JP2010170073A - Colored photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition, obtaining high contrast coating film and color filter. <P>SOLUTION: The colored photosensitive resin composition includes: a colorant (A); a binder resin (B); a photopolymerizable compound (C), a photo polymerization initiator (D) and a solvent (E). The colorant (A) is a colorant containing at least one selected from a group of compound expressed by the formula (I) and its salt. In the formula(I), R<SP>1</SP>-R<SP>4</SP>each independently indicate a hydrogen atom, 1-10C saturated aliphatic hydrocarbon group or a carboxyl group. R<SP>5</SP>-R<SP>12</SP>each independently indicate a hydrogen atom, a hologen atom, 1-10C saturated aliphatic hydrocarbon group, halogenated 1-10C saturated aliphatic hydrocarbon group, 1-8C alkoxyl group, carboxyl group, sulfo group, sulfamoyl group, or N-substitutional sulfamoyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition suitable for forming a colored image constituting a color filter used in a liquid crystal display element, and a color filter using the colored photosensitive resin composition.

In color filters, high definition, high brightness, and high contrast are desired.
In recent colored photosensitive resin compositions forming red pixels of color filters, the spectral characteristics of the red pixels are adjusted by including a yellow pigment as a colorant for complementary color of the red pigment. For example, Patent Document 1 discloses C.I. as a red pigment and a yellow pigment for complementary color. A red pixel composed of a red photosensitive resin composition containing I pigment yellow 150 is described.

JP 2007-133131 A

  In the conventional colored photosensitive resin composition, the contrast of the obtained coating film and the color filter may not always be sufficiently satisfactory.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors have determined that C.I. According to the colored photosensitive resin composition containing at least one selected from the group consisting of a compound represented by the formula (I) and a salt thereof without using I Pigment Yellow 150, a coating film and a color filter obtained The present inventors have found that the contrast can be improved, and have reached the present invention.

  That is, the present invention includes a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and the colorant (A) is represented by the formula ( A colored photosensitive resin composition which is a colorant containing at least one selected from the group consisting of the compound represented by I) and a salt thereof.

[In Formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group or a carboxyl group.
R ^{5 to} R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, or a carboxyl group. , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ]

The present invention, at least one of R ⁵ to R ¹² is the above-mentioned colored photosensitive resin composition is N- substituted sulfamoyl group.

The present invention ^is at least one of the colored photosensitive resin composition is N- substituted sulfamoyl group and at least one of ^R 9 ^{to R 12} of R 5 to R ^8.

The present invention also provides the above colored photosensitive resin composition, wherein at least one of R ⁶ and R ⁷ and at least one of R ¹⁰ and R ¹¹ is an N-substituted sulfamoyl group.

In the present invention, the N-substituted sulfamoyl group is a —SO ₃ NHR ¹⁵ group, and R ¹⁵ is a C _1-10 substituted aliphatic hydrocarbon group or a C _1-8 alkoxyl group substituted C _{1. It} is the said colored photosensitive resin composition showing a C- ₁₀ saturated aliphatic hydrocarbon group, a _C1-8 alkoxyl group, a _C6-20 aryl group, a _C7-20 aralkyl group, or a _C2-10 acyl group.

In the present invention, at least one of R ¹³ and R ¹⁴ is a —CON (R ¹⁶ ) R ¹⁷ group, and each of R ¹⁶ and R ¹⁷ independently represents a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon. The above-mentioned colored photosensitive group, which represents a C _1-10 saturated aliphatic hydrocarbon group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group substituted with a C _1-8 alkoxyl group It is an adhesive resin composition.

  Further, the present invention provides the above colored photosensitive resin, wherein the colorant (A) is a colorant containing a colorant different from at least one selected from the group consisting of the compound represented by formula (I) and a salt thereof. It is a composition.

  In the present invention, a colorant different from at least one selected from the group consisting of the compound represented by formula (I) and a salt thereof is C.I. I. Pigment Red 177 and C.I. I. The colored photosensitive resin composition is at least one selected from the group consisting of CI Pigment Red 254.

  Moreover, this invention is a coating film formed using the said colored photosensitive resin composition.

  Moreover, this invention is a color filter containing the said coating film.

  Moreover, this invention is the said coating film formed by the photolithographic method.

  According to the colored photosensitive resin composition of the present invention, a high-contrast coating film and a color filter can be obtained.

