JP2007206483A - Green color composition for color filter, method for manufacturing same, and color filter using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a stable green color composition for a color filter with high contrast and excellent fluidity by using a fine green pigment and a fine yellow pigment which show difficulty in dispersion due to a higher contrast of a color filter, and to provide a color filter with a high contrast by using the above composition. <P>SOLUTION: In the method for manufacturing a color composition for a color filter, pigments having difficulty in stabilizing dispersion are made uniform by repeating a plurality of times a step of kneading a mixture containing a green pigment, a yellow pigment, a dye derivative having a basic group or an acidic group, and a transparent resin by a roll mill into a sheet material, then pulverizing the material to obtain green co-chips, and dissolving the chips into an organic solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a colored composition for a color filter used in the production of a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a method for producing the same. The present invention also relates to a color filter used for a color liquid crystal display device, a color image pickup tube element and the like.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for contrast.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  In order to achieve high brightness and high contrast of the color filter, the pigment contained in the filter segment is refined. Various refining treatment methods for pigments (crude particles with a particle size of 10-100 μm produced by chemical reaction are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the size of the pigment is reduced, the pigment whose primary particles or secondary particles have been made finer is generally easily aggregated, and if the fineness is advanced too much, a huge lump of pigment solid is formed.

  Properly refined pigment is dispersed in a pigment carrier containing a resin, etc., and a dispersion in which the secondary particles are stabilized as close to the primary particles as possible is prepared, and an initiator and a monomer are blended. A color resist coating solution can be used to form filter segments. However, when the aggregation of the pigment is strong and cannot be dispersed, the brightness and contrast ratio of the color filter are reduced by going through the pigment refinement process. Also, when the dispersion stability is low, the aggregation of pigment particles progresses over time, causing the viscosity of the colored composition to increase and poor fluidity. When forming a filter segment, the coating liquid is spin-coated on a glass substrate. A coating film having a uniform film thickness cannot be obtained due to poor spin coatability and leveling failure.

As a means for uniformly dispersing such a pigment that is difficult to stabilize in a pigment carrier, it is effective to go through a pigment dispersion step using a roll mill such as a two-roll or three-roll.
In the production of a color filter coloring composition, a mixture containing a pigment, a pigment derivative and a pigment carrier is obtained by grinding a mixture of a mixture containing a pigment, a pigment derivative and a pigment carrier into a sheet-like product by a two-roll mill, and then pulverizing the mixture. Color chips are used.
The color chip manufactured as described above is easily dissolved by simply stirring and dissolving in an organic solvent. By using a pigment dispersion obtained by dispersing this organic solution with a media disperser such as a bead mill, the dispersibility, fluidity, number of foreign substances, and contrast ratio when formed into a coating film are excellent to some extent. Although a colored composition can be obtained, it is difficult to say that it is sufficient in view of the recent increasing level of demand for color filters.
In addition, a foreign material shows the pigment aggregate, the gel-like material derived from resin, etc.

In addition, since each color filter segment such as RGB (red, green, blue) forming a color filter generally cannot obtain a target spectral spectrum only with a single pigment, a colored composition containing two or more pigments is used. Although often used, different types of pigments tend to cause heteroaggregation, and when two or more types of pigments are included, it is particularly difficult to obtain a stable coloring composition.
For example, a copper phthalocyanine green pigment having excellent resistance is generally used for a coloring composition used for forming a green filter segment. However, since it is difficult to obtain a desired spectrum by using only a copper phthalocyanine green pigment, an yellow pigment is used. The spectral spectrum is adjusted by mixing. However, when a yellow pigment dispersion is mixed with a copper phthalocyanine green pigment dispersion, the balance of the dispersion system is often lost, and it is generally difficult to obtain a stable green coloring composition having high contrast.
JP-A-10-130547 JP 2000-119559 A Japanese Patent Laid-Open No. 2003-96196

  An object of the present invention is to produce a stable green coloring composition for a color filter having high contrast and excellent fluidity by using a fine green pigment and a fine yellow pigment that have become difficult to disperse due to the high contrast of the color filter. And providing a high-contrast color filter using the same.

  The green coloring composition for a color filter of the present invention comprises a step of kneading a mixture containing a green pigment, a yellow pigment, a pigment derivative having a basic group or an acidic group and a transparent resin into a sheet by a roll mill. It is characterized in that a green cochip obtained by performing a plurality of times and pulverizing is dissolved in an organic solvent.

