JP2012014053A - Photocurable color composition for color filter, color filter, method for manufacturing color filter, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable color composition for a color filter, the composition having excellent developability of a pattern, leaving little residue on a substrate, and giving a pattern with a large aperture diameter of a contact hole and a high residual ratio even after post-baking, to provide a method for manufacturing a color filter with excellent color reproducibility, and to provide a color filter and a liquid crystal display device.SOLUTION: The photocurable color composition for a color filter contains (A) an organic solvent, (B) a pigment, (C) a photopolymerization initiator, (D) a polymerizable compound and (E) a binder. The (D) polymerizable compound contains at least one kind of compound selected from the following compounds (I) and (II). The compounds are (I) a polymerizable compound having a (meth)acryloyl group having 2 to 6 carbon atoms, a hydroxyl group having 1 to 6 carbon atoms derived from a glycidyl group, and a cyclic structure except for an aromatic ring, and (II) a polymerizable compound having a (meth)acryloyl group having 3 to 12 carbon atoms, a hydroxyl group having 1 to 12 carbon atoms derived from a glycidyl group, and a branched structure.

Description

  The present invention relates to a photocurable coloring composition for color filters, a color filter using the same, a method for producing the same, and a liquid crystal display device using the color filter.

  Color filters are indispensable components for liquid crystal displays. The liquid crystal display is compact compared to the CRT as a display device, and can save power, and has become more than equivalent in terms of performance due to technological advancement. Therefore, TV screens, personal computer screens, and other display devices It is being replaced by CRT.

  In recent years, the development of liquid crystal displays has been expanded from the use of personal computers and monitors having a relatively small screen area to TV applications that require a large screen and high image quality. Therefore, in order to improve the productivity of the color filter used for this purpose, studies have been made to increase the substrate size. Furthermore, the mask size used for pattern exposure of this color filter is also used in accordance with this, so that the mask itself is very expensive, and it is important to keep the mask cost low. It has become a challenge.

For this reason, a method of forming a color filter using patterning with a laser beam is disclosed. (For example, refer to Patent Document 1) However, in this method using a semiconductor laser, the output of the laser is small, and it takes time for exposure, and the productivity cannot be increased.

  In addition, a method for manufacturing a color filter that does not use a large photomask at the time of exposure has been proposed in terms of reducing the total price when manufacturing the color filter. (For example, refer to Patent Documents 2 and 3.) However, when high-power laser exposure is combined in order to obtain high productivity, pattern chipping, peeling, or twisting occurs in the pixels, which improves productivity and is favorable. Therefore, there is a demand for compatibility with the formation of a pixel having a simple shape.

  In a color-filter on array (hereinafter, referred to as COA) type liquid crystal display device, an interlayer insulating film is formed on a thin film transistor (hereinafter, referred to as TFT). Forming a color filter layer that also serves as For this reason, the required characteristics for the color filter layer must include the required characteristics as an interlayer insulating film, such as contact hole formability, low dielectric constant, and resistance to stripping liquid, in addition to the normal required characteristics as described above. In order to satisfy the characteristics, a resin film is also provided as a protective layer on the color filter layer.

  On the other hand, phthalocyanine blue pigments are used for blue pixels for reasons such as heat resistance and light resistance. However, since the phthalocyanine blue pigment has a high absorbance in the ultraviolet region and does not easily transmit ultraviolet light, the patterning using the ultraviolet laser as described above does not sufficiently cure the pixel, and the pixel shape deteriorates. there were. In particular, in the case of the COA method, the length of one side is about 1 to 40 μm on the colored pixel in order to make the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer conductive. It is necessary to form a contact hole (conducting path) having a rectangular cross section from a rectangular shape, a circular shape or an elliptical shape having a diameter of 1 to 40 μmφ, or a U-shaped shape. When the absorbance at is high, there is a problem that curing due to exposure does not proceed and the pixels formed with a pattern heat flow at a high temperature during post-baking after pattern formation, and the formed contact holes are crushed.

  Also, it has been proposed to use a polymerizable compound having a triazine skeleton as a negative photosensitive composition used in the production of a COA color filter (see, for example, Patent Document 4). It was insufficient from the point. Although it has been proposed to use an epoxy acrylate having an aromatic ring as a polymerizable compound in a curable coloring composition (see, for example, Patent Documents 5 to 7), all of them have insufficient pattern formability.

JP 2007-114602 A JP 2008-76709 A JP 2008-51866 A JP 2006-28455 A Japanese Patent Laid-Open No. 11-133599 Japanese Patent No. 2894155 Japanese Patent No. 3901807

  The present invention is excellent in developability of the formed pattern, there is little residue on the substrate in the unexposed part after development, the formed pattern has a large contact hole opening diameter even after post-baking, and the contact An object of the present invention is to provide a photocurable coloring composition for a color filter having a high residual rate of holes, and a method for producing a color filter having a good hue and excellent color reproducibility using the photocurable coloring composition, It is an object to provide a color filter and a liquid crystal display device.

Means for solving the above-mentioned problems are as follows.
<1> (A) an organic solvent, (B) a pigment, (C) a photopolymerization initiator, (D) a polymerizable compound, and (E) a binder, wherein the (D) polymerizable compound is the following (I) And a photocurable coloring composition for a color filter comprising one or more compounds selected from (II).
(I): A polymerizable compound having 2 to 6 (meth) acryloyl groups, 1 to 6 hydroxyl groups derived from glycidyl groups, and a ring structure other than an aromatic ring (II): 3 to 12 (Meth) acryloyl group, 1 to 12 hydroxyl group derived from glycidyl group, and a polymerizable compound having a branched structure

<2> The ring structure other than the aromatic ring in (I) is a hexahydrophthalic acid skeleton, a tetrahydrophthalic acid skeleton, a hydrogenated bisphenol A skeleton, a cyclohexanedimethanol skeleton, an isocyanuric ring, or a tricyclodecane dimethanol skeleton. The photocurable coloring composition for color filters according to <1>, which is one type selected from the group consisting of:

<3> The color filter according to <1>, wherein the branched structure in (II) is one selected from the group consisting of a trimethylolpropane skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, a sorbitol skeleton, and a glycerin skeleton. Photocurable coloring composition.

<4> Further, (III) having a (meth) acryloyl group of 3 or more and 12 or less, and having an unsaturated group density represented by dividing the number of the (meth) acryloyl groups by the molecular weight of the polymerizable compound is 0. The photocuring for color filter according to any one of <1> to <3>, which contains a polymerizable compound having a structure different from that of (0067) to 0.0114 and having a structure different from that of (I) or (II). Coloring composition.

<5> The color according to any one of <1> to <4>, wherein when a cured film having a thickness of 2 μm after drying is formed, the transmittance of the cured film at a wavelength of 355 nm is 2% or less. Photocurable coloring composition for filters.
<6> The pigment (B) is C.I. I. The photocurable coloring composition for a color filter according to any one of <1> to <5>, which is Pigment Blue 15: 6.

<7> A colored layer forming step of forming a colored layer comprising the colored composition by applying the photocurable coloring composition for color filter according to any one of <1> to <6> on the substrate. And an exposure step of exposing the colored layer in a pattern-like manner, and a developing step of developing the colored layer after exposure to form a colored pattern.

<8> The method for producing a color filter according to <7>, wherein the exposure step is an exposure step of patternwise exposure using a 355 nm laser.
<9> The method for producing a color filter according to <7> or <8>, which is a method for producing a color filter of a Color-filter On Array method.

<10> A color filter manufactured by the method for manufacturing a color filter according to any one of <7> to <9>.
<11> A liquid crystal display device comprising the color filter according to <7>.

  According to the present invention, the developability of the formed pattern is excellent, there is little residue on the substrate in the unexposed area after development, and the formed pattern has a large contact hole opening diameter even after post-baking, In addition, a photocurable coloring composition for a color filter having a high contact hole residual ratio can be provided, and a method for producing a color filter having a good hue and excellent color reproducibility using the photocurable coloring composition. A color filter and a liquid crystal display device can be provided.

