JP2010275532A - Compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound having high solubility to a solvent. <P>SOLUTION: The compound is represented by formula (0) [in the formula (0), A represents a divalent aromatic hydrocarbon group which may have a substituent, R<SP>1</SP>and R<SP>2</SP>each independently represent a 1-20C saturated aliphatic hydrocarbon group which may have a substituent, a 7-20C aralkyl group which may have a substituent, or a 6-20C aryl group which may have a substituent, provided that the total of the carbon number in the substituent of R<SP>1</SP>and R<SP>2</SP>is ≥6 and ≤16, Z represents an oxygen atom or a sulfur atom, and X represents a carboxyl group or a sulfo group]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to compounds useful as dyes.

  Conventionally, pigments such as azo compounds have been used for color display using reflected light or transmitted light in various fields (for example, fiber materials, liquid crystal display devices, etc.). Discloses a compound represented by the formula (d-1).

JP 58-194958 A

  The compound represented by the above formula (d-1) may not have sufficient solubility in a solvent.

  Therefore, the present inventors have intensively studied to further improve the solubility of the compound in a solvent, and as a result, have reached the present invention.

〔式（０）中、Ａは、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよいＣ_１-２０飽和脂肪族炭化水素基、置換基を有していてもよいＣ_７-２０アラルキル基、又は置換基を有していてもよいＣ_６-２０アリール基を表す。ただし、Ｒ^１及びＲ^２の置換基における、炭素数の合計が６以上１６以下である。
Ｚは、酸素原子又は硫黄原子を表す。
Ｘは、カルボキシ基又はスルホ基を表す。〕
［２］式（０）で表される化合物が、式（Ｉ）で表される化合物である［１］記載の化合物。

〔式（Ｉ）中、Ａは、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよいＣ_１-２０飽和脂肪族炭化水素基、置換基を有していてもよいＣ_７-２０アラルキル基、又は置換基を有していてもよいＣ_６-２０アリール基を表す。ただし、Ｒ^１及びＲ^２の置換基における、炭素数の合計が６以上１６以下である。
Ｚは酸素原子又は硫黄原子を表す。〕 That is, the present invention is the following invention.
[1] A compound represented by the formula (0).

[In Formula (0), A represents the bivalent aromatic hydrocarbon group which may have a substituent.
R ¹ and R ² are each independently a C _1-20 saturated aliphatic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or a substituent. Represents a C _6-20 aryl group _optionally having. However, the total number of carbon atoms in the substituents R ¹ and R ² is 6 or more and 16 or less.
Z represents an oxygen atom or a sulfur atom.
X represents a carboxy group or a sulfo group. ]
[2] The compound according to [1], wherein the compound represented by the formula (0) is a compound represented by the formula (I).

[In formula (I), A represents a divalent aromatic hydrocarbon group which may have a substituent.
R ¹ and R ² are each independently a C _1-20 saturated aliphatic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or a substituent. Represents a C _6-20 aryl group _optionally having. However, the total number of carbon atoms in the substituents R ¹ and R ² is 6 or more and 16 or less.
Z represents an oxygen atom or a sulfur atom. ]

[3] The compound according to [1] or [2], wherein A is a phenylene group, and a hydrogen atom contained in the phenylene group may be substituted with a halogen atom, a methyl group, a methoxy group, or a sulfo group.

[4] The compound according to any one of [1] to [3], wherein any one of R ¹ and R ² is a C _6-20 aryl group which may have a substituent.

〔式（ＩＩ）中、Ｒ^１、Ｒ^２及びＺは上記と同じ意味を表す。
Ｒ^３は、ハロゲン原子、メチル基、メトキシ基又はスルホ基を表す。
ｍは、１又は２の整数を表す。ｍが２であるとき、複数のＲ^３は、同じ種類の基であっても異なる種類の基であってもよい。〕 [5] The compound according to any one of [1] to [4], wherein the compound represented by the formula (I) is a compound represented by the formula (II).

[In the formula (II), R ¹ , R ² and Z represent the same meaning as described above.
R ³ represents a halogen atom, a methyl group, a methoxy group or a sulfo group.
m represents an integer of 1 or 2. When m is 2, the plurality of R ³ may be the same type of group or different types of groups. ]

  The compound of the present invention has good solubility in a solvent.

