TWI431072B - Colored composition and method of preparing the same - Google Patents

Description

Color composition and preparation method thereof

The present invention relates to a color composition suitable for use in a color filter constituting a color liquid crystal display device, a color image pickup device element, or the like, and a method of preparing the same.

In recent years, liquid crystal display devices have been used for television monitors, for use in personal computer monitors, for mobile phones, etc., for color filters used for this purpose, for color and color purity, further for color filter formation. At the time of the segment, the requirements for various characteristics such as coating uniformity, sensitivity, developability, and pattern shape are increasing. Moreover, in consideration of long-term use, heat resistance, light resistance, and the like are strongly required in the quality surface. Among them, with the spread of the liquid crystal display device, it is particularly strongly desired to increase the brightness of the color filter from the viewpoint of energy saving and low manufacturing cost.

As a method of increasing the brightness of the color filter, there are a method of adjusting the hue of each color filter section and a method of increasing the brightness of the pigment constituting the color material of the color filter.

For the method of adjusting the hue of each color filter section, for example, in Japanese Laid-Open Patent Publication No. 2005-173278, the brightness improvement of the green filter section is described, which is subtly adjusted by the degree of white hue shift. To increase the brightness.

However, if the sections of the respective color filter sections are further adjusted to have high brightness, the hue of white will be deviated, and the display device will become a white display failure. In order to solve this malfunction, it is necessary to adjust the display control device for color filter. Problems occur in the chain of components other than the optical device. On the other hand, if the white hue of the Japanese Laid-Open Patent Publication No. 2005-173278 is finely adjusted, the brightness is not sufficiently improved, and a color filter having higher brightness is required.

Further, although the method for increasing the brightness of the pigment has a method of reducing the brightness-reducing component contained in the pigment, it is difficult to reduce the pigment content by the conventional pigment preparation step, that is, the conventional pigment synthesis step or the pigment purification step. The brightness reduction component is used to obtain a pigment having a high brightness. In the pigment synthesis step, since impurities such as unreacted materials or by-products which lower the brightness of the pigment are generated during the reaction, the reaction of the synthetic pigment does not occur all on average. Although the generation of impurities can be controlled to some extent by the production technique of the modified pigment synthesis step, there are limits. Further, as disclosed in Japanese Laid-Open Patent Publication No. 2000-66022, in the pigment purification step, by washing the pigment with an organic solvent, impurities which adversely affect the liquid crystal display in the pigment can be reduced.

However, washing the pigment with only an organic solvent reduces the ionic impurities which adversely affect the liquid crystal display, but does not remove the colored or colorless nonionic impurities which lower the brightness.

A pigment containing a color or a colorless nonionic impurity is used in an electronic material which requires a high-purity pigment, and particularly when used in a color filter which particularly requires a high-purity pigment, it is fatal. The reason.

Accordingly, it is an object of the present invention to provide a color composition capable of producing a color filter having high brightness and a method of preparing the same.

The present inventors have found that the pigment having the nonionic pigment removed has a high luminance and exhibits a hue of the original pigment, and when the nonionic impurity has been removed as much as possible, a change in the absorbance of the pigment is observed, and it is found that The absorbance of the high-intensity pigment at a specific wavelength will be concentrated in a certain range, and the present invention will be completed.

According to a first aspect of the present invention, there is provided a color composition comprising: a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a red pigment, The absorption value of the wavelength range of 400 to 575 nm is 8.0 to 14.0.

According to a second aspect of the present invention, there is provided a color composition comprising: a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a green pigment, Its absorption wavelength from 600 to 700 nm is 11.2 to 13.0.

According to a third aspect of the present invention, there is provided a color composition comprising: a pigment carrier consisting of a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a blue pigment The absorption value of the wavelength of 550 ~ 650nm is 9.0 ~ 12.0.

According to a fourth aspect of the present invention, there is provided a color composition comprising: a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a yellow pigment, The absorption value of the wavelength range of 400 to 500 nm is 5.0 to 10.0.

According to a fifth aspect of the present invention, there is provided a method for producing a color composition characterized by comprising the steps of: washing a pigment with a strong base and dispersing it in a transparent resin, a precursor thereof, or a transparent resin A pigment carrier consisting of a mixture of its precursors.

Since the color composition of the present invention utilizes a pigment having a specific light absorption value, it has excellent spectral characteristics, and by using the color composition to form a color filter, the brightness of each color filter section can be improved without changing the white hue. And improve the brightness of white.

Further, the color composition of the present invention is prepared by dispersing a pigment which has been washed with a strong alkali in a pigment carrier, and thus a color filter is produced by using the color composition prepared by the method of the present invention. The brightness of each color filter section can be increased without changing the hue of white and increasing the brightness of white.

By increasing the brightness of white, a liquid crystal display device superior in the past can be obtained from the viewpoint of energy saving and low manufacturing cost.

The pigment contained in the color composition of the present invention is characterized in that the light absorption value in a predetermined wavelength range of the hue is within a certain range, and the color filter can be made by using the color composition containing the pigment to improve the brightness of white. .

Specifically, regarding the red pigment, when the light absorption value at a wavelength of 400 to 575 nm is 8.0 to 14.0, the brightness of the pigment rises. Regarding the green pigment, when the absorbance at a wavelength of 600 to 700 nm is 11.2 to 13.0, the luminance rises. Regarding the blue pigment, when the absorbance at a wavelength of 550 to 650 nm is 9.0 to 12.0, the luminance rises. Regarding the yellow pigment, when the absorbance at a wavelength of 400 to 500 nm is 5.0 to 10.0, the luminance rises.

The light absorption value of the pigment is adjusted by the pigment powder, and the reflection absorbance of the obtained pigment particle in the wavelength range of 400 to 700 nm is measured by an ellipsometer ("M-220" manufactured by JASCO Corporation). The absorbance data is reflected and the reflected absorbance in a specific wavelength range is integrated and calculated.

The pigment granules were placed in a cylindrical container and compressed under a load of 400 kg to make the pigment powder a size of 16 mm in diameter and 1.6 mm in height. Since the weight of the pigment powder to be used varies depending on the specific gravity of the pigment, the amount of the pigment particles of the above size is appropriately adjusted and used.

The reflection absorbance of the pigment particles is measured by inclining the surface of the pigment particles by 45 degrees with respect to the light emission, reflecting the emitted light by 90 degrees, and sensing the reflected light by the light receiving portion. The wavelength of the emitted light is in the range of 400 to 700 nm, and is changed on a scale of 5 nm, and is irradiated onto the surface of the pigment powder to measure the reflection absorbance per 5 nm.

Since the pigment having a light absorption value lower than the above range in the above wavelength range is a colorless nonionic impurity in the pigment, the brightness of the filter section formed by the pigment is low. Further, the color filter having the filter section has a white luminance which is low.

Further, since the pigment having a light absorption value higher than the above range in the above wavelength range is a nonionic impurity containing color in the pigment, the brightness of the filter segment formed by the pigment is low. Further, the color filter having the filter section has a white luminance which is low.

Moreover, if the suitable absorbance range of each color pigment is exemplified, the light absorption value of the red pigment is preferably 9.0 to 13.0, and further preferably 10.0 to 12.0.

