TWI396736B - Cleaning fluid for pigment-dispersed colored resin composition - Google Patents

Description

Pigment dispersion type colored resin composition cleaning solution

The present invention relates to a cleaning liquid for washing a pigment dispersion type colored resin composition. More specifically, it relates to a cleaning liquid suitable for washing a production line or a pipe in a process of a pigment-dispersed colored resin composition or a color filter using the pigment-dispersed colored resin composition.

In the production of a color filter constituting a liquid crystal display (LCD), a method of forming a filter segment of a respective color by applying a pigment-dispersed colored resin composition to a glass substrate is generally employed. When a solid material such as a dust particle or a pigment-dispersed colored resin composition is mixed into the color filter process or the pigment-dispersed coloring resin composition, ruthenium occurs in the color filter. Therefore, it is extremely important to clean the production line or fittings. In many cases, the main solvent contained in the pigment-dispersed colored resin composition is used as a washing liquid for the above washing (for example, JP-A-2003-260404).

However, in the case of a manufacturing apparatus which washes the pigment dispersion type colored resin composition by the main solvent contained in the pigment dispersion type colored resin composition, the solubility of the cured material of the pigment dispersion type colored resin composition is poor or even when solubility When it is good, it also takes a long time to completely remove the cured material. Therefore, it is necessary to use a large amount of cleaning liquid or to substantially remove the solidified material. One problem is the occurrence of a mixture of reduced productivity or the possibility of foreign matter. Further, in the case of washing the coating liquid tube of the color filter manufacturing apparatus, even when the main solvent contained in the pigment dispersion type colored resin composition is used, the dispersion of the pigment is also due to the cleaning liquid and the pigment dispersion type. The colored resin composition is damaged by contact, and therefore, aggregation of the pigment may occur in some cases. When the above aggregates remain in the tube, a problem is that the aggregates will generate defects in the color filter.

An object of the present invention is to provide an excellent dispersibility and removability of a pigment-dispersed colored resin composition and a cured material thereof, and an aggregate of pigments is not produced even when it is in contact with a pigment-dispersed colored resin composition. The cleaning solution.

The present invention provides a cleaning solution for a pigment-dispersed colored resin composition comprising a ketone solvent (a) and an ester solvent (b) containing a monocarboxylic acid and a monohydric alcohol.

The cleaning liquid of the present invention contains a ketone solvent which is generally used as a main solvent of a pigment-dispersed colored resin composition and which is excellent in solubility of a cured material of a pigment-dispersed colored resin composition, and further includes an ester containing a monocarboxylic acid and a monohydric alcohol. The solvent, wherein the cured material of the pigment-dispersed colored resin composition of the ester solvent has poor solubility, but has the effect of promoting the peeling of the cured material from the base material. Therefore, when it is used in a manufacturing apparatus for cleaning a pigment-dispersed colored resin composition or a manufacturing apparatus using a color filter of a pigment-dispersed colored resin composition, the solubility of the cured substance of the pigment-dispersed colored resin composition Excellent and ready for immediate cleaning. Further, even when the cleaning liquid of the present invention is in contact with the pigment-dispersed colored resin composition, it does not generate aggregates. Therefore, by washing the manufacturing apparatus with the cleaning liquid of the present invention, the operation rate of the apparatus can be improved, and a high-quality coated substance can also be produced with high yield.

The cleaning solution for the pigment dispersion type colored resin composition provided by the present invention will be clearly described below.

The cleaning solution for the pigment dispersion type colored resin composition provided by the present invention comprises a ketone solvent (a) and an ester solvent (b) containing a monocarboxylic acid and a unit alcohol.

