JP2009098691A - Color filter and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter capable of providing a high contrast, and to provide a method of manufacturing the same. <P>SOLUTION: The color filter includes a colored pattern formed by applying a photo-curing composition containing a pigment having an average particle size of 15-150 nm. The coverage of secondary particles in an image of the colored pattern surface obtained by results of observation by AFM is 40% or less. The photo-curing composition contains the pigment having an average particle size of 15-150 nm; a polymer containing a copolymerization unit derived from a monomer, represented by the general formula (1); a photopolymerizable compound; and a photopolymerization initiator. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a color filter and a method for manufacturing the color filter, and more particularly to a color filter having excellent contrast and a method for manufacturing the color filter.

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

  In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. With this trend of application expansion, advanced color characteristics in chromaticity, contrast, etc. Has come to be required. In particular, contrast is particularly attracting attention because it significantly affects the image quality of the display device.

In response to the above requirements, it is required to disperse the pigment in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability). If the dispersibility is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is remarkably high. There is a problem of deterioration.
As a factor of lowering the contrast, there is a light leakage at the time of disposing the polarizing plate cross due to scattering of the backlight light by the pigment particles in the composition. For this reason, in order to increase the contrast of the color filter, it is considered that a smaller average particle size in the colored composition is preferable.
As a technique for improving the contrast by selecting pigment particles, a method using a pigment having an average particle size of 100 to 300 nm (see, for example, Patent Document 1) or an average particle size using an ultrasonic attenuation type particle size distribution measuring device. The diameter is measured, and particles within a predetermined range, specifically, D ₈₄ is 1.0 μm or less, D ₅₀ is 0.5 μm or less, D ₁₆ is 0.3 μm or less, and the maximum peak is 0.5 μm or less. A method of selecting and using pigment particles to be used (see, for example, Patent Document 2) is disclosed. However, since the surface area of the pigment particles is increased when the particle diameter of the pigment is reduced, the cohesive force between the pigment particles is increased, and it is difficult to achieve both dispersibility and dispersion stability at a high level. In many cases, even with the above-described technology, a practically satisfactory level of high contrast has not been achieved, and further higher contrast is desired.
JP 2003-248115 A JP 2005-165307 A

This invention is made | formed in view of the problem in the said prior art, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a color filter capable of obtaining a high contrast and a method for producing such a color filter.

As a result of intensive studies, the present inventors have found that the above problem can be solved by controlling the occupation ratio of the secondary pigment particles to a predetermined value or less in the formed colored pattern film, and completed the present invention. did.
That is, the means for solving the problems are as follows.

<1> Secondary particles in an image obtained as a result of observation by AFM of a colored pattern surface comprising a colored pattern formed by applying a photocurable composition containing a pigment having an average particle size of 15 to 150 nm The color filter characterized by having an occupation ratio of 40% or less.
<2> The photocurable composition includes an organic solvent, a pigment having an average particle size of 15 to 150 nm, and a polymer including a copolymer unit derived from a monomer represented by the following general formula (1): The color filter according to <1>, further comprising a photopolymerizable compound and a photopolymerization initiator.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1. ]

<3> The color filter according to <2>, wherein in the general formula (1), the cyclic structure formed by Y being connected to the N atom via an adjacent atomic group is a condensed ring structure.
<4> The <2> or <3>, wherein the polymer is a graft copolymer further comprising a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at a terminal. Color filter.
<5> The color according to any one of <2> to <4>, wherein the polymer is a polymer further including a copolymer unit derived from a monomer having an acid group. filter.

<6> The color filter according to any one of <2> to <5>, wherein the photocurable composition further contains an alkali-soluble resin.
<7> An organic solvent, a pigment having an average particle size of 15 to 150 nm, a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1), a photopolymerizable compound, and light A photosensitive film forming step of forming a photosensitive film by applying a photocurable composition containing a polymerization initiator directly or via another layer to a substrate, and pattern exposure to the formed photosensitive film And a colored pattern forming step of forming a colored pattern by sequentially performing development.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1. ]

  As one of the preferred embodiments of the present invention, even when a pigment having a fine particle size is used, a curable composition using a pigment dispersion composition having high pigment dispersibility and dispersion stability is formed into a colored pattern. For example, there is an embodiment in which a color filter excellent in light transmittance and contrast is obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the color filter which can obtain high contrast, and the manufacturing method of such a color filter can be provided.

  Hereinafter, the color filter of the present invention and the manufacturing method thereof will be described in detail.

The color filter of the present invention comprises a colored pattern formed by applying a photocurable composition containing a pigment having an average particle size of 15 to 150 nm, and in the image obtained as a result of observation of the colored pattern surface by AFM. The secondary particle occupancy is 40% or less. The occupation ratio of the secondary particles needs to be 40% or less, preferably 25% or less, more preferably 10% or less.
Here, the primary particle diameter of the pigment can be measured with an electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) at a magnification of 100,000 times and n = 100 or more.
The average particle size of the pigment can be measured by diluting with a dispersion medium, if necessary, using a dynamic light scattering type particle size distribution measuring device (Microtrack UPA-150 manufactured by Nikkiso Co., Ltd.).

