JP2007161866A - Coloring composition and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition reducing defects observed in a coated film when coated by a spin coating method and a die coating method, and to provide a color filter provided with a filter segment scarcely observing the defects of the coated film. <P>SOLUTION: The coloring composition comprises a dye carrier composed of a transparent resin, a precursor or a mixture thereof, a dye, an organic solvent and an antistatic agent. The coloring composition comprises the organic solvent A having ≤10.0 dielectric constant at 25°C, ≤1 nS/cm electroconductivity at 25°C and ≤1.5 mPa s viscosity at 25°C as the organic solvent in an amount within the range of ≥5 wt.% based on the total amount of the organic solvent. The coloring composition has ≥8.0 dielectric constant at 25°C, ≥100 nS/cm electroconductivity at 25°C and ≤20 mPa s viscosity at 25°C. The color filter is provided with the filter segment formed from the coloring composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a coloring composition used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter using the same.

For color filters that make up liquid crystal displays (LCDs), color image pickup tube elements (CCDs), etc., a coating solution (colored composition) is applied to a transparent substrate and dried to form a coating film with a thickness of about 1 to 3 μm. It is manufactured by doing. Examples of the coating method on the substrate include a spin coating method and a die coating method, which are appropriately used depending on the characteristics.
The spin coating method is widely used for forming a thin film on a relatively small-sized substrate. While rotating the transparent substrate at a constant rotational speed, the coating solution is dropped onto the central portion of the transparent substrate and centrifugal force is applied. Is a coating method in which a coating film having a desired film thickness is formed on the surface of the transparent substrate by extending the coating solution thinly and controlling the number of revolutions and the rotation time of the transparent substrate suitable for the coating solution. However, due to the principle of extending the coating film thinly by utilizing the centrifugal force due to rotation, there is a drawback that the coating film thickness at the rotation center portion and the peripheral portion of the transparent substrate becomes too thick compared to the intermediate portion.

The die coating method is a method suitable for forming a thin film on a large-sized substrate, and a coating method of discharging a coating liquid from a slit and forming a coating film having a desired film thickness on the surface of the transparent substrate while moving the slit. It is. However, due to the mechanism, stripe-like unevenness (straight unevenness) is likely to occur in a direction perpendicular to the direction of movement of the slit, and the outer peripheral portion of the coating film rises and the film thickness becomes thicker than the central portion of the substrate.
Further, there is a problem that pinholes (white spots) occur if the drying property and surface tension of the coating solution are not appropriate regardless of the coating method.
Various attempts have been made to solve the problem of non-uniformity of the coating film in the spin coating method and the die coating method. For example, Patent Document 1 discloses a composition containing 50% by weight or more of a solvent having a boiling point or vapor pressure within a specific range as a composition for a spin coating method having excellent surface smoothness of a coating film. Yes. Patent Document 2 discloses a coating solution and a coating method for adjusting the surface tension of the coating solution to a certain range in the die coating method to reduce unevenness of the coating surface, film thickness unevenness, and the like.

Further, in any coating method such as a spin coating method or a die coating method, it is preferable that the viscosity of the coloring composition is as low as possible in order to form a uniform thin film on the substrate. The more the colored composition having a higher viscosity is used, the more difficult it is to form a thin film. In addition, a colored composition in which a pigment is dispersed in an organic solvent and having a high viscosity tends to have a large difference between the viscosity in a dynamic state and the viscosity in a static state (high thixotropy). There are some, and when a thin film is formed using such a colored composition, a thin film with poor uniformity of film thickness is obtained.
Therefore, it is necessary to make a colored composition having as low a viscosity as possible. As one of the means, there is a method of containing a low-viscosity solvent. However, many low-viscosity solvents that can be used in the colored composition for color filters have high chargeability due to low dielectric constant and electrical conductivity, and are liable to cause coating unevenness due to charging.
On the other hand, Patent Document 3 discloses a method in which conductive fine particles are added to a colored composition, the electrical conductivity of the colored composition is adjusted to a certain level or more, and film thickness unevenness is reduced.
JP-A-6-3521 JP 2004-66232 A Japanese Patent Laid-Open No. 10-287816