The method for producing a coloring composition for a color filter according to the present invention is a sheet-like product obtained by kneading a mixture containing a green pigment, a yellow pigment, a pigment derivative having a basic group or an acidic group, and a transparent resin with a roll mill. The green co-chip obtained by carrying out the above-described process a plurality of times and pulverizing is dissolved in an organic solvent.
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.

  Since the green color composition for a color filter of the present invention uses a green co-chip composed of a mixture containing a green pigment and a yellow pigment, a pigment derivative having a basic group or an acidic group, and a transparent resin, the green pigment and the yellow pigment are used. It has higher contrast and excellent dispersion stability than a green coloring composition obtained by toning and blending each color coloring composition using a single color chip of pigment. Moreover, a color filter using this can form a high-contrast color filter.

First, the green co-chip contained in the green coloring composition for color filters of the present invention will be described.
The green coloring composition for a color filter of the present invention is obtained by co-chiping a mixture containing a green pigment and a yellow pigment, which are difficult to disperse, and a pigment derivative and a transparent resin. Aggregation can be suppressed as compared with the case where a colored composition is prepared using a monochromatic chip of a pigment, and the contrast is higher and the dispersion stability is excellent.

  As the green pigment used when producing the green co-chip contained in the green coloring composition of the present invention, two or more organic or inorganic pigments can be mixed and used. Particular preference is given to using pigments.

Hereinafter, specific examples of the green pigment and the yellow pigment that can be used for the green cochip contained in the green coloring composition of the present invention are shown by color index numbers.
Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37 can be used. Among these, C.I. I. Pigment Green 7, 36 is preferable.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 Or the like can be used 181,182,185,187,188,193,194,198,199,213,214, higher luminance Among them, C. in view of high contrast I. Pigment Yellow 138, 139, 150, 185 are preferred.
The content of the yellow pigment is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total amount of the pigment (total weight of the green pigment and the yellow pigment).

The green coloring composition of the present invention may be used in combination with a green dye or a yellow dye other than the pigment. Examples of pigments other than pigments include dyes and natural pigments.
The specific surface area of the green pigment is preferably 60 to 130 m ² / g, and the specific surface area of the yellow pigment is preferably 60 to 160 m ² / g.
As a means for controlling the specific surface area of the pigment, a method of controlling the specific surface area by mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and a desired specific surface area of the pigment is controlled. There are a method of precipitating a pigment (referred to as a precipitation method), a method of producing a pigment having a desired specific surface area at the time of synthesis (referred to as a synthetic precipitation method), and the like. Depending on the synthesis method and chemical properties of the pigment to be used, an appropriate method can be selected for each pigment.

When producing green cochips, the pigment green cochip is manufactured in order to prevent pigment aggregation, maintain a finely dispersed state of the pigment, and produce a color filter with high brightness and high contrast ratio and high color purity. Add the pigment derivative. The content of the pigment derivative is preferably 0.001 to 40 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of the green pigment and the yellow pigment.
A dye derivative is a compound in which a basic or acidic substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds that are not generally called dyes, such as naphthalene, anthraquinone, and acridone. Examples of the dye derivative include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-9-176511. What is described in the gazette etc. can be used and these can be used individually or in mixture of 2 or more types.

式（３）

式（４）

式（５）

Specific examples of the basic group possessed by the dye derivative include substituents represented by the following general formulas (2), (3), (4) and (5). In particular, a dye derivative having a basic group containing a triazine ring represented by the following general formula (5) is preferably used because of a large pigment dispersion effect.
Formula (2)

Formula (3)

Formula (4)

Formula (5)

In the equations (2) to (5),
X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, a phenyl group which may be substituted, or a combination of R ₁ and R ₂ Represents an optionally substituted heterocycle containing a nitrogen, oxygen or sulfur atom. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R _{3 represents} an alkyl group which may be substituted, an alkenyl group which may be substituted or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ₄ , R ₅ , R ₆ , R ₇ : each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.
Z: represents an alkylene group that may be substituted, an alkenylene group that may be substituted, or a phenylene group that may be substituted. As for carbon number of an alkylene group and an alkenylene group, 1-8 are preferable.
R: The substituent shown by Formula (6) or the substituent shown by Formula (7) is represented.
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (6) or a substituent represented by the formula (7).
In formulas (6) and (7), R _{1 to} R ₇ and n are as defined above.