The occupation ratio of secondary particles in the present invention refers to the ratio of secondary particles to the entire image in an image after processing for removing noise, fine particles and the like in the observation image of the film surface by AFM (atomic force microscope). The area fraction is calculated. In the present invention, a value measured by the following method is adopted.
<Occupancy of pigment secondary particles>
The film surface of the formed colored pattern was observed with AFM (Nanoscope IIIa tapping mode manufactured by Nanoworld), and an observation image of the surface was obtained.
Here, when it is going to evaluate the coloring pattern using a specific pigment dispersion composition, it apply | coated on the conditions from which a dry film thickness will be 2.0 micrometers on a 0.7 mm glass substrate, and the membrane | film | coat (formed by drying) Colored pattern) may be the subject.

Subsequently, the obtained image was processed using the image processing program “Image J” according to the following procedure, and the occupation ratio of secondary particles in the image was obtained.
1. After grayscale conversion and level correction, image noise and undulation were eliminated and binarized by discriminant analysis.
2. The contacting particles were divided by the Watershed method.
3. Occupancy was calculated by extracting particles of 50 nm or more.
As the image processing program, a program “Image J” manufactured by the National Institutes of Health was used.

When the occupancy of the secondary particles is measured under these conditions, when the occupancy exceeds 40%, for example, the occupancy is 42 to 45%, the contrast of the color filter having this coloring pattern is in a state that is practically sufficient. It has been confirmed that it is difficult to say.
In such a condition, that is, in a coloring pattern containing a pigment having an average particle diameter of 15 to 150 nm, as a means for setting the occupancy of secondary particles in the image measured under the above conditions to 40% or less, the formation of the coloring pattern In this case, it is possible to use a curable composition capable of suppressing pigment aggregation and to suppress dry aggregation in the coating film at the time of film formation. Specific means include, for example, dispersion of fine pigments. And a means for forming a colored pattern using a photocurable composition having excellent properties and stability.

Hereinafter, a means for forming a colored pattern using a photocurable composition excellent in dispersibility of fine pigment and its stability will be specifically described.
<Pigment dispersion composition>
In the present invention, a copolymer unit derived from a monomer represented by the following general formula (1) is used as one means for uniformly dispersing a fine pigment stably without fear of aggregation over time. The method of using the polymer containing as a pigment dispersion resin is employ | adopted.

[Polymer containing copolymerized units derived from monomer represented by general formula (1)]
The photocurable composition forming the colored pattern of the present invention preferably contains a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1).
In the photocurable composition according to the present invention, the specific polymer can function as a pigment dispersant. In the following description, the “polymer containing a copolymer unit derived from the monomer represented by the general formula (1)” may be referred to as a “specific pigment dispersant” as appropriate.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1.

  Hereinafter, the monomer represented by the general formula (1), which is an essential copolymer unit in the specific polymer that is an important component of the present invention, will be described in detail.

In the general formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ¹ is a substituted alkyl group, examples of the substituent that can be introduced include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen group.
Specific examples of the preferred alkyl group represented by R ¹ include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxy group. Examples thereof include an ethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.

R ² represents an alkylene group.
The alkylene group represented by R ² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group represented by R ² may have a substituent if it can be introduced, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like. It is done.
Specific examples of the preferable alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

  W represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and is —C (═O) O— or —CONH—. Is preferred.

Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure.
R ³ represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or a methyl group.
Y is particularly preferably -S-, -NH-, or -N =.

  Examples of the cyclic structure formed by linking Y with an N atom through an atomic group adjacent thereto include imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and the like, and , A condensed ring structure such as a benzimidazole ring, a benzthiazole ring, a benzoxazole ring, a purine ring, a quinazoline ring, and a perimidine ring, and a condensed ring structure is preferable from the viewpoint of affinity with a pigment. Of the condensed ring structures, a benzimidazole ring, a benzthiazole ring, and a benzoxazole ring are particularly preferred.

  X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. X is particularly preferably —O—, —S—, —CONH—, —NHCONH—, and —NHC (═O) S—.

  m and n each independently represents 0 or 1, and it is particularly preferred that both m and n are 1.

  Preferred specific examples (monomer M-1 to monomer M-18) of the monomer represented by the general formula (1) are listed below, but the present invention is not limited thereto.

  The specific polymer in the present invention has an ethylenically unsaturated bond at the terminal together with a copolymer unit derived from the monomer represented by the general formula (1) from the viewpoint of imparting dispersion stability of the pigment. A graft copolymer containing a copolymer unit derived from a polymerizable oligomer is particularly preferable.

  Such a polymerizable oligomer having an ethylenically unsaturated bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.

  The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.

  The polymerizable oligomer is preferably an oligomer represented by the following general formula (2).

In General Formula (2), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.
R ¹² represents a linking group containing an alkylene group having 1 to ¹² carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. R ¹² is preferably a group in which an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms is linked by breaking an ester bond. The alkylene group represented by R ¹² may further have a substituent (for example, a hydroxyl group).
Y represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms, or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or —COOR ¹⁴ where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  Preferred examples of the polymerizable oligomer (macromonomer) that can be used for the synthesis of the specific pigment dispersant in the present invention include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-butyl (meth). A polymer in which a (meth) acryloyl group is bonded to one molecular end of acrylate or polystyrene can be exemplified. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

  The specific pigment dispersant according to the present invention preferably further contains a copolymer unit derived from a monomer having an acid group. When the specific pigment dispersant further contains a copolymer unit derived from a monomer having an acid group, for example, when the pigment dispersion composition according to the present invention is applied to pattern formation by a photolithographic method, the pattern formability is improved. It can be improved further.

