KR20090129345A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition is provided to improve ink repellency, thereby allowing to be applied for the formation of the black matrix of a color filter. CONSTITUTION: A colored photosensitive resin composition comprises a photopolymerizable compound; an ink repelling compound; a photopolymerization initiator; and a colorant, wherein the ink repelling compound is a copolymer obtained by copolymerizing a monomer having an ethylenically unsaturated group and a fluorine atom and acrylic acid. The content of the unit derived from the monomer having an ethylenically unsaturated group and a fluorine atom is 30 ~ 80 mass %, and the content of the unit derived from the acrylic acid is 0.1 ~ 20 mass %.

Description

Colored photosensitive resin composition {COLORED PHOTOSENSITIVE RESIN COMPOSITION}

TECHNICAL FIELD This invention relates to a coloring photosensitive resin composition. Specifically, It is related with the coloring photosensitive resin composition preferable to be used when forming the black matrix of a color filter.

Display bodies, such as a liquid crystal display, have a structure which sandwiches a liquid crystal layer between two board | substrates with which the paired electrode was mutually opposed. And inside the one board | substrate, the color filter which has the pixel area which consists of each color, such as red (R), green (G), blue (B), is formed. In this color filter, a black matrix is usually formed in a matrix so as to partition pixel regions of each of R, G, and B colors in order to improve contrast, prevent light leakage, and the like.

Conventionally, a color filter forms a black matrix by the lithography method, and repeats application | coating, exposure, and image development for each photosensitive resin composition of each color of R, G, and B in each area | region partitioned by the said black matrix, It has been manufactured by forming a pattern at a predetermined position. However, in order to improve productivity, the method of manufacturing a color filter by the inkjet method is examined. In this inkjet method, a color filter is produced by discharging inks of R, G, and B colors from inkjet nozzles to respective regions partitioned by the formed black matrix, and curing the collected ink with heat or light.

By the way, in the photosensitive resin composition used for forming a black matrix in this inkjet method, in order to prevent the mixing of ink between adjacent pixel regions, the so-called foot (which is solvent repellent against ink solvents such as water and xylene) is used. I) Ink properties are required.

As the photosensitive resin composition which has such ink repellency, For example, patent document 1 contains the C20 or less alkyl group in which at least 1 of a hydrogen atom was substituted by the fluorine atom (However, the said alkyl group includes the thing which has an ether oxygen atom. The negative photosensitive resin composition which contained the ink repellent agent which consists of a polymer which has a polymer unit which has a polymerizing unit which has a polymerizable unit which has an), and an ethylenic double bond is disclosed. In this negative photosensitive resin composition, ink repellency is obtained by the fluoroalkyl group made from ink repellents. Moreover, since an ink repellent agent has the polymer unit which has an ethylenic double bond, it hardens | cures by light irradiation and ink repellency persists.

Patent Document 1: International Publication No. 2004/042474 Pamphlet

However, although the ink repellency can be sustained in the negative photosensitive resin composition described in this patent document 1, ink repellency itself is not still satisfactory, and it is desired to improve ink repellency further. . In particular, in manufacturing displays such as medium and small liquid crystal displays by the inkjet method, in order to cope with the miniaturization of the pixel size, it is necessary to further improve ink repellency.

This invention is made | formed in view of the above subject, and an object of this invention is to provide the colored photosensitive resin composition with which ink repellency was further improved.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by containing a specific ink repellent compound in a coloring photosensitive resin composition, and came to complete this invention. Specifically, the present invention provides the following.

The colored photosensitive resin composition which concerns on this invention is a colored photosensitive resin composition containing a photopolymerizable compound (A), ink repellent compound (B), a photoinitiator (C), and a coloring agent, The said ink repellent compound ( B) is a copolymer obtained by copolymerizing at least a monomer (b1) having an ethylenically unsaturated group and a fluorine atom and acrylic acid (b2).

According to this invention, the coloring photosensitive resin composition with more ink repellency can be provided. This coloring photosensitive resin composition is suitable for use, for example when forming the black matrix of a color filter.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

The colored photosensitive resin composition which concerns on this invention contains a photopolymerizable compound (A), ink repellent compound (B), a photoinitiator (C), and a coloring agent (D). Hereinafter, each component is demonstrated.

[Photopolymerizable Compound (A)]

The photopolymerizable compound (A) is a substance which is polymerized by being irradiated with light such as ultraviolet rays and cured. As a photopolymerizable compound (A), resin or monomer which has an ethylenically unsaturated group is preferable, and it is more preferable to combine these. By combining the resin which has an ethylenically unsaturated group, and the monomer which has an ethylenically unsaturated group, sclerosis | hardenability can be improved and pattern formation can be made easy. In the present specification, among the compounds having an ethylenically unsaturated group, those having a mass average molecular weight of 1000 or more are referred to as "resins having an ethylenically unsaturated group", and those having a mass average molecular weight of less than 1000 are referred to as "monomers having an ethylenically unsaturated group". do.