式（７）

Formula (6)

Formula (7)

Specific examples of the acidic group possessed by the dye derivative include a sulfonic acid group and a terephthalic acid monoamidomethyl group.
The sulfonic acid group may form a salt with a metal such as aluminum, potassium, sodium, calcium, or an amine. In particular, an aluminum salt of a pigment derivative having an acidic group is preferably used because of a large dispersion effect of the treated pigment.

  Examples of the organic dye constituting the dye derivative include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, Anthraquinone dyes such as pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complexes And system dyes.

  The transparent resin composed of the precursor or a mixture thereof used when producing the green co-chip contained in the green coloring composition of the present invention preferably has a transmittance in the entire wavelength region of 400 to 700 nm in the visible light region. Is 80% or more, more preferably 95% or more. The transparent resin includes a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin, and a precursor thereof includes a monomer or an oligomer that is cured by active energy ray irradiation to form a transparent resin. These may be used alone or in combination of two or more. The content of the transparent resin is preferably 30 to 700 parts by weight, more preferably 60 to 450 parts by weight with respect to 100 parts by weight of the total of the green pigment and the yellow pigment.

  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 resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), 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.

  The transparent resin preferably contains a transparent resin obtained by copolymerizing the compound [A] represented by the general formula (1) and another compound [B] having an ethylenically unsaturated double bond. Since the transparent resin exhibits an excellent dispersion effect for almost all pigments, it functions to prevent the pigments from agglomerating in the coloring composition and to maintain a finely dispersed state of the pigments. Therefore, when a filter segment is formed using the green coloring composition of the present invention obtained by dissolving the green co-chip containing the transparent resin in an organic solvent, a filter segment with less pigment aggregates can be formed. A color filter with high transmittance and high brightness can be produced.

（Ｒ_aは、水素原子またはメチル基、Ｒ_bは炭素数２または３のアルキレン基、Ｒ_cは水素原子またはベンゼン環などの置換基を含んでも良い炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） Formula (1)

(R _a represents a hydrogen atom or a methyl group, R _b represents an alkylene group having 2 or 3 carbon atoms, and R _c represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a substituent such as a benzene ring. n represents an integer of 1 to 15.)

The compound [A] represented by the general formula (1), which is a constituent component of the transparent resin, has good adsorption / orientation on the pigment surface due to the effect of π electrons on the benzene ring. In particular, when [A] is paracumylphenol ethylene oxide or propylene oxide modified (meth) acrylate, its steric effect is added and a better adsorption / orientation plane can be formed on the pigment, which is more effective. . Although the carbon number of the alkyl group of R _c is from 1 to 20, preferably 1 to 10. When the number of carbon atoms is from 1 to 10, the alkyl group becomes an obstacle to suppress the approach between the resins and promote the adsorption / orientation to the pigment. However, when the number of carbon atoms exceeds 10, the steric hindrance effect of the alkyl group increases and the benzene ring Even the adsorption / orientation to the pigment surface is hindered. This becomes more prominent as the chain length becomes longer, and when the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered.

  Examples of the compound [A] include phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, and nonylphenol propylene oxide modified (meth) acrylate.

  As the compound [B], (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate acid phosphooxyethyl (meth) Examples thereof include acrylate, acid phosphooxypropyl (meth) acrylate, 3 chloro 2-acid phosphooxyethyl (meth) acrylate, and acid phosphooxypolyethylene glycol mono (meth) acrylate.

The ratio of the compound [A] in the compound constituting the transparent resin is preferably 0.1 to 50 parts by weight, more preferably 10 to 35 parts by weight. When the ratio of the compound [A] is less than 0.1 parts by weight, a sufficient pigment dispersion effect cannot be obtained, and when it is more than 50 parts by weight, compatibility with other components in the coloring composition decreases. In some cases, precipitation of the monomer or photopolymerization initiator may occur.
The weight average molecular weight (Mw) of the transparent resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.

  The green cochip contained in the green coloring composition of the present invention can be added with a resin-type dispersant that is excellent in pigment dispersibility and has a large effect of preventing re-aggregation of the pigment after dispersion. The resin-type dispersant can be used in an amount of preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

  The resin-type dispersant has an acidic group or a basic group because it adsorbs to the surface of the pigment using an acidic group or a basic group as an anchor, and the rebound effect of the polymer acts effectively to express dispersion stability. A polymer is preferred. The acidic group is preferably a sulfone group from the viewpoint of excellent adsorption characteristics, and the basic group is preferably an amino group from the viewpoint of excellent adsorption characteristics. In addition, the combined use of a pigment derivative having an acidic group and a resin type dispersant having a basic group, or the combined use of a pigment derivative having a basic group and a resin type dispersant having an acidic group is compatible with a transparent resin. It is preferable because it is good.

