TW202212485A - Colored curable resin composition, color filter, display device capable of forming a dark-colored curable film with a thin film thickness - Google Patents

Abstract

The object of the present invention is to provide a colored curable resin composition capable of forming a dark-colored curable film with thickness. The colored curable resin composition of the present invention is characterized by including a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) includes a compound represented by the formula (a). The polymerizable compound (C) has a hydroxyl functional group value of 100 mgKOH/g or more.

Description

Colored curable resin composition

The present invention relates to a coloring curable resin composition, a color filter using the same, and a display device.

Display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays, or solid-state imaging devices such as Charge Coupled Device (CCD) or Complementary Metal-Oxide-Semiconductor Transistor (CMOS) sensors The color filter used in the element is made of a colored curable resin composition. As a blue color material used in such a colorable curable resin composition, C.I. pigment blue 24 represented by formula (i) having a triarylmethane skeleton is known (Non-Patent Document 1).

[現有技術文獻] [非專利文獻]

[Prior art literature] [Non-patent literature]

[Non-Patent Document 1] "Color Index International" (British Dyeing and Dyeing Society, American Fiber Chemical Technology-Dyeing Technology Association)

[The problem to be solved by the invention]

However, when a dark-colored cured film is formed from the colorable curable resin composition containing the said blue color material, the film thickness may become thick. Therefore, an object of the present invention is to provide a colored curable resin composition capable of forming a dark cured film with a thin film thickness, a color filter formed from the colored curable resin composition, and a display including the color filter device. [Means of Solving Problems]

[式（a）中， R ⁴¹～R ⁴⁴分別獨立地表示氫原子、可具有取代基的碳數1～20的飽和烴基、可具有取代基的碳數6～20的芳香族烴基、或可具有取代基的碳數7～30的芳烷基，該芳香族烴基及該芳烷基可具有的取代基可為-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f，於該飽和烴基的碳數為2～20的情況下，該飽和烴基中所含的-CH ₂-可經取代為-O-或-CO-；其中，該碳數2～20的飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-，末端的-CH ₂-不會經取代為-O-或-CO-；R ⁴¹與R ⁴²可鍵結並與該些鍵結的氮原子一同形成環，R ⁴³與R ⁴⁴可鍵結並與該些鍵結的氮原子一同形成環； R ⁴⁷～R ⁵⁴分別獨立地表示氫原子、鹵素原子、硝基、羥基、-SO ₃ ^-、-SO ₂-N ^--SO ₂-R ^f、或可具有取代基的碳數1～20的飽和烴基，於該飽和烴基的碳數為2～20的情況下，構成該飽和烴基的-CH ₂-可經取代為-O-或-CO-，R ⁴⁸與R ⁵²可彼此鍵結而形成-NH-、-S-、或-SO ₂-；其中，該飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-，末端的-CH ₂-不會經取代為-O-或-CO-； 環T ¹表示碳數3～10的芳香族雜環，該芳香族雜環可包含可具有取代基的碳數1～20的飽和烴基、經取代或未經取代的胺基、可具有取代基的碳數6～20的芳香族烴基、-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f；該芳香族烴基可具有的取代基可為-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f； M ^r+表示r價的金屬離子； k表示式（a）所表示的化合物所具有的-SO ₃ ^-的個數及-SO ₂-N ^--SO ₂-R ^f的個數的和； r表示1以上的整數； R ^f表示碳數1～12的氟烷基； 其中，式（a）所表示的化合物具有至少一個-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f]。 [2] 如[1]所述的著色硬化性樹脂組成物，其中所述聚合性化合物（C）的羥基價為200 mgKOH/g以上。 [3] 如[1]或[2]所述的著色硬化性樹脂組成物，其中所述著色劑（A）進而包含氧雜蒽染料。 [4] 如[3]所述的著色硬化性樹脂組成物，其中所述氧雜蒽染料為式（1）所表示的化合物，

[式（1）中，R ¹～R ⁴彼此獨立地表示氫原子、-R ⁸或碳數6～10的一價芳香族烴基，或者R ¹及R ²以及R ³及R ⁴分別一起形成包含氮原子的環；該芳香族烴基中所含的氫原子可經鹵素原子、-OH、-OR ⁸、-SO ₃ ^-、-SO ₃H、-SO ₃ ^-M ⁺、-CO ₂H、-CO ₂R ⁸、-SO ₃R ⁸或-SO ₂NR ⁹R ¹⁰取代； R ⁵表示-OH、-SO ₃ ^-、-SO ₃H、-SO ₃ ^-M ⁺、-CO ₂H、-CO ₂ ^-M ⁺、-CO ₂R ⁸、-SO ₃R ⁸或-SO ₂NR ⁹R ¹⁰； m表示0～5的整數，於m為2以上的整數的情況下，多個R ⁵可相同，亦可彼此不同； R ⁶及R ⁷彼此獨立地表示氫原子或碳數1～6的烷基； M ⁺表示 ⁺N(R ¹¹) ₄、Na ⁺或K ⁺，X表示鹵素原子； a表示0或1； R ⁸表示碳數1～20的一價飽和烴基，該飽和烴基中所含的氫原子可經碳數6～10的芳香族烴基、羧基、或鹵素原子取代，該飽和烴基中所含的-CH ₂-可經-S-、-O-、-CO-或-NR ¹¹-取代；其中，該飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-；R ¹¹表示氫原子、碳數1～20的一價飽和烴基或碳數7～10的芳烷基，於R ¹¹存在多個的情況下，該些的全部或一部分可相同； R ⁹及R ¹⁰彼此獨立地表示氫原子、或碳數1～20的一價飽和烴基，該飽和烴基中所含的氫原子可經-OH或鹵素原子取代，該飽和烴基中所含的-CH ₂-可經-S-、-O-、-CO-、-NH-或-NR ⁸-取代；其中，該飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-； R ⁹及R ¹⁰可彼此鍵結而形成包含氮原子的3員環～10員環的雜環]。 [5] 一種彩色濾光片，其是由如[1]至[4]中任一項所述的著色硬化性樹脂組成物形成。 [6] 一種顯示裝置，包含如[5]所述的彩色濾光片。 [發明的效果] The gist of the present invention is as follows. [1] A coloring curable resin composition comprising: a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) comprises the formula The compound represented by (a), wherein the polymerizable compound (C) has a hydroxyl value of 100 mgKOH/g or more,

[In formula (a), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a C 7-30 aralkyl group with substituent, the aromatic hydrocarbon group and the substituent which the aralkyl group may have can be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , in the When the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-; wherein, in the saturated hydrocarbon group of the carbon number of 2 to 20, adjacent The -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-; R ⁴¹ and R ⁴² can be bonded to these bonded nitrogens Atoms together form a ring, R ⁴³ and R ⁴⁴ can be bonded together to form a ring with these bonded nitrogen atoms; R ⁴⁷ to R ⁵⁴ independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, - CH ₂ - can be substituted with -O- or -CO-, and R ⁴⁸ and R ⁵² can be bonded to each other to form -NH-, -S-, or -SO ₂ -; wherein, in the saturated hydrocarbon group, the adjacent - CH ₂ - will not be substituted with -O- at the same time, and -CH ₂ - at the end will not be substituted with -O- or -CO-; Ring T ¹ represents an aromatic heterocycle with 3 to 10 carbon atoms, the aromatic heterocycle The heterocyclic ring may contain an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; the substituent that the aromatic hydrocarbon group may have can be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; M ^r+ represents a metal ion of r valence; k Represents the sum of the number of -SO ₃ ^- and the number of -SO ₂ -N ^- -SO ₂ -R ^f in the compound represented by the formula (a); r represents an integer of 1 or more; R ^f represents the number of carbon atoms A fluoroalkyl group of 1 to 12; wherein the compound represented by the formula (a) has at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ]. [2] The colored curable resin composition according to [1], wherein the polymerizable compound (C) has a hydroxyl value of 200 mgKOH/g or more. [3] The colorable curable resin composition according to [1] or [2], wherein the colorant (A) further contains a xanthene dye. [4] The colored curable resin composition according to [3], wherein the xanthene dye is a compound represented by the formula (1),

[In formula (1), R ¹ to R ⁴ independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are formed together, respectively A ring containing a nitrogen atom; the hydrogen atom contained in the aromatic hydrocarbon group may be passed through a halogen atom, -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ substituted; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, - CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be The same or different from each other; R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and X represents a halogen atom; a represents 0 or 1; R ⁸ represents a monovalent saturated hydrocarbon group with a carbon number of 1-20, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an aromatic hydrocarbon group with a carbon number of 6-10, a carboxyl group, or a halogen atom, the saturated hydrocarbon group The -CH ₂ - contained in the hydrocarbon group can be substituted by -S-, -O-, -CO- or -NR ¹¹ -; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted with -O at the same time -; R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and when there are more than one R ¹¹ , all or part of these may be the same; R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and the -CH ₂ contained in the saturated hydrocarbon group -Can be substituted by -S-, -O-, -CO-, -NH- or -NR ⁸ -; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted with -O- at the same time; R ⁹ and R ¹⁰ may be bonded to each other to form a 3-membered to 10-membered heterocyclic ring containing a nitrogen atom]. [5] A color filter formed from the colored curable resin composition according to any one of [1] to [4]. [6] A display device including the color filter described in [5]. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, the coloring curable resin composition which can form a deep dark cured film with a thin film thickness, the color filter which consists of this coloring curable resin composition, and the display apparatus containing this color filter can be provided.

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) contains the compound represented by the formula (a) (hereinafter, it may be referred to as the compound (a)). The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter, referred to as solvent (E) in some cases). The colored curable resin composition of the present invention may contain a leveling agent (hereinafter, it may be referred to as a leveling agent (F)). In this specification, unless otherwise specified, the compounds exemplified as the respective components can be used alone or in combination of two or more.

＜Colorant (A)＞ ＜＜Compound (a)＞＞ Colorant (A) contains compound (a). Hereinafter, the present invention will be described in detail using the formula (a). The compound (a) also includes its tautomer or salt.

[式（a）中， R ⁴¹～R ⁴⁴分別獨立地表示氫原子、可具有取代基的碳數1～20的飽和烴基、可具有取代基的碳數6～20的芳香族烴基、或可具有取代基的碳數7～30的芳烷基，該芳香族烴基及該芳烷基可具有的取代基可為-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f，於該飽和烴基的碳數為2～20的情況下，該飽和烴基中所含的-CH ₂-可經取代為-O-或-CO-；其中，該碳數2～20的飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-，末端的-CH ₂-不會經取代為-O-或-CO-；R ⁴¹與R ⁴²可鍵結並與該些鍵結的氮原子一同形成環，R ⁴³與R ⁴⁴可鍵結並與該些鍵結的氮原子一同形成環； R ⁴⁷～R ⁵⁴分別獨立地表示氫原子、鹵素原子、硝基、羥基、-SO ₃ ^-、-SO ₂-N ^--SO ₂-R ^f、或可具有取代基的碳數1～20的飽和烴基，於該飽和烴基的碳數為2～20的情況下，構成該飽和烴基的-CH ₂-可經取代為-O-或-CO-，R ⁴⁸與R ⁵²可彼此鍵結而形成-NH-、-S-、或-SO ₂-；其中，該飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-，末端的-CH ₂-不會經取代為-O-或-CO-； 環T ¹表示碳數3～10的芳香族雜環，該芳香族雜環可包含可具有取代基的碳數1～20的飽和烴基、經取代或未經取代的胺基、可具有取代基的碳數6～20的芳香族烴基、-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f；該芳香族烴基可具有的取代基可為-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f； M ^r+表示r價的金屬離子； k表示式（a）所表示的化合物所具有的-SO ₃ ^-的個數及-SO ₂-N ^--SO ₂-R ^f的個數的和； r表示1以上的整數； R ^f表示碳數1～12的氟烷基； 其中，式（a）所表示的化合物具有至少一個-SO ₃ ^-或-SO ₂-N ^--SO ₂-R ^f]

