KR20090103804A - Method for producing fine organic pigment, fine organic pigment, and fine organic pigment coloring composition - Google Patents

Abstract

PURPOSE: A method for producing fine organic pigment is provided to obtain a colored film with high transparency and excellent view-angle dependency. CONSTITUTION: A method for producing fine organic pigment comprises the steps of: obtaining a mixing composition by mixing organic pigment, water-soluble inorganic salt, water-soluble organic solvent, and resin; and removing water-soluble inorganic salt and water-soluble organic solvent in water. The resin has the solubility of 1 part by weight or more per 100 parts by weight of water-soluble organic solvent at 25°C. The resin has a group selected from an amino group and quaternary ammonium salt.

Description

Manufacturing method of fine organic pigment, fine organic pigment, and fine organic pigment coloring composition {METHOD FOR PRODUCING FINE ORGANIC PIGMENT, FINE ORGANIC PIGMENT, AND FINE ORGANIC PIGMENT COLORING COMPOSITION}

An object of the present invention is to provide a method for producing a fine organic pigment, a fine organic pigment obtained by the production method, and a fine organic pigment coloring composition containing the fine pigment. Furthermore, an object of the present invention is to provide a fine organic pigment coloring composition for offset ink, gravure ink, printing inkjet ink, resists and inks for color filters, and paints.

As the organic pigment, for example, fine particles of finely grained pigment particles can be obtained by selecting appropriate reaction conditions at the time of synthesis such as azo pigments. On the other hand, it is known to pigmentize extremely fine agglomerated particles produced at the time of synthesis, such as copper phthalocyanine green pigments, by grain growth and formulation in a later step. Moreover, it is known to pigmentize coarse and uneven particle | grains produced | generated at the time of synthesis | combination like a copper phthalocyanine blue pigment and a diketopyrrolopyrrole pigment by refine | purifying in a later process and sizing.

As a method of pigmenting coarse crude pigment particles, there are a solvent salt milling method and a dry grinding method which are widely used at present.

Dry grinding is a method of pigmenting coarse crude pigment particles by dry grinding by ball mill, attritor, vibrating mill or the like, and has a higher production efficiency per unit energy than solvent salt milling. However, since the gap of particle diameter is big and the cohesion force between particles is extremely strong, a huge aggregate in which many fine primary particles couple | bonded with very strong force is not obtained. For this reason, various improvement methods are examined about the dry grinding method, but it is difficult to obtain a pigment of high quality.

In the solvent salt milling method, coarse crude pigment particles are mechanically polished by a kneader or the like in the presence of inorganic salts such as sodium chloride or sodium sulfate and highly viscous water-soluble organic solvents such as ethylene glycol, diethylene glycol and polyethylene glycol. It is a method of pigmentation. By processing by kneading, a pigment having a predetermined degree of refinement can be obtained.

As a use use of the pigment with high refinement degree, a color filter is mentioned, for example.

Color filters are used in color liquid crystal display devices, and are arranged in parallel or intersecting two or more different fine strips (stripes) of different colors on the surface of transparent substrates such as glass, or fine pixels arranged in a vertical and horizontal constant array. consist of. By using a pigment having a high degree of miniaturization, the color liquid crystal display device can realize high contrast ratio and transparency.

In general, however, it is difficult to disperse pigment particles having a high degree of fineness in a pigment carrier such as a varnish to obtain a stable dispersion. In addition, such a dispersion sometimes becomes highly viscous by aggregation of pigment particles over time, and forms a thixotropic property. Such increase in viscosity and poor fluidity of the dispersion cause various problems in color filter manufacturing work and product value. For example, formation of the filter segment of a color filter is generally performed by apply | coating the coloring composition in which the pigment is disperse | distributed to the support | carrier containing a monomer and resin on a transparent substrate, such as glass. At this time, it is not preferable to use a colored composition having high viscosity and poor fluidity because a coating film with a uniform film thickness cannot be obtained due to poor coating properties, poor leveling, or the like. In addition, the color filter formed by using the dispersion in which the pigment particles are aggregated significantly lowers the contrast ratio. Here, the pigment is required to be stable fine particles which do not aggregate and are easy to handle.