  As a resin type dispersant having an acidic group or a basic group, a comb polymer having a structure in which a branch polymer part is graft-bonded to a trunk polymer part having an acidic group or a basic group has an excellent steric repulsion effect of the branch polymer part. It is preferable because it is more soluble in organic solvents. Furthermore, a comb polymer having a molecular structure in which two or more branch polymers are grafted to one molecule of the trunk polymer is more preferable for the above reason.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 320 manufactured by Abyssia 0, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  The green coloring composition of the present invention is obtained by performing the process of kneading the above mixture (pigment, dye derivative, transparent resin, and further optional components) with a two-roll mill to form a sheet-like material a plurality of times. The green co-chip obtained by pulverization is used, but the above mixture is a mixture in which each component is sufficiently mixed and homogeneously dispersed before being mixed with a two-roll mill. Is particularly preferred.

The kneader used to knead the mixture is a two-roll mill, which itself has a roll rotation speed ratio of 1: 1.1 to 1: 1.3, and a roll gap of 0.5 to 3. It is an absolute requirement to use it within the range of 0.0 mm. When the rotational speed ratio is less than 1: 1.1, the shearing force is hardly applied and the dispersion of the pigment does not proceed. On the other hand, when the rotation speed ratio exceeds 1: 1.3, the obtained sheet-like material slips, and the shearing force is hardly applied, and the dispersion of the pigment does not proceed. When the gap between the rolls is less than 0.5 mm, the mixture is not industrial because it is difficult for the mixture to pass between the two rolls. Further, the resulting sheet-like material has a strong impact, and there is a risk of ignition depending on the pigment used. When the gap between the rolls exceeds 3.0 mm, the shearing force is hardly applied and the pigment dispersion does not proceed.
In the step of kneading into a sheet, the mixture is passed through two rotating rolls of the two-roll mill to form a sheet. The material is folded into several sheets and passed through a roll mill a plurality of times. Also, instead of the above method of passing the mixture through the roll gap and kneading, a method of winding the mixture around two rolls and kneading can be adopted, and this method has the same effect as the above method. can get.

  The green co-chip manufacturing process can be performed in the presence of a solvent as necessary. Examples of the solvent include alcohols such as methyl alcohol and ethyl alcohol, esters such as ethyl acetate, propyl acetate, and propylene glycol methyl ether acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as benzene, toluene, and xylene. Etc. can be used. Further, the solvent is not limited to one type, and two or more types can be mixed and used, or the above components may be mixed to form the mixture.

  The said process is normally performed in a 20-120 degreeC temperature range. In addition, the rotational speed of the roll of the two-roll mill is usually 10 to 50 r. p. m. The rotational speed ratio of the two rolls is adjusted to the above value within this range.

Next, the green coloring composition for color filters of the present invention will be described.
The green coloring composition for a color filter of the present invention is necessary for a pigment dispersion excellent in dispersibility and fluidity obtained by stirring and dissolving the above-mentioned green co-chip in an organic solvent and dispersing with a media dispersing machine such as a bead mill. Accordingly, it can be adjusted by blending a transparent resin, a monomer or oligomer that is cured by irradiation with active energy rays to form a transparent resin, a photopolymerization initiator, a solvent and the like.

  The pigment is preferably contained in the green coloring composition (coloring composition including all components such as pigment, transparent resin, initiator and solvent) in a proportion of 0.5 to 10% by weight. Further, the pigment is finally contained in the filter segment in a proportion of preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the remainder is made of a transparent resin, an active energy ray curable resin and a monomer or oligomer. Become substantial.

In addition, the organic solvent is sufficiently dispersed in the transparent resin composition and applied on a transparent substrate such as a glass substrate so that the dry thickness of the green coloring composition of the present invention is 0.2 to 5 μm. Used to contain an organic solvent to facilitate the formation of the filter segment. The organic solvent can be used in an amount of preferably 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the pigment.
Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  As the transparent resin used in the green coloring composition of the present invention, the transparent resin can be used, and an active energy ray curable resin can also be used.

