TW202140684A - Colored curable resin composition comprising a colorant, a dispersant, a resin, a polymerizable compound, a polymerization initiator, and a solvent - Google Patents

Abstract

The subject of the present invention is to provide a colored curable resin composition capable of preventing fading of the cured product (which can reduce [Delta]E*ab). The present invention relates to a colored curable resin composition comprising a colorant, a dispersant, a resin, a polymerizable compound, a polymerization initiator, and a solvent. The colorant contains a squaraine onium dye having maximum absorption in the visible light region, and the dispersant has an amine value exceeding 0 mgKOH/g and being 30 mgKOH/g or less.

Description

Coloring curable resin composition

The present invention relates to a method for manufacturing a colored curable resin composition, a color filter, a liquid crystal display device, and a colored curable resin composition.

Used in display devices such as liquid crystal display devices, electroluminescence display devices, plasma displays, and solid-state imaging devices such as CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor) sensors The color filter is made of colored hardening resin composition. As a coloring agent used in such a coloring and curable resin composition, a squarylium dye is known (Patent Document 1, etc.). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-163233

[The problem to be solved by the invention]

However, in the case of the above colored curable resin composition containing a squarylium dye, it is necessary to prevent fading (decrease ΔE*ab) after baking after the film forming step. Therefore, the subject of the present invention is to provide a colored curable resin composition that can prevent fading of the cured product (can reduce ΔE*ab). In addition, there is also the problem of providing, in a preferred aspect of the present invention, a colored curable resin composition that can improve one or both of the absorbance retention and contrast of the cured product in addition to preventing color fading. [Technical means to solve the problem]

[式(AI)中， R¹ ～R⁴ 分別獨立地表示氫原子、鹵素原子、羥基、或可具有取代基之碳數1～20之1價飽和烴基；構成該1價飽和烴基之亞甲基可被取代為-O-或-S-； R⁵ ～R⁸ 分別獨立地表示氫原子或羥基； Ar¹ 及Ar² 分別獨立地表示式(i)所表示之基； [化2]

[式(i)中， R¹² 表示可具有羥基或羧基之碳數1～20之1價飽和烴基或者羥基或羧基，m表示0～5之整數；構成該1價飽和烴基之亞甲基可被取代為-O-或-S-；m為2以上時，複數個R¹² 各自可相同亦可不同；*表示與氮原子之鍵結鍵] R⁹ 及R¹⁰ 分別獨立地表示可具有取代基之碳數1～20之1價飽和烴基或者式(i)所表示之基；構成該1價飽和烴基之亞甲基可被取代為-O-或-S-]。 [3]如[1]或[2]記載之著色硬化性樹脂組合物，其中上述方酸鎓染料為式(AII)所表示之化合物。 [化3]

[式(AII)中， R¹ ～R⁴ 分別獨立地表示氫原子、鹵素原子、羥基、或可具有取代基之碳數1～20之1價飽和烴基；構成該1價飽和烴基之亞甲基可被取代為-O-或-S-； R⁵ ～R⁸ 分別獨立地表示氫原子或羥基； Ar¹ 及Ar² 分別獨立地表示式(i)所表示之基； [化4]

[式(i)中， R¹² 表示可具有羥基或羧基之碳數1～20之1價飽和烴基或者羥基或羧基，m表示0～5之整數；構成該1價飽和烴基之亞甲基可被取代為-O-或-S-；m為2以上時，複數個R¹² 各自可相同亦可不同；*表示與氮原子之鍵結鍵] R¹³ 及R¹⁴ 分別獨立地表示具有羥基或羧基之碳數1～20之1價飽和烴基，構成該1價飽和烴基之亞甲基可被取代為-O-或-S-]。 [4]如[1]至[3]中任一項記載之著色硬化性樹脂組合物，其中上述分散劑具有三級胺基或含氮雜環之鹼性官能基。 [5]如[1]至[4]中任一項記載之著色硬化性樹脂組合物，其中上述分散劑之含量相對於上述著色劑100質量份為0.1質量份以上50質量份以下。 [6]如[1]至[5]中任一項記載之著色硬化性樹脂組合物，其包含將上述著色劑藉由上述分散劑分散於溶劑中而成之分散液。 [7]一種彩色濾光片，其係由如[1]至[6]中任一項記載之著色硬化性樹脂組合物形成。 [8]一種液晶顯示裝置，其包含如[7]記載之彩色濾光片。 [9]一種著色硬化性樹脂組合物之製造方法，其包括：獲得將著色劑藉由分散劑分散於溶劑中而成之分散液之步驟；及 於上述分散液中添加樹脂、聚合性化合物、及聚合起始劑之步驟；且 上述著色劑包含於可見光區域具有極大吸收之方酸鎓染料， 上述分散劑之胺值超過0 mgKOH/g且為30 mgKOH/g以下。 [發明之效果]That is, the gist of the present invention is as follows. [1] A coloring and curable resin composition comprising: a colorant, a dispersant, a resin, a polymerizable compound, a polymerization initiator, and a solvent, the colorant includes a squarylium dye having a maximum absorption in the visible light region, the above The amine value of the dispersant exceeds 0 mgKOH/g and is less than 30 mgKOH/g. [2] The colored curable resin composition as described in [1], wherein the above-mentioned squarylium dye is a compound represented by formula (AI); [化1]

[In formula (AI), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms; methylene constituting the monovalent saturated hydrocarbon group The group may be substituted with -O- or -S-; R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxyl group; Ar ¹ and Ar ² each independently represent a group represented by formula (i); [化2]

[In formula (i), R ¹² represents a monovalent saturated hydrocarbon group with 1 to 20 carbons or a hydroxyl group or a carboxyl group that may have a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5; the methylene group constituting the monovalent saturated hydrocarbon group may It is substituted with -O- or -S-; when m is 2 or more, each of the plural R ¹² may be the same or different; * indicates the bond with the nitrogen atom] R ⁹ and R ¹⁰ each independently indicate that they may have substitution The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or the group represented by formula (i); the methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-]. [3] The coloring and curable resin composition according to [1] or [2], wherein the squarylium dye is a compound represented by formula (AII). [化3]

[In formula (AII), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms; methylene constituting the monovalent saturated hydrocarbon group The group may be substituted with -O- or -S-; R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxyl group; Ar ¹ and Ar ² each independently represent a group represented by formula (i); [化4]

[In formula (i), R ¹² represents a monovalent saturated hydrocarbon group with 1 to 20 carbons or a hydroxyl group or a carboxyl group that may have a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5; the methylene group constituting the monovalent saturated hydrocarbon group may Is substituted with -O- or -S-; when m is 2 or more, each of the plural R ¹² may be the same or different; * represents the bond with the nitrogen atom] R ¹³ and R ¹⁴ each independently represent a hydroxyl group or The carboxyl group has a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-]. [4] The colored curable resin composition according to any one of [1] to [3], wherein the dispersant has a tertiary amine group or a basic functional group of a nitrogen-containing heterocyclic ring. [5] The colored curable resin composition according to any one of [1] to [4], wherein the content of the dispersant is 0.1 parts by mass to 50 parts by mass relative to 100 parts by mass of the colorant. [6] The colored curable resin composition according to any one of [1] to [5], which comprises a dispersion liquid in which the colorant is dispersed in a solvent with the dispersant. [7] A color filter formed of the coloring curable resin composition as described in any one of [1] to [6]. [8] A liquid crystal display device comprising the color filter as described in [7]. [9] A method for producing a colored curable resin composition, comprising: obtaining a dispersion liquid in which a colorant is dispersed in a solvent by a dispersant; and adding a resin, a polymerizable compound, and the like to the dispersion liquid. And the steps of a polymerization initiator; and the colorant includes a squarylium dye with great absorption in the visible light region, and the amine value of the dispersant exceeds 0 mgKOH/g and is less than 30 mgKOH/g. [Effects of the invention]

According to the present invention, it is possible to provide a colored curable resin composition which can prevent the fading of the cured product. In addition, according to a preferred aspect of the present invention, it is also possible to provide a colored curable resin composition in which one or both of the absorbance retention rate and the contrast of the cured product are improved in addition to the prevention of fading.

<Colored curable resin composition> The colored curable resin composition of the present invention includes a colorant (hereinafter sometimes referred to as colorant (A)), a dispersant (hereinafter sometimes referred to as dispersant (P)), and resin (hereinafter sometimes referred to as resin ( B)), polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)), polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)), and solvent (hereinafter sometimes referred to as solvent ( E)), the colorant (A) contains a squarylium dye with great absorption in the visible light region, and the amine value of the dispersant (P) exceeds 0 mgKOH/g and is less than 30 mgKOH/g. In addition, in this specification, unless otherwise specified, the compound exemplified as each component can be used alone or in combination of plural kinds.

＜Colorant (A)＞ The colorant (A) contains a squarylium dye which has a great absorption in the visible light region. The above-mentioned squarylium dye is preferably a compound having a maximum absorption at 380 nm or more (preferably 400 nm or more) and less than 700 nm (preferably 650 nm or less).

The above-mentioned squaraine dye is not particularly limited as long as it is a compound having a maximum absorption in the visible light region, and a known squaraine dye can be used, preferably a compound represented by formula (AI).

[化5]

[式(i)中， R¹² 表示可具有羥基或羧基之碳數1～20之1價飽和烴基或者羥基或羧基，m表示0～5之整數。構成該1價飽和烴基之亞甲基可被取代為-O-或-S-。m為2以上時，複數個R¹² 各自可相同亦可不同。*表示與氮原子之鍵結鍵] R⁹ 及R¹⁰ 分別獨立地表示可具有取代基之碳數1～20之1價飽和烴基或者式(i)所表示之基。構成該1價飽和烴基之亞甲基可被取代為-O-或-S-]。[In the formula (AI), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbons. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxyl group. Ar ¹ and Ar ² each independently represent the group represented by formula (i). [化6]

[In the formula (i), R ¹² represents a monovalent saturated hydrocarbon group with 1 to 20 carbons or a hydroxyl group or a carboxyl group which may have a hydroxyl group or a carboxyl group, and m represents an integer of 0-5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When m is 2 or more, each of a plurality of R ¹² may be the same or different. *Represents a bond to a nitrogen atom] R ⁹ and R ¹⁰ each independently represent a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms or a group represented by formula (i) which may have a substituent. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-].

The halogen atom represented by R ¹ to R ⁴ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbons represented by R ¹ to R ⁴ , R ⁹ , R ¹⁰ and R ¹² include methyl, ethyl, propyl, butyl, pentyl, and hexyl. , Heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl and other linear alkyl groups with 1 to 20 carbons; isopropyl, isobutyl, second Butyl, tertiary butyl, isopentyl, neopentyl and 2-ethylhexyl and other branched chain alkyl groups with 3 to 20 carbons; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo Alicyclic saturated hydrocarbon groups with 3-20 carbons such as octyl, tricyclodecyl and adamantyl.

