JP5268230B2 - Novel dye compound and blue resist composition for color filter containing the dye compound - Google Patents

Description

The present invention relates to novel dye compounds,及 beauty the compound comprising color filter blue resist composition.

  In general, in the field of synthetic organic chemistry, a sulfonamide compound is synthesized by a condensation reaction between a corresponding sulfonyl chloride compound and a corresponding amine, and the sulfonyl chloride compound is synthesized by chlorinating a sulfonic acid group. The same applies to sulfonamidation of dyes such as dyes and pigments. When chlorinating a sulfonic acid group, a sulfonyl chloride body of the dye is produced using chlorosulfonic acid, phosphorus pentachloride or phosphorus trichloride. Yes. However, these methods have not only the intended chlorination of the sulfonic acid group, but also side reactions such as the introduction of a new sulfonic acid group into the dye skeleton itself or the decomposition of the dye skeleton itself. This was industrially unsatisfactory.

  In order to avoid the side reaction as described above, a method using thionyl chloride for chlorination of a sulfonic acid group has been disclosed (see Patent Document 1). However, the dye as the reaction substrate here is a xanthene dye, and no example of a triphenylmethane dye has been reported so far.

  On the other hand, with changes in lifestyles due to advances in science and technology, the use of these dyes is not limited to conventional dyeing or coloring of various materials such as fibers, plastics, leather, etc., and the information is recorded or displayed. Utilizing its characteristics, it has come to be used in various industrial fields. In particular, with the rapid spread of personal computers in recent years, the demand for color liquid crystal displays is rapidly increasing. The color filter is indispensable for the color display of the liquid crystal display, and is an important component that affects the performance of the liquid crystal display. As broadband becomes more advanced, in order to display higher-definition images, development of color filters capable of realizing spectral characteristics and a high contrast ratio is required.

  As a conventional method for producing a color filter, a dyeing method, a printing method, an ink jet method, a photoresist method and the like are known. In particular, the photoresist method has become the mainstream manufacturing method in recent years because it can easily control spectral characteristics and reproducibility, and can perform high-definition patterning because of its high resolution.

  In this photoresist method, a pigment is generally used as a colorant. However, since the pigment has a certain particle size, it is known that the pigment has a depolarizing action (polarized light is lost) and the contrast ratio of the color display of the liquid crystal display is lowered. Moreover, it is difficult to obtain a high backlight transmittance in a system using a pigment, and there is a limit to improving the brightness of the color filter. Furthermore, since the pigment is insoluble in organic solvents and polymers, the colored resist composition can be obtained as a dispersion, but it is difficult to stabilize the dispersion.

  In contrast, dyes are generally soluble in organic solvents and polymers, and are stable without causing aggregation even in a colored resist composition. For this reason, a color filter obtained from a resist composition using a dye as a colorant does not have a depolarizing action because the dye is dispersed at the molecular level, and has excellent backlight transmittance. So far, color filters using dyes have been reported in order to enable image display with good spectral characteristics and high display contrast.

  As a blue color filter dye, C.I. is a triphenylmethane dye. I. As a method using Acid Blue 104 (see Patent Document 2) and a red color filter dye, C.I. I. A method using Acid Red 6 (see Patent Document 3) is disclosed. This method, particularly the former method using a triphenylmethane dye, has a high molar extinction coefficient (ε) of the dye, a clear color tone, and good spectral characteristics.

  Further, as a blue color filter dye, a method using an anthraquinone dye (see Patent Document 4) and a method using a naphthoquinone dye (see Patent Document 5) are disclosed.

JP-A-7-242651 JP 2003-5362 A JP 2003-5361 A JP 2001-108815 A JP 2002-338839 A

  However, the methods described in Patent Documents 2 and 3 have problems such as easy elution of the dye during development because the solubility of the dye in the organic solvent and polymer is insufficient. Moreover, although the dyes described in Patent Documents 4 and 5 have sufficient solubility in organic solvents and polymers, the spectral characteristics are superior to pigments, but they do not reach a satisfactory level. As described above, no dye has been reported so far that has both good spectral characteristics and high solubility in organic solvents and polymers.

A first object of the present invention, as a colorant for color filters is to provide a dye compound having both a solubility excellent spectral characteristics and an organic solvent or a polymer. Furthermore, the second object of the present invention is to provide a blue resist composition for a color filter, which has high brightness and excellent hue, particularly excellent in blue hue, and enables image display with high spectral characteristics and display contrast. is there.

