TWI443456B - Photosensitive coloring composition and color filter - Google Patents

Description

Photosensitive coloring composition and color filter

The present invention relates to a photosensitive coloring composition, for example, a photosensitive coloring composition useful for forming a color filter for use in a color liquid crystal display device and a solid-state image sensor device. Further, the present invention relates to a color filter formed using the photosensitive coloring composition.

A representative display mode employed in a twisted nematic (TN) mode liquid crystal display device. A transmissive liquid crystal display device using a TN mode has a structure in which a liquid crystal layer is sandwiched between first and second polarizing plates. When the TN mode is adopted, the liquid crystal layer is directly incident on the second polarizing plate by the first linear polarized light of the first polarizing plate, or converted into circularly polarized light or elliptically polarized light, and is incident on the second polarizing plate. Or converted into a second linear polarized light whose polarization plane is 90° out of phase with the first linear polarized light, and is incident on the second polarizing plate. The amount of light penetrating through the second polarizing plate is thus controlled.

Liquid crystal display devices typically use color filters to display color images. The color filter is applied to a transparent substrate such as a glass substrate, and two or more kinds of fine band (striped) filter segments having different hue are arranged in parallel or intersecting each other, or in the longitudinal or lateral directions. Two or more types of fine filter segments having different hue are arranged in order. The filter segments have a fine size of several micrometers to several hundred micrometers, and are arranged neatly in a specific arrangement for each hue.

Generally, in the manufacture of a color liquid crystal display device, a transparent electrode for driving liquid crystal molecules is formed by evaporation or sputtering, and further, an alignment film for aligning liquid crystal molecules in a certain direction is formed thereon. . in order to The performance of the transparent electrode and the alignment film is sufficiently derived, and it is generally required to be formed at a temperature of 200 ° C or higher, more preferably 230 ° C or higher. Therefore, the current mainstream method for producing a color filter is a method of a pigment dispersion method, and the pigment dispersion method is not limited to a pigment which is excellent in light resistance and excellent in heat resistance.

Further, in the pigment dispersion method, a colored layer such as a filter segment constituting a color filter is formed by, for example, the following method. First, a coloring composition is prepared by dispersing a pigment in a resin such as an acrylic resin using a dispersing agent, a solvent, or the like. Next, a photopolymerizable monomer and a polymerization initiator are added to the colored composition to obtain a photosensitive coloring composition. Thereafter, the photosensitive coloring composition is applied onto a substrate such as a glass substrate, and then the coating film is patterned by photolithography. Further, the patterned coating film is post-baked at a high temperature of, for example, 200 ° C or higher, thereby imparting the resistance required in the subsequent step. Finish the color layer as above.

Color liquid crystal display devices have been widely used in television receivers and computer monitors in recent years. Therefore, the demand for improvement in color characteristics is high, and accordingly, the pigment content of the coloring composition used for the color filter tends to become high. However, in the above method using photolithography at the time of formation of a colored layer, when the pigment content rate of a coloring composition is raised, the following problems may arise.

In the above method, a photosensitive coloring composition is used as a coloring composition for a color filter. Therefore, when the pigment content of the coloring composition is high, the exposure amount of the substrate side region may be insufficient even if the exposure amount of the surface side region is sufficient in the exposed portion of the coating film composed of the photosensitive coloring composition. At this time, the exposed portion of the coating film obtained from the negative photosensitive coloring composition is on the substrate. In the side area, the light bridge is insufficient, and the coloring layer obtained by the subsequent development step has a drape (or undercut). For example, in this case, a coloring layer having a reversely tapered cross section is obtained, that is, a coloring layer having a shape in which the width becomes larger as the distance from the substrate side increases.

The cross section of the colored layer is a forward taper, that is, when the distance from the substrate side becomes larger and the width thereof is narrower, if the transparent electrode material is deposited by vapor deposition or sputtering on the colored layer, The transparent electrode material is not only coated on the colored layer but also on the inclined end faces thereof. Therefore, in this case, the electrical connection failure due to the occurrence of the discontinuous portion is less likely to occur on the transparent electrode.

On the other hand, when the transparent electrode material is deposited by vapor deposition or sputtering on the colored layer having the overhang, the transparent electrode material is less likely to be deposited under the overhang, and thus the discontinuous portion is likely to be generated in the transparent electrode. That is, in this case, an electrical connection failure is likely to occur at a position below the suspension.

Techniques for obtaining a colored layer having a forward tapered shape are described in several documents. For example, Japanese Laid-Open Patent Publication No. 2007-57655 describes the prevention of occurrence of overhang by using a specific plasticizer. Japanese Laid-Open Patent Publication No. 2007-114604 discloses at least one type of acrylate and methacrylate, at least one of acrylic acid and methacrylic acid, and hydroxyethyl acrylate and hydroxyethyl methacrylate. A copolymer of at least one copolymer and a structure of 2-isocyanate trimethylolethane triacrylate. Japanese Laid-Open Patent Publication No. 2003-167115 discloses that a coloring layer having a drape is heat-treated to deform its cross section into a forward taper.

As described above, it is required for the photosensitive coloring composition to form a coloring layer having a forward tapered shape even when the pigment content is increased.

Further, the photosensitive coloring composition is also required to have excellent long-term storage stability. Japanese Laid-Open Patent Publication No. 2004-101728 discloses a photosensitive coloring composition containing a copolymer resin. The copolymer resin is a side chain or a terminal, and has a phenoxy group in which a hydrogen atom having no substitution or para position is replaced by an alkyl group. The copolymer resin is easily adsorbed to the surface of the pigment by the effect of π-electrons of the benzene ring. The affinity of the pigment for the solvent is enhanced by adsorption of the previous copolymer resin. Therefore, this photosensitive coloring composition is excellent in long-term storage stability.

However, as the generalization of liquid crystal display devices progresses, it is expected that the price thereof will be greatly reduced. Along with this, various components of the liquid crystal display device have been attempted to reduce costs. For example, in recent years, it has been attempted to regenerate and reuse a glass substrate after the failure of the post-baking, thereby saving waste of the glass substrate, which is one of the methods effective for reducing the cost and being simple.

Hereinafter, a series of programs from reproduction to reuse is marked as "redo". Also, the efficiency of redo is marked as "reworkability."

The redoing method is a method in which the coloring layer after the post-baking is peeled off from the glass substrate by using a peeling liquid called a redo liquid, and the glass substrate is returned to the state before the photosensitive coloring composition is applied. After the post-baking coloring layer has high heat resistance and high solvent resistance, a high-temperature and high-concentration strong alkali solution is generally used as the redo liquid. Also, it is generally assumed that the redo liquid should be recycled and reused. In this case, the release sheet must be removed from the used reconstituted liquid using, for example, a filter.

The inventors of the present invention investigated and reported in Japanese Laid-Open Patent Publication No. 2004-101728. The reworkability of the photosensitive coloring composition was carried out, and as a result, the following facts were found. That is, the coloring layer obtained from the photosensitive resin is not treated for peeling after the post-baking treatment, and is used for the treatment of the use of the redo liquid even after the post-baking. It is possible to produce a release sheet in the form of a larger block. If the release sheet is present in the redo liquid in the form of a large block, the filter clogging easily occurs.

Therefore, an object of the present invention is to provide a coloring layer which can form a coloring layer which is excellent in dispersion stability of a pigment and has a good cross-sectional shape, and which can achieve good reworkability, and a color filter using the same.

According to a first aspect of the present invention, a photosensitive coloring composition comprising: a resin (A), a pigment (B), an active energy ray polymerization initiator (C), and an active energy ray-curable monomer is provided. (D) and the solvent (E); the resin (A) contains a vinyl resin (F) in a ratio of 50% by weight or more; and the vinyl resin (F) contains a carboxyl group in a ratio of 2 to 50% by weight. The constituent unit (a) contains an aromatic ring selected from the following general formula (1), an aromatic ring represented by the following general formula (2), and the following general ratio in a ratio of 2 to 50% by weight. a constituent unit (b) of one or more annular structures of the group consisting of the aliphatic ring represented by the formula (3) and the aliphatic ring represented by the following general formula (4), and The ratio of 80% by weight includes other constituent units (c).

General formula (2):

(In the above general formulas (1) and (2), R is a hydrogen atom, or may have a benzene ring and an alkyl group having 1 to 20 carbon atoms)

According to a second aspect of the present invention, there is provided a photosensitive coloring composition according to the first aspect, which is characterized by being selected from the group consisting of the constituent units (a), (b) and (c) One or more constituent units have ethylene bonding.

According to a third aspect of the present invention, there is provided a photosensitive coloring composition according to the first or second aspect, characterized in that the constituent unit (a) precursor (a1) is selected from the group consisting of acrylic acid and methacrylic acid. One or more monomers in the group formed.

According to a fourth aspect of the present invention, there is provided a photosensitive coloring composition according to the first or second aspect, characterized in that at least a part of the carboxyl group containing the structural unit (a) is obtained by having a hydroxyl group. The constituent unit is added with a polyvalent acid anhydride, or is introduced by adding a polyvalent acid anhydride to a hydroxyl group formed by adding a constituent unit having an epoxy group and an unsaturated monovalent acid.

According to a fifth aspect of the present invention, there is provided a photosensitive coloring composition according to any one of the first to fourth aspects, wherein the constituent unit (b) precursor (b1) is selected from the group consisting of benzene Ethylene, a-methylstyrene, anthracene, benzyl acrylate, methyl benzyl acrylate, a monomer represented by the following general formula (5), a monomer represented by the following general formula (6), and One or more monomers selected from the group consisting of the monomers represented by the general formula (7).

General formula (6):

(In the above general formulas (5) to (7), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a benzene ring and a carbon number of 1 to 20 alkyl, n is an integer from 1 to 15, and m is an integer from 0 to 2)

According to a sixth aspect of the present invention, there is provided a photosensitive coloring composition according to any one of the first aspect to the fifth aspect, characterized in that the component (c) precursor (c1) comprises a component selected from the group consisting of One or more monomers selected from the group consisting of acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate.

According to a seventh aspect of the present invention, a color filter comprising a filter segment and a black matrix formed of the photosensitive coloring composition of any one of the first to sixth aspects is provided. At least one party.

The photosensitive coloring composition-based pigment is excellent in dispersion stability. Further, the photosensitive coloring composition has sufficient shape retainability and high thermoplasticity until it is completely cured. Therefore, even if the coloring layer obtained from the photosensitive coloring composition has a dangling, it can be, for example, 150 ° C, typically It is a heat treatment at a high temperature of 200 ° C or higher, and its profile is deformed into a forward taper. That is, a coloring layer having a good cross-sectional shape can be formed. Further, when the photosensitive coloring composition is used, good reworkability can be achieved.

Hereinafter, a photosensitive coloring composition according to one embodiment of the present invention will be described.

The photosensitive coloring composition of one embodiment of the present invention is used in, for example, a display device such as a liquid crystal display device or a solid-state image sensor, or a color filter included in an electronic device. The photosensitive coloring composition contains a resin (A), a pigment (B), an active energy ray polymerization initiator (C), an active energy ray-curable monomer (D), and a solvent (E). The components are described in order below.

Resin (A)

In the photosensitive coloring composition, the resin (A) is contained in a ratio of 50% by weight or more to the resin (A), and more preferably in a ratio of 60 to 100% by weight. The vinyl resin (F) will be described in detail later.

The transmittance of the resin (A) in the full wavelength region of 400 to 700 nm is preferably 80% or more, more preferably 95% or more, from the viewpoint of pigment dispersibility, and the resin (A) is preferably the weight of the pigment (B). It is used in a ratio of 30 to 700% by weight, more preferably in a ratio of 60 to 450% by weight.

<Resin (A) may contain a resin other than the vinyl resin (F)>

The resin (A) may not contain a resin other than the vinyl resin (F), but may further contain other resins in addition to the vinyl resin (F). Before the description of the vinyl resin (F), the description will be made regarding the vinyl resin (F) which the resin (A) may contain. Resin.

Examples of the resin other than the vinyl resin (F) which may be contained in the resin (A) include a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin. These may be used alone or in combination of two or more.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane. Polyethylene such as resin, polyester resin, acrylic resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, high density polyethylene, and low density polyethylene , polybutadiene and polyimide resin. Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a rosin-denatured maleic acid resin, a rosin-denatured fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

As the active energy ray-curable resin, for example, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group, and a (meth) group having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group are used. A resin which reacts with an acrylic acid compound or cinnamic acid to introduce a photo-branching group such as a (meth)acryl fluorenyl group or a styryl group to a conventional linear polymer. Further, as the active energy ray-curable resin, for example, a styrene-maleic anhydride copolymer or a is used by having a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate. A linear polymer of an acid anhydride such as an olefinic carboxylic acid-maleic anhydride copolymer is semi-esterified.

In addition, in the present specification, when "(meth) propylene" is used for a certain compound, it means that the compound is a compound in which "(meth) propylene" is changed to "propylene", and "(meth) propylene is added. Changed to the combination of "methacryl" Any of the things can be. In addition, in the present specification, when "(meth)acrylyl group" is used for a certain functional group, it means that the functional group changes the "(meth)acrylyl group" to the "acrylic group" functional group, and (Meth)propenyl group can be changed to any of the functional groups of "methacryl". In other words, when "(meth) acrylate" is used for a certain compound, it means that the compound is a compound in which "(meth) acrylate" is changed to "acrylate", and "(meth) acrylate is used. Any one of the compounds of "methacrylate" can be changed.