Examples of substituents of these saturated hydrocarbon groups include halogen atoms such as fluorine atom, chlorine atom, and iodine atom; hydroxyl group; carboxyl group; -NR ^a R ^b (R ^a and R ^b are each independently a hydrogen atom or a carbon number of 1 to 20 alkyl); nitro; alkoxycarbonyl having 1 to 10 carbons such as methoxycarbonyl, ethoxycarbonyl, etc. As the substituted monovalent saturated hydrocarbon group having 1 to 20 carbons, for example, Take the basis represented by the following formula. In the following formula, * represents a bonding bond.

[化7]

As a group in which the methylene group constituting these saturated hydrocarbon groups is substituted with -O- or -S-, for example, a group represented by the following formula may be mentioned. In the following formula, * represents a bonding bond.

[化8]

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 12} may also be a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms. Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms in ^{R 12 include, for example,} Examples include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl.

R ¹ to R ^{4 are} preferably a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a hydroxyl group or a methyl group, and still more preferably a hydrogen atom.

As R ⁵ to R ^{8 , at least one of R 5} and R ⁶ is preferably a hydroxyl group, more preferably at least one of R 5 and R 6 is a hydroxyl group, at least one of R ⁷ and R ⁸ is a hydroxyl group, and more preferably R ⁵ and R ^{Any one of 6} is a hydroxyl group, ^{and any one of R 7} and R ⁸ is a hydroxyl group.

As R ⁹ and R ¹⁰ , a linear alkyl group having 1 to 20 carbons which may have a substituent, and a branched alkyl group having 3 to 20 carbons which may have a substituent are preferable, and it is more preferable that it has The substituent is a linear alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 3 to 10 carbon atoms that may have a substituent, and more preferably a linear chain having 1 to 5 carbon atoms with a hydroxyl group at the end Alkyl groups, linear alkyl groups having 1 to 5 carbon atoms with a carboxyl group at the end, and branched alkyl groups having 3 to 10 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms having a hydroxyl group at the end A straight-chain alkyl group having 1 to 5 carbon atoms with a carboxyl group at the end.

R ^{12 is} preferably a monovalent saturated hydrocarbon group having 1 to 10 carbons which may have a hydroxyl group or a carboxyl group, more preferably a linear alkyl group having 1 to 5 carbons which may have a hydroxyl group or a carboxyl group, and more preferably a carbon number A linear alkyl group of 1 to 5, or a linear alkyl group of 1 to 5 carbons having a hydroxyl group or a carboxyl group.

m is preferably 1 to 5, more preferably 1 to 3, and still more preferably 2 or 3.

Ar ¹ and Ar ^{2 are} preferably groups represented by formula (ii).

[化9]

[In the formula (ii), R ¹⁵ represents a monovalent saturated hydrocarbon group having 1-20 carbon atoms or a hydroxyl group or a carboxyl group having a hydroxyl group or a carboxyl group, and p represents an integer of 0-5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When p is 2 or more, each of a plurality of R ¹⁵ may be the same or different. R ¹⁶ represents an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbons or an optionally substituted monovalent unsaturated hydrocarbon group with 2 to 20 carbons, and q represents an integer of 0 to 5. Here, p+q represents an integer of 0-5. The methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-. When q is 2 or more, each of a plurality of R ¹⁶ may be the same or different. *Represents the bond with the nitrogen atom]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbons represented by R ¹⁵ include those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbons described above. Among them, a linear alkyl group having 1 to 20 carbon atoms is preferred, a linear alkyl group having 1 to 10 carbon atoms is more preferred, and a linear alkyl group having 1 to 5 carbon atoms is more preferred.

The hydroxyl or carboxyl group of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the end of the molecular chain of the saturated hydrocarbon group.

As a C1-C20 monovalent saturated hydrocarbon group which has a hydroxyl group or a carboxyl group, the group represented by the following formula is mentioned, for example. In the following formula, * represents a bonding bond. [化10]

R ^{15 is} preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms and having a hydroxyl group. Furthermore, it is preferable that at least one of the methylene groups constituting the monovalent saturated hydrocarbon group having 1 to 20 carbons represented by ^{R 15 is substituted with -O-.} As a group in which at least one of the methylene groups constituting the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 15 is substituted with -O-, for example, a group represented by the following formula may be mentioned.} In the following formula, * represents a bonding bond. [化11]

The monovalent saturated hydrocarbon group with 1 to 20 carbons and the monovalent unsaturated hydrocarbon group with 2 to 20 carbons that may have a substituent represented by ^{R 16 can be exemplified as described above.} The monovalent saturated hydrocarbon group with 1-20 carbon atoms which has a substituent, and the monovalent unsaturated hydrocarbon group with 2-20 carbon atoms which may have a substituent are exemplified. Examples of the substituent of the unsaturated hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom, and iodine atom; hydroxyl group; carboxyl group; -NR ^c R ^d (R ^c and R ^d are each independently a hydrogen atom or a carbon number 1-20 alkyl); nitro; methoxy, ethoxy and other alkoxy groups with 1 to 10 carbons; methoxycarbonyl, ethoxycarbonyl and other alkoxycarbonyl groups with 1 to 10 carbons; Wait. Among them, a monovalent saturated hydrocarbon group having 1 to 20 carbons which may have a substituent is preferable, a linear alkyl group having 1 to 5 carbons which may have a substituent is more preferable, and a carbon number of 1 to 3 is more preferable. The linear alkyl group is particularly preferably a methyl group.

p is preferably an integer of 0-3, more preferably an integer of 0-1, and still more preferably 1.

q is preferably an integer of 1-3, more preferably an integer of 1-2, and still more preferably 2.

More preferably, p is 0 or 1, and q is 2.

Ar ¹ and Ar ² may be the same or different, and are preferably the same.

Among the compounds represented by the formula (AI), the compound represented by the formula (AII) is more preferred. By making the above-mentioned squaraine dye into a compound represented by formula (AII), the reduction in the maximum absorption after post-baking can be further suppressed, and the fading change before and after post-baking can be further suppressed.

[化12]

[In formula (AII), R ¹ to R ⁸ , Ar ¹ and Ar ² are the same as described above. R ¹³ and R ¹⁴ each independently represent a monovalent saturated hydrocarbon group with 1 to 20 carbons having a hydroxyl group or a carboxyl group, and the methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbons represented by R ¹³ and R ¹⁴ include those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbons described above. Among them, a linear alkyl group having 1 to 20 carbon atoms is preferred, a linear alkyl group having 1 to 10 carbon atoms is more preferred, and a linear alkyl group having 1 to 5 carbon atoms is more preferred.

The hydroxyl or carboxyl group of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably bonded to the end of the molecular chain of the saturated hydrocarbon group.

As a C1-C20 monovalent saturated hydrocarbon group which has a hydroxyl group or a carboxyl group, the group represented by the following formula is mentioned, for example. In the following formula, * represents a bonding bond. [化13]

^{Preferred aspects of R 1} to R ⁸ , Ar ¹ and Ar ² in formula (AII) are the same as the above.

The squarylium dye (preferably a compound represented by formula (AI), more preferably a compound represented by formula (AII)) preferably has one or more hydroxyl groups, more preferably has two or more hydroxyl groups, and more Preferably it has 2 or more hydroxyl groups and 2 or more carboxyl groups, and more preferably has 3 or more hydroxyl groups.

As the compound represented by the formula (AI), for example, the compounds represented by the formula (AI-1) to the formula (AI-60) shown in Tables 1 to 2 and the like can be exemplified. Among them, from the viewpoint of the availability of raw materials, Preferably, it is a compound represented by formula (AI-1)-formula (AI-20). The compound represented by formula (AI) is more preferably a compound represented by formula (AI-1) to formula (AI-5), and formula (AI-11) to formula (AI-20), More preferably, it is a compound represented by formula (AI-11) to formula (AI-20), More preferably, it is a compound represented by formula (AI-15) or formula (AI-16).

[Table 1]

[Table 2]

In Tables 1 to 2, x-1 to x-4 represent groups represented by the following formulas (* means a bonding bond). [化14]

In Tables 1 to 2, y-1 to y-5 represent groups represented by the following formulas (* means a bonding bond). [化15]

The compound represented by the formula (AI) can be produced, for example, by reacting the compound represented by the formula (pt3) with the compound represented by the formula (pt1) or the compound represented by the formula (pt2). In this reaction, the total usage amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is preferably 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt3).

[化16]

In the formula, R ¹ to R ¹⁰ , Ar ¹ and Ar ² each have the same meaning as above.

The reaction temperature is preferably 30°C to 180°C, more preferably 80°C to 140°C. The reaction time is preferably 1 hour to 12 hours, more preferably 3 hours to 8 hours.

In terms of yield, the reaction is preferably carried out in an organic solvent. Examples of organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitro hydrocarbons such as nitrobenzene Solvents; ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone, etc., which may be mixed and used. Among them, a mixed solvent of butanol and toluene is preferred. Regarding the amount of organic solvent used, it is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 30 parts by mass relative to the total of 1 part by mass of the compound represented by formula (pt1) and the compound represented by formula (pt2) Above 150 parts by mass or less.

The method for extracting the compound represented by formula (AI) as the target compound from the reaction mixture is not particularly limited, and various known methods can be used. For example, a method of distilling off the solvent from the reaction liquid to obtain the target product; or a method of cooling after the reaction is completed, and filtering the precipitated crystals. The filtered crystals are preferably washed with water or the like, and then dried. In addition, it can be further refined by well-known methods such as column chromatography or recrystallization as needed.

The content of the above-mentioned squarylium dye in the colorant (A) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, or It is 95% by mass or more, and may be 100% by mass.

In addition to the above-mentioned squaraine dye, the colorant (A) may also include a coloring agent different from the above-mentioned squaraine dye, and the coloring agent different from the above-mentioned squaraine dye may be a dye (hereinafter sometimes referred to as dye (A1) ) And pigment (hereinafter sometimes referred to as pigment (A2)). The coloring agent different from the above-mentioned squarylium dye may include one or both of the dye (A1) and the pigment (A2).

染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、次甲基偶氮染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。其中，較佳為有機溶劑可溶性染料。The dye (A1) is not particularly limited as long as it does not contain the above-mentioned squarylium dye. Well-known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. As the dye, for example, the dye index (published by The Society of Dyers and Colourists) belongs to a compound having a hue other than a pigment, or a known dye described in Dyeing Note. Also, according to the chemical structure, examples can be: azo dyes, cyanine dyes, triphenylmethane dyes, 𠮿

Dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, methine azo dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitrocellulose Base dyes, etc. Among them, organic solvent-soluble dyes are preferred.