[In formula (a), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a C 7-30 aralkyl group with substituent, the aromatic hydrocarbon group and the substituent which the aralkyl group may have can be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , in the When the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-; wherein, in the saturated hydrocarbon group of the carbon number of 2 to 20, adjacent The -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-; R ⁴¹ and R ⁴² can be bonded to these bonded nitrogens Atoms together form a ring, R ⁴³ and R ⁴⁴ can be bonded together to form a ring with these bonded nitrogen atoms; R ⁴⁷ to R ⁵⁴ independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, - CH ₂ - can be substituted with -O- or -CO-, and R ⁴⁸ and R ⁵² can be bonded to each other to form -NH-, -S-, or -SO ₂ -; wherein, in the saturated hydrocarbon group, the adjacent - CH ₂ - will not be substituted with -O- at the same time, and -CH ₂ - at the end will not be substituted with -O- or -CO-; Ring T ¹ represents an aromatic heterocycle with 3 to 10 carbon atoms, the aromatic heterocycle The heterocyclic ring may contain an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; the substituent that the aromatic hydrocarbon group may have can be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; M ^r+ represents a metal ion of r valence; k Represents the sum of the number of -SO ₃ ^- and the number of -SO ₂ -N ^- -SO ₂ -R ^f in the compound represented by the formula (a); r represents an integer of 1 or more; R ^f represents the number of carbon atoms 1-12 fluoroalkyl groups; wherein, the compound represented by formula (a) has at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ]

The aromatic heterocyclic ring represented by ring T ¹ may be a monocyclic ring or a condensed ring. The number of carbon atoms of the aromatic heterocyclic ring represented by ring T ¹ is preferably 3-10, more preferably 3-8. In addition, the aromatic heterocycle is preferably a 5- to 10-membered ring, more preferably a 5- to 9-membered ring. Examples of monocyclic aromatic heterocycles include 5-membered rings containing nitrogen atoms such as pyrrole rings, oxazole rings, pyrazole rings, imidazole rings, and thiazole rings; 5-membered rings containing no nitrogen atoms such as furan rings and thiophene rings Rings; 6-membered rings including nitrogen atoms such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc. As the aromatic heterocyclic ring of the condensed ring, indole ring, benzimidazole ring, benzothiazole ring are exemplified Condensed rings containing nitrogen atoms such as quinoline rings; condensed rings containing no nitrogen atoms such as benzofuran rings, etc.

Examples of substituents which the aromatic heterocycle of ring T1 may have include optionally substituted saturated hydrocarbon groups having ¹ to 20 carbon atoms, substituted or unsubstituted amine groups, and optionally substituted 6 to 6 carbon atoms. 20 aromatic hydrocarbon group, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , etc., preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted amine group, or a A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. Ring T ¹ preferably contains an amine group which may have a substituent, and the substituent which the amine group may have is preferably a saturated hydrocarbon group with 1 to 20 carbon atoms which may have a substituent, or a saturated hydrocarbon group with 6 carbon atoms which may have a substituent -10 aromatic hydrocarbon groups, optionally substituted aralkyl groups having 7 to 30 carbon atoms, and the like. Among them, the aromatic heterocyclic ring of the ring T ¹ is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a 5-membered aromatic heterocyclic ring containing a nitrogen atom.

Ring T1 is preferably a ring represented by formula ( ^t1 ).

[In formula (t1), X2 represents -O-, -N(R ⁵⁷ )- or -S-; R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ⁴⁵ and R ⁴⁶ each independently represent hydrogen Atom, optionally substituted saturated hydrocarbon group with 1 to 20 carbon atoms, optionally substituted aromatic hydrocarbon group with 6 to 20 carbon atoms, or optionally substituted aralkyl group with 7 to 30 carbon atoms; R ⁵⁵ represents hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms; among the above R ⁴⁵ , R ⁴⁶ and R ⁵⁵ , the carbon atoms in the saturated hydrocarbon group are When the number is 2-20, the -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-; wherein, in the saturated hydrocarbon group with a carbon number of 2-20, the adjacent -CH ₂ - not substituted to -O- at the same time, -CH ₂ - not substituted to -O- or -CO- at the end; R ⁴⁵ and R ⁴⁶ can be bonded and form a ring together with these bonded nitrogen atoms ; * indicates a bond with a carbocation]

In addition, the ring T1 is also preferably ^a ring represented by the formula (t2).

[In formula (t2), ring T ³ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms having a nitrogen atom; R ⁵⁸ represents an optionally substituted saturated hydrocarbon group with 1 to 20 carbon atoms, and an optionally substituted carbon number 6-20 aromatic hydrocarbon group, -SO ₃ ^- , or -SO ₂ -N ^- -SO ₂ -R ^f ; R ⁵⁹ represents a hydrogen atom, optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, optionally substituted Aromatic hydrocarbon group with 6 to 20 carbon atoms or an aralkyl group with 7 to 30 carbon atoms that may have substituents; k2 represents 0, 1 or 2; * represents a bond with a carbocation]

The ring represented by the formula (t2) is also preferably a ring represented by the formula (t2-1).

[In formula (t2-1), R ⁶⁰ represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms; R ⁶¹ represents -SO ₃ ^- , or -SO ₂ -N ^- -SO ₂ -R ^f ; R ⁵⁹ has the same meaning as described; * represents a bond with a carbocation]

As ring T1, a ring represented by formula ( ^t1 ) or formula (t2) is preferable, and a ring represented by formula (t1) is more preferable.

A saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁵⁵ and R ⁵⁸ to R ⁶⁰ , a saturated hydrocarbon group having 1 to 20 carbon atoms that the ring T ¹ may have, and an amine group that the ring T ¹ may have. The saturated hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl Alkyl, icosyl and other linear alkyl groups; branched chain alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. The number of carbon atoms in the saturated hydrocarbon group is preferably 1-10, more preferably 1-8, still more preferably 1-6.

The cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. . The carbon number of the cyclic saturated hydrocarbon group is preferably 3-10, more preferably 6-10.

As the saturated hydrocarbon group represented by R ⁴¹ to R ⁵⁵ and R ⁵⁸ to R ⁶⁰ , the saturated hydrocarbon group which the ring T ¹ may have, and the saturated hydrocarbon group which the amine group which the ring T ¹ may have, a methyl group and an ethyl group are preferable. , isopropyl, propyl, butyl, pentyl, hexyl, isobutyl, 2-ethylhexyl, cyclohexyl, adamantyl, etc.

The saturated hydrocarbon group represented by R ⁴¹ to R ⁵⁵ and R ⁵⁸ to R ⁶⁰ , the saturated hydrocarbon group which the ring T ¹ may have, and the saturated hydrocarbon group which the amine group which the ring T ¹ may have may have a substituted or unsubstituted amine group or a halogen atom as a substituent. Examples of the substituted amino group include alkylamino groups such as a dimethylamino group and a diethylamino group. Moreover, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. When the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as trifluoromethyl, perfluoroethyl, and perfluoropropyl.

Moreover, as a C1-C10 alkyl group represented by ^R57 , the C1-C10 group in the linear or branched saturated hydrocarbon group exemplified as a saturated hydrocarbon group represented by ^R41 is mentioned.

When the carbon number of the saturated hydrocarbon group represented by R ⁴¹ to R ⁵⁵ is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-. Among them, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not substituted with -O- at the same time, and the terminal -CH ₂ - is not substituted with -O- or -CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (that is, a linear alkyl). The preferred carbon number of the saturated hydrocarbon group in which -CH ₂ - may be substituted with -O- or -CO- is 2-10, more preferably 2-8. In addition, when -CH ₂ - is substituted with -O- or -CO-, the carbon between the terminal and -O- or -CO-, or between -O- or -CO- and -O- or -CO- The number is 1 or more, preferably 1 to 5, more preferably 2 to 3, still more preferably 2.

In addition, carbons of the aromatic hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ and R ⁵⁸ to R ⁶⁰ , the aromatic hydrocarbon group which the ring T ¹ may have, and the aromatic hydrocarbon group which the amine group which the ring T ¹ may have may have The number is preferably 6-20, more preferably 6-15, and still more preferably 6-12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, and a phenyl group, a naphthyl group, a tolyl group, and a xylene group are preferred base. In addition, the aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl groups; sulfasulfonyl groups; methyl groups Alkoxycarbonyl with 1 to 6 carbon atoms such as sulfonyl group; -SO ₃ ^- ; -SO ₂ -N ^- -SO ₂ -R ^f , etc., may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . Among them, -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f are preferably an aromatic hydrocarbon ring directly bonded to an aromatic hydrocarbon group, that is, a hydrogen atom bonded to an aromatic hydrocarbon ring is substituted. The substituent in the aromatic hydrocarbon group represented by R ⁵⁵ is preferably a halogen atom.

As a specific example of the aromatic hydrocarbon group which may have a substituent, the group represented by the following formula is mentioned, for example. The group represented by the following formula may further have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . In the following formula, * represents a bond with a nitrogen atom or a carbon atom.

Examples of the aralkyl group represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ and the aralkyl group which the amine group which the ring T ¹ may have may have include a methylene group bonded to the group described as the above-mentioned aromatic hydrocarbon group, A group formed of an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as ethylidene and propylidene. The number of carbon atoms in the aralkyl group is preferably 7-30, more preferably 7-20, still more preferably 7-17. In addition, the aralkyl group may have one or two or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl groups; sulfasulfonyl groups; methyl groups Alkoxycarbonyl with 1 to 6 carbon atoms such as sulfonyl group; -SO ₃ ^- ; -SO ₂ -N ^- -SO ₂ -R ^f et al.

as a ring in which R ⁴¹ and R ⁴² are bonded and formed together with these bonded nitrogen atoms, a ring in which R ⁴³ and R ⁴⁴ are bonded and formed together with these bonded nitrogen atoms, and R ⁴⁵ and R ⁴⁶ are bonded The ring formed together with these bonded nitrogen atoms includes a nitrogen-containing non-aromatic 4- to 7-membered ring such as a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring, preferably pyrrole A pyridine ring, a piperidine ring, or the like is a 4- to 7-membered ring having only one nitrogen atom as a heteroatom.

Among them, as R ⁴¹ to R ⁴⁴ , R ⁵⁵ , and R ⁵⁸ to R ⁶⁰ , preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, more preferably each independently A saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In particular, R ⁴¹ and R ⁴³ are preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably each independently a saturated hydrocarbon group having 1 to 8 carbon atoms. R ⁴² and R ⁴⁴ are each independently preferably an aromatic hydrocarbon group which may have a substituent, more preferably a phenyl group which may have a substituent, a tolyl group which may have a substituent, and a diphenyl group which may have a substituent, each independently tolyl. R ⁵⁵ is further preferably an aromatic hydrocarbon group which may have a substituent. R ⁵⁵ and R ⁵⁸ to R ⁶⁰ are more preferably groups represented by the following formulae. The group represented by the following formula may further have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . In the following formula, * represents a bond with a nitrogen atom or a carbon atom.

Preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, and at least one -CH ₂ - constituting an alkyl group having 2 to 20 carbon atoms is substituted with -O- or -CO-. group, or an aromatic hydrocarbon group which may have a substituent, or R ⁴⁵ and R ⁴⁶ are bonded to form a ring together with these bonded nitrogen atoms. More preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ⁴⁵ and R ⁴⁶ are bonded to form only one nitrogen A 4-membered ring to a 7-membered ring in which the atom is a hetero atom is further preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula. The group represented by the following formula may further have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f as a substituent. In the following formula, * represents a bond with a nitrogen atom.

Among them, R ⁴⁵ is preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and R ⁴⁶ is preferably an o-tolyl group.

R ⁴⁷ to R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom, or a linear or branched saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, or a fluorine atom or a chlorine atom, more preferably each independently a hydrogen atom. In addition, as R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable. As R ⁶¹ , a hydrogen atom is preferred.

Examples of the r-valent metal ion represented by M ^r+ include alkali metal ions such as lithium ion, sodium ion, and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion; titanium ion , zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion and other transition metal ions; zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion and other typical metal ions Wait. r is preferably 1 or more, more preferably 2 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. As ^Mr+ , alkaline earth metal ions, typical metal ions, etc. are more preferred, alkaline earth metal ions and zinc ions are further preferred, and alkaline earth metal ions are further preferred.