The above object is thus achieved in the following. That is, to provide a dye compound characterized by having the structure represented by the following following general formula (1).

[Wherein, R _{1 to} R ₄ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ₅ and R ₆ each independently represents a hydrogen atom or an alkyl group. R ₇ represents any one of a hydrogen atom, a sulfonic acid group, an optionally substituted amino group, and —SO ₂ NR ₉ R _10. R ₉ and R ₁₀ are each independently a hydrogen atom. Represents an alkyl group, an aryl group, or an aralkyl group. Here, R ₉ and R ₁₀ may form a heterocyclic ring together with the nitrogen atom. N represents an integer of 1 to 3. Further, when R ₇ is not —SO ₂ NR ₉ R ₁₀ , at least one of R _{1 to} R ₄ is an alkylene group, an arylene group, or a group having —SO ₂ NR ₉ R ₁₀ as a substituent. Aralkylene group . ]

［式中、Ｒ₁乃至Ｒ₄はそれぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいアリール基及び置換されていてもよいアラルキル基の何れかを表わし、Ｒ₅及びＲ₆はそれぞれ独立して、水素原子及びアルキル基の何れかを表わす。又、Ｒ₇は、水素原子、スルホン酸基、置換されていてもよいアミノ基、若しくは−ＳＯ₂ＮＲ₉Ｒ₁₀の何れかを表わし、上記Ｒ₉及びＲ₁₀はそれぞれ独立して、アルキル基、アリール基及びアラルキル基の何れかを表わす。ここでＲ₉及びＲ₁₀は、窒素原子とともに複素環を形成してもよい。又、ｎは、１乃至３の整数を表わす。更に、上記Ｒ₇が−ＳＯ₂ＮＲ₉Ｒ₁₀ではない場合には、上記Ｒ₁乃至Ｒ₄のうち少なくとも１つが、置換基として−ＳＯ₂ＮＲ₉Ｒ₁₀を有するアルキレン基、アリーレン基、若しくはアラルキレン基である。］
本発明は、下記一般式（２）で表わされる構造を有することを特徴とする色素化合物を提供する。

［式中、Ｒ₉及びＲ₁₀はそれぞれ独立して、水素原子、アルキル基、アリール基及びアラルキル基の何れかを表わす。ここでＲ₉及びＲ₁₀は、窒素原子とともに複素環を形成してもよい。］ Further, to provide a dye compound characterized by having the structure represented by the following following general formula (1).

[Wherein, R _{1 to} R ₄ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ₅ and R ₆ each independently represents a hydrogen atom or an alkyl group. R ₇ represents any one of a hydrogen atom, a sulfonic acid group, an optionally substituted amino group, and —SO ₂ NR ₉ R ₁₀ , and R ₉ and R ₁₀ are each independently an alkyl group. Represents an aryl group or an aralkyl group. Here, R ₉ and R ₁₀ may form a heterocyclic ring together with the nitrogen atom. N represents an integer of 1 to 3. Further, when R ₇ is not —SO ₂ NR ₉ R ₁₀ , at least one of R _{1 to} R ₄ is an alkylene group, an arylene group, or a group having —SO ₂ NR ₉ R ₁₀ as a substituent. Aralkylene group. ]
This onset Ming provides a dye compound characterized by having the structure represented by the following general formula (2).

[Wherein, R ₉ and R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Here, R ₉ and R ₁₀ may form a heterocyclic ring together with the nitrogen atom. ]

Also, before Symbol manufacturing how sulfonyl halide compound having the structure represented by the useful following general formula (4) in the preparation of the dye compounds of the present invention includes a dye compound having the structure represented by the following general formula (3) It is characterized by having a step of reacting thionyl halide with N, N-dimethylformamide and an organic solvent.