<vinyl resin (F)>

The photosensitive coloring composition contains a vinyl resin (F) in a specific ratio with respect to the resin (A). Such photosensitive coloring compositions have the following characteristics (1) to (4).

(1) Excellent thermal mobility of the colored layer

Applying a photosensitive coloring composition to a substrate, and exposing and developing the coating film to obtain a coloring layer, that is, for example, a filter segment having a dangling, followed by heat treatment, that is, for example, 150 ° C or higher After baking, it is partially fluidized. As a result, the colored layer is deformed into a cross section having a forward taper.

(2) High dispersibility of the pigment of the photosensitive coloring composition

The vinyl resin (F) is easily adsorbed by the pigment (B), and when the pigment (B) adsorbs the vinyl resin (F), its affinity for a solvent becomes high, so that an excellent dispersion state can be maintained over a long period of time.

(3) Excellent developability of a coating film obtained from a photosensitive coloring composition

In the developing step, the unexposed portion can be easily removed with, for example, an alkali developing solution of a developing solution.

(4) Good redo

It is possible to remove the colored layer after post-baking with a redo liquid such as a strong alkaline liquid. Further, the release sheet of the colored layer does not become coarse.

The vinyl resin (F) contains the following constituent units (a) to (c). Furthermore, the term "constituting unit" is synonymous with a repeating unit and a single unit.

[constitutive unit (a)]

The constituent unit (a) contributes to the formation of the above feature (3). In other words, the constituent unit (a) is a substance having a carboxyl group and functions as an alkali-soluble portion during development. Further, the constituent unit (a) also contributes to the formation of the above feature (4). Here, the term "carboxyl" means a -COOH group, and does not include an ester-bonded (-COOR) or ion-ion-ion (-COOM)-containing substance other than a hydrogen ion.

The constituent unit (a) further contains an atom or a radical other than a carboxyl group. For example, the constituent unit (a) further contains a carbon atom constituting a part of the carbon chain of the vinyl resin (F). The carboxyl group may be directly bonded or indirectly bonded to a carbon atom constituting a part of the carbon chain of the vinyl resin (F). In the latter case, the carboxyl group may also be bonded to a carbon atom constituting a part of the carbon chain, for example, via ester bonding and any other atom or atomic group.

Further, the constituent unit (a) may further contain a functional group other than a carboxyl group, which is directly or indirectly bonded to a carbon atom constituting a part of the carbon chain of the vinyl resin (F). For example, the constituent unit (a) may also contain ethylene. Furthermore, the term "ethylene bonding" means double bonding of olefins and does not imply a dual combination of aromaticity.

The constituent unit (a) is obtained by subjecting the following precursor (a1) to polymerization, in particular, to radical polymerization such as vinyl polymerization.

The constituent unit (a) precursor (a1) is a compound having ethylene bonding. The component (a) is formed by radical polymerization such as polymerization, in particular, vinyl polymerization.

As the constituent unit (a), the precursor (a1) can be, for example, a compound having a carboxyl group and having an ethylene bond. As such a compound, for example, an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid or a-chloroacrylic acid, or an unsaturated dicarboxylic acid such as maleic acid or fumarene can be used. As the precursor (a1), a (meth) propylene compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate may be used, and an anhydride of an unsaturated carboxylic acid such as maleic anhydride may be subjected to half esterification. Things. Among these, from the viewpoint of e.g., ease of control of molecular weight, for example, (meth)acrylic acid is preferred, and methacrylic acid is more preferred. These may be used alone or in combination of two or more.

The ratio of the constituent unit (a) to the vinyl resin (F) is from 2 to 50% by weight, and more preferably from 10 to 40% by weight, from the viewpoint of developability. When the ratio is too small, the alkali developer may not sufficiently remove the unexposed portion. When the ratio is too large, the exposed portion may be dissolved in the alkali developer.

[constitutive unit (b)]

The constituent unit (b) functions as a pigment (B) or a pigment composition containing the pigment (B) and the dispersion, and functions as an affinity site.

The constituent unit (b) contains an aromatic ring represented by the following general formula (1), an aromatic ring represented by the following general formula (2), and an aliphatic ring represented by the following general formula (3). And one or more annular structures of the group consisting of the aliphatic rings represented by the following general formula (4).

General formula (1):

In the above general formulas (1) and (2), the R-based hydrogen atom may have a benzene ring or an alkyl group having 1 to 20 carbon atoms.

Further, in the general formula (1), for R, the alignment of the line segment does not mean that the methyl group is bonded to the benzene ring, but means that the benzene ring is aligned and bonded to other structures. Similarly, in the general formula (2), for R, the meta and para line segments do not indicate that the methyl group is bonded to the benzene ring, but rather indicates that the benzene ring is in the meta position and the para position is bonded to other structures. Further, in the general formula (3), the line segment extending from the five-membered ring at the left end does not mean that the methyl group is bonded to the five-membered ring, but that one of the carbon atoms constituting the five-membered ring is bonded to the other structure. Similarly, in the general formula (4), the line segment extending from the five-membered ring at the left end does not mean that the methyl group is bonded to the five-membered ring, but that one of the carbon atoms constituting the five-membered ring is bonded to the other structure.

The constituent unit (b) further contains other atoms or atomic groups in addition to the cyclic structures represented by the general formulae (1) to (4). For example, the constituent unit (b) further contains a carbon atom constituting a part of the carbon chain of the vinyl resin (F). The cyclic structures represented by the general formulae (1) to (4) may be bonded directly to the carbon atom or indirectly.

Further, the constituent unit (b) may further contain a functional group other than the cyclic structure represented by the general formulae (1) to (4), which is a carbon directly or indirectly bonded to a part of the carbon chain constituting the vinyl resin (F). Atomic bonding. For example, the constituent unit (b) may also contain ethylene.

The constituent unit (b) is obtained by subjecting the following precursor (b1) to polymerization, in particular, radical polymerization such as vinyl polymerization.

As the precursor (b1), for example, styrene, a-methylstyrene, stilbene, anthracene, acetylene naphthalene, benzyl acrylate, methyl benzyl acrylate, and the like can be used. One or more of the group consisting of the monomer represented by the general formula (5), the monomer represented by the following general formula (6), and the monomer represented by the following general formula (7) body.

In the above general formulas (5) to (7), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a benzene ring and have a carbon number of 1 to 20 The alkyl group, n is an integer from 1 to 15, and m is an integer from 0 to 2.

As the monomer represented by the general formula (5), for example, NEW-FRONTIER CEA [EO (ethylene oxide) modified cresol acrylate manufactured by First Industrial Pharmaceutical Co., Ltd., R ¹ : hydrogen atom, R ² : vinyl group can be used. , R ³ : methyl, n=1 or 2], NP-2 [n-nonylphenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : n-壬Base, n=2], N-177E[n-nonylphenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ :n-fluorenyl group, n=16~17 Or PEH [phenoxyethyl acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen atom, n=1].

As the monomer represented by the general formula (5), for example, IRR169 [ethoxylated phenyl acrylate (EO 1 mol) manufactured by DAICEL Co., Ltd., R ¹ : a hydrogen atom, R ² : a vinyl group, R ³ : a hydrogen atom can also be used. , n = 1] or Ebecry 1110 [ethoxylated phenyl acrylate (EO 2 mol), R ¹ : a hydrogen atom, R ² : a vinyl group, R ³ : a hydrogen atom, n = 2].

Alternatively, as the monomer represented by the general formula (5), for example, ARONIX M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (n≒2) acrylate, R ¹ : hydrogen atom, R ² : ethylene can also be used. Base, R ³ : hydrogen atom, n≒1], M-102 [phenol EO modified (n≒2) acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen atom, n≒4 ], M-110 [phenol EO modified (n≒2) acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : p-cumyl, n≒1], M-111 [n-fluorenyl] Phenol EO modified (n≒1) acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : n-fluorenyl group, n≒1], M-113 [n-nonylphenol EO modification ( N≒4) acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : n-fluorenyl group, n≒ 4] or M-111 [n-nonylphenol PO (epoxy propylene) modification ( N ≒ 2.5) acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : n-fluorenyl group, n ≒ 2.5]. Alternatively, as the monomer represented by the general formula (5), for example, a light acrylate PO-A manufactured by Kyoei Co., Ltd. [phenoxyethyl acrylate, R ¹ : a hydrogen atom, R ² : a vinyl group, R may be used. ³ : hydrogen atom, n=1], P-200A [phenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen atom, n≒2], NP-4EA [ Nonyl phenol EO addenda acrylate, R ¹ : hydrogen atom, R ² : vinyl, R ³ : n-fluorenyl, n≒ 4], or NP-8EA [nonylphenol EO addenda acrylate, R ¹ : hydrogen atom, R ² :vinyl group, R ³ :n-fluorenyl group, n≒8] or light ester PO [phenol methyl acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen Atom, n=1].

Alternatively, as the monomer represented by the general formula (5), for example, BLEMMER ANE-300 manufactured by Nippon Oil Co., Ltd. [Mercaptophenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : ethylene can also be used. Base, R ³ :n-fluorenyl, n≒5], ANP-300 [nonylphenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : propylene group, R ³ : n-fluorenyl group , n≒5], 43ANEP-500 [mercaptophenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom, R ² : propenyl and propenyl, R ³ :n-fluorenyl, n≒5+5], 70ANEP-550 [mercaptophenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom, R ² : propenyl and propenyl, R ³ : n-fluorenyl , n≒9+3], 75ANEP-600[mercaptophenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ¹ : hydrogen atom, R ² : propenyl and propenyl, R ³ :n-壬Base, n≒5+2], AAE-50 [phenoxy polyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen atom, n=1], AAE-300 [ nonylphenoxy polyethylene glycol acrylate, R ^1: a hydrogen atom, R ^2: vinyl, R ^3: a hydrogen atom, n ≒ 5.5], PAE- 50 [ phenoxy Polyethylene glycol methacrylate, R ^1: a methyl, R ^2: vinyl, R ^3: a hydrogen atom, n = 2], PAE- 100 [ phenoxy polyethylene glycol methacrylate, R ¹ :methyl, R ² :vinyl, R ³ :hydrogen atom, n=2] or 43PAPE-600B [phenoxy-polyethylene glycol-polypropylene glycol-methacrylate, R ¹ :methyl, R ² : vinyl and propenyl, R ³ : hydrogen atom, n≒6+6].

Alternatively, as the monomer represented by the general formula (5), for example, NK ESTER AMP-10G manufactured by Shin-Nakamura Chemical Co., Ltd. [phenoxyethylene glycol acrylate (EO 1 mol), R ¹ : hydrogen atom, R may be used. ² : vinyl group, R ³ : hydrogen atom, n=1], AMP-20G [phenoxy ethylene glycol acrylate (EO 2 mol), R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen atom , n≒2], AMP-60G [phenoxyethylene glycol acrylate (EO 6 mol), R ¹ : hydrogen atom, R ² : vinyl group, R ³ : hydrogen atom, n≒6] or PHE-1G [ Phenoxyethylene glycol methacrylate (EO 1 mol), R ¹ : a hydrogen atom, R ² : a vinyl group, R ³ : a hydrogen atom, n=1].

Alternatively, as the monomer represented by the general formula (5), for example, SR-339A manufactured by Nippon Kayaku Co., Ltd. [phenoxyethylene glycol acrylate, R ¹ : hydrogen atom, R ² : vinyl group, R may be used. ³ : a hydrogen atom, n = 1] or [ethoxylated decyl phenol acrylate, R ¹ : a hydrogen atom, R ² : a vinyl group, R ³ : n-fluorenyl group].

As the monomer represented by the general formula (5), materials other than those previously exemplified may be used. Further, as the monomer represented by the general formula (5), one type of material or two or more types of materials may be used at the same time.

As the monomer represented by the general formula (6), for example, FANCRYL FA-513A [dicyclopentyl acrylate, R ¹ : hydrogen atom, R ² : none, m=0] or FA-manufactured by Hitachi Chemical Co., Ltd. can be used. 513 M [dicyclopentyl acrylate, R ¹ : hydrogen atom, R ² : none, m=0]. As the monomer represented by the general formula (6), materials other than those exemplified herein may be used. Further, as the monomer represented by the general formula (6), one type of material or two or more types of materials may be used at the same time.

As a monomer represented by the general formula (7), for example, FANCRYL FA-511A [dicyclopentenyl acrylate, R ¹ : hydrogen atom, R ² : none, m=0], FA, manufactured by Hitachi Chemical Co., Ltd., can be used. -512M [bicyclopentaoxyalkenyl acrylate, R ¹ : hydrogen atom, R ² : vinyl group, m=1], FA-512A [bicyclopentaoxyalkenyl methacrylate, R ¹ :methyl, R ² :vinyl group, m=1] or FA-512MT [bicyclopentaoxyalkenyl methacrylate, R ¹ :methyl group, R ² :vinyl group, m=1]. As the monomer represented by the general formula (7), materials other than those exemplified herein may be used. Further, as the monomer represented by the general formula (7), one type of material or two or more types of materials may be used at the same time.