In the formula (a), the number of ^Mr+ is one less than the sum (k) of the number of -SO ₃ ^- and the number of -SO ₂ -N ^- -SO ₂ -R ^f in the compound (a) quantity. Therefore, the compound (a) is a compound whose valence is 0, that is, is electrically neutral.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include monofluoromethyl, difluoromethyl, perfluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl Fluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, difluoropropyl Fluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl, etc. Among them, the fluoroalkyl group represented by R ^f is preferably a perfluoroalkyl group. Moreover, 1-10 are preferable, as for carbon number of the fluoroalkyl group represented by R ^f , 1-5 are more preferable, and 1-3 are still more preferable.

In formula (a), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and ring T ¹ have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . The sum (k) of the numbers of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f of R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ and the ring T ¹ is 1 or more, preferably 1 or more and 7 or less, more preferably 2 or more and 7 or less, still more preferably 2 or more and 4 or less, still more preferably 2 or 3, and particularly preferably 2.

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f preferably satisfies at least one or more conditions selected from (Ia) to (Id) below, and more preferably satisfies (Ia) and (Ib) at least one or more of the conditions. (Ia) Any of the optionally substituted aromatic hydrocarbon groups represented by R ⁴¹ to R ⁴⁴ including (Ib) as any of the above R ⁴⁷ to R ⁵⁴ and having 6 to 20 carbon atoms (Ic) Bonded to any one of the optionally substituted aralkyl groups of 7 to 30 carbon atoms represented by R ⁴¹ to R ⁴⁴ (Id) bonded to hydrogen of the aromatic heterocyclic ring represented by T ¹ Any of aromatic hydrocarbon groups having 6 to 20 carbon atoms in which atoms are substituted

However, when -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is bonded to an aromatic hydrocarbon group or aralkyl group, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is preferably an aromatic hydrocarbon ring directly bonded to an aromatic hydrocarbon group or an aralkyl group. That is, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f preferably substitutes a hydrogen atom bonded to an aromatic hydrocarbon ring. -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent represented by R ⁴¹ to R ⁴⁴ or an aromatic hydrocarbon group represented by R ⁴¹ to R ⁴⁴ In the aromatic hydrocarbon ring (for example, a benzene ring) in the C7-C30 aralkyl group which may have a substituent shown, it couple|bonded with the para-position with respect to the binding position with a nitrogen atom. In the case where a plurality of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f is contained in compound (a), a plurality of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f Although it may be bonded to the same aromatic hydrocarbon ring, it is preferable to bond to a different aromatic hydrocarbon ring.

The compound (a) preferably does not have an ethylenically unsaturated bond.

Regarding the compound (a), it is preferable that R ⁴¹ and R ⁴³ are each independently a saturated hydrocarbon group having 1 to 10 carbon atoms (the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amine group) or halogen atom, in the case that the carbon number of the saturated hydrocarbon group is 2-10, the -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-), R ⁴² and R ⁴⁴ are each independently is an optionally substituted phenyl group, an optionally substituted tolyl group, or an optionally substituted xylyl group (the phenyl, tolyl, and xylyl groups may have a substituent that may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ), R ⁴⁷ to R ⁵⁴ are hydrogen atoms, and ring T ¹ is a 5-membered ring containing a nitrogen atom (the 5-membered ring may contain a saturated hydrocarbon group with 1 to 10 carbon atoms , a substituted or unsubstituted amine group or an aromatic hydrocarbon group with a carbon number of 6 to 10 that may have a substituent. The substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ); or a compound represented by formula (a-1) (hereinafter, sometimes referred to as "compound (a-1)").

[In formula (a-1), R ^47A to R ^54A each independently represent a hydrogen atom, -SO ₃ ^- , or a saturated hydrocarbon group having 1 to 10 carbon atoms; R ^41A and R ^43A each independently represent a hydrogen atom and a carbon number 1 to 10 saturated hydrocarbon groups, optionally substituted aromatic hydrocarbon groups with 6 to 20 carbon atoms, or optionally substituted aralkyl groups with 7 to 30 carbon atoms, the aromatic hydrocarbon groups and the aralkyl groups that the aralkyl groups may have The substituent may be -SO ₃ ^- ; R ^11A to R ^20A each independently represent -SO ₃ ^- , a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms or a halogen atom; R ^45A , R ^46A and R ^55A each independently represent A hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, the substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- ; In R ^47A to R ^54A , R ^41A , R ^43A , R ^11A to R ^20A , R ^45A , R ^46A and R ^55A , when the saturated hydrocarbon group has 2 to 10 carbon atoms, the saturated hydrocarbon group contains 2 to 10 carbon atoms. -CH ₂ - can be substituted with -O- or -CO-; wherein, in the saturated hydrocarbon group with 2 to 10 carbon atoms, the adjacent -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-; M ^r+ represents a metal ion with a valence of r; k represents the number of SO ₃ ^- groups possessed by the compound represented by the formula (a-1); wherein, the formula ( The compound represented by a-1) has at least two SO ₃ ^-groups ; r represents an integer of 2 or more]

As the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^47A to R ^54A , R ^41A , R ^43A , R ^11A to R ^20A , R ^45A , R ^46A and R ^55A , among the saturated hydrocarbon groups exemplified in R ⁴¹ can be mentioned. A base with 1 to 10 carbon atoms.

The substituents which the saturated hydrocarbon groups having 1 to 10 carbon atoms represented by R ^45A , R ^46A and R ^55A may have are the same as those exemplified as the substituents which the saturated hydrocarbon groups represented by R ⁴¹ may have.

The aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R ^41A , R ^43A , R ^45A , R ^46A and R ^55A are the same as those exemplified as the aromatic hydrocarbon groups having 6 to 20 carbon atoms represented by R ⁴¹ .

The aralkyl group having 7 to 30 carbon atoms represented by R ^41A and R ^43A is the same as the group exemplified as the aralkyl group having 7 to 30 carbon atoms represented by R ⁴¹ .

Substitutes that may be possessed by the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^41A , R ^43A , R ^45A , R ^46A and R ^55A and the aralkyl group having 7 to 30 carbon atoms represented by R ^41A and R ^43A Examples of the group include: halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; hydroxyl; sulfasulfonyl; methylsulfonyl Alkoxycarbonyl with 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; -SO ₃ ^- and the like.

Examples of the halogen atoms represented by R ^11A to R ^20A include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferred.

More preferably, R ^47A to R ^54A are each independently a hydrogen atom, -SO ₃ ^- , or a methyl group, and more preferably a hydrogen atom or a methyl group.

R ^41A and R ^43A are each independently preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted aralkyl group having 7 to 30 carbon atoms. ; More preferably, each independently is a saturated hydrocarbon group having 1 to 8 carbon atoms; a phenyl group; a tolyl group; a naphthyl group; a methylnaphthyl group; an unsubstituted aralkyl group; One or more of ethoxy group, sulfamoyl group, methylsulfonyl group, methoxycarbonyl group, and ethoxycarbonyl group, especially one kind of substituted aralkyl group, and preferably each independently has 1 to 1 carbon atoms 4 straight-chain alkyl.

In terms of heat resistance and light resistance, at least one of R ^11A to R ^12A is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably at least any one of a halogen atom or a carbon number of 1 A saturated hydrocarbon group of to 8, more preferably at least any one of a fluorine atom or a saturated hydrocarbon group of 1 to 4 carbon atoms.

In terms of heat resistance and light resistance, at least one of R ^13A to R ^14A is preferably a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably at least any one of a halogen atom or a carbon number of 1 A saturated hydrocarbon group of to 8, more preferably at least any one of a fluorine atom or a saturated hydrocarbon group of 1 to 4 carbon atoms.

In terms of ease of synthesis, R ^15A to R ^20A are each independently preferably a hydrogen atom, -SO ₃ ^- , or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, -SO ₃ ^- , or a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom, -SO ₃ ^- , or a methyl group.

R ^45A , R ^46A and R ^55A are each independently preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a halogen atom or a carbon number 1 Aromatic hydrocarbon group with 6 to 10 carbon atoms substituted by alkoxy group, hydroxyl group, or methylsulfonyl group; or saturated hydrocarbon group with 1 to 8 carbon atoms, more preferably a saturated hydrocarbon group with 1 to 8 carbon atoms or the following The aromatic hydrocarbon group represented by the above formula.

Especially about R ⁴⁵ and R ⁴⁶ , either one is preferably a saturated hydrocarbon group having 1 to 6 carbon atoms, and the other is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms; more preferably, either one is a saturated hydrocarbon group having 1 to 6 carbon atoms, and the other is an aromatic hydrocarbon group represented by the following formula. R ⁵⁵ is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having a halogen atom, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms having two or more halogen atoms. The number of halogen atoms in the aromatic hydrocarbon group represented by R ⁵⁵ is preferably 1-6, more preferably 1-4, still more preferably 2-3. The halogen atom is preferably a fluorine atom. R ⁵⁵ is also preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

In formula (a-1), the number of -SO ₃ ^- is 2 or more, preferably 6 or less, more preferably 4 or less.

-SO ₃ ^- is preferably (ia) included as any one of R ^47A to R ^54A and R ^11A to R ^20A , or (ib) bonded to optionally substituted represented by R ^41A and R ^43A Any one of an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an optionally substituted aralkyl group having 7 to 30 carbon atoms represented by R ^41A and R ^43A , or (ic) bonded to R ^45A and R ^46A , any of the optionally substituted aromatic hydrocarbon groups with 6 to 20 carbon atoms represented by R ^55A , or in the form of a combination of these (ia) to (ic), more preferably (ia), (ib) or a combination of (ia) to (ib) exists, and more preferably, it exists in the form of (ia). In addition, among R ^47A to R ^54A and R ^11A to R ^20A , it is particularly preferable to include -SO ₃ ^- as R ^16A and R ^19A .

In the above (ia) to (ic), -SO ₃ ^- is preferably an aromatic hydrocarbon ring directly bonded to an aromatic hydrocarbon group or an aralkyl group. That is, -SO ₃ ^- preferably substitutes a hydrogen atom bonded to an aromatic hydrocarbon ring. Two or more -SO ₃ ^- may be bonded to the same aromatic hydrocarbon ring, and preferably, they are bonded to different aromatic hydrocarbon rings.

As the compound (a), as shown in the following Tables 1 to 9, the compound 1 to the compound 514 represented by the formula (a-2) and the like can be mentioned.

Among them, the compound represented by the formula (a-2) has two -SO ₃ ^- , and the -SO ₃ ^- substitutes any two hydrogen atoms represented by R ^h and R ^11A to R ^14A , preferably Any two hydrogen atoms represented by R ^h are substituted, and it is more preferable to substitute R ^h at the para position with respect to the bonding position with the nitrogen atom in the benzene ring bonded to the nitrogen atom.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

In Tables 1 to 9, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, and Ph1 to Ph10 represent groups represented by the following formulae, respectively. In Ph1 to Ph10, * represents a bonding bond.

Among them, as compound (a), Preferred are compound 31 to compound 90, compound 121 to compound 180, compound 211 to compound 334, compound 365 to compound 424, compound 455 to compound 514, More preferably compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 271 to compound 334, compound 380 to compound 394, compound 470 to compound 484, Further preferred are compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 271 to compound 304, compound 380 to compound 394, compound 470 to compound 484, More preferably, compound 46 to compound 60, compound 61 to compound 90, compound 136 to compound 150, compound 226 to compound 240, compound 271 to compound 294, compound 380 to compound 394, compound 470 to compound 484, Particularly preferred are Compound 46 to Compound 60, Compound 61 to Compound 90, Compound 136 to Compound 150, Compound 226 to Compound 240, Compound 279 to Compound 294, Compound 380 to Compound 394, and Compound 470 to Compound 484. According to these compounds, particularly high heat resistance and light resistance are achieved at the same time, and the brightness can be improved.

The compound (a) having -SO ₃ ^- can be produced, for example, by sulfonating a compound represented by the formula (aC) (hereinafter, sometimes referred to as compound (aC)), and further mixing it with a metal containing an r-valence. Ionic halides (preferably chlorides), acetates, phosphates, sulfates, silicates or cyanides, etc. are reacted.