`` Resin having an ethylenically unsaturated group ''

Examples of the resin having an ethylenically unsaturated group include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, and ethylene Glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth ) Acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, butylene glycol dimethacrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, te Methylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylic Oligomers in which a rate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, and the like are polymerized; After reacting a polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing polyhydric alcohols with monobasic acid or polybasic acid, a compound having a polyol and two isocyanate groups, (meth) Polyurethane (meth) acrylates obtained by reacting acrylic acid; Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol or cresol novolak type epoxy resin, resor type epoxy resin, triphenol methane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol And epoxy (meth) acrylate resins obtained by reacting epoxy resins such as polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins with (meth) acrylic acid. Moreover, resin which made polybasic acid anhydride react with epoxy (meth) acrylate resin can be used.

Moreover, as resin which has an ethylenically unsaturated group, resin obtained by making the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) further react with polybasic acid anhydride (a3) can be used preferably. have.

<Epoxy compound (a1)>

As an epoxy compound (a1), glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type, bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, naphthalene type, fluorene type And phenol novolac type and orthocresol type epoxy resins. Especially, a biphenyl type epoxy resin is preferable. The biphenyl type epoxy resin has one or more biphenyl skeleton represented by following formula (a1-1) in a principal chain, and has one or more epoxy groups. Moreover, as an epoxy compound (a1), what has two or more epoxy groups is preferable. This epoxy compound (a1) can be used individually or in combination of 2 or more types.

In Formula (a1-1), some R <^1a> represents a hydrogen atom, the C1-C12 alkyl group, the halogen atom, or the phenyl group which may have a substituent each independently, and l represents the integer of 1-4.

Of the biphenyl type epoxy resins, epoxy resins represented by the following formula (a1-2) are preferably used, and epoxy resins represented by the following formula (a1-3) are particularly preferably used. By using the epoxy resin of Formula (a1-3), the coloring photosensitive resin composition excellent in the balance of a sensitivity and solubility, and also excellent in the sharpness and adhesiveness of a pixel edge can be obtained.

In Formula (a1-2) and (a1-3), some R <^2a> respectively independently represents a hydrogen atom, a C1-C12 alkyl group, a halogen atom, or the phenyl group which may have a substituent, p is 1-4 Represents an integer. q represents the number of 0-10 as an average value, and it is preferable that it is less than one.

Moreover, the epoxy resin represented by a following formula (a1-4) is also used preferably in biphenyl type epoxy resin. By using the epoxy resin of Formula (a1-4), the coloring photosensitive resin composition excellent in the balance of a sensitivity and solubility, and also excellent in the sharpness and adhesiveness of a pixel edge can be obtained.

In Formula (a1-4), a plurality of R ^{3a 's} each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent. r represents the number of 0-10 as an average value, and it is preferable that it is less than one.

<Ethylenic unsaturated group containing carboxylic acid compound (a2)>

As an ethylenic unsaturated group containing carboxylic acid compound (a2), the monocarboxylic acid compound containing reactive ethylenic double bonds, such as an acryl group and a methacryl group, in a molecule | numerator is preferable. Examples of such ethylenically unsaturated group-containing carboxylic acid compounds include acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfuryl acrylic acid, α-cyano cinnamic acid, and cinnamic acid. This ethylenically unsaturated group containing carboxylic acid compound (a2) can be used individually or in combination of 2 or more types.

A well-known method can be used as a method of making an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) react. For example, tertiary amines, such as triethylamine and benzylethylamine, dodecyl trimethylammonium chloride, tetramethylammonium chloride, and tetraethyl are used for the epoxy compound (a1) and the ethylenically unsaturated group-containing carboxylic acid compound (a2). Quaternary ammonium salts, such as ammonium chloride and benzyl triethylammonium chloride, a pyridine, a triphenylphosphine, etc. are used as a catalyst, and the method of making it react for several hours-several tens of hours in reaction temperature 50-150 degreeC in an organic solvent.

The usage-amount ratio in reaction of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) is a carbon equivalent of the epoxy equivalent of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2). In ratio of acid equivalent, it is usually 1: 0.5-1: 1, Preferably it is 1: 0.8-1: 1.25, More preferably, it is 1: 1. By setting it as the said range, there exists a tendency for crosslinking efficiency to improve.