［式（Ｉ）中、Ｒ¹〜Ｒ^４は、それぞれ独立に、水素原子、Ｃ_1-10飽和脂肪族炭化水素基又はカルボキシル基を表す。
Ｒ^５〜Ｒ^１２は、それぞれ独立に、水素原子、ハロゲン原子、Ｃ_1-10飽和脂肪族炭化水素基、ハロゲン化Ｃ_1-10飽和脂肪族炭化水素基、Ｃ_1-8アルコキシル基、カルボキシル基、スルホ基、スルファモイル基、又はＮ−置換スルファモイル基を表す。
Ｒ^１３及びＲ^１４は、それぞれ独立に、水素原子、シアノ基、カルバモイル基、又はＮ−置換カルバモイル基を表す。］
なお本明細書において、Ｃ_a-bとは、炭素数がａ以上、ｂ以下であることを意味する。 The colored photosensitive composition of the present invention contains a colorant (A), and the colorant (A) is a compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”) and a salt thereof. Containing at least one selected from the group consisting of:

Wherein (I), R ¹ ~R ⁴ each independently represent a hydrogen atom, C _1-10 saturated aliphatic hydrocarbon group or a carboxyl group.
R ^{5 to} R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, a C _1-8 alkoxyl group, or a carboxyl group. , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ]
In the present specification, C _ab means that the carbon number is a or more and b or less.

The saturated aliphatic hydrocarbon group for R ^{1 to} R ⁴ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is 1-10 normally, Preferably it is 2-8, More preferably, it is 3-6. Examples of the saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

For example, in order to increase color density, at least one of R ^{1 to} R ⁴ (preferably both) is a saturated aliphatic hydrocarbon group having 5 or less (preferably 3 or less) carbon atoms (for example, methyl group, ethyl group). Group) or a hydrogen atom.

The halogen atom for R ^{5 to} R ¹² is preferably a fluorine atom, a chlorine atom or a bromine atom.

As in the case of R ^{1 to} R ⁴ , the saturated aliphatic hydrocarbon group for R ^{5 to} R ¹² may be linear, branched or cyclic, and the carbon number is usually 1 to 10 , Preferably 2-8, more preferably 3-6. Specific examples of the saturated aliphatic hydrocarbon group for R ^{5 to} R ¹² are the same as those for R ^{1 to} R ⁴ . The saturated aliphatic hydrocarbon group of R ^{5 to} R ¹² may be substituted with a halogen atom, preferably a fluorine atom. Specific examples of the halogenated saturated aliphatic hydrocarbon group include a trifluoromethyl group.

The number of carbon atoms of the alkoxyl group R ⁵ to R ¹² is usually 1-8, preferably 1-4. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

The N-substituted sulfamoyl group of R ^{5 to} R ¹² is preferably an N-1 substituted sulfamoyl group, and can be represented by —SO ₂ NHR ¹⁵ . R ¹⁵ is, C _1-10 saturated aliphatic hydrocarbon group, C _1-8 C _1-10 saturated aliphatic hydrocarbon radical alkoxyl group is substituted, C _6-20 aryl group, C _7-20 aralkyl group Or a C _2-10 acyl group.

From the viewpoint of enhancing oil solubility, one or more of R ^{5 to} R ¹² (for example, one or more (especially one) from R ^{5 to} R ⁸ and one or more from R ^{9 to} R ¹² (particularly, particularly) 1)) or a relatively bulky group from the above examples, or one or more of R ^{5 to} R ¹² (for example, one or more (especially one from R ^{5 to} R ⁸ )) It is preferable that one or more (especially one) of R ^{9 to} R ^{12 be} substituted at the meta position or the ortho position with respect to the azo group. It is possible to reduce the stacking of the biphenyl moiety and improve the oil solubility by setting it to the meta position, selecting a bulky group, or making the substitution position ortho to the azo group. in, can protect the azo group, it is possible to enhance the light resistance. as bulky R ⁵ to R ¹² of said, t Saturated aliphatic carbonization in which two or more (especially three or more) halogen atoms such as branched saturated aliphatic hydrocarbon groups (particularly tertiary saturated aliphatic hydrocarbon groups) such as ert-butyl group and trifluoromethyl group are bonded. Examples thereof include a hydrogen group and an N-substituted sulfamoyl group.

Preferably, at least one of R ^{5 to} R ¹² is an N-substituted sulfamoyl group, more preferably at least one of R ^{5 to} R ⁸ and at least one of R ^{9 to} R ¹² is an N-substituted sulfamoyl group. It is particularly preferred that at least one of R ⁵ and R ⁸ and at least one of R ⁹ and R ¹² is an N-substituted sulfamoyl group.

