JP2007248778A - Blue coloring composition for color filter, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a blue coloring composition for a color filter satisfying a high contrast ratio required for a color filter, and to provide a color filter having a higher contrast ratio compared to a conventional one. <P>SOLUTION: The blue coloring composition for a color filter cocontains a pigment carrier comprising a transparent resin, its precursor or their mixture, and a pigment, wherein the pigment is an ε-type phthalocyanine pigment prepared by kneading a mixture of α-type phthalocyanine, ε-type phthalocyanine, a water soluble inorganic salt and a water soluble organic solvent, in a continuous kneading machine 10 having a pulverizing space formed of a gap between an annular fixed disk 21 coaxially placed in a cylindrical casing 11 and a rotation disk 23 rotating by a driving shaft 121. The color filter has a filter segment formed by using the above blue coloring composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a blue coloring composition for a color filter used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, and a color obtained using the blue coloring composition for the color filter. Regarding filters.

  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 that performs display by the above method is the mainstream, and color display is enabled by providing a color filter between the two polarizing plates. Currently, as a method for producing a color filter, a method called a pigment dispersion method in which a pigment having excellent light resistance and heat resistance is used as a colorant is mainly used. However, a color filter in which an organic pigment is dispersed is generally based on pigment particles. There is a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering or the like. That is, there is a phenomenon in which light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state). The above luminance ratio is called the contrast ratio.

  Generally, it is difficult to obtain a stable dispersion by dispersing fine pigment particles in a pigment carrier such as a varnish, and the dispersion often increases in viscosity due to aggregation of pigment particles over time and exhibits thixotropic properties. It becomes like this. Such an increase in viscosity and poor fluidity of the dispersion cause various problems in manufacturing work and product value. For example, the filter segment of a color filter is generally formed by applying a colored composition in which a pigment is dispersed in a carrier containing a monomer and a resin on a transparent substrate such as glass. If a coloring composition with poor coating properties is used, a coating film having a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, etc. In addition, since the color filter formed using the dispersion in which pigment particles are aggregated significantly reduces the contrast ratio, the pigment has stable fine particles without agglomeration and is easy to handle. It is hoped that.

On the other hand, in general, a phthalocyanine pigment having excellent resistance and color tone is often used for the coloring composition used for forming the blue filter segment. As this phthalocyanine pigment, those having various central metals such as copper, zinc, nickel, cobalt, and aluminum are known. Among them, copper phthalocyanine is the most vivid and widely used, but heterogeneous metal phthalocyanines such as metal-free phthalocyanine, zinc phthalocyanine, and cobalt phthalocyanine have been put into practical use.
In addition, phthalocyanine pigments have different crystal types such as α-type, β-type, δ-type, and ε-type. Among them, ε-type phthalocyanine pigments have a reddish color tone more than α-type phthalocyanine pigments, and are clear and have strong coloring power. In addition, it has excellent properties such as higher stability against crystal transition, and is excellent as a color filter pigment.

The phthalocyanine obtained by synthesis usually has a β-type crystal form and is coarse and needle-shaped particles of about 10 to 200 μm called crude phthalocyanine, and its value as a color filter pigment is very low. Therefore, in order to obtain an ε-type phthalocyanine pigment for a color filter, the crystal form is transferred to the ε-type, and the pigment is made finer to about 0.01 to 0.5 μm particles having a high color utility value. A process called is required.
As a method for producing an ε-type phthalocyanine pigment, as disclosed in Patent Document 1, as disclosed in Patent Document 1, after dry-grinding with a ball mill for a long period of time, a solvent treatment, or Patent Document 2 is disclosed. There is a method in which ε-type phthalocyanine semicrude containing α-type phthalocyanine is heat-treated in an organic solvent.

On the other hand, as disclosed in Patent Document 3, as a method by solvent salt milling, a method of kneading ε-type phthalocyanine crude together with a grinding aid and a binder in a kneader, α-type phthalocyanine and ε-type phthalocyanine There is a method of kneading the mixture in the presence of a pigment derivative in the same manner with a kneader or the like. In addition, Patent Document 4 discloses a technique in which an ε-type phthalocyanine semicrude containing α-type phthalocyanine is converted into a fine ε-type phthalocyanine by a solvent salt milling method.
Further, as disclosed in Patent Document 5, as a method by dry pulverization, there is a method of manufacturing by balancing the grinding by dry pulverization and the crystal growth by contact with an organic solvent.
Among them, the solvent salt milling method using a batch kneader is industrially most advantageous and most frequently used.
JP-A-48-101419 JP-A-4-252273 JP-A-57-149358 JP 2002-121420 A JP 2004-244563 A

Although the solvent salt milling method is industrially advantageous, in the conventional batch type kneader, etc., it is due to production scale restrictions derived from the batch type, variation in quality from lot to lot, foreign matter contamination due to open type and dust generation There were problems such as contamination of the work environment. Further, in order to realize the high contrast ratio required for the color filter, finer pigment particles are required, but it has been difficult to obtain this by the method described above.
The present invention has been made in view of such a situation, using finer ε-type phthalocyanine pigment particles compared to those manufactured by a conventional batch kneader or the like, and providing a high contrast ratio required for a color filter. An object of the present invention is to provide a blue coloring composition for a color filter to be satisfied, and a color filter having a higher contrast ratio than in the past.

The blue coloring composition for a color filter of the present invention is a coloring composition for a color filter containing a transparent resin, a precursor thereof, or a pigment carrier composed of a mixture thereof and a pigment, wherein the pigment is an α-type phthalocyanine and ε A kneaded mixture containing a type phthalocyanine, a water-soluble inorganic salt, and a water-soluble organic solvent is formed by an interval between an annular fixed disk concentrically housed in a cylindrical casing and a rotating disk rotated by a drive shaft An ε-type phthalocyanine pigment kneaded by a continuous kneader having a pulverized space.
Moreover, the color filter of this invention comprises the filter segment formed using the said blue coloring composition for color filters, It is characterized by the above-mentioned.