［式中、Ｒ₁乃至Ｒ₄はそれぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいアリール基及び置換されていてもよいアラルキル基の何れかを表わし、Ｒ₅及びＲ₆はそれぞれ独立して、水素原子及びアルキル基の何れかを表わす。又、Ｒ₇ は、水素原子、スルホン酸基、置換されていてもよいアミノ基、若しくは−ＳＯ₃Ｍの何れかを表わし、又、ｎは、１乃至３の整数を表わす。更に、上記Ｒ ₇ が−ＳＯ₃Ｍではない場合には、上記Ｒ₁乃至Ｒ₄のうち少なくとも１つが、置換基として−ＳＯ₃Ｍを有するアルキレン基、アリーレン基、若しくはアラルキレン基である。Ｍはスルホン酸基のカウンターカチオンを表わす。］

[Wherein, R _{1 to} R ₄ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ₅ and R ₆ each independently represents a hydrogen atom or an alkyl group. R ₇ represents any one of a hydrogen atom, a sulfonic acid group, an optionally substituted amino group, and —SO ₃ M; and n represents an integer of 1 to 3. Furthermore, when the R ₇ is not a -SO ₃ M, at least one of the R ₁ to R _4, alkylene group having -SO ₃ M as a substituent, an arylene group, or aralkylene group. M is to table rings counter cation of the sulfonic acid groups. ]

［式中、Ｒ₁乃至Ｒ ₇ はそれぞれ独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいアリール基及び置換されていてもよいアラルキル基の何れかを表わし、Ｒ₅及びＲ₆はそれぞれ独立して、水素原子及びアルキル基の何れかを表わす。又、Ｒ₇ は、水素原子、スルホン酸基、置換されていてもよいアミノ基、若しくは−ＳＯ₃Ｘの何れかを表わし、又、ｎは、１乃至３の整数を表わす。更に、上記Ｒ ₇ が−ＳＯ₃Ｘではない場合には、上記Ｒ₁乃至Ｒ₄のうち少なくとも１つが、置換基として−ＳＯ₃Ｘを有するアルキレン基、アリーレン基、若しくはアラルキレン基である。Ｘはハロゲン原子を表わす。］

[Wherein R _{1 to} R ₇ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, R ₅ and R ₆ each independently represents a hydrogen atom or an alkyl group. R ₇ represents any one of a hydrogen atom, a sulfonic acid group, an optionally substituted amino group, and —SO ₃ X, and n represents an integer of 1 to 3. Furthermore, when the R ₇ is not -SO ₃ X, at least one of the R ₁ to R _4, alkylene group having -SO ₃ X as a substituent, an arylene group, or aralkylene group. X is to table rings halogen atom. ]

［式中Ｒ₉及びＲ₁₀はそれぞれ独立して、水素原子、アルキル基、アリール基及びアラルキル基の何れかを表わす。ここでＲ₉及びＲ₁₀は、窒素原子とともに複素環を形成してもよい。］ Further, to provide a manufacturing method of the color-containing compound. The production method includes a step of subjecting a sulfonyl halide compound having a structure represented by the general formula (4) to a condensation reaction with an amine having a structure represented by the following general formula (5).

[Wherein R ₉ and R ₁₀ each independently represents any of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group. Here, R ₉ and R ₁₀ may form a heterocyclic ring together with the nitrogen atom. ]

The present invention also provides at least one of resin and monomer, the pre-Symbol color filter blue resist composition characterized by containing the color-containing compound.

According to the present invention, a novel dye compound excellent in spectral characteristics such as color developability and transparency is provided. The solubility of the novel dye compound in an organic solvent can be controlled by changing the amine species during the condensation reaction during the production of the dye compound. By using the novel dye compound, a resist composition for a color filter having a good blue color tone is provided.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.
As a result of intensive studies to solve the problems of the prior art described above, the present inventors have found that the dye compound having the structure represented by the general formula (1) is excellent in spectral characteristics such as color developability and transparency. As a result, the present invention was reached. In addition, the dye compound of the general formula (1) can be controlled in solubility in an organic solvent by changing the amine species during sulfonamidation at the time of production. When used as a resist composition, it is possible to provide a color filter having a good blue color tone.

Examples of the alkyl group represented by R _{1 to} R ₄ in the general formulas (1), (3) and (4) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- Examples thereof include a butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. R ₁ and R ₃ (or R ₁ and R ₄ ), R ₂ and R ₄ (or R ₂ and R ₃ ) may be the same or different, but are preferable in terms of color tone and raw material cost. Are the same. Particularly preferred is the case where all of them are ethyl groups, R ₁ and R ₃ (or R ₁ and R ₄ ) are ethyl groups, and R ₂ and R ₄ (or R ₂ and R ₃ ) are benzyl groups. These substituents may be substituted with —SO ₂ NR ₉ R ₁₀ .