As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or 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 in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid 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 used in the green coloring composition of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 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, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (Meth) 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- Examples include hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc., and these can be used alone or in combination of two or more. Rukoto can.

When the composition is cured by irradiation with light such as ultraviolet rays, a photopolymerization initiator or the like is added to the green coloring composition of the present invention. The photopolymerization initiator can be used in an amount of preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the total pigment.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p -Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, 2,4-bis (trick (Romethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -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, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.

  These photopolymerization initiators are used alone or in admixture of two or more. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanth Such as lenquinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. A compound can also be used in combination. The sensitizer can be used in an amount of preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

In the green coloring composition of the present invention, a dispersion aid such as a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in a transparent resin using the dispersion aid is used. A color filter having excellent transparency can be obtained. The dispersion aid can be used in an amount of preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as laurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

The green coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time. The storage stabilizer can be used in an amount of preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total pigment.
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 green coloring composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter, etc., and coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to remove the dust.

Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which comprises the filter segment formed from the green coloring composition for color filters of this invention. The color filter includes a subtractive color mixing type including an additive color mixing type including at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the green filter segment is the present invention. It is formed using the green coloring composition.

As each color coloring composition other than green, it can form using each color pigment, the said transparent resin, and each normal color coloring composition containing the said polyfunctional monomer.
Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 are used. The red coloring composition includes C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.

  Examples of the blue coloring composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the green coloring composition of this invention and each normal color coloring composition by the photolithographic method.
As the substrate, a glass plate having a high transmittance with respect to visible light, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, each color-colored photosensitive composition prepared as a color resist material of the above-mentioned solvent development type or alkali development type that is cured by light irradiation is applied to a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. To apply a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

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.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” and “%” mean “parts by mass” and “% by mass”. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).
(Preparation of green processing pigment)
[Green pigment 1]
Phthalocyanine green pigment C.I. I. Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.): 500 parts, sodium chloride: 2500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 100 ° C. for 2 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of green-treated pigment were obtained.

[Green pigment 2]
Green pigment 2 was obtained in the same manner except that the kneader kneading time was changed to 6 hours in the production method of green pigment 1.

[Green pigment 3]
Green pigment 3 was obtained in the same manner except that the amount of sodium chloride was changed to 5000 parts and the kneading time using a kneader was changed to 12 hours in the production method of green pigment 1.

(Preparation of yellow-treated pigment)
[Yellow Pigment 1]
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (BASF “Paliotol Yellow K0960-HD”): 500 parts, sodium chloride: 2500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 100 ° C. for 2 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of a yellow-treated pigment were obtained.

[Yellow Pigment 2]
A yellow pigment 2 was obtained in the same manner except that the kneader kneading time was changed to 6 hours in the method for producing yellow pigment 1.

[Yellow Pigment 3]
A yellow pigment 3 was obtained in the same manner except that the kneader kneading time was changed to 12 hours in the method for producing yellow pigment 1.
[Yellow Pigment 4]
A yellow pigment 4 was obtained in the same manner except that the amount of sodium chloride was changed to 5000 parts and the kneading time using a kneader was changed to 12 hours in the production method of yellow pigment 1.

(Synthesis of sulfonated dye derivative aluminum salt)
Quinophthalone yellow pigment C.I. I. 30 parts of Pigment Yellow 138 (“Pariotole Yellow K0960-HD” manufactured by BASF) was dissolved in 300 parts of 101% sulfuric acid and stirred at 70 ° C. for 8 hours for sulfonation reaction. The end point of the reaction was defined as the point at which no change in the spectrum was observed by measuring the spectrum of the sulfuric acid solution. Next, this reaction solution was poured into 3000 parts of ice water, and the precipitated sulfonated dye derivative was separated by filtration and washed with water to obtain a sulfonated dye derivative paste.
The obtained sulfonated dye derivative was subjected to LC-MASS analysis. In HPLC (column: “ODS-100S” manufactured by Tosoh Corporation), the molecular weight of the main peak occupying an area ratio of 80% is Mw = 774 (electron spray method, minus mode). I. Consistent with the molecular weight of the monosulfonated derivative of Pigment Yellow 138. Further, it was identified by 1H-NMR as a sulfonated dye derivative having the following structure.