The ketone solvent (a) is generally a solvent which is a main solvent of the pigment dispersion type colored resin composition. Examples of the ketone solvent include acetamidine acetone (140 ° C), acetophenone (202 ° C), acetone (55 ° C), isophorone (215 ° C), ethyl n-butyl ketone (144 ° C), diacetone alcohol (169 ° C), diisobutyl ketone (163 ° C), diisopropyl ketone (124 ° C), diethyl ketone (102 ° C), cyclohexanone (156 ° C), di-n-propyl ketone (144 ° C ), phorbolone (198 ° C), methyl n-amyl ketone (152 ° C), methyl isobutyl ketone (116 ° C), methyl ethyl ketone (80 ° C), methyl cyclohexanone (170 ° C ), methyl n-butyl ketone (127 ° C), methyl n-propyl ketone (103 ° C), methyl n-hexyl ketone (173 ° C) and methyl n-heptyl ketone (195 ° C). The values in parentheses refer to the boiling point.

The ketone solvent (a) may be used singly or in combination of at least two ketone solvents (a). In view of the drying property, the ketone solvent (a) preferably has a boiling point between 100 ° C and 200 ° C, more preferably between 115 ° C and 170 ° C. When a ketone solvent having a boiling point higher than 200 ° C is used, the drying property of the washing liquid is lowered and in some cases, a drying step after washing is required. When a ketone solvent having a boiling point of less than 100 ° C is used, the detergency property may be impaired in some cases due to too fast drying, and it is also unsatisfactory in view of safety.

In view of drying properties and solubility, the ketone solvent (a) is preferably a mixture of cyclohexanone, acetamidineacetone or cyclohexanone and acetamidine.

The ester solvent (b) containing a monocarboxylic acid and a monohydric alcohol is a solvent which has an effect of promoting the peeling of the cured material of the pigment dispersion type colored resin composition from the base material. Examples of the ester solvent (b) containing a monocarboxylic acid and a monohydric alcohol include amyl acetate (149 ° C), isoamyl acetate (142 ° C), isobutyl acetate (117 ° C), and isopropyl acetate (89 ° C). Ethyl acetate (77 ° C), 2-ethylhexyl acetate (199 ° C), cyclohexyl acetate (177 ° C), n-butyl acetate (126 ° C), dibutyl acetate (112 ° C), acetic acid Propyl ester (102 ° C), benzyl acetate (216 ° C), methyl acetate (57 ° C), isoamyl lactate (82 ° C), ethyl lactate (154 ° C), butyl lactate (187 ° C), lactate A Ester (144 ° C), isoamyl propionate (161 ° C), ethyl propionate (99 ° C), butyl propionate (147 ° C), benzyl propionate (220 ° C), methyl propionate (80 ° C ), isoamyl butyrate (185 ° C), isopropyl butyrate (128 ° C), ethyl butyrate (121 ° C), butyl butyrate (167 ° C) and methyl butyrate (103 ° C). The values in parentheses refer to the boiling point.

The ester solvent (b) may be used singly or at least two ester solvents (b) may be mixed and used in combination. In view of the drying property, the ester solvent (b) preferably has a boiling point between 100 ° C and 200 ° C, more preferably between 115 ° C and 170 ° C. When an ester solvent having a boiling point higher than 200 ° C is used, the drying property of the washing liquid is lowered and in some cases, a drying step after washing is required. When an ester solvent having a boiling point of less than 100 ° C is used, the detergency property may be impaired in some cases due to too fast drying, and it is also unsatisfactory in view of safety.

In view of the mixing stability and drying property with the pigment-dispersed colored resin composition, the above ester solvent (b) is preferably a mixture of n-butyl acetate, isobutyl acetate or n-butyl acetate and isobutyl acetate.

The weight ratio (a)/(b) of the ketone solvent (a) in the cleaning solution for the pigment dispersion type colored resin composition provided by the present invention and the ester solvent (b) containing the monocarboxylic acid and the unit alcohol is from 1 /9 to 9/1 is preferred, preferably from 1/3 to 3/1. When the amount of the ketone solvent (a) is less than 1/9 ((a)/(b)), the solubility of the cured material of the pigment-dispersed colored resin composition is poor, and in addition, if the cleaning liquid and the pigment are dispersed When the colored resin composition is contacted, in some cases, aggregates of the pigment are generated due to destruction of the dispersed state of the pigment. When the amount of the ketone solvent (a) is more than 9/1 ((a)/(b)), the pigment-dispersed colored resin composition cannot be quickly washed in some cases.