From the viewpoint of copolymerization with other precursors and the dispersibility of the pigment (B), the constituent unit (b) precursor (b1) is preferably styrene, a-methylstyrene, benzyl acrylate or benzyl. A methacrylic acid ester, a monomer represented by the general formula (5), a monomer represented by the general formula (6) or a monomer represented by the general formula (7). Among them, especially styrene, a-methylstyrene, benzyl acrylate, benzyl methacrylate and a monomer represented by the general formula (5), since benzene can be introduced into the side chain of the vinyl resin (F) The ring is therefore particularly suitable. The benzene ring introduced into the side chain may be aligned to form a ring-containing plane opposite to the surface of the pigment (B). Therefore, by introducing a benzene ring into the side chain of the vinyl resin (F), adsorption of the pigment to the pigment (B) can be promoted, and aggregation of the pigment (B) can be suppressed. Further, the polyethylene oxide or polypropylene oxide portion having a moderate length of a single system represented by the general formula (1) is most suitable for the solvent to function effectively as an affinity site.

In the monomer represented by the general formula (5), R ³ is an alkyl group having 1 to 20 carbon atoms. The carbon number of the alkyl group is preferably in the range of 1 to 10. The alkyl group may be either a linear alkyl group or a branched alkyl group. Further, the alkyl group may have one or more substituent groups containing a benzene ring in place of the hydrogen atom.

In the monomer represented by the general formula (5), when an alkyl group having a carbon number of from 1 to 10 is used as R ³ , the alkyl group-inhibiting vinyl resin (F) is brought close to each other, thereby promoting Adsorption of the surface of the pigment (B) by the vinyl resin (F) and alignment of the surface of the pigment (B) with the vinyl resin (F). However, when the carbon number of the alkyl group exceeds 10, the effect of the steric hindrance caused by the alkyl group becomes large, showing that the adsorption of the vinyl resin (F) on the pigment (B) or the vinyl resin (F) on the pigment is hindered ( B) The trend of alignment. This tendency becomes remarkable as the carbon chain of the alkyl group becomes longer, and when the carbon number exceeds 20, the previous adsorption or alignment is greatly hindered. Examples of the alkyl group having a benzene ring in R ³ include a benzyl group and a 2-phenyl (iso)propyl group. When the number of benzene rings introduced into the side chain of the vinyl resin (F) is increased, the affinity for the solvent and the ability to align the pigment (B) are improved. As a result, not only the dispersibility of the pigment (B) is enhanced, but also the developability of the photosensitive coloring composition and the thermal fluidity of the coloring layer obtained by the coating are improved.

In the monomer represented by the general formula (5), n is an integer of from 1 to 15. When n is increased, the affinity of the vinyl resin (F) for the solvent (E) is lowered, and the vinyl resin (F) is less likely to generate a solvent and the solvent (E). As a result, the dispersibility of the pigment (B) is lowered. From the viewpoint of solvent and from the viewpoint, n is preferably an integer of from 1 to 4. Moreover, when n is increased, the viscosity of the vinyl resin (F) becomes high. Therefore, the viscosity of the photosensitive coloring composition containing the same becomes high, and the thermal fluidity of the coloring layer may also be lowered.

From the above points, among the monomers represented by the general formula (5), p-cumylphenoxy (poly)ethylene glycol acrylate (p-cumylphenol EO denatured (n≒1) acrylate, R ¹ : a hydrogen atom, R ² : a vinyl group, and R ³ : p-cumyl (2-phenylisopropyl), n≒1) is most suitable. The vinyl resin (F) obtained by using the monomer is susceptible to the p-electron effect of the benzene ring and its steric hindrance effect, and is easily adsorbed on the surface of the pigment (B), and the alignment of the surface of the pigment (B) is also Excellent. From the viewpoint of the dispersibility of the pigment (B) and the thermal fluidity of the coloring layer, the ratio of the constituent unit (b) to the vinyl resin (F) should be in the range of 2 to 50% by weight, more preferably It is in the range of 4 to 50% by weight. When the ratio is too small, it is difficult to uniformly disperse the pigment (B), and the dispersion stability of the pigment (B) may not be sufficient. When the ratio is too large, the thermal fluidity of the colored layer may not be sufficient.

[constitutive unit (c)]

The constituent unit (c) is a constituent unit of the vinyl resin (F) other than the constituent units (a) and (b). The constituent unit (c) mainly contributes to the formation of the above feature (1), that is, it contributes to the excellent thermal fluidity of the colored layer. The constituent unit (c) may or may not have an ethylene bond.

When the constituent unit (c) has a side chain, the side chain is preferably smaller than the larger annular structure included in the constituent unit (b). The thermal fluidity of the colored layer is improved, and it is judged to be a constituent unit (b) having affinity for the pigment (B) and having a large side chain, and a constituent unit having affinity with the solvent (E) and having a small structure. (c) The effect of addition.

The constituent unit (c) is obtained, for example, by polymerizing the following precursor (c1), in particular, radical polymerization such as vinyl polymerization.

The precursor (c1) may be a monomer having ethylene bonding other than the precursors (a1) and (a2).

The precursor (c1) is, for example, a compound having ethylene bonding, and can be formed into a unit (c) by radical polymerization such as polymerization, particularly vinyl polymerization. As such a precursor (c1), for example, an alkyl (meth) acrylate or an alkenyl (meth) acrylate can be used. As the alkyl (meth) acrylate or alkenyl (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, or the like can be used. Propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Tert-butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Ester, hexadecyl (meth) acrylate, decyl (meth) acrylate, decyl methacrylate (iso) decyl (meth) acrylate, cyclohexyl (meth) acrylate Ester, allyl (meth) acrylate, oleyl acrylate. These may be used alone or in combination of two or more.

From the viewpoint of the dispersibility of the pigment (B) and the thermal fluidity of the coloring layer, the side chain constituting the unit (c) should be short. It is preferred to obtain methyl (meth) acrylate or ethyl (meth) acrylate as a precursor in 50% by weight or more of the constituent unit (c). Other monomers can also be used as the precursor (c1). Examples of the other monomer include (meth)acrylic acid having a heterocyclic substituent such as tetrahydroindenyl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate. Esters; alkoxy polyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolypropylene glycol (meth) acrylate; or (meth) propylene Indoleamine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone alcohol Methyl) acrylamide and (meth) acrylamide such as propylene morpholine.

Other monomers may be further used as the precursor (c1). Further examples of the other monomer include vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, or vinyl acetate and propionic acid. Fatty acids such as ethylene and ethylene.

When the vinyl resin (F) is introduced into the ethylene bond, a monomer having an epoxy group or a monomer having a hydroxyl group can also be used as the precursor (c1). However, depending on the modification, some of the monomers may not be utilized as constituent units (c). Therefore, when using such monomers, the reaction conditions must be considered for the weight of constituent units (a) to (c). The effect of the volume ratio.

From the viewpoint of the dispersibility of the pigment and the thermal fluidity of the coloring layer, the ratio of the constituent unit (c) to the vinyl resin (F) should be in the range of 10 to 80% by weight, more preferably 25 to 80. Within the range of % by weight. When the ratio is too small, the thermal fluidity of the colored layer may not be sufficient. When the ratio is too large, it is difficult to uniformly disperse the pigment (B).

[Polymerization of Vinyl Resin (F)]

The vinyl resin (F) is obtained by subjecting the above monomers to radical copolymerization. Bulk polymerization or solution polymerization using a radical polymerization initiator is generally carried out.

The radical polymerization initiator is preferably used in an amount of from 0.001 to 5 parts by weight when the total amount of the monomers is 100 parts by weight. The reaction temperature of the radical polymerization is preferably from 40 to 150 ° C, more preferably from 50 to 110 ° C. The reaction time of the radical polymerization is preferably from 3 to 30 hours, more preferably from 5 to 20 hours. As the radical polymerization initiator, for example, an azo compound or an organic peroxide can be used.

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexane). 1-carboxonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2- Hydroxymethylvaleronitrile) and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

Examples of the organic peroxide include benzammonium peroxide, tertiary hydrogen peroxide butadiene, diisopropyl peroxycarbonate, di-n-propyl peroxycarbonate, and di(2-ethoxylated). Base) peroxycarbonate, tertiary butyl peroxide Alginate, (3,5,5-trimethylhexyl) peroxide, dipropyl decyl peroxide, and diethyl hydrazine peroxide.

These polymerization initiators can be used singly or in combination of two or more.

The radical polymerization can be carried out without a solvent or using a solvent.

As the solvent, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, ketone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether ethyl ester, dipropylene glycol monomethyl can be used. Ethyl ether ethyl ester, ethylene glycol monoethyl ether ethyl ester, ethylene glycol monobutyl ether ethyl ester, diethylene glycol monoethyl ether ethyl ester or ethylene glycol monobutyl ether ethyl ester. These solvents may be used alone or in combination of two or more.

The amount of the solvent is preferably in the range of 0 to 300 parts by weight, more preferably in the range of 0 to 100 parts by weight, when the total amount of the monomers is 100 parts by weight. The solvent after use may be removed by distillation or the like after completion of the reaction, or may be used as a part of the product.

[Introduction of ethylene to vinyl resin (F)]

When ethylene is introduced into one or more of the constituent units (a) to (c), the dispersibility of the pigment, the thermal fluidity of the colored layer, and the pattern shape are not deteriorated, and the bridging density of the colored layer can be increased, so that The color filter is more resistant. Further, the following reaction can be carried out using a conventional catalyst.

<Introduction of ethylene bonding to constituent units (a)>

As a method of introducing ethylene bonding into the constituent unit (a), there is, for example, a side chain epoxy obtained by copolymerizing a precursor (b1), a precursor (c1), and a monomer having an epoxy group. A method in which an additional reaction of a carboxyl group of an unsaturated monovalent acid is carried out, and a hydroxyl group which has been formed is reacted as needed to cause a polyvalent acid anhydride to react. In this case, the ethylene monomer having an epoxy group is used as a precursor. The constituent unit of the substance will become a constituent unit (a) containing ethylene.

Examples of the monomer having an epoxy group include epoxypropyl (meth) acrylate, methyl epoxy propyl (meth) acrylate, and 2-glycidoxy (meth) acrylate. 3,4 epoxybutyl (meth) acrylate and 3,4 epoxy cyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. The viewpoint of reactivity with an unsaturated monovalent acid in the next step is preferably a glycidyl (meth) acrylate.

Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and a-halogenane, alkoxy, halogen, and nitrate of (meth)acrylic acid. And a monocarboxylic acid such as a cyanide substituent. These may be used alone or in combination of two or more.

Examples of the polyvalent acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. When necessary, for example, when the number of carboxyl groups in the constituent unit (a) is increased, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used, and a reaction with a hydroxyl group may be used. The unused anhydride groups are hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride is used as the polyvalent acid anhydride, more ethylene bonds can be introduced by the constituent unit (a).

<Introduction of ethylene bonding to constituent units (b)>

The method of introducing ethylene into the constituent unit (b) is, for example, the same as the one shown in the general formula (5) except that the monomer represented by the general formula (7) or R ³ has an ethylene bond. A method in which a monomer is used as a copolymer of the constituent (b) precursor (b1). However, the ethylene combination contained in the precursor (b1) may be used in polymerization. Since the reactivity of the ethylene bond in the ring structure is low, when the ethylene component is introduced into the constituent unit (b), the monomer represented by the general formula (7) is preferably used as the precursor (b1) in the ring structure. A monomer having an ethylene bond therein.

<Introduction of ethylene bonding to constituent units (c)>

As one method of introducing ethylene into the constituent unit (c), for example, a monomer having a hydroxyl group is used as a part of the constituent unit (c) precursor (c1) to be copolymerized, and a hydroxyl group in the side chain of the copolymer is used. A method of reacting an isocyanate group of a monomer having an isocyanate group. As another method of introducing ethylene into the constituent unit (c), for example, the monomer having the epoxy group is used as a part of the constituent (c) precursor (c1) to be copolymerized, and the side chain of the copolymer is used. The epoxy group is a method in which the carboxyl group of the above unsaturated monovalent acid is subjected to an additional reaction, and further, a hydroxyl group is used to react an isocyanate group of a monomer having an isocyanate group.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (A). A hydroxyalkyl (meth) acrylate such as acrylate, glycerol (meth) acrylate or cyclohexane dimethanol mono (meth) acrylate. These may be used alone or in combination of two or more. Further, it is also possible to use the above-mentioned hydroxyalkyl (meth) acrylate, and to carry out additional polymerization of the polyether mono (meth) acrylate after ethylene peroxide, propylene peroxide and/or butyl peroxide. Or (poly)ester mono (meth) acrylate such as (poly)g-valerolactone, (poly)e-caprolactone and/or (poly)12-hydroxystearic acid. From the viewpoint of the dispersibility of the pigment and the thermal fluidity of the coloring layer, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

Examples of the monomer of the isocyanate group include 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acryloxime]ethyl isocyanate. Other monomers may also be used as the monomer having an isocyanate group. Further, these may be used alone or in combination of two or more.