The absorbance of the green pigment is preferably from 11.5 to 12.9, and further preferably from 11.8 to 12.8.

The absorbance of the blue pigment is preferably 9.1 to 11.0, and further preferably 9.2 to 10.0.

The absorbance of the yellow pigment is preferably 5.5 to 9.0, and further preferably 6.0 to 8.0.

The pigments of the respective colors having the light absorption values in the above-mentioned range can be obtained by, for example, washing the pigment with a strong alkali, efficiently purifying the pigment in an all-round manner, and removing nonionic impurities which adversely affect the hue or brightness. Wash the strong alkali with a combination of strong acid or organic solvent.

The pigment contains many colorless impurities or colored impurities, and a method of reducing the ionic impurities contained in the pigment by washing with an organic solvent is known. Many nonionic impurities remain in the cleaning by the organic solvent, but by washing with a strong alkali, nonionic impurities which adversely affect the hue or brightness can be removed.

When washing with strong alkali and washing with strong acid, be careful not to damage the type of pigment. The form which does not destroy the pigment means that the crystal structure of the pigment or the size of the particles and the structure of the pigment itself are not changed. If the type of the pigment is destroyed, the hue changes and the brightness is lowered, so it is not suitable.

The strong base washing should be carried out using a strong base having a pH of 12.0 to 14.5. When the alkali is washed with a pH of more than 14.5, the structure of the pigment itself becomes unstable and is easily damaged. If the pigment itself is damaged, the color will be lost, and the absorbance of the pigment will leave the target range, failing to produce high brightness. Further, when the alkali is washed with an alkali having a pH of less than 12.0, the desired cleaning effect is not exhibited, and the light absorption value of the pigment is out of the target range, and high brightness cannot be exhibited. As the strong base, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide or the like can be used.

Moreover, the strong acid washing can be carried out before or after the washing of the strong alkali, and it is preferably carried out by using a strong acid having a pH of 1.0 to 3.5. If the acid is washed with an acid having a pH of less than 1.0, the structure of the pigment itself becomes unstable and easily damaged. If the pigment itself is damaged, the color will be lost, and the absorbance of the pigment will leave the target range, failing to produce high brightness. Further, if the acid is washed with an acid having a pH of more than 3.5, the desired cleaning effect is not exhibited. As the strong acid, for example, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid or the like can be used.

The organic solvent is washed and washed with a strong alkali and washed with a strong acid. When it is washed with an organic solvent, the coagulation power in the solvent is enhanced by the pigment characteristics. If the solvent is washed and then washed with a strong alkali or washed with a strong acid, the entire cleaning cannot be performed, and the cleaning efficiency is extremely lowered.

The organic solvent is preferably washed with an organic solvent having a solubility parameter (SP value) of 8.0 to 11.0. When the organic solvent having a solubility parameter outside the above range is used for washing, the desired cleaning effect cannot be exhibited. The solubility parameter (SP value) of the organic solvent is a value obtained from the physical quantity (evaporation heat, etc.) of the organic solvent, and the values described in various documents can be used. When the solubility parameter of the organic solvent is close to the solubility parameter of the colored or colorless nonionic impurity, the solubility of the nonionic impurity increases, and a high-purity pigment can be obtained. Although the solubility parameter of the non-ionic impurity is unknown, it is confirmed that the non-ionic property can be removed efficiently by washing with an organic solvent having a solubility parameter (SP value) of 8.0 to 11.0 as a result of washing with various types of organic solvents. Impurities, pigments having specific absorbance values can be easily obtained.

As the organic solvent, for example, ethylene glycol methyl ether (9.0), oxidized propanol (9.2), isochloropropene (8.1), ethyl bromide (8.9), chloroarylene (8.8), chloropropene (8.4), Propylamine (8.9), cyclopentane (8.1), acetone (9.6), 1,1-dichloroethane (8.9), chloroform (9.2), tetrahydrofuran (9.0), butylamine (8.7), chlorobutene (8.4) ), methyl ethyl ketone (9.0), benzene (9.1), cyclohexanone (8.2), 1,2-dichloroethane (9.9), propionitrile (10.8), propyl acetate (8.8), 3-pentyl Ketone (9.0), piperidine (9.4), dipropylamine (8.0), toluene (8.9), 3-pentanol (10.2), methyl isobutyl ketone (8.6), acrylamide (11.0), tetrachloroethylene (9.3) ), 2-ethylbutylamine (8.0), butyl acetate (8.7), 2-hexanone (8.7), 1-ethoxy-2-propanol (9.8), N-chlorohexene (8.4), 1-pentanol (10.9), p-xylene (8.8), methyl-xylene (8.9), 4-heptadecanol (8.7), n-xylene (9.0), 2-methoxyethyl acetate (9.0 ), propylene glycol methyl ether acetate (9.2), 2-ethyl-1-butanol (10.4), ethyl-N-butanone (8.5), 2-heptadecanone (9.0), cyclohexanone (10.4), 3-heptadecane (9.9), 1-hexanol (10.8), dibutylamine (8.2), 2-heptadecanone (9.8) Cyclohexanol (10.9), diisobutyl ketone (8.1), methyl-N-hexyl ketone (8.8), dipropylene glycol methyl ether (9.4), diethylene glycol diethyl ether (8.7), propylene glycol diacetic acid (8.9) Wait. Further, the value in parentheses is the solubility parameter (SP).

Moreover, the energy of washing time, temperature, sharing, etc. can be selected according to the type of each pigment. Regarding the time, in consideration of the mass production time, the temperature is practical and safely treatable, and the energy for sharing or the like is based on the use of a practical device.

Since the time and the sharing system are in a trade-off relationship, the cleaning time is increased by using a device that does not consume the sharing, and the cleaning time is shortened in the case of using a shared device. In the case of using a shared device, the pigment itself can be prevented from being damaged by a strong alkali, a strong acid or an organic solvent by shortening the washing time. Regarding the temperature, since the pigment itself does not change in order to manage the washing in a stable manner, it is preferably in the range of 25 to 85 °C.

It is preferable to use a pyrrolopyrroledione pigment as a red pigment, a copper halide phthalocyanine pigment as a green pigment, a copper phthalocyanine pigment as a blue pigment, and a metal complex structure as a yellow pigment. Nitrogen pigments.

The pigment-based pigment itself is high in brightness, and has a characteristic of high acidity, strong alkali, and high solvent resistance, and is preferable because it can maximize the effect of cleaning the pigment.

Examples of the red pigment include an anthraquinone pigment, a quinophthalone pigment, an azo pigment, and an anthraquinone pigment. However, the lanthanide pigments and lanthanide pigments have lower brightness than the pyrrolopyrroledione pigments due to the pigment structure. Further, the quinophthalone pigment or the azo pigment is less resistant to a strong acid or a strong base or an organic solvent than the pyrrolopyrroledione pigment, and the washing effect cannot be sufficiently exhibited.