<Polybasic acid anhydride (a3)>

The polybasic acid anhydride (a3) is an anhydride of a carboxylic acid having two or more carboxyl groups, and contains a compound having at least two benzene rings. As such polybasic acid anhydride (a3), for example, an acid anhydride having a biphenyl skeleton represented by the following formula (a3-1), and an acid anhydride in which two benzene rings represented by the following formula (a3-2) are bonded to an organic group. Can be mentioned.

In formula (a3-2), R <^4a> represents the alkylene group which may have a C1-C10 substituent.

By using the anhydride of the carboxylic acid which has the said 2 or more carboxyl groups, at least 2 benzene rings can be introduce | transduced in a photopolymerizable compound (A).

Moreover, polybasic acid anhydride (a3) may contain other polybasic acid anhydride other than the acid anhydride which has at least two said benzene rings. As other polybasic acid anhydride, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methylhexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, trimelli anhydride, for example. Acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3-ethylhexahydro phthalic anhydride, 4-ethylhexahydro phthalic anhydride, tetrahydro Phthalic anhydride, 3-methyl tetrahydro phthalic anhydride, 4-methyl tetrahydro phthalic anhydride, 3-ethyl tetrahydro phthalic anhydride, 4-ethyl tetrahydro phthalic anhydride is mentioned. These polybasic acid anhydrides can be used individually or in combination of 2 or more types.

After reacting an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2), a well-known method can be used as a method of making a polybasic acid anhydride (a3) react further. In addition, the usage-amount ratio is an equivalence ratio of the number-of-moles of OH group in the reaction material of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2), and the acid anhydride group of polybasic acid anhydride (a3), and is usually 1: 1. 1-1: 0.1, Preferably it is 1: 0.8-1: 0.2. By setting it as the said range, there exists a tendency for the solubility to a developing solution to become appropriate.

The acid value of resin obtained by making the reactant of an epoxy compound (a1) and an ethylenically unsaturated group containing carboxylic acid compound (a2) further react with a polybasic acid anhydride (a3) is 10-150 mgKOH / g in resin solid content. It is preferable, More preferably, it is 70-110 mgKOH / g. By making the acid value of resin into 10 mgKOH / g or more, sufficient solubility to a developing solution can be obtained, and by setting it as 150 mgKOH / g or less, sufficient hardenability can be obtained and surface quality can be made favorable.

Moreover, it is preferable that the mass mean molecular weight of resin is 1000-400000, More preferably, it is 2000-30000. By setting the mass average molecular weight to 1000 or more, heat resistance and film strength can be improved, and by setting it to 40000 or less, sufficient solubility in a developer can be obtained.

Moreover, as resin which has an ethylenically unsaturated group, resin which has a cardo structure in a molecule | numerator can be used preferably. Since resin which has a cardo structure has high heat resistance and chemical-resistance, it can improve the heat resistance and chemical-resistance of a coloring photosensitive resin composition by using it for a photopolymerizable compound (A). For example, resin represented by a following formula (a3-3) can be used preferably.

In formula (a3-3), X is a group represented by the following formula (a3-4).

In the formula (a3-3), Y is maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chloric anhydride, methyl It is a residue remove | excluding the carboxylic anhydride group (-CO-O-CO-) from dicarboxylic anhydrides, such as tetrahydro phthalic anhydride and glutaric anhydride.

In formula (a3-3), Z is tetracarboxylic acid such as pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. It is the residue which removed two carboxylic anhydride groups from dianhydride.

In addition, in formula (a3-3), s is an integer of 0-20.

<< monomer having an ethylenically unsaturated group >>

The monomer which has an ethylenically unsaturated group has a monofunctional monomer and a polyfunctional monomer.

As a monofunctional monomer, (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymeth Methoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, Citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic 2-phenoxy-2-hydroxypropyl (meth) acrylic , 2- (meth) acryloyloxy-2-hydroxypropylphthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl ( Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, half (meth) acrylate of phthalic acid derivatives, and the like. Can be mentioned. These monofunctional monomers can be used individually or in combination of 2 or more types.

On the other hand, as a polyfunctional monomer, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin Di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy 3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglyci Diester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate (ie, tolylene diiso cyanate), trimethylhexamethylene diisocyanate and hexa Methylene diisocyanate and the like, reactants of 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and the like. Multifunctional Meona furnace, and the like can be triacrylate formal. These polyfunctional monomers can be used individually or in combination of 2 or more types.

It is preferable that content of the monomer which has this ethylenically unsaturated group is 5-50 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 10-40 mass%. By setting it as the said range, since there exists a tendency which is easy to balance the sensitivity, developability, and resolution, it is preferable.