  The blue coloring composition for a color filter of the present invention is a concentric interior of a cylindrical casing containing a kneaded mixture containing α-type phthalocyanine, ε-type phthalocyanine, a water-soluble inorganic salt, and a water-soluble organic solvent. By kneading in a continuous kneader that has a grinding space formed by the distance between the annular fixed disk and the rotating disk rotated by the drive shaft, the crystal transition from α-type to ε-type phthalocyanine pigments and refinement In addition, since the ε-type phthalocyanine pigment that has been sized is included, by using the blue coloring composition for a color filter of the present invention, a color filter having a higher contrast ratio than before can be formed.

The blue coloring composition for a color filter of the present invention contains a pigment carrier and a pigment made of a transparent resin, a precursor thereof, or a mixture thereof, and the pigment contains α-type phthalocyanine, ε-type phthalocyanine, and water. A kneaded mixture containing a water-soluble inorganic salt and a water-soluble organic solvent is formed into a pulverizing space formed by an interval between an annular fixed disk concentrically housed in a cylindrical casing and a rotating disk rotated by a drive shaft. The greatest feature is that it is an ε-type phthalocyanine pigment kneaded by a continuous kneader.
First, the continuous kneader used in the present invention will be described with reference to FIG. FIG. 1 is a side sectional view showing an embodiment of a continuous kneader used in the present invention. Incidentally, as a continuous kneader suitably used in the present invention, there is one described in Japanese Patent Publication No. 2-92, for example, a continuous kneader (“Miracle K.C. K. ") can be mentioned as suitable.

  As shown in FIG. 1, a continuous kneader 10 has a basic configuration including a feed unit 1, a kneading unit 2, a discharge unit 3, and a quantitative feeder unit 4. The feed unit 1 includes a cylindrical casing 11 extending in the horizontal direction, and a spiral rod 12 that is concentrically inserted into the casing 11 and fitted in a sliding contact state. On the upper surface of the casing 11 on the upstream side, a raw material receiving port 111 for receiving the raw material from the quantitative feeder section 4 is opened. The spiral rod 12 is concentrically fixed to a drive shaft 121 of a drive motor (not shown) at the base end (right side in FIG. 1), and rotates about the shaft center via the drive shaft 121 by driving the drive motor. It is like that. A spiral fin 122 screwed in a predetermined direction is provided on the outer peripheral surface of the spiral rod 12, and the raw material supplied from the metering feeder unit 4 is sent to the kneading unit 2 by rotation around the axis of the spiral fin 122. It is designed to be pumped towards.

The quantitative feeder section 4 supplies a raw material (a mixture containing α-type phthalocyanine, ε-type phthalocyanine, a water-soluble inorganic salt, and a water-soluble organic solvent) to be fed to the feed section 1 as a target for continuous kneading. The raw material hopper 41 for storing the raw material, the spiral feeder 42 for feeding the raw material cut out from the bottom of the raw material hopper 41 toward the feed unit 1, and the downstream end of the spiral feeder 42 are covered. The casing 11 includes a connecting cylinder 43 erected from the peripheral edge of the raw material receiving port 111.
The spiral feeder 42 is mounted in a state in which a spiral fin is slidably contacted in an interposed cylinder 44 interposed between the bottom opening of the raw material hopper 41 and the upper opening of the connecting cylinder 43, and the proximal end side ( The right side in FIG. 1 is concentrically connected to a drive shaft of a feed motor (not shown). Therefore, the raw material in the raw material hopper 41 is conveyed by the spiral feeder 42 by rotating around the axis of the spiral feeder 42 driven by the feed motor, and is introduced into the casing 11 in advance via the interposed cylinder 44 and the connecting cylinder 43. It is designed to be supplied with a set conveyance amount.

The kneading section 2 includes a plurality of fixed disks 21, annular kneading cylinders 22 arranged alternately with the fixed disks 21 while being sandwiched between the fixed disks 21, front and back surfaces (the left and right surfaces in FIG. 1). ) Is provided with a rotating disk 23 concentrically inserted into the kneading cylinder 22 in a state of facing the fixed disk 21. A tie rod (not shown) passes through the plurality of fixed disks 21 and the kneading cylinders 22, and a base end portion of the tie rods is fixed to the casing 11 of the feed unit 1, whereby the fixed disks 21 and the kneading cylinders 22 are fed. It is integrated with part 1.
Each of the rotating disks 23 is externally fitted on a spline shaft (not shown) that is concentrically provided from the distal end surface of the spiral rod 12. A cylindrical intermediate screw 24 is interposed between the adjacent rotating disks 23, so that the rotating disks 23 and the screws 24 are alternately mounted on the spline shaft. The rotating disk 23 is set to have an outer diameter dimension slightly smaller than the inner diameter dimension of the kneading cylinder 22, and the intermediate screw 24 is set to have an outer diameter dimension slightly smaller than the inner diameter dimension of the fixed disk 21. Each rotary disk 23 and each intermediate screw 24 are alternately fitted on the spline shaft, and the outer peripheral surface thereof passes through a gap through which the raw material can pass with respect to the inner peripheral surface of the kneading cylinder 22 and the fixed disk 21. They are designed to face each other.