The pigment dispersion type colored resin composition provided by the present invention may comprise, in a washing solution of 100 parts by weight, at least one of the above ketone solvent (a) and a monocarboxylic acid and a unit alcohol in an amount of 30 parts by weight or less. A solvent other than the ester solvent (b). Examples of the solvent other than the ketone solvent (a) and the ester solvent (b) containing a monocarboxylic acid and a monohydric alcohol include an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an alcohol solvent, an ether solvent, a nitrogen-containing solvent such as an amine, a guanamine or An ester solvent other than a nitrile and an ester solvent containing a monocarboxylic acid and a monohydric alcohol. It is preferred to select such solvents in view of drying properties.

The cleaning solution for the pigment-dispersed colored resin composition of the present invention is suitable for use in a manufacturing apparatus for cleaning a pigment-dispersed colored resin composition or a color filter using a pigment-dispersed colored resin composition, and the like. Such as mixers, ducts, filters, tanks and coaters. Further, it is also suitable for washing the end face or the reverse side of the substrate of the coated pigment-dispersed colored resin composition.

The cleaning solution for a pigment-dispersed colored resin composition provided by the present invention can be used for washing a conventional pigment-dispersed colored resin composition. The pigment dispersion type colored resin composition generally comprises a pigment carrier made of a resin, a precursor thereof or a mixture thereof, a pigment, and an organic solvent. Further, when patterning is carried out by photolithography in the manufacture of a color filter or the like, it further contains a photoinitiator, a sensitizer, and the like.

Examples of the resin contained in the pigment-dispersed colored resin composition include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate. Copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, rubber-containing resin, resin containing cyclized rubber, epoxy resin, benzoguanamine Resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin and phenol resin. Among these resins, the cleaning liquid of the present invention is particularly useful for a pigment dispersion-type colored resin composition containing an acrylic resin as a pigment carrier.

Examples of the organic solvent contained in the pigment-dispersed colored resin composition include 2-heptanone, 4-heptanone, cyclohexanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, n-amyl acetate, Methyl isobutyl ketone, n-butanol, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, N, N-dimethyl Formamide, 1,2,3-trichloropropane, o-chlorotoluene, o-xylene, m-xylene, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-1,3-propanediol, diisobutylketone, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monobutyl ether Acid ester, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol Monomethyl ether, dipropylene Monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, 3-ethoxyethyl propionate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate Ester, γ-butyrolactone, N,N-dimethylacetamide, N-methylpyrrolidone, p-chlorotoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, o-dichlorobenzene , m-dichlorobenzene, n-butylbenzene, t-butylbenzene, t-butylbenzene, cyclohexanol and methylcyclohexanol. Among these organic solvents, the cleaning solution of the present invention contains, in particular, cyclohexanone, isoamyl acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate, ethylene glycol monobutyl ether, propionic acid 3- The pigment-dispersed colored resin composition of ethoxyethyl ester or γ-butyrolactone has high efficiency.

[Examples]

The invention will be more clearly described with reference to the following examples. The present invention is not limited to the embodiments unless the basic points are violated.

In the examples and comparative examples, "parts" means "parts by weight".

First, the preparation of the acrylic resin solution of the pigment dispersion type colored resin composition used in the examples and the comparative examples will be described. The molecular weight of the resin refers to the weight average molecular weight calculated in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of acrylic resin solution)

800 parts of cyclohexanone was added to the reaction vessel, and heated to 100 ° C while introducing nitrogen into the vessel. A mixture of 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyronitrile was added dropwise at the above temperature for 1 hour. To carry out the polymerization reaction.

