TW202136424A - Colored curable composition - Google Patents

Abstract

The purpose of the present invention is to provide a colored curable composition which is useful for the production of a color filter having a good pattern shape, while enabling a pattern to have high reflow resistance during post-baking. The present invention relates to a colored curable composition which comprises a coloring agent, an organic solvent, a resin, a polymerizable compound and a polymerization initiator, wherein: the coloring agent contains a compound represented by formula (I); and the polymerizable compound contains a compound represented by formula (II).

Description

Coloring curable composition

The present invention relates to a coloring and hardening composition. In detail, the present invention relates to a coloring and curable composition containing phthalocyanine dye.

Liquid crystal display devices, electroluminescence display devices, plasma displays and other display devices, CCD (Charge Coupled Device), CMOS (complementary metal oxide semiconductor, complementary metal oxide semiconductor) sensors and other solid-state imaging elements used The color filter is made of a colored curable resin composition. As a coloring agent used in the coloring curable resin composition for forming this color filter, a phthalocyanine dye is known (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-28236

[The problem to be solved by the invention]

However, the previously known colored curable resin composition using a phthalocyanine dye as a colorant as described in Patent Document 1 is not sufficiently satisfactory in the shape of the pattern because the pattern undergoes reflow during post-baking. The object of the present invention is to provide a coloring and curable composition which can be used to manufacture a color filter with a good pattern shape, and the pattern has better reflow resistance during post-baking. [Technical means to solve the problem]

[式(I)中，X表示氫原子或一價金屬原子； R¹ 表示經取代或未經取代之胺基或可具有取代基之碳數1～20之烴基； n表示1～4之整數； m表示0～4之整數； 於式(I)具有複數個X之情形時，X相互可相同亦可不同，於式(I)具有複數個R¹ 之情形時，R¹ 相互可相同亦可不同]，

[式(II)中，R^a 表示(q＋r)價之連結基； R^b 表示碳數1～20之烷二基； R^c 表示丙烯醯氧基或甲基丙烯醯氧基； p表示0以上之整數； q表示1以上之整數； r表示0以上之整數； 於式(II)具有複數個R^b 之情形時，R^b 相互可相同亦可不同，於式(II)具有複數個R^c 之情形時，R^c 相互可相同亦可不同，於式(II)具有複數個p之情形時，p相互可相同亦可不同； 其中，式(II)所具有之p所表示之整數之合計為2以上，q所表示之整數與r所表示之整數之合計為3以上]。 [2]如[1]所記載之著色硬化性組合物，其包含選自由C.I.直接藍86、C.I.直接藍87、C.I.直接藍199及C.I.活性藍25所組成之群中之至少1種作為上述式(I)所表示之化合物。 [3]如[1]或[2]所記載之著色硬化性組合物，其中於上述式(II)所表示之化合物中，R^a 表示自碳數3～30之脂肪族烴除去(q＋r)個氫原子後所得之基(上述脂肪族烴所含之亞甲基可被取代為氧原子而形成醚結構)。 [4]如[1]至[3]中任一項所記載之著色硬化性組合物，其中於上述式(II)所表示之化合物中，R^b 表示碳數1～10之烷二基。 [5]如[1]至[4]中任一項所記載之著色硬化性組合物，其中於上述式(II)所表示之化合物中，r表示0～6之整數。 [6]如[1]至[5]中任一項所記載之著色硬化性組合物，其中於上述式(II)所表示之化合物中，q表示2～12之整數。 [7]如[1]至[5]中任一項所記載之著色硬化性組合物，其中於上述式(II)所表示之化合物中，式(II)所具有之p所表示之整數之合計為2～60。 [8]如[1]至[7]中任一項所記載之著色硬化性組合物，其中上述樹脂具有於側鏈包含(甲基)丙烯醯基之結構單元。 [9]如[1]至[8]中任一項所記載之著色硬化性組合物，其中聚合起始劑包含O-醯基肟系化合物。 [10]一種彩色濾光片，其係由如[1]至[9]中任一項所記載之著色硬化性組合物所形成。 [11]一種顯示裝置，其包含如[10]所記載之彩色濾光片。 [12]一種固體攝像元件，其包含如[10]所記載之彩色濾光片。 [發明之效果]That is, the gist of the present invention is as follows. [1] A colored curable composition comprising a colorant, an organic solvent, a resin, a polymerizable compound, and a polymerization initiator, the colorant includes a compound represented by formula (I), and the polymerizable compound includes formula (II) ) Represented by the compound,

[In formula (I), X represents a hydrogen atom or a monovalent metal atom; R ¹ represents a substituted or unsubstituted amine group or a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms; n represents an integer of 1 to 4 M represents an integer from 0 to 4; when formula (I) has a plurality of Xs, X may be the same or different from each other, and when formula (I) has a plurality of R ^1s , R ¹ may be the same as each other May be different],

[In formula (II), Ra ^{represents a} linking group of (q+r) valence; R ^b represents an alkanediyl group with 1 to 20 carbon atoms; R ^c represents an acryloxy group or a methacryloxy group; p represents 0 or more Q represents an integer of 1 or more; r represents an integer of 0 or more; when formula (II) has a plurality of R ^b , R ^b may be the same or different from each other, and in formula (II), there is a plurality of R ^c In the case, R ^c may be the same or different from each other. When formula (II) has a plurality of p, p may be the same or different from each other; where, the sum of the integers represented by p in formula (II) Is 2 or more, and the total of the integer represented by q and the integer represented by r is 3 or more]. [2] The colored curable composition as described in [1], which contains at least one selected from the group consisting of CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 199 and CI Reactive Blue 25 as the above The compound represented by formula (I). [3] [1] or [2] Coloring described in the curable composition, wherein the compound of the above formula (II) represented by the in, R ^a represents from carbon aliphatic hydrocarbon having 3 to 30 of removing the (q + r) A group derived from a hydrogen atom (the methylene group contained in the aliphatic hydrocarbon can be substituted with an oxygen atom to form an ether structure). [4] The colored curable composition according to any one of [1] to [3], wherein in the compound represented by the above formula (II), R ^b represents an alkanediyl group having 1 to 10 carbon atoms. [5] The colored curable composition as described in any one of [1] to [4], wherein in the compound represented by the above formula (II), r represents an integer of 0-6. [6] The colored curable composition as described in any one of [1] to [5], wherein in the compound represented by the above formula (II), q represents an integer of 2-12. [7] The colored curable composition as described in any one of [1] to [5], wherein in the compound represented by the above formula (II), the integer represented by p in the formula (II) is The total is 2-60. [8] The colored curable composition as described in any one of [1] to [7], wherein the resin has a structural unit containing a (meth)acryloyl group in a side chain. [9] The colored curable composition as described in any one of [1] to [8], wherein the polymerization initiator includes an O-acetoxime-based compound. [10] A color filter formed of the colored curable composition as described in any one of [1] to [9]. [11] A display device comprising the color filter as described in [10]. [12] A solid-state imaging device comprising the color filter as described in [10]. [Effects of Invention]

According to the present invention, a coloring curable composition can be provided, which can be used to manufacture a color filter with a good pattern shape, and the pattern has better reflow resistance during post-baking.

The colored curable composition of the present invention contains a colorant (hereinafter sometimes referred to as colorant (A)), an organic solvent (hereinafter sometimes referred to as organic solvent (E)), and resin (hereinafter sometimes referred to as resin (B) ), a polymerizable compound (hereinafter may be referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter may be referred to as a polymerization initiator (D)). The coloring agent (A) contains a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). The coloring agent (A) may contain a coloring agent other than the compound (I) (hereinafter may be referred to as a coloring agent (A1)). The polymerizable compound (C) includes the compound represented by the formula (II) (hereinafter may be referred to as the compound (II)). The polymerizable compound (C) may include a polymerizable compound other than the compound (II) (hereinafter may be referred to as a polymerizable compound (C1)). The colored curable composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)). In addition, in this specification, the compound exemplified as each component can be used alone or in combination of plural kinds unless otherwise specified.

＜Colorant (A)＞ The colorant (A) contains the compound (I).

＜＜Compound (I)＞＞ The compound (I) is a compound represented by the following formula (I).