Further, from the viewpoint of dispersibility of the pigment and thermal fluidity of the coloring layer, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is used as a constituent unit (c) precursor ( The vinyl resin (F) obtained by reacting one part of c1) with a hydroxyl group in the side chain of the copolymer and reacting 2-hydroxyethyl (meth) acrylate is also suitable.

[Introduction of carboxyl group to vinyl resin (F) using polyvalent acid anhydride]

The vinyl resin (F) is preferably introduced into a carboxyl group by a polyvalent acid anhydride from the viewpoint of achieving both excellent thermal fluidity of the color layer and good reworkability with a substrate such as a glass substrate. The polyvalent acid anhydride can be used singly or in combination of two or more.

The method of introducing a carboxyl group in the constituent unit (a) using a polyvalent acid anhydride is described above in connection with the introduction of ethylene in the constituent unit (a). Further, it is not necessary to constitute a unit (a). When ethylene is introduced, a saturated monovalent acid may be used instead of the unsaturated monovalent acid.

Further, when it is not necessary to introduce ethylene into the constituent unit (a), a carboxyl group may be introduced into the vinyl resin (F) using a polyvalent acid anhydride by another method. That is, first, an epoxy group-containing monomer is subjected to an additional reaction such as a carboxyl group of an unsaturated monovalent acid, and a polyvalent acid anhydride is reacted with the generated hydroxyl group as needed. Thereby, a constituent unit (a) containing a carboxyl group can also be produced.

The additional reaction of the carboxyl group of the unsaturated monovalent acid with the epoxy group is carried out by gelation of the polyvalent acid anhydride with the hydroxyl group, and is added so that the residual ratio of the epoxy group of the vinyl resin (F) becomes, for example, 20%. the following. The residual ratio of epoxy groups is preferably Small, the total amount of epoxy groups is best consumed in the reaction.

Further, the additional reaction of the polyvalent acid anhydride with the hydroxyl group is preferably 10 to 100%, more preferably 20 to 100%, of the hydroxyl group of the copolymer, and more preferably reacted with the polyvalent acid anhydride. When the ratio of the hydroxyl group in which the additional reaction occurs is small, it may be difficult to achieve excellent developability and good reworkability. Further, it is not preferable to add an excessive amount of the polyvalent acid anhydride to leave a polyvalent acid anhydride in the vinyl resin (F).

Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidylethyl (meth) acrylate, and 3 , 4 epoxybutyl (meth) acrylate and 3, 4 epoxy cyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the viewpoint of the reactivity with the unsaturated monovalent acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, a-alkylhalane of (meth)acrylic acid, alkoxy, halogen, and nitrate. And a monocarboxylic acid such as a cyanide substituent. These may be used alone or in combination of two or more. It is preferred to use (meth)acrylic acid.

Examples of the polyvalent acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. When necessary, for example, when the number of carboxyl groups in the constituent unit (a) is increased, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used, and a reaction with a hydroxyl group may be used. The unused anhydride groups are hydrolyzed. Tetrahydrophthalic anhydride is preferred.

Further, the ratio of the hydroxyl group to the additional reaction with the polyvalent acid anhydride varies depending on the ratio of the hydroxyl group to the carboxyl group which is present during the reaction. Then, in hydroxy The compound to which the polyvalent acid anhydride is added is formed into a constituent unit (a) by introduction of a carboxyl group. On the other hand, a system in which a polyvalent acid anhydride is not introduced into a hydroxyl group forms a constituent unit (c).

The carboxyl group introduced by the additional reaction of a hydroxyl group with a polyvalent acid anhydride is longer than the carboxyl group of the vinyl resin (F), and thus is less susceptible to steric hindrance than the carboxyl group derived from a precursor such as (meth)acrylic acid. Impact. Further, since the carboxyl group is excellent in affinity with a redosolution such as a strong alkali aqueous solution, the rework liquid rapidly permeates the coating film having a high bridging density by exposure, and the coating film is swollen, reacted, and dissolved rapidly.

Further, in the case where a functional group which reacts with a carboxyl group is present in the photosensitive coloring composition, in the post-baking, the functional group is bridged even if a part of the carboxyl group is introduced by using a polyvalent acid anhydride, and the bridging portion is bridged. The distance from the main chain of the vinyl resin (F) is long, so that the penetration of the redo liquid into the coating film is not hindered. Therefore, in this case, the removal of the coating film is also promptly performed.

[Weight Average Molecular Weight Mw of Vinyl Resin (F)]

The weight average molecular weight Mw of the vinyl resin (F) is preferably in the range of from 2,000 to 20,000, more preferably in the range of from 4,000 to 19,000, from the viewpoint of achieving both excellent developability of the coating film and excellent thermal fluidity of the coloring layer. . When the weight average molecular weight Mw is too small, the optimum development time may be too short, or the pattern may not be sufficient for the adhesion of the substrate. When the weight average molecular weight Mw is too large, the optimum development time may be too long, or the thermal fluidity of the colored layer may not be sufficient.

"Pigment (B)"

The pigment (B) may be an organic pigment of an organic substance or an inorganic pigment of an inorganic substance, or may be a mixture thereof or the like. Generally used as organic pigments and inorganic pigments It can be called a dye or it can be used as a natural pigment. Among these, an organic pigment is suitably used, and it is excellent in heat resistance and color developability.

<organic pigment>

Hereinafter, specific examples of the organic pigments will be denoted by color index numbers.

For the red coloring composition used to form the red filter segments, for example, CIPigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81 can be used: 2, 81:3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, Red pigments such as 224, 226, 227, 228, 240, 242, 246, 254, 255, 264 and 272. In addition to the red pigment, the red coloring composition can also be used together with the yellow pigment and the orange pigment.

Among the red coloring compositions, yellow pigments which can be used together with the red pigments include, for example, CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123,125,126,127,128,129,137,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, and 199. Among these, C.I. Pigment Yellow 138, 139, 150 and 185 are preferred.

Among the red photosensitive coloring compositions, the orange pigments which can be used together with the red pigments include, for example, C.I. Pigment Orange 36, 43, 51, 55, 59, 61, and 71.

For the green coloring composition for forming the green filter segment, for example, C.I. Pigment Green 7, 10, 36, 37, and 58 can be used. In addition to the green pigment, the green coloring composition can also be used together with the yellow pigment.

Among the green coloring compositions, yellow pigments which can be used together with the green pigment include, for example, CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18 , 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73 , 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 ,123,125,126,127,128,129,137,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170 , 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, and 199. Among these, C.I. Pigment Yellow 138, 139, 150 and 185 are preferred.

For the blue colored composition for forming the blue filter segment, for example, CIPigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60 and 64 cyan pigments. In the blue coloring composition, in addition to the blue pigment, C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 and 50 can be used simultaneously. Wait for purple pigments.

For the yellow colored composition for forming the yellow filter segment, for example, CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20 can be used. , 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 , 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125,126,127,128,129,137,138,139,147,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171 Yellow pigments such as 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194 and 199.

For the orange coloring composition for forming the orange color filter section, an orange pigment such as C.I. Pigment Orange 36, 43, 51, 55, 59, 61, and 71 can be used.

For the cyan coloring composition for forming the cyan filter section, for example, blue pigments such as C.I. Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16 and 81 can be used.

For the magenta colored composition for forming the magenta filter segment, for example, a violet pigment such as C.I. Pigment Violet 1 and 19, and a red pigment such as C.I. Pigment Red 144, 146, 177, 169 and 81 can be used. In the magenta colored composition, in addition to the purple pigment and the red pigment, the same yellow pigment as described above may be used simultaneously with respect to the yellow colored composition for forming the yellow filter segment.

<Inorganic Pigments and Dyes>

In order to obtain a balance between chroma and brightness, and to ensure good coatability, sensitivity, developability, and the like, an inorganic pigment may be used in combination with the above organic pigment. Examples of the inorganic pigment include metal oxide powder such as yellow lead, zinc yellow, purple red paint (red iron oxide (III)), cadmium red, ultramarine blue, indigo, chrome oxide green, and cobalt green, metal sulfide powder, and metal powder. Wait.

Further, in the photosensitive coloring composition, a dye may be contained in a range that does not lower heat resistance for coloring.

<Black pigment for shading layer>

A light-shielding layer generally called a black matrix can be formed, for example, as a pigment (B) from a photosensitive coloring composition containing a black pigment. As the black pigment, for example, carbon black #2400, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88,# manufactured by Mitsubishi Chemical Corporation can be used. 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4100, #55, #52, #50, #47, #45, #44, #40 , # 33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, DIABLACK A, DIABLACK N220M, DIABLACK N234, DIABLACK I, DIABLACK LI , DIABLACK II, DIABLACK N339, DIABLACK SH, DIABLACK SHA, DIABLACK LH, DIABLACK H, DIABLACK HA, DIABLACK SF, DIABLACK N550M, DIABLACK E, DIABLACK G, DIABLACK R, DIABLACK N760M, DIABLACK LR; CANCAVE carbon black THERMAX N990, N991, N907, N908, N990, N991 or N908; ASAHI CARBON company's carbon black Asahi #80, Asahi #70, Asahi #70L, Asahi F-200, Asahi #66, Asahi #66HN, Asahi #60H, Asahi #60U, Asahi #55, Asahi #50H, Asahi #51, Asahi #50U, Asahi #50, Asahi #35, Asahi #15 or ASAHI THERMAL; or DEGUSSA's carbon black Color Black Fw200, Color Black Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Special Black 250, Special Black 350, Printex U, Printex V, Printex 140U, Printex 140V (all are trade names).

<Pigment Dispersant>

In order to uniformly disperse the pigment in the solvent, a pigment derivative may be used as at least a part of the pigment. Further, the pigment derivative is, for example, an organic pigment obtained by introducing a substituent having affinity for a solvent. In the case where the pigment derivative is used together with a general pigment, the dispersibility is improved. That is, the pigment derivative can function as a pigment dispersant.

Alternatively, a pigment dispersant such as a pigment, a resin type dispersant or a surfactant may be used in order to uniformly disperse the pigment in a solvent.

The pigment dispersant is excellent in the ability to disperse the pigment, and the effect of re-coagulation of the dispersed pigment is great. Therefore, if a pigment dispersing agent is used, a filter segment excellent in transparency can be obtained. The pigment dispersant is used in a ratio of, for example, 0.1 to 30 parts by weight for 100 parts by weight of the pigment.

<Pigment Derivative>

The pigment derivative is, for example, a compound represented by the following general formula (8). The pigment derivative includes a substance having a basic substituent and an substance having an acidic substituent.

General formula (8): X-Y

Further, in the general formula (8), X is an organic pigment residue, and Y is a basic substituent or an acidic substituent.

As the pigment derivative, for example, JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, and JP-A-5-9469 The contents described in the bulletin. These may be used alone or in combination of two or more. When the pigment derivative is used together with a general pigment, the pigment derivative pigment derivative is preferably used in a ratio of from 0.5 to 25 parts by weight based on 100 parts by weight of the total of the pigment derivative and the general pigment. When the ratio is too small, the effect of improving the dispersibility of the pigment is small. When the ratio is too large, the heat resistance and light resistance of the colored layer may not be sufficient.

In the general formula (8), as the organic pigment constituting the organic pigment residue X, for example, an azo-based pigment such as diketopyrrolopyrrole, disazo, or polyazo; copper phthalocyanine, copper oxyhalide and no Titanium-based pigments such as metal phthalocyanine; anthraquinone pigments such as amidoxime, diamine dioxime, pyrimidine, xanthone, indolinone, standard reduction blue, furanone, anthrone violet dye; Ketone pigment; quinophthalone pigment; dithiazide pigment; dioxopyrrolopyrrole pigment; anthraquinone pigment; anthraquinone pigment; thioindigo pigment; thiazin indigo pigment; isoindane pigment Isoprene-based ketone pigment; quinophthalone pigment; durene pigment; or metal complex pigment.

<Resin type pigment dispersant>

The resin type pigment dispersant has a pigment affinity site having a property of adsorbing to a pigment, and a site compatible with the pigment carrier. The resin type pigment dispersant functions to adsorb to the pigment to stabilize the dispersion of the pigment with respect to the pigment carrier (dispersion medium).

The resin type pigment dispersant can be classified into a polyethylene type, a polyurethane type, a polyester type, a polyether type, a formalin condensation system, an anthracene based system, or a composite dispersant thereof.