In order to develop a color liquid crystal display device for a large screen TV, a monitor, etc., other viewing angle characteristics, such as contrast and transparency, also become an important item, and the technology of wide viewing angle is advanced.

In general, the polymer film has birefringence, and when the birefringence is increased, light deflection occurs due to a difference in refractive index in a direction parallel to the film plane and a direction perpendicular to the film plane. Due to the deflection, the color filter becomes more retarded and a phase difference occurs in the transmitted light, so that the viewing angle dependency is increased and the display characteristics are lowered. In particular, it is known that the retardation of a polymer film becomes large by containing crystal | crystallization with a big retardation in a polymer film.

Diketophyllopyrrole pigments have a problem in that the increase in retardation (takes a positive value) is remarkable, and the viewing angle characteristic is deteriorated with the progress of miniaturization by the solvent salt milling method or the like. For this reason, it was necessary to make it refine | miniaturized in order to improve contrast, transparency, etc., without increasing the retardation of a diketopyrrolopyrrole pigment.

On the other hand, when a quinophthalone pigment is used as a material for color filters, it may be used in combination with a pigment with a large value of retardation or its dispersion. For this reason, it is necessary to reduce the retardation of the quinophthalone pigment itself. Patent Literature 1 discloses a technique for reducing the retardation of a colored film by using a colored polymer thin film having an average refractive index of 1.60 or more, 1.90 or less and a birefringence absolute value of 0.01 or less.

Patent Literature 2 discloses a technique for reducing retardation by containing a compound having two or more planar structural groups in a colored film, and further containing retardation particles containing a compound using a quinolyl group or a fluorene group. It is.

Patent Document 3 discloses a technique for mechanically kneading an organic pigment, a water-insoluble synthetic resin, a water-soluble inorganic salt, and a water-soluble organic solvent. Patent Document 4 discloses a technique for mechanically kneading a diketophyllopyrrole pigment, a pigment derivative, a water-soluble inorganic salt, and a water-soluble organic solvent, and there is a description that a resinous dispersant may be used.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2000-136253

[Patent Document 2] Japanese Patent Application Laid-Open No. 2000-187114

[Patent Document 3] Japanese Patent Application Laid-Open No. 7-13016

[Patent Document 4] Japanese Patent Application Laid-Open No. 2001-220520

The present invention has been devised in view of such drawbacks of the prior art, and the contrast ratio of the colored film obtained when the organic pigment refined in the production method of the present invention is formed into a coating film on a coloring composition comprising a pigment carrier and a non-aqueous solvent, Moreover, it aims at providing the fine organic pigment coloring composition with low retardation, excellent viewing angle dependence, and high transparency.

One embodiment of the present invention is characterized by mechanically kneading an organic pigment, a water-soluble inorganic salt, a water-soluble organic solvent and a resin to obtain a kneading composition, and then removing the water-soluble inorganic salt and the water-soluble organic solvent from water. In the method for producing a fine organic pigment, the resin (A) has a solubility of 100 parts by weight of the water-soluble organic solvent at 25 ° C. in an amount of 1 part by weight or more and an amino group and / or a quaternary ammonium base group. It relates to a method for producing an organic pigment.

Moreover, one Embodiment of this invention is related with the manufacturing method of the said fine organic pigment characterized by the resin (A) being acrylic resin.

Moreover, one Embodiment of this invention is related with the manufacturing method of the said fine organic pigment characterized by the said acrylic resin is acrylic resin synthesize | combined by random polymerization.

Moreover, one Embodiment of this invention is related with the manufacturing method of the said fine organic pigment, characterized in that resin (A) does not melt | dissolve in propylene glycol monomethyl ether acetate.