According to the configuration of the continuous kneader 10, the raw material loaded in the raw material hopper 41 is discharged from the bottom of the raw material hopper 41 by driving the spiral feeder 42, and is connected via the interposed cylinder 44 and the connecting cylinder 43. It is introduced into the casing 11 of the feed unit 1. The raw material introduced into the casing 11 is sequentially conveyed toward the kneading unit 2 on the downstream side by the rotation of the spiral fins 122 by the driving rotation of the spiral rod 12.
The raw material transported to the kneading unit 2 is first of all the outer peripheral surface of the intermediate screw 24 on the most upstream side (right side in FIG. 1) rotating around the axis and the drive shaft 121 on the most upstream side. 1 passes between the peripheral surface, and subsequently passes between the left side surface in FIG. 1 of the uppermost fixed disk 21 and the right side surface of the uppermost rotating disc 23 rotating around the axis, The raw material is kneaded when passing through these gaps. The kneading operation on the raw material is repeated in a plurality of stages for the amount of installation of the fixed disk 21, the kneading cylinder 22, the rotating disk 23, and the intermediate screw 24, whereby a plurality of components of the raw material (in the present invention, α-type phthalocyanine, Kneading treatment is applied to ε-type phthalocyanine, water-soluble inorganic salt and water-soluble organic solvent. The product obtained by the completion of the kneading process is discharged to the outside through the gap between the outer peripheral surface of the rotating disk 23 on the most downstream side and the inner peripheral surface of the fixed disk 21, that is, the discharge unit 3.

2 is a front view (viewed from the right side of FIG. 1) or a rear view (viewed from the left side of FIG. 1) showing an embodiment of a fixed disk and a rotating disk applied to the continuous kneader shown in FIG. (A) is a cavity fan-shaped fixed disk 21a, (b) is a cavity fan-shaped rotating disk 23b, (c) is a cavity chrysanthemum-shaped fixed disk 21c, and (d) is a cavity chrysanthemum mold. The rotating disks 23d and (e) show the cavity mortar-shaped fixed disk 21e, and (f) shows the cavity mortar-shaped rotating disk 23f, respectively.
As shown in FIG. 2, the fixed disk 21 is provided with a loose fitting hole 211 for loosely fitting to the concentric intermediate screw 24, and the front and back surfaces (front side and back surface) of the fixed disk 21. A plurality of concave portions (cavities (crushing spaces) 212) having an equal pitch are provided in the circumferential direction, which are recessed in the radial direction from the loose fitting holes 211. On the other hand, the rotating disk 23 is provided with an outer fitting hole 231 for fitting in close contact with a spline shaft (not shown) formed concentrically and on the front and back surfaces of the rotating disk 23, A cavity (crushing space) 232 corresponding to the cavity 212 of the disk 21 is recessed. The cavity 232 of the rotating disk 23 is open at the periphery.

  Then, the raw material introduced into the gap between the fixed disk 21 and the rotating disk 23 is sequentially pushed into the cavities 212 and 232 by being pressed by the drive of the spiral rod 12, and in this state the rotating disk 23 is pivoted. By rotating around the center, a shearing force is applied to the raw material in each of the cavities 212 and 232 at the interface between the cavities 212 and 232. That is, the raw materials in the cavities 212 and 232 of the fixed disk 21 and the rotating disk 23 facing each other are sliced at the ridges of the ridges of the cavities 212 and 232, and the raw materials are replaced with shearing force (sheared raw materials). Are released from the cavities 212 and 232, and new raw materials enter the cavities 212 and 232), whereby the raw materials are kneaded and dispersed.

The fixed disk 21 and the rotating disk 23 are formed into the cavity fan-shaped fixed disk 21a and the cavity fan-shaped rotating disk 23b shown in FIGS. 2 (a) and 2 (b) according to the shape of the cavities 212 and 232, and FIG. Cavity chrysanthemum type fixed disk 21c and cavity chrysanthemum type rotary disk 23d shown in (c) and FIG. 2 (d), cavity mortar type fixed disk 21e and mold shown in FIG. 2 (e) and FIG. 2 (f). The reason why it is divided into a plurality of types with the tee mortar type rotating disk 23f is to increase the shearing force on the raw material as the kneading and dispersing process proceeds.
That is, the porosity of each cavity 212, 232 (the ratio (%) of the area of each cavity 212, 232 to the surface area of the fixed disk 21 and the rotating disk 23) is the fan-shaped cavities 212, 232, chrysanthemum. The mold cavities 212 and 232 and the mortar mold cavities 212 and 232 decrease in this order, but the shearing force on the raw material increases as the porosity decreases.

In the present embodiment, the cavities 212 and 232 have the fan-shaped fixed disk 21 and the rotation from the upstream side toward the downstream side in order to increase the shearing force on the raw material as the kneading and dispersing process proceeds on the raw material. The disk 23, the cavities 212, 232 are arranged in a chrysanthemum-shaped fixed disk 21 and the rotating disk 23, and the cavities 212, 232 are arranged in the mortar-shaped fixed disk 21 and the rotating disk 23 in this order.
By doing so, a large shearing force does not act on the raw material suddenly, but as the kneading and dispersing process proceeds, the shearing force on the raw material gradually increases. As a result, the mixture of seed crystals of α-type phthalocyanine and ε-type phthalocyanine, water-soluble inorganic salt and water-soluble organic solvent, which are constituents of the raw material, can be reliably kneaded and dispersed with each other.
Further, according to the continuous kneader 10 having such a configuration, a mixture of α-type phthalocyanine and ε-type phthalocyanine seed crystal, which is one of the constituent elements of the raw material, is formed between the fixed disk 21 and the rotating disk 23 (particularly, each cavity). 212, 232), the α-type phthalocyanine can be crystallized to ε-type phthalocyanine and refined by applying a shearing force to the pigment particles by the rotation of the rotating disk 23.

Next, the kneaded composition subjected to the kneading and dispersing process by the continuous kneader 10 will be described in detail.
The α-type phthalocyanine and ε-type phthalocyanine used in the kneaded composition are metal phthalocyanine having a central metal or metal-free phthalocyanine, and can be produced by a known method. Using phthalocyanine with copper, zinc, nickel, or cobalt as the central metal, or metal-free phthalocyanine, copper, zinc, nickel, or cobalt, which is particularly vivid and highly useful as a coloring material, is used as the central metal. Ε-type metal phthalocyanine pigment or metal-free ε-type phthalocyanine pigment is obtained.