Examples of the pigment affinity site include a polar group such as a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphate group, a decanoic acid group, a hydroxyl group, an amine group, a quaternary ammonium salt group or a phosphonium group, and a polyperoxyethane or a poly Hydrophilic polymer chains such as peroxypropane and such composites. Further, examples of the site compatible with the dye carrier include a long-chain alkyl chain, a polyethylene chain, a polyether chain, and a polyester chain. The resin type dispersant may, for example, be a styrene-maleic anhydride copolymer, an olefin-maleic anhydride copolymer, a poly(meth)acrylate, a styrene-(meth)acrylic acid copolymer, or Methyl)acrylic acid-alkyl (meth)acrylate copolymer, (meth)acrylic acid-polyethylene polymer copolymer, phosphate-containing acrylic resin, aromatic carboxy-containing acrylic resin, polystyrene citrate, An anionic resin type pigment dispersant such as a acrylamide-(meth)acrylic acid copolymer, a carboxymethyl cellulose, a polyurethane having a carboxyl group, a hamarinate condensate of a naphthoic acid salt or an alginic acid soda; a polyvinyl alcohol, Nonionic resin type pigment dispersant such as polyalkylene polyamine, polypropylene decylamine or polymer starch; or polyethyleneimine, aminoalkyl (meth) acrylate copolymer, polyvinyl imidazoline, with amine A cationic resin type pigment dispersant such as a reaction product of a polyurethane, a poly(lower alkylenimine), and a polyester having a free carboxyl group. These may be used alone or in combination of two or more.

As a commercially available resin type pigment dispersant, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by BYK-Chemie Co., Ltd. can be used. 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2090, 2091, 2164 or 2163, or Anti-Terra-U, 203 or 204, or BYK-P104, P104S or 220S, or Lactimon or Lactimom-WS, or Bykumen; SOLSPERSE-3000 manufactured by Lubrizol, Japan , 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090 or 53095; or EFKA Chemical Company EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502 or 1503 .

Other resin type pigment dispersants can also be used as the pigment dispersant. Further, these may be used alone or in combination of two or more.

<Surfactant>

Examples of the surfactant include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, alkyl naphthalenesulfonate sodium, and alkyl diphenyl ether disulfonate. Sodium, laurylethanolamine, lauryl triethanolamine, ammonium lauryl sulfate, stearic acid ethanolamine, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer ethanolamine, polyethylene oxide ether phosphate Anionic surfactant such as ether; polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, poly(ethylene oxide decyl phenyl ether), polyethylene oxide ether phosphate, polyethylene oxide sorbitan glycerin hard a cationic surfactant such as a fatty acid such as a fatty acid; an alkyl 4-grade ammonium salt or an ethylene oxide additive such as an ethylene oxide add-on surfactant; an alkyl dimethylamine acetate quaternary ammonium carboxylate internal salt or the like An ammonium carboxylic acid inner salt; or an amphoteric surfactant such as an alkyl imidazoline. These may be used alone or in combination of two or more.

Active Energy Line Polymerization Starter (C)

The photopolymerization initiator (C), for example, a photopolymerization initiator, imparts a property of curing the resin by irradiation with active energy rays such as ultraviolet rays and electron beams. The active energy ray polymerization initiator (C) is preferably used in a ratio of 5 to 200% by weight for the pigment (B), and is more preferably for the pigment (B) from the viewpoint of inductivity and developability to the active energy ray. It is used in a ratio of 10 to 150% by weight.

As the active energy ray polymerization initiator (C), for example, an acetophenone-based active energy ray polymerization initiator, a benzo-based active energy ray polymerization initiator, a benzophenone-based active energy ray polymerization initiator, or the like can be used. Thioxanthone-based active energy ray polymerization initiator, triazine-based active energy ray polymerization initiator, borate-based active energy ray polymerization initiator, carbazole-based active energy ray polymerization initiator or imidazole-based active energy Line polymerization initiator.

Examples of the acetophenone-based active energy ray polymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, and 1 -(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyldimethylamine-1-(4-morpholinium benzene Butyl-1-butanone or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinpropan-1-one.

The benzoic active energy ray polymerization initiator may, for example, be benzo, benzomethyl ether, benzoethyl ether, benzoisopropyl ether or benzyl dimethyl ketal.

Examples of the benzophenone-based active energy ray polymerization initiator include benzophenone, benzoquinone benzoic acid, benzoquinone benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, and propylene. Deuterated benzophenone or 4-phenylhydrazine-4'-methyldiphenyl sulfide.

Examples of the thioxanthone-based active energy ray polymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 diisopropylthioxanthone.

The triazine-based active energy ray polymerization initiator may, for example, be 2,4,6-trichloro-secondary triazine or 2-phenyl-4,6-bis(trichloromethyl)-secondary triazine. , 2-(p-methoxyphenyl) 4,6-bis(trichloromethyl)-secondary triazine, 2-(p-tolyl) 4,6-bis(trichloromethyl)-sub-three Pyrazine, 2-piperidin-4,6-bis(trichloromethyl)-secondary triazine, 2,4-bis(trichloromethyl)-6-styryl-secondary triazine, 2-( Naphthacene-1-yl)-4,6-bis(trichloromethyl)-secondary triazine, 2-(4-methoxynaphthacene-1-yl)-4,6-bis(trichloromethane) Base) - secondary triazine, 2,4-trichloromethyl-(piperidyl)-6-triazine or 2,4-trichloromethyl (4'-methoxystyryl)-6-three Oxazine.

These may be used alone or in combination of two or more.

A sensitizer can be used simultaneously with the active energy ray polymerization initiator (C).

As the sensitizer, for example, a-methoxy ether, mercaptophosphoric acid hydroxide, tolyl glyoxylic acid, benzyl-9,10-phenanthrene, camphorquinone, ethylhydrazine, 4 can be used. 4'-Diethylfurfural ketone, 3,3',4,4'-tetrakis(tertiary butylperoxycarboxy)benzophenone, 4,4-dimethylamine benzophenone.

When the active energy ray polymerization initiator (C) and the sensitizer are simultaneously used, the sensitizer is preferably used in an amount of from 3 to 60% by weight for the active energy ray polymerization initiator (C), from the active energy ray. The viewpoint of inductivity and developability is preferably used in a ratio of 5 to 50% by weight for the active energy ray polymerization initiator (C).

<Active energy ray-curable monomer (D)>

The active energy ray-curable monomer (D) is a monomer and/or oligomer which is cured by irradiation with an active energy ray to form a resin.

As the active energy ray-curable monomer (D), for example, a linear or branched alkyl (meth) acrylate, a cyclic alkyl (meth) acrylate, or a fluoroalkyl (meth) acrylate can be used. Ester, (meth) acrylate having a hetero ring, (meth) acrylate having an aromatic ring, (poly) olefin diol monoalkyl ether (meth) acrylate, having a carboxyl group (Meth) acrylates, (meth) acrylates having a hydroxyl group, (poly) alkene diol di(meth) acrylates, di(meth) acrylates, having a tertiary amine group (Meth) acrylates, trifunctional or higher polyfunctional (meth) acrylates, epoxy (meth) acrylates, (meth) propylene oxime modified resin oligomers, ethylene, ethylene Ethers, guanamines or acrylonitrile.

As the linear or branched alkyl (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl can be used. (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, octyl ( Methyl) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexadecyl (meth) acrylate, decyl (meth) acrylate, isoindole (meth) acrylate, lauryl (meth) acrylate, thirteen (meth) acrylate, isomyristyl (meth) acrylate, stearin oxime (meth) acrylate and stearin oxime (Meth) acrylate.

Examples of the cyclic alkyl (meth) acrylate include cyclohexyl (meth) acrylate, tertiary butyl cyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate. Bicyclopentaethoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentene oxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

Examples of the fluoroalkyl (meth) acrylate include trifluoroethyl (meth) acrylate, octylfluoropentyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate. And tetrafluoropropyl (meth) acrylate.

Examples of the (meth) acrylate having a hetero ring include tetrahydroindenyl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate. Examples of the (meth) acrylate having an aromatic ring include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxy polyethylene glycol (meth) acrylate. Ester, p-cumylphenoxyethyl (meth) acrylate, p-cumyl phenoxy polyethylene glycol (meth) acrylate and nonyl phenoxy polyethylene glycol (meth) acrylate.

Examples of the (poly)olefin-based diol monoalkyl ether (meth) acrylate include 2-methoxyethyl (meth) acrylate and 2-ethoxy (meth) acrylate. 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl Ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate and polyethylene Alcohol monostearate (meth) acrylate.

Examples of the (meth) acrylate having a carboxyl group include (meth)acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, and 2-(methyl). Ethyl propylene oxime oxime, propyl 2-(methyl) propylene sulfonate, hexahydroethyl 2-(methyl) propylene sulfonate, 2-(methyl) propylene sulfonate Hydropropyl propyl ester, ethylene oxide modified succinic acid (meth)acrylic acid Ester, b-carboxyethyl (meth) acrylate and w-carboxycaprolactone (meth) acrylate.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Ester, 4-hydroxybutyl (meth) acrylate, 2-propenyl oxyethyl 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol single ( Methyl) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutane diol mono (meth) acrylate, Poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(ethylene glycol-butanediol) mono(meth)acrylate, poly(propylene glycol-butanediol) single (methyl) ) acrylate and glycerol (meth) acrylate.

Examples of the (poly)olefin-based diol di(meth) acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di( Methyl) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, polypropylene glycol II (Meth) acrylate, poly(ethylene glycol-propylene glycol) di(meth) acrylate, poly(ethylene glycol-trimethyl glycol) di(meth) acrylate, poly(propylene glycol-trimethyl) Glycol) di(meth)acrylate, polytetramethylethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(a) Acrylate, 1,6-hexanedioxane (meth) acrylate, 1,9-nonanediol di(meth) acrylate, and 2-methyl, 2-butyl-propylene glycol di(methyl) )Acrylate.

Examples of the di(meth)acrylates include dimethylol dicyclopentane. (Meth) acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth) acrylate, stearic acid modified neopentyl alcohol di(meth) acrylate, ethylene oxide modified bisphenol A Di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, butyl oxide modified bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol F Di(meth)acrylate, propylene oxide modified bisphenol F di(meth)acrylate, butyl oxide modified bisphenol F di(meth)acrylate, zinc diacrylate, ethylene oxide modification Phosphate triacrylate and glycerol di(meth)acrylate.

Examples of the (meth) acrylate having a tertiary amino group include dimethylamine ethyl (meth) acrylate, diethyl amine ethyl (meth) acrylate, and dimethyl methacrylate. Base (meth) acrylate and diethylaminopropyl (meth) acrylate.

Examples of the trifunctional or higher polyfunctional (meth) acrylate include glycerin tri(meth) acrylate, trimethylolpropane (meth) acrylate, and neopentyl alcohol (meth) acrylate. Ester, neopentyl alcohol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of the epoxy (meth) acrylate include glycerin triglycidyl ether-(meth)acrylic acid addenda, glycerol diglycidyl ether-(meth)acrylic acid addenda, and polyacrylic acid. Triol polyglycidyl ether-(meth)acrylic acid addenda, 1,6-butanediol diglycidyl ether, alkyl glycidyl ether-(meth)acrylic acid addenda, aryl glycidyl ether -(Meth)acrylic acid addenda, phenylglycidyl ether-(meth)acrylic acid addenda, epoxy styrene-(meth)acrylic acid addenda, bisphenol A diglycidyl ether-(methyl) Acrylic addenda, propylene oxide modified bisphenol diglycidyl ether Addition of (meth)acrylic acid, bisphenol A diglycidyl ether-(meth)acrylic acid addenda, epichlorohydrin-modified phthalic acid-(meth)acrylic acid addenda, epichlorohydrin-modified hexahydrobenzene Dicarboxylic acid-(meth)acrylic acid addenda, ethylene glycol diglycidyl ether-(meth)acrylic acid addenda, polyethylene glycol diglycidyl ether-(meth)acrylic acid addenda, propylene glycol diglycidyl Ethyl ether-(meth)acrylic acid addenda, polypropylene glycol diglycidyl ether-(meth)acrylic acid addenda, novolac type epoxy resin-(meth)acrylic acid addenda, cresol type epoxy resin-(A Acrylic addenda and other epoxy-(meth)acrylic addenda.

Examples of the (meth) propylene oxime modified resin oligomers include (meth) propylene oxime modified polyisocyanate, (meth) propylene oxime modified polyurethane, and (meth) propylene. Oxide modified polyester, (meth) propylene oxime modified melamine, (meth) propylene oxime modified ruthenium, (meth) propylene oxime modified baidene and (meth) propylene oxime Oxygen-modified rosin.

Examples of the ethylene compound include styrene, a-methylstyrene, vinyl acetate, ethylene (meth)acrylate, and allyl (meth)acrylate.

Examples of the vinyl ethers include hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and neopentyl alcohol trivinyl ether.

Examples of the guanamines include (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-vinylformamide.

Other compounds can also be used as the active energy ray-curable monomer (D). Further, the active energy ray-curable monomer (D) may be used singly or in combination of two or more kinds.

Solvent (E)

The solvent (E) functions to sufficiently disperse the pigment (B) in the pigment carrier. In addition, the solvent (E) can be applied to a substrate such as a transparent substrate, that is, for example, on a glass substrate, so that the photosensitive resin can be easily applied to a dry film thickness of, for example, 0.2 to 5 μm.

