JP2014109017A - Colored resin composition, color filter, liquid crystal display unit, and organic el display unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition which contains a xanthene-based compound with a high solubility in solvent so as to produce pixels with high brightness; and a high-quality color filter, a liquid crystal display unit, and an organic EL display unit, with use of the colored resin composition.SOLUTION: The colored resin composition includes a dye (A), a solvent (B), and a binder resin (C). The dye (A) includes a xanthene-based compound represented by the following formula (I). (Rrepresents -SOLi or -COLi. Rrepresents -SOH, -SOLi, -COH, -COR, -COLi, -SOR, -SONH, -SONHR, or -SONRR.)

Description

  The present invention relates to a colored resin composition, a color filter, a liquid crystal display device, and an organic EL display device.

  In recent years, color filters are desired to have high definition, high brightness, and high contrast. In order to achieve this, there is a tendency that the color filter is highly purified and the pigment concentration in the colored photosensitive resin composition is increased. However, since the pigment has a certain particle size and scatters light, the color filter formed using the colored photosensitive resin composition containing the pigment at a high concentration has a problem that the contrast is low.

Therefore, for example, a pyrazole-based squarylium compound as a dye that develops a color only by absorption, and a blue pigment Pigment as a pigment.
A technique for achieving high contrast of a color filter by using a combination of Blue (P.B.) 15: 6 is disclosed (Patent Document 1).
In addition, with the aim of further increasing the brightness, for example, P.I. B. The use of a combination of 15: 6 and a xanthene compound is disclosed (Patent Document 2).

Japanese Patent Application Laid-Open No. 2006-079012 JP 2010-32999 A

  However, as a result of the study by the present inventors, the xanthene compound described in Patent Document 2 has low solubility in a solvent. For example, xanthene compounds are likely to aggregate and aggregate in a colored resin composition. It has been found that the brightness of the obtained pixels may be insufficient or the storage stability may not be sufficient.

Then, this invention makes it a subject to provide the colored resin composition containing the xanthene type compound with high solubility with respect to a solvent.
Another object of the present invention is to provide a colored resin composition from which a pixel having high luminance, particularly a blue pixel having high luminance, can be obtained. Another object of the present invention is to provide a high-quality color filter, a liquid crystal display device, and an organic EL display device.

  As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by using a specific xanthene compound, and the present invention has been completed.

  That is, this invention contains (A) dye, (B) solvent, and (C) binder resin, and (A) dye is a xanthene type compound (henceforth "xanthene type compound" represented by following formula (I). (I) ”), a color filter having a pixel formed using the colored resin composition, and the color filter having the color filter The present invention resides in a liquid crystal display device and an organic EL display device.

(In formula (I), R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 6 carbon atoms. Represents 10 to 10 aromatic hydrocarbon ring groups.
R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.
R ⁵ represents —SO ₃ Li or —CO ₂ Li.
R ⁶ represents —SO ₃ H, —SO ₃ Li, —CO ₂ H, —CO ₂ R ⁷ , —CO ₂ Li, —SO ₃ R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ or —SO. ₂ represents NR ¹⁰ R ¹¹
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ⁶ may be the same or different.
R ^{7 to} R ¹¹ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, or an aromatic group having 4 to 10 carbon atoms. Represents a heterocyclic group. R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and the ring may have a substituent. )

  ADVANTAGE OF THE INVENTION According to this invention, the colored resin composition which contains a xanthene type compound with high solubility with respect to a solvent, and can form a high brightness | luminance pixel, especially a high brightness | luminance blue pixel is provided, and this colored resin composition is used. Thus, it is possible to provide a high-quality color filter, liquid crystal display device, and organic EL display device.

It is a section schematic diagram showing an example of an organic EL device which has a color filter of the present invention.

  Embodiments of the present invention will be described in detail below, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.

In the present invention, “(meth) acryl”, “(meth) acrylate” and the like mean “acryl and / or methacryl”, “acrylate and / or methacrylate” and the like, for example, “(meth) acrylic acid” "Means" acrylic acid and / or methacrylic acid ".
Further, “total solid content” means all components of the colored resin composition of the present invention other than the solvent components described later.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
In addition, free valences are those that can form bonds with other free valences as described in Organic Chemistry / Biochemical Nomenclature (above) (Revised 2nd edition, Nankodo, 1992).
A term such as “CI Pigment Green” means a color index (CI).

[Colored resin composition]
The colored resin composition of the present invention contains (A) a dye, (B) a solvent, and (C) a binder resin, and the (A) dye is a xanthene compound (I) represented by the following formula (I): It is characterized by containing.
The colored resin composition of the present invention preferably further contains (D) a polymerizable monomer, (E) a photopolymerization initiating component and / or a thermal polymerization initiating component, and (F) a pigment. The component may be contained.

(In formula (I), R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 6 carbon atoms. Represents 10 to 10 aromatic hydrocarbon ring groups.
R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.
R ⁵ represents —SO ₃ Li or —CO ₂ Li.
R ⁶ represents —SO ₃ H, —SO ₃ Li, —CO ₂ H, —CO ₂ R ⁷ , —CO ₂ Li, —SO ₃ R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ or —SO. ₂ represents NR ¹⁰ R ¹¹
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ⁶ may be the same or different.
R ^{7 to} R ¹¹ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, or an aromatic group having 4 to 10 carbon atoms. Represents a heterocyclic group. R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and the ring may have a substituent. )

[Xanthene compound (I)]
First, the xanthene compound (I) in the present invention will be described in detail.

<Action mechanism>
Although the detail of the reason why the xanthene compound (I) used in the present invention has good solubility in a solvent is not clear, it is presumed as follows.
The xanthene compound (I) of the present invention is a lithium salt. Lithium ions have a large charge, but are small, high-density, so-called hard ions. Therefore, a large amount of solvent is taken in a polar solvent to form a solvate. For this reason, it is considered that the solvent enters between the sulfonium ion and carboxyl ion derived from the xanthene skeleton, the ionic bondability becomes weak, and the solubility in the solvent becomes high.

  In addition, since the xanthene compound (I) is usually a red to violet dye having a maximum absorption wavelength λmax of about 500 to 600 nm, the colored resin composition of the present invention containing such a xanthene compound (I) is It can be used effectively in the formation of a blue pixel of a color filter. However, the use of the colored resin composition of the present invention is not limited to this.

<R ^{1 to} R ⁴ >
In the formula (I), R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon number. Represents 6 to 10 aromatic hydrocarbon ring groups.

The alkyl group in R ^{1 to} R ⁴ is a linear, branched or cyclic alkyl group, and the carbon number is usually 1 or more, usually 10 or less, preferably 8 or less, more preferably 5 The following are mentioned. Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.

The aromatic hydrocarbon ring group for R ^{1 to} R ⁴ may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 6 to 10, but for example, Examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, acenaphthene ring, fluoranthene ring, and fluorene ring having one free valence.

R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.
Examples of the ring formed by combining R ¹ and R ² , and R ³ and R ⁴ with each other include the following (Ring Group Q), but the present invention is not limited thereto.

NR ¹ R ² and NR ³ R ⁴ may be the same or different, but NR ¹ R ² and NR ³ R ⁴ are preferably the same for ease of synthesis.

As the substituent that the alkyl group, the aromatic hydrocarbon ring group, and the ring formed by connecting these to each other in R ^{1 to} R ⁴ may have, there is no particular limitation unless the effects of the present invention are impaired. no but, -SO ₃ below ^- other, for example, include those described below (substituent group Z).

(Substituent group Z)
C1-C8 alkyl group, C2-C8 alkenyl group, C1-C8 alkoxy group, C6-C15 aryl group, C2-C9 alkylcarbonyloxy group, C7 -16 arylcarbonyloxy group, C2-C9 alkoxycarbonyl group, C7-C16 aryloxycarbonyl group, carbamoyl group, C2-C9 alkylcarbamoyl group, C7-C16 arylcarbamoyl Group, sulfamoyl group, alkylsulfamoyl group having 1 to 8 carbon atoms, arylsulfamoyl group having 6 to 15 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, arylcarbonyl group having 7 to 16 carbon atoms, carbon An alkylsulfonyl group having 1 to 8 carbon atoms, an alkylsulfonylamino group having 1 to 8 carbon atoms, and an arylsulfonylamino group having 6 to 15 carbon atoms An amino group, an alkylamino group formed by bonding an alkyl group having 1 to 8 carbon atoms, a dialkylamino group formed by bonding an alkyl group having 1 to 4 carbon atoms, an arylamino group having 6 to 15 carbon atoms, or 6 carbon atoms An arylalkylamino group formed by bonding an aryl group of -15 and an alkyl group having 1 to 4 carbon atoms, a diarylamino group formed by bonding an aryl group of 6 to 15 carbon atoms, a phenethyl group, a hydroxyethyl group, 2 carbon atoms ˜8 alkylcarbonylamino group, C7-16 arylcarbonylamino group, dialkylaminoethyl group formed by bonding of C1-4 alkyl group, trifluoromethyl group, C1-8 trialkyl Silyl group, alkylthio group having 1 to 8 carbon atoms, arylthio group having 6 to 15 carbon atoms, hydroxy group, nitro group, cyano group, carboxy group, sulfo group Group, a fluorine atom, a halogen atom such as a chlorine atom.