[In formula (aC), R ^1c to R ^4c each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted The aralkyl group having 7 to 30 carbon atoms in the substituent, when the saturated hydrocarbon group has 2 to 20 carbon atoms, the -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO- ; Wherein, in the saturated hydrocarbon group with 2 to 20 carbon atoms, the adjacent -CH ₂ - will not be substituted into -O- at the same time, and the terminal -CH ₂ - will not be substituted into -O- or -CO-; R ^1c and R ^2c can be bonded to form a ring together with these bonded nitrogen atoms, and R ^3c and R ^4c can be bonded together with these bonded nitrogen atoms to form a ring; R ^7c to R ^14c represent each independently A hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH ₂ - constituting the saturated hydrocarbon group Can be substituted with -O- or -CO-; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-; R ^8c and R ^12c may be bonded to each other to form -NH-, -S-, or -SO ₂ -; Ring T ¹⁰ represents an aromatic heterocycle having 3 to 10 carbon atoms, and the aromatic heterocycle may be Contains optionally substituted saturated hydrocarbon groups with 1 to 20 carbon atoms, substituted or unsubstituted amine groups, or optionally substituted aromatic hydrocarbon groups with 6 to 20 carbon atoms; M ^1c represents Cl ^- , phosphate ion , perchlorate ion, BF ₄ ^- or PF ₆ ^- ]

Compound (a) having -SO ₂ -N ^- -SO ₂ -R ^f can be produced by making a compound (a) having -SO ₃ ^- group but not having -SO ₂ -N ^- -SO ₂ -R ^f Compound (a) reacts with a compound represented by formula (IB), and further reacts with a halide (preferably chloride), acetate, phosphate, sulfate, silicate or cyanide containing an r-valent metal ion wait for the reaction.

[In formula (IB), R ^f has the same meaning as described above]

As a method of sulfonation, various well-known methods, for example, the method described in "Journal of Organic Chemistry" ((1994), vol.59, #11, p.3232-3236) can be mentioned.

The compound (a) contains a dispersant and performs a dispersion treatment to obtain a dispersion liquid in which the compound (a) is uniformly dispersed in the solution.

Examples of the dispersing agent include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These dispersants may be used alone or in combination of two or more. As the dispersing agent, trade names can be listed: KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (manufactured by Kyeisha Chemical Co., Ltd.), Solsperse (Zeneca Co., Ltd.) ) (stock), EFKA (CIBA), Ajisper (Ajinomoto Fine-Techno (stock)), Disperbyk (Peak) chemistry (manufactured by BYK-chemie), BYK (manufactured by BYK-chemie), etc. When a dispersant is used, its usage amount is preferably 1 mass % or more and 100 mass % or less, more preferably 15 mass % or more and 100 mass % or less with respect to the compound (a). When the usage-amount of a dispersing agent exists in the said range, the dispersion liquid of the uniform dispersion state can be obtained.

In the dispersion liquid, the content of the compound (a) is preferably 1 mass % or more and 80 mass % or less, more preferably 1 mass % or more and 50 mass % or less, still more preferably 1 mass % or more and 30 mass % or less.

＜＜Xanthene Dyes＞＞ The colorant (A) preferably further contains a xanthene dye. As the xanthene dye, a known xanthene dye can be used, and among them, it is preferable to contain a compound represented by formula (1) (hereinafter, also referred to as "compound (1)") as a main component. In addition, in this specification, "comprising ... as a main component" means that it contains preferably 50 mass % or more, more preferably 70 mass % or more, further preferably 90 mass % or more, and particularly preferably 98 mass % As mentioned above, the upper limit may be 100 mass %.

[式（1）中，R ¹～R ⁴彼此獨立地表示氫原子、-R ⁸或碳數6～10的一價芳香族烴基，或者R ¹及R ²以及R ³及R ⁴分別一起形成包含氮原子的環；該芳香族烴基中所含的氫原子可經鹵素原子、-OH、-OR ⁸、-SO ₃ ^-、-SO ₃H、-SO ₃ ^-M ⁺、-CO ₂H、-CO ₂R ⁸、-SO ₃R ⁸或-SO ₂NR ⁹R ¹⁰取代； R ⁵表示-OH、-SO ₃ ^-、-SO ₃H、-SO ₃ ^-M ⁺、-CO ₂H、-CO ₂ ^-M ⁺、-CO ₂R ⁸、-SO ₃R ⁸或-SO ₂NR ⁹R ¹⁰； m表示0～5的整數，於m為2以上的整數的情況下，多個R ⁵可相同，亦可彼此不同； R ⁶及R ⁷彼此獨立地表示氫原子或碳數1～6的烷基； M ⁺表示 ⁺N(R ¹¹) ₄、Na ⁺或K ⁺，X表示鹵素原子； a表示0或1； R ⁸表示碳數1～20的一價飽和烴基，該飽和烴基中所含的氫原子可經碳數6～10的芳香族烴基、羧基或鹵素原子取代，該飽和烴基中所含的-CH ₂-可經-S-、-O-、-CO-或-NR ¹¹-取代；其中，該飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-；R ¹¹表示氫原子、碳數1～20的一價飽和烴基或碳數7～10的芳烷基，於R ¹¹存在多個的情況下，該些的全部或一部分可相同； R ⁹及R ¹⁰彼此獨立地表示氫原子、或碳數1～20的一價飽和烴基，該飽和烴基中所含的氫原子可經-OH或鹵素原子取代，該飽和脂肪族烴基中所含的-CH ₂-可經-S-、-O-、-CO-、-NH-或-NR ⁸-取代；其中，該飽和烴基中，鄰接的-CH ₂-不會同時經取代為-O-； R ⁹及R ¹⁰可彼此鍵結而形成包含氮原子的3員環～10員環的雜環]

[In formula (1), R ¹ to R ⁴ independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are formed together, respectively A ring containing a nitrogen atom; the hydrogen atom contained in the aromatic hydrocarbon group may be passed through a halogen atom, -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ substituted; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, - CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ may be The same or different from each other; R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and X represents a halogen atom; a represents 0 or 1; R ⁸ represents a monovalent saturated hydrocarbon group with a carbon number of 1-20, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an aromatic hydrocarbon group with a carbon number of 6-10, a carboxyl group or a halogen atom, the saturated hydrocarbon group The -CH ₂ - contained in can be substituted by -S-, -O-, -CO- or -NR ¹¹ -; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted with -O- at the same time ; R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and when there are multiple R ¹¹ , all or part of these may be the same; R ⁹ and R ¹⁰ independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, the -CH contained in the saturated aliphatic hydrocarbon group ₂ - can be substituted by -S-, -O-, -CO-, -NH- or -NR ⁸ -; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted into -O- at the same time; R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include phenyl, tolyl, xylyl, mesityl, propylphenyl and butylphenyl. Wait.

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include, for example, the following rings. In the following rings, * represents a bonding bond.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include the same groups as those exemplified as the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ .

As for R ⁸ , the aromatic hydrocarbon group having 6 to 10 carbon atoms which can replace the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may include those represented by R ¹ to R ⁴ having 6 to 10 carbon atoms. 10 of the monovalent aromatic hydrocarbon groups are the same as those exemplified.

A benzyl group, a phenylethyl group, a phenylbutyl group, etc. are mentioned as a C7-C10 aralkyl group in R11 in Formula ( ¹ ).

M ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ . ⁺ N(R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ¹¹ s. Moreover, 20-80 are preferable, and, as for the total carbon number of four R< ¹¹ >, 20-60 are more preferable.

More preferably, the xanthene dye contains the compound represented by formula (2) as a main component.

[In the formula (2), R ²¹ to R ²⁴ independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group can pass through -CO ₂ H, -SO ₃ ^- , -SO ₃ ^- M ^a+ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ substituted; X represents a halogen atom; as the halogen atom, fluorine atom, chlorine atom, Bromine atom, iodine atom; a1 represents 0 or 1; m1 represents an integer from 0 to 5; when m1 is an integer of 2 or more, a plurality of R ²⁵ may be the same or different; M ^a+ represents ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ ; R ²⁵ represents -SO ₃ ^- , -SO ₃ ^- Ma ⁺ , -SO ₃ H or -SO ₂ NHR ²⁶ ; R ²⁶ represents a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, the The hydrogen atom contained in the saturated hydrocarbon group may be substituted by a carboxyl group; the four R ²⁷ independently represent a monovalent saturated hydrocarbon group with a carbon number of 1 to 20 or a benzyl group]

As the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ²¹ to R ²⁴ in formula (2), the same groups as those listed as the aromatic hydrocarbon group in R ¹ to R ⁴ can be exemplified.

Examples of the monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those listed as the saturated hydrocarbon groups in R ⁸ to R ¹¹ . -R ²⁶ in R ²¹ to R ²⁴ in the formula (2) is preferably independently a carboxyl group-substituted linear alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. In addition, as R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ²⁶ , a branched alkyl group having 3 to 20 carbon atoms is preferable, a branched chain alkyl group having 6 to 12 carbon atoms is more preferable, and further Preferably it is 2-ethylhexyl.

Ma ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ . ⁺ N(R ²⁷ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ²⁷ . Moreover, 20-80 are preferable, and, as for the total carbon number of four R ^<27 >, 20-60 are more preferable.

In formula (2), it is preferable that R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are substituted In the case of , the group to be substituted is -SO ₃ ^- , -SO ₃ ^- M ⁺ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ . Furthermore, it is more preferable that R ²¹ and R ²³ are hydrogen atoms, and R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms (preferably a phenyl group, a tolyl group, or a xylyl group), The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -SO ₃ ^- M ⁺ or -SO ₂ NHR ²⁶ . When R ²¹ to R ²⁴ are these groups, it is advantageous in terms of forming a color filter excellent in heat resistance.

In formula (2), R ²⁵ is preferably -SO ₃ ^- or SO ₂ NHR ²⁶ .

In formula (2), a1 is preferably 0.

It is preferable that the xanthene dye contains any one or more of the compounds represented by formula (1-1) to formula (1-39) as a main component. In addition, in the formula, Ra represents a 2-ethylhexyl group.

The compounds represented by formula (1-1) to formula (1-16) can be produced, for example, by chlorinating a dye or dye intermediate having -SO ₃ H by a conventional method, and chlorinating the obtained dye having -SO 3 H or dye intermediate. A dye or dye intermediate of -SO ₂ Cl reacts with an amine represented by R ⁸ -NH ₂ . In addition, it can also be produced by a method of chlorinating the dye produced by the method described in the upper right column to the lower left column on page 3 of Japanese Patent Laid-Open No. 3-78702 in the same manner as described above, and then reacting with an amine. .

The compounds represented by the formulae (1-17) to (1-32) can be produced according to the method described in the upper right column to the lower left column on page 3 of Japanese Patent Laid-Open No. 3-78702. As said method, the method of making the compound represented by Formula (1a), the compound represented by Formula (1b), and the compound represented by Formula (1c) react, for example. In formula (1b) and formula (1c), R ¹ to R ⁴ have the same meanings as described above, respectively.

The compounds represented by the formulae (1-33) to (1-39) can be produced according to the method described in Japanese Patent Laid-Open No. 2017-226814.

＜＜Other colorants＞＞ In addition to the compound (a) and the xanthene dye, the colorant (A) may contain other dyes (hereinafter, referred to as dye (A1)) and other pigments (hereinafter, referred to as pigment (A2)) situation) either or both.

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds with hues other than pigments classified in the Color Index (published by The Society of Dyers and Colourists), or dyeing notes (color dyes). (Shikisensha Co., Ltd.) known dyes. In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes can be mentioned. Dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes, etc. Of these, organic solvent-soluble dyes are preferred.