  Monomers having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto It can be mentioned mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

The specific pigment dispersant according to the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.
In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group deprotectable by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  As a preferable aspect of the specific pigment dispersant according to the present invention, it contains 2 to 50% by mass of a copolymer unit derived from the monomer represented by the general formula (1), and is further ethylenically unsaturated at the terminal. 10 to 90% by mass of a copolymer unit derived from a polymerizable oligomer having a bond, 1 to 30% by mass of a copolymer unit derived from a monomer having an acid group, and 0 to a copolymer unit derived from a vinyl monomer A copolymer containing ˜20% by mass can be preferably mentioned.

  The preferable molecular weight of the specific pigment dispersant according to the present invention is preferably 15,000 to 200,000 in terms of weight average molecular weight (Mw) and 8,000 to 100,000 in terms of number average molecular weight (Mn). The molecular weight can be measured by GPC.

  Specific examples of the specific pigment dispersant [Exemplary Compound 1 to Exemplified Compound 16] that can be suitably used in the photocurable composition according to the present invention are listed below together with their weight average molecular weights, but the present invention is limited to these. It is not a thing.

Illustrative compound (1): Monomer M-2 / terminal methacryloylated polymethyl methacrylate copolymer (10/90 mass%, weight average molecular weight 50000)
Illustrative compound (2): monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Exemplary Compound (3): Monomer M-3 / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/10/85 mass%, weight average molecular weight 40000)
Exemplary Compound (4): Monomer M-3 / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/15/65 mass%, weight average molecular weight 60000)
Exemplary Compound (5): Monomer M-4 / terminal methacryloylated polymethyl methacrylate copolymer (10/90 mass%, weight average molecular weight 80000)

Exemplary Compound (6): Monomer M-4 / Methacrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 30000)
Exemplary Compound (7): Monomer M-5 / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight 60000)
Exemplary compound (8): Monomer M-5 / terminal methacryloylated polybutyl acrylate copolymer (15/85% by mass, weight average molecular weight 40000)
Exemplary compound (9): Monomer M-6 / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/75 mass%, weight average molecular weight 80,000)
Exemplary Compound (10): Monomer M-6 / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (12/88% by Mass, Weight Average Molecular Weight 50000)

Illustrative compound (11): monomer M-7 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Exemplary compound (12): Monomer M-7 / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 40000)
Exemplary Compound (13): Monomer M-10 / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/10/85 mass%, weight average molecular weight 20000)
Illustrative compound (14): monomer M-10 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 25000)
Exemplary Compound (15): Monomer M-10 / methoxypolyethylene glycol methacrylate copolymer (15: 85% by mass, weight average molecular weight 15000)
Illustrative compound (16): monomer M-13 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000)

The copolymer as described above, which is a specific pigment dispersant in the present invention, contains a monomer represented by the general formula (1), a polymerizable oligomer used in combination as required, and other monomers in a solvent. It can be obtained by radical polymerization. As the radical polymerization initiator, a known compound is used, and an azo initiator (for example, dimethyl-2,2′-azobis (2-methylpropionate), azobisisobutyronitrile, 2,2′- Azobis (2-amidinopropane) dihydrochloride, etc.) and peroxides (benzoyl peroxide, potassium persulfate, etc.) are preferably used. In addition to the initiator, a chain transfer agent (for example, 2-mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptoacetic acid, dodecyl mercaptan) may be added and synthesized.
A specific synthesis example will be described later.

  As content in the pigment dispersion composition of a specific pigment dispersant, 0.5-100 mass% is preferable with respect to the mass of the pigment mentioned later, and 3-70 mass% is more preferable. When the amount of the pigment dispersant is within this range, a sufficient pigment dispersion effect can be obtained. Even if the pigment dispersant is added in an amount of more than 100% by mass, a further improvement effect of the pigment dispersion effect may not be expected.

The pigment dispersion composition according to the present invention comprises a pigment and a specific pigment dispersant in an organic solvent, and can be constituted using other components such as a resin component as necessary. .
Since this pigment dispersion composition contains a specific pigment dispersant, the dispersion state of the pigment in the organic solvent is improved, and good color characteristics are obtained. For example, when a color filter is constructed, a high contrast is obtained. Can do. In particular, the organic pigment exhibits an excellent dispersion effect.

[Pigment having an average particle size of 15 to 150 nm]
In the present invention, it is necessary for the color filter coloring pattern to contain a pigment having an average particle size of 15 to 150 nm in order to achieve high contrast. Can be used by appropriately selecting various conventionally known inorganic pigments or organic pigments.
In consideration of the fact that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible. It needs to be in the above range and is more preferably in the range of 15 to 50 nm.
Here, the average particle diameter of the pigment represents the average particle diameter of the secondary particles, and can be specifically measured by the above-described method.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specific examples include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include the following.
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 37, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;

Although it does not specifically limit as a pigment in this invention, The following pigment is more preferable.
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, 37,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7,36;
C. I. Pigment Black 7

These organic pigments can be used alone or in various combinations to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment A mixture of these can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. By setting the mass ratio in this range, the light transmittance of 400 nm to 500 nm can be effectively suppressed, and the color purity can be increased. Further, a hue that is the NTSC target hue can be obtained without causing a shift in the target main wavelength. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. By setting the mass ratio in this range, the light transmittance of 400 nm to 500 nm can be effectively suppressed, and the color purity can be increased. Further, a hue that is the NTSC target hue can be obtained without causing a shift in the target main wavelength. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  Examples of the pigment for the black matrix include carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60. By setting the mass ratio within the range, good dispersion stability is achieved.