As the solvent (E), for example, 1,2,3-trichloropropane, 1,3-butanediol diacetate, 2-heptanone, 3,3,5-trimethyl-2-cyclohexene- can be used. 1-ketone, 3,5,5 trimethylcyclohexanone, 3-ethoxypropionic acid ethyl, 3-methoxy-3-methylacetate butyl ester, 3-methoxybutanol, 3- Butyl methoxyacetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, n-butylbenzene, n-propyl acetate, N-pyrrolidone , o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, dibutylbenzene, tertiary styrene, isophorone, ethylene glycol diethyl ether, ethylene Dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, diisobutyl ketone, cyclohexanol acetate, two Propylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monobutyl ether, diacetone alcohol, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether propionate, phenyl alcohol, methyl isobutyl ketone, methyl Hexyl alcohol, n-amine acetate, n-butyl acetate, isobutyl acetate, amine, iso-butyl acetate, propyl acetate, or a dibasic ester.

Among these, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monoethyl are preferably used from the viewpoint of good compatibility with the resin (A). An alcohol acetate such as an ether acetate or a ketone such as cyclohexanone.

Other solvents can also be used as the solvent (E). Further, these may be used alone or in combination of two or more.

When the solvent (E) is used, the photosensitive coloring composition can be adjusted to an appropriate viscosity to form a coloring layer having a uniform film thickness as a target. From this point of view, the solvent (E) is preferably used in a ratio of 800 to 4000% by weight with respect to the pigment (B).

Uniform dye

In order to easily form a coating film having good flatness on the substrate, the photosensitive coloring composition preferably further contains a leveling agent.

As the leveling agent, a dimethyl siloxane having a polyether structure or a polyester structure in the main chain is preferred. Examples of the dimethyl siloxane having a polyether structure in the main chain include FZ-2122 manufactured by TORAY‧Dow Corning Co., Ltd. and BYK-333 manufactured by BYK Corporation. Further, examples of the dimethyl methoxy olefin having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK. It is also possible to use dimethyl methoxyoxane having a polyether structure in the main chain and dimethyl methoxy oxane having a polyester structure in the main chain.

When a leveling agent is used, the concentration of the leveling agent in the photosensitive coloring composition is generally set in the range of 0.003 to 0.5% by weight.

In order to assist the function of the leveling agent, an anionic, cationic, nonionic or amphoteric surfactant may be added to the photosensitive coloring composition. In the photosensitive coloring composition, only one type of surfactant may be added, or two or more types may be mixed and added.

Examples of the anionic surfactant which is an auxiliary leveling agent include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, and sodium alkylnaphthalenesulfonate. , alkyl diphenyl ether disulfonate sodium, lauryl sulfate ethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid ethanolamine, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer Ethanolamine and polyethylene oxide ether phosphate ether.

The cationic surfactant as an auxiliary leveling agent may, for example, be an alkyl 4-based ammonium salt or the like.

Examples of the nonionic surfactant which is an auxiliary leveling agent include polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyepoxy phenyl phenyl ether, polyethylene oxide ether phosphate, and poly Ethylene ethene sorbitan glyceryl stearate and polyethylene glycol monolauryl ester.

The amphoteric surfactant which is an auxiliary leveling agent may, for example, be an alkyl quaternary ammonium carboxylate inner salt such as an alkyl dimethylamine acetate quaternary ammonium carboxylate inner salt or an alkyl imidazoline. As the surfactant for the auxiliary leveling agent, a fluorine-based surfactant or a sulfhydryl-based surfactant can also be used.

Other Ingredients

The photosensitive coloring composition may further contain other components. For example, in the photosensitive coloring composition, a storage stabilizer may be contained in order to improve the stability of the viscosity over time. Moreover, in order to improve the adhesion between the colored layer and the substrate, the photosensitive coloring composition may contain an adhesion promoter such as a decane coupling agent.

Examples of the storage stabilizer include four-stage ammonium chlorides such as benzyltrimethyl chloride and dimethylhydroxylamine; organic acids such as lactic acid and oxalic acid; methyl ethers of the above organic acids; and tertiary butyl 焦A catechol such as a tea phenol; an organic phosphine such as triphenylphosphine, tetraethylphosphine or tetraphenylphosphine; and a phosphite. The storage stabilizer is used in a ratio of, for example, 0.1 to 10 parts by weight of the 100 parts by weight of the pigment (B).

Examples of the decane coupling agent include ethylene decane such as ethylene tris(β-methoxy oxy) decane, ethylene ethoxy decane, and ethylene trimethoxy decane; γ-methacryloxy propylene trimethoxy decane; (meth)acrylic acid decane Class; β-(3,4-epoxycycloalkyl)ethyltrimethoxydecane, β-(3,4-epoxycycloalkyl)methyltrimethoxydecane, β-(3,4-ring Oxycycloalkyl)ethyltriethoxydecane, β-(3,4-epoxycycloalkyl)methyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ- Epoxy decanes such as glycidoxypropyl triethoxy decane; N-β (aminoethyl) γ-aminopropyl trimethoxy decane, N-β (amine ethyl) γ-aminopropyl three Ethoxy decane, N-β (amine ethyl) γ-aminopropyl methyl diethoxy decane, γ-aminopropyl triethoxy decane, γ-aminopropyl trimethoxy decane, N-benzene Amino decanes such as γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane; and γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyltrimethylacetate A thiononane such as a decane.

The decane coupling agent is preferably used in a ratio of, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the pigment (B), and more preferably used in a ratio of 0.05 to 5 parts by weight.

"Manufacturing method of photosensitive coloring composition"

The photosensitive coloring composition is produced by, for example, the following method.

First, the pigment (B) is prepared. As the pigment (B), it is preferred to use a material which is refined by a salt milling treatment.

The salt milling treatment refers to heating a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After mechanically mixing and stirring, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a pulverization aid, and when the salt is ground, the pigment is pulverized by the high hardness of the inorganic salt, and it is judged that the active surface is generated to cause crystal growth. Therefore, the pigment is caused by mixing and stirring. Since the pulverization and the crystal growth are carried out, the pigments having different primary particle diameters can be obtained in accordance with the conditions of the mixing and stirring.

In order to promote crystal growth by heating, the heating temperature is preferably in the range of 40 to 150 °C. When the heating temperature is less than 40 ° C, crystal growth is not sufficiently caused, and the shape of the pigment particles is close to an amorphous shape, which is not preferable. On the other hand, when the heating temperature exceeds 150 ° C, the crystal growth progresses excessively, and the primary particle diameter of the pigment becomes large. Therefore, it is not suitable as a coloring material for a coloring composition for a color filter.

Further, from the viewpoint of the balance between the particle size distribution of the primary particles of the salt-milling treatment pigment and the cost of the salt-milling treatment, the mixing and stirring time of the salt-milling treatment is preferably from 2 to 24 hours.

By optimizing the conditions for salt-milling the pigment, it is obtained that the average particle diameter of the primary particle diameter is very small, and the particle size distribution of the primary particles is narrow, that is, a pigment having a clear particle size distribution is obtained.

The primary particle diameter of the pigment (B) determined by TEM (transmission electron microscope) is preferably in the range of 20 to 100 nm. When the primary particle diameter is less than 20, it is difficult to disperse the pigment (B) in an organic solvent. Further, when the primary particle diameter is more than 100 nm, it is difficult to obtain a sufficient contrast ratio. A particularly suitable primary particle size ranges from 25 to 85 nm.

The water-soluble inorganic salt used in the salt milling treatment is, for example, sodium chloride, cesium chloride, potassium chloride or sodium sulfate. From the price point of view, sodium chloride (salt) should be used. From the viewpoint of processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in a ratio of 50 to 2000% by weight for the pigment, and more preferably in a ratio of 300 to 1000% by weight for the pigment.

The water-soluble organic solvent used in the salt milling treatment functions as a wet pigment and a water-soluble inorganic salt, and is dissolved (mixed) in water and substantially insoluble. Any of the water-soluble inorganic salts can be used, and is not particularly limited. However, in the salt milling treatment, the temperature rises and the solvent is in a state of being easily evaporated. Therefore, from the viewpoint of safety, the boiling point of the water-soluble organic solvent is preferably 120 ° C or higher.

The water-soluble organic solvent may, for example, be 2-(methoxymethoxy)ethane, 2-butoxyethane, 2-(isopropoxy)ethane or 2-(hexyloxy)ethane. 2-(hexyloxy)ethane, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol Alcohol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propane, 1-ethoxy-2-propane, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether Or liquid polypropylene glycol. The water-soluble organic solvent is preferably used in a ratio of 5 to 1000 parts by weight for the 100 parts by weight of the pigment, and more preferably 50 to 500 parts by weight for the 100 parts by weight of the pigment.

When salt grinding is used, the resin may be added as needed. The kind of the resin is not particularly limited, and for example, a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin is preferably solid at room temperature and insoluble in water, and in addition, a part of the resin is preferably soluble in the above organic solvent. The resin is preferably used in a ratio of 5 to 200 parts by weight for 100 parts by weight of the pigment.

In the production of the above-mentioned photosensitive coloring composition, after preparing the pigment (B), the resin (A), the pigment (B) and the solvent (E) are mixed. Next, the pigment (B) is uniformly dispersed in the mixed liquid containing the resin (A) and the solvent (E) by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. in. Further, an active energy ray polymerization initiator (C), an active energy ray-curable monomer (D), and the like are added to the dispersion. A photosensitive coloring composition was obtained as above. Furthermore, when producing a photosensitive coloring composition containing two or more kinds of pigments, the first First, a plurality of kinds of dispersions having different kinds of pigments are prepared, and then mixed or the like. From the photosensitive coloring composition obtained as described above, coarse particles of 5 μm or more are removed by means of centrifugation, a sintered filter, and a membrane filter, and it is preferable to remove coarse particles of 1 μm or more, and it is preferable to remove coarse particles of 0.5 μm or more. Particles and fine dust mixed in.

Color Filter

Next, a color filter relating to one embodiment of the present invention will be described.

A color filter according to one aspect of the present invention is provided on a transparent substrate and a reflective substrate, and includes a filter segment or a black matrix formed from the photosensitive coloring composition. A typical color filter includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or includes at least one magenta filter segment At least one cyan filter segment and at least one yellow filter segment.

As the transparent substrate, for example, a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene glycol can be used. Further, when used in a liquid crystal display device, a transparent electrode composed of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal molecules after the formation of the panel. When the filter segment and the black matrix are formed by the photolithography method, for example, the following method is employed.

First, the above-mentioned photosensitive coloring composition is applied onto a transparent substrate. This coating is carried out by a coating method such as spin coating or die coating.

After the coating film is dried as needed, a mask having a specific pattern is placed in contact with or away from the coating film, and the mask is interposed to irradiate the coating film with ultraviolet light or the like. Or, instead of using the exposure of the reticle, the coating film is subjected to lightning. Beam depiction or electron beam depiction. Thereby, the coating film is cured by irradiation to the irradiation portion of the light or the electron beam.

Next, the coating film is supplied to a development process. Thereby, the unexposed portion of the uncured portion is removed from the coating film. As the alkali liquid, an aqueous alkali solution such as a sodium carbonate aqueous solution or a sodium hydroxide aqueous solution or an organic base such as dimethylbenzylamine or triethanolamine is used. The developer may further contain an additive such as an antifoaming agent or a surfactant. The development treatment can be carried out, for example, by a spray development method, a spray development method, a dropping (immersion) development method, or a stirring (liquid) development method.

Thereafter, the pattern obtained by the development is applied to accelerate the polymerization reaction as needed. Each of the filter segments and the black matrix is obtained in this way. Furthermore, the black matrix is typically formed earlier than the formation of the filter segments. In the above method, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to the previous coating film after the coating film is dried and before the coating film is exposed, and then dried. A coating film composed of a water-soluble or alkali-soluble resin prevents oxygen from blocking the polymerization reaction upon exposure. Therefore, when the coating film is formed, the sensitivity of the coating film composed of the photosensitive coloring composition to the exposure light can be improved.

In the above method, each of the filter segments and the black matrix is directly formed on the substrate by photolithography.

In the above method, the black matrix is formed using the photosensitive coloring composition described above, but other materials may be used for the black matrix. For example, as the black matrix, a layer composed of a chromium layer, a multilayer film of a chromium layer and a chromium oxide layer, and an inorganic substance such as titanium nitride may be formed.

Thin film transistors (TFTs) may also be formed on the substrate before the formation of the filter segments. Active matrix driving type liquid crystal display device on TFT substrate When the color filter is formed thereon, a higher aperture ratio can be achieved as compared with the case where the filter segment is formed on the opposite substrate, thereby achieving higher brightness. A coating layer or an electrode may be formed on the color filter layer. When a coating layer and a plurality of pixel electrodes are sequentially formed on the color filter layer on the TFT substrate, through holes for electrically connecting the pixel electrode and the TFT may be provided on the color filter layer and the coating layer.

"Redo"

In the manufacturing process of the color filter, when a failure occurs in a colored layer such as a filter segment or a black matrix, for example, a high-concentration strong alkaline solution is used as a peeling liquid, and the colored layer is peeled off from the substrate to regenerate the substrate. The regenerated substrate can be reused for the manufacture of a color filter. That is, the substrate can also be reworked.