The pigment having a specific light absorption value contained in the color composition of the present invention is preferably a fine pigment having an average particle diameter of 10 to 300 nm as measured by a laser scattering method. When the average particle diameter of the pigment is less than 10 nm, the light resistance is lowered due to the decrease in the particle diameter, and when it exceeds 300 nm, it is difficult to stably maintain the dispersion, and pigment precipitation is likely to occur.

The refinement of the pigment can be carried out by the following method. In other words, a mixture of at least three components of a pigment, a water-soluble inorganic salt, and a water-soluble solvent is made into a clay-like mixture, and the mixture is vigorously kneaded by a kneading machine or the like, and the pigment is refined and put into water to be a high-speed mixer. Stir it to make a slurry. Next, the slurry is filtered and washed with water to remove the water-soluble inorganic salt and the water-soluble solvent. A resin, a pigment dispersant, or the like may be added to the pigment refining step. Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride. These inorganic salts are used in an amount of 3 times by weight or more, and preferably 20 times by weight or less. If the amount of the inorganic salt is less than 3 times by weight, a finely divided pigment of a desired size cannot be obtained. Further, if it is more than 20 times by weight, the water-soluble inorganic salt and the water-soluble solvent in the subsequent step are washed a lot, and the amount of fine treatment of the pigment is small.

The pigment carrier contained in the color composition of the present invention is a pigment which is dispersed by a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof. The transparent resin is preferably a resin having a transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. The transparent resin contains a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin, and the precursor thereof is cured by irradiation with an active energy ray to produce a monomer or oligomer of a transparent resin, and may be used alone or in combination of two or more. To use this. The pigment carrier may be used in an amount of from 50 to 700 parts by weight, more preferably from 100 to 400 parts by weight, based on 100 parts by weight of the pigment.

The thermoplastic resin may, for example, be a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, a polyvinyl acetate, a polyurethane resin, or a poly Ester resin, acrylic resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), butadiene resin, polyfluorene Imine resin and the like. Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a rosin-denatured maleic acid resin, a rosin-denatured fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

As the active energy ray-curing resin, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group, and a (meth)acrylic acid having a reactive substituent such as a polycyanate group, an aldehyde group or an epoxy group are used. The compound or cinnamic acid is reacted, and a resin having a photo-branching group such as a (meth) acrylonitrile group or a styryl group is introduced into the polymer. Further, a styrene-anhydrous maleic acid copolymer or an α-olefinic acid-anhydrous maleic acid is also used by having a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate. A linear polymer such as a copolymer or an acid anhydride is semi-esterified.

The pigment carrier contains a transparent resin obtained by copolymerizing a compound (a) represented by the following general formula (1) with a compound (b) having another ethylenic unsaturated double bond. Since the transparent resin exhibits an excellent dispersing effect for almost all of the pigments, the color composition functions to prevent the pigment from coagulating and maintain the state in which the pigment is finely dispersed. Therefore, when a color filter of the present invention obtained by dispersing a pigment in a pigment carrier containing the above transparent resin is used to form a filter segment, a filter segment in which a small amount of pigment condensation is formed can be formed. A color filter with high transmittance and high brightness can be manufactured.

Formula 1)

In the formula (1), R ₁₄ represents a hydrogen atom or a methyl group. R ₁₅ represents an alkylene group. R ₁₆ represents an alkyl group having 1 to 20 carbon atoms which may also contain a substituent such as a hydrogen atom or a benzene ring. m is an integer from 1 to 15.

The compound (a) represented by the general formula (1) which is a constituent component of the above transparent resin is excellent in the adsorption/orientation property to the surface of the pigment due to the effect of the π-electron of the benzene ring. In particular, when (a) is an ethylene oxide or propylene oxide-modified (meth) acrylate of p-cumylphenol, a stereoscopic effect is added, and a better adsorption/alignment surface can be formed for the pigment, and the effect is higher. Further, the alkyl group of R _{16 has a} carbon number of from 1 to 20, more preferably from 1 to 10. When the number of carbon atoms is from 1 to 10, the alkyl group becomes an obstacle and the resins are prevented from approaching each other, thereby promoting adsorption/alignment of the pigment. However, if the carbon number is more than 10, the stereoscopic hindrance effect of the alkyl group is improved, and even the benzene ring is impeded for the pigment. Adsorption/alignment of the surface. This line is often marked with chain length. If the carbon number exceeds 20, the adsorption/alignment of the benzene ring is extremely lowered.

Examples of the compound (a) include phenyl ethylene oxide-modified (meth) acrylate, p-cumyl phenol ethylene oxide-modified (meth) acrylate, nonyl phenol ethylene oxide-modified (meth) acrylate, and nonyl phenol. A propylene oxide denatured (meth) acrylate or the like.

Examples of the compound (b) include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, and (iso)(meth)acrylate. Ester, amyl (meth)acrylate, ethyl 2-hydroxy(meth)acrylate, propyl 2-hydroxy(meth)acrylate, amyl (meth)acrylate, cyclomethacrylate Ester, glycidyl (meth) acrylate, isobutyl carbonyl (meth) acrylate acid propyl methacrylate, propyl acrylate (meth) acrylate, trichloro diacid phosphate Ethyl (meth) acrylate, oxidized polyethylene glycol mono (meth) acrylate, etc.

The ratio of the compound (a) in the compound constituting the transparent resin is preferably from 0.1 to 50% by weight, more preferably from 10 to 35% by weight. When the ratio of the compound (a) is less than 0.1% by weight, a sufficient pigment dispersion effect cannot be obtained, and if it is more than 50% by weight, the compatibility with other constituent components in the color composition may be lowered, possibly causing a monomer. Or a photopolymerization initiator is precipitated.

The weight average molecular weight (Mw) of the above transparent resin is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000.

Examples of the monomer or oligomer of the pigment carrier include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (A). Acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di(meth) acrylate, 1,6-hexane diol (meth) acrylate Ester, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, 1,6-hexyl Glycol diglycidyl ether di(meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, neopentyl glycol diglycidyl ether di(meth) acrylate, dipentaerythritol hexa Acrylate, tricyclodecyl (meth) acrylate, esterified acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate, etc. Acrylates and methacrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol triethylene , (Meth) acrylamide, N- methylol (meth) acrylamide, N- vinyl formamide Amides, acrylonitrile and the like. These may be used alone or in combination of two or more.

The color composition of the present invention can be dispersed in a transparent resin, a precursor thereof, or a transparent resin by using a pigment, more preferably a pigment washed with a strong alkali, if necessary, together with a photopolymerization initiator described below. A pigment carrier composed of a mixture of precursors is produced. The dispersion of the pigment to the pigment carrier can be carried out by various dispersion means such as a 3-roll mill, a 2-roll mill, a sand mill, a kneader, and an attritor. The color composition containing two or more kinds of pigments may be preliminarily mixed with a pigment, and the obtained pigment mixture may be finely dispersed in a pigment carrier. Further, a color composition containing two or more kinds of pigments may be produced by mixing the respective pigments finely dispersed in a pigment carrier.

When the pigment is dispersed in the pigment carrier, a dispersion aid such as a pigment inducer, a resin type pigment dispersant, or a surfactant can be suitably used. The dispersing aid has a good effect of dispersing the pigment and preventing the re-coagulation of the pigment after dispersing. Therefore, when a coloring composition obtained by dispersing a pigment in a pigment carrier by using a dispersing aid is used, transparency is excellent. Color filter. The dispersing aid can be used in an amount of 0.1 to 30 parts by weight for 100 parts by weight of the pigment.