Specifically, examples include: CI Solvent Yellow 4 (hereinafter the description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98 , 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. Solvent Dyes, CI 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; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 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 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45 , 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1 , 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236 , 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80 , 104, 105, 106, 109 and other CI acid dyes, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84 , 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153 , 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196 , 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246 , 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. C.I. Direct Dyes, C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse Blue 1, 14, 56, 60, etc. C.I. Disperse Dyes, C.I. Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I. Basic Green 1, etc. C.I. Basic Dyes, C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive Red 36, etc. C.I. Reactive Dyes, C.I. Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI medium red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 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. Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI medium purple 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI medium blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Medium Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. C.I. Vat Green 1, etc. C.I. Vat Dyes, etc. These dyes can be appropriately selected as long as they match the spectroscopic spectrum of the required color filter.

The pigment (A2) is not particularly limited, and well-known pigments can be used, for example, pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists). Examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125 , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 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 and other red pigments; C.I. Pigment Blue 15: 6, 60 and other blue pigments; C.I. Purple pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Pigment Green 7, 36, 58 and other green pigments; C.I. Pigment Brown 23, 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments.

The pigment can be treated with rosin, surface treatment with pigment derivatives introduced with acidic or alkaline groups, etc., grafting treatment of the surface of the pigment with polymer compounds, etc., and micronization by sulfuric acid micronization method, etc. Treatment, washing treatment with organic solvent or water to remove impurities, treatment to remove ionic impurities by ion exchange method, etc. The pigment preferably has a uniform particle size. By containing the pigment dispersant for dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include: cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants, acrylic It is a surface active agent such as a surface active agent. These pigment dispersants may be used alone or in combination of two or more kinds. As a pigment dispersant, it is represented by a trade name, and examples include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Lubrizol), EFKA (manufactured by CIBA) , Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), etc. The pigment dispersant may be contained in the colored curable resin composition as the same component as the following dispersant (P), or may be contained in the colored curable resin composition as a component different from the following dispersant (P). In the case of using a pigment dispersant, the amount used relative to the total amount of the pigment (A2) is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less. If the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

The content of the colorant (A) in the colored curable resin composition relative to the total solid content is preferably 0.1% by mass to 70% by mass, more preferably 0.5% by mass to 60% by mass, and more Preferably, it is 1 mass% or more and 50 mass% or less. If the content of the colorant (A) is within the above range, the color density when the color filter is made is sufficient, and the required amount of resin (B) or polymerizable compound (C) can be contained in the composition, so It can form patterns with sufficient mechanical strength.

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

＜Dispersant (P)＞ The dispersant (P) is not particularly limited, as long as it is used to disperse the colorant, it has more than 0 mgKOH/g and 30 mgKOH/g or less, preferably 0.5 mgKOH/g or more and 25 mgKOH/g or less, more preferably The amine value is 1 mgKOH/g or more and 15 mgKOH/g or less, more preferably 10 mgKOH/g or less. In the present invention, when a dispersant having an amine value of 0 is mixed or dispersed to prepare a colored curable resin composition, there are cases where foreign matter is formed in the coating film using the colored curable resin composition, and a suitable coating film cannot be produced. situation. Furthermore, in the present invention, when a dispersant having an amine value of more than 30 mgKOH/g is mixed or dispersed to prepare a colored curable resin composition, the heat resistance of the coating film using the colored curable resin composition may be insufficient situation. Here, "coloring and curable resin composition prepared by mixing or dispersing a dispersant" refers to a dispersion prepared by mixing or dispersing a dispersant in a colorant, a solvent, etc., and other components. Colored curable resin composition; or directly mixed dispersant and other components to form a colored curable resin composition.

As the dispersant (P), for example, a polymer dispersant may be mentioned. The above-mentioned dispersant (P) is a component different from the following resin (B), and may be different in amine value and/or acid value.

The polymer dispersant may, for example, be an acrylic dispersant or a urethane dispersant. As the above-mentioned acrylic dispersant, for example, an acrylic block copolymer can be exemplified. As the acrylic block copolymer, it is preferable to use a block copolymer that contains a basic group as a colorant adsorption group (also The coloring agent adsorption block (called a dye adsorption group) further includes a coloring agent adsorption block containing an acid group as a coloring agent adsorption group, and a block that does not contain a coloring agent adsorption group. As the above-mentioned coloring agent adsorption block containing a basic group as a colorant adsorption group and further containing an acid group as a colorant adsorption group, for example, by using a monomer having a basic group and It is composed of monomers with acidic groups.

As the above-mentioned monomers with basic groups, monomers with primary amino groups, secondary amino groups, tertiary amino groups or quaternary ammonium groups, Specifically, examples include: N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-dimethylacrylic acid Amine, diethylacrylamide, dimethylaminopropylmethacrylamide, acrylamide, vinylimidazole, 2-vinylpyridine, monomers with an amine group and a caprolactone skeleton, ( A reaction product of a monomer having a glycidyl group such as glycidyl methacrylate and a compound having a secondary amine group in the molecule, an isocyanate (meth)acrylic acid alkyl ester compound, and 4-(2) -Aminomethyl)-pyridine, 4-(2-aminoethyl)-pyridine, 4-(2-hydroxyethyl)pyridine, 1-(2-aminoethyl)-piperidine, 2-amine The reactant of 6-methoxybenzothiazole, 1-(2-hydroxyethylimidazole), N,N-diallyl melamine, N,N-dimethyl-1,3-propanediamine Wait.

The monomer having an acidic group is a monomer having a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Specifically, the monomer having a carboxyl group may, for example, be unsaturated acrylic acid, methacrylic acid, crotonic acid, etc. Monocarboxylic acid compounds, maleic acid, fumaric acid, methylene succinic acid and other unsaturated dicarboxylic acid compounds and their half esters, etc.; as a monomer having a sulfonic acid group, for example: 2 -Acrylamide-2-methyl-1-propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, styrene sulfonic acid, etc.; as a monomer with a phosphoric acid group, it can Examples: (meth)acrylate phosphonate, (meth)acrylate phosphonate, and the like.

Examples of the constituent components of the block not containing the colorant adsorption group include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene, methyl (meth)acrylate, and (methyl) Unsaturated carboxylic acid alkyl esters such as ethyl acrylate and butyl (meth)acrylate, unsaturated carboxylic acid aryl alkyl esters such as benzyl (meth)acrylate, monomers containing polycaprolactone, polyalkylene Based glycol monoester monomers, etc. The above-mentioned acrylic block copolymer can be obtained by living anionic polymerization or the like, and a previously known polymerization method can be used.

The amine value of the acrylic block copolymer exceeds 0 mgKOH/g and is 30 mgKOH/g or less, preferably 0.5 mgKOH/g or more and 15 mgKOH/g or less. Furthermore, the amine value refers to the amine value per 1 g of the solid content of the acrylic block copolymer, and uses a 0.1 mol/L hydrochloric acid aqueous solution by potentiometric titration (such as COMTITE (AUTO TITRATOR COM-900, BURET B-900, TITSTATIO NK-900), manufactured by Hiranuma Sangyo Co., Ltd.) are measured and converted to potassium hydroxide equivalent.

Examples of commercially available products of the aforementioned acrylic block copolymer include: "Disperbyk (registered trademark)-2000 (amine value 4 mgKOH/g)" manufactured by BYK-Chemie Japan, and "Disperbyk (registered trademark)-2001 (Amine value 29 mgKOH/g)", "Disperbyk (registered trademark)-2009 (Amine value 4 mgKOH/g)", "Disperbyk (registered trademark)-2050 (Amine value 30 mgKOH/g)", "Disperbyk (registered trademark) Trademark)-2070 (amine value 20 mgKOH/g)" etc.

As the above-mentioned urethane-based dispersant, it is possible to use the isocyanate group of the polyisocyanate compound, the compound with the number average molecular weight of 300 to 10,000 having one or more hydroxyl groups in the molecule, and the compound having the ability to interact with the isocyanate group in the molecule. The functional group of the reaction is the result of the reaction of a basic group-containing compound. As a method of obtaining such a urethane-based dispersant, the method described in Japanese Patent Laid-Open No. 60-166318, etc. can be used.

Examples of the polyisocyanate compound constituting the urethane-based dispersant include: isocyanate compounds having two or more isocyanate groups, for example: 2,4-toluene diisocyanate, 2,4-toluene Dimer of diisocyanate, 2,6-toluene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3 Aromatic diisocyanate compounds such as'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate) , Aliphatic or alicyclic polyisocyanates such as methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3-(isocyanomethylene) cyclohexane; based on the above-mentioned diisocyanates Polyisocyanate with isocyanurate group (polyisocyanate with isocyanurate group formed by trimerization of the above-mentioned diisocyanate, etc.), polyisocyanate obtained by reacting polyol and diisocyanate, by diisocyanate Polyisocyanate obtained by biuret reaction of isocyanate compound, etc. Among the above-mentioned polyisocyanate compounds, for example, toluene diisocyanate, isophorone diisocyanate, and other diisocyanate-based polyisocyanates having isocyanuric groups are preferred.

As a compound which has 1 or more hydroxyl groups in a molecule|numerator which comprises the said urethane-type dispersing agent, a polyether compound, a polyester compound, etc. are mentioned, for example. As the above-mentioned polyether compound, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and poly 1,4-butanediol; ethylene glycol, propylene glycol, 1, 2 -Propylene glycol, 1,4-butanediol, 1,5-pentanediol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, di-trimethylolpropane, di Modified ethylene oxide, modified propylene oxide, modified butylene oxide, modified tetrahydrofuran, etc. of alkylene glycols such as pentaerythritol, and low-molecular-weight monohydric alcohols such as methanol and ethanol.

As the above-mentioned polyester compound, for example, ethylene glycol, propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, hexanediol, neopentyl glycol, glycerin, tris Alkylene glycols such as methylolpropane, pentaerythritol, diglycerol, di-trimethylolpropane, dipentaerythritol, low-molecular-weight monohydric alcohols such as methanol and ethanol ε-caprolactone modified products, γ-butane Lactone modified product, δ-valerolactone modified product, methyl valerolactone modified product; adipic acid or dimer acid and other aliphatic dicarboxylic acids and neopentyl glycol or methyl pentane glycol Alcohol esters are aliphatic polyester polyols; terephthalic acid and other aromatic dicarboxylic acids and neopentyl glycols and other polyols are polyester polyols such as aromatic polyester polyols; polycarbonate polyols Alcohol, acrylic polyol, polytetramethylene hexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin) and other polyvalent hydroxyl compounds, and fumaric acid, phthalic acid, isophthalic acid, methylene butane Diacid, adipic acid, sebacic acid, maleic acid and other dicarboxylic acid esters; through the transesterification reaction of glycerol and other polyhydroxy-containing compounds with fatty acid esters, monoglycerides, etc. Hydroxyl compounds, etc. Among the above-mentioned compounds having one or more hydroxyl groups in the molecule, ε-caprolactone adducts of alcohols are preferred.