α-type phthalocyanine can be produced, for example, by acid pasting crude phthalocyanine, and ε-type phthalocyanine can be produced by solvent salt milling of α-type phthalocyanine. Further, a mixture of α-type phthalocyanine and ε-type phthalocyanine can be produced by dry-grinding ε-type phthalocyanine crude in the presence of a grinding medium.
The α-type phthalocyanine and the ε-type phthalocyanine are preferably contained in the kneaded composition in a ratio of 2 to 40 parts by weight of the ε-type phthalocyanine with respect to 100 parts by weight of the total of the α-type phthalocyanine and the ε-type phthalocyanine. More preferably, it is contained at a ratio of 5 to 30 parts by weight. When the content of ε-type phthalocyanine is less than 2 parts by weight, the rate of crystal transition of α-type phthalocyanine to ε-type phthalocyanine is slow, and when it exceeds 30 parts by weight, total production from crude phthalocyanine Efficiency is reduced and both are industrially disadvantageous.

The water-soluble inorganic salt used in the kneaded composition is not particularly limited, and examples thereof include sodium chloride (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, and mixtures thereof.
The amount of the water-soluble inorganic salt in the kneaded composition is not particularly limited. However, if the amount is too small, crystal transition and refinement and sizing to the ε-type phthalocyanine pigment are difficult to proceed. Therefore, productivity is lowered and it is industrially disadvantageous. For this reason, the water-soluble inorganic salt is preferably in the range of 100 to 2000 parts by weight with respect to the total of 100 parts by weight of α-type phthalocyanine and ε-type phthalocyanine, and can be selected according to the intended particle size.

The water-soluble organic solvent used in the kneaded composition is one that is added so that α-type phthalocyanine, ε-type phthalocyanine, and water-soluble inorganic salt form a uniform mass, and can be mixed freely with water or freely. Although it is not mixed, it has a solubility that can be removed industrially by washing with water, and is not particularly limited as long as pigment particles grow, but the temperature rises during kneading, and the solvent easily evaporates. From this point, a high boiling point solvent is preferable.
The amount of the water-soluble organic solvent in the kneaded composition is not particularly limited, but if it is too small, the kneaded composition becomes too hard and difficult to operate stably, and if it is too much, the kneaded composition becomes too soft and fine. The level of crystallization and sizing decreases. Therefore, the water-soluble organic solvent is preferably in the range of 30 to 500 parts by weight with respect to 100 parts by weight of α-type phthalocyanine and ε-type phthalocyanine, and is selected according to the amount of water-soluble inorganic salt and the hardness of the kneaded composition. it can.

  Examples of the water-soluble organic solvent include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Low molecular weight polypropylene glycol, aniline, pyridine, tetrahydrofuran, dioxane, methanol , Ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, propylene glycol, propylene glycol glycol monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Can be mentioned. Two or more organic solvents may be mixed and used as necessary.

  The kneaded composition stabilizes the crystals of the produced ε-type phthalocyanine pigment, prevents transition to β-type crystals and α-type crystals, suppresses the growth of pigment particles, and efficiently produces fine ε-type phthalocyanine. In order to produce a pigment, it is preferable to contain at least one derivative selected from a pigment derivative, an anthraquinone derivative, an acridone derivative or a triazine derivative. Each of the derivatives is a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group into an organic pigment, anthraquinone, acridone, or triazine. The phthalimidomethyl group may have a substituent. Among these, a pigment derivative, particularly a phthalocyanine pigment derivative having phthalocyanine as a base skeleton is preferable because the effect of suppressing crystal growth of the phthalocyanine pigment is particularly high.

The pigment derivative is a compound represented by the following general formula (1).
AB Formula (1)
A: Organic pigment residue
B: Basic substituent, acidic substituent or phthalimidomethyl group In formula (1), the organic pigment constituting the organic pigment residue of A is an azo type such as diketopyrrolopyrrole pigment, azo, disazo, polyazo, etc. Pigment, copper phthalocyanine, halogenated copper phthalocyanine, phthalocyanine pigment such as metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, etc. anthraquinone pigment, quinacridone pigment And dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.

In the formula (1), examples of the basic substituent of B include substituents represented by the following formula (2), formula (3), formula (4), and formula (5). , Formula (6), formula (7), and substituents represented by formula (8).

In the above formulas (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 are each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, Alternatively, R ₁ and R ₂ together represent an optionally substituted heterocyclic ring containing a further nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or Represents an optionally substituted phenyl group.

Y represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents a group.
Z represents an alkylene group having 1 to 36 carbon atoms which may be substituted, an alkenylene group having 2 to 36 carbon atoms which may be substituted, or a phenylene group which may be substituted.
P represents a substituent represented by the formula (9) or a substituent represented by the formula (10).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (9) or a substituent represented by the formula (10). In formula (9) and formula (10), R _{1 to} R ₇ and n are as defined above.

In the above formulas (6) to (8),
M represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom or an aluminum atom.
i represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, It represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used for forming the substituent represented by the formulas (2) to (5), (9), and (10) include dimethylamine, diethylamine, N, N-ethylisopropyl, and the like. Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecyla , Diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N -Diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N- Tyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3 -Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Ethyl isonicopetinate, 2-Piperidinethanol, Pyrrolidine 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4 -Pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

The amine component used to form the sulfonic acid amine salt of formula (8) may be any of primary, secondary, tertiary and quaternary amines. For example, as the primary amine, hexylamine, heptylamine, octylamine, which may have a side chain, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexa Examples thereof include saturated amines such as decylamine, heptadecylamine, octadecylamine, nonadecylamine, eocosylamine, and unsaturated amines corresponding to the respective carbon numbers.
Examples of secondary amines include dioleylamine and distearylamine.
Examples of the tertiary amine include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, and trioctylamine.