[式(I)中，X表示氫原子或一價金屬原子； R¹ 表示經取代或未經取代之胺基或可具有取代基之碳數1～20之烴基； n表示1～4之整數； m表示0～4之整數； 於式(I)具有複數個X之情形時，X相互可相同亦可不同，於式(I)具有複數個R¹ 之情形時，R¹ 相互可相同亦可不同]。

[In formula (I), X represents a hydrogen atom or a monovalent metal atom; R ¹ represents a substituted or unsubstituted amine group or a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms; n represents an integer of 1 to 4 M represents an integer from 0 to 4; when formula (I) has a plurality of Xs, X may be the same or different from each other, and when formula (I) has a plurality of R ^1s , R ¹ may be the same as each other Can be different].

Compound (I) means a compound in which (n+m) hydrogen atoms contained in the compound represented by the following formula (I-0) are replaced by n -SO ₃ X and m -SO ₂ R ¹ .

As n, an integer of 1 to 3 is preferable, and m is preferably an integer of 0 to 3. The total of the integer represented by n and the integer represented by m is preferably 1 to 4, and more preferably 1 ~3.

Examples of the monovalent metal atom represented by X include alkali metal atoms such as Na, K, and Li. As X, any one of a hydrogen atom, Na, K, and Li is preferable, and a hydrogen atom or Na is more preferable.

Examples of the substituted or unsubstituted amine group represented by R ¹ include: amine group; N-methylamino group, N-ethylamino group, N-anilino group, N,N-dimethylamino group, N , N-diethylamino group and other amine groups bonded with one or two hydrocarbon groups (the hydrocarbon group is preferably a hydrocarbon group with 1 to 15 carbon atoms, more preferably a hydrocarbon group with 1 to 10 carbon atoms) and the like. The substituted or unsubstituted amine group represented by R ^{1 is preferably an unsubstituted amine group.}

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ may, for example, be an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon group represented by R ¹ include linear chain hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Alkyl, etc.; isopropyl, (1-ethyl) propyl, isobutyl, second butyl, tertiary butyl, (1-ethyl) butyl, (2-ethyl) butyl, isopropyl Branched alkyl groups such as pentyl, neopentyl, tertiary pentyl, (2-methyl)pentyl, isohexyl, (5-methyl)hexyl, (3-ethyl)heptyl, etc.; vinyl , 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-( 2-propenyl)) vinyl, (1,2-dimethyl)propenyl, 2-pentenyl and other alkenyl groups; etc. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1-15, more preferably 1-10, and still more preferably 1-8.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ¹ include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cycloalkyl groups; cyclohexene Cycloalkenyl groups (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl, etc.; nor𦯉yl, adamantyl, bicyclo[2.2.2]octyl, etc. The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3-18, more preferably 3-15, and still more preferably 4-15.

The aromatic hydrocarbon group represented by R ¹ may, for example, be a phenyl group, 1-naphthyl group, 2-naphthyl group, phenanthryl group, anthryl group, and pyrenyl group. The carbon number of the aromatic hydrocarbon group is preferably 6-20, more preferably 6-18, and still more preferably 6-15.

The hydrocarbon group represented by R ¹ may be a group obtained by combining two or more of the above-exemplified chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group, as long as the upper limit of the carbon number is 20 or less. Such a group may be, for example, a group obtained by combining an aromatic hydrocarbon group with at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Regarding such a hydrocarbon group obtained by combination, the chain may be The hydrocarbyl group is combined in the form of a divalent group (for example, an alkanediyl group). Examples of hydrocarbon groups obtained by combination include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenethyl; aralkenyl groups such as styryl (phenylvinyl); Arynyl groups such as phenylethynyl; o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl , 2,4-Dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2,5-diisopropylphenyl, Alkyl aryl groups such as 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-butylphenyl; 2,3-dihydro-4-indenyl, 1, 2,3,5,6,7-hexahydro-4-symmetric dicyclopentadienyl, 5,6,7,8-tetrahydro-1-naphthyl, 3,5,5,8,8 -Pentamethyl-5,6,7,8-tetrahydro-2-naphthyl and other aryl groups bonded with alkanediyl groups; biphenyl and triphenyl groups bonded with more than one aryl group Group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl, etc. In addition, the above-mentioned hydrocarbon group may be, for example, a hydrocarbon group obtained by a combination of a chain hydrocarbon group and an alicyclic hydrocarbon group. Examples thereof include: 1-methylcyclopropyl, 1-methylcyclohexyl, 2-methyl Cyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl and other alicyclic hydrocarbon groups bonded with more than one alkyl group; cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, Cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl, adamantylmethyl, etc. Alkyl groups bonded with more than one alicyclic hydrocarbon group Wait. The carbon number of the group obtained by combining two or more of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group is preferably 4-20, more preferably 6-18.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ is preferably an aliphatic hydrocarbon group, and more preferably a saturated chain aliphatic hydrocarbon group.

Examples of substituents that the hydrocarbon group with 1 to 20 carbons represented by R ¹ may have include halogen atoms; nitrile groups; nitro groups; amino groups; hydroxyl groups; 15 alkoxy; phenoxy, 1-naphthoxy, 2-naphthoxy and other aryloxy groups with 6 to 20 carbons; silyl; oxyboron; monomethylamino, dimethylamino, mono Alkylamino groups with 1 to 15 carbon atoms such as ethylamino and diethylamino groups; arylamino groups with 6 to 20 carbon atoms such as monoanilinyl and diphenylamino groups; aralkanes with carbon numbers 7 to 20 such as benzylamino groups Carboxyl; Carboxyl; Carboxyl; Acetyl, propionyl and other alkylcarbonyl groups with 2 to 15 carbons; benzyl, 1-naphthylcarbonyl, 2-naphthylcarbonyl, etc., carbon number 7 to 20 Arylcarbonyl; methoxycarbonyl, ethoxycarbonyl, and other alkoxycarbonyl groups with 2 to 15 carbons; phenoxycarbonyl, 1-naphthoxycarbonyl, 2-naphthoxycarbonyl, and other aryloxy groups with 7 to 20 carbons Group carbonyl and so on. As the substituent which the hydrocarbon group with 1 to 20 carbon atoms represented by ^{R 1 may have, a halogen atom is preferred.}

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a chlorine atom.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 is preferably a hydrocarbon group having a substituent.}

As the compound (I), as shown in the following Table 1, for example, compound 1 to compound 80 represented by the formula (Ix) can be exemplified. Among Compounds 1 to 80, when the total of the integer represented by n, the integer represented by m1, and the integer represented by m2 is 2 or more, -SO ₃ X, -SO ₂ NH ₂ , and/or- SO ₂ (CH ₂ ) _r Cl is preferably bonded to different benzene rings.

[Table 1]

Among them, as compound (I), compound 1, compound 11, compound 18, compound 22, compound 23, compound 30, compound 34, compound 35, compound 39, compound 40, compound 53, compound 56, compound 60, Compound 72 is more preferably compound 11, compound 18, compound 23, compound 30, compound 34, compound 35, compound 39, compound 53, compound 56, compound 60, compound 72.

As the compound (I), specifically, CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 199, and CI Reactive Blue 25 can be exemplified, and particularly preferably include at least one selected from the group consisting of the above dyes .

The method for producing the compound (I) is not particularly limited, and it can also be produced with reference to the synthesis example described in JP 2011-28236 A.

The compound (I) is preferably one that is soluble in water and hardly soluble in an organic solvent having a solubility parameter (SP value) such as propylene glycol monomethyl ether acetate that does not reach 11.0 (cal/cm ³ ) ^1/2. Furthermore, soluble and poorly soluble can be evaluated by the following methods. Put 0.1 g of compound (I) into a 20 mL sample vial, then use a 10 ml pipette to add water or organic solvent, close the cap, and perform ultrasonic treatment for 3 minutes. The obtained liquid was kept standing in a 23°C water bath for 60 minutes. 5 ml of the supernatant was filtered through a PTFE (Polytetrafluoroethylene) 5 μm membrane filter, and then filtered through a 0.25 μm membrane filter to remove insoluble matter. Using an ultraviolet-visible spectrophotometer (for example, UV-2500PC manufactured by Shimadzu Corporation) and using a 1 cm unit, measure the absorbance spectrum of the obtained filtrate to obtain the absorbance (abs) at the maximum absorption wavelength of compound (I). At this time, if the above absorbance (abs) does not reach 40% of the upper limit of measurement (when using UV-2500PC manufactured by Shimadzu Corporation, the absorbance (abs) does not reach 2), it is evaluated as poorly soluble. If the above absorbance If (abs) is 40% or more of the upper limit of the measurement, it is evaluated as soluble. Due to this dissolving property, the compound (I) has excellent solvent resistance, and can provide a colored and curable composition that does not reflow the pattern even if it is heated at a temperature of 150°C or higher.