Hereinafter, the present invention will be described in detail.
The photocurable coloring composition for a color filter of the present invention contains (A) an organic solvent, (B) a pigment, (C) a photopolymerization initiator, (D) a polymerizable compound, and (E) a binder, (D) The polymerizable compound contains one or more compounds selected from the following (I) and (II) (hereinafter referred to as “specific polymerizable compound” as appropriate).
(I): A polymerizable compound having 2 to 6 (meth) acryloyl groups, 1 to 6 hydroxyl groups derived from glycidyl groups, and a ring structure other than an aromatic ring (II): 3 to 12 The polymerizable compound having a (meth) acryloyl group, 1 to 12 hydroxyl groups derived from a glycidyl group, and a branched structure The photocurable coloring composition of the present invention is used for forming a colored pattern of a color filter. It is done.
Below, each structural component of the photocurable coloring composition of this invention is explained in full detail.
In this specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group.

<(D) Polymerizable compound>
The photocurable coloring composition of this invention contains the (D) polymeric compound which is 1 or more types of compounds chosen from following (I) and (II).
(I): a polymerizable compound having 2 to 6 (meth) acryloyl groups, 1 to 6 hydroxyl groups derived from a glycidyl group, and a ring structure other than an aromatic ring (hereinafter referred to as “polymerizable compound” (I) ".)
(II): a polymerizable compound having 3 to 12 (meth) acryloyl groups, 1 to 12 hydroxyl groups derived from a glycidyl group, and a branched structure (hereinafter referred to as “polymerizable compound (II)” as appropriate) Called.)

  The polymerizable compound (I) has an acryloyl group or a methacryloyl group alone or both in the molecule of 2 or more and 6 or less, a hydroxyl group derived from a glycidyl group in the molecule of 1 or more and 6 or less, and an aromatic ring Any compound having a ring structure other than that may be used.

Here, the ring structure other than the aromatic ring includes a cyclopropane ring skeleton, a cyclobutane ring skeleton, a cyclopentane ring skeleton, a cycloparaffin ring skeleton such as a cyclohexane ring skeleton, a cycloolefin ring skeleton such as cyclobutene, cyclopentene, and cyclohexene, and a furan ring. Cycloolefin ring skeleton such as skeleton, tetrahydrofuran ring skeleton and pyrrole ring skeleton, pyrrolidine ring skeleton, pyridine ring skeleton, piperidine ring skeleton, triazine ring skeleton, isocyanur ring skeleton and other heterocyclic skeletons, tricyclodecane ring skeleton, bicycloundecane Examples include a bridged ring skeleton such as a ring skeleton, and a spiro ring skeleton such as a spirooctane ring skeleton. Among them, a hexahydrophthalic acid skeleton and a tetrahydrophthalate are more preferable from the viewpoint of non-coloring property during heating and synthesis. Acid skeleton, hydrogenated bispheno Le A skeleton, cyclohexanedimethanol skeleton, isocyanuric ring, a tricyclodecane skeleton, tetrahydrophthalic acid skeleton, a hydrogenated bisphenol A skeleton is more preferable.
The skeletons of these preferable ring structures are shown below. In the following structural formulas, * represents a binding site with a structural unit containing a (meth) acryloyl group and a structural unit containing a hydroxyl group derived from a glycidyl group.

In the specific polymerizable compound, a hydroxyl group derived from a glycidyl group will be described. When, for example, glycidyl (meth) acrylate is added to a compound having an acid group or hydroxyl group having a ring structure and a compound having an acid group or hydroxyl group having a branched chain, an adduct of (meth) acryloyl group is obtained. At the same time, the glycidyl group is ring-opened to form a hydroxyl group. The hydroxyl group thus obtained is derived from a glycidyl group and is usually a secondary hydroxyl group. In the present invention, the hydroxyl group derived from a glycidyl group refers to a hydroxyl group generated by the reaction of a compound having a glycidyl group.
Although this secondary hydroxyl group facilitates dissolution of the photocurable coloring composition in alkali development, it does not show strong solubility like a carboxylic acid group, so it is considered that alkali development proceeds appropriately. It is considered that the effects of the present invention are exhibited by using such a polymerizable compound.

Particularly preferred polymerizable compound (I) has 2 to 4 acryloyl groups or methacryloyl groups alone or both in the molecule, and 2 to 4 hydroxyl groups derived from glycidyl groups in the molecule. Furthermore, it is a compound having a hexahydrophthalic acid skeleton and a hydrogenated bisphenol A skeleton as a ring structure other than an aromatic ring.
These polymerizable compounds (I) have a ring structure other than an aromatic ring as a central structure, have two or more acryloyl groups or methacryloyl groups at the ends, and further have one or more hydroxyl groups derived from glycidyl groups in the side chain. The structure which has is preferable.

  Specific examples of the polymerizable compound (I) include the following compounds.

  The polymerizable compound (II) has an acryloyl group or a methacryloyl group alone or both in the molecule of 3 or more and 12 or less, a hydroxyl group derived from a glycidyl group in the molecule of 1 or more and 12 or less, and a branched structure A compound having any structure may be used as long as it has a compound.

Here, the branched structure has a tertiary or quaternary carbon atom substituted with an element other than hydrogen, such as a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom in the molecule, and this branched structure is a central structure. And having a structure having three or more acryloyl groups or methacryloyl groups at the terminal. Specifically, it is a trimethylolpropane skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, a sorbitol skeleton, a glycerin skeleton, etc., and more preferably a trimethylolpropane skeleton, a pentaerythritol skeleton in terms of polymerizability, viscosity, and synthesis. , A dipentaerythritol skeleton, a sorbitol skeleton, or a glycerin skeleton, and a pentaerythritol skeleton, a dipentaerythritol skeleton, and a sorbitol skeleton are particularly preferable.
These preferred branched structures are shown below. In the following structural formulas, * represents a binding site with a structural unit containing a (meth) acryloyl group and a structural unit containing a hydroxyl group derived from a glycidyl group.

Particularly preferred polymerizable compound (II) has an acryloyl group or a methacryloyl group alone or both in the molecule of 4 or more and 6 or less, and a hydroxyl group derived from a glycidyl group in the molecule of 4 or more and 6 or less, It is a compound having a pentaerythritol skeleton, a dipentaerythritol skeleton, or a sorbitol skeleton as a branched structure.
These polymerizable compounds (II) preferably have a structure having a branched structure as a central structure, three or more acryloyl groups or methacryloyl groups at the terminals, and one or more hydroxyl groups derived from glycidyl groups in the side chain. .

  Specific examples of the polymerizable compound (II) include the following compounds.

  (D) In addition to the polymerizable compounds (I) and (II), the polymerizable compound further has (III) 3 to 12 (meth) acryloyl groups, and the number of (meth) acryloyl groups is The unsaturated group density represented by dividing by the molecular weight of the polymerizable compound is 0.0067 or more and 0.0114 or less, and the structure is different from the above (I) and (II) (hereinafter referred to as “appropriately” It is preferable to contain a polymerizable compound (III) ”. By further containing the polymerizable compound (III), a highly reliable color filter having high photothermal crosslinkability, excellent developability, excellent pixel shape, and the like can be provided.

  Specific examples of the polymerizable compound (III) include the following compounds. The numbers are unsaturated group densities.

In the present invention, the specific polymerizable compound may contain only one type, or two or more types may be used in combination.
That is, the specific polymerizable compound may include at least one of the polymerizable compound (I) or the polymerizable compound (II), and is polymerizable with at least one polymerizable compound (I). One or more compounds (II) may be used in combination, two or more polymerizable compounds (I) may be used, or two or more polymerizable compounds (II) may be used.
Furthermore, as the polymerizable compound in the present invention, not only one compound selected from the polymerizable compound (I) and the polymerizable compound (II) but also a polymerizable compound having a structure different from those polymerizable compounds may be used in combination. Good.

The polymerizable compound having a structure different from that of the specific polymerizable compound that can be used in combination may be a polymerizable compound having at least one ethylenically unsaturated double bond. It is a polymerizable compound having at least one terminal ethylenically unsaturated bond, preferably two or more, and having a structure different from that of the specific polymerizable compound.
Such a polymerizable compound is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof.
The polymerizable compound having a structure different from that of the specific polymerizable compound is preferably the above-described polymerizable compound (III). Two or more polymerizable compounds having different structures from the specific polymerizable compound may be used.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or A dehydration condensation reaction product with a polyfunctional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

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

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

Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59- Those having an aromatic skeleton described in Japanese Patent No. 5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used.
Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

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

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

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

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

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, penta Erisrito Preferred examples include tetraacrylate EO modified products, dipentaerythritol hexaacrylate EO modified products, and commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Nippon Paper Chemicals), DPHA (Nippon Kasei). Yakuhin Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) are preferred.