Specific examples of the aryl group in the substituent group Z include those described as the aromatic hydrocarbon ring groups in R ^{1 to} R ⁴ . The aryl group is a lower alkyl group such as a methyl group or an ethyl group, a lower alkoxy group such as a methoxy group or an ethoxy group, a nitro group, a trifluoromethyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a fluorine atom, or a chlorine atom. May be further substituted as a substituent.

Among them, the alkyl group, the aromatic hydrocarbon ring group in R ^{1 to} R ⁴ , and the substituent that may be formed by a ring formed by connecting these to each other are preferably —SO ₃ ^— , a carbon number of 1 to An alkyl group having 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a tolyl group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, a carbamoyl group, a sulfamoyl group, an alkylsulfamoyl group having 1 to 8 carbon atoms, tri A fluoromethyl group, a cyano group, a sulfo group and a fluorine atom;

<R ⁵ , R ⁶ , m>
In the formula (I), R ⁵ represents —SO ₃ Li or —CO ₂ Li.
The xanthene compound (I) has good solubility in a solvent because R ⁵ is —SO ₃ Li or —CO ₂ Li. In particular, the xanthene compound (I) may be referred to as propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”). The solubility in a certain) is good.

There is no particular restriction on the substitution position of R ^5, it is preferred in terms of easy synthesis that substituted benzene ring linked with xanthene ring.

R ⁶ represents —SO ₃ H, —SO ₃ Li, —CO ₂ H, —CO ₂ R ⁷ , —CO ₂ Li, —SO ₃ R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ or —SO. ₂ represents NR ¹⁰ R ¹¹

R ^{7 to} R ¹¹ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, or an aromatic group having 4 to 10 carbon atoms. Represents a heterocyclic group, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring.

The alkyl group in R ^{7 to} R ¹¹ is a linear, branched or cyclic alkyl group, and the carbon number is usually 1 or more, usually 30 or less, preferably 20 or less, more preferably 10 The following are mentioned. Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group. Group, heptyl group, cycloheptyl group, octyl group, 2-ethylhexyl group, cyclooctyl group, nonyl group, decanyl group, cyclodecanyl group and the like.

The aromatic hydrocarbon ring group for R ^{7 to} R ¹¹ may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 6 to 10, but for example, Examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, acenaphthene ring, fluoranthene ring, and fluorene ring having one free valence.

The aromatic heterocyclic group in R ^{7 to} R ¹¹ may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 4 to 10, but for example, 1 Furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolo Pyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, quinoline ring, isoquinoline ring , Quinoxaline ring, quinazoline ring, quinazolinone ring, etc. Group, and the like.

Examples of the ring formed by combining R ¹⁰ and R ¹¹ with each other include those described in the above (Ring group Q) and those described in the following (Ring group Q ′).

Examples of the substituent that the alkyl group, aromatic hydrocarbon ring group and aromatic heterocyclic group in R ^{7 to} R ^11, and the ring formed by combining R ¹⁰ and R ¹¹ with each other may have, are the present invention. As long as the effects of the above are not impaired, there is no particular limitation, but examples include those described in the above (Substituent group Z), preferably a lower alkyl group such as a methyl group or an ethyl group, a methoxy group, an ethoxy group or the like. A lower alkoxy group, a nitro group, a trifluoromethyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a halogen atom such as a fluorine atom or a chlorine atom.

The ^{R 7} in -CO ₂ R ^7, preferably an alkoxyalkyl group of the alkyl group and 2 to 10 carbon atoms having 1 to 10 carbon atoms.
—CO ₂ R ⁷ includes methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, Hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropyl Oxycarbonyl, ethoxypropyloxycarbonyl, hex B propyl oxycarbonyl, 2-ethylhexyloxy propyloxy, methoxy hexyloxycarbonyl and the like.

The ^{R 8} in -SO ₃ R ^8, preferably an alkyl group having 1 to 10 carbon atoms, and _-SO 3 ^{R 8,} methanesulfonyl, ethanesulfonyl, hexane sulfonyl, nonanesulfonyl, and the like.

R ^{9 in} —SO ₂ NHR ⁹ is preferably an alkyl group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms, and —SO ₂ NHR ⁹ includes methanesulfamoyl, ethanesulfur. Famoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentansulfamoyl, isopentansulfamoyl, neopentansulfamoyl, cyclopentansulfamoyl, hexanesulfamoyl, Cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl, 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, Deccan Sulfamoyl, tricyclodecane sulfamoyl, methoxypropane sulfamoyl, ethoxypropane sulfamoyl, propoxypropane sulfamoyl, isopropoxypropane sulfamoyl, hexyloxypropane sulfamoyl, 2-ethylhexyloxypropane sulfamoyl, Examples include methoxyhexane sulfamoyl, 3-phenyl-1-methylpropane sulfamoyl and the like.

R ¹⁰ and R ¹¹ contained in —SO ₂ NR ¹⁰ R ¹¹ include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, and a carbon number. An aralkyl group having 8 to 10 carbon atoms, a hydroxyl group-containing alkyl and aryl group having 2 to 8 carbon atoms, or an alkoxy group-containing alkyl or aryl group having 2 to 8 carbon atoms is preferable, and a 2-ethylhexyl group is particularly preferable.

The substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁷ to R ^11, an ethyl group, a propyl group, a phenyl group, dimethylphenyl group, _-SO 3 ^{R 8} or _-SO 2 NHR ⁹ is preferred.

m represents an integer of 0 to 4, preferably 0 to 2. When m is an integer of 2 or more, the plurality of R ⁶ may be the same or different.

<-SO ₃ ^->
In the xanthene compound (I) in the present invention, at least one of an alkyl group or an aromatic hydrocarbon ring group in R ^{1 to} R ⁴ or a ring formed by bonding these groups has —SO ₃ ^— as a substituent. Alternatively, the xanthene ring or the benzene ring bonded to the xanthene ring has —SO ₃ ^— , whereby at least one —SO ₃ ^— is contained in the formula (I).
—SO ₃ ^— is preferably present as a substituent of the alkyl group or aromatic hydrocarbon ring group in R ^{1 to} R ⁴ or a substituent of the benzene ring bonded to the xanthene ring.

In the xanthene compound (I) of the present invention, the negative charge of —SO ₃ ^— is usually such that NR ¹ R ² or NR ³ R ⁴ becomes an ammonium group, or the xanthene ring conjugated with this is located at the 5-position. The carbon atom is neutralized by being positively charged. In addition, when the xanthene compound (I) has a plurality of —SO ₃ ^— , some of them may form a salt with Li.

<Molecular weight>
The molecular weight of the xanthene compound (I) is usually 500 or more, preferably 600 or more, and usually 5000 or less, preferably 2000 or less.
It is preferable that it is within the above-mentioned range in terms of good solubility in a solvent and easy production.

<Synthesis Method of Xanthene Compound (I)>
Xanthene compounds (I) are, for example, “reviewed synthetic dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968), “theoretical manufacturing dye chemistry” (Toyo Hosoda, Gihodo, 1957), synthesis and application of functional dyes. Although it can synthesize | combine according to the method as described in a technique (supervision of Masaki Matsui, CM publishing, 2007), it is not restricted to this method.

Specifically, it can be obtained through the following two steps.
In the first step, a xanthene compound substituted with a sulfo group is obtained by the following methods (i) to (iii).
(I) A benzaldehyde substituted with a sulfo group is reacted with an N-substituted m-aminophenol.
(Ii) A phthalic anhydride and N-substituted m-aminophenol are reacted to sulfonate the obtained xanthene compound.
(Iii) A 3,6-dichloroxanthene derivative (for example, fluorescein chloride) is reacted with an N-substituted amine, and the resulting xanthene compound is sulfonated as necessary.
The xanthene compound obtained in the above (i) to (iii) may be chlorinated or aminated with an N-substituted amine as necessary.
In the second step, the sulfo group (or salt thereof) or carboxy group (or salt thereof) of the xanthene compound obtained in the first step is converted to a lithium salt by the following methods (iv) to (vi). .
(Iv) The xanthene compound obtained in the first step is mixed with a strong acid aqueous solution or passed through a cation exchange resin to obtain a free acid form, and then reacted with lithium hydroxide.
(V) The xanthene compound obtained in the first step is mixed with an aqueous lithium chloride solution, and a water-soluble organic solvent is added to precipitate the target product.
(Vi) The xanthene compound obtained in the first step is brought into contact with a cation exchange resin exchanged with a lithium salt.

<Specific example>
Although the preferable specific example of the xanthene-type compound (I) in this invention is shown below, this invention is not limited to these. In the following, “iBu” represents “isobutyl group”.

<Content>
The colored resin composition of the present invention contains xanthene compound (I) in the total solid content, preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight or more. The content is preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less.
It is preferable for the content of the xanthene compound (I) to be less than or equal to the above upper limit because the curability of the coating film is hardly lowered and the film strength is sufficient. Moreover, since it is sufficient for coloring power to be more than the said minimum, since the chromaticity of a desired density | concentration is easy to be obtained and it is hard to become thick, it is preferable.
In the colored resin composition of the present invention, only one type of xanthene compound (I) may be contained as the (A) dye, or two or more types may be contained.