Compound (I) is hardly soluble in organic solvents with an SP value of less than 11.0 (cal/cm ³ ) ^1/2 , so organic solvents with an SP value of less than 11.0 (cal/cm ³ ) ^{1/2 are used in the coloring curable composition.} In the case of a solvent, it is preferable to prepare a colored dispersion liquid in which the compound (I) is uniformly dispersed in an organic solvent by containing a dispersant for dispersion treatment. The colored dispersion may contain part or all of the organic solvent (E) contained in the colored curable composition. The colored curable composition can be adjusted using the above-mentioned colored dispersion.

As a dispersing agent, a surfactant etc. are mentioned, for example, and all may be sufficient as a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants, etc. may be mentioned. These dispersants can be used individually or in combination of 2 or more types. As a dispersant, if it is represented by a trade name, it can be, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.) ), EFKA (registered trademark) (manufactured by BASF Corporation), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno (stock)) and Disperbyk (registered trademark) (manufactured by BYK-Chemie (stock)), BYK (registered trademark) ( BYK-Chemie Co., Ltd.), etc. As a dispersant, the resin (B) mentioned later can also be used.

In the case of using a dispersant, the usage amount of the dispersant (solid component) is usually 1 to 500 parts by mass, preferably 5 to 300 parts by mass, more preferably 10 parts by mass relative to 100 parts by mass of compound (I) -200 parts by mass, more preferably 15-180 parts by mass. If the amount of the dispersant used is within the above range, there is a tendency to obtain a more uniform dispersion state of the colored dispersion.

The content of the compound (I) relative to 100 parts by mass of the resin (B) is preferably 50 to 250 parts by mass, more preferably 80 to 200 parts by mass, and still more preferably 100 to 180 parts by mass.

In the total amount of the coloring agent (A), the content of the compound (I) is preferably from 40 to 100% by mass, more preferably from 60 to 100% by mass, and even more preferably from 80 to 100% by mass.

＜＜Colorant (A1)＞＞ The coloring and curable composition of the present invention may contain dyes (hereinafter sometimes referred to as dyes (A1-1)) and/or pigments (hereinafter sometimes referred to as pigments (A1-2)) other than compound (I) as coloring Agent (A) (hereinafter, dye (A1-1) and pigment (A1-2) may be collectively referred to as colorant (A1)). These can be used individually or in combination of 2 or more types.

The dye (A1-1) is not particularly limited, and known dyes can be used as long as the compound (I) is not included. For example, solvent dyes, acid dyes, direct dyes, and mordant dyes may be mentioned. Examples of dyes include compounds classified as dyes in the Dyestuff Index (published by The Society of Dyers and Colourists), and known dyes described in the Dyeing Manual (Sei Dyers Co., Ltd.). Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, dibenzopyran dyes, thiazole dyes, quinone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, Methyl dyes, methine azo dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes, etc.

The pigment (A1-2) 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 classified as 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, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231 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; CI Pigment Red 9, 97, 105, 122, 144, 149, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268 , 269, 273 and other red pigments; C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments; C.I. Purple pigments such as pigment violet 1, 19, 23, 32, 36, 38; C.I. Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments; C.I. Pigment Brown 23, 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments; etc.

The pigment may be treated as follows: rosin treatment; surface treatment using derivatives with acidic or basic groups introduced; grafting treatment to the surface of the pigment using polymer compounds, etc.; microparticulation using sulfuric acid microparticulation method, etc. Treatment; cleaning treatment using organic solvents or water to remove impurities; removal treatment using ion exchange methods such as ionic impurities; etc. The particle size of the pigment is preferably approximately uniform. The pigment can be made into a pigment dispersion liquid in a uniformly dispersed state in the dispersant solution by dispersing treatment by containing a dispersant. In the case of using plural kinds of pigments, the dispersion treatment may be carried out separately, or plural kinds of pigments may be mixed for dispersion treatment. In addition, the pigment and the above-mentioned compound (I) may be mixed and dispersed. As the dispersant, the same dispersants as described above can be mentioned.

When a dispersant is used, the amount of the dispersant (solid component) used relative to 100 parts by mass of the pigment is usually 10 to 200 parts by mass, preferably 15 to 180 parts by mass, more preferably 20 to 160 parts by mass share. If the amount of the dispersant used is within the above range, there is a tendency to obtain a more uniform dispersion state of the pigment dispersion.

When the colorant (A) contains the colorant (A1), the content of the colorant (A1) in the total amount of the colorant (A) is preferably 1-60% by mass, more preferably 1-40% by mass %, more preferably 1 to 20% by mass.

The content of the coloring agent (A) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 60% by mass relative to the total amount of solid components of the colored curable composition , And more preferably 15 to 55% by mass. If the content of the colorant (A) is within the above range, the color density when the color filter is made is sufficient, and since the necessary amount of resin (B) can be contained in the composition, it can be formed with sufficient mechanical strength The pattern is therefore better. Among them, the "total amount of solid content" in this specification refers to the amount obtained by excluding the content of the organic solvent from the total amount of the colored curable composition. The total amount of solid components and the content of each component relative to the total amount of solid components can be measured, for example, by a known analysis method such as liquid chromatography or gas chromatography.

＜Resin (B)＞ The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. The resin (B) may, for example, be the following resins [K1] to [K6]. 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 acids and unsaturated carboxylic anhydrides, and derived from having carbon A copolymer of the structural unit of monomer (b) (hereinafter sometimes referred to as "(b)") with a cyclic ether structure of number 2 to 4 and ethylenically unsaturated bond; Resin [K2]; has a structural unit from (a), a structural unit from (b), and a monomer (c) that can be copolymerized with (a) (wherein (a) and (b) are different) (below Sometimes referred to as "(c)") a copolymer of structural units; Resin [K3]; a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]; a copolymer having a structural unit obtained by adding (b) to a structural unit derived from (a) and a structural unit derived from (c); Resin [K5]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c); Resin [K6]; a copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a polycarboxylic acid and/or 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, and p-vinyl benzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; Methyl-5-nor 𦯉ene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5 -Carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2 .1]Hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, Unsaturated dicarboxylic acid anhydrides such as 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. ； Unsaturation of succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, etc. Mono[(meth)acryloxyalkyl] esters; Unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule, such as α-(hydroxymethyl) acrylate. Among them, acrylic acid, methacrylic acid, etc. are preferred in terms of copolymerization reactivity or solubility of the obtained resin in an alkaline aqueous solution.

(b) For example, it refers to 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 ethylenic 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. In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The notations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

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 ethylenically unsaturated bond may be mentioned. The saturated bond monomer (b2) (hereinafter may be referred to as "(b2)"), the monomer having a tetrahydrofuran group and an ethylenically unsaturated bond (b3) (hereinafter may be referred to as "(b3)"), and the like.

As (b1), for example, a monomer having a linear or branched aliphatic unsaturated hydrocarbon epoxidized structure (b1-1) (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.

(B1-1) may, for example, be glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, 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.

As (b1-2), 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 (stock)), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Cyclomer M100; manufactured by Daicel (stock)), formula ( The compound represented by BI) and the compound represented by formula (BII), etc.

[式(BI)及式(BII)中，R^e 及R^f 表示氫原子、或碳數1～4之烷基，該烷基所含之氫原子可被取代為羥基； X^e 及X^f 表示單鍵、*-R^g -、*-R^g -O-、*-R^g -S-或*-R^g -NH-； R^g 表示碳數1～6之烷二基； *表示與O之鍵結鍵]。

[In formula (BI) and formula (BII), R ^e and R ^f represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group; X ^e and X ^f It represents a single ^{bond, * - R g -, *} - R g -O -, * - R g -S- or * -R ^g -NH-; R ^g represents alkanediyl group having a carbon number of 1 to 6; and * represents Bonding key of O].