The number average molecular weight of the compound having one or more hydroxyl groups in the molecule is, for example, 300 to 10,000, preferably 300 to 6,000. Furthermore, the number average molecular weight can be determined by column chromatography.

The basic group-containing compound having a functional group capable of reacting with an isocyanate group in the molecule constituting the above-mentioned urethane-based dispersant is not particularly limited, and is preferably selected from the group having N,N-di At least one compound from the group consisting of polyols, polythiols and amines substituted with amine groups or heterocyclic nitrogen atoms. As these compounds, conventionally known compounds in the technical field of dispersants can be used. These compounds have Zerewitinoff active hydrogen atoms and at least one basic group containing nitrogen atoms. As such a compound, for example, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,4-butanediamine, 2-dimethylaminoethanol, 1-(2-Aminoethyl)-piperidin, 2-(1-pyrrolidinyl)-ethylamine, 4-amino-2-methoxypyrimidine, 4-(2-aminoethyl) -Pyridine, 1-(2-hydroxyethyl)-piperidine, 4-(2-hydroxyethyl)-pyridine, 2-mercaptopyrimidine, 2-mercaptobenzimidazole, 2-amino-6-methoxy Benzothiazole, N,N-diallyl-melamine, 3-amino-1,2,4-triazole, 1-(2-hydroxyethyl)-imidazole, 3-mercapto-1,2, 4-triazole and so on. Among them, amines having a heterocyclic nitrogen atom are preferred.

The reaction in the synthesis of the above-mentioned urethane-based dispersant is not particularly limited, and can be carried out by a conventionally known method. In addition, the amine value of the above-mentioned urethane-based dispersant also exceeds 0 mgKOH/g and is 30 mgKOH/g or less, preferably 0.5 mgKOH/g or more and 15 mgKOH/g or less.

In addition, as commercial products of the above-mentioned urethane-based dispersants, Disperbyk (registered trademark)-161 (amine value 11 mgKOH/g, manufactured by BYK-Chemie), Disperbyk (registered trademark)-162 ( Amine value 13 mgKOH/g, manufactured by BYK-Chemie), Disperbyk (registered trademark)-167 (amine value 13 mgKOH/g, manufactured by BYK-Chemie), Disperbyk (registered trademark)-182 (amine value 13 mgKOH/g) , BYK-Chemie company manufacturing), Disperbyk (registered trademark)-2163 (amine value 10 mgKOH/g, BYK-Chemie company manufacturing), Disperbyk (registered trademark)-2164 (amine value 14 mgKOH/g, BYK-Chemie company manufacturing )Wait.

Among them, the dispersant is preferably the above-mentioned acrylic dispersant, and the dispersant is preferably a basic functional group having a tertiary amine group or a nitrogen-containing heterocyclic ring (for example, pyridine, pyrimidine, pyridine, isocyanate), and more Preferably, it has a tertiary amine group.

The content of the dispersant relative to 100 parts by mass of the coloring agent is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 45 parts by mass or less, more preferably 2 parts by mass or more and 40 parts by mass or less, and It is more preferably 3 parts by mass or more and 35 parts by mass or less, particularly preferably 4 parts by mass or more and 30 parts by mass or less, and may also be 20 parts by mass or less or 10 parts by mass or less. The content of the dispersant in 100% by mass of the solid content of the colored curable resin composition is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass, and still more preferably 0.10 to 1% by mass.

In order to improve handling properties, the dispersant is preferably mixed with a solvent before mixing with other components (hereinafter also referred to as a dispersant-containing solution). In the solution containing the dispersant, the content of the dispersant in terms of solid content is, for example, 10-60% by mass, preferably 20-50% by mass. In the present invention, the smaller the amine value of the dispersant, the smaller the content of the dispersant, and the more the colorant is subjected to dispersion treatment, the more it can prevent fading and improve the absorbance retention and contrast. The colorant is contained in a dispersion obtained by dispersing a dispersant or a solution containing the dispersant in a solvent, and the dispersion can be used for coloring a curable resin composition.

＜Resin (B)＞ The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. As the resin (B), the following resins [K1] to [K6], etc. may be mentioned. Resin [K1]; has a structural unit derived from at least one (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and derived from A copolymer of the structural unit of monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure with carbon number 2 to 4 and an ethylenically unsaturated bond; Resin [K2]; has a structural unit derived from (a) and a structural unit derived from (b), and is derived from a monomer (c) that can be copolymerized with (a) (which is different from (a) and (b) ) (Hereinafter sometimes referred to as "(c)") a copolymer of structural units; Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c); Resin [K4]; a copolymer with the structural unit derived from (a) added (b) and the structural unit derived from (c); Resin [K5]; a copolymer having a structural unit derived from (a) added to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]; a copolymer having a structural unit derived from the addition of (a) to the structural unit derived from (b), and then a carboxylic anhydride, and a structural unit derived from (c).

As (a), specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho/meta/p-vinyl benzoic acid, etc.; Maleic acid, fumaric acid, methyl maleic acid, methyl fumaric acid, methylene succinic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid Dicarboxylic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene Unsaturated dicarboxylic acids such as dicarboxylic acids; Methyl-5-norbiene-2,3-dicarboxylic acid, 5-carboxyl bicyclic [2.2.1]hept-2-ene, 5,6-dicarboxyl bicyclic [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 -Methyl bicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethyl bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, methyl maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetra Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxyl bicyclic ring [2.2.1] hept-2 -Unsaturated dicarboxylic acid anhydrates such as olefin anhydrates; Unsaturation of succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, etc. Mono[(meth)acryloxyalkyl] esters; α-(Hydroxymeth)acrylic acid and other unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule. Among them, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred in terms of copolymerization reactivity or solubility of the obtained resin in an alkaline aqueous solution.

(b) Refers to, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically different structure. Polymeric compounds with saturated bonds. (b) Preferably, it is a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

As (b), for example, a monomer having an oxirane group and an ethylenically unsaturated bond (b1) (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenic Unsaturated bond monomer (b2) (hereinafter may be referred to as "(b2)"), monomer having a tetrahydrofuran group and ethylenically unsaturated bond (b3) (hereinafter may be 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 may be referred to as "(b1-1)") , Monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure where an alicyclic unsaturated hydrocarbon is epoxidized.

Examples of (b1-1) include: glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylethylene 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-vinyl benzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl) Styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl) Styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl) (Methyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc.

Examples of (b1-2) include: vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Co., Ltd.), (meth)acrylic acid 3,4-epoxycyclohexyl methyl ester (for example, Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), formula The compound represented by (I) and the compound represented by formula (II), etc.

[化17]

[In the formula (I) and Formula (II), R ^a and R ^b represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group of which may be substituted with 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 having 1 to 6 carbon atoms. *Indicates the bond with O]

As the alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a tertiary butyl group may be mentioned. Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxy group include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. As R ^a and R ^b , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group can be exemplified, and more preferably, a hydrogen atom and a methyl group can be exemplified.

Examples of the alkanediyl group include: methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1, 5-diyl, hexane-1,6-diyl, etc. As X ^a and X ^b , there can be preferably exemplified: single bond, methylene, ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more preferably: Single bond, *-CH ₂ CH ₂ -O- (* represents the bond with O).

As the compound represented by formula (I), a compound represented by any one of formula (I-1) to formula (I-15), etc. may be mentioned. Among them, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I 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).

[化18]

[化19]

As the compound represented by formula (II), a compound represented by any one of formula (II-1) to formula (II-15), etc. may be 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).

[化20]

[化21]

The compound represented by the formula (I) and the compound represented by the formula (II) may each be used alone, 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 in combination, the content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is in moles The benchmark is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), a monomer containing an oxetanyl group and a (meth)acryloxy group is more preferable. As (b2), 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3 -Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-methacrylic acid Oxyethyl oxetane, 3-methyl-3-propenyl oxyethyl oxetane, 3-ethyl-3-methacryloyl oxyethyl oxetane, 3-Ethyl-3-propenyloxyethyloxetane and the like.

As (b3), a monomer having a tetrahydrofuran group and a (meth)acryloxy group is more preferable. As (b3), specifically, tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc. are mentioned.

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

(C) may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, first (meth)acrylate Tributyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, {tricyclo[5.2.1.0 ^2,6 ]decane-8-yl}(meth)acrylate ( In this technical field, the usual name is "dicyclopentyl (meth)acrylate". Also, sometimes called "tricyclodecyl (meth)acrylate"), (meth)acrylic acid {tricyclic [5.2 .1.0 ^2,6 ] decene-8-yl) ester (in the technical field, the usual name is "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate , Isoprimary (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, (meth) (Meth) acrylates such as naphthyl acrylate and benzyl (meth)acrylate; (meth)acrylic acid containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate Esters; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl methylene succinate; bicyclo[2.2.1]hept-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-ene, 5-hydroxymethyl bicyclic [2.2.1]hept-2-ene, 5-(2'-hydroxyethyl) bicyclic [2.2.1]hept-2-ene, 5-methoxy bicyclic [2.2 .1]Hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6- Bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di Methoxy bicyclic [2.2.1]hept-2-ene, 5,6-diethoxy bicyclic [2.2.1]hept-2-ene, 5-hydroxy-5-methyl bicyclic [2.2. 1]Hept-2-ene, 5-hydroxy-5-ethyl bicyclic [2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl bicyclic [2.2.1] hept-2- Ene, 5-tertiary butoxycarbonyl bicyclic [2.2.1] hept-2-ene, 5-cyclohexoxycarbonyl bicyclic [2.2.1] hept-2-ene, 5-phenoxycarbonyl bicyclic Cyclo[2.2.1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl) bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexoxycarbonyl) Bicyclic [2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide Endi N-succinimide, N-butanediimidate-3-maleimide benzoate, N-butanediimidate-4-maleimide butyrate, N -Succinylidene-6-maleimide caproate, N-butanediimidate-3-maleimide propionate, N-(9-acridine) Yl) maleimide and other dicarbonylimines derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxybenzene Ethylene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-di Methyl-1,3-butadiene, etc. Among them, in terms of copolymerization reactivity and heat resistance, 2-hydroxyethyl (meth)acrylate, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo[2.2.1]hept-2-ene, etc.