In addition, 1 type, or 2 or more types of other dyes other than a xanthene type compound (I) may be contained in the colored resin composition of this invention. Further, the content of the total (A) dye in the colored resin composition is preferably 0.1% by weight or more, and preferably 50% by weight or less in the total solid content of the colored resin composition.
In addition, in the colored resin composition of this invention, it is preferable that content of a xanthene type compound (I) is 30 weight% or more in solid content of all (A) dyes.

[Other dyes]
Other dyes other than the xanthene compound (I) that may be contained in the colored resin composition of the present invention are not particularly limited as long as the effects of the present invention are not impaired. For example, azo dyes and anthraquinones Preferable examples include dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, and triarylmethane dyes.

  Among these, triarylmethane dyes are preferable. For example, International Publication No. 2009/107734, International Publication No. 2010/123071, International Publication No. 2011/162217, International Publication No. 2011/152379, International Publication No. 2011/158794. And those described in each publication such as International Publication No. 2012/53211.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.

  The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and a solvent having a boiling point in the range of 100 to 200 ° C. is preferably selected. More preferably, it has a boiling point of 120-170 ° C.

  Examples of such solvents include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:

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

  Of these solvents, glycol monoalkyl ethers are preferred from the viewpoint of the solubility of the dye (A) in the present invention. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.

  In addition, for example, when the colored resin composition of the present invention contains a pigment (F) described later as an optional component, the balance of coatability, surface tension, etc. is good, and the solubility of the constituent components in the colored resin composition is compared. From the standpoint of high performance, it is more preferable to use a mixture of glycol alkyl ether acetates as a solvent. In addition, in the colored resin composition containing the (F) pigment, the glycol monoalkyl ethers have high polarity and tend to aggregate the (F) pigment, and increase the viscosity of the colored resin composition. May decrease. For this reason, it is preferable that the amount of the glycol monoalkyl ether used is not excessively large, and the proportion of the glycol monoalkyl ether in the solvent (B) is preferably 5 to 50% by weight, more preferably 5 to 40% by weight. .

  Further, from the viewpoint of suitability for a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight based on the total amount of the solvent (B). If the amount of the high boiling point solvent is too small, for example, a dye component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying speed of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

  The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .

  The colored resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 weight% or more in (B) solvent. When the ratio of such a high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the ink droplets may not be sufficiently exhibited.

  In the colored resin composition of the present invention, the content of the (B) solvent is not particularly limited, but the upper limit is usually 99% by weight. When the content of the (B) solvent in the composition exceeds 99% by weight, the concentration of each component excluding the (B) solvent may become too small to form a coating film. On the other hand, the lower limit of the content of the solvent (B) is usually 75% by weight, preferably 80% by weight, and more preferably 82% by weight in consideration of viscosity suitable for coating.

[(C) Binder resin]
The binder resin (C) used in the present invention is preferably different depending on the curing means of the colored resin composition.

  When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (C) binder resin include JP-A-7-2072111, JP-A-8-259876, and JP-A-10-300922. The polymer compounds described in JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and the like can be used. However, among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or an alkali-soluble resin (hereinafter referred to as “resin (C-1)”) obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes referred to as “resin (C-2)”)
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable.
The resin will be described below.

  The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. The preferred embodiment is also the same.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl group produced by the addition reaction

  As a particularly preferred resin of the resin (C-1), a copolymer of 5 to 90 mol% of an epoxy group-containing (meth) acrylate and 10 to 95 mol% of another radical polymerizable monomer, A resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy group of the copolymer, or a polybasic acid anhydride is added to 10 to 100 mol% of a hydroxyl group generated by the addition reaction. And alkali-soluble resins obtained.

  Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (7) Acrylate is preferred.

  In a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having a structure represented by the following formula (7) is “other radicals”. The repeating unit derived from the “polymerizable monomer” preferably contains 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%.

In the above formula (7), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (8).

The formula ^{(8), R} 91 ~R ⁹⁸ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

  Among these, among the structures represented by the formula (8), those represented by the following structural formulas (8a), (8b), or (8c) are particularly preferable.

  In addition, the mono (meth) acrylate which has a structure represented by the said Formula (8) may be used individually by 1 type, and may use 2 or more types together.

  As "other radical polymerizable monomers" other than the mono (meth) acrylate having the structure represented by the formula (8), the heat resistance and strength excellent in the colored resin composition can be improved. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  In the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer, the content of the repeating unit derived from at least one selected from the monomer group is 1 to 70 mol%. It is preferably 3 to 50% by mole.

  A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer.

  In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Are preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 70 of the former. What consists of mol% and the latter 70-30 mol% is especially preferable.

  Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.

  The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).

Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These may be used alone or in combination of two or more.
By adding such a component, it is possible to impart polymerizability to the (C) binder resin used in the present invention.

  These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is preferable for the amount of unsaturated monobasic acid added to be within this range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.
By adding such a component, alkali solubility can be imparted to the (C) binder resin used in the present invention.

These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. It is preferable that the addition amount of the polybasic acid anhydride is within this range because the remaining film ratio and solubility during development are sufficient.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

  Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

The polystyrene-reduced weight average molecular weight (Mw) of the above-described binder resin (C-1) measured by GPC (gel permeation chromatography) is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. When the molecular weight is within the above range, it is preferable in that heat resistance, film strength, and solubility in a developer are good.
Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.
In addition, the acid value of binder resin (C-1) is 10-200 mg-KOH / g normally, Preferably it is 15-150 mg-KOH / g, More preferably, it is 25-100 mg-KOH / g. If the acid value is too low, the solubility in the developer may be reduced. Conversely, if it is too high, film roughening may occur.

  Content of (C) binder resin in a colored resin composition is 0.1 to 80 weight% normally in a total solid, Preferably it is 1 to 60 weight%. When the content of the binder resin (C) in the colored resin composition is within the above range, the adhesion to the substrate is good, the permeability of the developer to the exposed area is appropriate, and the surface of the pixel is smooth. It is preferable in terms of good properties and sensitivity.

[(D) Polymerizable monomer]
The colored resin composition of the present invention preferably contains (D) a polymerizable monomer.

  (D) The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Is preferred).

  The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation component described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (D) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer in a narrow sense.

  (D) Examples of the ethylenic compound in the polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.

  The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane A reaction product with a group-containing hydroxy compound is exemplified.

  In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .

  Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These polymerizable monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (D) polymeric monomer as needed.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. When the acid value is within the above range, the development and dissolution characteristics are not easily lowered, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.

  In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

In the colored resin composition of the present invention, the content of the polymerizable monomer (D) is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more in the total solid content. Further, it is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less.
The ratio of the (D) polymerizable monomer to the (A) dye is usually 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 20% by weight or more. Moreover, it is 200 weight% or less normally, Preferably it is 100 weight% or less, More preferably, it is 80 weight% or less.

  When the content of the polymerizable monomer (D) in the colored resin composition of the present invention is within the above range, photocuring is appropriate, adhesion failure during development hardly occurs, and the cross section after development is reverse tapered. It is preferable because it does not easily become a shape and a peeling phenomenon and omission failure due to a decrease in solubility hardly occur.

[(E) Photopolymerization initiation component and / or thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains (E) a photopolymerization initiation component and / or a thermal polymerization initiation component for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.

  In particular, when the colored resin composition of the present invention includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain a photopolymerization initiating component that has a function of generating a polymerization active radical and / or a thermal polymerization initiating component that generates a polymerization active radical by heat. In the present invention, the component (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

<(E) Photopolymerization initiation component>
The (E) photopolymerization initiating component in the present invention is usually a mixture of (E1) a photopolymerization initiator and, if necessary, (E2) a polymerization accelerator and (E3) an additive such as a sensitizing dye. And is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197, etc .; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl-s -Radical activators such as triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives And oxime ester derivatives described in JP-A No. 2000-80068 and the like.

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734 pamphlet and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

  The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime), and a compound represented by the following formula (XI).

(In the above formula (XI),
Z represents an aromatic ring group which may have a substituent.
p represents an integer of 0 or 1.
q represents the integer of 0-20.
X ^{is, -CR 54 R 55 -, -} C (= CR 56 R 57) -, - CR 58 = CR 59 - and one group, or selected from the group consisting of -C≡C- these bound 2 or more Represents a group consisting of
R ^{56 to} R ⁵⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁵⁴ , R ⁵⁵ and R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or a carbon atom, each of which may have a substituent. C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 acyloxy Group, C1-C20 N-substituted amino group, C3-C20 cycloalkyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C1-C20 Alkylsulfinyl group, arylsulfinyl group having 6 to 20 carbon atoms, carbamoyl group, alkylcarbamoyl group having 2 to 20 carbon atoms, arylcarbamoyl group having 7 to 20 carbon atoms, and 1 to 20 carbon atoms Aminooxycarbonyl group, cyano group, nitro group, alkylsulfanyl group having 1 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, alkenyloxycarbonyl group having 3 to 12 carbon atoms, alkynyloxy having 3 to 12 carbon atoms Carbonyl group, aryloxycarbonyl group having 7 to 12 carbon atoms, heteroaryloxycarbonyl group having 3 to 12 carbon atoms, alkylsulfanylcarbonyl group having 2 to 12 carbon atoms, alkenylsulfanylcarbonyl group having 3 to 12 carbon atoms, carbon number An alkynylsulfanylcarbonyl group having 3 to 12 carbon atoms, an arylsulfanylcarbonyl group having 7 to 12 carbon atoms, a heteroarylsulfanylcarbonyl group having 3 to 12 carbon atoms, an alkylsulfanylalkoxy group having 2 to 12 carbon atoms, —O—N═CR ³⁰ R ^31, -N ^{(OR 30} It represents a group represented by ^{--OCO-R 31} or a group represented by the following formula (2).