Various defects are observed in the coating film due to the coating method such as the spin coating method and the die coating method, and the properties of the coating liquid used for the coating method (including the above-mentioned charging property). become that way.
White spots: "White spots = pinhole-like defects"
Color unevenness: "Edge color unevenness = frame-like color unevenness observed at the edge, the boundary is relatively clear" and "Overall color unevenness = blurred color unevenness of the boundary observed over the entire substrate" There are two categories.
Unevenness of film thickness: Insufficient film thickness uniformity, “film thickness uniformity (edge) = film thickness uniformity of end face” and “film thickness uniformity (other than edge) = substrate It is classified into “uniformity from the center to the front of the end face”.
Stripe: “Striped unevenness that occurs in the direction perpendicular to the direction of slit movement in the striped die-die coating method”

The problem is how to reduce these drawbacks. However, as described in the above-mentioned patent document, a method of selecting a specific solvent, a method of using a composition in which the surface tension and viscosity are adjusted within a certain range, and coloring. It is not sufficient to add conductive fine particles to the composition to adjust the conductivity of the colored composition to a certain level or more.
An object of this invention is to provide the coloring composition which can reduce the said fault observed by a coating film, when apply | coating by the spin coat method and the die coat method. Another object of the present invention is to provide a color filter having a filter segment in which the above-mentioned coating film defects are hardly recognized.

The coloring composition of the present invention is a coloring composition containing a dye carrier composed of a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and an antistatic agent, and is 25 ° C. as an organic solvent. Contains an organic solvent A having a dielectric constant of 10.0 or less at 25 ° C., an electrical conductivity of 1 nS / cm or less at 25 ° C. and a viscosity of 1.5 mPa · s or less at 25 ° C. in a range of 5% by weight or more based on the total amount of the organic solvent The coloring composition is characterized in that the dielectric constant at 25 ° C. is 8.0 or more, the conductivity at 25 ° C. is 100 nS / cm or more, and the viscosity at 25 ° C. is 20 mPa · s or less.
Moreover, the color filter of this invention comprises the filter segment formed from the coloring composition of this invention, It is characterized by the above-mentioned.

Although the coloring composition of the present invention contains a low-viscosity organic solvent having high chargeability due to low dielectric constant and electrical conductivity, it is necessary for forming a uniform thin film by containing an antistatic agent. It is possible to achieve both a reduction in viscosity of a coloring composition and suppression of chargeability, and to form a uniform coating film with reduced defects of the coating film.
Therefore, it is possible to provide a good color filter by forming a filter segment using the colored composition of the present invention.

First, the coloring composition of this invention is demonstrated concretely.
The coloring composition of the present invention is a coloring composition containing a dye carrier composed of a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and an antistatic agent, and is 25 ° C. as an organic solvent. Contains an organic solvent A having a dielectric constant of 10.0 or less at 25 ° C., an electrical conductivity of 1 nS / cm or less at 25 ° C. and a viscosity of 1.5 mPa · s or less at 25 ° C. in a range of 5% by weight or more based on the total amount of the organic solvent The coloring composition is characterized in that the dielectric constant at 25 ° C. is 8.0 or more, the conductivity at 25 ° C. is 100 nS / cm or more, and the viscosity at 25 ° C. is 20 mPa · s or less.

For the purpose of preventing charging, it is sufficient that the coloring composition has a dielectric constant at 25 ° C. of 8.0 or more and a conductivity at 25 ° C. of 100 nS / cm or more, and there is no particular upper limit. However, since the coloring composition is not water-based but solvent-based, its dielectric properties and conductivity are not as high as when ionic components are dissolved in water. The rate is approximately 200 or less, and the conductivity at 25 ° C. is approximately 1 × 10 ⁶ nS / cm or less.
Also, in order to reduce “white spots”, “color unevenness”, “film thickness unevenness” and “straightness unevenness” of the coating film, the viscosity of the colored composition at 25 ° C. (measured using an E-type viscometer at 20 rpm) The viscosity is not more than 20 mPa · s, and there is no particular lower limit. However, it does not fall below the viscosity of the organic solvent contained, and is generally 0.5 mPa · s or more. When the viscosity at 25 ° C. exceeds 20 mPa · s, stable coating becomes difficult by spin coating or die coating, and it is difficult to ensure the uniformity of the coating film.