〔式（０）中、Ａは、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有していてもよいＣ_１-２０飽和脂肪族炭化水素基、置換基を有していてもよいＣ_７-２０アラルキル基、又は置換基を有していてもよいＣ_６-２０アリール基を表す。ただし、Ｒ^１及びＲ^２の置換基における、炭素数の合計が６以上１６以下である。
Ｚは、酸素原子又は硫黄原子を表す。
Ｘは、カルボキシ基又はスルホ基を表す。〕 The compound of the present invention is a compound represented by the formula (0) (hereinafter sometimes referred to as “compound (0)”). In the present specification, C _ab means that the carbon number is a or more and b or less.

[In Formula (0), A represents the bivalent aromatic hydrocarbon group which may have a substituent.
R ¹ and R ² are each independently a C _1-20 saturated aliphatic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or a substituent. Represents a C _6-20 aryl group _optionally having. However, the total number of carbon atoms in the substituents R ¹ and R ² is 6 or more and 16 or less.
Z represents an oxygen atom or a sulfur atom.
X represents a carboxy group or a sulfo group. ]

〔式（Ｉ）中、Ａ、Ｒ^１、Ｒ^２及びＺは、前記と同じ意味を表す。〕 The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”).

[In the formula (I), A, R ¹ , R ² and Z represent the same meaning as described above. ]

A represents a divalent aromatic hydrocarbon group which may have a substituent. Examples of the divalent aromatic hydrocarbon group include a phenylene group and a naphthalenediyl group. Examples of the substituent that the divalent aromatic hydrocarbon group has include a halogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, and a sulfo group. Among them, a halogen atom, a methyl group, a methoxy group, or A sulfo group is preferred. The number of substituents is preferably 0 to 2, and more preferably 1 or 2.
Moreover, it is preferable to have a carboxy group in o-position with respect to the azo group of a compound from a soluble point.

R ¹ and R ² are each independently a C _1-20 saturated aliphatic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or a substituent. Represents a C _6-20 aryl group _optionally having. However, the total number of carbon atoms in the substituents R ¹ and R ² is 6 or more and 16 or less.
The C _1-20 saturated aliphatic hydrocarbon group may be linear, branched or cyclic. The carbon number of the C _1-20 saturated aliphatic hydrocarbon group includes all of the carbon atoms of the substituent, and the number is preferably 3 to 20, and more preferably 3 to 12.
Examples of the C _1-20 saturated aliphatic hydrocarbon group include n-propyl group, isopropyl group, n-butyl group, n-octyl group, methylhexyl group (such as 1,5-dimethylhexyl group), ethylhexyl group (2 -Ethylhexyl group, etc.), cyclohexyl group, methylcyclohexyl group (2,2-dimethylcyclohexyl group etc.), cyclohexylalkyl group and the like.
The hydrogen atom contained in the C _1-20 saturated aliphatic hydrocarbon group may be substituted with a C _1-8 alkoxy group or a carboxy group. The _{C 1-20} saturated aliphatic hydrocarbon group substituted with a C _1-8 alkoxy group, an alkoxycarbonyl propyl (2- (2-hydroxyethoxy) ethyl group, 3- isopropoxypropyl group, 3- (2 ' -Ethylhexyloxy) propyl group and the like. Examples of the C _1-20 saturated aliphatic hydrocarbon group substituted with a carboxy group include an 8-carboxyoctyl group.
—CH ₂ — contained in the C _1-20 saturated aliphatic hydrocarbon group may be replaced by —O—. As the C _1-20 saturated aliphatic hydrocarbon group in which —CH ₂ — is replaced by —O—, — (CH ₂ ) _a —O— (CH ₂ ) _b —H (a and b are each independently Represents an integer of 1 to 19), and a and b are preferably independently 1 to 10.

  The alkylene part of the aralkyl group may be linear, branched or cyclic. The aralkyl group has 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. Examples of the aralkyl group include phenylalkyl groups such as benzyl group and phenylbutyl group (3-amino-1-phenylbutyl group and the like).