(R ³⁰ and R ³¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)

R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, or a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroarylcarbonyl group group having 3 to 20 carbon atoms, or a carbon number Represents 2-20 alkylaminocarbonyl groups.
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. )

<About Z>
Z represents an aromatic ring group which may have a substituent.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
The aromatic hydrocarbon ring group may be a single ring or a condensed ring, and preferably has 5 to 18 carbon atoms forming the ring and has one free valence. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and indene ring.

  In addition, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and preferably has 3 to 10 carbon atoms to form the ring. Furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring , Thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline Ring, quinoxaline ring, phenanthridine ring, Zone imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, azulene ring, an acridine ring, a xanthene ring, a phenazine ring, a phenothiazine ring, a phenoxazine ring, groups such as a benzothiazole ring.

  In addition, as a substituent which the aromatic ring group in Z may have, the thing as described in the term of the following (substituent group W) is mentioned, for example.

(Substituent group W)
C1-C8 alkyl group, C1-C8 alkoxy group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, sulfo group and carboxy group

<About p>
p represents an integer of 0 or 1.
It is preferable that p is 0 in that the effect of forming an image in spray development can be easily obtained more favorably.

<About q>
q represents the integer of 0-20.
Q is preferably 0 to 5 in that the amount of radically active species generated per gram is high and the production is simple.

<About X and R ¹⁰¹ >
X ^{is, -CR 54 R 55 -, -} C (= CR 56 R 57) -, - CR 58 = CR 59 - and one group, or selected from the group consisting of -C≡C- these bound 2 or more Represents a group consisting of
When q is 2 or more, a plurality of X contained in one molecule may be the same or different.

R ^{56 to} R ⁵⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ⁵⁴ , R ⁵⁵ and R ¹⁰¹ are each independently a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or a carbon atom, each of which may have a substituent. C2-C20 monovalent non-aromatic heterocyclic group, C1-C20 alkoxy group, C6-C20 aryloxy group, C2-C20 acyl group, C2-C20 acyloxy Group, C1-C20 N-substituted amino group, C3-C20 cycloalkyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C1-C20 Alkylsulfinyl group, arylsulfinyl group having 6 to 20 carbon atoms, carbamoyl group, alkylcarbamoyl group having 2 to 20 carbon atoms, arylcarbamoyl group having 7 to 20 carbon atoms, and 1 to 20 carbon atoms Aminooxycarbonyl group, cyano group, nitro group, alkylsulfanyl group having 1 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, alkenyloxycarbonyl group having 3 to 12 carbon atoms, alkynyloxy having 3 to 12 carbon atoms Carbonyl group, aryloxycarbonyl group having 7 to 12 carbon atoms, heteroaryloxycarbonyl group having 3 to 12 carbon atoms, alkylsulfanylcarbonyl group having 2 to 12 carbon atoms, alkenylsulfanylcarbonyl group having 3 to 12 carbon atoms, carbon number A alkynylsulfanylcarbonyl group having 3 to 12 carbon atoms, an arylsulfanylcarbonyl group having 7 to 12 carbon atoms, a heteroarylsulfanylcarbonyl group having 3 to 12 carbon atoms, an alkylsulfanylalkoxy group having 2 to 12 carbon atoms, or the following formula (2) Represents the group represented.

(R ³⁰ and R ³¹ each independently represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent.)

R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom that are relatively stable against a nucleophilic substitution reaction are preferable.

  The aryl group having 6 to 20 carbon atoms which may have a substituent preferably has 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a mesityl group, a naphthyl group, and an anthracenyl group.

  The heteroaryl group having 2 to 20 carbon atoms which may have a substituent is an aromatic ring group containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a heteroatom, preferably having a carbon number. The thing of 2 or more and 12 or less is mentioned. When the heteroaryl group has a plurality of heteroatoms constituting a ring other than a carbon atom, these may be the same or different. The heteroaryl group may be a single ring or a condensed ring, and may be a pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, oxazolyl group, triazolyl group, thiadiazolyl group, pyridinyl group, pyrimidinyl group, triazinyl group. Quinolinyl group, isoquinolinyl group, benzothiazolinyl group, phthalimidoyl group, benzimidazolonyl group, furyl group, thiophenyl group, pyranyl group, indolinyl group, isoindolinyl group and the like. Examples of the group that may be substituted on the heteroaryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a sulfo group. And a carboxy group. Specific examples of the heteroaryl group include 2-pyrrolyl group, 2-imidazolyl group, 1-pyrazolyl group, 2-thiazolyl group, 2-oxazolyl group, 1,2,4-triazol-1-yl group, and 4-pyridinyl. Group, 2-pyrimidinyl group, 4,6-diamino-2-triazinyl group, 8-quinolinyl group, 8-isoquinolinyl group, 2-benzothiazolinyl group, 6-methyl-7-sulfo-2-benzothiazolinyl Group, 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl group, 1H-benzimidazol-2-yl group, 2-furyl group, 2-thiophenyl group, 1-indolinyl group, 2 -An isoindolinyl group is mentioned.

  The monovalent non-aromatic heterocyclic group having 2 to 20 carbon atoms which may have a substituent is a non-aromatic cyclic group containing any one of a nitrogen atom, a sulfur atom and an oxygen atom as a hetero atom. Yes, preferably those having 2 to 12 carbon atoms. When the monovalent non-aromatic heterocyclic group has a plurality of heteroatoms constituting a ring other than a carbon atom, these may be the same or different. The monovalent non-aromatic heterocyclic group may be a single ring or a condensed ring, and examples thereof include a piperidinyl group, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperazinyl group, and a morpholinyl group. Examples of the substituent that the monovalent non-aromatic heterocyclic group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, and diethylamino. Group, halogen atom, sulfo group and carboxy group. Specific examples of the monovalent non-aromatic heterocyclic group include 1-piperidinyl group, 1-pyrrolidinyl group, 1-imidazolidinyl group, 1-pyrazolidinyl group, 1-piperazinyl group and 1-morpholinyl group.

  The alkoxy group having 1 to 20 carbon atoms which may have a substituent is preferably an alkoxy group having 1 to 10 carbon atoms. Examples of the substituent that the alkoxy group may have include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Etc. Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, n-amyloxy group, t-amyloxy group, n- Hexyloxy group, n-heptyloxy group, n-octyloxy group, hydroxyethoxy group, 1,2-dihydroxypropoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2- (2 -Methoxyethoxy) ethoxy group, 2- (2-ethoxyethoxy) ethoxy group, 2- (2-butoxyethoxy) ethoxy group, benzyloxy group, phenethyloxy group, etc., linear or branched alkoxy having 1 to 18 carbon atoms Groups.

  The aryloxy group having 6 to 20 carbon atoms which may have a substituent is preferably an aryloxy group having 6 to 14 carbon atoms. Examples of the aryloxy group include a phenoxy group, a naphthoxy group, and an anthracenyloxy group. Examples of the substituent that the aryloxy group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and cyano. Group, sulfo group, carboxy group and the like. Specific examples of the aryloxy group include aryls optionally having a substituent such as a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, a 3-tolyloxy group, a 4-methoxyphenoxy group, and a 4-cyclohexylphenoxy group. An oxy group is mentioned.

Which may have a substituent alkylcarbamoyl group having 2 to 20 carbon atoms ^is represented by ^{-CO-NR 11b R 12b, R} 11 is an optionally substituted alkyl radical, R ^12b represents a hydrogen atom or an alkyl group which may have a substituent. The alkyl group usually has 1 or more carbon atoms and usually 19 or less, preferably 12 or less. Examples of the group that may be substituted with the alkyl group include an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group. 2-butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like. Specific examples of the alkylamino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, and a cyclohexylethyl group. Specific examples of the alkylcarbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a phenethylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a 2-ethoxyethylcarbamoyl group, a 2- (2-ethoxyethoxy) ethylcarbamoyl group, and a dimethylcarbamoyl group. Etc.

The arylcarbamoyl group having 7 to 20 carbon atoms which may have a substituent is represented by —CO—NR ^13b R ^14b , and R ^13b represents an aryl group which may have a substituent. R ^14b represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . The aryl group usually has 6 or more carbon atoms, usually 19 or less, preferably 12 or less, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the group which may be substituted on the aryl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, A sulfo group, a carboxy group, etc. are mentioned. Specific examples of the aryl group include a phenyl group, a p-tolyl group, an m-tolyl group, a p-methoxyphenyl group, a naphthyl group, and an anthracenyl group. Specific examples of the arylcarbamoyl group include a phenylcarbamoyl group, a naphthylcarbamoyl group, a p-tolylcarbamoyl group, a p-methoxyphenylcarbamoyl group, and a phenylmethylcarbamoyl group.

Optionally substituted acyl group having 2 to 20 carbon atoms is represented by ^{-COR 15b,} R ^15b may have an optionally substituted alkyl group or a substituted group Represents an aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable number of carbon atoms of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ⁴⁸ . Specific examples of the acyl group include acetyl group, ethylcarbonyl group, n-butylcarbonyl group, benzoyl group, p-tolylcarbonyl group, m-tolylcarbonyl group, p-methoxyphenylcarbonyl group and the like.