Quaternary amines include dimethyl didodecyl ammonium chloride, dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride. , Trimethyloctadecylammonium chloride, dimethyldodecyltetradecylammonium chloride, dimethylhexadecyloctadecylammonium chloride, and the like.
Moreover, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in formula (8) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

Specific examples of pigment derivatives are shown below with compound numbers, but are not limited thereto.

  The blending amount of the pigment derivative in the kneaded composition is preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the total of α-type phthalocyanine and ε-type phthalocyanine. In addition, since the pigment derivative also has an effect as a dispersant, it is preferable to select a pigment derivative having good dispersibility in the pigment carrier. However, as a pigment derivative having a high crystal growth preventing effect and a dispersion aid other than the pigment derivative, , Resin, resin-type pigment dispersant, surfactant and the like. These dispersing aids can be used not only when kneading in a continuous kneader but also when dispersing the pigment on the pigment carrier.

The resin as the dispersion aid is preferably poorly water-soluble and partially soluble in a water-soluble organic solvent. A resin that can be used as a pigment carrier constituting a blue coloring composition for a color filter is contained in the kneaded mixture. By adding, the aggregation of the phthalocyanine pigment can be prevented and it can be easily dispersed in the subsequent pigment carrier.
Although there is no restriction | limiting in particular as the usage-amount of resin in a kneaded mixture, 0.01-100 weight part with respect to a total of 100 weight part of (alpha) -type phthalocyanine and (epsilon) -type phthalocyanine, More preferably, it is 0.5-50 weight part is there. When the amount of the resin is less than 0.01 part by weight, the effect on dispersibility is reduced, and when it exceeds 100 parts by weight, the added dispersion effect cannot be obtained.

  The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Salt or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.

  Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfone. Anionic surfactants such as sodium acid, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, poly Oxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene Nonionic surfactants such as glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines Is mentioned. These can be used alone or in admixture of two or more.

  There are no particular restrictions on the operating conditions of the continuous kneader in the present invention. The kneading temperature is preferably from 50 to 150 ° C., particularly preferably from 80 to 130 ° C., in order to effectively promote the particle growth due to. By raising the temperature, it is possible to promote the crystal transition and growth rate of the pigment particles. The amount of processing and the quality of the ε-type phthalocyanine pigment to be obtained are controlled by the mixing ratio of the kneading composition, kneading temperature, mechanical energy input (main shaft (drive shaft 121) rotation speed, raw material supply amount, main shaft power load, etc.) It becomes possible by adjusting When the temperature is higher than 150 ° C., crystal transition to β-type phthalocyanine and particle growth become large, which is not preferable in terms of quality.

If necessary, the temperature of the continuous kneader 10 can be adjusted in two stages, and the former stage can be kneaded at a high temperature and the latter stage can be kneaded at a low temperature to more efficiently perform crystal transition, refinement, and sizing. is there. Moreover, you may pass through a continuous kneader twice or more, and may process by changing temperature each time.
In addition, after producing a ε-type phthalocyanine pigment by crystal transition from α-type phthalocyanine and ε-type phthalocyanine using a continuous kneader, a conventional method using a kneader or the like is used for further refinement and granulation. Further refinement processing may be performed.
The kneaded composition after kneading is processed by a conventional method. That is, the kneaded composition is treated with water or an aqueous mineral acid solution, and the water-soluble inorganic salt and the water-soluble organic solvent are removed by filtration and water washing, and the ε-type phthalocyanine pigment is isolated. The ε-type phthalocyanine pigment can be used in a wet state as it is or in a powder state by drying and grinding. If necessary, a resin, a surfactant, and other additives may be added after kneading.

Next, a blue coloring composition for a color filter containing the ε-type phthalocyanine pigment thus obtained and a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof will be described.
The pigment carrier constituting the blue coloring composition for a color filter in the present invention comprises a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Examples of the transparent resin include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and active energy ray curable resins are particularly preferable. Moreover, as the precursor, the monomer or oligomer which hardens | cures by active energy ray irradiation and produces | generates transparent resin is mentioned, These can be used individually or in mixture of 2 or more types.

  The pigment carrier can be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, with respect to 100 parts by weight of the pigment in the blue coloring composition for a color filter. Further, when a mixture of a transparent resin and its precursor is used as a pigment carrier, the transparent resin is 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the pigment in the blue coloring composition. It can be used in parts. The precursor of the transparent resin can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment in the blue coloring composition.

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

  Active energy ray-curable resins include (meth) acrylic having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group on a 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 polymer by reacting a compound or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

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

  In order to adjust the hue, for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 22, 60, 64, Blue pigments other than ε-type phthalocyanine pigments such as 81 can be contained. The blue coloring composition may further contain purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and the like.

In addition, the blue coloring composition for a color filter of the present invention is obtained by sufficiently dispersing a pigment in a pigment carrier and applying it on a transparent substrate such as glass so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate the formation of the segments. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These can be used alone or in combination.
A solvent can be used in the quantity of 800-4000 weight part with respect to 100 weight part of pigments in the blue coloring composition for color filters, Preferably it is 1000-2500 weight part.

When the blue colored composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the blue colored composition for a color filter of the present invention.
Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- 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. A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigments in the blue coloring composition for color filters, Preferably it is 10-150 weight part.

  These photopolymerization initiators are used alone or in admixture of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenance are used. 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 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the blue coloring composition for a color filter.

  In addition, the blue colored composition for color filters of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the blue colored composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the pigment in the blue coloring composition for a color filter.