The saturated aliphatic hydrocarbon group for R ¹⁵ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is usually 1 to 10, preferably 6 to 10, for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (1,5-dimethylhexyl group) Etc.), ethylhexyl group (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (such as 2-methylcyclohexyl group), cyclohexylalkyl group and the like. As described above, the saturated aliphatic hydrocarbon group for R ¹⁵ may be substituted with a substituent such as a C _1-8 (preferably C _1-4 ) alkoxyl group. Examples of the substituted saturated aliphatic hydrocarbon group include a propoxypropyl group (3- (isopropoxy) propyl group and the like).

The aryl group of R ¹⁵ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is counted including the carbon number of the substituent, and is usually 6 to 20, preferably 6 to 10. Examples of these aryl groups include unsubstituted or substituted phenyl groups such as a phenyl group, a hydroxyphenyl group (such as 4-hydroxyphenyl group), and a trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group).

The alkyl part of the aralkyl group for R ¹⁵ may be either linear or branched.
The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. The aralkyl is typically a phenylalkyl group such as a benzyl group or a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

The acyl group of R ¹⁵ may be unsubstituted or may be bonded to a substituent such as a saturated aliphatic hydrocarbon group or an alkoxyl group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10 normally, Preferably it is 6-10. Examples of the acyl group include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ¹⁵ may be further limited from the viewpoint of further increasing the color density, oil solubility, and the like. Such ^{R 15,} for example, (such as 1,1,3,3-tetramethylbutyl group) methylbutyl group, (such as cyclohexyl group 1,5-dimethyl) hexyl group methyl, cyclohexyl group ethyl (2 -Ethylhexyl group etc.), methylcyclohexyl group (2-methylcyclohexyl group etc.), saturated aliphatic hydrocarbon group having a branched carbon such as phenylbutyl group (3-amino-1-phenylbutyl group etc.), or aralkyl group Is mentioned.

The carbamoyl group of R ¹³ and R ¹⁴ is the structural formula of —CON (R ¹⁶ ) R ¹⁷ (wherein R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group, A C _1-10 saturated aliphatic hydrocarbon group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group substituted by a C _1-8 alkoxyl group. Can do. Descriptions and specific examples of the saturated aliphatic hydrocarbon group, aryl group, aralkyl group, and acyl group of R ¹⁶ and R ¹⁷ are the same as those described above for R ¹⁵ . However, specific examples of the acyl group further include a benzoyl group containing a halogen atom, such as a bromobenzoyl group (such as a p-bromobenzoyl group). It is preferred that at least one of R ¹³ and R ¹⁴ is a —CON (R ¹⁶ ) R ¹⁷ group.

In order to increase the color density, at least one of R ¹⁶ and R ¹⁷ (preferably both) is a saturated aliphatic hydrocarbon group having 3 or less carbon atoms (for example, a methyl group, an ethyl group, and particularly a methyl group), Or it is preferable that it is a hydrogen atom. In order to improve solubility, it is preferable that at least one of R ¹⁶ and R ¹⁷ is an acetyl group.

When two or more types of compound (I) are used in combination, the amount dissolved in an organic solvent (oil solubility) is greater than when one of them is used alone. Therefore, from the viewpoint of oil solubility, it is also a preferred embodiment to use a combination of two or more kinds of compound (I) as the dye of the liquid crystal display device. Compound (I) (disulfoamide) having two N-substituted sulfamoyl groups and compound (I) (monosulfoamide) having one N-substituted sulfamoyl group and one sulfo group as an example of a combination that improves oil solubility ) And a combination thereof. Among such combinations, one of R ^{5 to} R ⁸ and one of R ^{9 to} R ¹² is an N-substituted sulfamoyl group, and the remainder is a hydrogen atom, and R ^{5 to} R ^8. A combination with a monosulfoamide in which one of them is an N-substituted sulfamoyl group, one of R ^{9 to} R ¹² is a sulfo group and the rest is a hydrogen atom is preferred. Monosulfonamide is particularly preferred from the viewpoint of color density because it has a lower molecular weight than disulfonamide.

  Preferred examples of formula (I) include formulas (I-1) to (I-10).

さらに式（Ｉ）の好ましい例には、式（ＩＩ）で表されるような、Ｒ^５〜Ｒ^８の少なくとも１つ、並びにＲ^９〜Ｒ^１２の少なくとも１つが、−ＳＯ₂ＮＨＲ^１５基であり、残りの６つが水素原子である化合物も含まれる。

Further preferred examples of formula (I) include, as represented by formula (II), at least one of R ^{5 to} R ⁸ and at least one of R ^{9 to} R ¹² is a —SO ₂ NHR ¹⁵ group. There are also compounds in which the remaining six are hydrogen atoms.

式（ＩＩ）の好ましい例は、式（ＩＩ−１）〜（ＩＩ−８）である。

Preferred examples of formula (II) are formulas (II-1) to (II-8).