The redo liquid has a high pH and contains, for example, at least one of KOH and NaOH, an organic base, a hydrophilic solvent, a surfactant, and water. For the re-working liquid, for example, PK-CFR310, PK-CFR320 or PK-CFR370 manufactured by PARKER CORPORATION, SEMICLEAN DF-7 manufactured by Yokohama Oil & Fats Co., Ltd., EP-10, and MITSUKAWA Pure Chemical Research Institute Co., Ltd. UNLASTCLEANER-22 and so on.

In the redoing of the substrate, the coloring layer formed by firing a coating film composed of the photosensitive coloring composition at 230 ° C for 60 minutes is expected to exhibit 30 to 120 mg for a re-grinding liquid of 65 ° C. Solubility. When the solubility is too small, the colored layer cannot be peeled off from the substrate using the redo liquid, or the release sheet may be produced in a larger block form. If the release sheet is present in the redo liquid in the form of a large block, the filter is likely to be clogged in order to purify the used filter. Conversely, when the solubility is too large, even if a weak alkali solution is used as the redo liquid, The coloring liquid can still be peeled off from the substrate, but on the other hand, the development speed of the coating film composed of the photosensitive coloring composition is remarkably high. Therefore, it is difficult to manufacture a high-definition color filter.

When the photosensitive coloring composition is used, the solubility can be controlled to 30 to 120 mg by the addition effect of the constituent unit (a) and the constituent unit (b) and/or the constituent unit (c). The release sheet is produced in a sufficiently small size. Therefore, excellent reworkability can be achieved.

"Liquid Crystal Display Device"

The color filter described above can be used, for example, in a liquid crystal display device or a solid-state image sensor. An example of a liquid crystal display device including a color filter will be described below.

The color liquid crystal display device includes a liquid crystal display panel, and any backlight or front light including the illumination liquid crystal display panel. The liquid crystal display panel can display a color image using a color filter, for example, a twisted nematic (TN) mode, a super twisted nematic (STN) mode, an plane switching (IPS) mode, and a vertical alignment ( Any display mode such as VA) mode and optical compensation bend (OCB) mode can be used.

The liquid crystal display panel includes first and second substrates and a liquid crystal layer.

The first and second substrates are opposed to each other with a gap interposed therebetween. The distance between the first and second substrates is kept constant by the granular spacer interposed therebetween or the columnar spacer formed on at least one of them.

A sealing material layer having a frame shape is provided between the first and second substrates. In the sealing material layer, a notch portion that functions as an injection port is provided. The liquid crystal material is injected through the previous injection port in the space surrounded by the first and second substrates and the sealing material layer. A liquid crystal material filled with the space forms a liquid crystal layer. Furthermore, the injection port is sealed by a sealing material.

Each of the first and second substrates includes an insulating substrate. At least one of the first and second substrates further includes an electrode between the insulating substrate and the liquid crystal layer. The electrode is coated by an alignment film as needed. Further, one of the first and second substrates further includes a color filter. The color filter is located between the insulating substrate including the first and second substrates and the liquid crystal layer.

Typically, the liquid crystal display panel further includes a polarizing plate adhered to at least one of the first and second substrates. The liquid crystal display panel may further include a wavelength plate.

Embodiments of the invention are described below. In addition, it is to be understood that the embodiments are not intended to limit the scope of the invention.

(definition)

In the following examples and comparative examples, "part" and "%" mean "weight" and "% by weight", respectively.

Further, the molecular weight of the resin described below is a number average molecular weight or a weight average molecular weight measured in terms of polystyrene measured under the following conditions. Specifically, four separation columns were connected in series to a gel permeation chromatography apparatus "HLC-8120GPC" manufactured by TORAY Co., Ltd. For the filling materials of the separation columns, "TSK-GEL SUPER H5000", "TSK-GEL SUPER H4000", "TSK-GEL SUPER H3000" and "TSK-GEL SUPER" are used in the order of connection of the columns. H2000", the mobile phase uses tetrahydrofuran.

(Modulation of Resin Solution 1)

In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device, 233 portions of cyclohexanone were injected, and the temperature was raised to 80 °C. After replacing the gas in the flask with nitrogen, the tube was passed through 2 20 parts of methacrylic acid, 30 parts of p-cumylphenol ethylene oxide-modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 19 parts of benzyl methacrylate, and 16 parts of methyl methacrylate were dropped. A mixture of 15 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 16,000.

After cooling the resin solution to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure the non-volatile components. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 1 was thus obtained.

(Preparation of Resin Solutions 2 to 15 and Comparative Resin Solutions 1 to 6)

The resin solutions 2 to 15 and the comparative resin solutions 1 to 6 were prepared by the same method as described for the resin solution 1, except that the ratio of the various components was changed as shown in Tables 1 to 3. Tables 1 to 3 show the results of measurement of the weight average molecular weight.

Further, the substances or matters indicated by the abbreviations shown in Tables 1 to 3 are specifically as follows.

‧MAA: Methacrylic acid

‧AA: Acrylic

‧GMA: glycidyl

‧THPA: tetrahydro maleic anhydride

‧M110: ARONIX M110 (p- phenol oxirane modified acrylate) manufactured by Toagos Corporation

‧FA-513M: FANCRYL FA-513M (dicyclopentyl methacrylate) manufactured by Hitachi Chemical Co., Ltd.

‧FA-512MT: FANCRYL FA-512MT (bicyclopentaoxyalkenyl methacrylate) manufactured by Hitachi Chemical Co., Ltd.

‧BzMA: benzyl acrylate

‧2MTA: 2-methoxyethyl acrylate

‧ St: Styrene

‧MMA: Methacrylate

‧EMA: Ethyl acrylate

‧BMA: n-butyl acrylate

‧HEMA: 2-hydroxyethyl methacrylate

‧GLMA: glycerol methacrylate

‧MOI: Karenz MOI (2-methyl propylene oxyfluoride B) manufactured by Showa Denko Isocyanate

‧Mw: weight average molecular weight

Further, the notes of Tables 1 to 3 are described below.

‧ Note 1: GMA in the copolymer is supplemented with AA and THPA.

‧ Note 2: GMA in the copolymer is supplemented with MAA and THPA.

‧ Note 3: HEMA in the copolymer is attached to MAA.

‧ Note 4: GMA in the copolymer is attached to MAA.

‧Note 5: MAA is added to the MAA in the copolymer.

(Resin solution 16)

In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device, 207 portions of cyclohexanone were injected, and the temperature was raised to 80 °C. After the gas in the flask was replaced with nitrogen, 20 parts of methacrylic acid and 20 parts of cumylphenol ethylene oxide-modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and methyl group were dropped by dropping the tube over 2 hours. 45 parts of methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.

Next, the supply of nitrogen gas to the flask was stopped, and then, the total amount of the copolymer solution obtained by stirring for one hour was supplied to the inside of the flask. Thereafter, the copolymer solution was cooled to room temperature, and 2-methylpropenyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd.) was dropped at 70 ° C for 3 hours. Karenz MOI) 6.5 parts, 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone.

After the resin solution thus obtained was cooled to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure a nonvolatile component. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 16 was thus obtained. Tables 1 to 3 show the results of measurement of the weight average molecular weight obtained for the resin solution 16.

(Resin solution 17)

In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device, 207 portions of cyclohexanone were injected, and the temperature was raised to 80 °C. After the gas in the flask was replaced with nitrogen, 20 parts of methacrylic acid and 20 parts of cumylphenol ethylene oxide-modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and methyl group were dropped by dropping the tube over 2 hours. 45 parts of methyl acrylate, 8.5 parts of glycerol monomethacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer solution.

Next, the supply of nitrogen gas to the flask was stopped, and then, the total amount of the copolymer solution obtained by stirring for one hour was supplied to the inside of the flask. Thereafter, the copolymer solution was cooled to room temperature, and a mixture of 6.5 parts of 2-methylpropenyloxyethyl isocyanate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 ° C for 3 hours.

After the resin solution thus obtained was cooled to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure a nonvolatile component. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 17 was thus obtained. Tables 1 to 3 show the results of measurement of the weight average molecular weight obtained for the resin solution 17.

(Resin solution 18)

In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device, 370 parts of cyclohexanone were injected, and the temperature was raised to 80 °C. After the gas in the flask was replaced with nitrogen, 18 parts of the cumylphenol ethylene oxide-modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), benzyl group, were dropped from the liquid in the flask by dropping the tube over 2 hours. A mixture of 10 parts of methacrylate, 18.2 parts of glycerol monomethacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further carried out at 100 ° C for 1 hour.

Next, the liquid was dissolved in 50 parts of cyclohexanone to dissolve azobisisobutyronitrile, and further reacted at 100 ° C for 1 hour.

Next, the gas in the flask was replaced with air, and 9.3 parts of the acrylic acid (100% of the glycerol group), 0.5 part of trimethylaminophenol, and 0.1 part of hydroquinone were supplied to the inside of the flask. The reaction was continued at 100 ° C for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5.

Further to the previous liquid, 19.5 parts of tetrahydrophthalic anhydride were added (generated 100% of the hydroxyl group) and 0.5 parts of triethylamine were reacted at 120 ° C for 3.5 hours. Thereby an acrylic resin is obtained.

After the resin solution was cooled to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure a nonvolatile component. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 18 was thus obtained. The measurement results of the weight average molecular weight obtained for the resin solution 18 are shown in Tables 1 to 3.

(Resin solution 19)

In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, 233 portions of cyclohexanone were injected, and the temperature was raised to 110 °C. After replacing the gas in the flask with nitrogen, the liquid in the flask was dropped into 4 parts of styrene, 27 parts of glycerin methacrylate, 27 parts of methyl methacrylate, and 2 methoxy by dropping the tube over 2 hours. A mixture of 8 parts of ethyl acrylate, 6 parts of 2-hydroxyethyl acrylate, and 13 parts of dimethyl 2,2'-azobis(2-methylpropionate). After completion of the dropwise addition, the mixture was further reacted at 110 ° C for 3 hours to obtain a copolymer.

Next, the gas in the flask was replaced with air, and 16 parts of methacrylic acid (100% of glycerol group), 16 parts of cyclohexanone, 0.5 part of trimethylolamine phenol, and 0.1 part of hydroquinone were supplied to the flask. . The reaction was continued at 100 ° C for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5.

Further to the previous liquid, 11 parts of tetrahydrophthalic anhydride (acrylic acid tree) 30% of the hydroxyl groups in the lipid and 0.5 parts of triethylamine were reacted at 90 ° C for 3.5 hours. Thereby an acrylic resin is obtained.

After the resin solution was cooled to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure a nonvolatile component. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 19 was thus obtained. The measurement results of the weight average molecular weight obtained for the resin solution 19 are shown in Tables 1 to 3.

(Resin solution 20)

In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, 233 portions of cyclohexanone were injected, and the temperature was raised to 110 °C. After the gas in the flask was replaced with nitrogen, 30 parts of methacrylic acid, 10 parts of benzyl methacrylate, 16 parts of methyl methacrylate, and 2-methoxy were dropped from the liquid in the flask by dropping the tube over 2 hours. A mixture of 6 parts of ethyl acrylate, 6 parts of 2-hydroxyethyl acrylate, and 13 parts of dimethyl 2,2'-azobis(2-methylpropionate). After completion of the dropwise addition, the reaction was further carried out at 110 ° C for 3 hours.

Next, the gas in the flask was replaced with air, and 32 parts of glycerol methacrylate (66% of carboxyl groups), 32 parts of cyclohexanone, 0.5 part of trimethylolamine phenol, and 0.1 of hydroquinone were supplied to the flask. unit. The reaction was continued at 90 ° C for 6 hours to obtain a solution of an acrylic resin. Here, the reaction rate of glycerol methacrylate was determined from the change in the acid value of the polymer before and after the reaction. the result, The reaction rate was 99%.

After the resin solution was cooled to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure a nonvolatile component. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 20 was thus obtained. The measurement results of the weight average molecular weight obtained for the resin solution 20 are shown in Tables 1 to 3.

(Modulation of Resin Solution 21)

Into four separate flasks equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube and a stirring device, 233 parts of cyclohexanone, 20 parts of methacrylic acid, and p-cumylphenol ethylene oxide-modified acrylic acid were injected. 30 parts of ester, 19 parts of benzyl methacrylate, 16 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, and 15 parts of octyl thiol were heated to 80 °C. After replacing the gas in the flask with nitrogen, 1.33 parts of 2,2'-azobisisobutyronitrile was added to the liquid in the flask. The reaction was continued for 5 hours, whereby a resin solution having a weight average molecular weight (Mw) of 1,500 was obtained.

After cooling the resin solution to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure the non-volatile components. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 21 was thus obtained. The measurement results of the weight average molecular weight obtained for the resin solution 21 are shown in Tables 1 to 3.

(modulation of resin solution 22)

Into four separate flasks equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube and a stirring device, 233 parts of cyclohexanone, 20 parts of methacrylic acid, and p-cumylphenol ethylene oxide-modified acrylic acid were injected. 30 parts of ester, 19 parts of benzyl methacrylate, 16 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, and 11 parts of octyl thiol were heated to 80 °C. After replacing the gas in the flask with nitrogen, 0.9 parts of 2,2'-azobisisobutyronitrile was added to the liquid in the flask. The reaction was continued for 5 hours, whereby a resin solution having a weight average molecular weight (Mw) of 25,000 was obtained.