In the resin [K1], among all the structural units constituting the resin [K1], the ratio of the structural units derived from each is preferably Structural unit derived from (a): 2～60 mol% The structural unit derived from (b): 40～98 mol%; Better The structural unit derived from (a): 10-50 mol% Structural unit derived from (b): 50-90 mol%. If the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the obtained color filter are excellent tendency.

Resin [K1] can be referred to, for example, in the document "Experimental Method for Polymer Synthesis" (Otsu Takayuki (author), publishing house: Kazujin Co., Ltd., first edition, first printing, issued on March 1, 1972) The method and the citations recorded in the document are manufactured.

Specifically, the following method can be exemplified: adding specific amounts of (a) and (b), polymerization initiator, solvent, etc., to the reaction vessel, for example, replacing oxygen with nitrogen to form a deoxidizing atmosphere, and heating while stirring And insulation. Furthermore, the polymerization initiator, solvent, etc. used here are not particularly limited, and ordinary users in the field can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic The oxide (benzyl peroxide, etc.), as the solvent, may be one that dissolves each monomer, and examples thereof include the solvents described below as the solvent (E) of the colored curable resin composition of the present invention. .

Furthermore, as for the obtained copolymer, the solution after the reaction can be used directly, the solution after concentration or dilution can also be used, and the solid (powder) form extracted by methods such as reprecipitation can also be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during the polymerization, the reacted solution can be directly used to prepare the colored curable resin composition of the present invention. Therefore, the present invention can be simplified. The manufacturing steps of the colored curable resin composition of the invention.

In the resin [K2], among all the structural units constituting the resin [K2], the ratio of the structural units derived from each is preferably Structural unit derived from (a): 2～45 mol% Structural unit derived from (b): 2～95 mol% The structural unit derived from (c): 1～65 mol%; Better Structural unit derived from (a): 5～40 mol% Structural unit derived from (b): 5～80mol% Structural unit derived from (c): 5-60 mol%. If 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 when forming a colored pattern, and the solvent resistance and heat resistance of the color filter obtained Tendency to have excellent properties and mechanical strength.

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

In the resin [K3], among all the structural units constituting the resin [K3], the ratio of the structural units derived from each is preferably Structural unit derived from (a): 2～60 mol% The structural unit derived from (c): 40～98 mol%; Better The structural unit derived from (a): 10-50 mol% Structural unit derived from (c): 50-90 mol%. The resin [K3] can be manufactured in the same manner as the method described as the manufacturing method of the resin [K1], for example.

Resin [K4] can be manufactured by: obtaining a copolymer of (a) and (c), adding the carboxylic acid and/or carboxylic anhydride of (a) to the carbon number of (b) 2～ 4 cyclic ethers. 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 units derived from each is preferably the same ratio as exemplified in the resin [K3].

Then, 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 above-mentioned copolymer. Following the manufacture of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris(dimethylamine) (Methyl)phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) are put into the flask, and reacted at 60 to 130°C for 1 to 10 hours, for example, to produce resin [K4]. The amount of (b) used is preferably 5 to 80 mols, and more preferably 10 to 75 mols relative to (a) 100 mols. By setting it in this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern become good. tendency. In order for the cyclic ether to have high reactivity and not easily remain unreacted (b), as (b) for the resin [K4], (b1) is preferred, and (b1-1) is more preferred. Regarding the amount of the reaction catalyst used, it 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 addition method, reaction temperature, and time can be appropriately adjusted in consideration of manufacturing equipment or heat generation due to polymerization. In addition, as with the polymerization conditions, the method of addition or the reaction temperature can be appropriately adjusted in consideration of manufacturing equipment, heat generation due to 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 the method for producing the resin [K1] described above. Similar to the above, the obtained copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) form extracted by methods such as reprecipitation can also be used. Regarding the ratio of the structural units derived from (b) and (c), relative to the total number of moles of all the structural units constituting the above-mentioned copolymer, each is preferably Structural unit derived from (b): 5～95 mol% The structural unit derived from (c): 5～95 mol%; Better The structural unit derived from (b): 10～90mol% The structural unit derived from (c): 10-90 mol%.

Furthermore, under the same conditions as the production method of resin [K4], the carboxylic acid or carboxylic anhydride possessed by (a) and the copolymer of (b) and (c) possessed by the ring derived from (b) can be made The like ether reacts to obtain resin [K5]. The amount of (a) used to react with the above-mentioned copolymer is preferably 5 to 80 mol relative to (b) 100 mol. In order for the cyclic ether to have high reactivity and not easily remain unreacted (b), as (b) for the resin [K5], (b1) is preferred, and (b1-1) is more preferred.

Resin [K6] is a resin obtained by further reacting resin [K5] with carboxylic anhydride. The hydroxyl group produced by the reaction of the cyclic ether and the carboxylic acid or carboxylic acid anhydride is reacted with the carboxylic acid anhydride. Examples of carboxylic anhydrides include maleic anhydride, methyl maleic anhydride, methylene succinic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3 ,4,5,6-Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxyl ring [2.2.1] Hept-2-ene anhydride and so on. The usage amount of carboxylic anhydride is preferably 0.5-1 mol relative to the usage amount of (a) 1 mol.

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy tricyclic acrylate [5.2. 1.0 ^2.6 ] Resins such as decyl ester/(meth)acrylic acid copolymer [K1] etc.; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl ester/styrene/(meth)acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexyl maleic acid Imine copolymer, acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl ester/(meth)acrylic acid/N-cyclohexyl maleimide/(meth)acrylic acid 2- Hydroxyethyl copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer and other resins [K2]; (meth)acrylic acid Benzyl ester/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer and other resins [K3]; add (meth) to benzyl (meth)acrylate/(meth)acrylic acid copolymer A resin made of glycidyl acrylate, a resin made of (meth)acrylic acid tricyclodecyl ester/styrene/(meth)acrylic acid copolymer added with (meth)acrylic acid glycidyl ester, in (methyl) ) Resins such as tricyclodecyl acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer added with glycidyl (meth)acrylate [K4]; make (meth)acrylic acid three Cyclodecyl ester/glycidyl (meth)acrylate copolymer and (meth)acrylic acid are reacted to form a resin that makes tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate Copolymer and (meth)acrylic acid resin and other resins [K5]; make the copolymer of (meth)acrylic acid tricyclodecyl ester/(meth)acrylic acid glycidyl ester react with (meth)acrylic acid The resulting resin is further reacted with tetrahydrophthalic anhydride to obtain resins such as resins [K6], etc. Among them, as the resin (B), resin [K1] and resin [K2] are preferred, and resin [K1] is particularly preferred.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above range, the hardness of the color filter will increase, the residual film rate will be higher, the solubility of the unexposed part in the developer will be good, and the resolution of the colored pattern will tend to increase.

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

The acid value of the resin (B) is converted into solid content, and is preferably 10 to 170 mgKOH/g, more preferably 20 to 150 mgKOH/g, and still more preferably 30 to 135 mgKOH/g. 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 it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

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

＜Polymerizable compound (C)＞ The polymerizable compound (C) is a compound that can be polymerized by a living radical and/or acid generated from the polymerization initiator (D). For example, a compound having a polymerizable ethylenic unsaturated bond may be mentioned, preferably ( Meth)acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Esters, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol non(meth)acrylate Esters, tris(2-(meth)acryloxyethyl) isocyanurate, glycol modified pentaerythritol tetra(meth)acrylate, glycol modified dipentaerythritol hexa(meth)acrylate , Propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth)基)acrylate. Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

The content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 55% by mass relative to the total amount of solid components. When the content rate of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming the colored pattern and the chemical resistance of the color filter tend to improve.

＜Polymerization initiator (D)＞ The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acid, etc. by the action of light or heat, and known polymerization initiators can be used. As a polymerization initiator that generates living radicals, for example, O-amino oxime compounds, phenanone compounds, triphenyl compounds, phosphine oxide compounds, and biimidazole compounds can be exemplified.

As the above-mentioned O-acetoxime compound, for example, N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine Acetyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, etc. O-acetoxy oxime compound with diphenyl sulfide skeleton; N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl] Ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxane Pentylmethoxy) benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methyl Benzyl oxime)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and other O-acyloxime compounds with a carbazole skeleton; 1-[7-( 2-Methylbenzyl)-9,9-dipropyl-9H-phen-2-yl]ethanone O-acetoxime and other O-acetoxime compounds with a quinceline skeleton; etc. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), N-1919 (manufactured by ADEKA Corporation), and DFI-091 (manufactured by Daito Chemix Co., Ltd.) can also be used. Among them, the O-acetoxy oxime compound is preferably selected from N-benzyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-acetoxy -1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-{2- Methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzyl}-9H-carbazol-3-yl)ethane-1-imine And at least one of the group consisting of 1-[7-(2-methylbenzyl)-9,9-dipropyl-9H-茀-2-yl]ethanone O-acetoxime. In the case of these O-acetoxime compounds, there is a tendency to obtain high-brightness color filters.

As the above-mentioned alkylphenone compound, for example, 2-methyl-2-𠰌line-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1 -(4-𠰌olinyl)phenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ 4-(4-𠰌lineyl)phenyl]butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[ 4-(2-hydroxyethoxy)phenyl)propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane- 1-ketone oligomers, α,α-diethoxy acetophenone, benzyl dimethyl ketal, etc. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (manufactured by BASF Corporation above) can also be used.

As the above-mentioned tris compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris, 2,4-bis( Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6-sunflower-1,3,5- Tris, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6 -[2-(5-Methylfuran-2-yl)vinyl]-1,3,5-tris𠯤, 2,4-bis(trichloromethyl)-6-[2-(furan-2- Yl)vinyl]-1,3,5-tris, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl ]-1,3,5-Tris, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5- Three 𠯤 and so on.

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

As the above-mentioned 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 '-Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Special Kokai 62-174204 etc.), 4,4',5,5'-position phenyl group substituted with alkoxycarbonyl group biimidazole compound (for example, refer to Japanese Patent Laid-Open No. 7-10913 etc.).

As the polymerization initiator for generating acid, for example, 4-hydroxyphenyl dimethyl sulfonate p-toluenesulfonic acid, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetate p-toluenesulfonate Oxyphenyl dimethyl sulfonium, 4-acetoxyphenyl-methyl-benzyl sulfonium hexafluoroantimonate, triphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, p-toluenesulfonate Onium salts such as diphenyl iodonium acid, diphenyl iodonium hexafluoroantimonate, or nitrobenzyl tosylate, benzoin tosylate, etc.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like; benzophenone, methyl phthalate Ester, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl) two Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2 -Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc.