The alkyl group having 1 to 4 carbon atoms may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl. Examples of the alkyl group formed by substituting a hydrogen atom with a hydroxy group include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl Group, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc. As R ^e and R ^f , suitable examples are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more suitable examples are a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, hexane-1,6-diyl, etc. As X ^e and X ^f , suitable examples include single bond, methylene group, ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, and more suitable examples include single bond, *-CH ₂ CH ₂ -O- (* means the bond with O).

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

The compound represented by formula (BII) may, for example, be a compound represented by any one of formula (BII-1) to formula (BII-15), and the like. Among them, the formula (BII-1), the formula (BII-3), the formula (BII-5), the formula (BII-7), the formula (BII-9) or the formula (BII-11)～the formula (BII) are preferred. The compound represented by -15) is more preferably a compound represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, respectively, or two or more of them may be used in combination. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio (compound represented by formula (BI): compound represented by formula (BII)) is expressed in moles The benchmark is preferably 5:95 to 95:5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. (B2) may, for example, be 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-methacryloxy Ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methylpropenyloxyethyl 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 the reliability of heat resistance, chemical resistance, etc. of the obtained color filter can be improved further. Furthermore, in terms of excellent storage stability of the colored curable composition, (b1-2) is more preferable.

(C), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, benzene (meth)acrylate (Meth)acrylates (cf-1) that do not have polycyclic hydrocarbon rings such as naphthyl (meth)acrylate, benzyl (meth)acrylate, etc. (hereinafter sometimes referred to as "(cf-1) "); (Meth) acrylate tricyclo[5.2.1.0 ^2,6 ] decane-8-yl ester (in this technical field, its customary name is "(meth)acrylate dicyclopentyl ester". Also, Sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ] decene-8-yl (meth)acrylate (in this technical field, its usual name is ``Dicyclopentenyl (meth)acrylate''), dicyclopentyloxyethyl (meth)acrylate, iso(meth)acrylate, adamantyl (meth)acrylate, etc. have polycyclic hydrocarbons Cyclic (meth)acrylates (cf-2) (hereinafter sometimes referred to as "(cf-2)"); 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Hydroxyl-containing (meth)acrylates; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itconate, etc.; 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- Hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept- 2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 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-dimethoxybicyclo[2.2.1] Hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy- 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2. 1]Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis (Third butoxycarbonyl) bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyl (Oxycarbonyl) bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide Amine, N-butanediimidate-3-maleimide benzoate, N-butanediimidate-4-maleimide butyrate, N-butanediimidate Dicarbonyl-6-maleimide caproate, N-butanediimide-3-maleimide propionate, N-(9-acridinyl)maleimide and other dicarbonyl groups Amide derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride , Vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Among them, (meth)acrylates are preferred.

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

For resin [K1], for example, refer to the method described in the document "Experimental Method of Polymer Synthesis" (written by Takayuki Otsu, Chemical Tongjin of the issuing office (stock), the first edition of the first brush, issued on March 1, 1972) and the method described Manufactured by citing documents recorded in the literature.

Specifically, the following method can be exemplified: putting a specific amount of (a) and (b), polymerization initiator, solvent, etc. into a reaction vessel, for example, replacing oxygen with nitrogen to form a deoxygenated atmosphere. Heat and keep warm while stirring. 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 peroxides (benzyl peroxide, tert-butyl 2-ethylhexanoate, etc.) can be used as a solvent to dissolve each monomer, and can be exemplified as the coloring and hardening combination of the present invention. The organic solvent (E) of the organic solvent, etc. is described.

Furthermore, the resulting copolymer can be directly used as a solution after the reaction, a concentrated or diluted solution can be used, or a solid (powder) taken out by methods such as reprecipitation can also be used. In particular, since the solvent contained in the colored curable composition of the present invention is used as a solvent during the polymerization, the reacted solution can be directly used to prepare the colored curable composition of the present invention, so that the coloring of the present invention can be simplified The manufacturing steps of the curable composition.

In the resin [K2], among all the structural units constituting the resin [K2], the ratio of the structural units from each is as follows: Preferably Structural unit from (a); 2～45 mol% Structural unit from (b); 2～95 mol% The structural unit from (c); 1～65 mol%, Better The structural unit from (a); 5-40 mol% The structural unit from (b); 5～80mol% Structural unit from (c); 5-60 mol%. If the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored curable composition, the developability when forming a colored pattern, and the solvent resistance, heat resistance and heat resistance of the resulting color filter Trend of excellent 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 resin [K3], among all the structural units constituting resin [K3], the ratio of the structural units from each is as follows: Preferably The structural unit from (a); 2～60 mol% The structural unit from (c); 40～98 mol%, Better The structural unit from (a); 10-50 mol% The structural unit 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 obtained by obtaining a copolymer of (a) and (c) and adding the cyclic ether with 2 to 4 carbons in (b) to the carboxylic acid and/or carboxylic acid in (a) Manufactured from acid anhydride. First, the copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural units from each is preferably the same as that exemplified in the resin [K3].

Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms in (b). (a) After the manufacture of the copolymer with (c), the atmosphere in the flask is replaced from nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris(dimethylamino) (Methyl)phenol, etc.) and polymerization inhibitors (for example, hydroquinone, etc.) are put in a flask, and reacted at 60 to 130°C for 1 to 10 hours, for example, to produce resin [K4]. The usage amount of (b) 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 composition, the developability during pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tend to become better. Since the cyclic ether has high reactivity, the unreacted (b) is unlikely to remain, so (b) used as the resin [K4] is preferably (b1), and more preferably (b1-1). The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The reaction conditions such as the addition method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment or the heat generated by the polymerization. In addition, as with the polymerization conditions, the addition method or the reaction temperature can be appropriately adjusted in consideration of the production equipment or the heat generated by the polymerization.

The first stage of resin [K5] is the same as that of the above-mentioned resin [K1] to obtain a copolymer of (b) and (c). 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) taken out by a method such as reprecipitation can also be used. The ratios of the structural units from (b) and (c) to the total moles of all the structural units constituting the copolymer are as follows: Preferably Structural unit from (b); 5～95 mol% The structural unit from (c); 5～95 mol%, Better The structural unit from (b); 10～90mol% The structural unit from (c); 10 to 90 mol%.

Furthermore, under the same conditions as the production method of resin [K4], the cyclic ether derived from (b) contained in the copolymer of (b) and (c) and the carboxylic acid or carboxylic anhydride contained in (a) Reaction, thereby obtaining resin [K5]. The amount of (a) used to react with the copolymer is preferably 5-100 mol relative to (b) 100 mol. Since the cyclic ether has high reactivity, the unreacted (b) is unlikely to remain, so (b) used as the resin [K5] is preferably (b1), and more preferably (b1-1).

Resin [K6] is a resin obtained by further reacting resin [K5] with polycarboxylic acid and/or carboxylic anhydride. The hydroxyl group generated by the reaction of the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a) is further reacted with the polycarboxylic acid and/or the carboxylic anhydride. As the polyvalent carboxylic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, triphenylamine formic acid, etc. may be mentioned. The carboxylic acid anhydride may, for example, be succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2 -Acrylic anhydride, etc. The usage amount of the polycarboxylic acid and/or carboxylic anhydride is 1 mol relative to the usage amount of (a), preferably 0.05 to 1 mol, more preferably 0.1 to 0.5 mol. That is, the resin [K6] is more preferable to have no addition of polycarboxylic acid and/or carboxylic anhydride to produced by the reaction of the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride derived from (a) The hydroxy group, the structural unit obtained by adding (a) to the structural unit derived from (b).

The resin (B) is preferably a resin (resin [K4], resin [K5], or resin [K6]) having a structural unit having an ethylenically unsaturated bond in the side chain, and more preferably includes a resin having a side chain A resin whose chain contains a structural unit of (meth)acryloyl group.

As a resin having a structural unit containing a (meth)acryloyl group in a side chain, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-Methyl-3-methacryloxymethyloxetane, tetrahydrofurfuryl acrylate, and other monomers having (meth)acrylic acid groups (ba) (hereinafter sometimes referred to as "(ba) )”) as (b) resin [K4]; use acrylic acid, methacrylic acid, succinic acid mono[2-(meth)acryloyloxyethyl] ester and other monomers having (meth)acrylic acid groups (aa) (hereinafter sometimes referred to as "(aa)") as the resin [K5] of (a); or, use (aa) as the resin [K6] of (a). As a resin which has a structural unit containing a (meth)acryloyl group in a side chain, it is preferable to contain resin [K6] using (aa) as (a).