  In order to prepare the photocurable composition according to the present invention, it is preferable to obtain a pigment dispersion composition obtained by dispersing the pigment in a solvent in advance, and the pigment content in the pigment dispersion composition is as follows. Is preferably 40 to 90 mass%, more preferably 50 to 80 mass%, based on the total solid content (mass) of the composition. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

[Organic solvent]
Examples of the organic solvent used for preparing the pigment dispersion composition and the photocurable composition in the present invention include 1-methoxy-2-propyl acetate, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, acetic acid. Examples thereof include ethyl, butyl acetate, ethyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propanol, n-butanol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, xylene and the like.
The amount of the organic solvent added is appropriately selected according to the use of the pigment dispersion composition, etc. In the present invention, since it is used for the preparation of a photocurable composition described later, from the viewpoint of handleability, the pigment And the solid content concentration including the pigment dispersant can be added so as to be 5 to 50% by mass.

The method for preparing the pigment dispersion composition is not particularly limited. For example, a pigment or pigment dispersant and a solvent may be used in a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. It can be obtained by performing fine dispersion treatment with beads made of glass having a particle diameter of 01 to 1 mm, zirconia or the like.
Also, before carrying out bead dispersion, while applying a strong shearing force using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to perform a kneading and dispersing process.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  Since the pigment dispersion composition according to the present invention is used for preparing a photocurable composition for forming a color filter, it is preferable that the pigment dispersion composition is soluble in an alkaline aqueous solution.

<Photocurable composition>
The photocurable composition for forming a colored pattern comprises the above-described pigment dispersion composition, a photopolymerizable compound, and a photopolymerization initiator, and preferably further contains an alkali-soluble resin. Depending on the situation, other components may be included.
Since this photocurable composition contains the specific pigment dispersant described above, the pigment is maintained in a good dispersion state in the composition, and good color characteristics can be obtained. A high contrast can be obtained by suppressing the aggregation of the pigment in the glass.
Hereinafter, each component contained in the photocurable composition concerning this invention is explained in full detail.

(Pigment dispersion composition)
The photocurable composition for forming a colored pattern is configured using at least one of the pigment dispersion compositions. Details of the pigment dispersion composition of the present invention constituting the photocurable composition are as described above.
The content of the pigment dispersion composition in the photocurable composition is preferably such that the pigment content is in the range of 5 to 70% by mass with respect to the total solid content (mass) of the photocurable composition. More preferred is an amount in the range of 15 to 60% by mass. When the content of the pigment dispersion composition is within this range, the color density is sufficient and effective in securing excellent color characteristics.

[Alkali-soluble resin]
The photocurable composition of the present invention preferably contains at least one alkali-soluble resin. By containing the alkali-soluble resin in the photocurable composition, the pattern formability can be further improved when the photocurable composition is applied to pattern formation by a photolithography method.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.
Examples of the other monomer copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and CH _2. = CR ⁴ R ⁵ [wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁵ represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. ], CH ₂ = C (R ⁴ ) (COOR ⁶ ) [wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ represents an alkyl group having 1 to 8 carbon atoms or 6 carbon atoms. Represents -12 aralkyl groups. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Other preferred copolymerizable monomers are selected from CH ₂ ═CR ⁴ R ⁵ , CH ₂ ═C (R ⁴ ) (COOR ⁶ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ⁴ R ⁵ and / or CH ₂ ═C (R ⁴ ) (COOR ⁶ ). These R ⁴ , R ⁵ and R ⁶ have the same meanings as described above.

  As content of alkali-soluble resin in a photocurable composition, 1-20 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-15 mass%, Most preferably, it is 3 ˜12% by mass.

[Photopolymerizable compound]
The photocurable composition according to the present invention contains at least one photopolymerizable compound.
The photopolymerizable compound that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Chosen from. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

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

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

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

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

^{_{CH 2 = C (R 34)}} COOCH 2 CH (R 35) OH (A)
(However, R ³⁴ and R ³⁵ represent H or CH _3. )

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

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

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combination, addition amount and the like can be arbitrarily set in accordance with the performance design of the final photocurable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.

In addition, the selection of an addition polymerization compound is also required for compatibility with other components (for example, binder polymers such as alkali-soluble resins, photopolymerization initiators, and colorants (pigments)) and dispersibility. The usage method is an important factor, and for example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.
The addition polymerizable compound is preferably used in the range of 5 to 70% by mass, more preferably 10 to 60% by mass with respect to the non-volatile component in the photocurable composition. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can arbitrarily select an appropriate structure, blending, and addition amount from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging property, refractive index change, surface adhesiveness, and the like.

(Photopolymerization initiator)
The photocurable composition according to the present invention contains at least one photopolymerization initiator.
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318791, European Patent Publication EP-88050A, etc., described in US Pat. No. 4,1994,420. Aromatic thiophene compounds such as benzophenones, (thio) xanthones or acridine compounds described in Fr-2456541, compounds such as coumarin or biimidazole compounds described in JP-A-10-62986, JP-A Sulfonium organoboron complex, such as 8-015521 Etc., etc. can be mentioned.

  Among them, as photopolymerization initiators, acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (triazine, halomethyloxadiazole, coumarin), acridine, biimidazole And oxime ester systems are preferred.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, and the like are preferred. Can be mentioned.
Preferable examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. be able to.

Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.
Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the photopolymerization initiator of the active halogen photopolymerization initiator (triazine, oxadiazole, coumarin) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s -Triazine, 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl- 2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3, -Dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N -(Diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di ( Chloromethyl) -s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2 -Trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenyl Preferable examples include coumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin and the like.

