COLORED RESIN COMPOSITION

Abstract

Provided is a colored resin composition excellent in storage stability. The colored resin composition according to the present invention is a colored resin composition comprising a colorant, a resin and a solvent, the colorant comprising a dye, the solvent comprising a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent which is a ketone having 3 to 12 carbon atoms, and the ketone being a chain or branched saturated ketone comprising only an oxygen atom of a carbonyl group as a heteroatom.

Claims

1. A colored resin composition comprising a colorant, a resin and a solvent, the colorant comprising a dye, the solvent comprising a first solvent which is propylene glycol monomethyl ether acetate, and a second solvent which is a ketone having 3 to 12 carbon atoms, and the ketone being a chain or branched saturated ketone comprising only an oxygen atom of a carbonyl group as a heteroatom.

2. The colored resin composition according to claim 1, wherein the dye comprises a squarylium dye.

3. A cured film formed of the colored resin composition according to claim 1.

4. A color filter formed of the colored resin composition according to claim 1.

5. A cured film formed of the colored resin composition according to claim 2.

6. A color filter formed of the colored resin composition according to claim 2.

Description

EXAMPLES

[0141] Hereinafter, the present invention will be described in more detail by way of Examples, which should not be construed as limiting the present invention. In Examples, the term % and the term parts for expressing the content or the used amount are by mass unless otherwise specified.

[0142] In Synthesis Examples below, the structures of compounds were identified by NMR (JNM-EX-270 (manufactured by JEOL Ltd.)).

Synthesis Example 1

Synthesis of Squarylium Dye a1

[0143] 10.0 parts of 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.0 parts of 2-ethylhexane bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 44.0 parts of tetrabutylammonium bromide (manufactured by Wako Kagaku Kogyo K.K.) were mixed. The resulting mixture was stirred at 90 C. for 8 hours. After completion of the reaction, 50 parts of 10% sodium bicarbonate water was added, 100 parts of ethyl acetate was then added, and the aqueous layer was discarded. The operation of washing with water and 10% chloric acid was repeated twice, and the solvent was then distilled away. The obtained oil was dried under reduced pressure at 60 C. for 24 hours to give 9.3 parts of a compound represented by the following formula (d-1).

##STR00013##

[0144] .sup.1H-NMR of the compound represented by formula (d-1) (270 MHz, value (ppm, referenced to TMS), DMSO-d6) 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.59 (br, 1H), 2.04 (s, 3H), 2.12 (s, 3H), 2.91 (d, 2H), 4.37 (br, 1H), 6.38 (d, 1H), 6.75 (s, 1H), 6.77 (d, 1H)

[0145] 3.0 parts of the thus-obtained compound (d-1), 2.2 parts of 3-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.015 parts of palladium acetate, 3.2 parts of (tert-butoxy)sodium (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.055 parts of tri-tert-butylphosphine and 25.6 parts of toluene were mixed, and the resulting mixture was stirred at 100 C. for 15 hours. 30 parts of ethyl acetate and 100 parts of water were added to the resulting mixture, and the aqueous layer was discarded. The operation of washing with water was repeated twice, and the solvent was then distilled away. The residue was purified by silica gel chromatography (chloroform/hexane=1/1), and the obtained oil was dried under reduced pressure at 60 C. for 24 hours to give 1.9 parts of a compound represented by the following formula (d-2).

##STR00014##

[0146] .sup.1H-NMR of the compound represented by formula (d-2) (270 MHz, value (ppm, referenced to TMS), DMSO-d6) 0.85 (m, 6H), 1.23-1.42 (br, 8H), 1.55 (br, 1H), 1.94 (s, 3H), 2.27 (s, 3H), 2.90 (d, 2H), 6.37 (d, 1H), 6.75 (s, 1H), 6.76 (d, 1H), 6.92-7.14 (m, 4H), 8.93 (s, 1H)

[0147] 4.4 parts of the thus-obtained compound represented by formula (d-2), which is an intermediate, 0.8 parts of 3,4-dihydroxy-3-cyclobuten-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 90.0 parts of 1-butanol and 60.0 parts of toluene were mixed. The resulting mixture was stirred at 125 C. for 3 hours while water generated was removed using a Dean-Stark tube. After completion of the reaction, the solvent was distilled away, 15 parts of acetic acid was added, the resulting mixture was then added dropwise to 100 parts of a 18% salt solution, and the precipitated solid was taken by filtration. The solid taken by filtration was washed with hexane. The obtained solid was dried under reduced pressure at 60 C. for 24 hours to give 4.9 parts of a compound (squarylium dye al) represented by formula (AII-8) .

##STR00015##

[0148] .sup.1H-NMR of the compound represented by formula (AII-8) (270 MHz, value (ppm, referenced to TMS), DMSO-d6) 0.87 (m, 12H), 1.21-1.57 (m, 16H), 1.72 (br, 2H), 2.05 (s, 6H) , 2.36 (s, 6H) , 3.37 (br, 2H) , 3.78 (br, 2H) , 6.00 (br, 4H), 6.97-7.12 (m, 6H), 7.77-7.95 (m, 2H), 11.35 (s, 1H), 12.06 (s, 1H)

Synthesis Example 2

Synthesis of Yellow Dye a2

[0149] A compound (yellow dye a2) represented by the following formula was produced by a method for producing a compound represented by formula (Ad2-14) as disclosed in Japanese Patent Laid-Open No. 2016-11419. The compound represented by the following formula is the same compound as the compound represented by formula (Ad2-14) in Japanese Patent Laid-Open No. 2016-11419.