The acyloxy group having 2 to 20 carbon atoms that may have a substituent is represented by -O-COR ^16b , and R ^16b has an alkyl group or a substituent that may have a substituent. Represents a good aryl group. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the acyl group include an acetoxy group, an ethylcarbonyloxy group, an n-butylcarbonyloxy group, a benzoyloxy group, a p-tolylcarbonyloxy group, an m-tolylcarbonyloxy group, and a p-methoxyphenylcarbonyloxy group. Is mentioned.

The optionally substituted N-substituted amino group having 1 to 20 carbon atoms is represented by —NR ^17b R ^18b , where R ^17b is a hydrogen atom, an ^optionally substituted alkyl group, a substituted group. An aryl group which may have a group is represented. R ^18b represents an alkyl group which may have a substituent and an aryl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the N-substituted amino group include an ethylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, a di (2-ethoxyethyl) amino group, a diphenethylethylamino group, a cyclohexylethyl group, and a phenylamino group. , Diphenylamino group, di (p-tolyl) amino group, di (p-methoxyphenyl) amino group, ethylphenylamino group, n-butylphenylamino group and the like.

  The cycloalkyl group having 3 to 20 carbon atoms which may have a substituent is preferably a cycloalkyl group having 3 to 12 carbon atoms. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group. Examples of the group which may be substituted on the cycloalkyl group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, and a cyano group. , Sulfo group and carboxy group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a decalinyl group.

An alkylsulfonyl group having 1 to 20 carbon atoms that may have a substituent group _is represented by -SO ^{2 -R 19b, R 19b} represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a phenethylsulfonyl group, a 2-ethylhexylsulfonyl group, a 2-ethoxyethylsulfonyl group, a 2- (2-ethoxyethoxy) ethylsulfonyl group, and trifluoromethyl. A sulfonyl group etc. are mentioned.

The arylsulfonyl group having 6 to 20 carbon atoms which may have a substituent is represented by —SO ₂ —R ^20b , and R ^20b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a naphthylsulfonyl group, a p-tolylsulfonyl group, and a p-methoxyphenylsulfonyl group.

Alkylsulfinyl groups having 1 to 20 carbon atoms that may have a substituent group is represented by ^{-SO-R 21b, R 21b} represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a phenethylsulfinyl group, a 2-ethylhexylsulfinyl group, a 2-ethoxyethylsulfinyl group, a 2- (2-ethoxyethoxy) ethylsulfinyl group, and trifluoromethyl. Examples thereof include a sulfinyl group.

The arylsulfinyl group having 6 to 20 carbon atoms which may have a substituent is represented by —SO—R ^22b , and R ^22b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfinyl group include phenylsulfinyl group, naphthylsulfinyl group, p-tolylsulfinyl group, p-methoxyphenylsulfinyl group and the like.

The C1-C12 alkylsulfanyl group which may have a substituent is represented by -S-R ^23b , and R ^23b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a phenethylsulfanyl group, a 2-ethylhexylsulfanyl group, a 2-ethoxyethylsulfanyl group, a 2- (2-ethoxyethoxy) ethylsulfanyl group, and trifluoromethyl. And a sulfanyl group.

The C2-C12 alkoxycarbonyl group which may have a substituent is represented by -CO-OR ^24b , and R ^24b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, phenethyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 2-ethoxyethoxycarbonyl group and the like.

The alkenyloxycarbonyl group having 3 to 12 carbon atoms which may have a substituent is represented by —CO—OR ^25b , and R ^25b represents an alkenyl group which may have a substituent. The alkenyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group that may be substituted with the alkenyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group, and a carboxy group. Is mentioned. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a methanyl group. Specific examples of the alkenyloxycarbonyl group include alkenyloxycarbonyl groups having 3 to 12 carbon atoms such as vinyloxycarbonyl group and allyloxycarbonyl group.

Which may have a substituent alkynyloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 26b, R 26b} represents an alkynyl group which may have a substituent. The alkynyl group usually has 1 or more carbon atoms and usually 11 or less, preferably 8 or less. Examples of the group which may be substituted on the alkynyl group include an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, an amino group, a dimethylamino group, a diethylamino group, a halogen atom, a cyano group, a sulfo group and a carboxy group. Is mentioned. Specific examples of the alkynyl group include a methynyl group, a propynyl group, and a butynyl group. Specific examples of the alkynyloxycarbonyl group include alkynyloxycarbonyl groups having 3 to 12 carbon atoms such as methynyloxycarbonyl group and propynyloxycarbonyl group.

The aryloxycarbonyl group having 7 to 12 carbon atoms which may have a substituent is represented by —CO—OR ^27b , and R ^27b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the aryloxycarbonyl group include those having 7 to 12 carbon atoms such as phenyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, p-tolyloxycarbonyl group, p-methoxyphenyloxycarbonyl group and the like. An aryloxycarbonyl group is mentioned.

Which may have a substituent heteroaryloxy group having 3 to 12 carbon atoms is represented by ^{-CO-OR 28b,} R ^28b represents a heteroaryl group which may have a substituent. Examples of the preferable carbon number of the heteroaryl group and an optionally substituted substituent are the same as those of the preferable carbon number of the heteroaryl group in R ⁵⁴ , R ⁵⁵ and R ^{101 and} an optionally substituted substituent. is there. Specific examples of the heteroaryloxycarbonyl group include 8-quinolinyloxycarbonyl group, 2-furanyloxycarbonyl group, 3-furanyloxycarbonyl group, 2-pyridyloxycarbonyl group, 3-pyridyloxycarbonyl group, 4 -Heteroaryloxycarbonyl groups having 3 to 12 carbon atoms such as a pyridyloxycarbonyl group and a 2-benzothiazolyloxycarbonyl group.

The C2-C12 alkylsulfanylcarbonyl group which may have a substituent is represented by -CO-SR ^29b , and R ^29b represents an alkyl group which may have a substituent. The preferred carbon number of the alkyl group and examples of the substituent which may be present are the same as those exemplified for the alkyl groups of R ^11b and R ^12b . Specific examples of the alkylsulfanylcarbonyl group include methylsulfanylcarbonyl group, ethylsulfanylcarbonyl group, n-propylsulfanylcarbonyl group, isopropylsulfanylcarbonyl group, n-butylsulfanylcarbonyl group, n-hexylsulfanylcarbonyl group, n-octyl. C2-C12 alkyl sulfanyl carbonyl groups, such as a sulfanyl carbonyl group and n-dodecyl sulfanyl carbonyl group, etc. are mentioned.

The alkenylsulfanylcarbonyl group having 3 to 12 carbon atoms which may have a substituent is represented by —CO—SR ^30b , and R ^30b represents an alkenyl group which may have a substituent. Examples of the preferable number of carbon atoms of the alkenyl group and the substituent that may be included are the same as those exemplified for the alkenyl group of R ^25b . Specific examples of the alkenylsulfanylcarbonyl group include alkenylsulfanylcarbonyl having 3 to 12 carbon atoms such as vinylsulfanylcarbonyl group and allylsulfanylcarbonyl group.

Alkynyl Nils Alpha alkenyl group having 3 to 12 carbon atoms which may have a substituent group is represented by ^{-CO-SR 31b,} R ^31b represents an alkynyl group which may have a substituent. The preferred carbon number of the alkynyl group and examples of the substituent which may be present are the same as those exemplified for the alkynyl group of R ^26b . Specific examples of the alkynylsulfanylcarbonyl group include alkynylsulfanylcarbonyl groups having 3 to 12 carbon atoms such as methynylsulfanylcarbonyl group and propynylsulfanylcarbonyl group.

The arylsulfanylcarbonyl group having 7 to 12 carbon atoms which may have a substituent is represented by —CO—SR ^32b , and R ^32b represents an aryl group which may have a substituent. Examples of the preferable carbon number of the aryl group and the substituent which may be included are the same as those exemplified for the aryl group of R ^13b . Specific examples of the arylsulfanylcarbonyl group include 7 to 12 carbon atoms such as a phenylsulfanylcarbonyl group, a 1-naphthylsulfanylcarbonyl group, a 2-naphthylsulfanylcarbonyl group, a p-tolylsulfanylcarbonyl group, and a p-methoxyphenylsulfanylcarbonyl group. An arylsulfanylcarbonyl group is mentioned.

Heteroaryl sulfanyl group having 3 to 12 carbon atoms which may have a substituent group is represented by ^{-CO-SR 33b,} R ^33b represents a heteroaryl group which may have a substituent. Examples of the preferable carbon number of the heteroaryl group and an optionally substituted substituent are the same as those of the preferable carbon number of the heteroaryl group in R ⁵⁴ , R ⁵⁵ and R ^{101 and} an optionally substituted substituent. is there. Specific examples of the heteroarylsulfanylcarbonyl group include 8-quinolinylsulfanylcarbonyl group, 2-furanylsulfanylcarbonyl group, 3-furanylsulfanylcarbonyl group, 2-pyridylsulfanylcarbonyl group, 3-pyridylsulfanylcarbonyl group, 4 -C3-C12 heteroaryl sulfanyl carbonyl groups, such as a pyridyl sulfanyl carbonyl group and 2-benzothiazolyl sulfanyl carbonyl group, are mentioned.