  Preferred examples of the acridine-based photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer. And 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer and the like can be preferably exemplified.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

The photopolymerization initiator that can be used in the present invention is not limited to the above photopolymerization initiator, and other known photopolymerization initiators can also be used. For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon-substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, a triallylimidazole dimer / p-aminophenylketone combination described in US Pat. No. 3,549,367, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.
Moreover, these photoinitiators can also be used together.

  As content of the photoinitiator in a photocurable composition, 0.1-15.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-10.0. % By mass. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well to form a film with good strength.

The photocurable composition according to the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator (radical initiator) and increasing the photosensitive wavelength.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

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

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples thereof include donors and sulfur compounds described in JP-A-6-308727 (eg, trithian etc.).
The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the photocurable composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and the chain transfer. Is preferable, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

Next, components other than the above will be described.
〔solvent〕
In general, the photocurable composition according to the present invention can be suitably prepared using a solvent together with the above components.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropion 2-oxypropionic acid alkyl esters such as methyl, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg, 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-ethoxy 2-methyl methyl propionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl Ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

[Other ingredients]
In the photocurable composition according to the present invention, if necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, a filler, a specific pigment dispersant, and a polymer compound other than the alkali-soluble resin, a surfactant, and an adhesive Various additives such as an accelerator, an antioxidant, a UV absorber, and an aggregation inhibitor can be contained.

<Fluorine organic compounds>
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

Fluorine-based organic compounds are particularly effective in preventing coating unevenness and thickness unevenness when, for example, a coating film to be formed is thinned. It is also effective in slit coating that easily causes liquid breakage.
The addition amount of the fluorine-based organic compound is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, with respect to the total mass of the pigment dispersion composition or the photocurable composition. It is.

<Thermal polymerization initiator>
It is also effective to include a thermal polymerization initiator in the photocurable composition according to the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Surfactant>
The photocurable composition according to the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic, and anionic surfactants can be used. . Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

  In addition to the above, in the photocurable composition, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid Copolymers, acidic cellulose derivatives, polymers having hydroxyl groups, acid anhydrides added, alcohol-soluble nylons, alkali-soluble resins such as phenoxy resins formed from bisphenol A and epichlorohydrin; nonionics, kachins , Anionic surfactants, specifically phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)); 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 Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.);

  Examples of other additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, Sorbitan fatty acid esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 ( Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, E Polymer dispersing agents such as KA Polymer 401, EFKA Polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000 , 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Zeneca); P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2- Hydroxyphenyl) -5-chlorobenzo Riazor, ultraviolet absorbers such as alkoxy benzophenone; and it can be exemplified aggregation inhibitor such as sodium polyacrylate.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the photocurable composition is further improved, the photocurable composition is an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. 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 Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Thermal polymerization inhibitor>
It is preferable to further add a thermal polymerization inhibitor to the photocurable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, Benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful.

  The photocurable composition according to the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition described above, and if necessary, It can be prepared by mixing an additive such as a surfactant.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced by forming a colored film (colored pattern) on a substrate such as glass using the above-described photocurable composition according to the present invention.
Specifically, the photocurable composition is applied to the substrate directly or through another layer (preferably, applied by a coating method such as spin coating, slit coating, cast coating, roll coating, etc.) for photosensitivity. A colored pattern of each color (for example, 3 colors or 4 colors) is formed by exposing the formed photosensitive film through a predetermined mask pattern and developing and removing the uncured portion with a developer after the exposure. By forming (for example, colored pixels), a color filter can be most suitably manufactured.
Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.
In this case, the radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.

  Drying (prebaking) of the film with the photocurable composition of the present invention applied (preferably applied) on the substrate is performed under conditions of 10 to 300 seconds in a temperature range of 50 to 140 ° C. using a hot plate, an oven or the like. Can be done.

In development, the uncured part after exposure is eluted in the developer, leaving only the cured part. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the film of the photocurable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

  As said organic solvent, what was enumerated as the above-mentioned organic solvent or solvent which can be used when preparing the said photocurable composition is mentioned.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
In addition, when alkaline aqueous solution is used as a developing solution, generally it wash | cleans (rinse) with water after image development.

After the development, excess developer is washed away, dried, and then generally heated (post-baked) at a temperature of 100 to 240 ° C.
The post-baking is a post-development heating for complete curing, and is usually performed at a temperature of about 200 ° C. to 250 ° C. (hard baking). This post-bake treatment is performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the above operation in accordance with the desired number of hues and sequentially repeating for each color, a color filter in which a cured film colored with a plurality of colors is formed can be produced.

When the photocurable composition according to the present invention is applied to a substrate to form a film, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. Most preferably, the thickness is 1.0 to 2.5 μm.
The colored pattern formed on such a substrate has a fine particle size pigment uniformly and stably dispersed, so that the secondary particle occupancy in the image obtained as a result of observation by AFM on the coating surface is 40% or less can be achieved.

Examples of the substrate used for the color filter include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and solid-state imaging devices. For example, a photoelectric conversion element substrate, such as a silicon substrate, and a plastic substrate are used. On these substrates, usually, black stripes for isolating each pixel are formed.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  Examples of other layers in the case where the photocurable composition is applied to the substrate via another layer include a gas barrier layer and a solvent resistant layer.

In the above description, the description is mainly focused on the use of the color pattern of the color filter. However, the means of the present invention can be similarly applied to the formation of a black matrix that isolates the colored pixels constituting the color filter.
The black matrix is subjected to pattern exposure and development using the photocurable composition (pigment dispersion composition) of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-baked as necessary. And it can form by accelerating hardening of a film.