Specifically, the dyes of the following dye index (C.I.) numbers can be mentioned. For example, C.I. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. direct yellow 2,4,28,33,34,35,38,39,43,44,47,50,54,58,68,69,70,71,86,93,94,95 , 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I. Disperse yellow 51, 54, 76; C.I. reactive yellow 2, 76, 116; C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169 , 173; C.I. solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. reactive orange 16; C.I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76 , 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183 , 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315 , 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; C.I. solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169 , 172, 175, 181, 207, 222, 227, 230, 245, 247; C.I. direct red , 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37 , 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. acid violet 34; C.I. disperse violet 26, 27; C.I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. solvent blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104 , 105, 111, 112, 122, 128, 132, 136, 139; C.I. acid blue 25, 27, 40, 45, 78, 80, 112; C.I. direct blue 40; C.I. disperse blue 1, 14, 56, 60; C.I. solvent green 1, 3, 5, 28, 29, 32, 33; C.I. acid green 3, 5, 9, 25, 27, 28, 41; C.I. basic green 1; C.I. vat green 1 etc.

As the pigment, a well-known pigment can be used, and examples thereof include pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists). Two or more kinds may be combined. Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 , 266, 268, 269, 273 and other red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment green 7, 36, 58, 59 green pigment.

The pigment (A2) may be subjected to rosin treatment, surface treatment using a pigment derivative into which an acid group or basic group is introduced, etc., graft treatment of the surface of the pigment with a polymer compound or the like, and a sulfuric acid micronization method, if necessary. Micronization treatment, etc., cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment with an ion exchange method or the like for ionic impurities, and the like. The particle size of the pigment (A2) is preferably uniform. By containing a dispersant and performing dispersion treatment, a pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained.

As the dispersing agent, the dispersing agent can be used. When a dispersant is used, its usage amount is preferably 1 mass % or more and 100 mass % or less, more preferably 5 mass % or more and 50 mass % or less with respect to the total amount of the pigment (A2). When the usage-amount of a pigment dispersant is in the said range, the pigment dispersion liquid of the uniform dispersion state can be obtained.

The content rate of the compound (a) in the colorant (A) is preferably 50 mass % or more, more preferably 60 mass % or more, further preferably 70 mass % or more, particularly preferably 80 mass % or more, and may be 100 mass % or more. The mass % may be 98 mass % or less, or 95 mass % or less.

The content of the xanthene dye in the colorant (A) is preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more, and preferably 30 mass % or less, more preferably 20 mass % or less, more preferably 10 mass % or less.

The total content of the compound (a) and the xanthene dye in the colorant (A) is preferably 75% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass In the above, in addition, 100 mass % may be sufficient.

The content rate of the colorant (A) is preferably 5% by mass or more and 60% by mass or less, more preferably 8% by mass or more and 55% by mass or less, and still more preferably 10% by mass or more, with respect to the total amount of solid content. 50 mass % or less. If the content of the colorant (A) is within the above-mentioned range, the color density when used as a color filter is sufficient, and the composition can contain a necessary amount of the resin (B) or the polymerizable compound (C). Patterns with sufficient mechanical strength can be formed.

Here, the "total amount of solid content" in this specification refers to the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of solid components and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

＜Resin (B)＞ The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. As resin (B), the following resin [K1] - resin [K6] etc. are mentioned. Resin [K1]: a monomer (a) derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter, referred to as “(a)” in some cases) Structural unit and copolymer of structural unit derived from monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter referred to as "(b)" in some cases) ; Resin [K2]: has a structural unit derived from (a), a structural unit derived from (b), and a monomer (c) derived from copolymerizable with (a) (wherein, with (a) and (b) ) different) (hereinafter, there is a case referred to as "(c)") of the structural unit); Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]: a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, and p-vinyl benzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acids such as 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride acid anhydrides; Divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate Unsaturated mono[(meth)acryloyloxyalkyl]esters; Unsaturated acrylates etc. which contain a hydroxyl group and a carboxyl group in the same molecule like α-(hydroxymeth)acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable in terms of the copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) means, for example, having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenic A polymerizable compound with an unsaturated bond. (b) Preferably it is a monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group. In addition, in this specification, "(meth)acrylic acid" means at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include a monomer (b1) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(b1)"), a monomer having an oxetanyl group and an ethylene Monomer (b2) of unsaturated bond (hereinafter referred to as "(b2)"), monomer (b3) having tetrahydrofuran group and ethylenically unsaturated bond (hereinafter referred to as "( b3)").

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1) "), a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, there is a case called "(b1-2)").

As (b1-1), glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-ethylene Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) base) styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene oxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4, 5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc.

As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel) (stock)), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer A400; Daicel (stock)), (meth)acrylic acid 3,4 -Epoxycyclohexyl methyl ester (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[In formula (I) and formula (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ^a and X ^b Represents a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-; R ^c represents an alkanediyl group with 1 to 6 carbon atoms; * represents a O's bond key]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and the like. Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxypropyl, -Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. Preferable examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferable examples include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylidene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. -diyl, hexane-1,6-diyl, etc. Preferable examples of X ^a and X ^b include a single bond, a methylene group, an ethylidene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably a single bond, * -CH ₂ CH ₂ -O- (* denotes a bond with O).

As a compound represented by Formula (I), the compound etc. which are represented by any one of Formula (I-1) - Formula (I-15) are mentioned. Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-11) are preferred. The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

As a compound represented by Formula (II), the compound etc. which are represented by any one of Formula (II-1) - Formula (II-15) are mentioned. Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II) are preferred The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound represented by formula (I) and the compound represented by formula (II) may be used independently, respectively, or two or more of them may be used in combination. When the compound represented by the formula (I) and the compound represented by the formula (II) are used together, the content ratio of these [the compound represented by the formula (I): the compound represented by the formula (II)] is in moles The reference value is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-propenyloxymethyl oxetane, 3-methyl-3-methyl Acryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl Oxetane, 3-ethyl-3-propenyloxyethyl oxetane, etc.

As (b3), a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), (b1) is preferable in terms of further improving reliability such as heat resistance and chemical resistance of the obtained color filter. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a colored curable resin composition.

(c), methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd (meth)acrylate Butyl, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, ring (meth)acrylate Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (this technology In the field, it is called "dicyclopentyl (meth)acrylate" as a common name. In addition, it may be called "tricyclodecyl (meth)acrylate"), (meth)acrylate tricyclo [5.2.1.0 ^2,6 ] Decen-8-yl ester (in this technical field, it is called "(meth)acrylic acid dicyclopentenyl ester" as a common name), (meth)acrylic acid dicyclopentenyl ester Alkyloxyethyl ester, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, benzene (meth)acrylate (Meth)acrylates such as base ester, naphthyl (meth)acrylate, benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; Diethyl maleate, diethyl fumarate, diethyl itaconic acid and other dicarboxylic acid diesters; Bicyclo[2.2.1]heptyl -2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2- alkene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2. 1] Hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide Imidinobenzoate, N-succinimidino-4-maleimidobutyrate, N-succinimidino-6-maleimidohexanoate, N -Succinimidyl-3-maleimidopropionate, N-(9-acridyl)maleimide and other dicarbonylimide derivatives; styrene, α -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methyl Acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among these, in terms of copolymerization reactivity and heat resistance, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N -Cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc.

Among all the structural units constituting the resin [K1], the ratio of the structural units derived from each in the resin [K1] is preferably Structural unit derived from (a): 2 mol% to 60 mol% Structural units derived from (b): 40 mol% to 98 mol%, better Structural units derived from (a): 10 mol% to 50 mol% Structural units derived from (b): 50 mol % to 90 mol %. When the ratio of the structural unit of the resin [K1] is within the above-mentioned range, the storage stability of the colored curable resin composition, the developability at the time of forming the colored pattern, and the solvent resistance of the obtained color filter can be excellent. .

For resin [K1], for example, the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Takashi Otsu, Chemical Doujin Publishing Co., Ltd., 1st edition, first printing, issued on March 1, 1972) and Manufactured by citing the literature described in this literature.

Specifically, the predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are put into a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized environment, and stirring is performed. A method of heating and keeping warm at the same time. In addition, the polymerization initiator, solvent, etc. used here are not specifically limited, Those generally used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides can be mentioned. The oxide (benzyl peroxide, etc.) may be used as a solvent as long as it dissolves each monomer, and examples thereof include the solvent (E) described later as the solvent (E) of the colored curable resin composition of the present invention.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use the thing extracted as a solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, so it is possible to The manufacturing process of the coloring curable resin composition of this invention is simplified.

Among all the structural units constituting the resin [K2], the ratio of the structural units derived from each in the resin [K2] is preferably Structural unit derived from (a): 2 mol% to 45 mol% Structural unit derived from (b): 2 mol% to 95 mol% Structural units derived from (c): 1 mol% to 65 mol%, better Structural units derived from (a): 5 mol% to 40 mol% Structural units derived from (b): 5 mol% to 80 mol% Structural units derived from (c): 5 mol% to 60 mol%. When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance and heat resistance of the obtained color filter Properties and mechanical strength can be excellent.

The resin [K2] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

Among all the structural units constituting the resin [K3], the ratio of the structural units derived from each in the resin [K3] is preferably Structural unit derived from (a): 2 mol% to 60 mol% Structural units derived from (c): 40 mol% to 98 mol%, better Structural units derived from (a): 10 mol% to 50 mol% Structural units derived from (c): 50 mol % to 90 mol %. The resin [K3] can be produced, for example, in the same manner as the method described as the production method of the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid contained in (a). and/or carboxylic acid anhydride. First, the copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural unit derived from each is preferably the same ratio as the ratio listed in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer. Following the production of the copolymers of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and the reaction catalyst (for example, tris(dimethyl)) of (b), carboxylic acid or carboxylic anhydride and cyclic ether resins [ K4]. The amount of (b) used is preferably 5 mol to 80 mol, more preferably 10 mol to 75 mol, relative to 100 mol of (a). By setting it as this range, the storage stability of a coloring curable resin composition, the developability at the time of pattern formation, and the solvent resistance of the obtained pattern, heat resistance, mechanical strength, and the balance of sensitivity can become favorable. As the (b) used for the resin [K4], (b1) is preferred, and (b1-1) is more preferred, since the cyclic ether has high reactivity and is unlikely to remain unreacted (b). The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production facility, the calorific value due to the polymerization, and the like. In addition, similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility, the heat generation due to the polymerization, and the like.

Regarding the resin [K5], as the first stage, the copolymer of (b) and (c) was obtained in the same manner as in the production method of the resin [K1]. In the same manner as described above, the obtained copolymer may be used as it is in the solution after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by methods such as reprecipitation. The ratios of the structural units derived from (b) and (c) with respect to the total number of moles of all the structural units constituting the copolymer are preferably respectively Structural units derived from (b): 5 mol% to 95 mol% Structural units derived from (c): 5 mol% to 95 mol%, better Structural units derived from (b): 10 mol% to 90 mol% Structural units derived from (c): 10 mol% to 90 mol%.

Furthermore, the carboxylic acid or carboxylic anhydride contained in (a) and the cyclic ether derived from (b) contained in the copolymer of (b) and (c) were prepared under the same conditions as in the production method of resin [K4]. By reacting, resin [K5] can be obtained. The amount of (a) used to react with the copolymer is preferably 5 mol to 80 mol relative to 100 mol of (b). As the (b) used for the resin [K5], the cyclic ether is preferably (b1), more preferably (b1-1), since the reactivity of the cyclic ether is high and the unreacted (b) hardly remains.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride and resin [K5]. The carboxylic acid anhydride is reacted with the hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride. Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrakis Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2- alkene anhydride, etc. The usage-amount of the carboxylic anhydride is preferably 0.5 mol to 1 mol per 1 mol of the usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylic acid/(meth)acrylic acid copolymer, 3,4-epoxytricycloacrylic acid [5.2.1.0 ^2,6 ] Resin [K1] such as decyl ester/(meth)acrylic acid copolymer; Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleic acid Imide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/(meth)acrylic acid 2 - Resins such as hydroxyethyl ester copolymer, 3-methyl-3-(meth)acryloyloxymethyl oxetane/(meth)acrylic acid/styrene copolymer [K2]; (methyl) ) resins such as benzyl acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer [K3]; benzyl acrylate/(meth)acrylic acid copolymer addition ( Resin made of glycidyl meth)acrylate, resin obtained by adding glycidyl (meth)acrylate to tricyclodecyl p-(meth)acrylate/styrene/(meth)acrylic acid copolymer, p-(meth)acrylate base) resins such as tricyclodecyl acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer added with glycidyl (meth)acrylate [K4]; (meth)acrylic acid A resin obtained by reacting with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, a mixture of (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/( Resins such as resins [K5] obtained by reacting a copolymer of glycidyl meth)acrylate; a copolymer of (meth)acrylic acid and tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate Resin [K6] etc., such as the resin which reacted with the resin which reacted with tetrahydrophthalic anhydride, etc. further. Among these, as resin (B), resin [K1] and resin [K2] are preferable, and resin [K1] is especially preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and still more preferably 5,000 or more and 30,000 or less. When the molecular weight is within the above-described range, the hardness of the color filter can be improved, the residual film ratio can be high, the solubility of the unexposed portion in the developer solution can be improved, and the resolution of the colored pattern can be improved.