##STR00016##

Synthesis Example 3

Synthesis of Resin b1

[0150] An appropriate amount of nitrogen was fed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere within the flask with a nitrogen atmosphere, and 290 parts of propylene glycol monomethyl ether acetate was put in the flask, and heated to 85 C. with stirring. Subsequently, a mixed solution of 94 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0.sup.2..sup.6]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0.sup.2.6]decan-9-yl acrylate (content ratio: 1:1), 61 parts of 4-vinylbenzoic acid, 157 parts of phenyl methacrylate and 250 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours.

[0151] On the other hand, a mixed solution obtained by dissolving 9 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 110 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition, the inside of the flask was held at 85 C. for 3 hours, and then cooled to room temperature to give a copolymer (resin bl) solution having a B-type viscosity of 70 mPas (23 C.) and a solid content of 28.2 wt %. The generated resin bl had a weight average molecular weight (Mw) of 17000 and a molecular weight distribution (Mw/Mn) of 2.23. The resin bl has the structural units shown below.

##STR00017##

[0152] The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin b1 in terms of polystyrene were measured by a GPC method under the following conditions.

[0153] Apparatus: HLC-8120GPC (manufactured by TOSOH Corporation)

[0154] Column: TSK-GELG2000HXL

[0155] Column temperature: 40 C.

[0156] Solvent: THF

[0157] Flow rate: 1.0 mL/min

[0158] Test liquid solid content concentration: 0.001 to 0.01 mass %

[0159] Injection amount: 50 L

[0160] Detector: RI

[0161] Standard substances for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500 and A-500 (manufactured by TOSOH Corporation)

[0162] The ratio between the thus-obtained weight average molecular weight and number average molecular weight (Mw/Mn) in terms of polystyrene was defined as a molecular weight distribution.

[Preparation of Colored Resin Composition]

[0163] The colored resin compositions of Examples 1 to 15 and Comparative Examples 1 to 3 were obtained by mixing the ingredients in accordance with the compositions shown in Tables 2 and 3 below. The compositions shown in Tables 2 and 3 each represent an amount in terms of solid content except for the solvent (E). The unit of the numerical value for each ingredient in Tables 2 and 3 is the number of parts by mass.

[0164] The ingredients in Tables 2 and 3 are shown below. The ingredients of the second solvent are as described in Tables 2 and 3.

[0165] Squarylium dye a1: compound synthesized in Synthesis Example 1

[0166] Yellow dye a2: compound synthesized in Synthesis Example 2

[0167] Resin b1: resin synthesized in Synthesis Example 3 PGMEA: propylene glycol monomethyl ether acetate Leveling agent f1: MEGAFAC (R) F554 (manufactured by DIC Corporation)

<Evaluation of Storage Stability>

[0168] Sealed sample tubes containing the colored resin compositions of Examples 1 to 15 and Comparative Examples 1 to 3, respectively, were stored at 5 C. in incubators (MIR-554PJ and MIR-154PJ manufactured by Panasonic). After the sample tubes were stored for 4 weeks, whether insoluble substances in the colored rein composition were precipitated was examined, and evaluation was performed as follows. Tables 2 and 3 show the evaluation results. [0169] A: Insoluble substances are not present. [0170] B: Insoluble substances are present.

TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 Colorant (A) Squarylium dye a1 (parts by part) 13 13 13 13 13 13 13 13 13 Yellow dye a2 (parts by part) 29 29 29 29 29 29 29 29 29 Resin (B) Resin b1 (parts by part) 100 100 100 100 100 100 100 100 100 Leveling agent (F) Leveling agent f1 (parts by part) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (E) First solvent PGMA (parts by part) 587 666 766 587 666 766 587 666 766 Second solvent 2-Heptane (parts by part) 252 285 328 2-Octane (parts by part) 252 285 328 Diisobutyl ketone 252 285 328 (parts by part) Acetone (parts by part) Methyl isobutyl ketone (parts by part) Solid content concentration (%) 14.5 13.0 11.5 14.5 13.0 11.5 14.5 13.0 11.5 Storage stability A A A A A A A A A

TABLE-US-00003 TABLE 3 Compara- Compara- Compara- tive tive tive Example Example Example Example Example Example Example Example Example 10 11 12 13 14 15 1 2 3 Colorant (A) Squarylium dye a1 (parts by part) 13 13 13 13 13 13 13 13 13 Yellow dye a2 (parts by part) 29 29 29 29 29 29 29 29 29 Resin (B) Resin b1 (parts by part) 100 100 100 100 100 100 100 100 100 Leveling agent (F) Leveling agent f1 (parts by part) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Solvent (E) First solvent PGMA (parts by part) 587 666 766 587 666 766 839 951 1094 Second solvent 2-Heptane (parts by part) 2-Octane (parts by part) Diisobutyl ketone (parts by part) Acetone (parts by part) 252 285 328 Methyl isobutyl ketone 252 285 328 (parts by part) Solid content concentration (%) 14.5 13.0 11.5 14.5 13.0 11.5 14.5 13.0 11.5 Storage stability A A A A A A B B B

[0171] As shown in Tables 2 and 3, Examples 1 to 15 which are the colored resin compositions of the invention of the present application had storage stability superior over Comparative Examples 1 to 3.