Examples of the alkyl group represented by R ₅ and R ₆ in the general formulas (1), (3), and (4) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. A more preferred form is when R ₅ and R ₆ are either a hydrogen atom or a methyl group.

The amino group of R _{7 in} the general formulas (1), (3) and (4) includes an alkyl group such as a methyl group or an ethyl group, a phenyl group, a methoxyphenyl group, an ethoxyphenyl group, a benzenesulfonic acid group May be substituted. R ₉ and R ₁₀ in the general formula (1) represent any one of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group, and correspond to a substituted residue of the amine of the general formula (5).

R ₉ and R ₁₀ which are substituents of the amine in the general formula (5) greatly affect the solubility of the dye compound of the general formula (1). For this reason, it is possible to obtain a desired soluble dye compound by appropriately changing R ₉ and R ₁₀ . Examples of R ₉ and R ₁₀ include the following. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-pentyl group, n-octyl group Chain or cyclic alkyl groups such as 2-ethylhexyl group and cyclohexyl group;
Examples thereof include aryl groups such as phenyl group, 1-naphthyl group and 2-naphthyl group, and aralkyl groups such as benzyl group and phenethyl group.

R ₉ and R ₁₀ may form a heterocyclic ring with a nitrogen atom. Specific examples include piperidino group, piperazino group, pyrrole group, indole group, carbazole group, pyrazole group, indazole group, imidazole group, benzimidazole group, triazole group, benzotriazole group, tetrazole group and the like. From the viewpoint of sulfonamidation reactivity, R ₉ and R ₁₀ having a smaller steric hindrance have higher reactivity of the compound of the general formula (5), and the dye of the general formula (1) can be obtained in a high yield. Since a compound can be obtained, it is preferable. On the other hand, from the viewpoint of solubility in organic solvents, R ₉ and R ₁₀ are preferably those having a high fat solubility such as a long-chain alkyl group.

The method for producing the novel dye compound of the present invention will be described below. Method for manufacturing a dye compound of the present invention, the pre-Symbol absence Ruhoniruharaido compound having a structure represented by the general formula (4), the general formula (5) to the structure by a condensation reaction with amines having represented the having as engineering obtaining a dye compound represented by general formula (1).

  Specific examples of M in the general formula (3) include metal ions such as a hydrogen atom, sodium ion, lithium ion, and potassium ion. Specific examples of X in the general formula (4) include chlorine. Halogen atoms such as atoms and bromine atoms can be mentioned.

  Specific examples of the dye compound having the structure represented by the general formula (3) include, but are not limited to, the dye compounds having the structures represented by the following general formulas (6) to (9). Not a translation.

[In General Formulas (6) to (9), M represents a counter cation of a sulfonic acid group as in General Formula (3). ]

  These dye compounds may be used alone or in combination with two or more kinds to react with thionyl halide. The thionyl halide is preferably thionyl chloride. The reaction solvent is preferably a halogenated aliphatic hydrocarbon solvent. Specific examples include chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, amyl chloride, dichloropentane, tetrachloroethane and 1,2-dibromoethane. . Of these, chloroform is more preferred.

  In the reaction of the dye compound of the general formula (3) and the thionyl halide, the amount of N, N-dimethylformamide (B) used relative to the thionyl halide (A) is preferably A: B = 1: 0 in molar ratio. .3 to 1: 0.8. The amount of thionyl halide used (A) varies depending on the type and purity of the dye compound (C) used, but is usually in the range of A: C = 1: 1 to 1:20 in molar ratio to the dye compound. is there. In general, when the purity of the dye compound is high, the amount of thionyl halide used may be stoichiometrically equivalent or slightly higher. On the other hand, when there are many impurities such as salt or mirabilite and the dye purity is low, the amount of thionyl halide is preferably used in excess of the stoichiometric equivalent. The reaction is usually carried out by slowly dropping thionyl halide into a mixture of the dye compound of general formula (3), N, N-dimethylformamide and a halogenated aliphatic hydrocarbon solvent. The reaction temperature is usually about 0 ° C. to about 70 ° C., preferably about 30 ° C. to 60 ° C., and the reaction time is usually about 30 minutes to 6 hours. The usage-amount of the halogenated aliphatic hydrocarbon solvent with respect to a pigment | dye compound is set suitably.