It is preferable that content of a photopolymerizable compound (A) is 5-50 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 10-40 mass%. By setting it as the said range, since there exists a tendency which is easy to balance the sensitivity, developability, and resolution, it is preferable.

[Ink repellent compound (B)]

 An ink repellent compound (B) is a copolymer which copolymerized at least the monomer (b1) which has an ethylenically unsaturated group and a fluorine atom, and acrylic acid (b2). By using such ink repellent compound (B), the coloring photosensitive resin composition which has high ink repellency can be obtained.

<Monomer (b1) which has an ethylenically unsaturated group and a fluorine atom>

 The monomer having an ethylenically unsaturated group and a fluorine atom (hereinafter also referred to as "monomer (b1)") is not particularly limited as long as it has an ethylenically unsaturated group and a fluorine atom. As such a monomer (b1), the compound etc. which are represented by following formula (b1-1) are mentioned. These monomers (b1) can be used individually or in combination of 2 or more types.

In formula (b1-1), X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom, a methyl group, or a perfluoromethyl group, and X ⁴ and X ⁵ are A hydrogen atom, a fluorine atom, or a perfluoromethyl group, Rf represents a C1-C40 fluorine-containing alkyl group or a C2-C100 ether bond, a represents an integer of 0-3, b and c each independently represent 0 or 1;

It is preferable that content of the unit guide | induced from a monomer (b1) is 30-80 mass% with respect to an ink repellent compound (B), More preferably, it is the range of 40-60 mass%. By setting it as the said range, since there exists a tendency for compatibility with other components of ink repellency and colored photosensitive resin composition to become favorable, it is preferable.

It is noted that in the monomer (b1), - it is preferable to have a group represented by _{(CF 2) t F (t} = 1 ~ 10). It is more preferable that it is 1-8, and it is still more preferable that it is 2-6. By having said group, compatibility with other components of ink repellency and colored photosensitive resin composition tends to become favorable, and it is preferable.

<Acrylic acid (b2)>

 In order to adjust an acid value and to improve developability, an ink repellent compound (B) needs to copolymerize the monomer which has a carboxyl group. As a monomer which has a carboxyl group, various monomers, such as (meth) acrylic acid, are mentioned. Especially, acrylic acid is more preferable than methacrylic acid. By copolymerizing acrylic acid (b2), the contact angle with respect to a solvent becomes high compared with methacrylic acid, and ink repellency can be improved more.

It is preferable that content of the unit guide | induced from acrylic acid (b2) is 0.1-20 mass% with respect to ink repellent compound (B). By setting it as said range, ink repellency and developability tend to become suitable, and it is preferable.

 <Other monomer>

 You may copolymerize another monomer with an ink repellent compound (B) as needed. As such another monomer, the various monomers described below are mentioned.

<Monomer (b3) which has an ethylenically unsaturated group and an epoxy group>

 The ink repellent compound (B) is preferably a copolymer obtained by copolymerizing a monomer having an ethylenically unsaturated group and an epoxy group (hereinafter also referred to as "monomer (b3)"). By copolymerizing a monomer (b3), ink repellency can be improved more.

As a monomer (b3), an alicyclic epoxy compound represented by glycidyl (meth) acrylate, following formula (b3-1)-(b3-3), the carboxyl group of (meth) acrylic acid, and the epoxy group of the bifunctional or more functional epoxy compound The monomer etc. which are obtained by making the hydroxyl group or the carboxyl group of the acryl-type monomer which have a hydroxyl group and a carboxyl group react with the epoxy group of the epoxy compound of a bifunctional or more than 2 functional group in the monomer obtained by reaction, and a side chain are mentioned. Especially, glycidyl (meth) acrylate is preferable. These monomers (b3) can be used individually or in combination of 2 or more types.

In formulas (b3-2) and (b3-3), R ^1b represents a hydrogen atom or a methyl group, u represents an integer of 1 to 10, and ｖ and w each independently represent an integer of 1 to 3.

Although the unit guide | induced from a monomer (b3) is an arbitrary component, it is preferable that content when it contains is 1-40 mass% with respect to ink repellent compound (B), More preferably, it is 5-15 mass% Range. By setting it as the said range, ink repellency tends to improve and it is preferable.

<Monomer (b4) which has a structure represented by Formula (b4-1)>

 It is preferable that the ink repellent compound (B) is a copolymer obtained by further copolymerizing a monomer having a structure represented by an ethylenically unsaturated group and the following formula (b4-1) (hereinafter also referred to as "monomer (b4)"). . By copolymerizing a monomer (b4), compatibility with other components of developable and colored photosensitive resin composition can be improved.