Formula (8)

The obtained paste of the sulfonated dye derivative was redispersed in 10,000 parts of water (pH 2.5). Next, the solution was adjusted to pH 11 with an aqueous sodium hydroxide solution and dissolved to give a red solution. To this solution, 278 parts of an aqueous aluminum sulfate solution (liquid sulfuric acid band) was gradually added. Precipitates appeared one after another from the dropped portion, and the pH decreased with the addition. At the end of the addition, pH 3.6 and bleed were not observed. The slurry containing this precipitate was filtered off and washed with water. I. An aluminum salt of a sulfonated derivative of Pigment Yellow 138 was obtained.
The yield after drying was 334 parts, and the yield was 99%. The resulting aluminum salt of the sulfonated dye derivative is presumed to have the following structure.

Formula (9)

(Synthesis of ammonium salt of sulfonated dye derivative)
Quinophthalone yellow pigment C.I. I. 6 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF) was added to 78 parts of fuming sulfuric acid (25% SO 3) at 15 ° C. with stirring. After stirring for 3 hours, it was added onto 150 parts of ice. After standing for 30 minutes, the resulting suspension was filtered and the resulting product was washed with 30 parts of water. The product was put into 200 parts of water and neutralized with an aqueous ammonia solution (added aqueous ammonia until pH was 7). 45 parts of ammonium chloride was added and stirred at 80 ° C. for 30 minutes, and the deposited precipitate was filtered at 60 ° C. The obtained wet crystals were washed with water, dried at 80 ° C., and 10 parts of C.I. I. An ammonium salt of a sulfonated derivative of Pigment Yellow 138 was obtained.
The resulting ammonium salt of the sulfonated dye derivative is presumed to have the following structure.

Formula (10)

(Synthesis Example 1 of transparent resin)
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained.
After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. A resin solution was prepared by addition. The obtained transparent resin 1 had a weight average molecular weight Mw of 40000.

合成例２の透明樹脂溶液 ２０．０部 (Synthesis example 2 of transparent resin)
70 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 5.5 methacrylic acid at the same temperature. 3 parts, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.) as monomer (a), 0.4 part of 2,2'-azobisisobutyronitrile Was added dropwise over 2 hours to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin copolymer solution was obtained.
After cooling to room temperature, about 2 g of the transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized transparent resin solution so that the nonvolatile content was 20% by weight. A resin solution was prepared by addition. The weight average molecular weight Mw of the obtained transparent resin 2 was 27000.
[Example 1]
(Chip manufacturing method)
A mixture having the following composition was mixed in advance, and then kneaded with a two-roll mill to obtain a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. After repeating this process 10 to 40 times, a green cochip was produced by pulverization with a pulverizer.
Green pigment: C.I. I. Pigment Green 36 7.1 parts ("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Yellow pigment 1 3.9 parts Basic pigment derivative containing a triazine ring (formula (11) below) 1.0 part formula (11)

20.0 parts of transparent resin solution of Synthesis Example 2

(Method for producing pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 3 hours with an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 1 mm, and then filtered through a 5 µm filter. A pigment dispersion was prepared.
Green co-chip prepared in Example 1 16.0 parts Transparent resin solution of Synthesis Example 2 20.0 parts Cyclohexanone 64.0 parts

(Method for producing green coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.
Pigment dispersion prepared in Example 1 67.0 parts Transparent resin solution of Synthesis Example 2 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals) 1 .4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 22.4 parts

[Example 2]
(Chip manufacturing method)
A mixture having the following composition was mixed in advance, and then kneaded with a two-roll mill to obtain a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. After repeating this process 10 to 40 times, a green cochip was produced by pulverization with a pulverizer.
Green pigment 1 7.1 parts Yellow pigment 2 3.9 parts Basic pigment derivative containing triazine ring (the above formula (11)) 1.0 part Transparent resin solution of Synthesis Example 1 20.0 parts

(Method for producing pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 3 hours with an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 1 mm, and then filtered through a 5 µm filter. A pigment dispersion was prepared.
Green cochip prepared in Example 2 16.0 parts Transparent resin solution of Synthesis Example 1 20.0 parts Cyclohexanone 64.0 parts

(Method for producing green coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.
Pigment dispersion prepared in Example 2 67.0 parts Transparent resin solution of Synthesis Example 1 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization initiator (“Irgacure 907” manufactured by Ciba Specialty Chemicals) 1 .4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts cyclohexanone 22.4 parts