  The C2-C12 alkyl sulfanyl alkoxy group which may have a substituent refers to the alkoxy group which the C1-C10 alkyl sulfanyl group substituted. The alkylsulfanyl group in the alkylsulfanylalkoxy group may be substituted with an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group or the like. The alkoxy group in the alkylsulfanylalkoxy group may be substituted with an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or the like in addition to the alkylsulfanyl group. Specific examples of the alkylsulfanylalkoxy group include alkylsulfanylalkoxy groups having 2 to 12 carbon atoms such as methylsulfanylmethoxy group, methylsulfanylethoxy group, ethylthiomethoxy group, ethylsulfanylethoxy group, methylsulfanylpropoxy group, and ethylsulfanylpropoxy group. Is mentioned.

Examples of the alkyl group having 1 to 12 carbon atoms which may have a substituent of R ³⁰ and R ³¹ are the same as those exemplified in the case of the alkyl group of R ^11b and R ^12b . Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent are the same as those exemplified for the aryl group of R ^13b .

R ¹⁰¹ may be bonded to Z to form a ring, and the ring may have a substituent.

<About ^{R 102>}
R ¹⁰² may have a substituent, which may have a substituent, an alkylcarbonyl group having 2 to 20 carbon atoms, an alkenylcarbonyl group having 3 to 25 carbon atoms, a cycloalkylcarbonyl group having 4 to 8 carbon atoms, or a carbon number having 7 to 20 carbon atoms. An arylcarbonyl group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroarylcarbonyl group having 3 to 20 carbon atoms, or 2 carbon atoms Represents an alkylaminocarbonyl group of ˜20.

  Examples of the alkylcarbonyl group having 2 to 20 carbon atoms which may have a substituent include an acetyl group, a propanoyl group, a butanoyl group, and the like, and preferably an acetyl group. Carbon number becomes like this. Preferably it is 2-10, More preferably, it is 2-7.

  Examples of the alkenylcarbonyl group having 3 to 25 carbon atoms which may have a substituent include a crotonoyl group and an acryloyl group, and a crotonoyl group is preferable. Carbon number becomes like this. Preferably it is 3-12, More preferably, it is 3-7.

  Examples of the cycloalkylcarbonyl group having 4 to 8 carbon atoms which may have a substituent include a cyclohexylcarbonyl group, a methylcyclohexylcarbonyl group and a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group is preferable. The number of carbon atoms is preferably 4-7.

  Examples of the arylcarbonyl group having 7 to 20 carbon atoms which may have a substituent include a benzoyl group, a methylbenzoyl group, and a naphthoyl group, and a benzoyl group is preferable. Carbon number becomes like this. Preferably it is 7-12, More preferably, it is 7-10.

  Examples of the C2-C10 alkoxycarbonyl group which may have a substituent include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group, and a methoxycarbonyl group is preferable. The number of carbon atoms is preferably 2-8.

  Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent include a phenoxycarbonyl group, a p-methylphenoxycarbonyl group, and a naphthoxycarbonyl group, and a phenoxycarbonyl group is preferable. Carbon number becomes like this. Preferably it is 7-15, More preferably, it is 7-10.

  Examples of the heteroaryl group having 2 to 20 carbon atoms which may have a substituent include a thienyl group, a pyrrolyl group, and a pyridyl group, and a thienyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-7.

  Examples of the heteroarylcarbonyl group having 3 to 20 carbon atoms which may have a substituent include a thiophenecarbonyl group, a pyrrolylcarbonyl group, a pyridinecarbonyl group, and the like, and preferably a thiophenecarbonyl group. Carbon number becomes like this. Preferably it is 5-15, More preferably, it is 7-10.

  Examples of the alkylaminocarbonyl group having 2 to 20 carbon atoms which may have a substituent include a morpholinocarbonyl group, a dimethylaminocarbonyl group, and a methylaminocarbonyl group, and a dimethylaminocarbonyl group is preferable. Carbon number becomes like this. Preferably it is 2-12, More preferably, it is 2-10.

Of the above groups, from the viewpoint of exposure sensitivity, R ¹⁰² is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group, and more preferably an alkylcarbonyl group or an arylcarbonyl group.

Examples of the substituent that each group described above as R ¹⁰² may have include those described in the following (Substituent group W ¹ ) section, and each group described above has a substituent. Those that do not are particularly preferred.

(Substituent group W ¹ )
C1-C8 alkyl group, C1-C10 alkoxy group, phenyl group, hydroxyl group, amino group, dimethylamino group, diethylamino group, halogen atom, cyano group, sulfo group and carboxy group

<About ^R103 >
R ¹⁰³ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, cyclohexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2 -Butoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2-butoxyethoxy) ethyl group, benzyl group, phenethyl group and the like can be mentioned. Carbon number becomes like this. Preferably it is 1-10, More preferably, it is 1-6.

  Examples of the alkenyl group include allyl group and methanyl group. The number of carbon atoms is preferably 3-4.

The aryl group is the same as that described in the section <About X and R ¹⁰¹ >.

Examples of the substituent that each group described above as R ¹⁰³ may have include those described in the above section (Substituent group W ¹ ), and each group described above has a substituent. Those that do not are particularly preferred.
R ¹⁰³ is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an ethyl group, from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.

<Regarding ^R 104 ^{to R 109>}
R ^{104 to} R ¹⁰⁹ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
R ^{104 to} R ¹⁰⁹ are particularly preferably hydrogen atoms from the viewpoint that the generation amount of radical active species per gram is high and the production is simple.

  Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like.

  Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable, and oxime ester derivatives are particularly preferable.

  Examples of the (E2) polymerization accelerator used as necessary include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto Examples thereof include mercapto compounds having a heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

  Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.

  Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. As the sensitizing dye, an appropriate one is used according to the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc. Coumarin dyes having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dyes; Pyrromethene dyes described in JP-A-6-19240 and the like; JP, 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP 5-10. 761 No., JP-A-5-210240, dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

  (E3) A sensitizing dye may also be used alone or in combination of two or more.

  In the colored resin composition of the present invention, the content of these (E) photopolymerization initiating components is usually 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 0.8% by weight in the total solid content. It is 5% by weight or more, usually 40% by weight or less, preferably 30% by weight or less, and more preferably 20% by weight or less. When the content of the (E) photopolymerization initiating component in the colored resin composition of the present invention is within the above range, the sensitivity to the exposure light is good, and the solubility of the unexposed part in the developer is also good. This is preferable in that it is difficult to induce defects.

<(E) Thermal polymerization initiating component>
Specific examples of the (E) thermal polymerization initiating component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating components may be used alone or in combination of two or more.

  When the ratio of the (E) thermal polymerization initiating component in the colored resin composition of the present invention is too small, the film is not sufficiently cured and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. Moreover, the tendency for storage stability to fall is seen. Therefore, the content ratio of the (E) thermal polymerization initiating component is preferably in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored resin composition of the present invention.

[Other optional ingredients]
In addition to the above components, the colored resin composition of the present invention comprises a surfactant, an organic carboxylic acid and / or an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface It may contain a protective agent, an adhesion improver, a development improver, an antioxidant, a heat stabilizer and the like. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. Moreover, when it contains the below-mentioned (F) pigment, you may contain a dispersing agent and a dispersing aid.

<(F) Pigment>
The colored resin composition of the present invention may contain (F) a pigment within a range not impairing the effects of the present invention for the purpose of improving the heat resistance of the obtained color filter.

  As the (F) pigment, for example, when forming a pixel of a color filter, pigments of various colors such as red, orange, yellow, blue, and purple can be used. Examples of the chemical structure include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, perylene, azo, quinophthalone, and anthraquinone. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 17 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203 , 204, 205, 206, 207, 208 and a pigment defined by <Pigment Y> below (hereinafter referred to as “Pigment Y”).

<Pigment Y>
A compound obtained by inserting another compound into a 1: 1 complex of azobarbituric acid represented by the following structural formula (II) with nickel or an compatible isomer thereof.

  Examples of the other compound include a compound represented by the following formula (II-1).

  Of these, C.I. I. Pigment Yellow 138 and 139, and Pigment Y.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.
Among these, a blue copper phthalocyanine pigment is preferable, and examples of the copper phthalocyanine pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and the like are preferable, and C.I. I. Pigment Blue 15: 6.
For this reason, when the colored resin composition of this invention contains a blue pigment, it is 80 weight% or more with respect to the total content of a blue pigment, Especially 90 weight% or more, Especially 95-100 weight% is C.I. I. Pigment Blue 15: 6 is preferable.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
Among these, a purple dioxazine pigment is preferable, and as the dioxazine pigment, C.I. I. Pigment Violet 19 and 23 are preferable, and C.I. I. Pigment Violet 23.

  These (F) pigments may be used alone or in a combination of two or more in any combination and ratio.

As described above, the xanthene compound (I) used in the present invention is a red to violet dye.
Therefore, when the colored resin composition of the present invention includes a pigment and is used to form a red pixel, the pigment preferably includes at least one of the red pigment, the orange pigment, and the yellow pigment. . These pigments may be used individually by 1 type, and may contain 2 or more types by arbitrary combinations and ratios.