As for this monomer (b4), it is more preferable to have a structure represented by an ethylenically unsaturated group and following formula (b4-2).

In formulas (b4-1) and (b4-2), R ^2b represents an alkylene group having 1 to 5 carbon atoms, and may be linear or branched. Especially, a C1-C3 alkylene group is preferable and an ethylene group is the most preferable. R ^3b represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and may be linear or branched. Especially, a C1-C3 alkyl group is preferable and a methyl group is the most preferable. As said substituent, a carboxyl group, a hydroxyl group, a C1-C5 alkoxy group, etc. are mentioned. x represents an integer of 1 or more, an integer of 1 to 60 is preferable, and an integer of 1 to 12 is more preferable.

As such a monomer (b4), the compound etc. which are represented by following formula (b4-3) are mentioned. These monomers (b4) can be used individually or in combination of 2 or more types.

In formula (b4-3), R ^4b represents a hydrogen atom or a methyl group. R <^2b> , R <^3b> , and x are synonymous with the said Formula (b4-1) and (b4-2).

It is preferable that content of the unit guide | induced from a monomer (b4) is 1-40 mass% with respect to an ink repellent compound (B), More preferably, it is the range of 5-15 mass%. By setting it as said range, since there exists a tendency for compatibility with the other component of developability and a coloring photosensitive resin composition to become favorable, it is preferable.

<Monomer (b5) having a silicon atom>

 It is preferable that an ink repellent compound (B) is a copolymer which further copolymerized the monomer which has a silicon atom (henceforth "monomer (b5)"). Monomer (b5) will not be specifically limited if it has an ethylenically unsaturated group and at least 1 alkoxy group couple | bonded with the silicon atom. By copolymerizing this monomer (b5), ink repellency can be improved more. At the time of image development of the coating film which consists of colored photosensitive resin composition, this alkoxy group detach | desorbs by the action of the water contained in a developing solution, a silanol is produced | generated, and a post-baking superposes | polymerizes a silanol with another organic component, It is thought that the surface is hardened.

As such a monomer (b5), the compound etc. which are represented by following formula (b5-1) are mentioned. These monomers (b5) can be used individually or in combination of 2 or more types.

In formula (b5-1), R ^5b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group. R <^6b> represents a C1-C20 alkylene group or a phenylene group, Preferably it is a C1-C10 alkylene group. R <^7b> , R <^8b> represent a C1-C10 alkyl group or a phenyl group each independently, Preferably they are a C1-C3 alkyl group. When some R <^7b> is couple | bonded with Si, the some R <^7b> may be same or different. Moreover, when some ( ^OR8b ) is couple | bonded with Si, the some ( ^OR8b ) may be same or different. m represents 0 or 1, Preferably it is 1. n represents the integer of 1-3, Preferably it is n = 2, 3, More preferably, it is n = 3.

It is preferable that content of the unit guide | induced from a monomer (b5) is 20 mass% or less with respect to an ink repellent compound (B), More preferably, it is the range of 10 mass% or less. By setting it as said range, since there exists a tendency for the compatibility with other components of ink repellency and colored photosensitive resin composition to become favorable, it is preferable.

As another monomer, the monomer which has the ethylenically unsaturated group mentioned above is mentioned. Especially, an acryl-type monomer is preferable. Examples of such acrylic monomers include 2-hydroxyethyl methacrylate (HEMA), N-hydroxymethylacrylamide (N-MAA), methyl methacrylate (MAA), cyclohexyl methacrylate (CHMA), Isobornyl methacrylate (IBMA) etc. are mentioned. It is preferable that content of the unit guide | induced from another monomer is 0-20 mass% with respect to an ink repellent compound (B).

As a method of obtaining a copolymer by making monomer (b1) and (b2) and another monomer react as needed, a well-known method can be used.

It is preferable that the mass mean molecular weights of an ink repellent compound (B) are 2000-50000, More preferably, it is 5000-20000. By setting the mass average molecular weight to 2000 or more, heat resistance and film strength can be improved, and by setting it as 50000 or less, developability can be improved.

Moreover, it is preferable that mass ratio of a photopolymerizable compound (A) and an ink repellent compound (B) is 99.9: 0.1-70: 30, as content of ink repellent compound (B). By setting it as the said range, it exists in the tendency to balance the sensitivity, developability, resolution, ink repellency, and it is preferable.