In order to control the viscosity of the coloring composition within the above range, an organic solvent A having a dielectric constant at 25 ° C. of 10.0 or less, an electrical conductivity at 25 ° C. of 1 nS / cm or less, and a viscosity at 25 ° C. of 1.5 mPa · s or less. In an amount of 5% by weight or more based on the total amount of the organic solvent (100% by weight). There is no particular lower limit to the dielectric constant and conductivity of the organic solvent A, but the dielectric constant is approximately 1.8 or more, and the conductivity is approximately 1 × 10 ⁻³ nS / cm or more. Further, the viscosity of the organic solvent A is not limited, but is generally 0.5 mPa · s or more.
When the content of the organic solvent A based on the total amount of the organic solvent is less than 5% by weight, the advantage of low viscosity, which is a feature of the organic solvent A, cannot be utilized.

The organic solvent A has low dielectric constant, electrical conductivity, and viscosity, and from the viewpoint of boiling point, evaporation rate, and affinity with pigments and resins, isoamyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether At least one organic solvent selected from the group consisting of acetates is particularly preferably used.
Other preferable organic solvents A include toluene, o-xylene, m-xylene, p-xylene, methyl 3-methoxypropionate, butyl acetate, isobutyl acetate, propyl acetate and the like. However, it is not limited to these, and any material that meets the conditions of the organic solvent A of the present invention may be used.

The colored composition of the present invention can contain an organic solvent other than the organic solvent A in a range of less than 95% based on the total amount of the organic solvent.
Organic solvents other than organic solvent A include cyclohexanone, propylene glycol diacetate, propylene glycol monomethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, n-butyl alcohol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol mono Propyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl butyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether acetate, 1,3-butylene glycol diacetate, ethylene Glycol monobutyl A Ter, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxybutanol, 1,3-butylene glycol, triacetin, 3,3,5-trimethyl-2-cyclohexen-1-one, ethylene glycol mono Examples include ethyl ether and γ-butyrolactone. These may be used alone or in admixture of two or more.
The organic solvent (organic solvent other than organic solvent A and organic solvent A) is used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, based on 100 parts by weight of the dye in the colored composition. be able to.

The organic solvent A retains the ability to reduce coating unevenness from the viewpoint of low viscosity, but is easy to be charged because of its high insulating property, and increases the chargeability when contained in a colored composition. The charging effect causes the liquid to easily collect at the edge of the coating film. In addition, the organic solvent A may cause coating unevenness when the dye is charged with a polarity opposite to that of the organic solvent.
Therefore, lowering the charging property of the coloring composition containing the organic solvent A having the advantage of low viscosity is an important factor in forming a uniform coating film. The dielectric constant at 25 ° C. is 8.0 or more, and the conductivity at 25 ° C. is 100 nS / cm or more.

Antistatic agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. It has a hydrophilic group but has low solubility in water. When added to a coloring composition, its surface tension is reduced. In addition, it is useful to have good wettability to the glass plate despite its low surface tension reducing ability, and it is sufficiently charged at an added amount that does not cause defects in the coating film due to foaming. Those that can suppress the property can be preferably used.
As the antistatic agent, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used.
Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ -2207, but is not limited thereto.