After cooling the resin solution to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure the non-volatile components. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. The resin solution 22 was thus obtained. The measurement results of the weight average molecular weight obtained for the resin solution 22 are shown in Tables 1 to 3.

(modulation of dispersion resin solution)

In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device, 233 portions of cyclohexanone were injected, and the temperature was raised to 80 °C. After the gas in the flask was replaced with nitrogen, 13 parts of methacrylic acid, 10 parts of methacrylic acid methyl group, 77 parts of methacrylic acid butyl group, and 2,2'- were dropped by dropping the tube over 2 hours. A mixture of azobisisobutyronitrile 1.33. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution having a weight average molecular weight (Mw) of 25,000.

After cooling the resin solution to room temperature, it was sampled at about 2 g, and heated at 180 ° C for 20 minutes to measure the non-volatile components. Using this measurement result, cyclohexanone was added so that the non-volatile component in the previously synthesized resin solution became 20% by weight. A dispersion resin solution was obtained as above.

(Modulation of photosensitive coloring composition for color filters)

Each of the pigment dispersions of Examples 1 to 18 and 20 to 26, and Comparative Examples 1 to 10 was prepared by the following method.

First, a pigment, a dispersing agent ("Solsparz 200000" manufactured by Lubrizol Co., Ltd.), a dispersion resin solution, and a solvent (propylene glycol monomethyl ether acetate) were mixed to uniformly disperse the pigment in the mixed solution. This mixing and dispersion system uses a planetary ball mill using zirconia beads as a pulverization medium. Thus, each of the pigment dispersions of Examples 1 to 18 and 20 to 26, and Comparative Examples 1 to 10 was obtained.

Further, the pigment dispersion of Example 19 was prepared by the following method.

First, a pigment, a dispersing agent ("Solsparz 200000" manufactured by Lubrizol Co., Ltd.), a resin solution 3, and a solvent (propylene glycol monomethyl ether acetate) were mixed to uniformly disperse the pigment in the mixed liquid. This mixing and dispersion system uses a planetary ball mill using zirconia beads as a pulverization medium. Thus, the pigment dispersion of Example 19 was obtained.

Tables 4 to 6 describe the types and content ratios of the respective components of the pigment dispersions, and the color index numbers of the pigments.

Further, the substances or matters indicated by the abbreviations listed in Tables 4 to 6 are specifically as follows.

‧P.R.254: C.I. Pigment Red 254 (diketopyrrolopyrrole red pigment)

‧P.R.177: C.I.Pigment Red 177 (蒽醌 red pigment)

‧P.Y.150: C.I.Pigment Yellow 150 (Azomethine yellow pigment)

‧P.G.36: C.I. Pigment Green 36 (copper copper phthalocyanine green pigment)

‧P.B.15:6:C.I.Pigment Blue 15:6 (copper phthalocyanine blue pigment)

‧P.V.23: C.I. Pigment Violet 23 (dioxazine violet pigment)

‧CB: carbon black (Pritex75 made by DEGUSSA)

Further, the notes of Tables 4 to 6 are described below.

‧Note 6: Change to resin solution 3.

Next, each of the pigment dispersions of Examples 1 to 26 and Comparative Examples 1 to 6 and 8 to 10, as shown in Tables 7 to 9, was mixed with a resin solution, an active energy ray-curable monomer (dipentaerythritol Acrylate), active energy ray polymerization initiator (2-(dimethylamine)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl) ]-1-butanone), a sensitizer (2,4-diethylthioxanthone) and a solvent (propylene glycol monomethyl ether acetate) were mixed. After sufficiently stirring, it was filtered with a filter, and coarse particles having a diameter of 1 μm or more were removed from the dispersion. Each of the photosensitive coloring compositions of Examples 1 to 26 and Comparative Examples 1 to 6 and 8 to 10 was prepared as above.

Further, the photosensitive coloring of Comparative Example 7 was prepared by the same method as that described for Comparative Example 1, except that a mixed solution of the comparative resin solution and the resin solution 3 was used in a weight ratio of 1:1 to obtain a resin solution. Composition.

(Dispersion stability assessment)

The viscosity of the photosensitive colored composition obtained by the above method at 25 ° C was measured using an E-type viscometer (TUE-20L type manufactured by TOKI SANGYO Co., Ltd.). Specifically, the number of rotations was set to 20 rpm, and the viscosity was measured after storing the photosensitive colored composition on the same day and storing it in a constant temperature room at 40 ° C for 7 days. Then, the viscosity of the photosensitive coloring composition will be produced on the day, That is, the initial viscosity (η 0 : mPa ‧ s), and the viscosity after storage for 7 days in a thermostatic chamber at 40 ° C (η 7 : mPa ‧ s) were evaluated with reference to the following criteria, and the storage stability of the photosensitive coloring composition was evaluated. The results are summarized in Tables 10 to 12 below.

○: The ratio η 7 / η 0 was less than 1.20, and the viscosity was hardly increased, and the dispersion stability was good.

△: The ratio η 7 / η 0 is 1.20 or more and less than 1.50, and the viscosity is slightly increased, and the dispersion stability is somewhat poor.

(Coloring pattern formation and developability evaluation)

On the transparent glass substrate of 10 × 10 cm, a red, green, and blue photosensitive coloring composition was spin-coated, and this was prebaked at 70 ° C for 20 minutes to obtain a coating film having a dried film thickness of about 2.0 μm.

Next, an intermediate mask is used to irradiate the coating film with ultraviolet rays. Here, the exposure amount was 50 mJ/cm ² . Further, the mask is provided in a stripe shape using the light shielding portion and the light transmission portion.

Next, the coating film was developed with an alkali developing solution. Here, by observing the progress of development, the elapsed time (T1) from the start of development required for the entire unexposed portion to be dissolved is determined, and development is continued for 1.5 times of the time T1.

The color patterns of the red, green, and blue colors are obtained as above.

In addition, a black coloring pattern was obtained in the same manner as described above except that the black photosensitive coloring composition was used and the exposure amount was changed to 100 mJ/cm ² .

The coloring pattern obtained as described above was observed, and the presence or absence of peeling was examined. The results were compared with the time T1 with reference to the following criteria, and the developability of each photosensitive coloring composition was evaluated. The results are summarized in Tables 10 to 12 below.

○: Time T1 was less than 60 sec and no pattern peeling occurred.

×: Time T1 was 60 sec or more or pattern peeling occurred.

(pattern shape evaluation)

A glass substrate having a colored pattern was formed by the above method, and cut into a half size (5 cm × 10 cm) to prepare two test pieces.

Only one of the test pieces was post-baked in a high temperature oven set at 230 ° C for 20 minutes. Next, each of the test pieces after the post-baking was cut into 1 cm square, and Pt and Pd were vapor-deposited using a sputtering apparatus (E-1030) manufactured by Hitachi, Ltd. on the surface on which the colored pattern was provided. Next, using a scanning electron microscope (S-4300) manufactured by Hitachi, Ltd., the acceleration voltage was set at 15 kV, and the observation magnification was set at 10,000 times, and the cross-sectional shape of the colored pattern was observed. Then, the cross-sectional shape of the colored pattern and the angle (θ) formed by the edge portion of the cross section of the glass substrate main surface and the colored pattern were evaluated with reference to the following criteria, and the pattern shape was evaluated. The results are indicated in the fields after "post-baking" in Tables 10 to 12 below.

Further, regarding the remaining test pieces which were not post-baked, the pattern shape evaluation was also carried out by the same method as described above. The results shown in the following Tables 10 to 12 are indicated as "after development", and the results are described.

◎: a positive taper of θ<20.

○: a forward taper of 20 ≦ θ ≦ 45.

△: a forward taper of 45 ≦ θ ≦ 80.

×: θ>80 is clear and tapered or has a drape.

Further, in the comparative example, the development time T1 was 60 sec, which was a defective product, and therefore the pattern shape evaluation was not performed.

<Reworkability Assessment>

The sample for the above-mentioned developability evaluation, that is, the substrate on which the colored pattern was formed, was post-baked at 230 ° C for 90 minutes.

2 mL of a reconstituted liquid heated to 65 ° C (SEMICLEAN DF-7 manufactured by Yokohama Oil & Fats Co., Ltd.) was placed in a petri dish, and the sample was immersed in the redo liquid for 5 minutes. After 5 minutes, the redo liquid and the sample were transferred from the culture dish to the round bottom flask, and then the redo liquid was filtered through a filter paper having a pore size of 5 μm and a diameter of 3 cm. Then, using an optical microscope with a size measuring function, the size of the peeling sheet spread out on the filter paper was measured.

Specifically, the measurement was carried out in the following manner. That is, the following area is observed at a magnification of 500: the central area of the filter paper; the distance from the central area is 1 cm, the central area is sandwiched therebetween and arranged in two areas in the lateral direction; and the distance from the previous central area is 1 cm, The central area is sandwiched between them and arranged in two areas in the longitudinal direction. Next, in each field of view, 10 peeling pieces are sequentially selected from the largest maximum length, and 50 peeling pieces are selected for the total of the selection. Find the average of the maximum length. Then, the average of the maximum lengths thus obtained, that is, the average maximum length, is evaluated with reference to the following criteria, and the redo is evaluated. The results are summarized in Tables 10 to 12 below.

◎: Dissolved (there was no peeling sheet confirmed by an optical microscope).

○: The average maximum length is less than 300 μm.

△: The average maximum length is 300 μm or more and less than 500 μm.

×: The average maximum length is 500 μm or more.

In Examples 1 to 22 and Comparative Examples 1 and 4 to 10 in which the resin solutions 1 to 18 were used, the change in viscosity with time was small, and the dispersion stability was good. Further, in Comparative Examples 2 and 3, the ratio η 7 / η 0 was 1.20 or more, with time The viscosity between the passes is greatly increased.

Further, in any of Examples 1 to 26 and Comparative Examples 1 to 10, the colored patterns before post-baking were suspended. That is, in any of Examples 1 to 26 and Comparative Examples 1 to 10, the pattern shape before post-baking was poor. Then, in Comparative Examples 1 to 10, the pattern shape remained poor even after post-baking.

On the other hand, in Examples 1 to 26, the pattern shape after post-baking has a cross section of a forward taper. That is, the coloring patterns of Examples 1 to 26 confirmed the thermal fluidity. Among these, the color patterns of Examples 3, 16, 19 to 24, and 26 have the most excellent pattern shapes.

Further, in Examples 1 to 26, reworkability superior to that of Comparative Example 3 was achieved, and reworkability equivalent to or superior to Comparative Examples 3, 5 to 8, and 10 was achieved. Among these, particularly in Examples 18 and 23, particularly good reworkability can be achieved.

Claims (6)

A photosensitive coloring composition comprising: a resin (A), a pigment (B), an active energy ray polymerization initiator (C), an active energy ray-curable monomer (D), and a solvent (E); The resin (A) contains a vinyl resin (F) in a ratio of 50% by weight or more; the vinyl resin (F) contains a constituent unit (a) having a carboxyl group in a ratio of 2 to 50% by weight, and The ratio of 2 to 50% by weight includes a fat having an aromatic ring represented by the following general formula (1), an aromatic ring represented by the following general formula (2), and the following general formula (3). a constituent unit (b) of one or more cyclic structures of a group consisting of a group ring and an aliphatic ring represented by the following general formula (4), and having a composition of 10 to 80% by weight The unit (c), wherein the precursor (c) precursor (c1) comprises one or more selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl acrylate. The monomer, and methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl acrylate are contained in the constituent unit (c) in a weight percentage of 50% or more. (In the above general formulas (1) and (2), R is a hydrogen atom, or may have a benzene ring and an alkyl group having 1 to 20 carbon atoms) General formula (4): The photosensitive coloring composition according to claim 1, wherein one or more constituent units selected from the group consisting of the constituent units (a), (b), and (c) have ethylene bonding. . The photosensitive coloring composition according to the first aspect of the invention, wherein the component (a) precursor (a1) is one or more monomers selected from the group consisting of acrylic acid and methacrylic acid. . The photosensitive coloring composition according to claim 1, wherein at least a part of the carboxyl group of the structural unit (a) is added by adding a polyvalent acid anhydride to a constituent unit having a hydroxyl group, or by additionally The constituent unit of the epoxy group and the hydroxyl group formed by the unsaturated monovalent acid are introduced by adding a polyvalent acid anhydride. The photosensitive coloring composition according to Item 1, wherein the constituent unit (b) precursor (b1) is selected from the group consisting of styrene, a-methylstyrene, anthracene, benzyl acrylate, and benzyl. a group consisting of a methyl acrylate, a monomer represented by the following general formula (5), a monomer represented by the following general formula (6), and a monomer represented by the following general formula (7); One or more monomers. General formula (5): (In the above general formulas (5) to (7), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a benzene ring and a carbon number of 1 to 20 alkyl, n is an integer from 1 to 15, and m is an integer from 0 to 2) A color filter comprising at least one of a filter segment and a black matrix formed by the photosensitive coloring composition according to any one of claims 1 to 5.