  The sulfonyl halide compound represented by the general formula (4) is usually removed from the reaction mixture by cooling the reaction mixture if necessary and then pouring it into water or ice water to decompose the remaining thionyl halide, followed by extraction and washing. And using conventional means such as concentration. More preferably, the obtained reaction mixture (the sulfonyl halide compound and the remaining halogenated aliphatic hydrocarbon solvent solution of thionyl halide) is directly subjected to a condensation reaction with the amine represented by the general formula (5). The method to provide is mentioned.

  The condensation reaction of the sulfonyl halide compound represented by the general formula (4) and the amine represented by the general formula (5) is preferably performed in the presence of a basic catalyst. Specific examples of the basic catalyst include aliphatic and aromatic amines such as triethylamine, pyridine, piperidine, piperazine, and triethanolamine, with tertiary amines being preferred. When the reaction mixture is directly subjected to the reaction with the amine represented by the general formula (5) and a basic catalyst is used, the total amount of use of the amine of the general formula (5) and the basic catalyst (D) Is preferably in the range of D: A = 1: 2.2 to 1: 2.5 in molar ratio to the thionyl halide (A) used in the reaction.

  When a basic catalyst is used, the amount (E) of the catalyst used is usually E: F = 1: 0.5 to 1: 5 in molar ratio to the amines (F) of the general formula (5). 1.5, preferably E: F = 1: 0.8 to 1: 1.2. The amount of the condensation reaction solvent such as a halogenated aliphatic hydrocarbon solvent is appropriately set. The condensation reaction is usually from 0 ° C to 60 ° C, preferably from 5 ° C to 40 ° C, and the condensation reaction time is usually from 30 minutes to 6 hours. The dye compound represented by the general formula (1) is usually taken out from the condensation reaction mixture using conventional means such as neutralization, extraction, washing and concentration after cooling the reaction mixture if necessary. More preferably, after neutralization, extraction and washing, the solvent is concentrated and purified by recrystallization or column chromatography.

  The coloring compound according to the present invention has a vivid blue color tone, and can be used as a coloring material, preferably a color filter coloring agent, due to its spectral characteristics. Specifically, it can be used as a material for a blue resist composition, which will be described in detail below, as well as printing ink, paint, or writing instrument ink.

Hereinafter, the blue resist composition for a color filter of the present invention will be described.
The blue resist composition of the present invention comprises at least one of a binder resin and a photopolymerizable monomer and a dye compound represented by the general formula (1). Furthermore, it is preferable to contain a photopolymerization initiator and a solvent.

  Further, in a color filter in which two or more kinds of pixels having different spectral characteristics are arranged adjacent to each other on a substrate, at least one of the plurality of pixels (for example, red, green, and blue) is provided in the present invention. By using the dye compound represented by the general formula (1), a highly transparent pixel with high color purity can be obtained. However, since the spectral characteristics can be improved by mixing the pigment and the dye, a mixture of the pigment and the coloring compound of the present invention may be used. Also, other dyes may be used in combination as a toning agent for adjusting the spectral characteristics. Further, the pigment used including the pigment compound of the present invention may be either water-soluble or oil-soluble, and the dye is preferably completely dissolved, but can be dispersed in a sufficiently fine particle state. If so, it is not necessarily dissolved. Therefore, many can be selected from commercially available colorants.

Specific examples of the coloring matter that can be used as the toning agent include, but are not limited to, the following dyes and pigments. Furthermore, these dyes and pigments may be used in combination of two or more in order to obtain the desired hue.
For example, specific examples of dyes include Acid Red 52, 87, 92, 122, 486;
Solvent Red 8, 24, 83, 109, 125, 132;
Disperse Red 60, 72, 88, 206;
Basic Red 12, 27;
Acid Blue 1, 7, 9, 40, 83, 90, 129, 249;
Solvent Blue 25, 35, 36, 55, 67, 70;
Disperse Blue 56, 81, 60, 87, 149, 197, 211, 214;
Basic Blue 1, 7, 26, 77;
Acid Green 18;
Solvent Green 3;
Basic Green 1;
Acid Yellow 38, 99;
Solvent Yellow 25, 88, 89, 146;
Disperse Yellow 42, 60, 87, 198;
Examples include Basic Yellow 21 and the like.