The pigment inducing system is a compound represented by the following compound (2), and includes those having a basic substituent and having an acidic substituent.

A-B type (2)

A: Organic pigment residue

B: base substitution group or acid replacement group

In the formula (2), examples of the organic pigment constituting the organic pigment residue of A include, for example, a pyrrolopyrroledione pigment; an azo such as azo, disazo or polyazo; Pigment; copper phthalocyanine, copper halide phthalocyanine, phthalocyanine-free pigments such as metal-free phthalocyanine; amine onion, diamine, onion, pyrimidine, xanthone, indolinone, standard reduction blue, furanone , anthraquinone violet dyes and other onion pigments; quinophthalone pigments; dithiazide pigments; anthraquinone pigments; anthraquinone pigments; thiazin indigo pigments; isoindane pigments; isoindanoquinones Pigments; quinophthalone pigments; durene pigments; and metal complex pigments.

In the formula (2), examples of the basic substituent of B include a substituent represented by the formula (3), the formula (4), the formula (5), and the formula (6), and examples of the acidic group include the following formula. (9), a substituent represented by the formula (10) and the formula (11).

X: represents -SO ₂ -, -CO-, -CH ₂ NHCOCH ₂ -, -CH ₂ - or a direct bond.

n: represents an integer from 1 to 10.

R ₁ and R ₂ each independently represent an alkyl group having 1 to 36 carbon atoms which may be substituted, an alkynyl group having 2 to 36 carbon atoms which may be substituted, or a phenyl group which may be substituted. R ₁ and R ₂ may be integrated to form a heterocyclic ring which may be substituted. Further, R ₁ and R ₂ may be integrated to form a hetero ring further containing a nitrogen, oxygen or sulfur atom.

R ₃ : represents an alkyl group having 1 to 36 carbon atoms which may be substituted, an alkynyl group having 2 to 36 carbon atoms which may be substituted, or a phenyl group which may be substituted.

R ₄ , R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group having 1 to 36 carbon atoms which may be substituted, an alkynyl group having 2 to 36 carbon atoms which may be substituted, or a benzene which may be substituted. base.

Y: represents -NR ₈ -Z-NR ₉ - or directly bonded.

R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group having 1 to 36 carbon atoms which may be substituted, an alkynyl group having 2 to 36 carbon atoms which may be substituted, or a phenyl group which may be substituted.

Z: represents an alkane group having 1 to 36 carbon atoms which may be substituted, an olefin group having 2 to 36 carbon atoms which may be substituted, or a benzene hydrocarbon group which may be substituted.

R: represents a substituent represented by the formula (7)) or a substituent represented by the formula (8).

Q: represents a hydroxyl group, an alkoxy group, a substituent represented by the formula (7) or a substituent represented by the formula (8). In the formulae (7) and (8), R ₁ to R ₇ and n are as defined above.

-SO ₃ M/i type (9) -COOM/i type (10)

M: a hydrogen atom, a calcium atom, a ruthenium atom, a ruthenium atom, a manganese atom or an aluminum atom.

i: indicates the price of M.

R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 36 carbon atoms which may be substituted, an alkynyl group having 2 to 36 carbon atoms which may be substituted, and a benzene which may be substituted. base.

Examples of the amine component used to form the substituent represented by the formulae (3) to (8) include dimethylamine, diethylamine, N,N-ethylisopropylamine, and N,N. -ethylpropylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butylethylamine, N,N-tert-butylethylamine, diisobutylamine, two Propylamine, N,N-second butyl propylamine, dibutylamine, di-second butylamine, diisobutylamine, diisobutylamine, N,N-isobutyl second butylamine, diamylamine, diiso Pentylamine, dihexylamine, bis(2-ethylhexyl)amine, dioctylamine, N,N-methyloctadecylamine, diamine, diarylamine, N,N-methyl-1,2- Dimethylpropylamine, N,N-methylhexylamine, dioleylamine, distearylamine, N,N-dimethylamine methylamine, N,N-dimethylamineethylamine, N,N-dimethylamine Methylamine, N,N-dimethylamine, N,N-diethylamine ethylamine, N,N-diethylamine propylamine, N,N-diethylamine hexylamine, N,N-diethylamine Amine, N,N-diethylamine pentylamine, N,N-dipropylamine butylamine, N,N-dibutylamine propylamine, N,N-dibutylamine ethylamine, N,N-dibutylamine butylamine, N,N-Diisobutylamine pentylamine, N,N-methyl-lauramide, N,N-ethyl- Hexamine ethylamine, N,N-distearylamine ethylamine, N,N-dioleylamine, N,N-distearate butylamine, piperidine, 2-methylpiperidine, 4-methyl Piperidine, 2,4-dimethylpiperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 3-piperidinemethanol, methylpiperidine acid, isopiperidinecarboxylic acid , Isopiperidine methyl, isopiperidine ethyl, 2-piperidinemethanol, pyrrole, 3-hydroxypyrrole, N-amineethylpiperidine, N-amineethyl-4-methylpiperidine, N -amine ethylmorpholine, N-aminopropyl piperidine, N-aminopropyl-2-methylpipecolic acid, N-aminopropyl-4-methylpipecolic acid, N-amino group Propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-ring Penipiperazine and the like.

The amine component used for forming the decanoic acid amine salt of the formula (11) may be any of the amines of the first, second, third, and fourth grades. For example, the first amine may have a side chain. An amine such as hexylamine, heptylamine, octylamine, decylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentaamine, heptadecylamine or octadecylamine, or with each carbon A number of corresponding unsaturated amines.

Examples of the amines of the second, third and fourth grades include dioleylamine, distearylamine, dimethyloctylamine, dimethylguanamine, dimethyl laurylamine, dimethylstearylamine, and dilauryl. Monomethylamine, trioctylamine, dimethyl behenium dichloride, dimethyl ammonium chlorate, dimethyl dimercapto ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl hard Ethyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl ammonium chloride, dimethyl hexadecyl octadecyl ammonium chloride, and the like.

The resin type pigment dispersant has a pigment affinity site having a property of adsorbing to a pigment, and a site compatible with the pigment carrier, and has a function of adsorbing the pigment to stabilize the dispersion of the pigment to the pigment carrier. As the resin type pigment dispersant, polycarboxylates such as polyurethane and polyacrylate, unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamines can be used. a salt, a polyoxyalkylene, a long-chain polyamine phthalamide phosphate, a hydrocarbon-containing polycarboxylate or a denatured product thereof, by reacting with a polyester having a polymerized (lower alkylenimine) and a free carboxyl group An oily dispersant such as a guanamine or a salt thereof, a (meth)acrylic acid-(meth)acrylate copolymer, a styrene-maleic acid copolymer, a polyvinyl alcohol, a polyvinylpyrrolol or the like Or a water-soluble polymer compound, a polyester type, a modified polyacrylate type, an ethylene oxide / propylene oxide addition compound, a phthalate type, etc., These can be used individually or in mixture of 2 or more types.