[Photoinitiator (C)]

As a photoinitiator (C), 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, ethanone- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphineoxide, 4 -Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoate butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4 Dimethylamino-2-isoamylbenzoic acid, benzyl-β- Oxyethylacetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, 2,4-diethyl thioxanthone, 2-chloro Thioxanthone, 2,4-dimethyl thioxanthone, 1-chloro-4-propoxy thioxanthone, thioxanthene, 2-chloro thioxanthene, 2,4-diethyl thioxanthene, 2-methyl thi Oxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, Cumeneperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl)- Imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3 -Dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoinme Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroaceto Phenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropyl thioxanthone, dibenzosuberon, pentyl-4-dimethylaminobenzoate, 9- Phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxysty Reyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6 -(2-bromo-4-methoxy) styrylphenyl-s-triazine, etc. are mentioned. Especially, using an oxime system photoinitiator is especially preferable at the point of a sensitivity. These photoinitiators can be used individually or in combination of 2 or more types.

It is preferable that content of a photoinitiator (C) is 0.5-30 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is the range of 1-20 mass%. By setting it as the said range, sufficient heat resistance and chemical-resistance can be obtained, a coating film formation ability can be improved, and a photocuring defect can be suppressed.

[Colorant (D)]

As a coloring agent (D), light-shielding agents, such as carbon black and titanium black, are mentioned. Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, Al, etc. Inorganic pigments such as various metal oxides, complex oxides, metal sulfides, metal sulfates, or metal carbonates.

As carbon black, well-known carbon black, such as channel black, furnace black, thermal black, and lamp black, can be used, Especially since channel black is excellent in light-shielding property, it can be used preferably. Moreover, resin coating carbon black can also be used. Specifically, the resin-coated carbon black obtained by mixing the carbon black and the resin having reactivity with the carboxyl group, hydroxyl group, carbonyl group present on the surface of the carbon black and heating at 50 to 380 degrees, or a water-organic solvent mixture system or water- The resin coating carbon black etc. which were obtained by disperse | distributing an ethylenic monomer to surfactant mixed system and radical polymerization or radical copolymerization in presence of a polymerization initiator are mentioned. Since the resin-coated carbon black has lower conductivity than carbon black without a resin coating, when used as a color filter such as a liquid crystal display, there is little leakage of current, and a highly reliable low power display can be formed.

As a coloring agent, you may add an organic pigment as an auxiliary pigment to said inorganic pigment. By appropriately selecting and adding an organic pigment which shows the complementary color of an inorganic pigment, the following effects are acquired. Carbon black, for example, exhibits a reddish black color. Therefore, by adding the organic pigment which shows blue which is a red complementary color to carbon black as an auxiliary pigment, the red tinge of carbon black disappears and it shows more preferable black as a whole. It is preferable to use an organic pigment in 10-80 mass% with respect to the sum total of an inorganic pigment and an organic pigment, More preferably, it is 20-60 mass%, More preferably, it is 20-40 mass%.

As said inorganic pigment and organic pigment, the solution which disperse | distributed the pigment to appropriate density | concentration using the dispersing agent can be used. For example, as an inorganic pigment, the carbon dispersion liquid CF black (containing 20% of carbon concentration) by the Mikuni dye company, the carbon dispersion liquid CF black (containing 24% of high resistance carbon) by the Mikuni dye company, the titanium product made by Mikuni dyeing company And black dispersion CF black (containing 20% black titanium pigment). Moreover, as an organic pigment, the blue pigment dispersion liquid CF blue (20% of blue pigment containing) from Mikuni dye company, the violet pigment dispersion liquid (10% of violet pigment production) from Mikuni dye company are mentioned, for example. Moreover, as a dispersing agent, the polymer dispersing agent of a polyethyleneimine system, a urethane resin system, and an acrylic resin system is used preferably.

It is preferable that content of a coloring agent is 10-70 mass% with respect to solid content of a coloring photosensitive resin composition. By making content into 70 mass% or less, the photocuring defect can be suppressed, and by making it into 10 mass% or more, sufficient light-shielding property can be obtained. Moreover, it is preferable to adjust the density | concentration of a coloring agent so that OD (Optical Density) value per 1 micrometer of film thickness may be 1.5 or more, when forming a black matrix using the coloring photosensitive resin composition of this invention as mentioned later. . When the OD value per 1 micrometer of film thickness is 1.5 or more, sufficient contrast can be obtained when it is used for the black matrix of a liquid crystal display.

[solvent]

It is preferable that the coloring photosensitive resin composition which concerns on this invention contains the solvent for dilution. As this solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether (Poly) alkylene glycols such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether No ether; (Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methyl Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methyl moiety Methyl carbonate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-acetic acid Butyl, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate Methyl acetoacetate, acetoacetic acid Butyl, and other esters such as ethyl 2-oxo-butanoic acid; Aromatic hydrocarbons such as toluene and xylene; Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like. These solvents can be used individually or in combination of 2 or more types.