Specific examples of the pigment include Pigment Red 9, 19, 38, 43, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 208, 215, 216, 217, 220. 223, 224, 226, 227, 228, 240;
Pigment Blue 15, 15: 6, 16, 22, 29, 60, 64;
Pigment Green 7, 36;
Pigment Yellow 20, 24, 81, 83, 86, 93, 108, 109, 110, 117, 125, 137, 138, 139, 147, 148, 153, 154, 166, 168, 185;
Pigment Orange 36;
And CI Pigment Violet 23.

  As content of the pigment | dye compound represented by the said General formula (1), 0.1 to 400 mass% is preferable with respect to the mass of the following binder resin, and 1 to 200 mass% is more preferable. .

  The binder resin that can be used in the blue resist composition for the color filter of the present invention is not particularly limited as long as the light irradiation part or the light shielding part can be dissolved by an organic solvent, an alkaline aqueous solution, water, or a commercially available developer. It is not limited. However, from the viewpoint of workability, waste disposal, etc., those having a composition that can be developed with water or alkali are more desirable.

  As such a resin, generally, a binder resin obtained by copolymerizing a hydrophilic monomer and a lipophilic monomer at an appropriate mixing ratio by a known method is known. As the hydrophilic monomer, a monomer represented by (meth) acrylic acid, 2-hydroxyethyl, acrylamide, N-vinylpyrrolidone, a monomer having an ammonium salt, or the like is used. Moreover, as a lipophilic monomer, monomers represented by (meth) acrylic acid ester, vinyl acetate, styrene, N-vinylcarbazole and the like are used. These binder resins are negative-type by combining with radical polymerizable monomers having ethylenically unsaturated groups, cationic polymerizable monomers having oxirane or oxetane rings, radical generators, acid generators and base generators. That is, it can be used as a type of resist in which the light shielding portion is removed by development.

  In addition, a binder resin typified by tert-butyl carbonate, tert-butyl ester, tetrahydroxypyranyl ester or tetrahydroxypyranyl ether of polyhydroxystyrene can also be used. This type of binder resin can be used as a positive type resist in combination with an acid generator, that is, a type in which a light irradiated portion is removed by development.

The blue resist composition for a color filter of the present invention contains a photopolymerizable monomer having at least one ethylenically unsaturated double bond as a monomer having an ethylenically unsaturated double bond that undergoes addition polymerization upon irradiation with light. be able to. Examples of the photopolymerizable monomer include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. For example, monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate;
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
Trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate;
Neopentyl glycol di (meth) acrylate;
Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate;
Hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether;
Polyfunctional (meth) acrylates such as tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate;
Examples thereof include polyfunctional acrylates such as those obtained by adding propylene oxide to ethylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated, and polyfunctional methacrylates.

  Furthermore, polyfunctional acrylates and methacrylates such as urethane acrylates, polyester acrylates, and epoxy acrylates that are a reaction product of an epoxy resin and (meth) acrylic acid are also included. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

  The photopolymerizable monomer having two or more ethylenically unsaturated double bonds may be used alone or in combination of two or more. As content of the said polymeric compound, 5 mass% or more and 50 mass% or less of the mass (total solid content) of a coloring photosensitive composition are common, and 10 mass% or more and 40 mass% or less are especially preferable. When the content is less than 5% by mass, the photosensitivity and the pixel strength may be lowered. When the content is more than 50% by mass, the adhesiveness of the photosensitive resin layer may be excessive.

  When the blue resist composition for a color filter of the present invention is ultraviolet curable, it contains a photopolymerization initiator. Examples of the photopolymerization initiator include vicinal polyketoaldonyl compounds, α-carbonyl compounds, acioin ethers, various quinone compounds, triallylimidazole dimer / p-aminophenyl ketone combinations, and trioxadiazole compounds. It is done. Preferably, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (Irgacure 369: trade name, manufactured by Ciba Specialty Chemicals) is used. In addition, when using an electron beam in the case of pixel formation by the colored resist of this invention, said photoinitiator is not essential.

The blue resist composition for a color filter of the present invention contains a solvent for dissolving or dispersing the binder resin, photopolymerizable monomer, photopolymerization initiator, colorant and the like. Solvents that can be used include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether;
Ethylbenzene, 1,2,4-trichlorobenzene;
Ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone;
Examples thereof include ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These can be used alone or in combination.