Examples of the surfactant include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, alkylnaphthalenesulfonate sodium, and alkyl diphenyl ether disulfonate. Sodium, laurylethanolamine, lauryl triethanolamine, ammonium lauryl sulfate, stearic acid ethanolamine, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer ethanolamine, polyethylene oxide ether phosphate Anionic surfactant such as ether; polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, poly(ethylene oxide decyl phenyl ether), polyethylene oxide ether phosphate, polyethylene oxide sorbitan glycerin hard a cationic surfactant such as a fatty acid such as a fatty acid; an alkyl 4-grade ammonium salt or an ethylene oxide additive such as an ethylene oxide add-on surfactant; an alkyl dimethylamine acetate quaternary ammonium carboxylate internal salt or the like An amphoteric surfactant such as an ammonium carboxylic acid inner salt or an alkyl imidazoline; these may be used alone or in combination of two or more.

When the composition is cured by ultraviolet irradiation in a color composition, a photopolymerization initiator or the like is added.

As a photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-benzyldimethylamine-1-(4-morpholinylphenyl)-butane-1 - ketone-based photopolymerization initiators such as ketones; benzo-based photopolymerization initiators such as benzo, benzoxyl ether, benzoether, benzoisopropyl ether, benzyldimethylketal; diphenyl Ketone, benzoquinone benzoic acid, benzoquinone benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, propylene benzophenone, 4-benzoquinone-4'-methyldiphenyl Benzosulfide, benzophenone photopolymerization initiator such as 3,3',4,4'-tetrakis(t-butylperoxycarboxy)benzophenone; thioxanthone, 2-chlorothioxanthone a thioxanthone photopolymerization initiator such as 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone; , 4,6-trichloro-o-triazine, 2-phenyl-4,6-bis(trichloromethyl)-o-triazine, 2-(p-methoxyphenyl)-4,6-bis ( Chloromethyl)-o-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-o-triazine, 2-piperidin-4,6-bis(trichloromethyl)- O-triazine, 2,4-bis(trichloromethyl)-6-styryl-o-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-ortho Triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-o-triazine, 2,4-trichloromethyl-(piperidinyl)-6 a triazine-based photopolymerization initiator such as triazine or 2,4-trichloromethyl (4'-methoxystyryl)-6-triazine; a borate ester photopolymerization initiator; carbazole A photopolymerization initiator; and an imidazole photopolymerization initiator. The photopolymerization initiator can be used in an amount of 5 to 150 parts by weight based on 100 parts by weight of the pigment.

The photopolymerization initiator may be used singly or in combination of two or more. As the sensitizer, α-methoxyl ether, decylphosphoric acid hydroxide, tolyl glyoxylic acid, benzyl-9,10 may be used together. - phenanthrene, camphorquinone, ethyl hydrazine, 4,4'-diethyl phenol ketone, 3,3', 4,4'-tetra (tertiary butyl peroxycarboxyl) Compounds such as benzophenone and 4,4-dimethylamine benzophenone. The sensitizer can be used in an amount of 0.1 to 150 parts by weight based on 100 parts by weight of the photopolymerization initiator.

The color composition of the present invention may contain a solvent so that the pigment is sufficiently dispersed in the pigment carrier, and coated on a transparent substrate such as a glass substrate to have a dry film thickness of 0.5 to 5 μm to form a filter segment. The solvent may, for example, be cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propylacetic acid, diethylene glycol dimethyl ether, ethylbenzene or ethyl Diol dimethyl ether, xylene, ethyl cellosolve, methyl-n-pentanone, propylene glycol monomethyl ether, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropanol, butanol, isobutyl A ketone, a petroleum solvent, or the like may be used singly or in combination. The solvent can be used in an amount of 500 to 4,000 parts by weight based on 100 parts by weight of the pigment.

Moreover, the colored composition of the present invention may contain a storage stabilizer for stabilizing the viscosity of the composition over time. Examples of the storage stabilizer include a 4-grade ammonium chloride such as benzyltrimethyl chloride or dimethylhydroxyamine; an organic acid such as lactic acid or oxalic acid; and a methyl ether; p-butyl pyrocatechol and tetraethyl An organic phosphine such as phosphine or tetraphenylphosphine; and a phosphite. The storage stabilizer can be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the pigment.

The color composition of the present invention can be prepared in the form of a solvent developing type or an alkali developing type color resist material, a gravure offset printing ink, a screen printing ink, an inkjet ink or the like. The color resist material is a pigment dispersed in a composition containing the thermoplastic resin, the thermosetting resin, the active energy ray-curable resin, the monomer, and the photopolymerization initiator.

The color composition of the present invention removes coarse particles of 5 μm or more by means of centrifugation, a sintered filter, a membrane filter, etc., and more preferably removes coarse particles of 1 μm or more, and particularly removes coarse particles of 0.5 μm or more and fine dust mixed therein. .

The color composition of the present invention is suitable for use in the preparation of color filters. The color filter is formed by selecting a red, green, blue, cyan, yellow, and magenta color on a transparent substrate or a reflective substrate by using a color composition of the present invention by a printing method or a photolithography method. A filter section of 2 to 6 colors is prepared.

As the transparent substrate, a glass plate such as quartz glass, low alkali borosilicate glass, alkali-free aluminoborosilicate glass, or soda lime glass coated with a cerium oxide film, or polycarbonate or polymethyl methacrylate is used. A resin plate such as polyethylene glycol.

The formation of the color filter segments by the printing method can be patterned by merely repeating the printing and drying of the color composition prepared as the various printing inks. Therefore, the color filter is low in manufacturing method. Cost and excellent mass production. Moreover, by the development of printing technology, it is possible to perform printing with a fine pattern having high dimensional accuracy and smoothness. For printing, it is preferred that the ink does not dry and solidify on the printing plate or on the felt cloth. Moreover, the control of the fluidity of the ink on the printing press is also important, and the viscosity of the ink can be adjusted by a dispersing agent or an extender pigment.

When the color filter sections are formed by the photolithography method, the solvent development type or alkali development is performed on the transparent substrate by a coating method such as spray coating or spin coating, slit coating, or roll coating. The color composition prepared by the color resist material is applied to a dry film thickness of 0.5 to 5 μm. Ultraviolet exposure is carried out on a film which is dried as needed, through a mask having a specific pattern which is placed in contact or non-contact with the film. Thereafter, the color filter is prepared by immersing in a solvent or an alkali developer, or by spraying a developing solution by spraying or the like, removing the uncured portion to form a desired pattern, and repeating the same operation for other colors. Further, in order to promote polymerization of the color resist material, heating may be applied as needed. If the photolithography method is used, a color filter with high precision can be prepared by a printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developer.

Further, in order to increase the ultraviolet exposure sensitivity, the color resist material may be coated and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied and dried to form a film which prevents polymerization inhibition by oxygen. After that, ultraviolet exposure is performed.

In addition to the above methods, the color filter may be produced by an electrodeposition method, a transfer method, or the like, but the color composition of the present invention may be utilized in any method. In addition, the electrodeposition method is a method of manufacturing a color filter by electrodepositing color filter segments on a transparent conductive film by electrophoresis of colloidal particles by using a transparent conductive film formed on a transparent substrate. .