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

(D) The content of the polymerizable compound is preferably 5% by mass to 55% by mass and preferably 10% by mass to 50% by mass in the total nonvolatile content in the photocurable coloring composition in the present invention. Is more preferable, and it is still more preferable that it is 15 mass%-45 mass%.
When the amount of the polymerizable compound used is within this range, it becomes easy to obtain desired chromaticity, luminance, and film thickness, and the shape of the pixel and contact hole is also improved.
The total content of the polymerizable compound (I) and the polymerizable compound (II) in the polymerizable compound (D) is 5% by mass to 95% by mass, preferably 30% by mass to 70% by mass. is there.
In addition, the total non volatile matter of the photocurable coloring composition in this invention is the total content of all the components of the photocurable coloring composition except the (A) solvent which comprises a photocurable coloring composition. Yes, when forming a color filter, it usually refers to the content of a component that forms a photocurable coloring composition layer by drying.
Furthermore, it is preferable that polymeric compound (III) is 5 mass%-80 mass% in mass conversion in (D) polymeric compound, Preferably it is 20 mass%-60 mass%. By containing the polymerizable compound (III) in this range, a photocurable coloring composition having high photothermal crosslinkability, excellent developability, and excellent pixel shape can be obtained.

<(B) Pigment>
The photocurable coloring composition of the present invention contains (B) at least one pigment.
(B) The pigment may be an inorganic pigment or an organic pigment, but it is preferable to use a pigment having a particle size as small as possible from the viewpoint of high transmittance. The average primary particle diameter is preferably 0.01 μm to 0.1 μm, more preferably 0.01 μm to 0.05 μm.
In the photocurable coloring composition of the present invention, the use of the binder (E) described later improves dispersibility and dispersion stability even when the particle size of the pigment is small. Excellent in color, good hue, and excellent color reproducibility.

  Furthermore, in the present invention, among the pigments contained in the photocurable coloring composition, the proportion of the pigment having a primary particle size of less than 0.02 μm is less than 10% in the total amount of the pigment, and the primary The proportion of the pigment having a particle diameter exceeding 0.08 μm is preferably less than 5% in the total amount of the pigment.

When the ratio of the pigment having a primary particle diameter of less than 0.02 μm is less than 10%, the heat resistance and chromaticity change can be prevented, and the ratio of the pigment having a primary particle diameter exceeding 0.08 μm is 5 If it is less than%, the contrast is good, the photocurable coloring composition has good stability over time, and foreign matter failure can be prevented.
The proportion of the pigment having a primary particle size of less than 0.02 μm is more preferably less than 5% from the viewpoints of heat resistance and chromaticity change prevention.
The proportion of the pigment having a primary particle diameter exceeding 0.08 μm is preferably less than 3% from the viewpoint of improving contrast.

  The primary particle diameter of the pigment can be measured using a TEM (transmission electron microscope). That is, the TEM photograph is subjected to image analysis to examine the particle size distribution. For example, the particle size distribution can be grasped by measuring the total number of particles in the observation sample at 3 to 100,000 times and the number of pigment particles less than 0.02 μm and more than 0.08 μm. More specifically, the pigment powder is observed with a transmission electron microscope at 3 to 100,000 times, photographed, the major axis of 1000 primary particles is measured, less than 0.02 μm, and more than 0.08 μm Calculate the percentage of primary particles. This operation is performed for a total of three locations by changing the location of the pigment powder, and the results are averaged.

  (B) Examples of the inorganic pigment that can be used as the pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, Examples thereof include metal oxides such as magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment that can be used as the (B) pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 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, 264, 270, 272, 279,

  C. I. Pigment Yellow 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, 17 4, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214

C. I. 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,
C. I. Pigment Green 7, 10, 36, 37, 58
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37, 58

The photocurable coloring composition of the present invention is preferably used for forming blue colored pixels because the effects of the present invention can be exhibited well. The phthalocyanine-based blue pigment used for blue has high absorbance in the ultraviolet region and is difficult to transmit ultraviolet light, so patterning using ultraviolet light as an exposure light source does not sufficiently cure the pixel, and the pixel shape deteriorates. When the present invention is used for a blue photocurable coloring composition, the effects of the present invention can be exhibited without regret.
Examples of phthalocyanine blue pigments used for blue include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16,17: 1, 75, 79, and the like. Especially, C.I. I. Pigment Blue 15: 6 is excellent in terms of heat resistance, light resistance, and contrast, and can be used more suitably.

  The content ratio of the phthalocyanine blue pigment with respect to the total amount of the (B) pigment used in the photocurable coloring composition of the present invention is preferably 50% by mass or more. By setting the ratio of the phthalocyanine blue pigment to the total pigment to 50% by mass or more, it becomes possible to obtain high heat resistance, light resistance, and contrast value.

In addition to the phthalocyanine blue pigment, the photocurable coloring composition of the present invention preferably contains a violet pigment as a pigment for adjusting chromaticity. By including a violet pigment, a deep blue color that can achieve a high NTSC ratio can be provided.
Examples of violet pigments include C.I. I. Pigment Violet 19, 23, 32, etc. can be used. Especially, C.I. I. Pigment Violet 23 is more preferable because it provides brightness, light resistance, heat resistance, and high contrast.

(B) Although the addition amount in the photocurable coloring composition of a pigment can be selected at any time according to desired chromaticity, luminance, and film thickness, it is based on the total nonvolatile content (total solid content excluding the solvent). The range of 5 mass% or more and 50 mass% or less is preferable. More preferably, they are 10 mass% or more and 40 mass% or less, and it is further more preferable that they are 15 mass% or more and 30 mass% or less.
(B) When the added amount of the pigment is within this range, it is easy to obtain desired chromaticity, luminance, and film thickness, and the shape of the pixel and contact hole is also improved.
The total nonvolatile content of the photocurable coloring composition in the present invention is the total content of all components of the photocurable coloring composition excluding the solvent (A) constituting the photocurable coloring composition, In the case of forming a color filter, it usually refers to the content of a component that forms a photocurable coloring composition layer by drying.

(Coating pigment)
In the present invention, it is particularly preferable to use an organic pigment and (B) a pigment coated with a polymer compound in the step of refining or dispersing the pigment. Even in pigments refined by coating the pigment with a polymer compound, the formation of secondary aggregates is suppressed, and the coated pigment with improved dispersibility that can be dispersed in the form of primary particles It is more preferable to use a coating pigment excellent in dispersion stability in which primary particles are stably maintained.
You may use the binder (E) mentioned later as a high molecular compound used for coating | cover.

By coating the pigment with the polymer compound, the formation of secondary aggregates can be suppressed even in the miniaturized pigment, and the pigment can be dispersed in the form of primary particles. In other words, the coated pigment has improved dispersibility and excellent dispersion stability in which the dispersed primary particles are stably maintained.
Regarding the polymer compound used for the coating pigment and the coating method of the pigment, it is more preferable to use the treatment method and the polymer compound described in paragraphs [0025] to [0078] of JP-A-2009-144269. .

In the present invention, the pigment is preferably used as a pigment dispersion composition by dispersing the pigment using at least one dispersant. The same applies to the case where the above-described coated pigment is used. By using this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

Specifically, many types of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.) such as 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Ionette S-20 (manufactured by Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 62,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (manufactured by BYK-CHEMIE Co., Ltd.).
In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content of a dispersing agent, 1 mass%-100 mass% are preferable with respect to the mass of (B) pigment, and 3 mass%-70 mass% are more preferable.

In addition, when adding the pigment (B) to the photocurable coloring composition, it is preferable from the viewpoint of pigment dispersibility that a pigment dispersion composition containing a pigment and a dispersant is prepared in advance and then blended. However, a pigment derivative is added to the pigment dispersion composition as necessary.
The pigment is dispersed in the pigment dispersion composition in the form of fine particles by adsorbing the pigment derivative having a part having affinity with the dispersant or a polar group-introduced pigment to the pigment surface and using it as the adsorption point of the dispersant. Can be made. Since the photocurable coloring composition containing such a pigment dispersion composition can prevent re-aggregation of the pigment, it is effective in forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into the base skeleton as a substituent.
Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments. In general, pale yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds that are not called pigments can also be used as the base skeleton.
Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of a pigment derivative, 1 mass%-30 mass% are preferable with respect to the mass of a pigment, and 3 mass%-20 mass% are more preferable. When the content is within the above range, the dispersion can be performed satisfactorily while keeping the viscosity low, and the dispersion stability after dispersion can be improved. As a result, the photocurable coloring composition containing such a pigment dispersion composition has a high transmittance, an excellent color characteristic, and a high contrast color filter having a good color characteristic. Is preferred.