In one embodiment of the present invention, the organic pigment is at least one organic pigment selected from the group consisting of diketopyrrolopyrrole organic pigments, quinophthalone organic pigments, dioxazine organic pigments, and phthalocyanine organic pigments. It relates to a method for producing the fine organic pigment, characterized in that.

Moreover, one Embodiment of this invention relates to the fine organic pigment characterized by being obtained by the said manufacturing method.

Moreover, one embodiment of this invention relates to the fine organic pigment coloring composition containing the said fine organic pigment and a pigment carrier.

Furthermore, one Embodiment of this invention is related with the said fine organic pigment coloring composition characterized by including a non-aqueous solvent.

When the fine organic coloring composition of this invention is made into a coating film, since the pigment refinement degree is high and the retardation is low, the coloring film with high transparency and excellent viewing angle dependence can be obtained. In this case, there is provided a color filter capable of expressing vivid colors in a liquid crystal TV or the like and exerting an excellent effect with less viewing angle dependence.

The fine organic pigment of the present invention is prepared by kneading an organic pigment, a resin (A), a water-soluble inorganic salt, and a water-soluble organic solvent to obtain a kneading composition, and then removing the water-soluble inorganic salt and the water-soluble organic solvent from water.

The organic pigment used for the kneading composition is at least one organic pigment selected from the group consisting of diketopyloporopyrrole organic pigments, quinophthalone organic pigments, dioxazine organic pigments and phthalocyanine organic pigments.

The diketopyrrolopyrrole organic pigment is a red-orange pigment, and has excellent light resistance and heat resistance. When the specific example of a diketophyllopyrrole organic pigment is represented by a color index number, C.I. Pigment Red 254, 255, 264, or 272, or C.I. Pigment Orange 71, 73, 81, etc. are mentioned.

The quinophthalone organic pigment is a yellow organic pigment and has excellent light resistance and heat resistance. When the specific example of a quinophthalone type organic pigment is represented by a color index number, C.I. Pigment Yellow 138 etc. are mentioned.

Dioxazine-based organic pigments are purple organic pigments and exhibit excellent light resistance and heat resistance. When the specific example of a dioxazine pigment is represented by a color index number, C.I. Pigment Violet 23, 34, 35, 37, etc. are mentioned.

Phthalocyanine-based organic pigments are blue or green organic pigments and have excellent light resistance and heat resistance. When the specific example of the phthalocyanine type organic pigment for blue is shown with the color index number, CIPigment blue 15: 1, 2, 3, 4, 5, 6, 16, or 17, etc. The specific example of the phthalocyanine type organic pigment for green When an example is represented by a color index number, CIPigment # Green 7, 36, 58, etc. are mentioned.

The water-soluble inorganic salt used as the kneading composition serves as a crushing aid. The salt is crushed by using the hardness of the inorganic salt at the time of salt milling, and the primary particles of the pigment are refined. Although it does not specifically limit, if it melt | dissolves in water, For example, salt (sodium chloride), potassium chloride, sodium sulfate, zinc chloride, calcium chloride, magnesium chloride, or a mixture thereof is mentioned, It is preferable to use sodium chloride from a price point of view. Do.

Although the quantity of the water-soluble inorganic salt in a kneading composition is not specifically limited, The range of 1-30 weight times is preferable with respect to a pigment weight, It is more preferable that it is the range of 5-20 weight times, It selects according to the target particle size. . If it is 1 weight or more, it will be easy to refine | miniaturize and size, and if it is 30 weight or less, since the throughput of the pigment in a kneaded material is large, productivity is high and industrially advantageous.

Although the particle diameter of water-soluble inorganic salt is not specifically limited, It is preferable that it is 1-50 micrometers by the median (median) particle diameter (D50) of a volume basis, and if D50 is 50 micrometers or less, it is for making a fine organic pigment. If the treatment time is short and D50 is 1 µm or more, the energy for obtaining the water-soluble inorganic salt is small and economical. In addition, the particle diameter of a water-soluble inorganic salt can be calculated | required using the laser diffraction type particle size distribution analyzer of a dry specification.