As a resin having a structural unit containing a (meth)acryloyl group in the side chain, it is more preferable to include a resin having the following structural unit [K6], and the structural unit is a side chain containing a (meth)acryloyl group and a resin derived from The structural unit of the carboxylic acid group of the polycarboxylic acid and/or carboxylic anhydride (the structural unit obtained by adding (aa) to the structural unit from (b) and then adding the polycarboxylic acid and/or carboxylic anhydride), on the side The chain contains (meth)acrylic acid groups, and does not contain structural units derived from polycarboxylic acids and/or carboxylic acid anhydrides (structural units obtained by adding (aa) to structural units derived from (b)), and The structural unit derived from (c); further preferably, it contains a resin [K6] having the following structural unit, the structural unit containing (meth)acrylic acid group in the side chain, containing carboxylic acid derived from polycarboxylic acid and/or carboxylic anhydride The structural unit of the acid group (the structural unit obtained by adding (aa) to the structural unit from (b) and further adding polycarboxylic acid and/or carboxylic anhydride) contains a (meth)acryloyl group in the side chain, Does not contain structural units derived from polycarboxylic acids and/or carboxylic anhydrides of carboxylic acid groups (structural units obtained by adding (aa) to structural units derived from (b)), and derived from (cf-1) and/or ( The structural unit of cf-2); it is particularly preferred to include a resin with the following structural unit [K6], the structural unit is in the side chain containing (meth)acrylic acid group, containing carboxylic acid derived from polycarboxylic acid and/or carboxylic anhydride The structural unit of the group (the structural unit obtained by adding (aa) to the structural unit from (b) and further adding polycarboxylic acid and/or carboxylic anhydride), contains (meth)acrylic acid group in the side chain, not Structural units containing carboxylic acid groups derived from polycarboxylic acids and/or carboxylic anhydrides (structural units obtained by adding (aa) to the structural units derived from (b)), and derived from (cf-1) and (cf-2) ) The structural unit.

In addition, as the resin (B), from the viewpoint of increasing the residual film rate, it is preferable to remove the resin (resin [K4], resin [K5], or resin In addition to [K6]), resin [K1] is further included.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 4,000 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 developer in the unexposed area will be good, and the resolution of the colored pattern will 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.

When the acid value of the resin (B) is converted into solid content, it is preferably 20 to 170 mg-KOH/g, more preferably 25 to 150 mg-KOH/g, and still more preferably 30 to 130 mg-KOH/g . The acid value is a value measured in the form of 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 amount of solid components of the colored curable composition is preferably 7-65% by mass, more preferably 13-60% by mass, and still more preferably 17-55% by mass. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to increase.

＜Polymerizable compound (C)＞ The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D). The polymerizable compound (C) includes the compound (II).

＜＜Compound (II)＞＞ The compound (II) is a compound represented by the following formula (II).

[式(II)中，R^a 表示(q＋r)價之連結基； R^b 表示碳數1～20之烷二基； R^c 表示丙烯醯氧基或甲基丙烯醯氧基； p表示0以上之整數； q表示1以上之整數； r表示0以上之整數； 於式(II)具有複數個R^b 之情形時，R^b 相互可相同亦可不同，於式(II)具有複數個R^c 之情形時，R^c 相互可相同亦可不同，於式(II)具有複數個p之情形時，p相互可相同亦可不同； 其中，式(II)所具有之p所表示之整數之合計為2以上，q所表示之整數與r所表示之整數之合計為3以上]。

[In formula (II), Ra ^{represents a} linking group of (q+r) valence; R ^b represents an alkanediyl group with 1 to 20 carbon atoms; R ^c represents an acryloxy group or a methacryloxy group; p represents 0 or more Q represents an integer of 1 or more; r represents an integer of 0 or more; when formula (II) has a plurality of R ^b , R ^b may be the same or different from each other, and in formula (II), there is a plurality of R ^c In the case, R ^c may be the same or different from each other. When formula (II) has a plurality of p, p may be the same or different from each other; where, the sum of the integers represented by p in formula (II) Is 2 or more, and the total of the integer represented by q and the integer represented by r is 3 or more].

As R ^a is represented by the (q + r) price of the linking group, for example, include removal of carbon atoms of the aliphatic hydrocarbon having 3 to 30 of the contained the (q + r) hydrogen atoms become compounds bonded group of the aliphatic hydrocarbons The methylene group contained can be substituted with an oxygen atom to form an ether structure.

The aliphatic hydrocarbon having 3 to 30 carbon atoms may be saturated or unsaturated, and is preferably saturated. In addition, the aliphatic hydrocarbon with 3 to 30 carbon atoms may be chain aliphatic hydrocarbons, alicyclic hydrocarbons, or a combination of chain aliphatic hydrocarbons and alicyclic hydrocarbons, preferably chain aliphatic hydrocarbons. Shape aliphatic hydrocarbons.

Examples of the aforementioned chain aliphatic hydrocarbons include propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane. , Straight-chain aliphatic hydrocarbons such as pentadecane; branched-chain aliphatic hydrocarbons such as hydrocarbons represented by the following formulas (ac-1) to (ac-15); etc.

The carbon number of the chain aliphatic hydrocarbon is preferably 3-25, more preferably 4-20, and still more preferably 6-20. In addition, the chain aliphatic hydrocarbon is preferably a branched aliphatic hydrocarbon, preferably having three or more carbon atoms, more preferably having quaternary carbon atoms, and still more preferably having two or more quaternary carbon atoms atom. Among them, hydrocarbons represented by formula (ac-7) to formula (ac-15) are preferred, and formula (ac-7), formula (ac-10), formula (ac-11), and formula ( ac-15) hydrocarbon represented by.

Examples of the above-mentioned alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclodecane. Cyclohydrocarbons such as alkanes, cyclotridecane, cyclotetradecane, and cyclopentadecane; norrethane, adamantane, bicyclo[2.2.2]octane, etc. The carbon number of the alicyclic hydrocarbon is preferably 3-28, more preferably 5-25, and still more preferably 8-23.

The hydrocarbon obtained by combining the chain aliphatic hydrocarbon and the alicyclic hydrocarbon may be a hydrocarbon obtained by combining two or more of the chain aliphatic hydrocarbons and alicyclic hydrocarbons exemplified above. Among the hydrocarbons obtained by combination, chain aliphatic hydrocarbons can be combined in the form of monovalent or divalent groups (for example, alkyl groups, alkanediyl groups). Examples of hydrocarbons obtained by combination include methylcyclopropane, 1,3-dimethylcyclobutane, 1,2,4,5-tetramethylcyclohexane, dicyclohexylmethane, and the like. The carbon number of the hydrocarbon obtained by combining the chain aliphatic hydrocarbon and the alicyclic hydrocarbon is preferably 6-30, more preferably 6-28, and still more preferably 6-25.

The methylene group contained in the aliphatic hydrocarbon is preferably substituted with an oxygen atom to form an ether structure, more preferably 1 to 3 ether structures, and still more preferably 1 ether structure.

In the above-mentioned aliphatic hydrocarbon, as a site where a hydrogen atom is removed to become a bonding group, a carbon atom (including a terminal carbon atom) _{of the -CH 3 part contained in the aliphatic hydrocarbon is preferable.} Moreover, it is more preferable to _{remove only one hydrogen atom from one -CH 3} part to become a linking group.

Examples of the alkanediyl group having 1 to 20 carbons represented by R ^b include: methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, and pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane- 1,10-diyl and other linear alkanediyl groups; ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, 2-methylpropane-1, 2-diyl, 2-methylpropane-1,3-diyl, butane-1,3-diyl, 2-methylbutane-1,4-diyl, pentane-1,4-di Branched chain alkanediyl groups such as groups; etc.

The carbon number of the alkanediyl group represented by R ^b is preferably 1-10, more preferably 1-8, still more preferably 1-5, and still more preferably 2-4.

As R ^c , propyleneoxy group is preferred.