［比較例１］
（緑色チップ製造方法）
下記の組成の混合物を予め充分混合した後、２本ロールミルにて練肉し、シート状物とした。このシート状物を数枚に折り畳み、再度２本ロールミルに通した。この工程を１０〜４０回繰り返し行った後、粉砕機で粉砕することでカラーチップを作製した。
緑色顔料：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ３６ １１．０部
（東洋インキ製造社製「リオノールグリーン ６ＹＫ」）
トリアジン環を含む塩基性顔料誘導体（上記式（１１）） １．０部
合成例２の透明樹脂溶液 ２０．０部
（緑色顔料分散体の製造方法）
下記の組成の混合物を均一に撹拌混合した後、直径１ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ−２５０ ＭＫII」）で３時間分散した後、５μｍのフィルタで濾過し、顔料分散体を作製した。
比較例１で調整した緑色チップ １６．０部
合成例２の透明樹脂溶液 ２０．０部
シクロヘキサノン ６４．０部 [Examples 3 to 10]
The pigment, dye derivative, transparent resin, and resin type dispersant shown in Table 1 were blended in the same manner as in Example 1 or 2 to obtain a photosensitive green coloring composition (green resist material). In addition, when adding the resin-type dispersant, 6.0 parts of the transparent resin solution was recorded at the time of manufacturing the chip, and 1.2 parts of the resin-type dispersant shown in Table 1 was added instead. As the basic pigment derivative not containing a triazine ring, a compound of the following formula (12) was used.
Formula (12)

[Comparative Example 1]
(Green chip manufacturing method)
A mixture having the following composition was mixed in advance, and then kneaded with a two-roll mill to obtain a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. After repeating this process 10 to 40 times, a color chip was produced by pulverizing with a pulverizer.
Green pigment: C.I. I. Pigment Green 36 11.0 parts (“Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.)
Basic pigment derivative containing triazine ring (formula (11)) 1.0 part 20.0 parts of transparent resin solution of Synthesis Example 2 (Method for producing green pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 3 hours with an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 1 mm, and then filtered through a 5 µm filter. A pigment dispersion was prepared.
Green chip prepared in Comparative Example 1 16.0 parts Transparent resin solution of Synthesis Example 2 20.0 parts Cyclohexanone 64.0 parts

(Yellow chip manufacturing method)
A mixture having the following composition was mixed in advance, and then kneaded with a two-roll mill to obtain a sheet. The sheet was folded into several sheets and passed through a two-roll mill again. After repeating this process 10 to 40 times, a color chip was produced by pulverizing with a pulverizer.
Yellow pigment: 11.0 parts Basic pigment derivative containing a triazine ring (formula (11)) 1.0 part Transparent resin solution of Synthesis Example 2 20.0 parts (Method for producing yellow pigment dispersion)
After the mixture having the following composition is stirred and mixed uniformly, the mixture is dispersed for 3 hours with an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads having a diameter of 1 mm, and then filtered through a 5 µm filter. A pigment dispersion was prepared.
Yellow chip prepared in Comparative Example 1 16.0 parts Transparent resin solution of Synthesis Example 2 20.0 parts Cyclohexanone 64.0 parts

(Method for producing green coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a green colored composition having photosensitivity.
Green pigment dispersion prepared in Comparative Example 1 43.2 parts Yellow pigment dispersion prepared in Comparative Example 1 23.8 parts Transparent resin solution of Synthesis Example 2 5.0 parts Dipentaerythritol hexaacrylate 4.0 parts Photopolymerization Initiator ("Irgacure 907" manufactured by Ciba Specialty Chemicals) 1.4 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts 22.4 parts cyclohexanone [Comparative Examples 2 to 10]
A pigment, dye derivative, transparent resin, and resin-type dispersant shown in Table 1 were blended in the same manner as in Comparative Example 1 to obtain a green colored composition (green resist material) having photosensitivity. In addition, when adding the resin-type dispersant, 6.0 parts of the transparent resin solution was recorded at the time of manufacturing the chip, and 1.2 parts of the resin-type dispersant shown in Table 1 was added instead. As the basic pigment derivative containing no triazine ring, the compound of the above formula (12) was used.

  The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. For the measurement, an automatic vapor adsorption amount measuring device (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) was used. The results are shown in Table 1.