  As described above, since the blue resist composition for a color filter of the present invention contains the dye compound represented by the general formula (1) as a colorant, the formed pixel has a good hue and is transparent. Property and translucency can be improved.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples at all. In the text, “parts” and “%” are based on mass unless otherwise specified.

[Example 1]
A dye compound having a structure represented by the general formula (1) was obtained as follows.
<Synthesis Example (Production of Dye Compound Represented by Formula (10) below)>

A mixture of 10 g of the compound represented by the general formula (6) in which M is a sodium salt, 80 mL of chloroform and 2.4 g of N, N-dimethylformamide was added with 5.1 mL of thionyl chloride at room temperature over 1 hour. It was dripped. After completion of the dropwise addition, the solution was heated and stirred at 60 ° C. for 3 hours. At 0 ° C., a mixture of 15.5 g of di (2-ethylhexyl) amine and 7.7 g of triethylamine was added dropwise to the resulting reaction mixture over 1 hour. After completion of dropping, the solution was heated to 60 ° C. and stirred for 3 hours. After completion of the reaction, the reaction mixture was neutralized with acetic acid, poured into 250 mL of water, extracted with chloroform, and the organic layer was washed twice with 250 mL of water. After drying the organic layer with anhydrous sodium sulfate, the precipitate was filtered off, the solvent of the filtrate was distilled off, and the residue was purified by column chromatography to obtain the compound of the above formula (10).
The structure is identified by NMR analysis of ¹ H and ¹³ C nuclei using a nuclear magnetic resonance spectrometer (ECA-400, manufactured by JEOL Ltd.), and HPLC (high performance liquid chromatography, LC2010A, Inc.) Purity test was performed by Shimadzu Corporation analysis. The analysis results are shown below.

[Results of analysis for compound represented by formula (10)]
[1] NMR (400 MHz, CDCl ₃ , room temperature) result of ¹ H nucleus (FIG. 1):
δ = 0.80-0.89 (m, 24H), 1.22-1.39 (m, 42H), 2.81-3.00 (m, 8H), 3.60-3.70 (m 4H), 4.75-4.85 (m, 4H), 6.77-6.79 (m, 4H), 6.95 (dd, 1H), 7.32 (d, 1H), 7. 38 (m, 2H), 7.49-7.57 (m, 7H), 7.62 (br, 2H), 7.69-7.75 (m, 2H), 8.31 (d, 1H)
[2] Results of ¹³ C nucleus NMR (100 MHz, CDCl ₃ , room temperature):
δ = 10.1, 12.5, 14.0, 23.0, 23.4, 28.6, 30.3, 37.7, 46.6, 53.4, 113.2, 125.2, 126.6, 126.8, 128.0, 128.7, 129.1, 130.0, 130.1, 130.3, 130.4, 136.2, 137.0, 140.4, 141. 7, 147.4, 156.1, 182.1
[3] HPLC result Purity = 96.7 area%, retention time 9.3 minutes (MeOH / H ₂ O = 95/5)

<Synthesis Example (Production of Dye Compounds of Compound Nos. (11) to (24))>
A series of dye compounds (11) to (24) represented by the general formula (2) were synthesized according to the method for producing the dye compound (compound No. 10) represented by the formula (10). The structures corresponding to R ₉ and R ₁₀ in the general formula (2) in the synthesized series of dye compounds (11) to (24) are shown in Tables 1 and 2 below. Moreover, in the manufacturing method of the pigment | dye compound represented by said Formula (10), it replaced with the pigment | dye compound represented by the said General formula (7)-(9) instead of the pigment | dye compound of General formula (6), respectively. In the same manner, a series of dye compounds (25) to (27) ( all corresponding to Reference Examples) were synthesized. The structures corresponding to R ₉ and R ₁₀ in the synthesized series of dye compounds are shown in Table 3 below.

[Example 2]
<Evaluation of solubility of dye compound>
The solubility of the series of dye compounds (10) to (27) synthesized in Example 1 in cyclohexanone was evaluated according to the following criteria. Further, as a comparative compound, a compound (Compound No. 6) in which M of the dye compound represented by the general formula (6) included in the general formula (3) is a sodium salt was used as it was, and the same evaluation was performed. The results are shown in Tables 1-3.
○: Solubility in cyclohexanone is 10% or more.
Δ: The solubility in cyclohexanone is 5% or more and less than 10%.
X: Solubility in cyclohexanone is less than 5%.