The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 or more and 6 or less, and more preferably 1.2 or more and 4 or less.

The acid value of the resin (B) is preferably 50 mg-KOH/g or more and 170 mg-KOH/g or less in terms of solid content, more preferably 60 mg-KOH/g or more and 150 mg-KOH/g or less, and further Preferably, it is 70 mg-KOH/g or more and 135 mg-KOH/g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7% by mass or more and 65% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and still more preferably 17% by mass or more and 55% by mass relative to the total amount of solid content. mass % or less. When the content rate of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern can be improved.

<Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), and has a hydroxyl value of 100 mgKOH/g or more. According to the colored curable resin composition of the present invention containing the polymerizable compound (C), the obtained cured film can be thinned. Moreover, in a preferable aspect, the brightness|luminance of the obtained cured film can become favorable.

The polymerizable compound (C) may contain one type of polymerizable compound whose hydroxyl value is 100 mgKOH/g or more, or may contain two or more types of polymerizable compounds whose hydroxyl value is 100 mgKOH/g or more. In addition, the polymerizable compound (C) may be a mixture of one or two or more polymerizable compounds having a hydroxyl value of 100 mgKOH/g or more, and one or two or more polymerizable compounds having a hydroxyl value of less than 100 mgKOH/g . When two or more types of polymerizable compounds are contained as the polymerizable compound (C), the hydroxyl value of the polymerizable compound (C) means the hydroxyl value of the mixture. In addition, the hydroxyl value of a polymerizable compound (C) was measured according to the description of the Example mentioned later.

The hydroxyl value of the polymerizable compound (C) is preferably 110 mgKOH/g or more, more preferably 180 mgKOH/g or more, still more preferably 200 mgKOH/g or more, and particularly preferably 250 mgKOH/g or more. When the hydroxyl value of a polymerizable compound (C) exists in the said range, thinning of the cured film obtained can be achieved, and the brightness of the cured film obtained in a preferable aspect can become favorable. In addition, from the viewpoint of availability, the hydroxyl value of the polymerizable compound (C) is preferably 500 mgKOH/g or less, more preferably 450 mgKOH/g or less, still more preferably 400 mgKOH/g or less, still more preferably It is 350 mgKOH/g or less, and it is especially preferable that it is 300 mgKOH/g or less.

As a polymerizable compound (C), the compound which has a polymerizable ethylenically unsaturated bond and a hydroxyl group is mentioned. The average number of double bonds of the polymerizable compound (C) is 1.0 or more, preferably 2.0 or more, more preferably 2.5 or more, and preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3.0 or less. In addition, the average double bond number of a polymerizable compound (C) can be measured by analytical means, such as high performance liquid chromatography (High Performance Liquid Chromatography, HPLC), for example.

Specific examples of the polymerizable compound having a hydroxyl value of 100 mgKOH/g or more include pentaerythritol tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol mono(meth)acrylate, and ethylene glycol. Modified pentaerythritol tri(meth)acrylate, propylene glycol modified pentaerythritol triacrylate, trimethylolpropane di(meth)acrylate, ethylene glycol modified trimethylolpropane di(meth)acrylate, Ethylene glycol modified glycerol di(meth)acrylate, propylene glycol modified glycerol di(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, ethylene glycol modified di-trihydroxy Methylpropane tri(meth)acrylate, propylene glycol modified di-trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, etc. The polymerizable compound (C) preferably contains at least pentaerythritol tri(meth)acrylate, and more preferably contains pentaerythritol triacrylate. When the polymerizable compound (C) contains pentaerythritol tri(meth)acrylate (preferably pentaerythritol triacrylate), the content of the polymerizable compound (C) is preferably 10% by mass or more, more preferably It is 25 mass % or more, more preferably 40 mass % or more, and may be 100 mass %, 90 mass % or less, or 80 mass % or less.

The content of the polymerizable compound having a hydroxyl value of 100 mgKOH/g or more in the polymerizable compound (C) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and may be 100 mass %, 98 mass % or less may be sufficient, and 93 mass % or less may be sufficient.

In the case where the polymerizable compound (C) is a mixture of two or more polymerizable compounds, as long as the hydroxyl value of the mixture is not less than 100 mgKOH/g, the polymerizable compound (C) may also contain a hydroxyl value of less than 100 mgKOH/g. The polymerizable compound of g. Specific examples of the polymerizable compound having a hydroxyl value of less than 100 mgKOH/g include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol pentamethacrylate, di- Pentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol ten(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate , ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate base) acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate.

The content of the polymerizable compound (C) is preferably 7% by mass or more, more preferably 13% by mass or more, still more preferably 20% by mass or more, and more preferably 65% by mass or less with respect to the total amount of solid content , more preferably 55 mass % or less, still more preferably 45 mass % or less. When the content rate of the polymerizable compound (C) is within the above range, the obtained cured film can be thinned, and the residual film rate at the time of color pattern formation and the chemical resistance of the color filter can be improved. .

<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, an acid, or the like by the action of light or heat to initiate polymerization, and known polymerization initiators can be used. As a polymerization initiator which generate|occur|produces an active radical, a phenalkyl ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound are mentioned, for example.

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond key.

Examples of the O-acyl oxime compound include N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyl Acyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3 -Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxo Cyclopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- (2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl- 6-(2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-( 4-Phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine. Irgacure OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA), PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials) can also be used ) and other commercially available products. Wherein, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, Alkyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3- Cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine At least one of the group consisting of, more preferably selected from N-benzyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-acetylene at least one of the group consisting of oxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine. With these O-acyl oxime compounds, a high-brightness color filter can be obtained.

The phenylalkyl ketone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylene aminoamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (the above, manufactured by BASF) can also be used. Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Oligomers of ketones, α,α-diethoxyacetophenone, benzil dimethyl ketal. In terms of sensitivity, the phenylalkyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

As the triazine compound, for example, 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-pipronyl-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2- yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl ]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5- Triazine.

As said acyl phosphine oxide compound, 2, 4, 6- trimethylbenzyl diphenyl phosphine oxide etc. are mentioned. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can also be used.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Japanese Patent Laid-Open No. 62-174204, etc.), biimidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913, etc.) .

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, etc. , 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)diphenyl Benzophenone compounds such as ketone, 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthraquinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2- Chloracridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiator (D1) (especially amines) described later.

As the acid generator, for example, 4-hydroxyphenyldimethylperylene p-toluenesulfonate, 4-hydroxyphenyldimethylperylene hexafluoroantimonate, and 4-acetoxyphenyldimethylene are mentioned. Peri-p-toluenesulfonate, 4-Acetyloxyphenyl·methyl·benzyl perylene hexafluoroantimonate, triphenyl perylene p-toluenesulfonate, triphenyl perylene hexafluoroantimonate, diphenyl perylene hexafluoroantimonate Onium salts such as iodonium p-toluenesulfonate, diphenyl iodonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, and the like.

The polymerization initiator (D) preferably contains at least one selected from the group consisting of a phenylalkyl ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound The polymerization initiator is more preferably a polymerization initiator containing an O-acyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 20 parts by mass or less. When the content of the polymerization initiator (D) is within the above range, the sensitivity can be increased and the exposure time can be shortened, so that the productivity of the color filter is improved.

<Polymerization Initiating Auxiliary (D1)> The polymerization initiation adjuvant (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D). As a polymerization initiation aid (D1), an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4 ,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4' -Bis(ethylmethylamino)benzophenone, etc., among them, 4,4'-bis(diethylamino)benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-Chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include thiophenylacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxybenzene Thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine acid, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine acid, naphthoxyacetic acid, etc.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , more preferably 1 part by mass or more and 20 parts by mass or less. When the amount of the polymerization initiation aid (D1) is within the above range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter can be improved.

<Solvent (E)> The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. For example, ester solvents (solvents that contain -COO- and do not contain -O- in the molecule), ether solvents (solvents that contain -O- and do not contain -COO- in the molecule), ether ester solvents (solvents that contain -O- in the molecule) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- and not containing -COO- in the molecule), alcohol solvent (containing OH in the molecule and not containing -O-, -CO - and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

As the ether solvent, 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 monoethyl ether, Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl butanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl, 2-methoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methylpropionate ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate acid esters, etc.

Examples of the ketone solvent include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

As an amide solvent, N,N- dimethylformamide, N,N- dimethylacetamide, N-methylpyrrolidone, etc. are mentioned.

Among the solvents, an organic solvent having a boiling point at 1 atm of 120° C. or higher and 180° C. or lower is preferable in terms of coatability and drying properties. The solvent is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethyl ether Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, Ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone.

The content of the solvent (E) is preferably 70% by mass or more and 95% by mass or less, more preferably 75% by mass or more and 92% by mass or less, with respect to the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5% by mass or more and 30% by mass or less, and more preferably 8% by mass or more and 25% by mass or less. When the content rate of the solvent (E) is within the above range, the flatness at the time of coating becomes favorable, and the color density does not become insufficient during the formation of the color filter, so that the display characteristics become favorable.

＜Leveler (F)＞ As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, a silicone-based surfactant having a fluorine atom, and the like are exemplified. These may also have a polymerizable group in the side chain. As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan) Co., Ltd. manufacture), etc.

As said fluorine type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac ) F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC (stock)), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass) (stock) and E5844 (Daikin Fine Chemical Research Institute (stock)), etc.

As a silicone type surfactant which has the said fluorine atom, the surfactant etc. which have a siloxane bond and a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (DIC) (stock) manufacturing), etc.

The content of the leveling agent (F) is preferably 0.001 mass % or more and 0.2 mass % or less, more preferably 0.002 mass % or more and 0.2 mass % or less, with respect to the total amount of the colored curable resin composition, and still more preferably 0.01 mass % or more and 0.2 mass % or less. In addition, the said dispersing agent is not included in this content rate. When the content rate of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

＜Other ingredients＞ The colored curable resin composition of the present invention may optionally contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents. Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidyloxypropyltrimethoxysilane Silane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-thiopropyl Trimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amine ethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Silane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane, etc.

<Manufacturing method of colored curable resin composition> The colored curable resin composition of the present invention can be prepared, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent used as needed (E), leveling agent (F), polymerization initiator (D1) and other ingredients are mixed.

The colorant (A) can be used in a state where it is mixed with a part or all of the solvent (E) in advance, and is dispersed to an average particle size of about 0.2 μm or less using a bead mill or the like as necessary. At this time, a part or all of the said dispersing agent and resin (B) may be mix|blended as needed. It is preferable to prepare a target coloring composition by mixing the remaining components in the dispersion liquid obtained in this way so that it may become predetermined density|concentration. When a bead mill is used, the diameter of the beads is preferably 0.05 mm or more and 0.5 mm or less, and the material of the beads includes glass, ceramics, metal, and the like.

<Manufacturing method of color filter> As a method of producing the coloring pattern of a color filter from the coloring curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a composition layer, and exposing and developing the composition layer through a photomask. In the photolithography method, a colored coating film that is a cured product of the composition layer can be formed by not using a photomask and/or not performing development during exposure.

The film thickness of the color filter (cured film) is, for example, 0.1 μm or more and 30 μm or less, preferably 0.1 μm or more and 20 μm or less, and more preferably 0.5 μm or more and 6 μm or less.