  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” means “part by mass”.

[Synthesis Example 1]
(Synthesis of monomer 1)
9.51 parts of 2-aminopyrimidine are dissolved in 30 parts of pyridine and heated to 45 ° C. To this, 17.1 parts of 2-methacryloyloxyethyl isocyanate is dropped, and the mixture is stirred at 50 ° C. for 5 hours. The reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 23.8 parts of monomer 1.

(Synthesis of polymer 1)
5.0 parts of the monomer 1, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 7.5 parts of methacrylic acid, and 167 parts by mass of methoxypropylene glycol were added to nitrogen. It introduce | transduces into the substituted three necked flask, and stirs with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heats up flowing nitrogen in a flask, and heats up to 78 degreeC. To this was added 0.1 part of dimethyl-2,2′-azobis (2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 78 ° C. for 2 hours. Two hours later, 0.1 part of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of Polymer 1 (Exemplary Compound (2) described above).

[Synthesis Example 2]
(Synthesis of polymer 2)
In the same manner as in Synthesis Example 1 except that 9.51 parts of 2-aminopyrimidine used in the synthesis of Monomer 1 of Synthesis Example 1 were changed to 13.3 parts of 2-aminobenzimidazole, Polymer 2 (Exemplary Compound described above) A 30% solution of (6)) was obtained.

[Synthesis Example 3]
(Synthesis of monomer 3)
13.3 parts of 2-mercaptobenzimidazole and 13.8 parts of potassium carbonate are dissolved in 30 parts of dimethyl sulfoxide and heated to 45 ° C. To this, 22.9 parts of chloromethylstyrene is added dropwise and stirred at 50 ° C. for another 5 hours. The reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 25.6 parts of monomer 3.

(Synthesis of Polymer 3)
A 30% solution of Polymer 3 (Exemplary Compound (14) described above) was obtained in the same manner as in Synthesis of Polymer 1 of Synthesis Example 1 except that Monomer 1 in Synthesis Example 1 was changed to Monomer 3.

[Example 1]
<Preparation of pigment dispersion composition>
[Composition (1)]
-10 parts of a red pigment (CI Pigment Red 254) with a primary particle size of 28 nm-26.6 parts of a 30% solution of polymer 1 (specific pigment dispersant)-63.4 parts of propylene glycol monomethyl ether acetate To the composition (1), 0.3 mm zirconia beads were added and dispersed for 4 hours by a bead mill to obtain a pigment dispersion (colored paste) (1). It was 50 nm when the average particle diameter of the pigment of the obtained pigment dispersion was measured with a particle size distribution meter (Microtrack manufactured by Nikkiso Co., Ltd.).
In addition, the average particle diameter of the primary particle of the red pigment was measured with an electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation).

<Preparation of photocurable composition>
The following composition was mixed and the photocurable composition (1) for color filter preparation was prepared.
Pigment dispersion (1) 48.0 partsMethacrylic acid / benzyl methacrylate copolymer 3.3 parts (molar ratio 30/70, weight average molecular weight 10,000, 45% propylene glycol monomethyl ether acetate solution)
・ Dipentaerythritol hexaacrylate 2.9g
・ Irgacure 369 (Ciba Specialty Chemicals Co., Ltd.) 0.2g
・ Hydroquinone monomethyl ether 0.01g
・ Propylene glycol monomethyl ether acetate 45g

<Preparation of colored pattern>
The photocurable composition (1) obtained by the method described above is applied to a 0.7 mm glass substrate, cured under the condition of 100 mJ / cm ² (illuminance 20 mW / cm ² ), and red light having a thickness of 2.0 μm. A curable composition layer (colored pattern) was formed.

<Measurement of occupancy of secondary particles>
The film surface of the formed colored pattern was observed with AFM (Nanoscope IIIa tapping mode manufactured by Nanoworld), and an observation image of the surface was obtained.
Subsequently, the obtained image was processed using the image processing program “Image J” according to the following procedure, and the occupation ratio of secondary particles in the image was obtained.
1. After grayscale conversion and level correction, image noise and undulation were eliminated and binarized by discriminant analysis.
2. The contacting particles were divided by the Watershed method.
3. Occupancy was calculated by extracting particles of 50 nm or more.
The secondary particle occupancy of the dispersion obtained in Example 1 was calculated by the above method and found to be 22%.

[Example 2]
<Preparation of pigment dispersion composition>
[Composition (2)]
-14.0 parts of a green pigment having a primary particle diameter of 20 nm (CI Pigment Green 36)-37.3 parts of a 30% solution of polymer 1 (specific pigment dispersant)-48.7 propylene glycol monomethyl ether acetate Part 0.3 mm zirconia beads were added to the composition (2) and dispersed for 5 hours in a bead mill to obtain a pigment dispersion (colored paste) (2). When the average particle diameter of the pigment in the obtained pigment dispersion was measured with a particle size distribution meter, the result was 55 nm.

<Preparation of photocurable composition>
The following composition was mixed and the photocurable composition (2) for color filter preparation was prepared.
-Pigment dispersion (2) 48.0 parts-Methacrylic acid / benzyl methacrylate copolymer 4.0 parts (molar ratio 30/70, weight average molecular weight 10,000, 45% propylene glycol monomethyl ether acetate solution)
・ Dipentaerythritol hexaacrylate 3.5g
・ Irgacure 369 (Ciba Specialty Chemicals Co., Ltd.) 0.2g
・ Hydroquinone monomethyl ether 0.01g
・ 44 g of propylene glycol monomethyl ether acetate

<Preparation of colored pattern>
A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (2) was used.