  The pigment is dispersed by, for example, finely dispersing a pigment and a dispersant previously dispersed with a homogenizer or the like using a bead disperser using zirconia beads or the like.

[dye]
In the photocurable coloring composition of the present invention, a dye may be used in combination as a colorant in addition to the pigment as long as the effects of the present invention are not impaired.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

<(A) Organic solvent>
The photocurable coloring composition of the present invention can be prepared using a general solvent. Moreover, the pigment dispersion composition mentioned above can also be prepared using a solvent. The organic solvent used in the present invention is preferably an organic solvent having a boiling point of 110 ° C. or higher and 200 ° C. or lower from the viewpoints of coating properties, suppression of nozzle clogging during coating, and solvent removability when forming a colored layer.

  Examples of the organic solvent that can be used in the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl. Esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate, 3 -3-oxypropionic acid alkyl esters such as ethyl oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2- Oki 2-oxypropionic acid alkyl esters such as methyl propionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate) Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 1,3-butane Diol diacetate, etc.

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol di Cetate, propylene glycol n-butyl ether acetate, propylene glycol phenyl ether, propylene glycol phenyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol n-propyl ether acetate, dipropylene glycol n-butyl ether acetate, tripropylene glycol mono n- Butyl ether, tripropylene glycol methyl ether acetate, etc .;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Alcohols such as ethanol, isopropyl alcohol, propylene glycol methyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether,
Aromatic hydrocarbons such as toluene and xylene are exemplified.

Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, Propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.
The content of the (A) organic solvent in the photocurable coloring composition of the present invention is appropriately selected according to the purpose, but from the viewpoint of applicability, the concentration of the nonvolatile content of the photocurable coloring composition is 10 mass. It is preferable to prepare so that it may become% -30 mass%.

<(C) Photopolymerization initiator>
The photocurable coloring composition in the present invention contains (C) a photopolymerization initiator.
The photopolymerization initiator is a compound that is decomposed by light and initiates and accelerates polymerization of the polymerizable compound (D).
The photopolymerization initiator preferably has absorption at the exposure wavelength of ultraviolet rays. Even when there is no absorption at the wavelength of ultraviolet rays, the photopolymerization initiator is sensitive to the wavelength of ultraviolet rays when used in combination with a sensitizing dye described later. It is possible to Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator used in the present invention include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, Examples include metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-3070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241. JP, 62-21401, JP 63-70243, 63-298339, M.M. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol) Linophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholino Acetophenone derivatives such as butyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p- Examples thereof include benzoic acid ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

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

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797 And the compounds described. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Among these, as photopolymerization initiators, from the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocenes. Compound, oxime ester compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3 -Compounds selected from the group consisting of aryl-substituted coumarin compounds are preferred.

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime ester compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
Examples of the oxime ester compound suitable as a photopolymerization initiator in the present invention include oxime ester compounds represented by the following general formula (5) or (6).

In the general formula (5), R ⁸ and P each independently represent a monovalent substituent, Q ¹ and Q ² each independently represent a divalent organic group, and Ar represents an aryl group. n is an integer of 0-5. When a plurality of P are present, each of the plurality of P independently represents a monovalent substituent.
Photopolymerization initiators that can be suitably used for the photocurable coloring composition of the present invention are the compounds described in paragraphs [0089] to [0173] of JP 2010-72633 A.

  The compound represented by the general formula (5) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  (C) It is preferable that content of a photoinitiator is 0.1 mass%-20 mass% with respect to the total non volatile matter in a photocurable coloring composition, More preferably, it is 0.5 mass%- It is 15 mass%, Most preferably, it is 3 mass%-15 mass%. Within this range, good sensitivity and pattern formability can be obtained.

[Sensitizing dye]
A sensitizing dye is preferably added to the photocurable coloring composition of the present invention from the viewpoint of improving sensitivity. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the photopolymerization initiator component and polymerization reaction of the polymerizable compound thereby.
Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

  Preferred spectral sensitizing dyes or dyes that can be used in the present invention include polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, Rose bengal), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, Chloroflavin, acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyllin) Phil, chlorophyllin, center metal-substituted chlorophyll), metal complexes, anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  The content of the sensitizing dye is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass with respect to the total nonvolatile content in the photocurable coloring composition. is there.

[Thiol compound]
It is preferable that the photocurable coloring composition in this invention contains a thiol compound.
The thiol compound in the present invention acts as a co-sensitizer or exhibits an effect of improving the adhesion between the formed colored pixel and the substrate. The co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the photopolymerization initiator to actinic radiation, or suppressing polymerization inhibition due to oxygen of the polymerizable compound.

Specific examples of the thiol compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate ( PETP), mercaptopropionic acid derivatives such as THEIC-BMPA represented by the following formula; ethylene glycol bisthioglycolate (EGTG), butanediol bisthioglycolate (BDTG), hexanediol bisthioglycolate (HDTG), triglyceride Thioglycolic acid derivatives such as methylolpropane tristhioglycolate (TMTG) and pentaerythritol tetrakisthioglycolate (PETG); 1,2-benzenedithiol, 1,3-benzene Thiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2 ′-(ethylenedithio) diethanethiol, meso-2,3-dimercaptosuccinic acid, p- Examples include thiols such as xylenedithiol and m-xylenedithiol; mercaptoethers such as di (mercaptoethyl) ether.
These can be used alone or in combination of two or more.

  As for the thiol compound used by this invention, what is represented by the following general formula (I) is more preferable.

  In general formula (I), R represents a hydrogen atom, an alkyl group, or an aryl group, and A represents an atomic group that forms a heterocycle with N═C—N.

In general formula (I), R represents a hydrogen atom, an alkyl group, or an aryl group.
Examples of the alkyl group represented by R include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a linear or carbon atom having 1 to 12 carbon atoms. A branched alkyl group having 3 to 12 and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.
Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.

  As the aryl group represented by R, in addition to those having a single ring structure, one to three benzene rings form a condensed ring, a benzene ring and a five-membered unsaturated ring form a condensed ring, etc. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

  These alkyl groups and aryl groups may further have a substituent. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and the number of carbon atoms. A linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, and 2 carbon atoms -20 alkoxycarbonyloxy group, aryloxycarbonyloxy group having 7-20 carbon atoms, carbamoyloxy group having 1-20 carbon atoms, carbonamido group having 1-20 carbon atoms, 1-20 carbon atoms Sulfonamide group, carbamoyl group having 1 to 20 carbon atoms, sulfamoyl group, substituted sulfamoyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon atom An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an N-acylsulfamoyl group having 1 to 20 carbon atoms, and 1 carbon atom -20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C2-C20 alkoxycarbonylamino group, C7-20 Aryloxycarbonylamino group, amino group, substituted amino group having 1 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonio group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy group, Mercapto group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, and 1-2 carbon atoms Alkylthio group, arylthio group having 6 to 20 carbon atoms, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, sulfamoylamino group A substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, A nitro group, an onium group, etc. are mentioned.

In the general formula (I), A represents an atomic group that forms a heterocycle with N═C—N.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocycle formed by A and N═C—N may further have a substituent. Examples of the substituent that can be introduced include substituents that can be introduced into the alkyl group and aryl group. The same thing is mentioned.

  Further, the thiol compound is more preferably a compound represented by the following general formula (II) or general formula (III).

In general formula (II), R ¹ represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In general formula (III), R ² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

  In general formula (II) and general formula (III), as a halogen atom represented by X, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

  In the general formula (II) and general formula (III), the alkoxy group represented by X includes a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, and a dodecyloxy group. Group, benzyloxy group, allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy Group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group Chlorophenyl group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.

Formula (II) and general formula (III), the alkyl group represented by R ² or X has the same meaning as the alkyl group represented by R in formula (I), and also the preferred ranges thereof .
In the general formulas (II) and (III), the aryl groups represented by R ¹ , R ² , and X are each independently an aryl group represented by R in the general formula (I) It is synonymous and the preferable range is also the same.