The blue coloring composition for color filters can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. A solvent development type or alkali development type colored resist material generally comprises a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and a solvent. It is dispersed. The blue coloring composition for a color filter of the present invention can be produced by finely dispersing a pigment in a pigment carrier using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. it can. The photopolymerization initiator may be added at the stage of preparing the blue coloring composition, or may be added later to the prepared blue coloring composition.
Moreover, the blue coloring composition for color filters of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  When dispersing the pigment in the pigment carrier, a dispersion aid such as at least one derivative selected from the above-mentioned pigment derivatives, anthraquinone derivatives, acridone derivatives, triazine derivatives, resin-type pigment dispersants, surfactants, and the like is appropriately added. Can be 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 the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment in the coloring composition.

Among them, at least one derivative selected from pigment derivatives, anthraquinone derivatives, acridone derivatives, and triazine derivatives is excellent in preventing the aggregation of fine organic pigments and maintaining the finely dispersed state of organic pigments. By using the coloring composition to be contained, a color filter having a high contrast ratio and high color purity can be produced, which is preferable as a dispersion aid.
The blue colored composition for a color filter of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove particles and mixed 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 using the blue coloring composition for color filters of this invention. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment. The blue filter segment and the cyan filter segment are formed using the blue coloring composition for a color filter of the present invention.
The color filter of the present invention can be produced by forming filter segments of each color on a transparent substrate using the blue colored composition of the present invention and the colored composition of each color by a printing method or a photolithography method. .

Red pigmented compositions for forming red filter segments are CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81. : 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226 227, 228, 240, 246, 254, 255, 264, 272 and the like, a pigment carrier, and a solvent, a photopolymerization initiator, and various additives as necessary. In the red coloring composition, yellow pigments exemplified later and orange pigments such as CI Pigment orange 36, 43, 51, 55, 59, 61 can be used in combination.
The green coloring composition for forming the green filter segment includes, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37, the pigment carrier, and a solvent, a photopolymerization initiator, and various additives as necessary. And the like. A yellow pigment can be used in combination with the green coloring composition.

The yellow coloring composition for forming the yellow filter segment is CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24. 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 182, 185, 187, 188, 193, 194, 199, etc., and the pigment carrier, as required Accordingly, it is a composition containing a solvent, a photopolymerization initiator, various additives and the like.
A magenta colored composition for forming a magenta color filter segment comprises a purple pigment such as CI Pigment Violet 1, 19 and / or a red pigment such as 4, 146, 177, 169, 81, and the pigment carrier. Depending on the composition, it is a composition containing a solvent, a photopolymerization initiator, various additives and the like. A yellow pigment can be used in combination with the magenta composition.

As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink is not dried and solidified on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When each color filter segment is formed by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. 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 alkali developer or spraying the developer by spraying 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, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above 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, a water-soluble or alkaline water-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.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”.
Prior to Examples, the measurement method of pigment crystal type, average primary particle diameter, aspect ratio, specific surface area, contrast ratio measurement method, adjustment of acrylic resin solutions used in Examples and Comparative Examples, and ε-type phthalocyanine pigment Manufacturing will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

The crystal type was measured by X-ray diffraction measurement (CuKα1 line).
The average primary particle diameter of the pigment was measured by a general method for directly measuring the size of primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was defined as the average primary particle size. The same result can be obtained by using either a transmission type (TEM) or a scanning type (SEM).

The aspect ratio of the pigment was calculated by the following formula by measuring the short axis diameter and the long axis diameter of the primary particles of each pigment from an electron microscope. The closer the aspect ratio is to 1, the more preferable the crystal state of the particles approaches a square.
(Aspect ratio) = (Long axis diameter) / (Short axis diameter)
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 contrast ratio of the coating film was measured by the following method using the measuring apparatus shown in FIG. The light emitted from the backlight unit (7) for liquid crystal display 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). To 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.

(Preparation of acrylic resin solution)
Put 450 parts of cyclohexanone in a reaction vessel, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate Then, 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, and 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 solution was obtained. The weight average molecular weight of the acrylic resin was about 40,000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

(Production of ε-type phthalocyanine pigment 1)
65 parts of α-type copper phthalocyanine, 35 parts of ε-type copper phthalocyanine, 1000 parts of sodium chloride, and 200 parts of diethylene glycol were premixed for 5 minutes with a convert mixer (manufactured by Asada Tekko) so as to be substantially uniform. This mixture is supplied to a continuous kneader 10 (“Miracle KKK-42 type” manufactured by Asada Tekko Co., Ltd.) with a screw-type quantitative feeder (quantitative feeder section 4 (FIG. 1)), and the mixture is ground. Thus, an ε-type copper phthalocyanine pigment was produced. The conditions of the continuous kneader 10 are as follows: the screw diameter of the feed section is 120 mmφ, the number of kneading sections is 8 consisting of a fixed disk and a rotating disk, the extrusion rate of the kneaded composition is 24 kg / hour, the residence time is 8 minutes, the spindle speed is 50 rpm, The crushing temperature was operated at 70 ° C. The kneaded composition obtained here was taken out into 3500 parts of 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water, and dried. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The obtained ε-type copper phthalocyanine pigment had a specific surface area of 91 m ² / g, an average primary particle size of 38 nm, and all the pigment particles were refined, and no coarse particles were observed. In addition, the ε-type copper phthalocyanine pigment obtained had an aspect ratio of 1.74.

(Production of comparative ε-type phthalocyanine pigment 1)
65 parts of α-type copper phthalocyanine, 35 parts of ε-type copper phthalocyanine, 1000 parts of sodium chloride and 200 parts of diethylene glycol were charged into a 1500-volume part double-arm kneader and kneaded for 10 hours while maintaining a dense lump at 110 ° C. did. After grinding, the mixture was taken out into 3500 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water and dried to obtain a pigment. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The specific surface area of the obtained ε-type copper phthalocyanine pigment was 78 m ² / g. When observed with a TEM photograph, all the pigment particles were fine and coarse particles were not observed, but the average primary particle size was 49 nm. In addition, the aspect ratio was 1.81.