In addition, when the colored resin composition of the present invention contains a pigment and is used to form a blue pixel, the pigment preferably contains the blue pigment and / or the violet pigment. These pigments may be used individually by 1 type, and may contain 2 or more types by arbitrary combinations and ratios.
In the above case, when the colored resin composition of the present invention is for forming a blue pixel and further contains a purple pigment, C.I. I. It is preferable that Pigment Violet 23 is 80% by weight or more, particularly 90% by weight or more, and particularly 95 to 100% by weight, based on the total content of the purple pigment.

  The (F) pigment used in the colored resin composition of the present invention preferably has a small average primary particle diameter from the viewpoint of forming a high-contrast pixel. Specifically, the average primary particle diameter is 40 nm or less. Is preferable, and it is more preferable that it is 35 nm or less.

Particularly for the blue copper phthalocyanine pigment, the average primary particle size is preferably 40 nm or less, more preferably 35 nm or less, and still more preferably 20 to 30 nm.
Moreover, about a dioxazine pigment, an average primary particle diameter becomes like this. Preferably it is 40 nm or less, More preferably, it is 25-35 nm.
From the viewpoint that the pigment is less likely to aggregate in the colored resin composition, it is preferable that the average primary particle size is not too small.

Here, the average primary particle size of the (F) pigment is a value measured and calculated by the following method.
First, (F) a pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.
The particle diameter of each pigment _{particle: X 1, X 2, X} 3, X 4, ····, X i, ······ X m

When the colored resin composition of the present invention contains the (F) pigment, the content of the (F) pigment in the colored resin composition is usually 80% by weight or less, preferably 50% by weight or less in the total solid content. .
Further, the content of the pigment (F) with respect to 100 parts by weight of the (A) dye is usually 2000 parts by weight or less, preferably 1000 parts by weight or less.
By making the content of the (F) pigment in the colored resin composition of the present invention not more than the above upper limit, the heat resistance of the resulting pixel is improved without greatly affecting the transmittance by the (A) dye. It is preferable because it is easy to become.

<Dispersant>
When the colored resin composition of the present invention contains (F) a pigment, it is preferable to further contain a dispersant.

The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.
Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having a quaternary ammonium base and / or an amino group in the side chain, while the solvophilic A block includes a quaternary ammonium. Examples include a unit structure having no base and amino group.

The B block constituting the acrylic block copolymer has a unit structure having a quaternary ammonium base and / or an amino group, and has a pigment adsorption function.
In addition, when the B block has a quaternary ammonium base, the quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group. Good.
Examples of such block copolymers include those described in JP-A-2009-025813.
Moreover, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648, for example.

  When the colored resin composition of the present invention contains (F) a pigment, the content of the dispersant in the total solid content is 2 to 1000% by weight, particularly 5 to 500% by weight of the total content of (F) pigment. %, Particularly 10 to 250% by weight. By setting the content of the dispersant of the colored resin composition of the present invention within the above range, (A) good pigment dispersibility can be secured without affecting the heat resistance of the dye, and the pigment It is preferable in that the dispersion stability of is improved.

<Dispersing aid>
When the colored resin composition of the present invention contains (F) a pigment, it may further contain a dispersion aid in addition to the dispersant. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in, for example, No. 113000 and JP-A No. 2007-186681 can be used.

  The content of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, based on the total solid content of the (F) pigment. More preferably, it is 10 weight% or less, More preferably, it is 5 weight% or less. By controlling the content of the dispersion aid within the above range, the effect as the dispersion aid is exhibited, and the dispersibility and dispersion stability are more preferable.

<Dispersed resin>
The colored resin composition of the present invention may contain a part or all of the resin selected from the (C) binder resin or other binder resins as the following dispersion resin.
Specifically, in [Preparation Method of Colored Resin Composition], which will be described later, by adding (C) binder resin together with the components such as the above-mentioned dispersant, the (C) binder resin is combined with the dispersant. A synergistic effect is preferable because it contributes to the dispersion stability of the pigment (F), and as a result, the amount of the dispersant added may be reduced. Further, it is preferable because the developability is improved, the undissolved material does not remain in the non-pixel portion of the substrate, and the adhesion of the pixel to the substrate is improved.

  Thus, the (C) binder resin used in the dispersion treatment step may be referred to as a dispersion resin. The dispersion resin is preferably used in an amount of about 0 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the (F) pigment in the colored resin composition.

[Preparation Method of Colored Resin Composition]
The colored resin composition of the present invention can be prepared by an appropriate method. For example, the (A) dye and the (C) binder resin containing the xanthene compound (I), the (B) solvent and, if necessary, the It can be prepared by mixing together with optional components used.
Moreover, as a preparation method in case (F) a pigment is included, the following methods are preferable.
First, (F) in a solvent containing a pigment, in the presence of a dispersant and, if necessary, a dispersion aid to be added, optionally with (C) a part of the binder resin, for example, a paint shaker, a sand grinder, a ball mill, Using a roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while grinding. (A) dye containing xanthene compound (I), (C) binder resin, and (D) polymerizable monomer, (E) photopolymerization initiating component and / or thermal polymerization initiating The colored resin composition of the present invention is prepared by adding and mixing components and the like.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.

  Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display device using them will be described.

[Color filter]
The color filter of the present invention has a pixel formed from the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.

  The pixel of the color filter can be formed by various methods. Here, a case where a photopolymerizable colored resin composition is used and formed by photolithography will be described as an example. However, a method for forming a pixel is not limited thereto.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

  The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made of epoxy resin, a thermosetting resin, and various types of glass.

  In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.

  Examples of the method for applying the colored resin composition to the substrate include a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, and a spray coating method. Of these, the slit and spin method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, particularly preferably 0.8 to 5.0 μm, as the film thickness after drying.
Within the above range, it is preferable in that the gap can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.

As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.
Exposure of radiation, 10~10,000J / ^{m 2} is preferred.

  Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di-, or tri -Methylamine, mono-, di-, or tri-ethylamine, mono-, or di-isopropylamine, n-butylamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium Hydroxide (TMAH) Aqueous solution of an organic alkaline compound choline are preferred.

  An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or the like can be added to the alkaline developer.

Examples of the development method include immersion development, spray development, brush development, and ultrasonic development.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. In particular, it is preferably performed at room temperature (23 ° C.) for 5 to 300 seconds.
In addition, it is usually washed with water after alkali development.

  When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Further, a column structure (photo spacer) by a photolithography method may be formed instead of the bead dispersion type spacer.

[Liquid Crystal Display]
The liquid crystal display device of the present invention uses the above-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

[Organic EL display device]
When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, the organic EL display device is formed on the color filter in which the pixel 20 is formed on the transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element is produced by laminating the organic light-emitting body 500 through the protective layer 30 and the inorganic oxide film 40.

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

  Next, although a synthesis example, a preparation example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.

[Synthesis example]
{Synthesis of xanthene compound (I)}
<Synthesis Example 1>
A xanthene compound represented by the following structural formula (I-1) was synthesized through the following steps (1-a) to (1-c).

(1-a) A mixture of 3.69 g of 3,6-dichlorofluorane, 3.58 g of indoline, 2.10 g of zinc chloride and 20 g of sulfolane was stirred at 140 ° C. for 6 hours to condense. After cooling, the mixture was added to 150 g of ice water and 10 ml of concentrated hydrochloric acid was added. The resulting precipitate was then filtered, washed with water and dried.
(1-b) 1.0 g of the product of (1-a) and 15 g of 100% sulfuric acid were stirred at 20 ° C. for 2 hours for sulfonation. Then it was added to 75 g of ice water, filtered and washed with water.
(1-c) The product obtained in (1-b) was mixed with 30 ml of water, neutralized with a 5% aqueous lithium hydroxide solution to pH 8.5 to 9.0, and dissolved. And it salted out with lithium chloride, filtered and washed. The obtained wet cake was dissolved in 50 ml of water, dialyzed with an electrodialyzer until no chloride ions were detected, concentrated and dried.
The obtained xanthene compound (I-1) was a cyan dye having a maximum absorption wavelength λmax of 636 nm.

<Synthesis Example 2>
A xanthene compound represented by the following structural formula (I-2) was synthesized through the following steps (2-a) to (2-c).

(2-a) A mixture of 3.69 g of 3,6-dichlorofluorane, 2.79 g of aniline, 2.10 g of zinc chloride and 20 g of sulfolane was stirred at 160 ° C. for 5 hours to condense. After cooling, the mixture was added to 150 g of ice water and 10 ml of concentrated hydrochloric acid was added. The resulting precipitate was then filtered, washed with water and dried.
(2-b) 1.0 g of the product of (2-a) and 15 g of 100% sulfuric acid were stirred at 20 ° C. for 4 hours to be sulfonated. Then it was added to 75 g of ice water, filtered and washed with water.
(2-c) The product obtained in (2-b) was mixed with 30 ml of water, neutralized and dissolved to pH 8.5 to 9.0 with a 5% aqueous lithium hydroxide solution. And it salted out with lithium chloride, filtered and washed. The obtained wet cake was dissolved in 50 ml of water, dialyzed with an electrodialyzer until no chloride ions were detected, concentrated and dried.
The obtained xanthene compound (I-2) was a reddish purple pigment having a maximum absorption wavelength λmax of 323 nm.

<Synthesis Example 3>
A xanthene compound represented by the following structural formula (I-3) was synthesized through the following steps (3-a) to (3-c).