The aryl group may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group, an alkoxy group, or a carboxy group. The carbon number of the aryl group is counted including the carbon number of the substituent, and is 6 to 20, preferably 6 to 10. Examples of these aryl groups include a phenyl group, an alkylphenyl group (4-methylphenyl group), an alkenylphenyl group (4-vinylphenyl group), an alkoxyphenyl group (4-methoxyphenyl group), and a carboxyphenyl group (2-carboxyl group). And a non-substituted or substituted phenyl group such as an alkoxycarbonylphenyl group (such as 4-methoxycarbonylphenyl group) and a trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group).
By selecting a bulky group for R ¹ and R ² , the solubility of the compound in the solvent can be increased. Examples of bulky R ¹ include branched saturated aliphatic hydrocarbon groups such as 2-ethylhexyl group (particularly tertiary saturated aliphatic hydrocarbon groups).
From the viewpoint of improving solubility, it is preferable that either ^one of R ¹ and R ² is a C _6-20 aryl group which may have a substituent.
Compound (0) also includes tautomers thereof. In other words, enol type and keto type are included.
Compound (0) may form a dimer or more multimer at an arbitrary position.

化合物（０）としては、式（Ｉ）で表される化合物（以下「化合物（Ｉ）」という場合がある）及び式（Ｉｓ）で表される化合物（以下「化合物（Ｉｓ）」という場合がある）が挙げられる。化合物（０）としては、化合物（Ｉ）であることが好ましい。


〔式（Ｉ）及び式（Ｉｓ）中、Ａ、Ｒ^１、Ｒ^２及びＺは上記と同じ意味を表す。〕

Examples of the compound (0) include a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”) and a compound represented by the formula (Is) (hereinafter referred to as “compound (Is)”). There is). Compound (0) is preferably compound (I).


[In formula (I) and formula (Is), A, R ¹ , R ² and Z have the same meaning as described above. ]

〔式（ＩＩ）中、Ｒ^１、Ｒ^２及びＺは上記と同じ意味を表す。
Ｒ^３は、ハロゲン原子、メチル基、メトキシ基又はスルホ基を表す。
ｍは、１又は２の整数を表す。ｍが２であるとき、複数のＲ^３は、同じ種類の基であっても異なる種類の基であってもよい。〕 Compound (I) is preferably a compound represented by Formula (II).

[In the formula (II), R ¹ , R ² and Z represent the same meaning as described above.
R ³ represents a halogen atom, a methyl group, a methoxy group or a sulfo group.
m represents an integer of 1 or 2. When m is 2, the plurality of R ³ may be the same type of group or different types of groups. ]

  Examples of compound (I) include compounds represented by formula (I-1) to formula (I-12).

  Examples of compound (Is) include compounds represented by formula (I-17) to formula (I-19). * In the table represents a bond with a nitrogen atom.

Examples of the salt of compound (I) include carboxylate. The cations forming these salts are not particularly limited, but considering solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; ammonium salts; and ethanolamine salts and alkylamine salts. Organic amine salts; heavy metal salts such as cobalt salts, nickel salts, chromium salts, copper salts, zinc salts; and the like are preferable. In particular, an alkali metal salt (preferably a sodium salt) is useful when contained in a polarizing film substrate. In addition, the organic amine salt is useful when it is contained in a resin curable compound. Furthermore, since it is a non-metallic salt, it is also useful in fields where insulation is important.
Examples of the salt of compound (I) include a salt represented by the following formula.

〔Ｍ⁺は、それぞれ独立に、無機又は有機カチオンを表す。
Ｒ^１、Ｒ^２、Ｒ^３、ｍ、Ａ及びＺは、上記と同じ意味を表す。
Ｒ’^１はＲ^１と、Ｒ’^２はＲ^２と、Ｒ’^３はＲ^３と、ｍ’はｍと、Ｚ’はＺと、それぞれ同じ意味を表す。〕

[M ⁺ independently represents an inorganic or organic cation.
R ¹ , R ² , R ³ , m, A and Z represent the same meaning as described above.
R ′ ¹ represents R ¹ , R ′ ² represents R ² , R ′ ³ represents R ³ , m ′ represents m, and Z ′ represents Z. ]

  Examples of the inorganic cation include lithium ion, sodium ion, and potassium ion. Examples of the organic cation include triethylammonium ion and N, N-didodecylphenylammonium ion. Sodium ion or N, N-didodecyl. A phenylammonium ion is preferred.

Compound (I) can be produced, for example, by subjecting a compound represented by formula (b) and a compound represented by formula (c) to a coupling reaction.
The compound represented by the formula (b) is obtained by diazotizing the compound represented by the formula (a) with nitrous acid, nitrite or nitrite. The compound represented by the formula (c) can be produced using a known production method.
In addition, compound (Is) can be obtained by the same production method as compound (I) by using HO ₃ S—A—NH ₂ as a raw material instead of the compound represented by formula (a).