化合物（Ｉ）の塩としては、Ｒ^５〜Ｒ^１２がスルホ基の場合のスルホン酸塩、Ｒ^５〜Ｒ^１２がカルボキシル基の場合のカルボン酸塩が挙げられる。またこれら塩を形成するカチオンは特に限定されないが、溶媒に対する溶解性を考慮すると、リチウム塩、ナトリウム塩、カリウム塩のようなアルカリ金属塩；アンモニウム塩；及びエタノールアミン塩、アルキルアミン塩のような有機アミン塩などが好ましい。特にアルカリ金属塩（好ましくはナトリウム塩）は、偏光膜基材に含有させる場合に有用である。また有機アミン塩は、樹脂硬化性化合物に含有させる場合に有用であり、さらには非金属塩であるため、絶縁性が重要視される分野でも有用である。

The salt of compound ^(I), sulfonates where R 5 ^{to R 12} is a sulfo ^group, R 5 ^{to R 12} may be mentioned carboxylic acid salts for the carboxyl group. 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 and the like are preferred. 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.

Compound (I) can be produced by coupling a diazonium salt and a pyridone, as is well known in the dye field. For example, a compound of the formula (b) obtained by diazotizing a benzidine compound (diazo component) represented by the formula (a) with nitrous acid, nitrite or nitrite can be used as the diazonium salt (formula ( In a) and (b), R ^{5 to} R ¹² represent the same meaning as described above.

そしてジアゾニウム塩（ｂ）と、式（ｃ）及び／又は（ｄ）で表されるピリドン類（カップリング成分）とを、通常、水性溶媒中２０〜６０℃で反応させることにより、化合物（Ｉ）を製造することができる（式（ｃ）及び（ｄ）中、Ｒ¹〜Ｒ^４、Ｒ^１３及びＲ^１４は、前記と同じ意味を表す。なお、式（ｃ）及び（ｄ）とは、同一であってもよい。）。

Then, by reacting the diazonium salt (b) with the pyridones represented by the formula (c) and / or (d) (coupling component) usually in an aqueous solvent at 20 to 60 ° C., the compound (I (In the formulas (c) and (d), R ^{1 to} R ⁴ , R ¹³ and R ¹⁴ have the same meanings as described above. In the formulas (c) and (d), , May be the same).

The target compound in which at least one of R ^{5 to} R ¹² in formula (I) is a sulfamoyl group or an N-substituted sulfamoyl group can also be produced by using the compound (a) having a sulfamoyl group or an N-substituted sulfamoyl group. After the coupling reaction using the compound (a) having a sulfo group, it is sure to produce the sulfo group by sulfonamidation. For example, a compound in which at least one of R ^{5 to} R ¹² in formula (I) is a sulfo group (hereinafter referred to as “azosulfonic acid (I)”) is synthesized, and a sulfo group (—SO ₃ H) is obtained by using a halogenated thionyl compound. ) Is a sulfone halide (—SO ₂ X; X is a halogen atom) to obtain a sulfone halide compound, and then the sulfo group is sulfonamidated by reacting the sulfone halide compound with an amine to form a sulfonamide compound (compound (I)) can be obtained.

  Preferable examples of azosulfonic acid (I) include compounds represented by formulas (I-1) to (I-7), (I-9) and (I-10), and particularly preferable examples include: Examples thereof include compounds represented by formulas (I-1) to (I-3), (I-9) and (I-10). Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl bromide, thionyl iodide and the like, preferably thionyl chloride and thionyl bromide, and particularly preferably thionyl chloride. The amount of thionyl halide used is, for example, about 1 to 10 moles with respect to 1 mole of azosulfonic acid (I). When water is brought into the reaction system, it is preferable to use an excessive amount of the thionyl halide compound.

  The sulfonation is usually performed in a solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly preferably cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, Halogenated hydrocarbons such as amyl chloride and 1,2-dibromoethane can be used. The amount of the solvent used is, for example, about 3 parts by mass (preferably 5 parts by mass or more) and 10 parts by mass or less (preferably 8 parts by mass or less) with respect to 1 part by mass of azosulfonic acid (I).

  In sulfonation, it is preferable to use N, N-dialkylformamide (for example, N, N-dimethylformamide, N, N-diethylformamide, etc.) in combination. When N, N-dialkylformamide is used, the amount used is, for example, about 0.05 to 1 mol with respect to 1 mol of the thionyl halide compound. When azosulfonic acid (I) and N, N-dialkylformamide are mixed in advance in a solvent and then a thionyl halide compound is added, heat generation can be suppressed.