  The antistatic agent can be used in an amount of preferably 0.01 to 10.00 parts by weight, more preferably 0.05 to 5.00 parts by weight with respect to 100 parts by weight of the dye in the coloring composition. When the amount of the antistatic agent is less than 0.01 parts by weight with respect to 100 parts by weight of the dye, the “end color unevenness length” of the thin film formed on the substrate becomes long. On the other hand, when the amount is more than 10.00 parts by weight with respect to 100 parts by weight of the dye, problems such as foaming of the coating solution occur.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the antistatic agent. Two or more kinds of surfactants may be mixed and used.
Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine laurylsulfate , Lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

Examples of chaotic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts.
Nonionic surfactants include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. And amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

The dye carrier contained in the coloring composition of the present invention is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Examples of the transparent resin include thermoplastic resins, thermosetting resins, and photosensitive resins, and precursors thereof include monomers or oligomers that are cured by irradiation with radiation to form transparent resins. Or a mixture of two or more.
The dye carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition. Moreover, when using the mixture of transparent resin and its precursor as a pigment | dye carrier, transparent resin is 20-400 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 50-250 weight part. Can be used. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the colored composition.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that are precursors of transparent resins include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (me Acrylate), neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy ( Various acrylic and methacrylic esters such as (meth) acrylate and urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy Examples include methyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

As the dye contained in the colored composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be preferably used for the coloring composition of this invention is shown by a color index number.
Red pigmented compositions for forming red filter segments include, for example, CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2. 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224 Red pigments such as 226, 227, 228, 240, 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20. 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 It can be used yellow pigments such 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199.

For example, an orange pigment such as CI Pigment orange 36, 43, 51, 55, 59, 61 can be used as the orange coloring composition for forming the orange filter segment.
As the green coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green coloring composition.
Examples of blue coloring compositions for forming blue filter segments include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. Blue pigments can be used. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue coloring composition.
For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan coloring composition for forming a cyan filter segment. Can do.

For the magenta coloring composition for forming the magenta color filter segment, for example, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. A yellow pigment can be used in combination with the magenta colored composition.
Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium oxide. And metal oxide powders such as iron tetroxide, metal sulfide powders, metal powders and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator is added to the colored composition of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine and other triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators and the like are used. It is done. A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators can be used alone or in combination of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the colored composition.

  The coloring composition of the present invention comprises one or two or more dyes, together with the above photopolymerization initiator, if necessary, in a three-roll mill, two-roll mill, sand mill, kneader, attritor in a dye carrier and an organic solvent. It can be produced by finely dispersing using various dispersing means such as. Moreover, the coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what each disperse | distributed finely in the pigment | dye carrier and the organic solvent separately. When the dye is dispersed in the dye carrier and the organic solvent, a dye dispersant such as a resin-type pigment dispersant, a dye derivative, and a surfactant can be appropriately used. The dye dispersant is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, a color composition obtained by dispersing a pigment in a dye carrier and an organic solvent using a dye dispersant is used. If so, a color filter excellent in transparency can be obtained. A pigment | dye dispersing agent can be used in the quantity of 0.1-40 weight part with respect to 100 weight part of pigment | dyes in a coloring composition, Preferably it is 0.1-30 weight part.

  Resin-type pigment dispersants are resins that have a pigment-affinity part that has the property of adsorbing to the pigment, and a part that is compatible with the dye carrier. It works to do. Specific examples of resin-type pigment dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Such organic dyes also include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.
As the surfactant, those which can be used in combination with the above-mentioned antistatic agent can be used.

The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the dye in the coloring composition.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the dye in the coloring composition.

The coloring composition of the present invention can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The solvent development type or alkali development type colored resist material is a composition containing a thermoplastic resin, thermosetting resin or photosensitive resin as a dye carrier, a monomer, a photopolymerization initiator, a surface conditioner, and an organic solvent. A pigment is dispersed in a product.
The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

Below, the manufacturing method of the color filter using the coloring composition of this invention is demonstrated.
The color filter of the present invention includes a filter segment on a substrate, and can include, for example, a black matrix and red, green, and blue filter segments. The filter segment is formed on the substrate by applying the coloring composition of the present invention by a spin coat method or a die coat method.
Color filter substrates include glass plates such as soda-lime glass, low alkali borosilicate glass, and non-alkali aluminoborosilicate glass that have a high transmittance for visible light, and resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. A plate is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
First, Table 1 shows the results obtained by actually measuring the dielectric constant, conductivity, and viscosity characteristics of the organic solvent A used in the examples with the following measuring instrument.
Dielectric constant: 870 LIQUID DIELECTRIC CONSTANT METER manufactured by BROOKHAVEN INSTRUMENTS CORPORATION
Conductivity: Scientific Conductivity Meter Model 645 and 627
Viscosity: Measured with an E-type viscometer (TUE-20L type manufactured by TOKI SANGYO) at a rotation speed of 100 rpm.