(In the formulas (a) to (c), A, R ¹ , R ² and Z represent the same meaning as described above. X ⁻ represents an inorganic or organic anion.)

Examples of inorganic anions include fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, and hypochlorite ions. Organic anions include CH ₃ —COO ⁻ and Ph—COO ^−. Etc. Of these, chloride, bromide or _CH 3 -COO ^- is preferably.

  The coupling reaction between the compound represented by the formula (b) and the compound represented by the formula (c) is preferably performed at 20 to 60 ° C. in an aqueous solvent. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

  The method for obtaining the target compound (0) from the reaction mixture is not particularly limited, and various known techniques (such as acid precipitation or salting out) can be employed. The crystal collected by filtration is usually washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  Compound (0) exhibits high solubility in a solvent. Examples of the solvent in which compound (0) exhibits high solubility include hydroxycarboxylic acid esters (such as ethyl lactate), hydroxyketones (such as diacetone alcohol), and ethers (propylene glycol monomethyl ether, propylene glycol monomethyl ether). A solvent having low volatility such as acetate).

Since the compound (0) exhibits high solubility in a solvent and high spectral density, it can be used as a dye for fiber materials, liquid crystal display devices, and the like that display colors using reflected light or transmitted light. Moreover, since compound (0) has maximum absorption in a wavelength range of 400 to 450 nm when an absorption spectrum is measured, it is preferably used as a yellow dye.
When used as a dye, compound (0) may be used alone or in combination of two or more. For example, it is preferable to use a compound represented by the formula (I-2) in combination with a compound represented by the formula (I-3) because the solubility in a solvent is improved. In addition, when two or more compounds (0) are used in combination, solubility in an organic solvent is improved as compared with the case where one of them is used alone. Therefore, from the viewpoint of solubility in a solvent, it is also preferable to use a combination of two or more kinds of the compound (0) as a dye for a liquid crystal display device.

  The colored photosensitive resin composition of the present invention may be a colorant containing the compound (0) (hereinafter sometimes referred to as “colorant (A)”) or an alkali-soluble resin (hereinafter referred to as “alkali-soluble resin (B)”). A photopolymerizable compound (hereinafter sometimes referred to as “photopolymerizable compound (C)”), a photopolymerization initiator (hereinafter sometimes referred to as “photopolymerization initiator (D)”) and a solvent (hereinafter referred to as “solvent”). (E) ").

The colorant (A) may further contain a dye and / or pigment (A-2) other than the compound (0) in addition to the compound (0).
As dyes other than compound (0), Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, Reactive, Direct ( Examples thereof include compounds classified as Direct, Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Blue 35, 37, 38, 44, 59, 64, 67, 70;
C. I. Acid Blue 40, 45, 78, 80, 83, 90, 100, 171, 185;
C. I. Basic blue 65,140;
C. I. Reactive Blue 15, 38;
C. I. Disperse Blue 143;
C. I. Direct Blue 86, 87;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1;
C. I. Acid Black 58, 60, 107;
C. I. Solvent black 27, etc.

Examples of the pigment (A-2) include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and other metal compounds. Oxides or mixed metal oxides may be mentioned.
Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment in the Color Index (published by The Society of Dyers and Colorists). More specifically, the following color index (C.I.
) Numbered pigments, but are not limited thereto.

C. I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;
C. I. Pigment green 7, 10, 15, 25, 36 and 47;
C. I. Pigment brown 28;
C. I. Pigment Black 1 and 7, etc.

Content of a coloring agent (A) becomes like this. Preferably it is 5-60 mass% with respect to solid content in a colored photosensitive resin composition, More preferably, it is 8-55 mass%, More preferably, it is 10-10. 50% by mass. Here, solid content means the sum total of the component except a solvent in a coloring photosensitive resin composition.
When the colorant (A) further contains a dye and / or pigment (A-2) other than the compound (0), the content of the compound (0) in the colorant (A) is 3 to 80% by mass. , Preferably it is 3-70 mass%, More preferably, it is 3-50 mass%.
Content of the pigment (A-2) in a coloring agent (A) is 20-97 mass%, Preferably it is 30-97 mass%, More preferably, it is 50-97 mass%.