As p is preferably an integer of 0-15, more preferably an integer of 1-10, still more preferably an integer of 1-8, still more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 4 , Particularly preferably an integer of 2 to 3. Wherein, the sum of the integers represented by p in the formula (II) is 2 or more, and the sum is preferably 2-60, more preferably 4-50, still more preferably 4-40, and still more preferably 5- 30, particularly preferably 8-20. By including the compound (II) of the integer represented by p in the above range as a polymerizable compound, it is possible to provide a colored curable composition that does not reflow even when heated at a temperature of 150°C or higher. .

As q, the integer of 1-12 is preferable, the integer of 2-10 is more preferable, and the integer of 4-8 is still more preferable.

As r, the integer of 0-6 is preferable, the integer of 0-4 is more preferable, the integer of 0-2 is still more preferable, the integer of 0-1 is still more preferable, and 0 is especially preferable.

The total of the integer represented by q and the integer represented by r is 3 or more, and the sum is preferably 3-12, more preferably 4-10, still more preferably 5-10, and still more preferably 6-10.

As the compound (II), as shown in Tables 2 to 4, the most preferred are the compound II-1 to the compound II-240 represented by the formula (II-x).

[Table 2]

[table 3]

[Table 4]

In Tables 2 to 4, Ax-1 and Ax-2 mean the groups represented by the following formula (Ax-1) and formula (Ax-2), respectively, Bx-1 means ethyl group, and Bx-2 means Propane-1,2-diyl, Cx-1 means acryloxy, Cx-2 means methacryloxy, tPx means the total of integers represented by px in formula (II-x) number. In the following formula (Ax-1) and formula (Ax-2), * represents a bonding bond.

Among them, the compound (II) is preferably compound II-1 to compound II-120, more preferably compound II-1 to compound II-96, still more preferably compound II-1 to compound II-48, and even more Preferred are compound II-13 to compound II-36, and more preferred are compound II-13, compound II-14, compound II-17, compound II-18, compound II-21, compound II-22, compound II-25 , Compound II-26, Compound II-29, Compound II-30, Compound II-33, Compound II-34, particularly preferably Compound II-21, Compound II-22, Compound II-33, Compound II-34.

As the compound (II), commercially available products can be used, for example, A-DPH6E (manufactured by Shinnakamura Chemical Industry Co., Ltd., number of ethylene oxide chains: 6), A-DPH12E (manufactured by Shinnakamura Chemical Industry Co., Ltd. ) Manufacturing, the number of ethylene oxide chains: 12), A-DPH18E (manufactured by Shinnakamura Chemical Industry Co., Ltd., the number of ethylene oxide chains: 18), A-DPH24E (manufactured by Shinnakamura Chemical Industry Co., Ltd.) , The number of ethylene oxide chains: 24), A-DPH48E (manufactured by Shinnakamura Chemical Industry Co., Ltd., the number of ethylene oxide chains: 48), A-DPH6PO (manufactured by Shinnakamura Chemical Industry Co., Ltd.), The number of oxypropane chains: 6) and so on. Furthermore, the above-mentioned ethylene oxide chain corresponds to the "-OR ^b -" ^{in compound (II) where R b} is an ethylene group (chain), and the propylene oxide chain corresponds to the "-" in compound (II). ^{The R b} of OR ^b -" is the group (chain) of propylene oxide, and the number of ethylene oxide chains or propylene oxide chains is equivalent to the total number of integers represented by p of compound (II).

In the total amount of the polymerizable compound (C), the content of the compound (II) is preferably from 50 to 100% by mass, more preferably from 60 to 100% by mass, and even more preferably from 80 to 100% by mass.

＜＜Polymerizable compound (C1)＞＞ The colored curable composition of the present invention may contain a polymerizable compound (polymerizable compound (C1)) other than the compound (II) as the polymerizable compound (C). The polymerizable compound (C1) is a compound that can be polymerized by the active radical and/or acid generated from the polymerization initiator (D). For example, polymerizable compounds other than the compound (II) can be exemplified. The compound with a saturated bond and the like are preferably (meth)acrylate compounds other than the compound (II).

Among them, the polymerizable compound (C1) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. As such a polymerizable compound (C1), for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Base) acrylate, dipentaerythritol hexa(meth)acrylate, etc.

The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, and more preferably from 250 to 1,500.

The content of the polymerizable compound (C) is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass relative to the total amount of solid components of the colored curable composition %.

＜Polymerization initiator (D)＞ The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc., to initiate polymerization by the action of light or heat, and known polymerization initiators can be used. As a polymerization initiator that generates living radicals, for example, a benzophenone compound, a triphenylene compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound can be exemplified.

The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by the following formula (d1). In the following, * represents a bonding key.

As the above-mentioned O-acetoxime compound, for example, N-benzyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl Acetyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl)-3 -Cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3- Ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxide Cyclopentylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2- Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2 -Methylbenzyl)-9H-carbazol-3-yl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4-phenylsulfide) (Phenyl)-3-cyclohexylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) can be used. Among them, the O-acetoxy oxime compound is preferably selected from N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one-2-imine, N- Benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyloxy-1-(4-phenylthiophenyl) It is composed of octane-1-one-2-imine and N-benzyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine At least one in the group, more preferably N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-benzyl Acetyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine. In the case of these O-acetoxime compounds, there is a tendency to obtain high-brightness color filters.

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

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl] -1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF) can be used.

As the compound having the partial structure represented by the formula (d3), for example, 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. In terms of sensitivity, the benzophenone compound is preferably a compound having a partial structure represented by formula (d2).

As the above-mentioned tris compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris, 2,4-bis(tris Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-tris 𠯤、2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tris𠯤、2,4-bis(trichloromethyl)-6- [2-(5-Methylfuran-2-yl)vinyl]-1,3,5-tris, 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-tris Wait.

As the said phosphine oxide compound, 2,4,6-trimethylbenzyl diphenyl phosphine oxide etc. are mentioned. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can 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 Laid-Open Sho 62-174204, etc.), a biimidazole compound in which the phenyl group at the 4,4'5,5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Laid-Open No. 7-10913 etc.).

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, methyl benzoin benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloro acridine Pyridone, diphenylethylenedione, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with the polymerization initiation aid (D1) (especially amines) described later.

As the polymerization initiator for generating acid, for example, 4-hydroxyphenyl dimethyl sulfonium p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxybenzene Dimethyl sulfonate p-toluenesulfonate, 4-acetoxy phenylmethyl benzyl sulfonate hexafluoroantimonate, triphenyl sulfonate p-toluenesulfonate, triphenyl sulfonate hexafluoroantimonate, Onium salts such as diphenyl iodonium p-toluenesulfonate, diphenyl iodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate, benzoin toluenesulfonate, etc.

As the polymerization initiator (D), it is preferable to include at least one selected from the group consisting of phenalkanone compounds, triphenyl compounds, phosphonium oxide compounds, O-oxime 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 range, there is a tendency to increase sensitivity and shorten the exposure time, so the productivity of the optical filter is improved.

、N-苯基甘胺酸等。<Polymerization initiation aid (D1)> The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). As the polymerization initiation aid (D1), 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler’s ketone), 4,4'-bis(diethylamino)bis Benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl 9-oxythio𠮿

, N-phenylglycine and so on.

In the case of using these polymerization initiation aids (D1), the content is preferably 0.1-30 parts by mass, more preferably 0.1-30 parts by mass relative to 100 parts by mass of the total amount of resin (B) and polymerizable compound (C) 1-20 parts by mass. If the amount of polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

＜Organic solvent (E)＞ The organic solvent (E) is not particularly limited, and organic solvents commonly used in this field can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (containing-in the molecule) COO- and -O- solvents), ketone solvents (solvents containing -CO- in the molecule, and solvents not containing -COO-), alcohol solvents (containing OH in the molecule, not containing -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, acetic acid Cyclohexyl ester and γ-butyrolactone, etc.

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

As the ether ester solvent, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, etc.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4- Methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

As an alcohol solvent, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, etc. are mentioned.

The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene, 1,3,5-trimethylbenzene, and the like.

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

The organic solvent (E) preferably contains one or more selected from the group consisting of ether solvents, ether ester solvents, and ketone solvents, more preferably contains ether ester solvents and ketone solvents, and more preferably contains propylene glycol monomers. Methyl ether acetate, and 4-hydroxy-4-methyl-2-pentanone.