  The reaction temperature in sulfonation is, for example, 0 ° C. or higher (preferably 30 ° C. or higher) and 70 ° C. or lower (preferably 60 ° C. or lower). The reaction time is, for example, about 0.5 hours or more (preferably 3 hours or more) and 8 hours or less (preferably 5 hours or less).

  The sulfone halide compound prepared as described above may be isolated and then reacted with the amine, or may be reacted with the amine in the form of a reaction mixture without isolation. In the case of isolation, for example, the reaction mixture and water may be mixed, and the precipitated crystals may be collected by filtration. The obtained sulfone halide compound crystals may be washed with water and dried as necessary before the reaction with the amine. In this specification, in order to distinguish this amine from the basic catalyst described later, hereinafter, it may be referred to as a reactive amine.

Examples of the reactive amine include a primary amine, and the primary amine is represented by the formula H ₂ N—R ¹⁵ (R ¹⁵ is the same as described above).
Specific examples of H ₂ N—R ¹⁵ include n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine and the like), tetramethylbutylamine (1,1,3,3). 3-tetramethylbutylamine and the like), ethylhexylamine (such as 2-ethylhexylamine), aminophenylbutane (such as 3-amino-1-phenylbutane), and isopropoxypropylamine. The amount of the reactive amine used is usually about 3 mol or more and 10 mol or less (preferably 7 mol or less) with respect to 1 mol of the sulfone halide compound.

  The order of addition of the sulfone halide compound and the reactive amine is not particularly limited, but the reactive amine is often added (dropped) to the sulfone halide compound. The reaction between the sulfone halide compound and the reactive amine is usually carried out in a solvent. Examples of the solvent include the same solvents as those used when preparing the sulfone halide compound.

  The reaction between the sulfone halide and the reactive amine is preferably carried out in the presence of a basic catalyst. Examples of the basic catalyst include tertiary amines (particularly aliphatic tertiary amines such as triethylamine and triethanolamine), pyridine bases such as pyridine and methylpyridine, and the like. Among these, tertiary amines, particularly aliphatic tertiary amines such as triethylamine are preferable. The usage-amount of a basic catalyst is about 1.1 mol or more and 6 mol or less (preferably 5 mol or less) normally with respect to a reactive amine (the said amine reacted with a sulfone halide).

  When a reactive amine and a basic catalyst are added to the sulfone halide compound, the timing of adding the basic catalyst is not particularly limited, and may be before or after the addition of the reactive amine. You may add at the same timing. Further, it may be added after mixing with the reactive amine in advance, or may be added separately from the reactive amine.

  The reaction temperature between the sulfone halide compound and the reactive amine is, for example, 0 ° C. or higher and 50 ° C. or lower (preferably 30 ° C. or lower). The reaction time is usually about 1 to 5 hours.

  A method for obtaining the target sulfonamide compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture is preferably mixed with an acid (acetic acid) and water, and the precipitated crystals are collected by filtration. It is preferable that the acid and water are prepared in advance as an aqueous acid solution and then the reaction mixture is added to the aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C. or higher, preferably 20 ° C. or higher and 50 ° C. or lower, preferably 30 ° C. or lower. Moreover, after addition, it is common to stir at the same temperature for about 0.5 to 2 hours. 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.

  The colored photosensitive resin composition of the present invention contains a colorant different from compound (I) in addition to compound (I). Examples of the colorant different from the compound (I) include dyes and pigments. One or two or more colorants may be combined. In that case, in addition to a combination of only a dye and a pigment, a dye and a pigment may be used in combination.

  Examples of the dye include acid dyes, basic dyes, direct dyes, sulfur dyes, vat dyes, naphthol dyes, reactive dyes, and disperse dyes, which can be selected from conventionally known dyes for use in color filters.

  Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 808,501, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6 -51115 gazette, Unexamined-Japanese-Patent No. 6-194828, etc. are mentioned.

  The chemical structure of the dye includes pyrazole azo, anilino azo, aryl azo, pyrazolo triazole azo, pyridone azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, cyanine, polymethine, Phenothiazine, pyrrolopyrazole, azomethine, xanthene, phthalocyanine, quinophthalone, benzopyran, indigo, dioxazine, coumarin, squarylium, and preferably pyrazole azo, anilinoazo, pyrazolotriazole azo , Pyridone azo, anthraquinone, anthrapyridone, phthalocyanine, dioxazine, quinophthalone, xanthene, more preferably pyrazole azo, pyridone azo, Taroshianin system, quinophthalone, and the like xanthene.

  Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments according to the color index (published by The Society of Dyers and Colorists).