In general formula (II) and general formula (III), each group represented by R ¹ , R ² , or X may further have a substituent, and as the substituent, the general formula (I The same as those listed as substituents that can be introduced into the alkyl group or aryl group represented by R).

In general formula (II) and general formula (III), it is more preferable that X is a hydrogen atom from the viewpoint of solubility of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA as appropriate).
In general formula (II), R ¹ is most preferably a phenyl group from the viewpoints of sensitivity and PGMEA solubility.
In general formula (III), R ² is more preferably a methyl group, an ethyl group, a phenyl group, or a benzyl group from the viewpoints of sensitivity and PGMEA solubility.

  Of the compounds represented by the general formula (II) and the compounds represented by the general formula (III), the compounds represented by the general formula (III) are most preferable from the viewpoint of solubility of PGMEA.

  These thiol compounds are described in J. Org. Appl. Chem. , 34, 2203-2207 (1961).

  In the photocurable coloring composition of the present invention, the compound represented by the general formula (I) may be used singly or in combination of two or more, or represented by the general formula (II). A compound selected from the above compounds, a compound selected from the compounds represented by the general formula (III), and a compound selected from the above may be used in combination.

  The content of the thiol compound in the photocurable coloring composition is preferably 0.1% by mass to 5.0% by mass with respect to the solid content of the photocurable coloring composition, and is 0.2% by mass. More preferably, it is -4 mass%. It exists in this range since it does not impair the polymerizability of a photocurable coloring composition.

<(E) Binder>
The photocurable coloring composition used in the present invention contains (E) a binder for the purpose of improving film properties and imparting development properties. Here, as the binder (E), polymer compounds such as alkali-soluble resins, epoxy resins, pigment coating resins, and polymer dispersants are shown. In consideration of development with an alkali, it is preferable to include at least an alkali-soluble resin.
The alkali-soluble resin and epoxy resin of these binders will be described in detail below.

  The alkali-soluble resin used in the photocurable coloring composition of the present invention is a linear organic high molecular polymer, and has a molecule (preferably an acrylic copolymer or a styrene copolymer as the main chain). It can be appropriately selected from alkali-soluble resins having at least one group that promotes alkali solubility (for example, carboxyl group, phosphate group, sulfonate group, hydroxyl group, etc.) in the molecule.

  More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54- No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, Acrylics such as crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group added with an acid anhydride The thing of a system copolymer is mentioned.

  The acid value is preferably in the range of 20 mgKOH / g to 200 mgKOH / g, preferably 30 mgKOH / g to 180 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g.

The alkali-soluble resin used in the present invention is particularly preferably a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith.
Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
As the alkyl (meth) acrylate and aryl (meth) acrylate, CH ₂ ═C (R) (COOR ′) [wherein R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ′ represents carbon. An alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms is represented. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate , Octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is 1 to 3 carbon atoms) 8 alkyl group), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

As the vinyl _compounds, CH ² = ^CR 1 ^R 2 [wherein, ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.

The other copolymerizable monomers as described above can be used singly or in combination of two or more.
Of the above, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferable as the alkali-soluble resin.
As the polyalkylene oxide chain, a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof can be used, and the end of these chains is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable.
Examples of the acrylic copolymer having a polyalkylene oxide chain in the side chain include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like. A compound in which these terminal OH groups are alkyl-blocked, for example, methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate, etc. as a copolymerization component The acrylic copolymer containing is preferable.

The acrylic copolymer has an acid value in the range of 20 mgKOH / g to 200 mgKOH / g, as already described. If the acid value is 200 mgKOH / g or less, the acrylic resin does not become too soluble in alkali, and the appropriate development range (development latitude) can be prevented from becoming narrow. On the other hand, if it is 20 mgKOH / g or more, the solubility in alkali is unlikely to be reduced, so that it is possible to prevent the development time from being prolonged.
In addition, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used to realize a viscosity range in which the photocurable coloring composition can be easily used in a process such as coating, and the film strength. In order to ensure, it is preferable that it is 2,000-100,000, More preferably, it is 3,000-50,000.

Moreover, in order to improve the crosslinking efficiency of the photocurable coloring composition that can be used in the present invention, it is preferable to use an alkali-soluble resin having a polymerizable group. This alkali-soluble resin having a polymerizable group may be used alone or in combination with an alkali-soluble resin having no polymerizable group.
As the alkali-soluble resin having a polymerizable group, a polymer containing an aryl group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain is useful. Such an alkali-soluble resin having a polymerizable double bond is preferable because it can be developed with an alkaline developer and further has photocurability and thermosetting properties. Among them, a resin having an aryl group as a side chain polymerizable group is more preferable because it has high resist curability and high thermal decomposition resistance.
Hereinafter, suitable examples of the alkali-soluble resin containing a polymerizable group will be shown, but in one molecule, an alkali-soluble group such as a COOH group and an OH group, and a polymerizable double bond (carbon-carbon unsaturated bond). Are not limited to those shown below.

That is,
(1) By reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting with a compound containing at least one (meth) acryloyl group and an acrylic resin containing a carboxyl group Urethane-modified polymerizable double bond-containing acrylic resin obtained (2) Contains unsaturated group obtained by reaction of acrylic resin containing carboxyl group and compound having both epoxy group and polymerizable double bond in molecule Acrylic resin (3) Acid pendant type epoxy acrylate resin (4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

As a specific example, a copolymer of an OH group, for example, 2-hydroxyethyl acrylate, a COOH group, for example, methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable therewith. A compound obtained by reacting a compound with an epoxy ring having reactivity with an OH group and a compound having a polymerizable double bond (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, in addition to the epoxy ring, a compound having an acid anhydride, an isocyanate group, or an acryloyl group can also be used.
Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and a polymerizable double bond include, for example, Dainar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Photomer 6173 (COOH group-containing Polyanethane acrylic oligomer, Diamond Shamrock Co., Ltd.). Ltd.); Biscote R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel Cytech) Etc.).

  (E) As an addition amount when using an alkali-soluble resin as a binder, it is preferable that it is the range of 3 mass%-50 mass% in the total non volatile matter of a photocurable coloring composition, and 5 mass%-30 mass. % Is more preferable.

In preparing the photocurable coloring composition, it is preferable to add the following epoxy resin in addition to the alkali-soluble resin. Examples of the epoxy resin include compounds having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolak type, biphenyl type, and alicyclic epoxy compound.
For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( As described above, manufactured by Toto Kasei Co., Ltd.), Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase ChemteX Corporation), Plaxel GL-61, GL-62, G101, G102 (and above, Daicel Chemical Industries, Ltd.) and the like, and bisphenol F type and bisphenol S type epoxy resins similar to these can also be used.
Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel Cytec Co., Ltd.) can also be used.

  Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Toto Kasei Co., Ltd.), Denacol EM-125, etc. (above, manufactured by Nagase ChemteX) As the biphenyl type, 3,5,3 ′, 5′-tetramethyl-4,4′-diglycidylbiphenyl and the like, and as the alicyclic epoxy compound, ceroxide 2021, 2081, 2083, 2085, Epolide GT-301 GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100, etc. Manufactured by Co., Ltd.), Epiclon 430, 673, 695, 85 S, the 4032 (manufactured by DIC (Ltd.)), and the like.

  1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient, the reliability is poor, and the flatness is deteriorated.
Specific preferred compounds satisfying this condition include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3, 5, 3 ′, 5 Examples include '-tetramethyl-4,4' diglycidyl biphenyl, ceroxide 2021, 2081, epolide GT-302, GT-403, and EHPE-3150.

  (E) As an addition amount in the case of using an epoxy resin as a binder, it is preferably in the range of 0.1% by mass to 30% by mass in the total nonvolatile content of the photocurable coloring composition, and 0.5% by mass. -20% by mass is more preferable, and 1% by mass to 10% by mass is most preferable. When the addition amount is within this range, sufficient exposure sensitivity can be obtained without impairing photopolymerizability, and high heat resistance and chemical resistance can be imparted because it also has thermal polymerizability. The storage stability of can also be maintained.

<Other additives>
In addition to the above components, various known additives can be used in the photocurable coloring composition used in the present invention depending on the purpose.
Hereinafter, such additives will be described.