  The alkali-soluble resin (B) is not particularly limited, and any resin may be used. For example, the alkali-soluble resin (B) contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Specific examples of the alkali-soluble resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid. / Styrene / benzyl methacrylate / N-phenylmaleimide copolymer, copolymer of compound represented by formula (b1) and compound represented by formula (b2), compound represented by formula (b1) and formula ( A copolymer of the compound represented by b3) and a copolymer represented by the formula (B-1) are preferred.

  The weight average molecular weight in terms of polystyrene of the alkali-soluble resin (B) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000.

  50-150 are preferable, as for the acid value of alkali-soluble resin (B), More preferably, it is 60-135, Most preferably, it is 70-135.

  Content of alkali-soluble resin (B) is 7-65 mass% with respect to solid content of a coloring photosensitive resin composition, Preferably it is 13-60 mass%, More preferably, it is 17-55 mass%. It is.

  The photopolymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light. Examples thereof include compounds having a polymerizable carbon-carbon unsaturated bond.

  The photopolymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.

  It is preferable that content of a photopolymerizable compound (C) is 5-65 mass% with respect to solid content of a coloring photosensitive resin composition, More preferably, it is 10-60 mass%.

As said photoinitiator (D), an active radical generator, an acid generator, etc. are mentioned. An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and the like. Can be mentioned.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxide). Oxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl Like 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical, and for example, a triazine compound is also used as an acid generator.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 30% by mass and more preferably 1 to 30% by mass with respect to the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). 20% by mass. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

  Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, anisole, phenetole, and the like methyl anisole.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropion Methyl, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (E) in a colored photosensitive resin composition becomes like this. Preferably it is 70-95 mass% with respect to a colored photosensitive resin composition, More preferably, it is 75-90 mass%.

The colored photosensitive resin composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (product name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (product name) F142D, F171, F172, F173, F177, F177, F183, R30 (DIC) ), Ftop (trade name) EF301, EF303, EF351, EF351, EF352 (Mitsubishi Materials Denkasei), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass) Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (both trade names: manufactured by BM Chemie), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.

  The content of the surfactant (G) is preferably 0.00001 to 0.1% by mass, more preferably 0.00005 to 0.01% by mass, based on the colored photosensitive resin composition. When the content of the surfactant (G) is in the above range, the flatness tends to be good.

  The colored photosensitive resin composition of the present invention can be suitably used for forming a color filter or a colored pattern, and has a good colored pattern and color such as color density, brightness, contrast, sensitivity, resolution, and heat resistance. A filter can be obtained. Further, an optical film, an array substrate, a color filter substrate or the like provided with these color filters or colored patterns as a part of its constituent parts, and further comprising these color filters or colored patterns, an optical film, an array substrate, and a color filter substrate. A display device having at least one selected from the group, for example, a known liquid crystal display device, an organic EL device, a solid-state image sensor, and other devices related to various colored images can be used in a known manner. it can.

As a method of forming a color filter or a pattern thereof using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, on the substrate). The colored layer is applied on another colored photosensitive resin composition layer formed in advance, and a volatile component such as a solvent is removed / dried to form a colored layer, and the colored layer is exposed through a photomask. And a developing method and a method using an ink jet apparatus which does not require a photolithography method.
The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material used, application, etc., preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and still more preferably 1 to 6 μm. is there.

  Examples of the method for applying the colored photosensitive resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Moreover, you may apply | coat using coaters, such as a dip coater, a bar coater, a spin coater, a slit & spin coater, and a slit coater (it may also be called a die coater, a curtain flow coater, and a spinless coater). Especially, it is preferable to apply using a spin coater.

Examples of solvent removal and drying include natural drying, ventilation drying, and drying under reduced pressure. The specific drying temperature is preferably 10 to 120 ° C, more preferably 25 to 100 ° C.
The drying time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples and comparative examples, “%” and “parts” are mass% and mass parts unless otherwise specified.

Example 1
After adding 84 parts of water to 12.0 parts of anthranilic acid represented by the formula (a-1), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 18.0 parts of sodium nitrite was added and stirred for 30 minutes. After adding 54.3 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 16.9 parts of amidosulfuric acid in 168.7 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  After adding 192 parts of water to 27.8 parts of the barbituric acid derivative represented by the formula (c-1), the pH was adjusted to 8 to 9 with a 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a brown suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 29.4 parts (yield 77%) of the compound represented by the formula (I-2).