<Measurement of occupancy of secondary particles>
When the occupation ratio of the secondary particles was calculated by the same method as in Example 1, it was 28%.

[Example 3]
<Preparation of pigment dispersion composition>
[Composition (3)]
-10.0 parts of a blue pigment having a primary particle diameter of 25 nm (CI Pigment Blue 15: 6)-30% solution of polymer 1 (specific pigment dispersant) 23.3 parts-Propylene glycol monomethyl ether acetate 66 .6 parts 0.3 mm zirconia beads were added to the composition (3) and dispersed for 6 hours in a bead mill to obtain a pigment dispersion (colored paste) (3). When the average particle diameter of the pigment in the obtained pigment dispersion was measured with a particle size distribution meter, the result was 46 nm.

<Preparation of photocurable composition>
A photocurable composition (3) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (3) was changed.

<Preparation of colored pattern>
A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (3) was used.

<Measurement of occupancy of secondary particles>
When the occupation ratio of the secondary particles was calculated by the same method as in Example 1, it was 38%.

[Example 4]
A pigment dispersion (4), a photocurable composition (4) and a colored pattern were obtained in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 2.
In addition, when the average particle diameter of the pigment of the obtained pigment dispersion liquid (4) was measured with a particle size distribution meter, the result was 60 nm.
<Measurement of occupancy of secondary particles>
When the occupation ratio of the secondary particles was calculated by the same method as in Example 1, it was 25%.

[Example 5]
A pigment dispersion (5), a photocurable composition (5), and a colored pattern were obtained in the same manner as in Example 2 except that the polymer 1 was changed to the polymer 2.
The average particle diameter of the pigment in the obtained pigment dispersion (5) was measured with a particle size distribution meter, and the result was 58 nm.
<Measurement of occupancy of secondary particles>
The occupation ratio of the secondary particles was calculated by the same method as in Example 2. As a result, it was 30%.

[Example 6]
A pigment dispersion (6), a photocurable composition (6) and a colored pattern were obtained in the same manner as in Example 3 except that the polymer 1 was changed to the polymer 2.
In addition, when the average particle diameter of the pigment of the obtained pigment dispersion (6) was measured with a particle size distribution meter, the result was 52 nm.
<Measurement of occupancy of secondary particles>
When the occupation ratio of the secondary particles was calculated by the same method as in Example 3, it was 38%.

[Example 7]
A pigment dispersion (7), a photocurable composition (7) and a colored pattern were obtained in the same manner as in Example 1 except that the polymer 1 was changed to the polymer 3.
In addition, when the average particle diameter of the pigment of the obtained pigment dispersion liquid (7) was measured with a particle size distribution meter, the result was 62 nm.
<Measurement of occupancy of secondary particles>
The occupation ratio of secondary particles was calculated by the same method as in Example 1. As a result, it was 27%.

[Example 8]
A pigment dispersion (8), a photocurable composition (8) and a colored pattern were obtained in the same manner as in Example 2 except that the polymer 1 was changed to the polymer 3.
The average particle size of the pigment in the obtained pigment dispersion (8) was measured with a particle size distribution meter and found to be 63 nm.
<Measurement of occupancy of secondary particles>
The occupation ratio of the secondary particles was calculated by the same method as in Example 2. As a result, it was 33%.

[Example 9]
A pigment dispersion (9), a photocurable composition (9), and a colored pattern were obtained in the same manner as in Example 3 except that the polymer 1 was changed to the polymer 3.
The average particle diameter of the pigment in the obtained pigment dispersion (9) was measured with a particle size distribution meter and found to be 54 nm.
<Measurement of occupancy of secondary particles>
When the occupation ratio of the secondary particles was calculated by the same method as in Example 3, it was 39%.

[Comparative Example 1]
<Preparation of pigment dispersion composition>
[Composition (10)]
-10.0 parts of red pigment (CI pigment red 254) having a primary particle diameter of 28 nm-Dispersant (BYK-161 manufactured by BYK Chemie) (comparative pigment dispersant) 6.0 parts-Propylene glycol monomethyl ether acetate 84.0 parts 0.3 mm zirconia beads were added to the composition (10) and dispersed for 2 hours in a bead mill to obtain a pigment dispersion (colored paste) (10). The average particle size of the pigment in the obtained pigment dispersion was measured with a particle size distribution meter and found to be 90 nm.

<Preparation of photocurable composition>
A photocurable composition (10) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (10) was changed.
<Preparation of colored pattern>
A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (10) was used.
<Measurement of occupancy of secondary particles>
The occupation ratio of the secondary particles was calculated by the same method as in Example 1. As a result, it was 49%.

[Comparative Example 2]
<Preparation of pigment dispersion composition>
[Composition (11)]
Green pigment (CI Pigment Green 36) having a primary particle diameter of 20 nm 14.0 parts Dispersant (BYK-161 manufactured by BYK Chemie) (Comparative pigment dispersant) 8.4 parts Propylene glycol monomethyl ether acetate 77.6 parts 0.3 mm zirconia beads were added to the composition (11) and dispersed for 2 hours in a bead mill to obtain a pigment dispersion (colored paste) (11). The average particle size of the pigment in the obtained pigment dispersion was measured with a particle size distribution meter and found to be 81 nm.