As the polymerization initiator (D), it is preferable to include at least one selected from the group consisting of O-oxime compounds, phenanone compounds, tris compounds, phosphine oxide compounds, and biimidazole compounds The polymerization initiator is more preferably a polymerization initiator containing an O-acetoxime compound.

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

＜Solvent (E)＞ The colored curable resin composition of the present invention contains a solvent (E). The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. For example, ester solvents (solvents that contain -COO- and no -O- in the molecule), ether solvents (solvents that contain -O- and no -COO- in the molecule), ether ester solvents (the molecule (Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule and no -COO-), alcohol solvents (containing OH in the molecule and no -O-, -CO -And -COO- solvent), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfide.

Examples of the ester solvent include: methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, Cyclohexanol acetate and γ-butyrolactone, etc.

The ether solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, two Ethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

As the ether ester solvent, for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropane Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, 2-methoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-ethoxypropionate, 2-methoxy-2-methylpropionate, 2 -Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetic acid Ester, 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, etc. .

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone (hereinafter sometimes referred to as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4 -Heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

Examples of alcohol solvents 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.

The amide solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above-mentioned solvents, in terms of coating properties and drying properties, an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm is preferred. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether are preferred. Glycol monoethyl ether, diacetone alcohol and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diacetone alcohol, ethyl lactate and 3-ethoxypropane The ethyl ester is more preferably propylene glycol monomethyl ether acetate or a combination of propylene glycol monomethyl ether acetate and diacetone alcohol.

When the solvent (E) contains propylene glycol monomethyl ether acetate, the content of propylene glycol monomethyl ether acetate in the total amount of the solvent (E) is preferably 40-100% by mass, more preferably 50- 90% by mass, and more preferably 60-80% by mass, the content of a solvent (preferably diacetone alcohol) different from propylene glycol monomethyl ether acetate in the total amount of solvent (E) is preferably 0 ~60% by mass, more preferably 10-50% by mass, and still more preferably 20-40% by mass.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass relative to the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid components of the colored curable resin composition is preferably 5-30% by mass, more preferably 8-25% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed, so the display characteristics tend to become good.

＜Leveling agent (F)＞ The colored curable resin composition of the present invention may further contain a leveling agent (F). The leveling agent (F) may, for example, be a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. It may have a polymerizable group in the side chain. As the polysiloxane-based surfactant, a surfactant containing a siloxane bond in the molecule, etc. may be mentioned. Specifically, examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

As the above-mentioned fluorine-based surfactant, a surfactant containing a fluorocarbon chain in the molecule, etc. may be mentioned. Specifically, examples include: 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 Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381 , Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), etc.

As the polysiloxane-based surfactant having a fluorine atom, for example, a surfactant containing a siloxane bond and a fluorocarbon chain in the molecule can be mentioned. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC Co., Ltd.), etc. can be mentioned.

The content of the leveling agent (F) relative to the total amount of the colored curable resin composition is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.2% by mass or less, and still more preferably 0.005 Mass% or more and 0.2 mass% or less. In addition, the content rate does not include the content rate of the above-mentioned dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be optimized.

＜Other ingredients＞ The colored curable resin composition of the present invention may contain additives known in the technical field such as polymerization initiation aids, fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like as needed.

<Manufacturing method of colored curable resin composition> The method for producing the colored curable resin composition of the present invention includes: obtaining a dispersion (also referred to as a colorant dispersion) in which a colorant (A) is dispersed in a solvent (E) through a dispersant (P) Step; and the step of adding resin (B), polymerizable compound (C), polymerization initiator (D) and optionally added leveling agent (F), and other components to the above-mentioned dispersion, and the above-mentioned coloring The agent contains a squarylium dye with great absorption in the visible light region, and the amine value of the above-mentioned dispersant exceeds 0 mgKOH/g and is less than 30 mgKOH/g. The colored curable resin composition can also be prepared by mixing all the components, but it is preferably mixed or dispersed in the colorant dispersion in advance, and more preferably includes: obtaining the colorant (A) by the dispersant (P ) The step of dispersing the dispersion in the solvent (E). If this dispersion liquid is used, more than one of the prevention of fading, the retention of absorbance, and the contrast can be improved compared to the case where the dispersion liquid is not used.

Method for manufacturing colorant dispersion The colorant (A) is dispersed in the solvent (E) with the dispersant (P), and the resin (B) is dispersed in the above-mentioned solvent (E) as necessary to produce a colorant dispersion . The dispersion treatment refers to mixing until the colorant (A), resin (B), etc. become a dispersed state of particles. By this dispersion treatment, the particles are pulverized into smaller particles. In addition, the dispersed state may mean that each particle is distributed in another component, and it is preferable that each particle is substantially uniformly distributed in another component.

The colorant dispersion liquid preferably contains a colorant (A), a dispersant (P), a resin (B), and a solvent (E). The content of the coloring agent (A) in the coloring agent dispersion of the present invention relative to the total amount of the coloring agent dispersion is preferably 2% by mass or more, more preferably 3% by mass or more, and preferably 30% by mass or less , More preferably 20% by mass or less.

In addition, the content of the solvent (E) relative to the total amount of the colorant dispersion is preferably 60% by mass or more, more preferably 75% by mass or more, and preferably 95% by mass or less, more preferably 93% by mass or less , The best is 91% by mass or less. When the colorant dispersion contains the resin (B), the content of the resin (B) relative to the total amount of the colorant dispersion is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 15% by mass or less, more preferably 7% by mass or less. If the content of the resin (B) is within the above range, the dispersion state of the colorant tends to become stable. The content of the dispersant (P) in the colorant dispersion relative to the total amount of the colorant dispersion is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 20% by mass or less, more preferably It is 10% by mass or less, and more preferably 7% by mass or less. If the content of the dispersant (P) is within the above range, the dispersion state of the colorant tends to become stable.

The temperature at the time of dispersing the colorant (A) in the solvent (E) and at the time of dispersing the mixture is preferably 120°C or lower, more preferably 70°C or lower. The lower limit of the temperature at the time of dispersion is not particularly limited, but it is usually 20°C. The dispersion time is preferably 0.5 hours or more, more preferably 2 hours or more, and preferably 48 hours or less, and more preferably 20 hours or less. As a device used for dispersion, for example, a roll mill, a high-speed stirring device, a bead mill, a ball mill, a sand mill, a paint conditioner, an ultrasonic dispersion machine, a high-pressure dispersion machine, etc. may be mentioned. The obtained coloring agent dispersion is preferably filtered through a filter with a pore size of about 1.0 to 5.0 μm.

＜Manufacturing method of color filter＞ As a method of producing a colored pattern from the colored curable resin composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. may be mentioned. Among them, the photolithography method is preferred. The photolithography method is a method of coating the colored curable resin composition on a substrate, drying to form a colored composition layer, and then exposing and developing the colored composition layer through a photomask. In the photolithography method, by not using a photomask during exposure and/or not performing development, a colored coating film as a cured product of the colored composition layer can be formed. The colored pattern or colored coating film thus formed is the color filter of the present invention. The thickness of the color filter produced is not particularly limited, and can be appropriately adjusted depending on the purpose or application. For example, it is 0.1-30 μm, preferably 0.1-20 μm, and more preferably 0.5-6 μm.

As the substrate, you can use: quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica, or polycarbonate, polymethylmethacrylate, polyterephthalate Resin board such as ethylene formate, silicon, formed by forming aluminum, silver, silver/copper/palladium alloy thin film, etc. on the above-mentioned substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates. In addition, a substrate obtained after HMDS treatment on a silicon substrate can also be used.

When the pixels of each color are formed by the photolithography method, it can be performed using known or customary devices or conditions. For example, it can be produced as follows. First, a colored curable resin composition is applied on a substrate, and then heated and dried (pre-baked) and/or dried under reduced pressure to remove volatile components such as a solvent and dry it to obtain a smooth colored composition layer. The coating method may, for example, be a spin coating method, a slit coating method, a slit-spin coating method, and the like. The temperature in the case of heating and drying is preferably 30 to 120°C, more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing reduced-pressure drying, it is preferable to perform reduced-pressure drying at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the target film thickness of the color filter.

Then, the colored composition layer is exposed to light to form a colored coating film. In addition, when the colored pattern is formed, the colored composition layer is exposed through the mask. The pattern on the mask is not particularly limited, and a pattern corresponding to the target application is used. As a light source for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferred. For example, for light that does not reach 350 nm, you can use a filter that shields the wavelength region for shielding, or for light near 436 nm, 408 nm, and 365 nm, you can use bandpass filters that extract these wavelength regions. Perform selective extraction. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. can be mentioned. In order to irradiate the entire exposure surface with parallel light uniformly, or to correctly align the photomask with the substrate on which the coloring composition layer is formed, it is preferable to use a photomask alignment exposure machine and a stepping exposure machine to reduce the projection. Exposure device or proximity exposure device.

The exposed coloring composition layer is contacted with a developing solution for development, thereby forming a coloring pattern on the substrate. By development, the unexposed part of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01-10% by mass, more preferably 0.03-5% by mass. Furthermore, the developer may contain a surfactant. The development method may be any method such as a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development. It is preferable to wash with water after development.

Furthermore, it is preferable to post-bak the obtained colored coating film or colored pattern. The post-baking temperature is preferably 80 to 250°C, more preferably 100 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

According to the present invention, it is possible to provide a coloring curable resin composition with higher suitability in the film forming step. The color filter made from the colored curable resin composition can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL display devices, electronic paper, etc.) and solid-state imaging devices. [Example]

The following examples illustrate the present invention more specifically, but the present invention is of course not limited by the following embodiments, and of course it can be implemented with appropriate changes within the scope that conforms to the above and the following gist, all of which include Within the technical scope of the present invention. In the examples, as long as there is no special description, the% and parts indicating the content or usage amount are mass% and mass parts, respectively.