(Production of ε-type phthalocyanine pigment 2)
100 parts of ε-type copper phthalocyanine containing 70% by weight of α-type copper phthalocyanine, 1000 parts of sodium chloride, and 200 parts of diethylene glycol were premixed for 5 minutes with a convert mixer (manufactured by Asada Tekko Co., Ltd.) so as to be almost uniform. This mixture is supplied to a continuous kneader 10 (“Miracle KKK-42 type” manufactured by Asada Tekko Co., Ltd.) with a screw-type quantitative feeder (quantitative feeder section 4 (FIG. 1)), and the mixture is ground. Thus, an ε-type copper phthalocyanine pigment was produced. The conditions of the continuous kneader 10 are as follows: the screw diameter of the feed section is 120 mmφ, the number of kneading section sets is 8 consisting of a fixed disk and a rotating disk, the extrusion rate of the kneaded composition is 24 kg / hour, the residence time is 10 minutes, the spindle rotation speed is 50 rpm, The crushing temperature was operated at 110 ° C. The kneaded composition obtained here was taken out into 3500 parts of 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water, and dried. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The obtained ε-type copper phthalocyanine pigment had a specific surface area of 98 m ² / g, an average primary particle size of 36 nm, and all the pigment particles were refined, and no coarse particles were observed. The obtained epsilon-type copper phthalocyanine pigment had an aspect ratio of 1.70.

(Comparative ε-type phthalocyanine pigment 2)
100 parts of ε-type copper phthalocyanine containing 70% by weight of α-type copper phthalocyanine, 1000 parts of sodium chloride, and 200 parts of diethylene glycol were charged into a 1500-volume part double-arm kneader and kept at 110 ° C. in a dense lump (dough). Kneaded for hours. After grinding, the mixture was taken out into 3500 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water and dried to obtain a pigment. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The specific surface area of the obtained ε-type copper phthalocyanine pigment was 80 m ² / g. When observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle size was 40 nm. In addition, the aspect ratio was 1.77.

(Production of ε-type phthalocyanine pigment 3)
Convert mixer (made by Asada Tekko Co., Ltd.) so that 75 parts of α-type copper phthalocyanine, 17 parts of ε-type copper phthalocyanine, 8 parts of copper phthalocyanine having a phthalimidomethyl group (compound 3), 800 parts of sodium chloride and 150 parts of diethylene glycol were almost uniform. ) For 5 minutes. This mixture is supplied to a continuous kneader 10 (“Miracle KKK-42 type” manufactured by Asada Tekko Co., Ltd.) with a screw-type quantitative feeder (quantitative feeder section 4 (FIG. 1)), and the mixture is ground. Thus, an ε-type copper phthalocyanine pigment was produced. The conditions of the continuous kneader 10 are as follows: the screw diameter of the feed section is 120 mmφ, the number of kneading section sets is 8 consisting of a fixed disk and a rotating disk, the extrusion rate of the kneaded composition is 20 kg / hour, the residence time is 10 minutes, the spindle rotation speed is 50 rpm, The crushing temperature was operated at 120 ° C. The kneaded composition obtained here was taken out into 3000 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water and dried. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The obtained ε-type copper phthalocyanine pigment had a specific surface area of 105 m ² / g, an average primary particle size of 34 nm, and all the pigment particles were refined, and no coarse particles were observed. The obtained epsilon-type copper phthalocyanine pigment had an aspect ratio of 1.65.

(Production of comparative ε-type phthalocyanine pigment 3)
A double-arm kneader having a capacity of 1500 parts by weight was charged with 75 parts of α-type copper phthalocyanine, 17 parts of ε-type copper phthalocyanine, 8 parts of copper phthalocyanine having a phthalimidomethyl group (compound 3), 800 parts of sodium chloride and 150 parts of diethylene glycol. And kneading for 10 hours while maintaining a dense lump. After grinding, it was taken out in 3000 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water and dried to obtain a pigment. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The specific surface area of the obtained ε-type copper phthalocyanine pigment was 89 m ² / g, and when observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle diameter was 41 nm. In addition, the aspect ratio was 1.78.

(Ε-type phthalocyanine pigment 4)
Convert mixer (made by Asada Tekko Co., Ltd.) so that 73 parts of α-type copper phthalocyanine, 17 parts of ε-type copper phthalocyanine, 10 parts of copper phthalocyanine having a basic group (compound 2), 800 parts of sodium chloride, and 150 parts of diethylene glycol were almost uniform. ) For 5 minutes. This mixture is supplied to a continuous kneader 10 (“Miracle KKK-42 type” manufactured by Asada Tekko Co., Ltd.) with a screw-type quantitative feeder (quantitative feeder section 4 (FIG. 1)), and the mixture is ground. Thus, an ε-type copper phthalocyanine pigment was produced. The conditions of the continuous kneader 10 are as follows: the screw diameter of the feed section is 120 mmφ, the number of kneading section sets is 8 consisting of a fixed disk and a rotating disk, the extrusion rate of the kneaded composition is 24 kg / hour, the residence time is 10 minutes, the spindle rotation speed is 50 rpm, The crushing temperature was operated at 110 ° C. The kneaded composition obtained here was taken out into 3000 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water and dried. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The obtained ε-type copper phthalocyanine pigment had a specific surface area of 103 m ² / g, an average primary particle size of 34 nm, and all the pigment particles were refined, and no coarse particles were observed. Moreover, the aspect ratio of the obtained ε-type copper phthalocyanine pigment was 1.66.