It is preferable that content of a solvent is 50-500 mass parts with respect to 100 mass parts of solid content of a coloring photosensitive resin composition.

[Other ingredients]

The coloring photosensitive resin composition of this invention can be made to contain an additive as needed. As an additive, a thermal polymerization inhibitor, an antifoamer, surfactant, a sensitizer, a hardening accelerator, an optical crosslinking agent, a photosensitizer, a dispersing agent, a dispersal auxiliary agent, a filler, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, etc. are mentioned. .

[Preparation method of colored photosensitive resin composition]

The colored photosensitive resin composition which concerns on this invention is obtained by mixing each said component with a stirrer. Moreover, you may filter using a filter so that the obtained mixture may be uniform.

[Method for producing color filter]

 First, the coloring photosensitive resin composition which concerns on this invention is apply | coated on a board | substrate using contact transfer type | mold coating apparatuses, such as a roll coater, a reverse coater, and a bar coater, and non-contact type coating apparatuses, such as a spinner (rotary coating apparatus) and a curtain flow coater. . As the substrate, a substrate having light transmittance is used.

Next, the applied coloring photosensitive resin composition is dried to form a coating film. The drying method is not particularly limited, and for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120 ° C., preferably 90 to 100 ° C. with a hot plate, and (2) several hours to several days at room temperature. You may use the method of leaving to stand and (3) the method of removing a solvent in a hot air heater or an infrared heater for several tens of minutes-several hours.

Next, this coating film is partially exposed by irradiating active energy rays, such as an ultraviolet-ray and an excimer laser beam, through a negative mask. Although the energy dose to irradiate differs also with the composition of a coloring photosensitive resin composition, about 30-2000mJ / cm <2> is preferable, for example.

Subsequently, the coating film after exposure is developed with a developing solution, and is patterned in a desired shape. The image development method is not specifically limited, For example, an immersion method, a spray method, etc. can be used. Examples of the developing solution include organic compounds such as monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts.

Next, post-baking is performed about 200 degreeC of the pattern after image development. At this time, it is preferable to expose the formed pattern to the whole surface. By the above, the black matrix which has a predetermined pattern shape can be formed.

Subsequently, the ink of each of R, G, and B colors is discharged from the inkjet nozzle in each area partitioned by the black matrix, and the collected ink is cured by heat or light. Thereby, a color filter can be manufactured.

Example

<Example 1>

As a photopolymerizable compound (A), dipentaerythritol hexaacrylate was used as following resin (A-1) and monomer (A-3).

[Synthesis of Resin (A-1)]

 The synthesis | combining method of resin (A-1) is as follows.

235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were used at a rate of 25 ml / min. It heated and melt | dissolved in 90-100 degreeC, blowing air into the furnace, and it heated up slowly to 120 degreeC. In the meantime, the acid value was measured and heating and stirring was continued for about 12 hours until it became less than 1.0 mgKOH / g. And it cooled to room temperature and obtained the colorless transparent solid bisphenol fluorene type epoxy acrylate.

Subsequently, 350 g of propylene glycol monomethyl ether acetate (PGMEA) was added to and dissolved in 307.0 g of the bisphenol fluorene type epoxy acrylate obtained, followed by mixing 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. The reaction was carried out at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydro phthalic anhydride was mixed and reacted at 90 ° C for 6 hours to obtain a resin (A-1). In addition, the disappearance of the acid anhydride group was confirmed by IR spectrum. As for the obtained resin (A-1), the mass average molecular weight measured by GPC was 5000 and the acid value was 80 mgKOH / g. This resin (A-1) was adjusted to 55 mass% of solid content concentration with 3-methoxybutyl acetate.

 As ink repellent compound (B), the following compound (B-1) was used.

[Synthesis of Compound (B-1)]

 The synthesis method of a compound (B-1) is as follows.

Fluorinated monomer (CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ (CF ₂ ) ₄ F) 100 g, glycidyl methacrylate 8 g, acrylic acid 25 g, methoxydiethylene glycol methacrylate 32 g, chain transfer agent n-dode 7 g of silmercaptan and 2 g of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are dissolved in 384 g of 3-methoxybutyl acetate and stirred at 60 ° C. under a nitrogen atmosphere. The polymerization was carried out to obtain a copolymer. The obtained compound (B-1) had a mass average molecular weight of 8000 measured by GPC. In addition, this compound (B-1) was adjusted to 30 mass% of solid content concentration with 3-methoxybutyl acetate.

As a photoinitiator (C), CGI242 (Chiba Specialty Chemical Co., Ltd.) was used.