As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass whose surface is coated with silica; or polycarbonate, polymethyl methacrylate, poly Resin plates such as ethylene terephthalate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates. In addition, a silicon substrate can also be used as a substrate processed by hexamethyldisilazane (Hexamethyldisilazane, HMDS).

The formation of each color pixel by photolithography can be performed under known or conventional devices or conditions. For example, it can be produced as follows. First, the coloring composition is applied on a substrate, and is dried by heat drying (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby obtaining a smooth composition layer. As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned. The temperature at the time of heating and drying is preferably 30°C or higher and 120°C or lower, more preferably 50°C or higher and 110°C or lower. Moreover, as a heating time, 10 seconds or more and 60 minutes or less are preferable, and 30 seconds or more and 30 minutes or less are more preferable. When drying under reduced pressure, it is preferable to carry out in the temperature range of 20 degreeC - 25 degreeC under the pressure of 50 Pa - 150 Pa. The film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the mask is not particularly limited, and a pattern according to the intended use is used. In addition, in order to form a colored coating film, exposure was performed without using a photomask. As a light source used for exposure, a light source that generates light having a wavelength of 250 nm to 450 nm is preferable. For example, for light less than 350 nm, a filter that cuts off this wavelength range can be used to cut off, or for light near 436 nm, 408 nm, and 365 nm, a bandpass filter that extracts these wavelength ranges can be used for selection. Sexual removal. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. In order to uniformly irradiate the entire exposure surface with parallel light, or to perform accurate alignment of the mask and the substrate, it is preferable to use a reduction projection exposure device such as a mask aligner and a stepper, or Proximity exposure device.

A colored pattern is formed on the substrate by contacting the exposed composition layer with a developing solution for development. By development, the unexposed portion of the composition layer is dissolved in the developing solution and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.03 mass % or more and 5 mass % or less. Furthermore, the developer may contain a surfactant. The development method may be any of a liquid coating method, a dipping method, a spray method, and the like. Furthermore, you may incline a board|substrate to an arbitrary angle at the time of image development. After development, it is preferable to wash with water.

Furthermore, it is preferable to post-bake the obtained colored pattern and colored coating film. The post-baking temperature is preferably 80°C or higher and 250°C or lower, more preferably 100°C or higher and 245°C or lower. The post-baking time is preferably 1 minute or more and 120 minutes or less, and more preferably 2 minutes or more and 30 minutes or less.

The colored pattern and colored coating film thus obtained are useful as color filters for display devices (eg, liquid crystal display devices, organic electroluminescence (EL) devices, etc.), electronic paper, and solid-state imaging devices. It is useful as a color filter used in elements and the like. [Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In an example, the % and the part indicating the content and the usage amount are based on the mass unless otherwise specified.

Hereinafter, the structure of the compound was confirmed by mass analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD type).

[Colorant Synthesis Example 1] The following reactions were carried out under nitrogen atmosphere. Into the flask including a cooling pipe and a stirring device, 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were put, and then stirred at room temperature for 30 minutes. Into the flask, 40.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour. Into the flask, 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring at room temperature for 1 hour. An aqueous solution obtained by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchanged water was put into the flask, and 60.4 parts of a 30% aqueous sodium hydroxide solution was added, followed by stirring at room temperature for 18 hours. To the flask was further added 600 parts of ion-exchanged water, followed by stirring for 1 hour, and the precipitated yellow-white solid was collected by filtration. The obtained yellow-white solid was washed with 120 parts of acetonitrile, and then washed with 560 parts of ion-exchanged water. The washed yellow-white solid, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 156 parts of toluene were put into a flask including a stirring device, and stirred at room temperature for 2 hours. To this, 80.8 parts of 30% aqueous sodium hydroxide solutions were added dropwise over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 156 parts of ion-exchanged water was added, and liquid separation washing was performed, and then 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added, and liquid separation washing was performed. The obtained organic layer was concentrated by an evaporator, and then dried under reduced pressure at 35° C. to obtain the compound represented by the formula (B-I-1) as a white solid. The yield was 43.4 parts, and the yield was 58.0%.

The following reactions were carried out under nitrogen atmosphere. 13.2 parts of compounds represented by formula (B-I-1), 19.0 parts of compounds represented by formula (C-I-1), and 38 parts of toluene were put into a flask including a cooling pipe and a stirring device, and then 9.2 parts of phosphonium chlorides were added. and stirred at 100°C for 7 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of a 35% hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was solvent-distilled by an evaporator, and then, it was dried under reduced pressure at 60 degreeC, and the compound represented by Formula (X-II-1) was obtained as a blue-violet solid. The obtained amount of blue-violet solid was 39.4 parts.

The following reactions were carried out under nitrogen atmosphere. 38.4 parts of compounds represented by formula (X-II-1) and 112 parts of dichloromethane were put into a flask including a cooling pipe and a stirring device, and stirred for 30 minutes. The reaction solution was ice-cooled and the internal temperature was kept at 10° C., 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in this state, and the reaction solution was heated to room temperature and stirred for 9 hours. Next, the reaction solution was cooled in an ice bath and the internal temperature was kept at 10° C., and diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion-exchanged water in this state. After pouring the diluted reaction solution into 1120 parts of toluene, the mixture was stirred for 30 minutes to precipitate a viscous solid. After the oil layer was discharged by decantation, 320 parts of toluene was added to the obtained viscous solid, followed by stirring for 30 minutes. 832 parts of 20% brine was added to the viscous solid obtained by decantation to remove the oil layer, followed by stirring for 1 hour, and then the blue solid was collected by filtration. The obtained blue solid was washed with 576 parts of 20% brine, and dried under reduced pressure at 35°C. The obtained solid and 128 parts of methanol were put into a flask including a stirring device, stirred for 30 minutes, and then filtered to separate into a solid and a filtrate. This filtrate was called filtrate A3. The solid collected by filtration was washed with 192 parts of methanol, and was separated into a solid and a filtrate by filtration. This filtrate was called filtrate B3. The filtrate A3 and the filtrate B3 were mixed, the solvent was removed by an evaporator, and the compound represented by formula (X-I-1) was obtained as a blue-violet solid after drying under reduced pressure at 40°C. The obtained amount of blue-violet solid was 38.3 parts.

28.0 parts of the compound represented by formula (X-I-1), 43.2 parts of barium chloride dihydrate, and 356 parts of ion-exchanged water were added to a flask including a cooling pipe and a stirring device, and the reaction was stirred at 40° C. for 2 hours. The suspension is filtered. Into a flask including a stirring device, 350 parts of the solid collected by filtration and ion-exchanged water were put and stirred for 30 minutes, after which the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water, and then dried at 60° C. under reduced pressure to obtain the compound represented by the formula (A-I-1) as a blue-violet solid. The obtained amount was 24.5 parts, and the yield was 81.7%.

Identification (mass analysis) of the compound represented by the formula (AI-1) Ionization mode=ESI-: m/z=949.5[M-Ba+2H] ^-Exact Mass (Exact Mass) [M-Ba]: 947.28

[Colorant Synthesis Example 2] 40.5 parts of the compound represented by the formula (1a) and 60.5 parts of 2,6-xylidine (2,6-xylidine) (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under light-shielding conditions, and added to N-methylpyridone. 200 parts were stirred at 150 degreeC for 8 hours. After cooling the obtained reaction liquid to room temperature, it added to the mixed liquid of 1200 parts of water and 75 parts of 35% hydrochloric acid, and it stirred at room temperature for 1 hour, as a result, crystal|crystallization was precipitated. The precipitated crystal was obtained as the residue of suction filtration, washed with 100 parts of methanol, and then dried under reduced pressure at 60° C. overnight to obtain 49 parts of the compound represented by formula (1-32). The yield was 85%.

[Resin Synthesis Example 1] An appropriate amount of nitrogen was circulated in a flask including a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was put in and heated to 80°C while stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, and 3,4-epoxytricyclo[5.2.1.0 ² acrylate were added dropwise over 5 hours. ^,6 ] A mixed solution of 289 parts of a mixture of decane-9-yl esters (the content ratio is 1:1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the solution was kept at 80°C for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution with a solid content of 35.1% and a viscosity of 125 mPas measured by a B-type viscometer (23°C). The weight average molecular weight Mw of the produced copolymer was 9.2×10 ³ , the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin B1 has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) under the following conditions. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: THF (tetrahydrofuran, tetrahydrofuran) Flow rate: 1.0 mL/min Test liquid solid content concentration: 0.001% by mass to 0.01% by mass Injection volume: 50 μL Detector: RI Standard material for calibration: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio (Mw/Mn) of the weight-average molecular weight and number-average molecular weight obtained in terms of polystyrene described above was defined as the degree of dispersion.

[Preparation of Colorant Dispersion Liquid 1] 23.1 parts of compound represented by formula (A-I-1), dispersant (BYKLPN-6919 manufactured by BYK-chemie; 60% solution of propylene glycol monomethyl ether acetate), 28.8 parts of resin B1 (with In terms of solid content) 5.8 parts, 28.9 parts of 4-hydroxy-4-methyl-2-pentanone, and 202 parts of propylene glycol monomethyl ether acetate were mixed, and 600 parts of 0.4 μm zirconia beads were added, and adjusted with paint A Paint Conditioner (manufactured by LAU Corporation) was shaken for 1 hour. Then, the zirconia beads were removed by filtration, and a colorant dispersion liquid 1 was obtained.

[Comparative Example 1] [Preparation of Colored Curable Resin Composition 1] Colorant dispersion 1, a compound represented by formula (1-32), a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent are mixed so as to have the composition shown below to obtain coloring Curable resin composition 1. The colored curable resin composition 1 is a colored curable resin composition containing 2.5 parts of the compound represented by the formula (A-I-1) as the colorant (A), and 0.2 parts of the compound represented by the formula (1-32) The compound represented; 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK-Chemie) as a dispersant; 7.8 parts (in terms of solid content) of resin (B) Resin B1; 5.2 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value: 10 mgKOH/g) as a polymerizable compound (C); As a polymerization initiator (D), 0.4 parts of PBG-327 (manufactured by Changzhou Qiangli Electronic New Material (stock), N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexyl Propane-1-keto-2-imine, oxime compound); as solvent (E) 78.9 parts of propylene glycol monomethyl ether acetate, 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; as solvent (E) 0.01 part of leveling agent (F) (in terms of solid content) Toray silicone (SH8400) (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[Comparative Example 2] [Preparation of Colored Curable Resin Composition 2] Colorant dispersion 1, a compound represented by formula (1-32), a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent are mixed so as to have the composition shown below to obtain coloring Curable resin composition 2. The colored curable resin composition 2 is a colored curable resin composition containing 2.5 parts of the compound represented by the formula (A-I-1) as the colorant (A), and 0.2 parts of the compound represented by the formula (1-32) The compound represented; 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK-Chemie) as a dispersant; 7.8 parts (in terms of solid content) of resin (B) Resin B1; as a polymerizable compound (C), 3.8 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value: 10 mgKOH/g), 1.5 parts of Aronix (registered trademark) M-933 (manufactured by Toagosong Co., Ltd., hydroxyl value: 280 mgKOH/g); 0.4 parts of PBG-327 (Changzhou) as a polymerization initiator (D) Manufactured by Strong Electronic New Materials (Stock), N-Acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, oxime compound); as solvent (E) 78.9 parts of propylene glycol monomethyl ether acetate, 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; 0.01 part (in terms of solid content) as leveling agent (F) Toray silicone (SH8400) (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil). In addition, the hydroxyl value of the mixture of the polymerizable compound (C) was 86 mgKOH/g.