Further, the transfer method is a method in which a color filter layer is formed in advance on the surface of the transferable transfer substrate, and the color filter layer is transferred to a desired transparent substrate.

Before the filter segment is formed on the transparent substrate or the reflective substrate, if a black matrix is formed in advance, the contrast of the liquid crystal display panel can be further improved. The black matrix is a multilayer film using chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed, but is not limited thereto. Further, a thin film transistor (TFT) is formed on the transparent substrate or the reflective substrate in advance, and a filter segment may be formed thereafter. By forming the filter segments on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased, and the brightness can be improved.

On the color filter, a film or a column spacer, a transparent conductive film, a liquid crystal alignment layer, or the like is formed as needed.

The color filter is bonded to the counter substrate by a sealant, and the liquid crystal is injected from the injection port provided in the sealing portion, and then the injection port is sealed, and if necessary, the polarizing film or the retardation film is bonded to the outside of the substrate. In order to prepare a liquid crystal display panel.

The liquid crystal display panel can be used for color filters using twisted nematic (TN), super twisted nematic (STN), planar switching (IPS), vertical alignment (VA), optical compensation bending (OCB), and the like. Colorized liquid crystal display mode.

The invention is further illustrated by the following examples, but the following examples are not intended to limit the scope of the invention. In addition, the "part" of an embodiment shows the "weight part."

<Preparation of Acrylic Resin Solution> In a reaction vessel in which a thermometer, a cooling chamber, a nitrogen gas introduction tube, and a stirring device were attached to four separate flasks, 70.0 parts of cyclohexanone was charged and the temperature was raised to 80 ° C. After nitrogen substitution, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and p-cumyl phenol ethylene oxide-modified acrylic acid were dropped by dropping the tube over 2 hours. Ester (AROMIX M110, manufactured by Toagosei Co., Ltd.), a mixture of 7.4 parts and 0.4 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was dried by heating at 180 ° C for 20 minutes, and the nonvolatile component was measured. According to the measured value, cyclohexanone was added to the previously synthesized resin solution to make the nonvolatile content of the resin solution 20%. , an acrylic resin solution was obtained.

<Preparation of Red Pigment 1> CIPigment Red 254 pigment: 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and mixed at 80 ° C After 8 hours, a red mixture was obtained.

The obtained red mixture was placed in 10 liters of warm water, heated to 80 ° C, and stirred for 10 hours to form a slurry. After repeated washing with water and filtration to remove sodium chloride and diethylene glycol, the mixture was dried at 80 ° C. One day and one night, 400 red pigments were obtained.

<Preparation of Red Pigment 2> The red mixture obtained in the same manner as the preparation of the red pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the water was washed and filtered to adjust the pH of the slurry to 7.0, and then sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 red pigment 2 .

<Preparation of Red Pigment 3> The red mixture obtained in the same manner as the preparation of the red pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. Then, the water was washed and filtered to adjust the pH of the slurry to 7.0, and then methyl ethyl ketone (SP value: 9.0) was added thereto, and the mixture was stirred for 4 hours while maintaining 40 °C. Thereafter, water and a solvent were removed by drying under reduced pressure to obtain 390 red pigments 3.

<Preparation of Red Pigment 4> The red mixture obtained in the same manner as in the preparation of the red pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 4 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 4 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 red pigments 4.

<Preparation of Red Pigment 5> The red mixture obtained in the same manner as the preparation of the red pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 3.0, and the mixture was stirred for 2 hours while heating to 70 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 13.0, and the mixture was stirred for 2 hours while heating to 70 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 red pigments 5.

<Preparation of Green Pigment 1> CIPigment Green 36 pigment: 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and mixed at 80 ° C 8 hours, a green mixture was obtained.

The obtained green mixture was placed in 10 liters of warm water, heated to 80 ° C, and stirred for 10 hours to form a slurry. After repeated washing with water and filtration to remove sodium chloride and diethylene glycol, the mixture was dried at 80 ° C. One day and one night, 400 green pigments were obtained.

<Preparation of Green Pigment 2> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the water was washed and filtered to adjust the pH of the slurry to 7.0, and then sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 parts of green pigment 2 .

<Preparation of Green Pigment 3> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, methyl ethyl ketone (SP value: 9.0) was added, and the mixture was stirred for 4 hours while maintaining the temperature at 25 °C. Thereafter, water and a solvent were removed by drying under reduced pressure to obtain 390 green pigments 3.

<Preparation of Green Pigment 4> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 4 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 4 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 parts of green pigment 4 .

<Preparation of Green Pigment 5> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 3.0, and the mixture was stirred for 2 hours while heating to 70 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 13.0, and the mixture was stirred for 2 hours while heating to 70 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 green pigments 5.

<Preparation of Blue Pigment 1> CIPigment Blue 36 pigment: 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and mixed at 80 ° C Stir for 8 hours to obtain a blue mixture.

The obtained blue mixture was placed in 100 liters of warm water, heated to 80 ° C, and stirred for 10 hours to form a slurry. The mixture was washed with water and filtered to remove sodium chloride and diethylene glycol, and then 80 ° C. Drying one day and one night, 400 parts of blue pigment 1 were obtained.

<Preparation of Blue Pigment 2> The blue mixture obtained in the same manner as the preparation of the blue pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water. After filtering to remove sodium chloride and diethylene glycol, hydrochloric acid was added to adjust the pH of the slurry to 2.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the water was washed and filtered to adjust the pH of the slurry to 7.0, and then sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and night to obtain 380 parts of blue pigment 2.

<Preparation of Blue Pigment 3> The blue mixture obtained in the same manner as the preparation of the blue pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, and the water was washed repeatedly. After filtering to remove sodium chloride and diethylene glycol, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, methyl ethyl ketone (SP value: 9.0) was added, and the mixture was stirred for 4 hours while maintaining the temperature at 25 °C. Thereafter, water and a solvent were removed by drying under reduced pressure to obtain 390 blue pigments 3.

<Preparation of Blue Pigment 4> The blue mixture obtained in the same manner as the preparation of the blue pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water. After filtering to remove sodium chloride and diethylene glycol, hydrochloric acid was added to adjust the pH of the slurry to 2.0, and the mixture was stirred for 4 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 4 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 parts of blue pigment 4.

<Preparation of Blue Pigment 5> The blue mixture obtained in the same manner as the preparation of the blue pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water. After filtering to remove sodium chloride and diethylene glycol, hydrochloric acid was added to bring the pH of the slurry to 3.0, and the mixture was stirred while heating to 70 ° C for 2 hours. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 13.0, and the mixture was stirred for 2 hours while heating to 70 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 parts of blue pigment 5.

<Preparation of Yellow Pigment 1> CIPigment Yellow 150 pigment: 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and mixed at 80 ° C After 8 hours, a yellow mixture was obtained.

The obtained yellow mixture was placed in 100 liters of warm water, heated to 80 ° C, and stirred for 10 hours to form a slurry. The mixture was washed with water and filtered to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. One day and one night, 400 yellow pigments were obtained.