The structure of the compound (I-2) was confirmed using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).
Mass spectrometry:
Ionization mode = FD +: m / z = 438

Compound volume was dissolved in ethyl lactate (I-2) 0.35g and 250 cm ^3, a 2 cm ³ of its volume and diluted with ethyl lactate as a 100 cm ³ (density: 0.028g / L), spectrophotometric The absorption spectrum was measured using a total (quartz cell, cell length is 1 cm). This compound showed an absorbance of 2.0 (arbitrary unit) at λmax = 396 nm.

Comparative Example 1
The compound represented by the formula (d-1) was synthesized by the method described in Example 21 of Patent Document 1.
0.35 g of compound (d-1) was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with N, N-dimethylformamide to a volume of 100 cm ³ (concentration: 0 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.1 (arbitrary unit) at λmax = 394 nm.

<Evaluation of solubility in solvent>
The solubility of the compounds of Example 1 and Comparative Example 1 in the solvent was determined as follows:

In a 50 mL sample tube, each compound and each solvent shown in Table 8 were mixed at a mixing ratio of 1% (W / V) and 3% (W / V), respectively, and the mixture was ultrasonically shaken at 40 ° C. for 10 minutes after sealing. Gave. Next, the mixture was allowed to stand at room temperature for 30 minutes and then filtered to check for the presence of unnecessary substances.
1% (W / V) adjusted mixed solution with insoluble matter is made less than 1% solubility (×), 1% (W / V) adjusted mixed solution has no insoluble matter, 3% (W / V) The adjusted mixed solution with insoluble matter is defined as 1% to less than 3% solubility (Δ), and the 3% (W / V) adjusted mixed solution with no insoluble matter is 3% soluble. It was expressed as (○) as described above. The results are shown in Table 8.

ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＤＡＡ：ジアセトンアルコール

PGME: Propylene glycol monomethyl ether DAA: Diacetone alcohol

（Ｃ−１）重合性化合物：ジペンタエリスリトールヘキサアクリレート ５０％プロピレングリコールモノエチルエーテルアセテート溶液（日本化薬社製）
（Ｄ−１）光重合開始剤：ＯＸＥ-０１（オキシム化合物；チバ・ジャパン社製）
（Ｇ−１）界面活性剤：ＳＨ８４００（ポリエーテル変性シリコーンオイル；東レ・ダウコーニング（株）製） １％プロピレングリコールモノエチルエーテルアセテート溶液
（Ｅ−１）溶剤：プロピレングリコールモノメチルエーテルアセテート
を混合して着色感光性樹脂組成物を得る。 Example 2
[Preparation of colored photosensitive resin composition]
(I-2) Colorant: Compound (B-1) synthesized in Example 1 Resin: Resin having the following structure (average molecular weight 7500, acid value 111 mgKOH / g) 44.3% propylene glycol monoethyl ether acetate solution

(C-1) Polymerizable compound: dipentaerythritol hexaacrylate 50% propylene glycol monoethyl ether acetate solution (manufactured by Nippon Kayaku Co., Ltd.)
(D-1) Photopolymerization initiator: OXE-01 (oxime compound; manufactured by Ciba Japan)
(G-1) Surfactant: SH8400 (polyether-modified silicone oil; manufactured by Toray Dow Corning) 1% propylene glycol monoethyl ether acetate solution (E-1) Solvent: propylene glycol monomethyl ether acetate is mixed To obtain a colored photosensitive resin composition.

[Production of color filters]
On the glass, the colored photosensitive resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, it is baked to produce a color filter.

Example 3
After adding 150 parts of water to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 7.4 parts of sodium nitrite was added and stirred for 30 minutes. After adding 22.3 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 5.0 parts of amidosulfuric acid was dissolved in 50.3 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  After adding 155 parts of water and 155 parts of acetone to 15.5 parts of the barbituric acid derivative represented by the formula (c-1), the pH was adjusted to 8 to 9 with a 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a brown suspension. The yellow solid obtained by filtration was washed with 30% aqueous acetone. The washed yellow solid was dried at 60 ° C. under reduced pressure to obtain 12.1 parts (yield 46%) of the compound represented by formula (I-17).

The structure of the compound (I-17) was confirmed using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).
Mass spectrometry:
Ionization mode = FD +: m / z = 488

Compound (I-17) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), spectrophotometer The absorption spectrum was measured using a total (quartz cell, cell length is 1 cm). This compound showed an absorbance of 1.8 (arbitrary unit) at λmax = 397 nm.