(Surfactant)
Since the thixotropy of the coating liquid generally increases when the pigment concentration is increased, the film after the photocurable coloring composition layer (colored layer coating film) is formed by applying or transferring the photocurable coloring composition on the substrate Thickness unevenness is likely to occur. In particular, in the photocurable coloring composition layer (colored layer coating film) formation by the slit coating method, the coating liquid for forming the photocurable coloring composition layer is leveled before drying to form a uniform thickness coating film. It is important to. For this reason, it is preferable to contain an appropriate surfactant in the photocurable coloring composition. Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorosurfactants, silicone surfactants, and the like are added as surfactants for improving coating properties.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acids Ester, there is nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, the Adeka Pluronic series, the Adecanol series, the Tetronic series (above, manufactured by ADEKA Corporation), the Emulgen series, the Leodol series (above, produced by Kao Corporation), the Eleminor series, the Noni series, Pole series, Octapole series, Dodecapol series, New Pole series (Sanyo Kasei Co., Ltd.), Pionein series (Takemoto Yushi Co., Ltd.), Nissan Nonion series (Nippon Yushi Co., Ltd.) ) Etc. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, Megafax F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08 (above, manufactured by DIC Corporation), Florard FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (above, manufactured by JEMCO Corporation).

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( As mentioned above, Momentive Performance Materials Japan, etc.) can be mentioned.

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the coating liquid for forming the photocurable coloring composition layer. When the amount of the surfactant exceeds 5 parts by mass, surface roughness due to coating and drying tends to occur, and smoothness tends to deteriorate.

  In addition, in order to promote alkali solubility of the uncured part and further improve the developability of the photocurable coloring composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. Can be done. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

(Alkoxysilane compound)
In the photocurable coloring composition used in the present invention, an alkoxysilane compound, especially a silane coupling agent can be used from the viewpoint of improving the adhesion to the substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material, and (meth) acryloyl or phenyl that exhibits affinity by interacting or forming a bond with an organic resin. , Mercapto, and epoxysilane, and (meth) acryloylpropyltrimethoxysilane is more preferable among them.
As the addition amount in the case of using a silane coupling agent, the total solid content in the photocurable coloring composition used in the present invention is preferably in the range of 0.2% by mass to 5.0% by mass, 0.5 mass%-3.0 mass% are more preferable.

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

  Another example of the co-sensitizer includes sulfides such as disulfide compounds disclosed in JP-A-56-75643, and specifically includes 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like.

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

  The content of these co-sensitizers is 0.1% by mass to 30% by mass with respect to the total solid content of the photocurable coloring composition, from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range is preferable, the range of 1% by mass to 25% by mass is more preferable, and the range of 1.5% by mass to 20% by mass is still more preferable.

(Polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound that can be polymerized during the production or storage of the photocurable coloring composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, phenoxazine, phenothiazine and the like.

  The addition amount of the thermal polymerization inhibitor is preferably 0.01% by mass to 5% by mass with respect to the photocurable coloring composition. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide can be added to prevent polymerization inhibition due to oxygen and can be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The addition amount of the higher fatty acid derivative is preferably 0.5% by mass to 10% by mass of the photocurable coloring composition.

(Plasticizer)
Furthermore, in the present invention, an inorganic filler, a plasticizer, or the like may be added in order to improve the physical properties of the photocurable coloring composition.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, and the like. 10 mass% or less can be added with respect to the total mass of.
The photocurable coloring composition of the present invention containing the above components is cured with high sensitivity to ultraviolet laser exposure, has excellent pattern formability, and the formed colored pattern has a shape and transmission of visible light. It has good properties and is suitably used for forming a colored pattern for a color filter.

<Method for producing color filter for liquid crystal display device>
The photocurable coloring composition and the method for producing a color filter of the present invention are suitable for a color filter for a liquid crystal display device. Hereinafter, although the photocurable coloring composition of this invention and the manufacturing method of a color filter are demonstrated, this invention is not limited to this method.
The color filter is manufactured by forming a colored pattern on the light-transmitting substrate using a photocurable coloring composition, but other steps can be provided as necessary.

The method for producing a color filter in the present invention is a colored layer forming step in which the above-described photocurable coloring composition for a color filter of the present invention is provided on a substrate to form a colored layer comprising the photocurable coloring composition. And an exposure step of exposing the colored layer in a pattern, and a development step of developing the colored layer after exposure to form a colored pattern.
Furthermore, you may provide the process (baking process) of baking the said colored layer and the process (baking process) of baking the developed said colored layer as needed. These processes may be collectively referred to as a pattern formation process.

[Colored layer forming step]
In the colored layer forming step in the present invention, the photocurable coloring composition of the present invention is applied on a substrate to form a colored layer. As the substrate, for example, non-alkali glass, soda glass, borosilicate glass, quartz glass used for liquid crystal display devices and the like, and a substrate obtained by attaching a transparent conductive film thereto, a photoelectric conversion element substrate used for a solid-state imaging device, etc. Is mentioned. Furthermore, a plastic substrate can also be used. It is preferable that a black matrix is formed in a lattice shape or the like using these substrates, and a colored pattern is formed in an empty portion of the lattice.

  If necessary, an undercoat layer may be provided on these substrates in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate surface. It is preferable that the substrate is large (generally 1 m or more per side) from the standpoint of achieving the effects of the present invention.

As a method for forming the colored layer on the substrate, various application methods such as slit coating, ink-jet method, spin coating, cast coating, roll coating, and screen printing can be applied. Of these, slit coating is preferred from the viewpoints of accuracy and speed.
Moreover, the method of transferring on the board | substrate the coating film previously provided and formed by the said application | coating method on the temporary support body can also be applied.
Regarding the transfer method, the production methods described in paragraph numbers [0023] and [0036] to [0051] of JP-A-2006-23696 and paragraph numbers [0096] to [0108] of JP-A-2006-47592 are used. It can be suitably used in the present invention.

  The thickness of the colored layer in the present invention (for example, coating thickness) is 0.5 μm to 3.0 μm after drying to obtain a sufficient color reproduction region and sufficient panel luminance. It is preferable to form so that it may become, and it is more preferable to set it as 1.5 micrometers-2.5 micrometers.

  Further, when a colored layer (cured film) made of a photocurable coloring composition having a thickness of 2 μm after drying is formed, the transmittance of the cured film at a wavelength of 355 nm is 2% or less. The effect can be exhibited well, which is a preferred embodiment. That is, the wavelength of the exposure light used in the exposure process described later is usually in the range of 300 nm to 380 nm, but the photocurable coloring composition of the present invention can be used for patterning even when irradiated with exposure light having such a wavelength. Good pattern shape, less residue generation, excellent developability, and no excessive heat flow even in the post-baking process, so that the pattern shape after development can be maintained, preventing contact hole crushing Is particularly effective.

[Exposure process]
In the exposure step of the present invention, the colored layer is exposed with a patterned ultraviolet laser, or exposed to ultraviolet rays or the like through a mask having a pattern to form a latent image. By the exposure step of the present invention, (D) the polymerization curing reaction of the polymerizable compound occurs and proceeds by the initiation species generated from the (C) photopolymerization initiator in the patterned exposure region in the photocurable coloring composition. At the same time, a thermal reaction is caused by the heat generated by the ultraviolet laser exposure, and a curing reaction occurs and progresses, and the exposure area is dually cured by light and heat to form a pattern composed of a cured area and an uncured area. It is considered a thing.

  One feature of the ultraviolet laser used in the present invention is that the illuminance is high, and heat is generated in the photocurable coloring composition in the exposure process, which causes uneven curing inside the formed pixel. is there. Therefore, in order to control the temperature of the object to be exposed (photocurable coloring composition) used for pixel formation, it is preferable to keep the exposure stage constant, and it is necessary to consider the shape of the exposure stage. Further, since the ultraviolet laser has a high degree of parallelism of light, the influence of the distance to the substrate is small, and it is also preferable that the exposure is performed while the substrate is lifted with air and conveyed.

  Laser excitation media include crystals, glass, liquids, dyes, gases, etc., and lasers having oscillation wavelengths for known ultraviolet light, such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers, are used from these media. Can do. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  The exposure wavelength of the ultraviolet laser used in the present invention is preferably in the range of 300 nm to 380 nm, more preferably in the range of 310 nm to 360 nm, particularly 355 nm, in terms of good sensitivity that matches the photosensitive wavelength of the colored photosensitive resin composition. Wavelength laser exposure is preferred.