<Preparation of Yellow Pigment 2> The yellow mixture obtained in the same manner as the preparation of the yellow pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the water was washed and filtered to adjust the pH of the slurry to 7.0, and then sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and night to obtain 380 parts of yellow pigment 2.

<Preparation of Yellow Pigment 3> The yellow mixture obtained in the same manner as the preparation of the yellow pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, methyl ethyl ketone (SP value: 9.0) was added, and the mixture was stirred for 4 hours while maintaining the temperature at 25 °C. Thereafter, water and a solvent were removed by drying under reduced pressure to obtain 390 parts of yellow pigment 3.

<Preparation of Yellow Pigment 4> The yellow mixture obtained in the same manner as in the preparation of the yellow pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 4 hours while heating to 40 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 4 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and night to obtain 380 parts of yellow pigment 4.

<Preparation of Yellow Pigment 5> The yellow mixture obtained in the same manner as the preparation of the yellow pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was washed with water and filtered to remove After sodium chloride and diethylene glycol, hydrochloric acid was added to make the pH of the slurry 3.0, and the mixture was stirred for 2 hours while heating to 70 °C. Subsequently, the mixture was washed with water and filtered to adjust the pH of the slurry to 7.0. Then, sodium hydroxide was added to adjust the pH of the slurry to 13.0, and the mixture was stirred for 2 hours while heating to 70 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and night to obtain 380 parts of yellow pigment 5.

<Preparation of Green Pigment 8> The previously obtained 14.99 parts of the green pigment 2 and 0.01 parts of sodium chloride were mixed to obtain a green pigment 8.

<Preparation of Green Pigment 9> The previously obtained 14.99 parts of the green pigment 2 and 0.01 parts of tetrabutylammonium chloride were mixed to obtain a green pigment 9.

<Preparation of Green Pigment 10> C.I. Pigment Green 36 pigment was wetted with a small amount of methanol: 5 parts, placed in 5000 parts of ion-exchange water, and stirred for 1 hour. After filtering by a centrifugal separator, the pigment was placed in 5000 parts and stirred for 1 hour. After filtering by a centrifugal separator, the pigment was again placed in 5,000 acetone and stirred for 1 hour. After filtration by a centrifugal separator, it was dried and pulverized to obtain a green pigment 10.

<Preparation of Green Pigment 11> In C.I. Pigment Green 36 pigment: 1500 parts of fuming sulfuric acid was added to 50 parts, and it was made to melt by stirring at normal temperature for 30 minutes. Next, the solution was warmed to 80 ° C and stirred for 4.5 hours. This was gently poured into 40,000 parts of ion-exchanged water, and stirred sufficiently to precipitate and recrystallize. The obtained pigment was filtered, washed with ion-exchanged water, and dried under vacuum at 70 ° C for 48 hours to obtain a green pigment 11.

<Preparation of Green Pigment 12> The previously obtained 14.99 parts of the green pigment 2 and the sacrificial enthalpy of 0.01 were mixed to obtain a green pigment 12.

<Preparation of Green Pigment 13> The previously obtained 14.99 parts of the green pigment 2 and the carbon black 0.01 were mixed to obtain a green pigment 13.

<Preparation of Green Pigment 14> The previously obtained 14.99 parts of the green pigment 2 and 0.01 parts of C.I. Pigment Black 32 pigment ("Paliogen Black L 0086" manufactured by BASF Corporation) were mixed to obtain a green pigment 14.

<Preparation of Green Pigment 15> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, nitric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 2 hours while heating to 40 °C. Subsequently, the water was washed and filtered to adjust the pH of the slurry to 7.0, and then sodium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 parts of green pigment 2 .

<Preparation of Green Pigment 16> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol, nitric acid was added to make the pH of the slurry 2.0, and the mixture was stirred for 2 hours while heating to 40 °C. Then, the washing and filtration were repeated to adjust the pH of the slurry to 7.0, and then potassium hydroxide was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. The water was washed repeatedly, filtered to adjust the pH of the slurry to 7.0, and dried at 80 ° C for one day and one night to obtain 380 parts of green pigment 2 .

<Preparation of Green Pigment 17> The green mixture obtained in the same manner as the preparation of the green pigment 1 was placed in 10 liters of warm water, and heated to 80 ° C while stirring for 2 hours to form a slurry, which was repeatedly washed with water and filtered to remove After sodium chloride and diethylene glycol were added, an aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 14.0, and the mixture was stirred for 2 hours while heating to 40 °C. After washing with water and filtration to adjust the pH of the slurry to 7.0, p-xylene (SP value: 8.8) was placed, and the mixture was stirred for 4 hours while maintaining 25 °C. Thereafter, the water and the solvent were removed by drying under reduced pressure to obtain 390 green pigments 3.

The light absorption value of the pigment was measured for each of the obtained pigments by the method described in the best mode for carrying out the invention. The results are shown in Table 1-A and Table 1-B.

Examples 1 to 26 and Comparative Examples 1 to 27

According to the formulation shown in Table 1-A and Table 1-B, the mixture was uniformly stirred and mixed, and dispersed in a pico mill for 10 hours using zirconium beads having a diameter of 0.1 mm, and then filtered through a filter of 5 μm to prepare pigments of various colors. Dispersions.

Next, the mixture of the following composition was stirred and mixed until it was uniform, and then filtered through a filter of 1 μm to prepare a color composition.

Pigment dispersion 60.0 photopolymerization initiator ("IGGACURE 907" manufactured by Chiba Special Chemical Co., Ltd.) 1.2 dipentaerythritol triacrylate and hexaacrylate ("ARONIX M400" manufactured by Toagosei Co., Ltd.) 4.2 sensitizer (guarantee) "EAB-F" manufactured by Toya Chemical Co., Ltd.) 0.4 parts of previously prepared acrylic resin solution 11.0 parts of cyclohexanone 23.2 parts

The obtained color composition was applied onto a glass substrate of 100 mm × 100 mm and a thickness of 1.1 mm by a spin coater, dried at 70 ° C for 20 minutes, and then exposed to ultraviolet light at 150 mJ using an ultrahigh pressure mercury lamp. The substrate was heated and applied at 230 ° C for 1 hour, and after cooling, the chromaticity Y of the obtained coating film under the F10 light source was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.). The measurement results are shown in Table 1-A and Table 1-B. Further, the coating film thickness of the color-color composition was adjusted as follows: x for the red color composition under the F10 light source was 0.582, y for the green color composition under the F10 light source was 0.505, and the blue color composition was for the F10 light source. The lower y is 0.181, and the x of the yellow color composition under the F10 light source is 0.438.