After the dropwise addition was completed, the reaction mixture was further reacted at 100 ° C for 3 hours. Then, a solution of 2.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the resulting mixture was further reacted at 100 ° C for 1 hour to prepare a solution of an acrylic resin. This acrylic resin has a weight average molecular weight of about 40,000.

After cooling to room temperature, about 2 g of the resin solution was sampled and dried under heat at 180 ° C for 20 minutes, and the nonvolatile content was measured. The cyclohexanone was added to the above-prepared resin solution so that the nonvolatile content was 20% by weight, and thus an acrylic resin solution was prepared.

Next, the preparation of the pigment dispersion type colored resin composition used in the examples and comparative examples will be explained.

(Preparation of pigment-dispersed blue resin composition)

Prepared in the preparation of 12.0 parts of blue pigment (BASF supply, "Heliogen Blue L-6700F"), 2.4 parts of pigment dispersant (Avecia KK supplied, "Solsperse 20000"), and 28.1 parts of acrylic resin solution. The acrylic resin solution and 57.5 parts of cyclohexanone were uniformly stirred and mixed, and then dispersed by a sand mill using a glass bead having a diameter of 1 mm for 5 hours. Filtration was carried out using a 5 micron filter to prepare a blue pigment dispersion.

Then, 45.0 parts of the blue pigment dispersion thus obtained, 12.5 parts of the acrylic resin solution prepared in the preparation of the acrylic resin solution, and 4.8 parts of trimethylolpropane triacrylate (Shin-Nakamura Chemical Co) were prepared. ., Ltd. supplied, "NK ester ATMPT"), 2.5 parts of photoinitiator ("Irgacure 907" supplied by Ciba Specialty Chemicals Co.), and 0.2 parts of sensitizer (Supply supplied by Hodogaya Chemical Co., Ltd., " EAB-F"), 25.0 parts of cyclohexanone and 10.0 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. Then, filtration was carried out using a 1 μm filter to obtain a pigment-dispersed blue resin composition.

(Preparation of pigment-dispersed red resin composition)

5.08 parts of red pigment ("Irgaphor Red B-CF" supplied by Ciba Specialty Chemicals Co.), 0.82 parts of red pigment ("Chromophthal Red A2B" supplied by Ciba Specialty Chemicals Co.), and 0.20 parts of yellow pigment (Ciba) Acquired by Specialty Chemicals Co., "Chromophthal Yellow GT-AD"), 2.4 parts of pigment dispersant (Avecia KK supplied, "Solsperse 20000"), 28.1 parts of acrylic resin solution prepared in the preparation of acrylic resin solution And 57.5 parts of cyclohexanone were uniformly stirred and mixed, and then dispersed by a sand mill using a glass bead having a diameter of 1 mm for 5 hours. Filtration was carried out using a 5 micron filter to prepare a red pigment dispersion.

Then, 50.9 parts of the red pigment dispersion thus obtained, 6.8 parts of the acrylic resin solution prepared in the preparation of the acrylic resin solution, and 4.8 parts of trimethylolpropane triacrylate (Shin-Nakamura Chemical CO.) were prepared. , Ltd. supply, "NK ester ATMPT"), 2.5 parts of photoinitiator ("Irgacure 907" supplied by Ciba Specialty Chemicals Co.), 0.2 parts of sensitizer (Supply supplied by Hodogaya Chemical Co., Ltd., "EAB -F"), 10.0 parts of cyclohexanone and 25.0 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. Then, filtration was carried out using a 1 μm filter to prepare a pigment-dispersed red resin composition.

(Preparation of pigment-dispersed green resin composition)

3.25 parts of green pigment (available from Toyo Ink Mfg. Co., Ltd., "Lionol Green 6YK"), 2.35 parts of yellow pigment (Bayer supply, "Fanchon Fast Yellow Y-5688"), 2.4 parts of pigment dispersant (Available from Avecia KK, "Solsperse 20000"), 28.1 parts of the acrylic resin solution prepared in the preparation of the acrylic resin solution and 57.5 parts of cyclohexanone were uniformly stirred and mixed, and then used by a sand mill using a diameter of 1 mm. The glass beads were dispersed for 5 hours. Filtration was carried out using a 5 micron filter to prepare a green pigment dispersion.