(Comparative ε-type phthalocyanine pigment 4)
Charge a 1500-capacity double arm kneader with 73 parts of α-type copper phthalocyanine, 17 parts of ε-type copper phthalocyanine, 10 parts of copper phthalocyanine having a basic group (compound 2), 800 parts of sodium chloride and 150 parts of diethylene glycol at 110 ° C. And kneading for 10 hours while maintaining a dense lump. After grinding, it was taken out in 3000 parts of a 1% aqueous sulfuric acid solution at 70 ° C., stirred for 1 hour with heat, filtered, washed with water and dried to obtain a pigment. The obtained pigment was an ε-type copper phthalocyanine pigment having a strongest peak at a Bragg angle 2θ (acceptable range ± 0.2 degrees) = 9.2 degrees according to X-ray diffraction measurement (CuKα1 line). The specific surface area of the obtained ε-type copper phthalocyanine pigment was 89 m ² / g, and when observed with a TEM photograph, all the pigment particles were refined and no coarse particles were observed, but the average primary particle size was 44 nm. In addition, the aspect ratio was 1.78.

[Example 1]
After the resulting mixture having the following composition containing the ε-type phthalocyanine pigment 1 was uniformly stirred, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm. The mixture was filtered through a 5 μm filter to prepare a blue pigment dispersion.
ε-type phthalocyanine pigment 1 10.0 parts Copper phthalocyanine having a basic group (Compound 1) 1.0 part Phosphoric ester pigment dispersant (“BYK111” manufactured by BYK Chemie) 1.0 part Acrylic resin solution 40.0 parts 48.0 parts of cyclohexanone

Furthermore, the mixture of the following composition containing the obtained blue pigment dispersion was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare an alkali developing blue resist material.
Blue pigment dispersion 45.0 parts Acrylic resin solution 15.0 parts Trimethylolpropane triacrylate 9.0 parts ("NK ester ATMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator 2.0 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.2 part Cyclohexanone 28.8 parts

[Examples 2 to 4, Comparative Examples 1 to 4]
An alkali-developable blue resist material was prepared in the same manner as in Example 1 except that the ε-type phthalocyanine pigment 1 was changed to the ε-type phthalocyanine pigment shown in Table 1.
The alkali-developable blue resist material obtained in the examples and comparative examples was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater at 500 rpm, 1000 rpm, 1500 rpm, and a calibration curve. In order to create the above, three types of coated substrates having different film thicknesses were obtained. The coated substrate was dried at 70 ° C. for 20 minutes, exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultra-high pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then the contrast ratio was measured. Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). For the resist material-coated substrate, the contrast ratio at y = 0.14 was determined by an approximation method from the measurement results of the three contrast ratios and chromaticity. The results are shown in Table 1. Table 1 shows the measurement results of the specific surface area, average primary particle diameter, and aspect ratio of the ε-type phthalocyanine pigment used in Examples and Comparative Examples.

  Since the resist materials obtained in Examples 1 to 4 contain an ε-type phthalocyanine pigment that has undergone crystal transition from an α-type to an ε-type phthalocyanine pigment by using a continuous kneader and is sized with refinement. The coated substrate produced using this resist material showed a high contrast ratio compared to the coated substrate produced using the resist material obtained in Comparative Examples 1 to 4.

It is sectional drawing of a side view which shows an example of the continuous kneader used by this invention. FIG. 2 is a front view or a rear view showing one embodiment of a fixed disk and a rotating disk applied to the continuous kneader shown in FIG. 1, (a) is a cavity fan-shaped fixed disk, and (b) is a cavity fan-shaped rotating disk. (C) is a cavity chrysanthemum type fixed disk, (d) is a cavity chrysanthemum type rotary disk, (e) is a cavity mortar type fixed disk, and (f) is a cavity mortar type rotary disk. It is a conceptual diagram of the measuring apparatus for measuring a contrast ratio.

Explanation of symbols

(FIGS. 1 and 2)
DESCRIPTION OF SYMBOLS 10 Continuous kneader 1 Feed part 11 Casing 111 Raw material receiving port 12 Spiral rod 121 Drive shaft 122 Spiral fin 2 Kneading part 21 Fixed disk 21a Cavity fan type fixed disk 21b Cavity chrysanthemum type fixed disk 21c Cavity mortar type fixed disk 211 Free fitting hole 212 Cavity (grinding space)
22 Kneading cylinder 23 Rotating disk 23b Cavity fan-shaped rotating disk 23d Cavity chrysanthemum-shaped rotating disk 23d Cavity mortar-shaped rotating disk 231 External fitting hole 232 cavity (grinding space)
DESCRIPTION OF SYMBOLS 3 Discharge part 4 Fixed_quantity | feed_rate feeder part 41 Raw material hopper 42 Spiral feeder 43 Connection cylinder 44 Interposition cylinder

(Figure 3)
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 (4)

  In a coloring composition for a color filter comprising a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof and a pigment, the pigment comprises α-type phthalocyanine, ε-type phthalocyanine, a water-soluble inorganic salt, and water-soluble A kneaded mixture containing an organic solvent is kneaded in a continuous kneader having a pulverization space formed by an interval between an annular fixed disk concentrically housed in a cylindrical casing and a rotating disk rotated by a drive shaft. A blue coloring composition for a color filter, which is an ε-type phthalocyanine pigment.   The blue colored composition for a color filter according to claim 1, wherein the kneaded mixture further contains at least one derivative selected from a pigment derivative, an anthraquinone derivative, an acridone derivative or a triazine derivative.   3. The color filter according to claim 1, wherein the ε-type phthalocyanine pigment is an ε-type metal phthalocyanine pigment having copper, zinc, nickel, or cobalt as a central metal, or a metal-free ε-type phthalocyanine pigment. Blue coloring composition. A color filter comprising a filter segment formed using the blue coloring composition for a color filter according to any one of claims 1 to 3.

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