Example 4
After adding 150 parts of water to 10.0 parts of p-anisidine-3-sulfonic acid represented by the formula (a-3), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 6.8 parts of sodium nitrite was added and stirred for 30 minutes. After adding 20.5 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 4.6 parts of amidosulfuric acid in 46.3 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  After adding 135 parts of water and 135 parts of acetone to 13.5 parts of the barbituric acid derivative represented by the formula (c-2), the pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a brown suspension. The yellow solid obtained by filtration was washed with 30% aqueous acetone. The washed yellow solid was dried at 60 ° C. under reduced pressure to obtain 11.5 parts (yield 48%) of the compound represented by the formula (I-18).

The structure of the compound (I-18) was confirmed using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).
Mass spectrometry:
Ionization mode = FD +: m / z = 488

Compound (I-18) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), spectrophotometric The absorption spectrum was measured using a total (quartz cell, cell length is 1 cm). This compound showed an absorbance of 2.2 (arbitrary unit) at λmax = 419 nm.

Example 5
After adding 150 parts of water to 10.0 parts of 2-amino-1-naphthalenesulfonic acid represented by the formula (a-4), the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 6.2 parts of sodium nitrite was added and stirred for 30 minutes. 18.7 parts of 35% hydrochloric acid was added in small portions to give a brown solution, and the mixture was stirred for 2 hours. An aqueous solution in which 4.2 parts of amidosulfuric acid was dissolved in 42.2 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  After adding 133 parts of water and 133 parts of acetone to 12.2 parts of the barbituric acid derivative represented by the formula (c-2), the pH was adjusted to 8-9 with a 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a brown suspension. The yellow solid obtained by filtration was washed with 30% aqueous acetone. The washed yellow solid was dried at 60 ° C. under reduced pressure to obtain 11.5 parts (yield 50%) of the compound represented by formula (I-19).

The structure of the compound (I-19) was confirmed by using a mass spectrometer JMS-700 (manufactured by JEOL Ltd.).
Mass spectrometry:
Ionization mode = FD +: m / z = 508

Compound (I-19) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L), spectrophotometer The absorption spectrum was measured using a total (quartz cell, cell length is 1 cm). This compound exhibited an absorbance of 2.1 (arbitrary unit) at λmax = 403 nm.

<Evaluation of solubility in solvent>
The solubility of the compounds of Examples 3 to 5 in the solvent was determined in the same manner as in Example 1. The results are shown in Table 9.

ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＤＡＡ：ジアセトンアルコール

PGME: Propylene glycol monomethyl ether DAA: Diacetone alcohol

  The compound of the present invention has good solubility in a solvent.

Claims (5)

Compound represented by formula (0).

[In Formula (0), A represents the bivalent aromatic hydrocarbon group which may have a substituent.
R ¹ and R ² are each independently a C _1-20 saturated aliphatic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or a substituent. Represents a C _6-20 aryl group _optionally having. However, the total number of carbon atoms in the substituents R ¹ and R ² is 6 or more and 16 or less.
Z represents an oxygen atom or a sulfur atom.
X represents a carboxy group or a sulfo group. ] The compound according to claim 1, wherein the compound represented by the formula (0) is a compound represented by the formula (I).

[In formula (I), A represents a divalent aromatic hydrocarbon group which may have a substituent.
R ¹ and R ² are each independently a C _1-20 saturated aliphatic hydrocarbon group which may have a substituent, a C _7-20 aralkyl group which may have a substituent, or a substituent. Represents a C _6-20 aryl group _optionally having. However, the total number of carbon atoms in the substituents R ¹ and R ² is 6 or more and 16 or less.
Z represents an oxygen atom or a sulfur atom. ]   The compound according to claim 1 or 2, wherein A is a phenylene group, and a hydrogen atom contained in the phenylene group may be substituted with a halogen atom, a methyl group, a methoxy group, or a sulfo group. The compound according to any one of claims 1 to 3, wherein any one of R ¹ and R ² is a C _6-20 aryl group which may have a substituent. The compound according to any one of claims 1 to 4, wherein the compound represented by the formula (I) is a compound represented by the formula (II).

[In the formula (II), R ¹ , R ² and Z represent the same meaning as described above.
R ³ represents a halogen atom, a methyl group, a methoxy group or a sulfo group.
m represents an integer of 1 or 2. When m is 2, the plurality of R ³ may be the same type of group or different types of groups. ]