Next, preparation of the acrylic resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
(Preparation of acrylic resin solution)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Methacrylic acid 20.0 parts
Methyl methacrylate 10.0 parts
Butyl methacrylate 55.0 parts
2-Hydroxyethyl methacrylate 15.0 parts
Azobisisobutyronitrile 4.0 parts After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and further at 100 ° C. The reaction was continued for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

[Example 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a copper phthalocyanine pigment dispersion.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 12.0 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Dye dispersant (“Solsperse 20000” manufactured by Zeneca) 2.4 parts Acrylic resin solution 28.1 parts Organic solvent 1 (cyclohexanone) 57.5 parts Then, the mixture of the following composition was stirred and mixed to be uniform, It filtered with a 1 micrometer filter and obtained the coloring composition adjusted as a blue resist material. Table 2 shows the composition of the colored composition (weight ratio with the total amount of the colored composition taken as 100 / the right column is the weight relative to 100 parts by weight of the pigment).
Copper phthalocyanine pigment dispersion 45.0 parts Acrylic resin solution 12.5 parts Trimethylol propane triacrylate 4.8 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 2.5 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part Antistatic agent A 0.09 part (dimethylpolysiloxane having polyalkylene oxide units: "FZ-2122" manufactured by Toray Dow Corning)
Organic solvent 1 (cyclohexanone) 0.91 part Organic solvent 2 (isoamyl acetate) 34.0 parts

[Examples 2-6 and Comparative Examples 1-3]
The pigment, the organic solvent, and the antistatic agent corresponding to the colors of the examples and comparative examples shown in Table 2 were selected from the following, and the pigment, dispersion aid, acrylic resin, monomer, and photopolymerization started Except that the composition of the colorant, sensitizer, organic solvent and antistatic agent was changed to the ratio shown in Table 2 (weight ratio with the total amount of the colored composition being 100, the right column is the weight relative to 100 parts by weight of the pigment) In the same manner as in 1, a colored composition prepared as each color resist material was obtained.

Red pigment: 5.08 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals)
Anthraquinone pigment (CI Pigment Red 177) 0.82 parts
("Chromophthal Red A2B" manufactured by Ciba Specialty Chemicals)
Anthraquinone pigment (CI Pigment Yellow 199) 0.20 parts
("Chromoval Yellow GT-AD" manufactured by Ciba Specialty Chemicals)
6.10 parts in total Green pigment: 3.60 parts of halogenated copper phthalocyanine pigment (CI Pigment Green 36)
("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Nickel azo complex pigment (CI Pigment Yellow 150) 2.00 parts
("E4GN-GT" manufactured by LANXESS)
5.60 parts in total Blue pigment: ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 5.40 parts
(BASF "Heliogen Blue L-6700F")
Organic solvent 1: Cyclohexanone Organic solvent 2: Isoamyl acetate Organic solvent 3: Ethyl 3-ethoxypropionate Organic solvent 4: Propylene glycol monomethyl ether acetate Antistatic agent A: Dimethylpolysiloxane having polyalkylene oxide units
"FZ-2122" manufactured by Toray Dow Corning
Antistatic agent B: dimethylpolysiloxane having polyalkylene oxide units
"FZ-2110" manufactured by Toray Dow Corning
Surfactant C: Aralkyl-modified silicone surfactant, BYK-323 "BYK-323"
Surfactant D: Fluorosurfactant, “BL-20” manufactured by Dainippon Ink & Chemicals, Inc.