[Comparative Example 3] [Preparation of Colored Curable Resin Composition 3] The colorant dispersion liquid 1, the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the composition shown below, and the colored curable resin composition 3 was obtained. The colored curable resin composition 3 is a colored curable resin composition containing the following components: 2.7 parts of a compound represented by the formula (A-I-1) as a colorant (A); 2.0 parts (in solid content) as a dispersant. conversion) BYKLPN-6919 (manufactured by BYK-Chemie); 7.7 parts (in terms of solid content) of resin B1 as resin (B); 5.2 parts of polymerizable compound (C) KAYARAD (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate, hydroxyl value: 10 mgKOH/g); 0.4 parts of PBG- as a polymerization initiator (D) 327 (manufactured by Changzhou Qiangli Electronic New Materials (stock), N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, oxime compound) ; 78.6 parts of propylene glycol monomethyl ether acetate as solvent (E), 3.4 parts of 4-hydroxy-4-methyl-2-pentanone; 0.01 part of leveling agent (F) (in terms of solid content Toray silicone SH8400) (Toray Dow Corning (Toray Dow Corning) Co., Ltd., polyether-modified silicone oil).

[Example 1] [Preparation of Colored Curable Resin Composition 4] Colorant dispersion 1, a compound represented by formula (1-32), a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent are mixed so as to have the composition shown below to obtain coloring Curable resin composition 4. The colored curable resin composition 4 is a colored curable resin composition containing 2.5 parts of the compound represented by the formula (A-I-1) as the colorant (A), and 0.2 parts of the compound represented by the formula (1-32) The compound represented; 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK-Chemie) as a dispersant; 7.8 parts (in terms of solid content) of resin (B) Resin B1; 5.2 parts of A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hydroxyl value: 110 mgKOH/g) as a polymerizable compound (C); 0.4 parts as a polymerization initiator (D) Parts of PBG-327 (manufactured by Changzhou Qiangli Electronic New Materials (stock), N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine , oxime compound); as solvent (E) 78.9 parts of propylene glycol monomethyl ether acetate, 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; as leveling agent (F) 0.01 part ( Toray silicone SH8400) (Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[Example 2] [Preparation of Colored Curable Resin Composition 5] Colorant dispersion 1, a compound represented by formula (1-32), a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent are mixed so as to have the composition shown below to obtain coloring Curable resin composition 5. The colored curable resin composition 5 is a colored curable resin composition containing 2.5 parts of the compound represented by the formula (A-I-1) as the colorant (A), and 0.2 parts of the compound represented by the formula (1-32) The compound represented; 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK-Chemie) as a dispersant; 7.8 parts (in terms of solid content) of resin (B) Resin B1; 5.2 parts of Aronix (registered trademark) M-933 (manufactured by Toagosei Co., Ltd., hydroxyl value: 280 mgKOH/g) as a polymerizable compound (C); as a polymerization initiator ( D) 0.4 parts of PBG-327 (manufactured by Changzhou Qiangli Electronic New Material (stock), N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one- 2-imine, oxime compound); as solvent (E) 78.9 parts of propylene glycol monomethyl ether acetate, 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; as leveling agent (F) 0.01 part (in terms of solid content) of Toray silicone SH8400) (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[Example 3] [Preparation of Colored Curable Resin Composition 6] Colorant dispersion 1, a compound represented by formula (1-32), a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent are mixed so as to have the composition shown below to obtain coloring Curable resin composition 6. The colored curable resin composition 6 is a colored curable resin composition containing 2.5 parts of the compound represented by the formula (A-I-1) as the colorant (A), and 0.2 parts of the compound represented by the formula (1-32) The compound represented; 1.9 parts (in terms of solid content) of BYKLPN-6919 (manufactured by BYK-Chemie) as a dispersant; 7.8 parts (in terms of solid content) of resin (B) Resin B1; 2.5 parts of A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hydroxyl value: 110 mgKOH/g) as a polymerizable compound (C), 2.8 parts of Aronix ( Registered trademark) M-933 (manufactured by Donga Gosei Co., Ltd., hydroxyl value: 280 mgKOH/g); 0.4 part of PBG-327 as a polymerization initiator (D) (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd., N -Acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, oxime compound); 78.9 parts of propylene glycol monomethyl as solvent (E) Ether acetate, 3.1 parts of 4-hydroxy-4-methyl-2-pentanone; 0.01 part (in terms of solid content) of Toray silicone SH8400 as leveling agent (F) (Manufactured by Toray Dow Corning (stock), polyether-modified silicone oil). In addition, the hydroxyl value of the mixture of the polymerizable compound (C) was 200 mgKOH/g.

[Example 4] [Preparation of Colored Curable Resin Composition 7] The colorant dispersion liquid 1, the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the composition shown below, and the colored curable resin composition 7 was obtained. The colored curable resin composition 7 is a colored curable resin composition containing the following components: 2.7 parts of a compound represented by the formula (A-I-1) as a colorant (A); 2.0 parts (as a solid content) as a dispersant. conversion) BYKLPN-6919 (manufactured by BYK-Chemie); 7.7 parts (in terms of solid content) of resin B1 as resin (B); 5.2 parts of polymerizable compound (C) Aronix (registered trademark) M-933 (manufactured by Donga Synthetic Co., Ltd., hydroxyl value: 280 mgKOH/g); 0.4 parts of PBG-327 (Changzhou Qiangli Electronics New Co., Ltd.) as a polymerization initiator (D) Material (stock) manufacture, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, oxime compound); as solvent (E) 78.6 parts of propylene glycol monomethyl ether acetate, 3.4 parts of 4-hydroxy-4-methyl-2-pentanone; 0.01 part (in terms of solid content) of Toray Silicon as a leveling agent (F) Ketone (Toray silicone) SH8400) (manufactured by Toray Dow Corning Co., Ltd., polyether-modified silicone oil).

[Measurement of hydroxyl value of polymerizable compound] According to Japanese Industrial Standards (JIS) K 0070-1992, add an acetylation reagent to the sample, heat it in a glycerol bath, leave it to cool, add phenolphthalein solution as an indicator, use potassium hydroxide ethanol solution Perform titration to determine. The measurement results were as described above.

[Preparation of colored coating film (color filter)] On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the film thickness after baking was 2.5 μm. The colored curable resin composition 1 to the colored curable resin composition 7 were applied by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored composition layer. After standing to cool, the coloring composition layer was irradiated with light at an exposure amount of 80 mJ/cm ² (365 nm reference) in an atmospheric environment using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Then, post-baking was performed at 230 degreeC for 30 minutes in an oven, and the colored coating film was obtained.

[Measurement of film thickness change rate] The chromaticity and film thickness of the obtained colored coating film were measured, and the film thickness 1, the x value 1, and the Y value 1 when the y value met 0.092 were calculated. Then, this colored coating film was heated in an oven at 230 degreeC for 3 hours. The chromaticity and film thickness of the colored coating film after heating were measured, and the film thickness 2, x value 2, and Y value 2 when the y value met 0.092 were calculated, and the film thickness change rate was calculated based on the following formula. The results are shown in Table 10. Film thickness change rate = (film thickness 2/film thickness 1) × 100

In addition, the film thickness measurement apparatus (DEKTAK 3; Nippon Vacuum Technology Co., Ltd. product) was used for the film thickness measurement of the said colored coating film. The chromaticity is based on the spectral data measured by a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) and a characteristic function of the C light source, as the International Commission on Illumination (Commission Internationale de I'Eclairage, The xy chromaticity coordinates (x, y) and the stimulus value Y in the XYZ colorimetric system of CIE) are obtained. In addition, the color difference ΔE*ab was calculated by the method described in JIS Z 8730:2009 (7. Calculation method of color difference) based on the measured chromaticity values before and after heating. The results are shown in Table 10.

[Table 10] Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Example 3 Example 4 x value 2 0.143 0.143 0.139 0.143 0.143 0.143 0.139 y value 2 10.4 10.5 10.1 10.5 10.7 10.7 10.7 Film thickness change rate 111.9% 111.6% 114.4% 110.4% 108.7% 109.9% 110.6% ΔE*ab 8.6 8.4 9.6 7.9 6.5 7.2 7.2

From these results, although the colorable curable resin composition of the present invention tends to increase in film thickness by heating, the film thickness change rate is small. That is, it can be said that the phenomenon that the color fades due to heating can be suppressed, and the dark color can be maintained. In addition, the color change caused by heating is also small, and a high-brightness color filter can be obtained. [Industrial Availability]

According to the colored curable resin composition of the present invention, a dark cured film with a thin film thickness can be provided. The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used in display devices (eg, liquid crystal display devices, organic EL display devices, electronic paper, etc.) and solid-state imaging elements.

none

none

Claims (6)

A colored curable resin composition, comprising: a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) comprises formula (a) The compound represented by which the hydroxyl value of the polymerizable compound (C) is 100 mgKOH/g or more,

[In formula (a), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or a A substituted aralkyl group having 7 to 30 carbon atoms, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , When the carbon number of the saturated hydrocarbon group is 2-20, -CH ₂ - contained in the saturated hydrocarbon group may be substituted with -O- or -CO-; wherein, the carbon number of the saturated hydrocarbon group is 2-20. In the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-; R ⁴¹ and R ⁴² can be bonded and combined with the These bonded nitrogen atoms form a ring together, and R ⁴³ and R ⁴⁴ can be bonded to form a ring together with these bonded nitrogen atoms; R ⁴⁷ to R ⁵⁴ independently represent a hydrogen atom, a halogen atom, a nitro group, and a hydroxyl group. , -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, when the saturated hydrocarbon group has 2 to 20 carbon atoms, -CH ₂ - constituting the saturated hydrocarbon group may be substituted with -O- or -CO-, and R ⁴⁸ and R ⁵² may be bonded to each other to form -NH-, -S-, or -SO ₂ -; wherein, the In the above saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted with -O- at the same time, and the terminal -CH ₂ - will not be substituted with -O- or -CO-; Ring T ¹ represents a carbon number of 3-10 Aromatic heterocycles, which may include optionally substituted saturated hydrocarbon groups having 1 to 20 carbon atoms, substituted or unsubstituted amine groups, and optionally substituted aromatic groups having 6 to 20 carbon atoms Hydrocarbon group, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; the substituent that the aromatic hydrocarbon group may have can be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ; M ^r+ represents an r-valent metal ion; k represents the sum of the number of -SO ₃ ^- and the number of -SO ₂ -N ^- -SO ₂ -R ^f in the compound represented by the formula (a); r represents an integer of 1 or more; R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms; wherein the compound represented by the formula (a) has at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f ]. The colored curable resin composition according to claim 1, wherein the polymerizable compound (C) has a hydroxyl value of 200 mgKOH/g or more. The colorable curable resin composition according to claim 1 or claim 2, wherein the colorant (A) further contains a xanthene dye. The colored curable resin composition according to claim 3, wherein the xanthene dye is a compound represented by formula (1),

[In formula (1), R ¹ to R ⁴ independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or R ¹ and R ² and R ³ and R ⁴ are formed together, respectively A ring containing a nitrogen atom; the hydrogen atom contained in the aromatic hydrocarbon group may be passed through a halogen atom, -OH, -OR ⁸ , -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ substituted; R ⁵ represents -OH, -SO ₃ ^- , -SO ₃ H, -SO ₃ ^- M ⁺ , -CO ₂ H, -CO ₂ ^- M ⁺ , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ⁵ They may be the same or different from each other; R ⁶ and R ⁷ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; M ⁺ represents ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and X represents a halogen atom ; a represents 0 or 1; R ⁸ represents a monovalent saturated hydrocarbon group with a carbon number of 1-20, and the hydrogen atom contained in the saturated hydrocarbon group can be replaced by an aromatic hydrocarbon group with a carbon number of 6-10, a carboxyl group, or a halogen atom, The -CH ₂ - contained in the saturated hydrocarbon group can be substituted by -S-, -O-, -CO- or -NR ¹¹ -; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted at the same time. Substituted with -O-; R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When there are more than one R ¹¹ , all or part of these may be The same; R ⁹ and R ¹⁰ independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and the saturated hydrocarbon group in the saturated hydrocarbon group The contained -CH ₂ - can be substituted by -S-, -O-, -CO-, -NH- or -NR ⁸ -; wherein, in the saturated hydrocarbon group, the adjacent -CH ₂ - will not be substituted at the same time is -O-; R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom]. A color filter formed of the coloring curable resin composition according to any one of Claims 1 to 4. A display device comprising the color filter as claimed in claim 5.