<Preparation of photocurable composition>
A photocurable composition (11) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (11) was changed.
<Preparation of colored pattern>
A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (11) was used.
<Measurement of occupancy of secondary particles>
The occupation ratio of the secondary particles was calculated by the same method as in Example 1. As a result, it was 55%.

[Comparative Example 3]
<Preparation of pigment dispersion composition>
[Composition (12)]
-10.0 parts of a blue pigment having a primary particle diameter of 25 nm (CI Pigment Blue 15: 6)-Dispersant (BYK-161 manufactured by BYK Chemie) (comparative pigment dispersant) 6.0 parts-Propylene glycol monomethyl 84.0 parts of ether acetate 0.3 mm zirconia beads were added to the composition (12) and dispersed for 2 hours in a bead mill to obtain a pigment dispersion (colored paste) (12). When the average particle diameter of the pigment in the obtained pigment dispersion was measured with a particle size distribution meter, the result was 97 nm.

<Preparation of photocurable composition>
A photocurable composition (12) was prepared in the same manner as in Example 1 except that the pigment dispersion liquid (12) was changed.
<Preparation of colored pattern>
A colored pattern was obtained in the same manner as in Example 1 except that the photocurable composition (12) was used.
<Measurement of occupancy of secondary particles>
The occupation ratio of the secondary particles was calculated by the same method as in Example 1. As a result, it was 60%.

<Measurement of contrast>
In contrast, the color filter produced in the above-mentioned examples and comparative examples is installed between two polarizing plates, a light source is installed on one side, and a luminance meter (BM-5A manufactured by TOPCON) is installed on the opposite side. The transmitted light intensity) was measured. The contrast was calculated from the ratio of the luminance when the polarization axis was parallel to the luminance when the polarization axis was vertical. The results are shown in Table 1 below.

  From Table 1, it can be seen that the color filter coloring pattern of the present invention achieves high contrast.

<Preparation of color filter using photocurable composition>
A black photocurable composition CK-9910L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was applied on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) and dried on a 120 ° C. hot plate for 120 seconds. (Pre-bake). Then, it exposes at 100 mJ / cm < ² > (illuminance 20 mW / cm < ² >) through a photomask, The coating film after exposure is 1% aqueous solution of alkali developing solution CDK-1 (made by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. The coating film that had been exposed and developed as described above was heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a color filter BM pattern on the glass substrate.
Next, the photocurable composition (1) was applied so as to have a film thickness of 2.0 μm, and dried on a hot plate at 90 ° C. for 60 seconds. Then, it exposed at 100 mJ / cm < ² > (illuminance 20mW / cm < ² >) through a photomask, the coated film after exposure was covered with 1% aqueous solution of alkali developing solution CDK-1, and it left still for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film exposed and developed as described above was heat-treated in a 220 ° C. oven for 1 hour (post-baking) to form a red pattern (colored resin film) for the color filter on the glass substrate. A colored pattern (colored resin film) for a color filter was formed on a glass substrate in the same manner as described above using the photocurable compositions (2) and (3), and a colored filter substrate (color filter) A was produced. .
A color filter B was prepared in the same manner except that the photocurable composition was changed to (4), (5), and (6).
Further, except that the photocurable composition was changed to (4), (5), and (6), the colored filter substrate (color filter) B was changed in the same manner, and the photocurable composition was changed to (7) and (8). ), Except that the color filter substrate (color filter) C is changed in the same manner except that the photocurable composition is changed to (10), (11), (12). A colored filter substrate (color filter) D was produced.

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 2 below.

(3) Contrast A polarizing plate is placed on the colored resin film of the colored filter substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using a BM-5A manufactured by Topcon Corporation. Then, a value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast. Larger values indicate higher contrast.
If the contrast is 3500 or more, there is no practical problem.

Claims (7)

  A color pattern formed by applying a photocurable composition containing a pigment having an average particle size of 15 to 150 nm, and the occupancy of secondary particles in an image obtained as a result of observation by AFM on the surface of the color pattern Is a color filter, characterized by being 40% or less. The photocurable composition includes an organic solvent, a pigment having an average particle diameter of 15 to 150 nm, a polymer including a copolymer unit derived from a monomer represented by the following general formula (1), and photopolymerization. The color filter according to claim 1, further comprising a functional compound and a photopolymerization initiator.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1. ]   3. The color filter according to claim 2, wherein in the general formula (1), the cyclic structure formed by connecting Y to the N atom via an adjacent atomic group is a condensed ring structure.   4. The color filter according to claim 2, wherein the polymer is a graft copolymer further comprising a copolymer unit derived from a polymerizable oligomer having an ethylenically unsaturated bond at a terminal. .   The color filter according to any one of claims 2 to 4, wherein the polymer is a polymer further including a copolymer unit derived from a monomer having an acid group.   The color filter according to any one of claims 2 to 5, wherein the photocurable composition further contains an alkali-soluble resin. An organic solvent, a pigment having an average particle size of 15 to 150 nm, a polymer containing a copolymer unit derived from a monomer represented by the following general formula (1), a photopolymerizable compound, and a photopolymerization initiator And a photosensitive film forming step of forming a photosensitive film by applying a photocurable composition containing the composition directly or via another layer to the substrate, and pattern exposure and development on the formed photosensitive film. A color filter manufacturing method comprising: a color pattern forming step of forming a color pattern by performing sequentially.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-. Y represents —NR ³ —, —O—, —S—, or —N═, and is linked to an N atom through an atomic group adjacent thereto to form a cyclic structure. R ³ represents a hydrogen atom, an alkyl group, or an aryl group. m and n each independently represents 0 or 1. ]