The dielectric constant, conductivity, and viscosity at 25 ° C. of each color resist material obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were measured using the following measuring instruments and measurement conditions, respectively.
Dielectric constant: 870 LIQUID DIELECTRIC CONSTANT METER manufactured by BROOKHAVEN INSTRUMENTS CORPORATION
Conductivity: Scientific Conductivity Meter Model 645 and 627
Viscosity: Measured at a rotation speed of 20 rpm using an E-type viscometer (TUE-20L type manufactured by TOKI SANGYO).
In addition, using a die coating method and a spin coating method coating apparatus, coating was performed on a glass substrate having a size of 360 mm × 465 mm so as to have an average film thickness of 2.0 μm, and the resulting coated substrate was treated at 70 ° C. for 20 minutes. Pre-baked to obtain a dry coating film. The evaluation items / contents and how to express the results are described below.

(Clear white)
“White blank”: For the coated substrate, the whole substrate was visually observed with white transmitted light. When there was no white void, “◯”, when the white void was 1 to 3, “Δ”, and four white voids. The case where it observed above was set as x.
(Color unevenness)
"Edge color unevenness length": White light is transmitted through the coated surface, the edge of the coating film is visually observed, and the length of the unevenness boundary is less than 5mm ○, 5mm or more and less than 10mm Δ, 10mm The above was set as x.
“Overall color unevenness”: White light was transmitted through the coated surface, and the edge of the coating film was visually observed to evaluate the degree of unevenness. When there was no unevenness, it was marked as ◯, when it was observed slightly, and when it was severe, it was marked as x.

(Thickness uniformity)
“Thickness uniformity (edge)”: The film thickness was measured every 5 mm from the center of the short edge of the coated film to the center of the substrate up to 5 cm. The maximum film thickness was _Tmax , the minimum film thickness was _Tmin , the average film thickness was _Tavg, and the film thickness uniformity (edge) was calculated by the following equation (6).
“Thickness uniformity (other than edge)”: The film thickness was measured every 2 cm from the center of the coated substrate to 26 cm in the diagonal direction. Similarly to the above, the film thickness uniformity (other than the end) was calculated by the following formula (6).
Film thickness uniformity [%] = ((T _max −T _min ) / (T _avg × 2)) × 100 (6)
The film thickness uniformity [%] is preferably 5% or less, and if it is 2% or less, it can be judged that the uniformity is sufficiently high.
(Sujimura)
“Striped unevenness”: Evaluation was performed on the die-coated substrate using a white transmitted light. The case where there was no stripe unevenness by visual observation was marked with ○, and the case where stripe unevenness was observed was marked with ×.
The results of each evaluation are shown in Table 3.

Since the colored compositions obtained in Examples 1 to 6 had a dielectric constant of 8.0 or more and the conductivity sufficiently exceeded 100 nS / cm, good results were obtained in any evaluation.
Since the colored compositions obtained in Comparative Examples 1 to 3 have a dielectric constant of less than 8.0 and an electric conductivity of less than 100 nS / cm, a good thin film could not be obtained.

Claims (4)

  A coloring composition comprising a dye carrier comprising a transparent resin, a precursor thereof or a mixture thereof, a dye, an organic solvent, and an antistatic agent, wherein the organic solvent has a dielectric constant at 25 ° C. of 10.0 or less, 25 An organic solvent A having a conductivity of 1 nS / cm or less at 25 ° C. and a viscosity of 1.5 mPa · s or less at 25 ° C. in a range of 5% by weight or more based on the total amount of the organic solvent; A colored composition having a dielectric constant of 8.0 or more, an electric conductivity at 25 ° C. of 100 nS / cm or more, and a viscosity at 25 ° C. of 20 mPa · s or less.   The colored composition according to claim 1, wherein the organic solvent A is at least one organic solvent selected from the group consisting of isoamyl acetate, ethyl 3-ethoxypropionate, and propylene glycol monomethyl ether acetate.   The coloring composition according to claim 1 or 2, wherein the antistatic agent is dimethylpolysiloxane having a polyalkylene oxide unit. A color filter comprising a filter segment formed from the colored composition according to claim 1.