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
As the exposure amount of the exposure object ^(pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  The ultraviolet laser used in the present invention is preferably a pulse laser oscillated at a frequency of 20 Hz to 2000 Hz from the viewpoint of productivity.

  There are no particular restrictions on the exposure apparatus that can be used in the present invention, but commercially available ones such as EGIS (buoy technology) or DF2200G (Dainippon Screen Co., Ltd.) can be used. These devices are also preferably used.

Also. Actinic rays having a wavelength of 300 nm to 450 nm can also be preferably used. For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used.

[Development process]
In the developing step in the present invention, the colored layer on which the latent image is formed is developed to form a pattern. The exposed area is hardened in a pattern, and in the development process, by performing an alkali development process, the unirradiated part (uncured part) in the exposure process is eluted and removed in an alkaline aqueous solution and photocured. By leaving only the part, a pattern can be formed.

As the developer, an organic alkali developer, an inorganic alkali developer or a mixture thereof is used.
Examples of the alkali agent used in the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxy. And organic alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, and the concentration of these alkaline compounds is 0.001 to 0.001. An alkaline aqueous solution diluted with pure water so as to be 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

The development temperature is preferably 20 ° C to 35 ° C, more preferably 23 ° C to 30 ° C. The development time is preferably 30 seconds to 120 seconds, and more preferably 40 seconds to 90 seconds. Among these, a preferable combination of the development temperature and the development time is, for example, 50 seconds to 100 seconds at a temperature of 25 ° C. and 40 seconds to 80 seconds at a temperature of 30 ° C.
The shower pressure is preferably 0.01 MPa to 0.5 MPa, preferably 0.05 MPa to 0.3 MPa, and preferably 0.1 MPa to 0.3 MPa. By selecting these conditions, it is possible to arbitrarily design the pattern shape to be rectangular or forward tapered.

[Bake process]
In the present invention, in order to complete the curing of the photocurable coloring composition, it is preferable to provide a baking step for baking the developed colored layer. Baking is performed by heating a substrate having a pattern after development and rinsing in a continuous or batch manner using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like. It can be carried out.
As conditions for baking, the temperature is preferably 150 ° C to 260 ° C, more preferably 180 ° C to 260 ° C, and most preferably 200 ° C to 240 ° C. The baking time is preferably 10 minutes to 150 minutes, more preferably 20 minutes to 120 minutes, and most preferably 20 minutes to 90 minutes.

  In addition, when forming a colored pattern of multiple hues such as RGB three-color layer, light-shielding layer, etc., the cycle of forming the colored layer, exposing, developing, and baking may be repeated for the desired number of hues, or for each hue. In addition, after the colored layer is formed, exposed and developed, all the hues may be finally baked. As a result, a color filter including colored pixels having a desired hue is produced.

[Other processes]
In this invention, you may provide the process of prebaking in order to dry the colored layer formed by application | coating etc. before an exposure process. The prebaking temperature of the colored layer is preferably 60 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The pre-bake time is preferably 30 seconds to 300 seconds, and more preferably 80 seconds to 200 seconds.

≪Liquid crystal display device≫
The color filter of the present invention is suitable for the production of a liquid crystal display device, and the liquid crystal display device using the color filter produced by the pattern forming method of the present invention can display a high-quality image.
For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)). The liquid crystal display device is described in, for example, “Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Issued in 1994 by Industrial Research Co., Ltd.)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
In addition, the color filter of the present invention is particularly suitable for use in a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer must be the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics as described above. The color filter of the present invention is considered to enhance the transparency of the ultraviolet light laser that is the exposure light by selecting the hue and film thickness of the pixels defined by the present invention in addition to the exposure method using the ultraviolet light laser. As a result, the curability of the colored pixel is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, the resistance to the peeling liquid of the colored layer provided directly or indirectly on the TFT substrate is improved. Useful for liquid crystal display devices. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

  Further, the colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 40 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. Alternatively, it is necessary to form a contact hole (conduction path) having a pixel cross-sectional shape that is rectangular to tapered, such as a circle or ellipse having a diameter of 1 to 40 μmφ, or a U-shape, and the dimension of the conduction path ( That is, the length of one side is preferably 5 μm or less, but it is possible to form a conduction path of 5 μm or less by using the present invention. When the shape of the pixel cross section of the contact hole is not rectangular or tapered, or when the opening is insufficient, the transparent conductive film is disconnected or defective in conduction, and such a color filter is used for an image display device. In some cases, it may cause display defects, but the use of the colored composition of the present invention also has the advantage that the occurrence of problems due to deterioration and collapse of the contact hole is suppressed.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, 18-24 pages (Yasuhiro Shima), 25-30 pages (Yukiaki Yagi), etc. Are listed.

  When the color filter produced by the pattern forming method of the present invention is used in a liquid crystal display device and combined with a conventionally known three-wavelength tube of a cold cathode tube, a high contrast can be realized. By using a light source (RGB-LED) as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

-Synthesis of polymer compounds having a heterocyclic ring in the side chain-
(Synthesis of polymer 1)
M-6 (the following structure) 27.0 g, methyl methacrylate 126.0 g, methacrylic acid 27.0 g, and 1-methoxy-2-propanol 420.0 g were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto) The mixture was stirred with a scientific (three-motor) and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.80 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.80 g of V-65 was further added, and after heating and stirring for 3 hours, a 30% by mass solution of polymer 2 was obtained. It was 21,000 as a result of measuring the weight average molecular weight of the obtained polymer 1 by the gel permeation chromatography method (GPC) which used polystyrene as the standard substance. Moreover, the acid value per solid content was 99 mgKOH / g from the titration using sodium hydroxide.

(Preparation of coated pigment 1)
50 g of pigment (CI Pigment Blue 15: 6), 500 g of sodium chloride, 20 g of the above polymer 1 solution, and 100 g of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, this mixture was poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, and dried to prepare coated pigment 1.

(Preparation of coated pigment 2)
The coated pigment 2 was prepared in the same manner except that the pigment (CI Pigment Blue 15: 6) used in the adjustment of the coated pigment 1 was changed to a pigment (CI Pigment Violet 23).

-Photocurable coloring composition layer forming step-
(Preparation of pigment dispersion composition 1)
Pigment dispersion composition 1 was prepared as follows.
That is, with the composition described below, using a homogenizer, the rotational speed was 3,000 r. p. m. The mixture was stirred for 3 hours to prepare a mixed solution, and further subjected to a dispersion treatment for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads. In addition, the organic solvent propylene glycol methyl ether acetate was described as PGMEA.

・ Coated pigment 1 16.5%
-Dispersant: Disperbyk161 manufactured by Big Chemie [30% solution] 8%
Alkali-soluble resin: benzyl methacrylate / methacrylic acid = 75/25 [mass ratio] copolymer (weight average molecular weight Mw: 5000 PGMEA solution (solid content 50%)) 2%
・ PGMEA 73.5%

(Preparation of pigment dispersion composition 2)
・ Coating pigment 1 11.55%
・ Coated pigment 2 4.95%
-Dispersant: Disperbyk161 manufactured by Big Chemie [30% solution] 8%
Alkali-soluble resin: benzyl methacrylate / methacrylic acid = 75/25 [mass ratio] copolymer (weight average molecular weight Mw: 5000 PGMEA solution (solid content 50%)) 2%
・ PGMEA 73.5%

<Example 1>
(Preparation of photocurable coloring composition)
The composition 1 shown below was stirred and mixed to prepare a blue photocurable coloring composition.
-Pigment dispersion composition 1 9.08 parts-Pigment dispersion composition 2 5.59 parts-Surfactant: F-554 DIC 0.2% PGMEA solution 5.00 parts-Silane coupling agent (structure below) 0.20 part. Photopolymerization initiator (the following structure) 0.68 part. Polymerizable compound (species and amount of compounds described in Table 1)
Binder: Allyl methacrylate / methacrylic acid = 80/20 mol% copolymer Weight average molecular weight 30000 20% PGMEA solution 18.54 parts Solvent: PGMEA 8.72 parts

(Photocurable coloring composition layer formation)
The obtained blue photocurable coloring composition was slit-coated on a glass substrate.
Specifically, coating is performed at a coating speed of 120 mm / sec by adjusting the distance between the slit and the glass substrate and the discharge amount so that the thickness of the post-baked photocurable coloring composition layer is 3.2 μm. did.