(3-a) A mixture of 3.69 g of 3,6-dichlorofluorane, 3.64 g of 2,6-dimethylaniline, 2.10 g of zinc chloride and 20 g of sulfolane was stirred at 170 ° C. for 6 hours to condense. After cooling, the mixture was added to 150 g of ice water and 10 ml of concentrated hydrochloric acid was added. The resulting precipitate was then filtered, washed with water and dried.
(3-b) 1.0 g of the product of (3-a) and 15 g of 95% sulfuric acid were stirred at 20 ° C. for 4 hours to be sulfonated. Then it was added to 75 g of ice water, filtered and washed with water.
(3-c) The product obtained in (3-b) was mixed with 30 ml of water, and neutralized and dissolved to pH 8.5 to 9.0 with a 5% aqueous lithium hydroxide solution. And it salted out with lithium chloride, filtered and washed. The obtained wet cake was dissolved in 50 ml of water, dialyzed with an electrodialyzer until no chloride ions were detected, concentrated and dried.
The obtained xanthene compound (I-3) was a red pigment having a maximum absorption wavelength λmax of 527 nm.

<Synthesis Example 4>
A xanthene compound represented by the following structural formula (I-4) was synthesized through the following steps (4-a) to (4-c).

(4-a) A mixture of 3.69 g of 3,6-dichlorofluorane, 4.06 g of N-ethyl-p-toluidine, 2.10 g of zinc chloride and 20 g of sulfolane was stirred at 160 ° C. for 4 hours to condense. . After cooling, the mixture was added to 150 g of ice water and 10 ml of concentrated hydrochloric acid was added. The resulting precipitate was then filtered, washed with water and dried.
(4-b) 1.0 g of the product of (4-a) and 15 g of 100% sulfuric acid were stirred at 20 ° C. for 3 hours to be sulfonated. Then it was added to 75 g of ice water, filtered and washed with water.
(4-c) The product obtained in (4-b) was mixed with 50 ml of water, and neutralized and dissolved to pH 8.5 to 9.0 with a 5% aqueous lithium hydroxide solution. And it salted out with lithium chloride, filtered and washed. The obtained wet cake was dissolved in 50 ml of water, dialyzed with an electrodialyzer until no chloride ions were detected, concentrated and dried.

<Synthesis Example 5>
25 g of Acid Red 52 (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 250 mL of water and dialyzed until no chloride ion was detected with an electrodialyzer. This solution was ion-exchanged with a cation exchange resin SK1BH (manufactured by Mitsubishi Chemical Corporation). The obtained aqueous solution was neutralized with an aqueous solution of lithium hydroxide monohydrate until the pH became 7.0, then concentrated and dried, and a xanthene compound represented by the following structural formula (I-5) Was synthesized.
This xanthene compound (I-5) was a red pigment having a maximum absorption wavelength λmax of 533 nm.

<Synthesis Example 6>
15 g of Acid Red 289 (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 300 ml of water, salted out with 45 g of sodium chloride, and the precipitate was collected by filtration. The obtained cake was dissolved in 700 ml of water and dialyzed with an electrodialyzer until no chloride ions were detected. This solution was ion-exchanged with a cation exchange resin SK1BH (manufactured by Mitsubishi Chemical Corporation). The obtained aqueous solution was neutralized with an aqueous solution of lithium hydroxide monohydrate until the pH became 7.0, concentrated and dried.
The obtained xanthene compound (I-6) was a red pigment having a maximum absorption wavelength λmax of 527 nm.

{Synthesis of binder resin}
<Synthesis Example 7>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by weight of styrene, 132 parts by weight of glycidyl methacrylate, 4.4 parts by weight of monomethacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 2,2′-azobis-2-methylbutyrate 8.47 parts by weight of nitrile was added dropwise over 3 hours, and stirring was further continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 1.1 parts by weight of trisdimethylaminomethylphenol and 0.19 parts by weight of hydroquinone were added to 67.0 parts by weight of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 15.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.2 parts by weight of triethylamine were added and reacted at 100 ° C. for 3.5 hours to obtain a resin solution having a solid content concentration of 61.6% by weight.
The binder resin (c) thus obtained had a weight average molecular weight (Mw) measured by GPC of about 9000 and an acid value of 25 mg-KOH / g. The structure of the binder resin (c) was as shown below (polymer compound containing the following four types of repeating units).

[Preparation Example]
{Preparation of blue pigment dispersion}
<Preparation Example 1>
As a blue pigment, C.I. I. Pigment Blue 15: 6 11.36 parts by weight, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 3.02 parts by weight, 0.5 mm in diameter, in terms of solid content, a dispersant “Dispervic 2000” manufactured by Big Chemie 215.7 parts by weight of zirconia beads were filled in a stainless steel container and dispersed for 6 hours with a paint shaker to prepare a blue pigment dispersion (1) (pigment concentration: 15.8% by weight).

<Preparation Example 2>
As a blue pigment, C.I. I. Pigment Blue 15: 6 and Violet 23 in a weight ratio of 9.20: 3.81, 11.36 parts by weight, 57.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, a dispersant “Disperbic 2000” manufactured by BYK Chemie The solid content of 3.02 parts by weight and 215.7 parts by weight of zirconia beads having a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours with a paint shaker to obtain a blue pigment dispersion (2) (pigment concentration 5 .8 wt%) was prepared.

[Examples and Comparative Examples]
{Preparation of colored resin composition}
Each material was mixed so that it might become the composition described in Table 1, and the colored resin composition was prepared.
In addition, all the numerical values in Table 1 represent parts by weight of each material to be added, and indicate the amount of mixing as a solid content except for the blue pigment dispersions (1) and (2) and the solvent.
During mixing, a predetermined amount of each material was collected and stirred for 1 hour or longer, and finally filtered through a 5 μm piece filter to remove foreign substances.

  In Table 1, the details of each material are as follows, and the dyes used in Examples 1 and 2 and Comparative Examples 1 and 2 are as shown in Table 2.

Polymerizable monomer: Dipentaerythritol hexaacrylate Photopolymerizable initiator: “OXE02” (ethanone, 1- [9-ethyl-6- 6] manufactured by BASF
(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1-
(O-acetyloxime)
Surfactant: “F475” (fluorine surfactant) manufactured by Dainippon Ink & Chemicals, Inc.
Antioxidant: “Irganox 1010” manufactured by BASF (hindered phenol-based oxidation)
Inhibitor)
Heat stabilizer: “JPP-100” manufactured by Johoku Chemical Industry Co., Ltd. (phosphite ester heat stabilizer)
PGMEA: Propylene glycol monomethyl ether acetate PGME: Pyropyrene glycol monomethyl ether

{Verification of solubility}
When the colored resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared, the solubility of the dye was determined based on whether or not the dye was completely dissolved.
When it melt | dissolved completely, it was set as "(circle)", and the case where the undissolved residue was confirmed visually was set as "*".
The results are shown in Table 2.

{Production of colored resin film and evaluation of heat resistance}
The colored resin compositions of Examples 1 and 2 and Comparative Example 3 were applied on a glass substrate cut into 5 cm square by spin coating so that the sy of the coating film after drying was 0.096 with a C light source. After drying under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Then, after exposing the entire surface at an exposure amount of 60 mJ / cm ² , after baking at 230 ° C. for 30 minutes in a clean oven, the spectral transmittance was measured with a spectrophotometer “U-3310” manufactured by Hitachi, Comparison of LY (luminance) was performed. The results are shown in Table 3.

  From the above results, the xanthene compound (I) used in the present invention has high solubility in a solvent, and the pixel formed using the colored resin composition of the present invention containing this xanthene compound (I) has high luminance. I understand that.

DESCRIPTION OF SYMBOLS 100 Organic EL element 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 500 Organic light-emitting body 51 Hole injection layer 54 Electron injection layer

Claims (7)

(A) a dye, (B) a solvent and (C) a binder resin,
(A) A colored resin composition, wherein the dye contains a xanthene compound represented by the following formula (I).

(In formula (I), R ^{1 to} R ⁴ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted carbon atom having 6 carbon atoms. Represents 10 to 10 aromatic hydrocarbon ring groups.
R ¹ and R ² , and R ³ and R ⁴ may be independently bonded to each other to form a ring, and the ring may have a substituent.
R ⁵ represents —SO ₃ Li or —CO ₂ Li.
R ⁶ represents —SO ₃ H, —SO ₃ Li, —CO ₂ H, —CO ₂ R ⁷ , —CO ₂ Li, —SO ₃ R ⁸ , —SO ₂ NH ₂ , —SO ₂ NHR ⁹ or —SO. ₂ represents NR ¹⁰ R ¹¹
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ⁶ may be the same or different.
R ^{7 to} R ¹¹ are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an aromatic hydrocarbon ring group having 6 to 10 carbon atoms, or an aromatic group having 4 to 10 carbon atoms. Represents a heterocyclic group. R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and the ring may have a substituent. )   The colored resin composition according to claim 1, further comprising (D) a polymerizable monomer.   The colored resin composition according to claim 1, further comprising (E) a photopolymerization initiation component and / or a thermal polymerization initiation component.   The colored resin composition according to any one of claims 1 to 3, further comprising (F) a pigment.   It has a pixel formed using the colored resin composition as described in any one of Claims 1-4, The color filter characterized by the above-mentioned.   A liquid crystal display device comprising the color filter according to claim 5.   An organic EL display device comprising the color filter according to claim 5.

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