As the coloring agent (D), black pigment (manufactured by Mikuni Dyestuff Co., CF Black: 25% by mass of carbon black, solvent: 3-methoxybutyl acetate) was used.

Each said component and the solvent (3-methoxybutyl acetate: cyclohexanone = 60: 40) were mix | blended, and it mixed with the stirrer for 2 hours, and filtered with a 5 micrometer membrane filter, and prepared the coloring photosensitive resin composition.

<Comparative Example 1>

 A colored photosensitive resin composition was prepared in the same manner as in Example 1 except that acrylic acid was used instead of methacrylic acid.

<Evaluation>

 After apply | coating the coloring photosensitive resin composition prepared in the said Example 1 and the comparative example 1 on the glass substrate, it dried at 90 degreeC for 2 minutes, and obtained the photosensitive layer which has a film thickness of about 2 micrometers. Next, the photosensitive layer was selectively irradiated with ultraviolet light at an exposure dose of 200 mJ / cm 2 through a negative mask, and was developed at 25 ° C. using a solution of N-a3K (manufactured by Tokyo Oka Industry Co., Ltd.): pure water = 1: 25 as a developing solution. The pattern was formed by spray development for 60 seconds. Thereafter, the formed pattern was post-baked at 220 ° C. for 30 minutes to form a lattice black matrix pattern having a line width of 20 μm. And the solvent contact angle on a pattern was propylene glycol monomethyl ether (PM), 1, 3- butylene glycol diacetate (1, 3-BGDA), diethylene glycol monobutyl ether acetate (BDGAC), and diethylene glycol. Monoethyl ether acetate (EDGAC) and pure water were measured. The results are shown in Table 1.

Contact angle (PM) Contact angle (1,3-BGDA) Contact angle (BDGAC) Contact angle (EDGAC) Contact angle (pure) Example 1 45 degree 55.2 degrees 56.3 degrees 57.0 degrees 100 degree Comparative Example 1 40 degrees 54.3 degrees 55.0 degrees 55.8 degrees 102.3 degrees

PM: Propylene Glycol Monomethyl Ether Acetate

BGDA: 1,3-butylene glycol di-acetate

BDGAC: Dietelin Glycol Monobutyl Ether Acetate

EDGAC: Diethylene Glycol Monoethyl Ether Acetate

From Table 1, it turned out that the contact angle with respect to the organic solvent becomes large by using acrylic acid (Example 1) instead of methacrylic acid (comparative example 1). From this, it turned out that the ink repellency of the coloring photosensitive resin composition of this invention improves compared with the conventional thing. Moreover, when acrylic acid and methacrylic acid are compared, since methacrylic acid has many carbon numbers, it is generally considered that lipophilic property is high and hydrophilicity is low, but the coloring photosensitive resin composition which concerns on this invention has a surprisingly opposite effect. I knew it was.

Claims (8)

As colored photosensitive resin composition containing a photopolymerizable compound (A), an ink repellent compound (B), a photoinitiator (C), and a coloring agent (D), The ink repellent compound (B) is a copolymer obtained by copolymerizing at least a monomer (b1) having an ethylenically unsaturated group and a fluorine atom with acrylic acid (b2), wherein the colored photosensitive resin composition is used. The method of claim 1, Content of the unit guide | induced from the monomer (b1) which has the said ethylenically unsaturated group and a fluorine atom in the said ink repellent compound (B) is 30-80 mass%, and content of the unit guide | induced from acrylic acid (b2) is 0.1- Colored photosensitive resin composition which is 20 mass%. The method of claim 1, The said ink repellent compound (B) is a coloring photosensitive resin composition which is a copolymer which further copolymerized the monomer (b3) which has an ethylenically unsaturated group and an epoxy group. The method of claim 3, wherein The coloring photosensitive resin composition whose content of the unit guide | induced from the monomer (b3) which has the said ethylenically unsaturated group and an epoxy group in the said ink repellent compound (B) is 2-40 mass%.  The method of claim 1, The colored photosensitive resin composition whose mass average molecular weight of the said ink repellent compound (B) is 2000-50000. The method of claim 1, The coloring photosensitive resin composition whose content mass ratio of the said photopolymerizable compound (A) and the said ink repellent compound (B) is 99.9: 0.1-70: 30. The method of claim 1, Colored photosensitive resin composition containing resin obtained by making the said photopolymerizable compound (A) react with the epoxy compound (a1) and the reaction product of an ethylenically unsaturated group containing carboxylic acid compound (a2) with polybasic acid anhydride (a3) further. . The method of claim 1, The coloring photosensitive resin composition whose said coloring agent (D) is a light-shielding agent.