The photosensitive composition of claim 14, which further contains an alkali-soluble resin. A color filter having a colored pattern formed using the photosensitive composition of claim 14 or 15. A liquid crystal display device or solid-state image sensor having a color filter as in claim 16 of the patent application. A method for producing a color filter comprising: applying a photosensitive composition according to claim 14 or 15 directly or on another substrate to a photosensitive film forming step of forming a photosensitive film, And a pattern forming step of forming a colored pattern by sequentially performing pattern exposure and development on the formed photosensitive film.