Then, 46.5 parts of the green pigment dispersion thus obtained, 11.2 parts of the acrylic resin solution prepared in the preparation of the acrylic resin solution, and 4.6 parts of trimethylolpropane triacrylate (Shin-Nakamura Chemical Co.) were prepared. , Ltd. supply, "NK ester ATMPT"), 2.5 parts of photoinitiator ("Irgacure 907" supplied by Ciba Specialty Chemicals Co.), 0.2 parts of sensitizer (Supply supplied by Hodogaya Chemical Co., Ltd., "EAB -F"), 10.0 parts of cyclohexanone and 25.0 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. Then, filtration was carried out using a 1 μm filter to prepare a pigment-dispersed green resin composition.

[Examples 1 to 6 and Comparative Examples 1 to 4]

A washing liquid was prepared by mixing the solvents in the amounts shown in Table 1. The solubility, mixing stability, and removability of each of the washing liquids were evaluated by the following methods. Table 2 shows the results.

(solubility test)

1 g of the pigment-dispersed red resin composition, the pigment-dispersed green resin composition, and the pigment-dispersed blue resin composition were respectively dropped on a glass substrate, and allowed to stand for 2 hours to obtain respective cured substances. . 0.3 g of each of the cured materials was mixed with 2 g of the cleaning solution, and after 2 days, the dissolved state was visually observed. Evaluation is performed on a scale of 1 to 4.

⊙: Completely dissolved.

○: A small amount of fine aggregates was observed.

△: The solidified substance was dissolved but a large amount of precipitate was found.

×: Almost undissolved.

(mixing stability)

Each of 1 g of the pigment-dispersed red resin composition, the pigment-dispersed green resin composition, and the pigment-dispersed blue resin composition was mixed with 6 g of the washing liquid, and after 2 days, the mixed state was visually observed. . Evaluation is performed on a scale of 1 to 4.

⊙: Dissolved completely compatible.

○: A small amount of fine aggregates was observed.

△: A large amount of precipitate was found.

×: The pigment contents were completely aggregated and precipitated and the supernatant was transparent.

(Removal of coated film)

Each of the pigment-dispersed red resin composition, the pigment-dispersed green resin composition, and the pigment-dispersed blue resin composition was applied to a stainless steel substrate by a spin coating method so that the dried film had a thickness of 2.5 μm. Each coated substrate was immersed in a washing liquid stirred by a magnet stirrer, and the state in which the coated film was removed from the substrate was visually observed. Evaluation is performed on a scale of 1 to 4.

⊙: Remove completely within 20 seconds from the immersion.

○: Completely removed within 40 seconds from the immersion.

△: Completely removed within 60 seconds from the immersion.

×: Even after 60 seconds, it was not completely removed.

The cleaning liquid of the present invention obtained in Examples 1 to 6 is excellent in solubility and removability to the pigment-dispersed colored resin composition. Even when it is in contact with the pigment-dispersed colored resin composition, pigment aggregates hardly appear. On the other hand, the cleaning liquids prepared in Comparative Examples 1 to 4 could not satisfy all three of solubility, mixing stability, and removability.

Claims (2)

A cleaning solution for a pigment-dispersed colored resin composition comprising a ketone solvent (a) and an ester solvent (b) containing a monocarboxylic acid and a monohydric alcohol, wherein the ketone solvent (a) is cyclohexanone Ethylacetone or a mixture thereof, the ester solvent (b) is a mixture of n-butyl acetate, isobutyl acetate or the like. The cleaning solution according to claim 1, wherein the weight ratio (a)/(b) of the ketone solvent (a) to the ester solvent (b) is from 1/9 to 9/1.