[Colorant Synthesis Example 1] 50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0°C. , 48 parts of tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise. After the dropwise addition, the temperature was raised to 23°C and stirred for 16 hours. After the reaction, water was added, the organic layer was extracted, and the solvent was concentrated, and then separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by formula (1-7). Hereinafter, the structure of the compound was confirmed by mass analysis (LC; 1200 type manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 287.0 accurate mass: +286.0

[化22]

15 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 35 parts of the compound represented by formula (1-7), 14 parts of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.6 part of bis(tri-tertiarybutylphosphine) palladium (0) (manufactured by Aldrich Co., Ltd.) dissolved in toluene (manufactured by Kanto Chemical Co., Ltd.) ) In 250 parts and 15 parts of water, heat to 90°C and stir for 30 minutes. After the reaction, the organic layer was extracted, concentrated, and separated and purified by silica gel column chromatography to obtain 14 parts of the compound represented by formula (1-8).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 328.3 accurate mass: +327.2

[化23]

14 parts of the compound represented by formula (1-8) and 10 parts of methyl 4-chloro-4-oxobutanoate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in toluene (manufactured by Kanto Chemical Co., Ltd.) 255 parts In the middle, the temperature was raised to 90°C and stirred for 1 hour. After the reaction, water was added, the organic layer was extracted, and the solvent was concentrated, and then separated and purified by silica gel chromatography to obtain 15 parts of the compound represented by formula (1-9).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 442.3 accurate mass: +441.2

[化24]

15 parts of the compound represented by formula (1-9) was dissolved in 150 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, a 1 M tetrahydrofuran solution of tetra-n-butylammonium fluoride (Tokyo Chemical Industry Co., Ltd.) was added dropwise. Industrial Co., Ltd.) 15 copies. After the dropwise addition, the temperature was raised to 23°C and stirred for 2 hours. After the completion of the reaction, the solvent was concentrated, and the silica gel column chromatography was used for separation and purification to obtain 12 parts of the compound represented by formula (1-10).

Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 328.2 accurate mass: +327.2

[化25]

Dissolve 12 parts of the compound represented by formula (1-10) in 240 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, add dropwise a borane-1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) ) 180 copies. After the dripping was completed, the mixture was stirred for 30 minutes, and after water was added, the tetrahydrofuran was concentrated, and the organic layer was extracted with ethyl acetate. After concentrating the solvent, it was separated and purified by silica gel column chromatography to obtain 6 parts of the compound represented by formula (1-11).

Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 314.2 accurate mass: +313.2

[化26]

6 parts of the compound represented by formula (1-11) and 0.2 part of lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries Co., Ltd.) were dissolved in 20 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), and tetrahydrofuran (Kanto Chemical Co., Ltd.) Co., Ltd.) 20 parts and 10 parts of water were stirred at 23°C for 1 hour. After the reaction, the organic solvent was concentrated, and the organic layer was extracted with ethyl acetate, and then separated and purified by silica gel column chromatography to obtain 4 parts of the compound represented by formula (1-12).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 300.2 accurate mass: +299.2

[化27]

4 parts of the compound represented by formula (1-12) and 0.8 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in toluene (Kanto The temperature was raised to 140°C in 40 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) and 10 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) and stirred for 2 hours. After concentrating the solvent, it was separated and purified by silica gel column chromatography to obtain 1.6 parts of the compound represented by formula (AI-16).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 677.3 accurate mass: +676.3

[化28]

[Colorant Synthesis Example 2] 50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0°C. , 48 parts of tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise. After the dropwise addition, the temperature was raised to 23°C and stirred for 16 hours. After the reaction, water was added, the organic layer was extracted, and the solvent was concentrated, and then separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by formula (2-10). In the following, the structure of the compound was confirmed by mass analysis (LC; 1200 type manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 287.0 accurate mass: +286.0

[化29]

45 parts of 4-amino-3,5-xylenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.). 127 parts of di-tertiary butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution to dissolve it. The reaction was carried out by stirring at 23°C for 16 hours. After the reaction, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was stirred and purified at 23°C for 2 hours in a mixed solvent of 90 parts of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) and 272 parts of n-hexane (manufactured by Kanto Chemical Co., Ltd.) to obtain the formula ( 47 parts of the compound represented by 1-33).

Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 238.3 accurate mass: +237.1

[化30]

20 parts of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 333 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.). Put 32.4 parts of triethylamine (manufactured by Kanto Chemical Co., Ltd.) and 0.156 parts of 4-dimethylaminopyridine (manufactured by Kanto Chemical Co., Ltd.) into this solution, and add tertiary butyldimethyl chloride while stirring. 28.95 parts of silane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved. The reaction was carried out by stirring at 23°C for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of the compound represented by formula (1-34).

Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 239.1 accurate mass: +238.0

[化31]

47 parts of the compound represented by the formula (1-33) were dissolved in 141.5 parts of the compound represented by the formula (1-34) and 447 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.). 138.2 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) was added to this solution, and it was stirred at 70 degreeC for 16 hours, and it reacted. After the completion of the reaction, the solvent was distilled off, and extraction operation with an organic solvent was performed to obtain 49 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 41 parts of the compound represented by formula (1-35).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+Ht-Bu ⁺ ] ⁺ 339.2 accurate mass: +395.3

[化32]

Dissolve 41 parts of the compound represented by formula (1-35) in 424 parts of 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.), and put in hydrogen chloride (about 4 mol/L 1,4-dioxane solution ) (Manufactured by Tokyo Chemical Industry Co., Ltd.) 263 parts, stirred at 23°C for 1 hour to deprotect. After the reaction, the solvent was distilled off to obtain 36 parts of a crude product. The crude product obtained was separated and purified by column chromatography to obtain 22 parts of the compound represented by formula (1-36).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 182.2 accurate mass: +181.1

[化33]

22 parts of the compound represented by formula (1-36) was dissolved in 293 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.). Into this solution, 10.8 parts of imidazole (manufactured by Kanto Chemical Co., Ltd.) and 22 parts of tertiary butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved. The reaction was carried out by stirring at 23°C for 16 hours. The solvent was distilled off to obtain 23 parts of a crude product. The crude product obtained was separated and purified by column chromatography to obtain 20 parts of the compound represented by formula (1-37).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 296.3 accurate mass: +295.2

[化34]

15 parts of the compound represented by the formula (2-10) were dissolved in 14.5 parts of the compound represented by the formula (1-37) and 130 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), and potassium hydroxide ( Kanto Chemical Co., Ltd.) 5.7 parts, water 15 parts, tetrabutylammonium bromide (Tokyo Kasei Kogyo Co., Ltd.) 2 parts, bis (tri-tertiary butyl phosphine) palladium (0) (Tokyo Kasei Kogyo Co., Ltd.) Co., Ltd.) 0.26 copies. After heating to 90°C and stirring for 20 minutes, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 15 parts of a crude product. The crude product obtained was separated and purified by column chromatography to obtain 12 parts of the compound represented by formula (1-38).

Identification: (mass analysis) ionization mode=ESI+: m/z=[M+H] ⁺ 502.4 accurate mass: +501.3

[化35]

Add 12 parts of the compound represented by the formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutanoate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 41.6 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) Mix, stir at 90°C for 1 hour and heat. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of the compound represented by the formula (1-39).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 616.3 accurate mass: +615.3

[化36]

Dissolve 5.9 parts of the compound represented by formula (1-39) in 52.4 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, dropwise add tetrabutylammonium fluoride 1 M tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) 11 parts, and after the dropwise addition, the mixture was stirred at 23°C for 2 hours. After the reaction, water was added and the tetrahydrofuran solvent was distilled off to obtain a crude product. The crude product was subjected to an extraction operation with an organic solvent and concentrated to obtain 4.3 parts of the compound represented by formula (1-40).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 388.2 accurate mass: +387.2

[化37]

4.3 parts of the compound represented by formula (1-40), 56.4 parts of borane 1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.), and 38.2 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed at 0°C, and the temperature was increased. Bring to 23°C and stir for 16 hours. After the reaction is completed, water is added, quenched, and extraction is performed with an organic solvent. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.3 parts of the compound represented by the formula (1-41).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 346.3 accurate mass: +345.2

[化38]

Dissolve 2.3 parts of the compound represented by the formula (1-41) and 0.38 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (Fujifilm Wako Pure Chemical Industries, Ltd.) in toluene (Kanto In 80 parts of Chemical Co., Ltd. and 19 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.), they were stirred and heated at 120°C for 4 hours. After the reaction, the solvent was distilled off to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by formula (AI-15).

Identification: (mass analysis) ionization mode = ESI +: m/z = [M+H] ⁺ 769.8 accurate mass: +768.4

[化39]

[Resin synthesis example] A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Then, 38 parts of acrylic acid, acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester and acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ^{2] were added dropwise over 5 hours. ,6} ] A mixed solution of 289 parts of a mixture of decane-9-yl esters (mixing ratio of 1:1) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed 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 dripping, the flask was kept at 80°C for 4 hours and then cooled at room temperature to obtain a type B viscosity (23°C) of 125 mPa·s and a copolymer (resin ( B-1)) Solution. The resulting copolymer has a weight average molecular weight Mw of 9,200, a dispersion degree of 2.08, and a solid content acid value of 77 mg-KOH/g. The resin (B-1) has the following structural unit.

[化40]

[Preparation Example 1: Preparation of Dispersion Liquid 1] Weigh the compound represented by formula (AI-16) (colorant (A-1)) 5.0 parts, dispersant (P-1) (solid content) 1.5 parts, resin (B-1) (solid content) After 4.0 parts and 89.5 parts of solvent (E-1), 300 parts of 0.2 μm zirconia beads were added and shaken for 1 hour using a paint conditioner (manufactured by LAU), and the zirconia beads were removed by filtration to prepare dispersion liquid 1.

[Preparation Example 2: Preparation of Dispersion 2] Except having replaced with 0.5 part of the solid content of the dispersant (P-1) and 90.5 parts of the solvent (E-1), the dispersion 2 was prepared in the same manner as in the preparation example 1.

[Preparation Example 3: Preparation of Dispersion 3] Except having replaced 1.5 parts of the solid content of the dispersant (P-1) with 1.5 parts of the solid content of the dispersant (P-2), a dispersion 3 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 4: Preparation of Dispersion 4] Replace 1.5 parts of dispersant (P-1) solid content with 0.5 parts of dispersant (P-2) solid content, and replace 89.5 parts of solvent (E-1) with 90.5 parts of solvent (E-1), except that Except for this, dispersion 4 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 5: Preparation of Dispersion Solution 5] Except having replaced 1.5 parts of the solid content of the dispersant (P-1) with 1.5 parts of the solid content of the dispersant (P-3), dispersion 5 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 6: Preparation of Dispersion Liquid 6] Replace 1.5 parts of dispersant (P-1) solid content with 0.5 parts of dispersant (P-3) solid content, replace 89.5 parts of solvent (E-1) with 90.5 parts of solvent (E-1), except Except for the above, dispersion 6 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 7: Preparation of Dispersion 7] Change 5.0 parts of colorant (A-1) to 5.0 parts of colorant (A-2), change 1.5 parts of dispersant (P-1) to 5.0 parts of dispersant (P-1), and change solvent (E-1) ) 89.5 parts were changed to 76.0 parts of solvent (E-1), and 10 parts of solvent (E-2) were added, and dispersion 7 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 8: Preparation of Dispersion 8] Change 5.0 parts of colorant (A-1) to 5.0 parts of colorant (A-2), change 1.5 parts of dispersant (P-1) to 2.5 parts of dispersant (P-1), and change solvent (E-1) ) 89.5 parts were changed to 78.5 parts of solvent (E-1), and 10 parts of solvent (E-2) were added, and dispersion 8 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 9: Preparation of Dispersion 9] Change 5.0 parts of colorant (A-1) to 5.0 parts of colorant (A-2), change 89.5 parts of solvent (E-1) to 79.5 parts of solvent (E-1), and add solvent (E-2) Except 10 parts, dispersion 9 was prepared in the same manner as in Preparation Example 1.