As the water-soluble organic solvent used in the kneading composition, the organic pigment, the resin (A) and the water-soluble inorganic salt are added so as to form a uniform mass, and they are freely mixed with water or removed freely by water washing industrially. It is required to have solubility to the extent possible. In addition, since the temperature of the kneading composition rises during kneading and the water-soluble organic solvent tends to evaporate, a high boiling point solvent is preferable from the viewpoint of safety.

Specifically as water-soluble organic solvent, 2- (methoxy) 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 monomethyl ether acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, Or N-methylpyrrolidone. Moreover, you may mix and use two or more types of solvents as needed.

Although the quantity of the water-soluble organic solvent in a kneading composition is not specifically limited, It is preferable that the ratio in a kneading composition is 3-40 weight%, It selects according to the quantity of water-soluble inorganic salt and the hardness of a kneading composition. When the water-soluble organic solvent is insufficient, the kneading composition is not formed, and since the energy is not given, it is difficult to make it fine, or the kneading composition becomes too hard, so that it is difficult to maintain a stable operating state. In addition, when excessively added, the kneading composition becomes so soft that it may be difficult to obtain a predetermined degree of fineness or grain size.

As for resin (A) used for a kneading composition, it is essential that the solubility in the vicinity of 100 weight part of water-soluble organic solvents used in the kneading composition at 25 degreeC is 1 weight part or more, and it is more preferable that solubility is 3 weight part or more. If the solubility is 1 part by weight or more, the compatibility with the water-soluble organic solvent is high, so that the resin is uniformly adsorbed onto the pigment surface, and effects such as a predetermined degree of refinement and reduction of retardation can be easily obtained.

Furthermore, it is essential for resin (A) to have group chosen from an amino group and a quaternary ammonium base group. By the presence of these groups, it is considered that the affinity to an organic pigment becomes high and it is possible to express effects, such as a degree of refinement and birefringence. The amino group refers to a functional group selected from the group consisting of primary amino group, secondary amino group, and tertiary amino group. Among these, it is preferable that resin (A) has a tertiary amino group or a quaternary ammonium base group.

Among these, the quaternary ammonium salt is represented by following General formula (1) or following General formula (2).

General formula (1):

^{-N + (-R 1) (-} R 2) (- R 3) · Z 1 -

(In General Formula (1), R <^1> and R <^2> is respectively independently a C1-C9 alkyl group or a C1-C9 hydroxyalkyl group, R <^3> is a hydrogen atom or a C1-C1- A benzyl group which may have an alkyl group of 9 or an alkyl group having 1 to 9 carbon atoms, Z ¹ is a halogen atom, R ⁴ SO ₃ ⁻ , or R ⁴ OSO ₃ ⁻ , and R ⁴ is an alkyl group having 1-20 carbon atoms or It is a phenyl group which may have an alkyl group having 1-20 carbon atoms.)

General formula (2):

^{-N + (-R 5) (-} R 6) (- R 7 -COO -)

(In General Formula (2), R ⁵ and R ⁶ are each independently an alkyl group having 1 to 9 carbon atoms or a hydroxyalkyl group having 1 to 9 carbon atoms, and R ⁷ is 1 to 6 carbon atoms, preferably 1-5, more preferably 1-3 alkylene group.)

Although the main skeleton of resin (A) is not specifically limited, It is preferable that it is acrylic resin. As acrylic resin, it is obtained by making into an essential component the ethylenically unsaturated monomer which has acryloyl group or a methacryloyl group, and superposing | polymerizing with other ethylenically unsaturated monomer as needed.

When using the fine organic pigment of this invention as a fine organic pigment coloring composition and expressing the characteristic as a color filter, it is required to use resin of the same kind as resin which comprises a fine organic pigment coloring composition. In this invention, since acrylic resin is used preferably for a fine organic pigment coloring composition, it is required that resin (A) is acrylic resin. In order to obtain acrylic resin which has an amino group which is a preferable aspect of this invention, some or all of the monomers should just have an amino group and / or a quaternary ammonium base group. For example, it is preferable to mention the method of copolymerizing the ethylenically unsaturated monomer which has an amino group, and another ethylenically unsaturated monomer.