  The viscosity of the resist material was measured at 20 rpm using an E-type viscometer (“ELD viscometer” manufactured by Toki Sangyo Co., Ltd.). Furthermore, the ratio of the viscosity at 6 rpm and 60 rpm (referred to as thixo index, the higher the value, the higher the thixotropic property) was obtained, and the thixotropic property was evaluated. The results are shown in Table 2.

Next, a method for measuring the contrast ratio of a coating film prepared using a resist will be described. The light emitted from the backlight unit for liquid crystal display (7) passes through the polarizing plate (6), is polarized, and passes through the dried coating film (4) of the colored composition applied on the glass substrate (5). And reaches the polarizing plate (3). If the polarization planes of the polarizing plate (6) and the polarizing plate (3) are parallel, light is transmitted through the polarizing plate (3), but if the polarization plane is perpendicular, the light is transmitted by the polarizing plate (3). Blocked. However, when light polarized by the polarizing plate (6) passes through the dried coating film (4) of the colored composition, scattering by pigment particles or the like occurs, and a part of the polarization plane is displaced. Is parallel, the amount of light transmitted through the polarizing plate (3) is reduced. When the deflecting plate is perpendicular, a part of the light is transmitted through the polarizing plate (3). This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)

Accordingly, when scattering occurs due to the pigment of the dried coating film (4) of the coloring composition, the brightness when parallel is reduced and the brightness when perpendicular is increased, the contrast ratio is lowered.
A color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used as the luminance meter (1), and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask (2) having a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

(Method for producing a coating film substrate for contrast ratio measurement)
Using the obtained resist material, a spin coater was used to produce three coated substrates so that the dry film thickness was about 2 μm by changing the number of rotations. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and then the film thickness and contrast ratio were measured, and the contrast ratio at a film thickness of 2 μm was determined from the three-point data by the primary correlation method. The results are shown in Table 2.

Compared to the case where a green coloring composition is prepared by co-chiping green and yellow pigments as in the examples, and then the green pigment and the yellow pigment are each converted into a single color chip and blended to prepare a green coloring composition. With high contrast and excellent dispersion stability. The effect is great when finer pigments are used.

It is a conceptual diagram of the measuring apparatus for measuring a contrast ratio.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Luminometer 2 Mask 3 Polarizing plate 4 Colored composition dry coating film 5 Glass substrate 6 Polarizing plate 7 Backlight unit

Claims (10)

  A green pigment obtained by grinding a mixture containing a green pigment, a yellow pigment, a pigment derivative having a basic group or an acidic group, and a transparent resin into a sheet by milling with a roll mill multiple times. A green coloring composition for a color filter, comprising a chip dissolved in an organic solvent.   The green pigment is C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 is at least one green pigment selected from C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. The green coloring composition for a color filter according to claim 1, which is at least one yellow pigment selected from Pigment Yellow 185. The green coloring composition for a color filter according to claim 1 or 2, wherein the specific surface area of the green pigment is 60 to 130 m ² / g, and the specific surface area of the yellow pigment is 60 to 160 m ² / g.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the mixture contains a resin-type dispersant.   When the resin type dispersant uses a pigment derivative having a basic group in the mixture, the resin type dispersant is an acidic resin type dispersant. When using a pigment derivative having an acidic group, the resin type dispersant is a basic resin type dispersant. The coloring composition for a color filter according to any one of claims 1 to 4, wherein the coloring composition is provided. The transparent resin is a transparent resin obtained by copolymerizing a compound (A) represented by the following general formula (1) and another compound (B) having an ethylenically unsaturated double bond. The coloring composition for color filters according to any one of claims 1 to 5.
Formula (1)

(R _a represents a hydrogen atom or a methyl group, R _b represents an alkylene group having 2 or 3 carbon atoms, and R _c represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a substituent such as a benzene ring. n represents an integer of 1 to 15.)   The coloring composition for a color filter according to any one of claims 1 to 6, wherein the pigment derivative having a basic group contains a triazine ring.   The coloring composition for a color filter according to any one of claims 1 to 6, wherein the pigment derivative having an acidic group is an aluminum salt of a pigment derivative having an acidic group.   A green pigment obtained by grinding a mixture containing a green pigment, a yellow pigment, a pigment derivative having a basic group or an acidic group, and a transparent resin into a sheet by milling with a roll mill multiple times. A method for producing a coloring composition for a color filter, wherein the chip is dissolved in an organic solvent. A color filter comprising a filter segment formed from the colored composition according to claim 1.

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