From the results of Tables 1 to 3, the dye compound represented by the general formula (1) of the present invention has a sulfonamide group, and therefore, compared with the dye compound (6) represented by the general formula (3) compared with each other. It was found that the solubility in cyclohexanone was dramatically improved. This suggests that the dye compound having a sulfonamide group of the present invention does not cause aggregation or the like and can provide a stable resist composition when used as a colorant for the resist composition. In particular, it was confirmed that the solubility in cyclohexanone was particularly excellent when R ₉ and R ₁₀ were alkyl groups, particularly long-chain alkyl groups.

Example 3
<Evaluation of spectral characteristics of dye compound>
The dye compound (10) represented by the above formula (10) was dissolved in cyclohexanone and prepared so that the absorbance was 2.0. About the obtained solution, the ultraviolet visible absorption spectrum at room temperature was measured with the spectrophotometer (U-3310 type spectrophotometer, Hitachi Ltd. make) (FIG. 2). The absorption maximum wavelength (λmax [nm]) was determined from the measured spectrum. Further, the spectral characteristics of the dye compound were evaluated by the absorbance ratio (absorbance at the maximum absorption wavelength / absorbance at the minimum absorption wavelength) of the maximum absorption wavelength from 500 nm to 650 nm of the spectrum and the minimum absorption wavelength from 400 nm to 500 nm. Here, the absorbance ratio means that a color filter having pixels with higher brightness can be created as the value increases.

  The brightness can also be evaluated using the Y value of the XYZ (Yxy) notation established by the CIE (Commission Internationale de I'Eclairage), but there are very different Y values due to small deviations in hue. In this example, the brightness was evaluated based on the absorbance ratio.

  The same evaluation as the spectral characteristic evaluation performed for the dye compound (10) represented by the formula (10) was performed in the same manner as in the same method. The pigment compound used for the evaluation is C.I. which is an anthraquinone dye represented by the following formula (28) for comparison with the aforementioned pigment compounds (14) and (25) to (27). I. Solvent Blue 35. The evaluation results are shown in Table 4.

  From the results in Table 4, first, it was found from the comparison between the dye compound (10) and the dye compound (14) that those having the same dye skeleton showed no significant difference in spectral characteristics. In addition, the dye compounds (10), (14), (25) to (28) represented by the series of general formula (1) have better spectral characteristics than the dye compound (28) which is an anthraquinone dye compared. I understood. Furthermore, it was suggested that the dye compounds (10) and (14) having the dye skeleton represented by the general formula (2) have good brightness and good spectral characteristics as colorants for color filters. .

Example 4
<Preparation of blue resist composition>
Using the dye compound (10) obtained in the synthesis example described above, a blue resist composition was prepared by the following method. Specifically, 6.7 parts of acrylic copolymer composition, 1.3 parts of dipentaerythritol penta (meth) acrylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Photopolymerization initiator) 2.0 parts of the dye compound (10) was added to 0.4 part and 116 parts of cyclohexanone, and the mixture was stirred at room temperature for 3 hours. This was filtered with a 1.5 μm filter to obtain a blue resist composition.

Example 5
<Creation of coating sample>
The blue resist composition obtained above was spin-coated on glass, then dried at 90 ° C. for 3 minutes, exposed on the entire surface, and post-cured at 180 ° C. to prepare a coated sample. The obtained coated sample was good in both light transmittance and color tone.

  As an application example of the present invention, the dye compound according to the present invention has high solubility in an organic solvent, and the solubility can be easily controlled according to the application by converting the amine species used for sulfonamidation. Therefore, it can be applied to various uses. That is, due to this remarkable physical property, the dye compound according to the present invention is not limited to use as a colorant, but can be sufficiently applied to application to electronic materials such as dyes for optical recording.

NMR spectra of the ¹ H nucleus of the dye compounds of the present invention _{(10) (400MHz, CDCl 3} , room temperature) is a diagram showing a. It is a figure showing the ultraviolet visible absorption spectrum at room temperature in the cyclohexanone of the pigment | dye compound (10) of this invention.

Claims (2)

A dye compound having a structure represented by the following general formula (2):

[Wherein, R ₉ and R ₁₀ each independently represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. Here, R ₉ and R ₁₀ may form a heterocyclic ring together with the nitrogen atom. ] A blue resist composition for a color filter, comprising at least one of a resin and a monomer and the dye compound according to claim 1 .

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