Specifically, for example,
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;

In particular, in the case of a red pixel, C.I. I. It is preferable to contain at least one pigment selected from at least one pigment selected from CI Pigment Red 177, 209, and 254. These pigments may be used alone or in combination of two or more. In particular, C.I. I. Pigment Red 177, C.I. I. Pigment Red 254 is preferable.

  Among the above pigments, organic pigments may be rosin-treated, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group is introduced, or grafting to the pigment surface with a polymer compound, if necessary. Treatment, atomization by sulfuric acid atomization, or the like, cleaning by an organic solvent or water for removing impurities, removal by ion exchange of ionic impurities, or the like may be performed.

As the pigment dispersant, commercially available surfactants can be used, for example, silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. Each is used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by DIC Corporation), and Florard (Sumitomo 3M). Manufactured by Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by GENECA), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by Ajinomoto Co., Inc.), Disperbyk (Bicchemy) Manufactured).
When the pigment dispersant is used, the amount used is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less per 1 part by mass of the pigment. When the amount of the pigment dispersant used is in the above range, it is preferable because a pigment dispersion in a uniform dispersion state tends to be obtained.

  Content of a coloring agent (A) is a mass fraction with respect to solid content in a coloring photosensitive resin composition, Preferably it is 5-60 mass%, More preferably, it is 8-55 mass%, Furthermore, Preferably it is 10-50 mass%. Here, solid content means the sum total of the components except a solvent in a coloring photosensitive resin composition.

  When the content of the colorant (A) is in the above range, the color density when a color filter is obtained is sufficient, and a necessary amount of the binder polymer can be contained in the composition. It is preferable because a sufficient pattern can be formed.

  The content of the compound (I) in the colorant (A) is preferably 1% to 60% with respect to the colorant (A). Moreover, when a coloring agent (A) contains a pigment, it is preferable that content of a pigment is 40%-99% with respect to a coloring agent (A).

When the content of the compound (I) in the colorant (A) is in the above range, it is easy to optimize the transmission spectrum, and it is good for obtaining high contrast and high brightness. It is preferable because of its good chemical resistance.
Other dyes may be used in combination as long as the effects of the present invention are not affected.

  The colored photosensitive resin composition of the present invention contains a binder resin (B). The binder resin (B) preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 in terms of mole fraction in all the structural units constituting the binder resin (B). It is from mol% to 38 mol%. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility of the non-pixel portion is good during development, and the residue tends not to remain in the non-pixel portion after development. Yes, it is preferable.

  Examples of the other monomer that leads to the constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain Examples thereof include macromonomers having a methacryloyl group, units represented by the formula (III), and units represented by the formula (IV).

(In Formula (III) and Formula (IV), R ²³ and R ²⁵ each independently represent a hydrogen atom or a methyl group. R ²⁴ and R ²⁶ each independently represent a hydrogen atom or a C _1-6 alkyl. Represents a group.)

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (III) (wherein, in formula (III), R ²³ represents a methyl group and R ²⁴ represents a hydrogen atom) ) / Benzyl methacrylate copolymer, component represented by formula (III) (wherein, in formula (III), R ²³ represents a methyl group and R ²⁴ represents a hydrogen atom). / Benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (IV) (however, Here, in formula (IV), R ²⁵ represents a methyl group and R ²⁶ represents a hydrogen atom.) / Styrene copolymer / Tricyclodecanyl methacrylate copolymer and the like are preferable.

  The acid value of binder resin (B) used by this invention is 50-150 normally, Preferably it is 60-135, Most preferably, it is 70-135. When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. Is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. it can.

  Content of binder resin (B) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, and is 7-65 mass% normally, Preferably it is 13-60 mass%, More preferably 17-55 mass%. When the content of the binder resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

Binder resin having a component represented by the formula (III), for example, methacrylic acid / a component represented by the formula (III) (wherein, in the formula (III), R ²³ represents a methyl group, R ²⁴ represents a hydrogen atom.) / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer is represented by the formula (V). Wherein R ²⁷ represents a hydrogen atom in the formula (V).

Methacrylic acid / constituent component represented by formula (IV) (wherein, in formula (IV), R ²⁵ represents a methyl group and R ²⁶ represents a hydrogen atom) / styrene copolymer / tricyclo The decanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.

  The weight average molecular weight in terms of polystyrene of the binder resin is usually 5,000 to 35,000, preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  In particular, the binder resin (B) represented by the formula (VI) is preferable in terms of curability and developability.