The content of the organic solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass relative to the total amount of the coloring curable composition of the present invention. In other words, the solid content of the colored curable composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. If the content of the organic solvent (E) is within the above-mentioned range, the flatness at the time of coating becomes good, and since the color density is sufficient when the color filter is formed, the display characteristics tend to become good.

＜Leveling agent (F)＞ As the leveling agent (F), a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom, etc. may be mentioned. These may have a polymerizable group in the side chain. The silicone-based surfactant may, for example, be a surfactant having a silicone bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Dow Corning Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Advanced Materials Japan Co., Ltd.) )Wait.

As the above-mentioned fluorine-based surfactant, a surfactant having a fluorocarbon chain in the molecule, etc. may be mentioned. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M (stock)), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC (Stock)), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381 , Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC Co., Ltd. (formerly: Asahi Glass Co., Ltd.)) and E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.), etc.

As the aforementioned silicone-based surfactant having a fluorine atom, a surfactant having a silicone 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.

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.1% by mass relative to the total amount of the colored curable composition. In addition, this content rate does not include the content rate of the said pigment dispersing agent. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

＜Other ingredients＞ The colored curable composition of the present invention may optionally include fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as well as additives known in the technical field.

＜Method for producing coloring curable composition＞ The colored curable composition of the present invention can be used, for example, by combining a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an organic solvent (E), and optionally The leveling agent (F) and other ingredients are mixed to prepare. The colorant (A) can be prepared using the above-mentioned coloring dispersion liquid or pigment dispersion liquid. The target colored curable composition can be prepared by mixing the residual components in the colored dispersion liquid or the pigment dispersion liquid at a specific concentration. When the dye (A1-1) is included, the dye (A1-1) may be dissolved in part or all of the organic solvent (E) in advance to prepare a solution. Preferably, the solution is filtered through a filter with a pore size of about 0.01 to 1 μm. Moreover, it is preferable to filter the colored curable composition after mixing with a filter with a pore diameter of about 0.01 to 10 μm.

＜Manufacturing method of color filter＞ As a method of producing a colored pattern from the colored curable 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 applying the colored curable composition to a substrate and drying to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, since a photomask is not used during exposure and/or development is not performed, it is possible to form a colored coating film that is a hardened product of the colored composition layer. The colored pattern or colored coating film thus formed is the color filter of the present invention.

As the substrate, you can use: quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silicon dioxide and other glass plates; polycarbonate, polymethyl methacrylate, poly-p-phenylene Resin plates such as ethylene dicarboxylate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the above-mentioned substrate. Other color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of the pixels of each color using the photolithography method can be performed by well-known or customary devices or conditions. For example, it can be produced as follows. First, the colored curable composition is coated on a substrate, and heated and dried (pre-baked) and/or reduced-pressure drying is performed to dry and remove volatile components such as solvents to obtain a smooth colored composition layer. As a coating method, a spin coating method, a slit coating method, a slit-spin coating method, etc. are mentioned. 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. In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa and a temperature of 20 to 25°C. The film thickness of the colored composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through the mask for forming the target coloring pattern. The pattern on the mask is not particularly limited, and a pattern corresponding to the target application can be used. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a filter that cuts off the wavelength region can be used to cut off light that does not reach 350 nm, or a bandpass filter that extracts these wavelength regions can be used to selectively extract around 436 nm, around 408 nm, and around 365 nm Light. Specifically, as the light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. may be mentioned. In order to uniformly irradiate the entire exposure surface with parallel light, or to perform accurate position alignment of the mask and the substrate on which the colored composition layer is formed, it is preferable to use exposure devices such as a mask alignment exposure machine and a stepping exposure machine. .

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 of the basic compounds in the aqueous solution 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 of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate may be tilted to an arbitrary angle during development. After development, it is preferable to wash with water.

Furthermore, it is preferable to post-bak the obtained colored pattern. The post-baking temperature is preferably 150-250°C, more preferably 170-245°C, and still more preferably 180-240°C. The post-baking time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes.

The thickness of the coating film after post-baking is, for example, preferably 3 μm or less, more preferably 2.0 μm or less. The lower limit of the film thickness of the coating film is not particularly limited, and it is usually 0.3 μm or more, but may also be 0.5 μm or more.

According to the coloring curable composition of the present invention, a coloring curable composition can be provided, which can be used to manufacture a color filter with a good pattern shape, and the pattern has better reflow resistance during post-baking. The color filter can be used as a filter for display devices (such as liquid crystal display devices, organic EL (electroluminescence, electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices. [Example]

Hereinafter, the present invention will be described in more detail with examples. However, the present invention is of course not limited by the following examples. In the example, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

(Synthesis Example 1) A suitable amount of nitrogen was poured into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to form a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put in, and the mixture was heated to 80°C while stirring. Secondly, using a drip pump, will make 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 ^2,6 ] Decane-9-yl ester mixture (content ratio 1:1) 289 parts dissolved in 125 parts of propylene glycol monomethyl ether acetate solution was dropped into the flask over about 5 hours. On the other hand, using another drop pump, 33 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved in 235 parts of propylene glycol monomethyl ether acetate The resulting solution was added dropwise to the flask over a period of about 6 hours. After the dripping was completed, the solution was maintained at 80°C for 4 hours, and then cooled to room temperature to obtain a polymer (resin (B-1)) solution with a polymer solid content of 35.1%. The resulting copolymer (polymer; resin (B-1)) has a weight average molecular weight Mw of 9200, a dispersion degree of 2.08, and an acid value of 77 mg-KOH/g when converted to solid content. The resulting copolymer has the following structural units.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin is carried out under the following conditions using the GPC method (Gel Permeation Chromatography). Device; K2479 (manufactured by Shimadzu Corporation) String; SHIMADZU Shim-pack GPC-80M Column temperature; 40℃ Solvent; THF (tetrahydrofuran, tetrahydrofuran) Flow rate; 1.0 mL/min Detector; RI (refractive index detector, differential refractive index detector) Standard materials for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.) The ratio of the weight average molecular weight and the number average molecular weight (Mw/Mn) in terms of polystyrene obtained above is taken as the degree of dispersion.

(Synthesis Example 2) 276.8 g of propylene glycol monomethyl ether acetate was put into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the temperature was raised to 120°C while stirring with nitrogen replacement. Secondly, 35.3 g of 2-ethylhexanoic peroxide will be added to a monomer mixture containing 92.4 g of 2-ethylhexyl acrylate, 184.9 g of glycidyl methacrylate and 12.3 g of dicyclopentyl methacrylate. The tributyl ester (polymerization initiator) was added dropwise from the dropping funnel to the aforementioned flask over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120°C for 30 minutes to carry out a copolymerization reaction, and an addition copolymer was produced. After that, the inside of the flask was replaced with air, and 93.7 g of acrylic acid, 1.5 g of triphenylphosphine (catalyst), and 0.8 g of p-methoxyphenol (polymerization inhibitor) were put into the above-mentioned addition copolymer solution at 110°C. The reaction was continued for 10 hours, and the epoxy group was cleaved by the reaction between the epoxy group derived from glycidyl methacrylate and acrylic acid, and at the same time, a polymerizable unsaturated bond was introduced into the side chain of the polymer. Next, 24.2 g of succinic anhydride was added to the reaction system, and the reaction was continued at 110° C. for 1 hour to react the hydroxyl group generated by the cleavage of the epoxy group with the succinic anhydride, and a carboxyl group was introduced into the side chain to obtain a polymer. Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a polymer (resin (B-2)) solution with a polymer solid content of 40%. The weight average molecular weight Mw of the resulting copolymer (polymer; resin (B-2)) is 6.3×10 ³ , and the acid value in solid content conversion is 34 mg-KOH/g.

(Preparation of Dispersion 1) 14 parts of CI Direct Blue 86, 4.1 parts of dispersant (BYKLPN-6919 manufactured by BYK), 2.8 parts of resin (B-1) (solid content conversion), propylene glycol monomethyl ether acetic acid 79.1 parts of esters were mixed, 300 parts of 0.4 mm zirconia beads were added, and a paint conditioner (manufactured by LAU) was used to shake for 1 hour. After that, the zirconia beads were removed by filtration, and dispersion liquid 1 was obtained.