[Preparation Example 10: Preparation of Dispersion Solution 10] Change 5.0 parts of colorant (A-1) to 5.0 parts of colorant (A-2), change 1.5 parts of dispersant (P-1) to 0.5 parts of dispersant (P-1), and change solvent (E-1) ) 89.5 parts were changed to 80.5 parts of the solvent (E-1), and 10 parts of the solvent (E-2) were added, and dispersion 10 was prepared in the same manner as in Preparation Example 1.

[table 3] The unit is (parts) Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Preparation Example 10 Colorant (A) (A-1) 5.0 5.0 5.0 5.0 5.0 5.0 (A-2) 5.0 5.0 5.0 5.0 Dispersant (P) (P-1) 1.5 0.5 5.0 2.5 1.5 0.5 Dispersant (P) (P-2) 1.5 0.5 Dispersant (P) (P-3) 1.5 0.5 Resin (B) (B-1) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Solvent (E) (E-1) 89.5 90.5 89.5 90.5 89.5 90.5 76.0 78.5 79.5 80.5 (E-2) 10 10 10 10

[Examples 1-14, Comparative Example 1] [Preparation of colored curable resin composition] Add each dispersion liquid 1-10, resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) so as to have the composition shown in Table 4. They were mixed to obtain a colored curable resin composition (dispersion 1 was used in Example 1, and dispersions 2 to 10 were similarly used in each of Examples 2 to 10). Furthermore, in Table 4, the unit of the content of each composition is "parts". Furthermore, in Examples 11 to 14 and Comparative Example 1, the colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E ), a leveling agent (F), and a dispersing agent (P) if necessary to prepare a colored curable resin composition.

[Table 4] The unit is (parts) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative example 1 Colorant (A) (A-1) 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.3 3.2 (A-2) 2.8 2.7 2.7 2.7 Dispersant (P) (P-1) 1.0 0.2 2.8 1.4 0.8 0.1 0.2 Dispersant (P) (P-2) 1.0 0.2 1.0 0.2 Dispersant (P) (P-3) 1.0 0.2 0.2 Resin (B) (B-1) 57.4 57.4 57.4 57.4 57.4 57.4 57.8 57.8 57.8 57.4 60.0 60.0 60.0 60.0 60.0 (B-1)※ 2.6 2.6 2.6 2.6 2.6 2.6 2.2 2.2 2.2 2.6 Polymeric compound (C) (C-1) 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Polymerization initiator (D) (D-1) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Solvent (E) (E-1) 515 511 515 511 515 511 397 391 388 385 570 574 570 570 569 (E-1)※ 59 59 59 59 59 59 42 43 43 44 (E-2) 182 179 179 177 (E-2)※ 6 6 5 5 Leveling agent (F) (F-1) 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.07 0.06 0.07 0.07 0.07 0.06 ∆E*ab 13.7 10.7 15.5 14.0 15.5 13.8 14.0 13.1 12.5 11.9 15.3 15.7 15.3 15.3 15.9 Absorbance retention rate (∆Abs.Max) 36% 41% 34% 36% 32% 34% 31% 35% 36% 38% 33% 29% 33% 33% 33% Contrast 19864 21066 20548 21331 17,935 18718 17628 19399 20078 19493 17869

In Table 4, each component represents the following compound (※ represents the amount of self-dispersion liquid). Coloring agent (A): (A-1): compound represented by formula (AI-16) Coloring agent (A): (A-2): compound represented by formula (AI-15) Dispersant (P): Dispersant (P-1) acrylic dispersant (amine value 1 mgKOH/g, with tertiary amine group) Dispersant (P): Dispersant (P-2) acrylic dispersant (amine value 14 mgKOH/g, with tertiary amine group) Dispersant (P): Dispersant (P-3) acrylic dispersant (amine value 28 mgKOH/g, with tertiary amine group) Resin (B): Resin (B-1) (conversion of solid content) Polymerizable compound (C): (C-1): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D): (D-1): N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG -327; O-acetoxime compound; manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) Solvent (E): (E-1): Propylene glycol monomethyl ether acetate Solvent (E): (E-2): 4-hydroxy-4-methyl-2-pentanone Leveling agent (F): (F-1): Polyether modified silicone oil ("Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

[Production of colored coating film (color filter)] By spin coating method, it is coated on a 5 cm square glass substrate (EAGLE 2000; manufactured by Corning) and the film thickness after baking becomes 2.0 μm. After coloring the curable resin composition, it is pre-baked at 100°C for 3 minutes to form a coloring composition layer. After being left to cool, an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used to irradiate the colored composition layer with light at an exposure amount of ^{100 mJ/cm 2 (based on 365 nm) in an atmosphere.} Thereafter, post-baking was performed in an oven at 230°C for 30 minutes to obtain a color filter.

[Evaluation] 1. Fading resistance (ΔE*ab) Measure the chromaticity before pre-baking and after post-baking, use a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) to measure the spectroscopy, and use the characteristic function of the C light source to measure CIE's XYZ color system The xy chromaticity coordinates (x, y) and stimulus value Y in. Based on the measured value, the color difference ΔE*ab was calculated by the method described in JIS Z 8730:2009 (7. Color difference calculation method), and the results are shown in Table 4. The smaller the ΔE*ab, the smaller the color change (the higher the heat resistance).

2. Absorbance retention rate After pre-baking and post-baking, use a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.) to measure, and obtain the maximum absorbance in the visible light region based on the measured spectroscopy, according to the following formula Calculate the retention rate of the maximum absorbance. The results are shown in Table 4. Absorbance retention (ΔAbs.Max) = maximum absorbance after post-baking/maximum absorbance after pre-baking The higher the absorbance retention rate, the higher the suitability in the film forming step.

3. Contrast For the post-baked color filter, use a contrast meter (CT-1: manufactured by Kosaka Electric Co., Ltd., color difference meter BM-5A: manufactured by TOPCON Co., Ltd., light source: F-10, polarizing film: Kosaka Electric Co., Ltd. Manufactured by the company), set the blank value to 30000 to measure the contrast. If the contrast of the colored coating film is high, it can be said that the colored pattern is also high in contrast. The results are shown in Table 4.

Compared with Comparative Example 1, Examples 1 to 14 have lower ΔE*ab, and exhibit fading resistance. On the other hand, comparing Examples 2 and 11, Examples 3 and 12, Examples 4 and 13, and Examples 6 and 14 with respect to the presence or absence of the colorant dispersion, it can be seen that when the colorant dispersion is used, At least one of fade resistance, absorbance retention, and contrast is further improved. [Industrial availability]

According to the present invention, it is possible to provide a colored curable resin composition capable of forming a colored coating film in which fading is prevented (preferably, one of absorbance retention and contrast is improved or both are improved), and therefore can be used as a display Coloring curable resin composition used in color filters of devices or solid-state imaging devices.

Claims (9)

A coloring and curable resin composition comprising a colorant, a dispersant, a resin, a polymerizable compound, a polymerization initiator and a solvent, The above-mentioned colorant contains a squarylium dye which has great absorption in the visible light region, The amine value of the above dispersant exceeds 0 mgKOH/g and is less than 30 mgKOH/g. The colored curable resin composition of claim 1, wherein the above-mentioned squarylium dye is a compound represented by formula (AI), [化1]

[In formula (AI), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms; methylene constituting the monovalent saturated hydrocarbon group The group may be substituted with -O- or -S-; R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxyl group; Ar ¹ and Ar ² each independently represent a group represented by formula (i); [化2]

[In formula (i), R ¹² represents a monovalent saturated hydrocarbon group with 1 to 20 carbons or a hydroxyl group or a carboxyl group that may have a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5; the methylene group constituting the monovalent saturated hydrocarbon group may It is substituted with -O- or -S-; when m is 2 or more, each of the plural R ¹² may be the same or different; * indicates the bond with the nitrogen atom] R ⁹ and R ¹⁰ each independently indicate that they may have substitution The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or the group represented by formula (i); the methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-]. The colored curable resin composition of claim 1 or 2, wherein the above-mentioned squarylium dye is a compound represented by formula (AII); [化3]

[In formula (AII), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, or an optionally substituted monovalent saturated hydrocarbon group with 1 to 20 carbon atoms; methylene constituting the monovalent saturated hydrocarbon group The group may be substituted with -O- or -S-; R ⁵ to R ⁸ each independently represent a hydrogen atom or a hydroxyl group; Ar ¹ and Ar ² each independently represent a group represented by formula (i); [化4]

[In formula (i), R ¹² represents a monovalent saturated hydrocarbon group with 1 to 20 carbons or a hydroxyl group or a carboxyl group that may have a hydroxyl group or a carboxyl group, and m represents an integer of 0 to 5; the methylene group constituting the monovalent saturated hydrocarbon group may Is substituted with -O- or -S-; when m is 2 or more, each of the plural R ¹² may be the same or different; * represents the bond with the nitrogen atom] R ¹³ and R ¹⁴ each independently represent a hydroxyl group or The carboxyl group has a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, and the methylene group constituting the monovalent saturated hydrocarbon group may be substituted with -O- or -S-]. The colored curable resin composition according to any one of claims 1 to 3, wherein the dispersant has a tertiary amino group or a basic functional group of a nitrogen-containing heterocyclic ring. The colored curable resin composition according to any one of claims 1 to 4, wherein the content of the dispersant is 0.1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the colorant. The colored curable resin composition according to any one of claims 1 to 5, which comprises a dispersion liquid in which the colorant is dispersed in a solvent by the dispersant. A color filter, which is formed of the colored curable resin composition according to any one of claims 1 to 6. A liquid crystal display device comprising the color filter as claimed in claim 7. A method for manufacturing a colored curable resin composition, which includes: The step of obtaining a dispersion liquid formed by dispersing the colorant in the solvent by the dispersant; and The step of adding resin, polymerizable compound, and polymerization initiator to the dispersion; and The above-mentioned colorant contains a squarylium dye which has great absorption in the visible light region, The amine value of the above dispersant exceeds 0 mgKOH/g and is less than 30 mgKOH/g.