  Copolymerization is generally carried out in a solvent using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (methyl 2-methylpropionate), benzoyl peroxide and tert-butyl peroxide. A peroxide such as is used. The solvent may be any solvent that dissolves each monomer. For example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Is used. The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator and the boiling points of the solvent and the monomer. The side chain of the copolymer thus obtained can be modified with a compound having a polymerizable group to form a photosensitive binder resin (B). At this time, a catalyst for introducing a polymerizable group into the resin may be added. An example of the catalyst is trisdimethylaminomethylphenol. Moreover, you may add the additive for preventing a side reaction. Examples of the additive include hydroquinone.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) 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, and is, for example, polymerizable carbon-carbon unsaturated. Examples thereof include compounds having a bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The photopolymerizable compound (C) may be used alone or in combination of two or more, and the content thereof is 7 to 65% by mass with respect to the solid content of the colored photosensitive resin composition. It is preferable that it is, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the photopolymerizable compound (C) is within the above range, curing is sufficiently performed, the film thickness ratio before and after the development is improved, and the pattern is less likely to be undercut and adhesion is improved. It is preferable because it tends to be good.

  The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include acetophenone compounds, active radical generators, and acid generators.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) 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-methylthiophenyl) propan-1-one and the like. It is done.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

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

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) 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) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] ethanone 1-O-acetate, 1- [9-ethyl-6- (2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl) -9H -Carbazol-3-yl] ethanone 1-O-acetate and the like.

  Examples of active radical generators other than those exemplified above 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, etc. can also 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. For example, a triazine photopolymerization initiator is also used as an acid generator.

  Content of a photoinitiator (D) is a mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C), Preferably it is 0.1-30 mass%, More preferably Is 1-20 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.

  The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (F). The photopolymerization initiation assistant (F) is usually used in combination with the photopolymerization initiator (D), and is a compound used to accelerate the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. is there.

  Examples of the photopolymerization initiation assistant (F) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9 , 10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene 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.

  The photopolymerization initiation assistant (F) may be used alone or in combination of two or more. Moreover, as a photopolymerization start adjuvant (F), a commercially available thing can also be used, and as a commercially available photopolymerization start adjuvant (F), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (F) in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylke / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

  When using these photoinitiators (F), the amount used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of photopolymerization initiator (D). .

  The colored photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethyl sulfoxide, 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, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol 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, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

  Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone are preferable, and it is more preferable to use these in combination.
Furthermore, the said solvent may be used individually or in combination of 2 or more types.

  Content of the solvent (E) in a colored photosensitive resin composition is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 70-95 mass%, More preferably, it is 75-90 mass%. . If the content of the solvent (E) is in the above range, the flatness at the time of application is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. preferable.

  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, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) .

  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 (manufactured by Shin-Akita Kasei Co., Ltd.), 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, MegaFac (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.

  Content of surfactant (G) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 0.00001-0.1 mass%, More preferably, it is 0.00005-0.01 mass%. It is. When the content of the surfactant (G) is in the above range, the flatness tends to be good, which is preferable.

  As a method for forming a color filter pattern 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 a substrate). To another colored photosensitive resin composition layer, etc. formed on the substrate, removes volatile components such as a solvent to form a colored layer, exposes the colored layer through a photomask, and develops it. Examples thereof include a method using an inkjet apparatus that does not require a method and a photolithography method.

  According to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film with excellent brightness.

  The colored photosensitive resin composition of the present invention can be formed on an element such as a liquid crystal display element, and is useful for coloring these.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are by weight and parts by weight unless otherwise specified.

Synthesis example 1
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 136 g of propylene glycol monomethyl ether acetate, a solution obtained by adding 3.6 g of 2,2′-azobisisobutyronitrile was added dropwise, and stirring was continued at 100 ° C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin solution B1 having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 3.0 × 10 ⁴ .

  About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-1, A-2500, A-500
(Manufactured by Tosoh Corporation)
Example 1
[Preparation of colored photosensitive resin composition 1]
(A) Colorant: C.I. I. Pigment Red 177 31 parts (A) Colorant: C.I. I. Pigment Red 254 58 parts Acrylic pigment dispersant 5 parts Propylene glycol monomethyl ether acetate 137 parts are mixed and the pigment is sufficiently dispersed using a bead mill.
(A) Colorant: Compound represented by formula (Ia) 11 parts (B) Resin: Resin solution B1 157 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 Part (D) Photopolymerization initiator: OXE-01
(Ciba Specialty Chemicals) 15 parts (E) Solvent: 289 parts of propylene glycol monomethyl ether acetate was mixed to obtain a colored photosensitive resin composition 1.

[Formation of pattern]
The colored photosensitive resin composition 1 was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) , And was irradiated with light at an exposure dose of 150 mJ / cm ² (based on 365 nm). After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. And post-baked for 20 minutes. After standing to cool, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm.