In Table 1-A and Table 1-B, red pigment 6: "IRGAFORRED BT-CF" red pigment manufactured by Chiba Special Chemical Co., Ltd. 7: "IRGAFORRED B-CF" green pigment manufactured by Chiba Special Chemical Co., Ltd. 6: Toyo Ink Manufacturing Co., Ltd. "Lionol Green 6YK" green pigment 7: "Lionol Green 6Y501" made by Toyo Ink Co., Ltd. Blue pigment 6: "Lionol Blue ES" made by Toyo Ink Co., Ltd. Blue pigment 7: "Firstgenblue EP" manufactured by Dainippon Ink Chemical Industry Co., Ltd. -7S" yellow pigment 6: "BAYFASR yellow Y-5688" yellow pigment manufactured by Lanxess Co., Ltd. 7: "BAYPLAST yelolw 5GN" dispersing agent manufactured by Lanxess Co., Ltd.: "PB-821" manufactured by Ajinomoto Fine-Techno Co., Ltd. Solvent: methoxypropyl acetate

Example 27

The red color composition of Example 27 was mixed with the red color composition of 45 obtained in Example 3 and the yellow color composition obtained in Example 15, and the red color composition of Example 27 was obtained. The obtained color composition was adjusted in film thickness so as to be 0.602 after completion under the F10 light source. After drying under reduced pressure, an ultrahigh pressure mercury lamp was used, and ultraviolet light exposure was performed with an integrated light amount of 150 mJ and an illuminance of 30 mW. The substrate was heated and coated at 230 ° C for 1 hour, and after cooling, the color of the obtained red filter segment under the F10 light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) (Y , x, y).

Comparative Example 18

The red color composition obtained in Example 3 was changed to the red color composition obtained in Comparative Example 1, and the yellow color composition obtained in Example 15 was changed to the red color composition of Comparative Example 18 to obtain A red filter segment was produced in the same manner as in Example 27 except that the red color composition of Comparative Example 18 was used, and a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) was used to measure under the F10 light source. Chromaticity (Y, x, y).

Comparative Example 20

The red color composition obtained in Example 3 was changed to the red color composition obtained in Comparative Example 2, and the yellow color composition obtained in Example 15 was changed to the yellow color composition of Comparative Example 11 to obtain A red filter segment was produced in the same manner as in Example 27 except that the red color composition of Comparative Example 20 was used, and a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) was used to measure under the F10 light source. Chromaticity (Y, x, y).

Example 28

The green color composition of Example 28 was obtained by mixing 30 parts of the green color composition obtained in Example 5 and 20 parts of the yellow color composition obtained in Example 15. The obtained color composition was adjusted in film thickness so as to be 0.556 after completion under the F10 light source, and after drying under reduced pressure, ultraviolet light exposure was performed using an ultrahigh pressure mercury lamp with an integrated light amount of 150 mJ and an illuminance of 30 mW. The substrate was heated and coated at 230 ° C for 1 hour, and after cooling, the color of the obtained green filter section under the F10 light source was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) (Y). , x, y).

Comparative Example 19

The green color composition obtained in Example 5 was changed to the green color composition obtained in Comparative Example 4, and the yellow color composition obtained in Example 15 was changed to the yellow color composition of Comparative Example 11 to obtain A green filter segment was produced in the same manner as in Example 28 except that the green color composition of Comparative Example 19 was used, and a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) was used to measure under the F10 light source. Chromaticity (Y, x, y).

Comparative Example 21

The green color composition obtained in Example 5 was changed to the red color composition obtained in Comparative Example 6, and the yellow color composition obtained in Example 15 was changed to the yellow color composition of Comparative Example 12 to obtain A green filter segment was produced in the same manner as in Example 28 except that the green color composition of Comparative Example 21 was used, and a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optics Co., Ltd.) was used to measure under the F10 light source. Chromaticity (Y, x, y).

Comparing the results of Example 27 and Comparative Examples 18, 20, and Example 28 with Comparative Examples 19 and 21, it is understood that the filter region is used in the case of Examples 27 and 28 in which the pigment having a light absorption value is within a specific range. The brightness of the segment is high and excellent. On the contrary, in the case of Comparative Examples 19 and 20 in which the pigment absorption value exceeded the specific range of the pigment, or in the case of Comparative Examples 18 and 21 in which the pigment was less than the specific range, the brightness improvement effect was not obtained.

Example 29 and Comparative Examples 22, 23

The white brightness as a color filter is further compared.

Using the chromaticity (Y, x, y) of each color filter section measured in Examples 12, 27, and 28 under the F10 light source, the white luminance of the color filter was calculated by calculation as Example 29. The white luminance calculated from the chromaticity of each color filter section measured in Comparative Examples 7, 18, and 20 was used as Comparative Example 22, and the color of each color filter section measured from Comparative Examples 9, 19, and 21 was used. The white luminance calculated by the degree is used as Comparative Example 23. The results are shown in Table 3.

As shown in Table 3, color filters of Comparative Examples 22 and 23 having red, green, and blue filter segments formed using color compositions of respective colors using pigments having a light absorption value outside a specific range are shown. The color filter of Example 29 having a red, green, and blue filter section formed using color compositions of respective colors of the pigment having a light absorption value within a specific range exhibits a very high white luminance Y.

Claims (9)

A color composition comprising: a pigment carrier consisting of a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a red pigment obtained by washing with a strong alkali, The light absorption value of the wavelength of 400 to 575 nm is 8.0 to 14.0, and the above-mentioned strong alkali washing includes adjusting the pH of the slurry containing the red pigment to 13.0 to 14.0. A color composition comprising: a pigment carrier consisting of a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a green pigment obtained by washing with a strong alkali, The absorption value of the wavelength of 600 to 700 nm is 11.2 to 13.0, and the above-mentioned strong alkali washing comprises adjusting the pH of the slurry containing the green pigment to 13.0 to 14.0. A color composition comprising: a pigment carrier consisting of a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a blue pigment obtained by washing with a strong alkali, The absorbance at a wavelength of 550 to 650 nm is 9.0 to 12.0, wherein the washing of the strong alkali comprises adjusting the pH of the slurry containing the blue pigment to 13.0 to 14.0. A color composition comprising: a pigment carrier consisting of a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; and a yellow pigment obtained by washing with a strong alkali, The absorbance at a wavelength of 400 to 500 nm is 5.0 to 10.0, wherein the washing of the strong alkali comprises adjusting the pH of the slurry containing the yellow pigment to 13.0 to 14.0. A method for preparing a colored composition, comprising the steps of: washing a pigment with a strong alkali and dispersing it in a pigment composed of a transparent resin, a precursor thereof, or a mixture of a transparent resin and a precursor thereof; The above-mentioned strong alkali washing comprises adjusting the pH of the slurry containing the pigment to 13.0 to 14.0. The method for producing a color composition according to claim 5, wherein the pigment is a red pigment, and the red pigment obtained by washing with the strong alkali has an absorbance at a wavelength of 400 to 575 nm of 8.0 to 14.0. The method for producing a color composition according to claim 5, wherein the pigment is a green pigment, and the green pigment obtained by washing with the strong alkali has an absorbance at a wavelength of 600 to 700 nm of 11.2 to 13.0. The method for preparing a color composition according to claim 5, wherein the pigment is a blue pigment, and the blue pigment obtained by washing with the strong alkali has an absorbance at a wavelength of 550 to 650 nm of 9.0 to 12.0. . The method for producing a color composition according to claim 5, wherein the pigment is a yellow pigment, and the red pigment obtained by washing with the strong alkali has an absorbance at a wavelength of 400 to 500 nm of 5.0 to 10.0.