-Pre-bake process, exposure process-
Next, after performing heating (pre-baking treatment) at 100 ° C. for 120 seconds using a hot plate, with an exposure apparatus using an Nd: YAG laser (Pulseo, third harmonic 355 nm, manufactured by Spectra-Physics), The optical system was adjusted so that the irradiation energy was about 1.0 mJ / cm ² with respect to the surface of the photocurable coloring composition layer, and exposure was performed through a photomask (mask aperture 25 μmφ). Pattern exposure was performed by performing 20 times multiple exposure with respect to the photocurable coloring composition layer surface.

-Development process, post-bake process-
Thereafter, using a developing device (manufactured by Hitachi High-Technologies Corporation), 1 part of a 1.0% developer (CDK-1) of potassium hydroxide developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) A time obtained by adding 20 seconds to the time when the unexposed photocurable coloring composition layer is dissolved and the glass surface is exposed by setting the shower pressure to 0.2 MPa with a solution diluted with 99 parts of pure water (25 ° C.). Developed and washed with pure water.
Next, a post-baking process was performed for 30 minutes in a 220 ° C. clean oven to form a substrate having heat-treated blue pixels. The following evaluation was performed and the results are shown in Table 2.

(Evaluation)
[Contact hole opening diameter, contact hole remaining rate after post-baking]
Using a mask having a perfect circular pattern (mask diameter: 25 μmφ) for forming a contact hole (hereinafter sometimes referred to as CH) of 25 μmφ in the pixel portion, exposure GAP = 150 μm, and blue for a color filter in the above process Pixels were formed, and the CH opening diameter after the post-baking step was measured. Moreover, the CH residual ratio was calculated using the following equation based on the CH opening diameter before post-baking and the CH opening diameter after the post-baking step.
CH residual ratio (%) =
[CH opening diameter (after post-baking) / CH opening diameter (before post-baking)] × 100

[Developability]
The glass substrate with a photocurable coloring composition layer that has been subjected to the coating step, the pre-bake step, and the exposure step is developed under the conditions of the developing step, and the photocurable coloring composition layer in the unexposed area is dissolved. Measure the time until the glass surface is exposed. A smaller value is preferred.

(Line width sensitivity)
The glass substrate with a photocurable coloring composition layer subjected to the coating step and the pre-bake step described above was exposed under the conditions of the exposure step through a mask having a mask line width of 170 μm and developed under the conditions of the development step. The line width of the pixel formed later is measured. The higher the line width, the higher the sensitivity.

[Residue]
The glass surface of the pixel peripheral part of the glass substrate with a photocurable coloring composition layer used for the line width sensitivity measurement was observed with a scanning electron microscope (SEM), and the residue was evaluated according to the following criteria.
-Evaluation criteria-
○: No residue is generated.
X: Residue is generated.

<Examples 2-8, Comparative Examples 1-3>
A substrate having a blue pixel was formed in the same manner as in Example 1 except that the photocurable coloring composition was prepared by changing the type and content of the polymerizable compound to the amounts described in Table 1 below. . Further, in the same manner as in Example 1, CH opening diameter, CH residual ratio, developability, line width sensitivity, and residue were evaluated. The results are summarized in Table 2.

Specific polymerizable compounds 1 to 6 used in Table 1 are as follows. The structure is shown below.
DPHA is dipentaerythritol hexaacrylate (trade name: DPHA) manufactured by Nippon Kayaku Co., Ltd., and corresponds to the polymerizable compound (III) of the present invention. In Examples 1 to 6 and Comparative Examples 2 to 3, two kinds of polymerizable compounds were used.
Specific polymerizable compound 1: Product name DA-722, manufactured by Nagase ChemteX Corporation
Specific polymerizable compound 2: Product name EA-5420 manufactured by Shin-Nakamura Chemical Co., Ltd.
Specific polymerizable compound 3: Product name EA-5421, manufactured by Shin-Nakamura Chemical Co., Ltd.
Specific polymerizable compound 4: Product name EA-5323, manufactured by Shin-Nakamura Chemical Co., Ltd.
Specific polymerizable compound 5: Product name EA-5324, manufactured by Shin-Nakamura Chemical Co., Ltd.
Specific polymerizable compound 6: Shin-Nakamura Chemical Co., Ltd. trade name EA-5721
Moreover, the comparative compound 1 used by the comparative example 2 is a polymeric compound which has an aromatic ring, and is the new Nakamura Chemical Co., Ltd. brand name EA-6320 of the following structure. Moreover, the comparative compound 2 used by the comparative example 3 is a polymeric compound which has OH group which is not derived from glycidyl, and is the Toagosei Co., Ltd. brand name Aronics M-305 of the following structure.

  From the results of Table 2, it can be seen that the color filters of the examples (color filters having colored pixels obtained by the photocurable coloring composition of the present invention) have a wide CH opening diameter and a good CH residual ratio. It was. From this, it can be seen that in the colored pattern formed by the photocurable coloring composition of the present invention, thermal deformation due to post-baking was moderately suppressed, and collapse of contact holes due to heat treatment was suppressed. In addition, it can be seen that the developability of the examples is good, the line width sensitivity of the examples is equivalent to that of the comparative example, and the residue of the examples is good, which is far superior to the comparative example. As described above, it can be seen that the photocurable coloring composition of the present invention is superior in the use for forming a colored pattern of a color filter, and particularly excellent in forming a contact hole, as compared with a conventional product.

Claims (11)

(A) an organic solvent, (B) a pigment, (C) a photopolymerization initiator, (D) a polymerizable compound, and (E) a binder, wherein the (D) polymerizable compound is the following (I) and ( A photocurable coloring composition for a color filter comprising one or more compounds selected from II).
(I): A polymerizable compound having 2 to 6 (meth) acryloyl groups, 1 to 6 hydroxyl groups derived from glycidyl groups, and a ring structure other than an aromatic ring (II): 3 to 12 (Meth) acryloyl group, 1 to 12 hydroxyl group derived from glycidyl group, and a polymerizable compound having a branched structure   The group other than the aromatic ring in (I) is a group consisting of a hexahydrophthalic acid skeleton, a tetrahydrophthalic acid skeleton, a hydrogenated bisphenol A skeleton, a cyclohexanedimethanol skeleton, an isocyanuric ring, and a tricyclodecane dimethanol skeleton. The photocurable coloring composition for a color filter according to claim 1, which is one kind selected from the group consisting of:   The photocuring for a color filter according to claim 1, wherein the branched structure in (II) is one selected from the group consisting of a trimethylolpropane skeleton, a pentaerythritol skeleton, a dipentaerythritol skeleton, a sorbitol skeleton, and a glycerin skeleton. Coloring composition.   Further, (III) having an (meth) acryloyl group of 3 or more and 12 or less, and an unsaturated group density expressed by dividing the number of the (meth) acryloyl groups by the molecular weight of the polymerizable compound is 0.0067 or more The photocurable coloring composition for a color filter according to any one of claims 1 to 3, comprising a polymerizable compound having a structure of 0.0114 or less and having a structure different from that of (I) and (II). object.   The light for a color filter according to any one of claims 1 to 4, wherein when a cured film having a thickness of 2 µm after drying is formed, the transmittance of the cured film at a wavelength of 355 nm is 2% or less. Curable coloring composition.   The (B) pigment is C.I. I. It is Pigment Blue 15: 6. The photocurable coloring composition for color filters of any one of Claims 1-5.   A colored layer forming step of forming a colored layer comprising the colored composition by applying the photocurable coloring composition for a color filter according to any one of claims 1 to 6 on a substrate; A method for producing a color filter, comprising: an exposure step of exposing a colored layer in a pattern-like manner; and a developing step of developing the colored layer after exposure to form a colored pattern.   The method for producing a color filter according to claim 7, wherein the exposure step is an exposure step of patternwise exposure using a 355 nm laser.   The method for producing a color filter according to claim 7 or 8, wherein the color filter is a method for producing a color-filter on array type color filter.   The color filter manufactured by the manufacturing method of the color filter of any one of Claims 7-9.   A liquid crystal display device comprising the color filter according to claim 7.