[Evaluation]
About the coating film on the obtained glass substrate, xy chromaticity coordinates (Rx, Ry) in the XYZ color system of CIE using a C light source with a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) Was measured, and the contrast was measured using a contrast meter (color / color difference meter BM-5A; manufactured by Topcon Corporation). The results are shown in Table 1.

Comparative Example 1
[Preparation of Comparative Colored Photosensitive Resin Composition 1]
(A) Colorant: C.I. I. Pigment Red 177 46 parts (A) Colorant: C.I. I. Pigment Red 254 43 parts Acrylic Pigment Dispersant 5 parts Propylene Glycol Monomethyl Ether Acetate 137 parts are mixed, the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: Compound represented by formula (VII) containing melamine as a guest compound (commonly known as Pigment Yellow 150) 11 parts

（Ｂ）樹脂：樹脂溶液Ｂ１ １５７ 部
（Ｃ）光重合性化合物：ジペンタエリスリトールヘキサアクリレート
（日本化薬（株）製） ５０ 部
（Ｄ）光重合開始剤：ＯＸＥ−０１
（チバ・スペシャリティ・ケミカルズ社製） １５ 部
（Ｅ）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 ２８９ 部
を混合して比較着色感光性樹脂組成物１を得た。実施例１と同様にして膜厚２．２μｍのパターンを形成し、評価した。結果を表１に示す。

(B) Resin: Resin solution B1 157 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) 50 parts (D) Photopolymerization initiator: OXE-01
(Ciba Specialty Chemicals Co., Ltd.) 15 parts (E) Solvent: 289 parts of propylene glycol monomethyl ether acetate were mixed to obtain comparative colored photosensitive resin composition 1. A pattern having a thickness of 2.2 μm was formed and evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As is clear from Table 1, in Examples using Compound (I), when Rx and Ry were the same, high contrast was confirmed.

  According to the colored photosensitive resin composition of the present invention, a high-contrast coating film and a color filter can be obtained.

Claims (11)

A colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E) are included, and the colorant (A) is represented by the formula (I). A colored photosensitive resin composition, which is a colorant containing at least one selected from the group consisting of a compound and a salt thereof.

[In Formula (I), R ^{1 to} R ⁴ each independently represents a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group or a carboxyl group.
R ⁵ to R ¹² are each independently a hydrogen atom, a halogen atom, a C _1-10 saturated aliphatic hydrocarbon group, a halogenated C _1-10 saturated aliphatic hydrocarbon group, C _1-8 alkoxyl group, a carboxyl group , A sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group.
R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group. ] The colored photosensitive resin composition according to claim 1, wherein at least one of R ^{5 to} R ¹² is an N-substituted sulfamoyl group. The colored photosensitive resin composition according to claim 1 or 2, wherein at least one of R ^{5 to} R ⁸ and at least one of R ^{9 to} R ¹² are N-substituted sulfamoyl groups. At least one of R ⁶ and ^{R 7,} and at least one of ^{R 10} and ^{R 11,} colored photosensitive resin composition according to any one of claims 1 to 3 which is N- substituted sulfamoyl group. The N-substituted sulfamoyl group is a —SO ₃ NHR ¹⁵ group, and R ¹⁵ is a C _1-10 saturated aliphatic group substituted with a C _1-10 saturated aliphatic hydrocarbon group or a C _1-8 alkoxyl group. The colored photosensitive resin composition according to any one of claims 1 to 4, which represents a hydrocarbon group, a C _1-8 alkoxyl group, a C _6-20 aryl group, a C _7-20 aralkyl group, or a C _2-10 acyl group. object. At least one of R ¹³ and R ¹⁴ is a —CON (R ¹⁶ ) R ¹⁷ group, and each of R ¹⁶ and R ¹⁷ independently represents a hydrogen atom, a C _1-10 saturated aliphatic hydrocarbon group, C _{1— 8} C _1-10 saturated aliphatic hydrocarbon radical alkoxyl group is substituted, _{C 6-20} aryl group, any one of claims 1 to 5 representing the _{C 7-20} aralkyl group, or a _{C 2-10} acyl group The colored photosensitive resin composition described   The colorant (A) is a colorant further comprising a colorant different from at least one selected from the group consisting of the compound represented by formula (I) and a salt thereof. Colored photosensitive resin composition.   A colorant different from at least one selected from the group consisting of the compound represented by formula (I) and a salt thereof is C.I. I. Pigment Red 177 and C.I. I. The colored photosensitive resin composition according to claim 7, which is at least one selected from the group consisting of CI Pigment Red 254. The coating film formed using the colored photosensitive resin composition in any one of Claims 1-8.     A color filter comprising the coating film according to claim 9.   The coating film of Claim 9 formed by the photolithographic method.