(Production of Dispersion 2) Mix 14 parts of CI Direct Blue 199, 4.1 parts of dispersant (BYKLPN-6919 manufactured by BYK), 2.8 parts of resin (B-1) (solid content conversion), and 79.1 parts of propylene glycol monomethyl ether acetate, and add 300 parts of 0.4 mm zirconia beads were shaken for 1 hour using a paint conditioner (manufactured by LAU). After that, the zirconia beads were removed by filtration, and dispersion liquid 2 was obtained.

[Examples 1 to 4, Comparative Examples 1 to 2] (Preparation of colored curable composition) The components shown in Table 5 were mixed to obtain each colored curable composition.

[table 5] The unit is (parts) Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Dispersion 1 480 480 480 480 Dispersion 2 480 Compound (z) 57 Resin (B) 47 47 47 47 60 47 Polymeric compound (C-1) 40 40 Polymeric compound (C-2) 40 Polymeric compound (C-3) 40 40 Polymeric compound (C-4) 40 Polymerization initiator (D) 5 5 5 5 5 5 Organic solvent (E-1) 458 Organic solvent (E-2) 708 708 708 708 458 708

In Table 5, the components are as follows. Compound (z): A compound represented by the following formula (z)

樹脂(B)：樹脂(B-2)(固形物成分換算) 聚合性化合物(C-1)：二季戊四醇聚丙烯酸酯(新中村化學工業(股)製造之「A9550」、固形物成分換算) 聚合性化合物(C-2)：環氧乙烷改性二季戊四醇六丙烯酸酯(新中村化學工業(股)製造之「A-DPH6E」、環氧乙烷鏈之數：6、固形物成分換算) 聚合性化合物(C-3)：環氧乙烷改性二季戊四醇六丙烯酸酯(新中村化學工業(股)製造之「A-DPH12E」、環氧乙烷鏈之數：12、固形物成分換算) 聚合性化合物(C-4)：環氧乙烷改性二季戊四醇六丙烯酸酯(新中村化學工業(股)製造之「A-DPH48E」、環氧乙烷鏈之數：48、固形物成分換算) 聚合起始劑(D)：N-乙醯氧基-1-(4-苯基硫基苯基)-3-環己基丙烷-1-酮-2-亞胺 有機溶劑(E-1)：4-羥基-4-甲基-2-戊酮 有機溶劑(E-2)：丙二醇單甲醚乙酸酯

Resin (B): Resin (B-2) (Solid content conversion) Polymerizable compound (C-1): Dipentaerythritol polyacrylate ("A9550" manufactured by Shinnakamura Chemical Industry Co., Ltd., solid content conversion) Polymerizable compound (C-2): Ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH6E" manufactured by Shinnakamura Chemical Industry Co., Ltd.), number of ethylene oxide chains: 6, solid content conversion ) Polymeric compound (C-3): ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH12E" manufactured by Shinnakamura Chemical Industry Co., Ltd.), number of ethylene oxide chains: 12, solid content Conversion) Polymeric compound (C-4): ethylene oxide modified dipentaerythritol hexaacrylate ("A-DPH48E" manufactured by Shinnakamura Chemical Industry Co., Ltd.), number of ethylene oxide chains: 48, solid matter Component conversion) Polymerization initiator (D): N-acetoxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine organic solvent (E- 1): 4-hydroxy-4-methyl-2-pentanone organic solvent (E-2): propylene glycol monomethyl ether acetate

(Production of coloring pattern) On a 4-inch silicon substrate, the coloring curable composition is applied by spin coating to make the film thickness after baking become 0.8 μm, and then pre-baked at 80°C 2 Minutes, and a colored composition layer is obtained. After cooling, an exposure machine (NSR-1755i7A; manufactured by Nikon Co., Ltd.) was used to irradiate the substrate on which the colored composition layer was formed with an exposure amount of ^{300 mJ/cm 2 (based on 365 nm).} The mask with a dot pattern of 1.0 μm square is used as the mask. The coloring composition layer after light irradiation was immersed and developed in an aqueous developer containing tetramethylammonium hydroxide at 23° C. for 30 seconds, and washed with water to obtain a coloring pattern I after development (before post-baking). Furthermore, the substrate on which the colored pattern I is formed is post-baked at 230° C. for 10 minutes to obtain the post-baked colored pattern II.

(Evaluation of Reflow Resistance of Colored Patterns) For the silicon wafer substrate with the colored pattern I or the colored pattern II obtained above, an electron microscope (S-4100, manufactured by Hitachi High-Tech Co., Ltd.) was used to observe the formed colored pattern at a magnification of 30,000 times. In the side view of the colored pattern (refer to Figure 1), the width of the colored pattern at 90% of the height hb (height indicated by hb in Figure 1) of the film thickness la (the length indicated by la in Figure 1) (Width represented by lc in Fig. 1) was measured, the rate of change of lc before and after post-baking was calculated (lc of coloring pattern II/lc of coloring pattern I×100(%)), and evaluation was performed according to the following criteria. The results are shown in Table 6. ○: The change rate of lc before and after post-baking is more than 90% △: The change rate of lc before and after post-baking is more than 70% and less than 90% ×: The change rate of lc before and after post-baking has not reached 70%

[Table 6] Reflow resistance Example 1 〇 Example 2 〇 Example 3 〇 Example 4 〇 Comparative example 1 X Comparative example 2 △

la: film thickness lc: width hb: height

Fig. 1 is a schematic side view of a colored pattern obtained from the colored curable composition of an example or a comparative example.

Claims (12)

A coloring and curable composition comprising a colorant, an organic solvent, a resin, a polymerizable compound, and a polymerization initiator. The colorant includes a compound represented by formula (I), and the polymerizable compound includes a compound represented by formula (II) The compound,

[In formula (I), X represents a hydrogen atom or a monovalent metal atom; R ¹ represents a substituted or unsubstituted amine group or a substituted or unsubstituted hydrocarbon group with 1 to 20 carbon atoms; n represents an integer of 1 to 4 M represents an integer from 0 to 4; when formula (I) has a plurality of Xs, X may be the same or different from each other, and when formula (I) has a plurality of R ^1s , R ¹ may be the same as each other May be different],

[In formula (II), Ra ^{represents a} linking group of (q+r) valence; R ^b represents an alkanediyl group with 1 to 20 carbon atoms; R ^c represents an acryloxy group or a methacryloxy group; p represents 0 or more Q represents an integer of 1 or more; r represents an integer of 0 or more; when formula (II) has a plurality of R ^b , R ^b may be the same or different from each other, and in formula (II), there is a plurality of R ^c In the case, R ^c may be the same or different from each other. When formula (II) has a plurality of p, p may be the same or different from each other; where, the sum of the integers represented by p in formula (II) Is 2 or more, and the total of the integer represented by q and the integer represented by r is 3 or more]. Such as the coloring and curable composition of claim 1, which comprises at least one selected from the group consisting of CI Direct Blue 86, CI Direct Blue 87, CI Direct Blue 199 and CI Reactive Blue 25 as the formula (I) Represents the compound. The requested item colored curable composition of 1 or 2, wherein the compound of the above formula (II) represented by the in, R ^a represents a carbon number within aliphatic hydrocarbon having 3 to 30 of removing the (q + r) obtained from the group after the hydrogen atom (The methylene group contained in the aliphatic hydrocarbon may be substituted with an oxygen atom to form an ether structure). The colored curable composition according to any one of claims 1 to 3, wherein in the compound represented by the above formula (II), R ^b represents an alkanediyl group having 1 to 10 carbon atoms. The colored curable composition according to any one of claims 1 to 4, wherein in the compound represented by the above formula (II), r represents an integer of 0-6. The colored curable composition according to any one of claims 1 to 5, wherein in the compound represented by the above formula (II), q represents an integer of 2-12. The colored curable composition according to any one of claims 1 to 5, wherein in the compound represented by the above formula (II), the sum of the integers represented by p in the formula (II) is 2-60. The colored curable composition according to any one of claims 1 to 7, wherein the above-mentioned resin has a structural unit containing a (meth)acryloyl group in a side chain. The colored curable composition according to any one of claims 1 to 8, wherein the polymerization initiator comprises an O-acetoxime-based compound. A color filter, which is formed of the colored curable composition according to any one of claims 1 to 9. A display device comprising the color filter as claimed in claim 10. A solid-state imaging device including the color filter as claimed in claim 10.

Images