As an ethylenically unsaturated monomer which has an amino group, the ethylenically unsaturated monomer which has a tertiary amino group, and the ethylenically unsaturated monomer which has a quaternary ammonium base group are mentioned, for example.

As an ethylenically unsaturated monomer which has a tertiary amino group, it is N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (for example, N, N-dialkylamino group-containing (meth) acrylates, such as meta) acrylate or N, N-diethylaminopropyl (meth) acrylate, or N, N-dimethylaminoethyl (meth) acrylamide N, N-dialkyl, such as N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, or N, N-diethylaminopropyl (meth) acrylamide Amino group containing (meth) acrylamides etc. are mentioned. Among these, N, N-dimethylaminoethyl (meth) acrylate is preferable.

As an ethylenically unsaturated monomer which has a quaternary ammonium base group, what added the quaternization agent to the ethylenically unsaturated monomer which has the said tertiary amino group is mentioned, for example.

As the quaternizing agent, for example, sulfonic acid esters such as alkyl sulfuric acid such as dimethyl sulfuric acid, diethyl sulfuric acid, or dipropyl sulfuric acid, methyl p-toluenesulfonic acid, or methyl benzene sulfonate, methyl chloride, ethyl chloride, propyl chloride, or Alkyl chlorides such as octyl chloride, methyl bromide, ethyl bromide, propyl bromide, or alkyl bromide such as octyl crobromide, or benzyl chloride or benzyl bromide.

Reaction of the ethylenically unsaturated monomer which has a tertiary amino group, and a quaternization agent can be normally performed by dripping the quaternization agent of equimolar or less with respect to an amino group to the ethylenically unsaturated monomer solution which has a tertiary amino group. The temperature at the time of quaternization reaction is about 90 degreeC or less, Especially when quaternizing a vinyl monomer, about 30 degreeC or less is preferable, and reaction time is about 1-4 hours.

In particular, an alkoxycarbonylalkyl halide may be used as the quaternizing agent. The alkoxycarbonylalkyl halide is represented by the following general formula (3).

General formula (3):

Z ² -R ⁸ -COOR ⁹

(In General Formula (3), Z ² is halogen, such as chlorine or bromine, preferably bromine, and R ⁸ is 1-6 carbon atoms, preferably 1-5, more preferably 1-3. Is an alkylene group, and R ⁹ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1-3.)

The reaction of an ethylenically unsaturated monomer having a tertiary amino group with an alkoxycarbonylalkyl halide is carried out by reacting an alkoxycarbonylalkyl halide having an equimolarity or less with the amino group with the quaternizing agent, followed by hydrolysis of -COOR ⁹ to carboxyl. It is obtained by conversion as the ^rate-ion (-COO). Thereby, the ethylenically unsaturated monomer which has a quaternary ammonium base group which has a carboxyventine structure represented by General formula (3) can be obtained.

As another ethylenically unsaturated monomer, monomers other than an acryl-type monomer and an acryl-type monomer are mentioned.

In addition, in this application, "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate", "(meth) acryloyloxy", or "(meth) ) Acrylamide ", unless otherwise specified," acryloyl and / or methacryloyl "," acrylic and / or methacrylic "," acrylic acid and / or methacrylic acid ", respectively. "Acrylate and / or methacrylate", "acryloyloxy and / or methacryloyloxy", or "acrylamide and / or methacrylamide" shall be shown.

As an acryl-type monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl, for example (Meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetra Hydroprryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, (Meth) acrylates, such as methoxy polypropylene glycol (meth) acrylate or ethoxy polyethylene glycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl ( L) may be mentioned acrylamide, N- isopropyl (meth) acrylamide, diacetone (meth) (meth) acrylamides, such as one morpholine acrylamide, or acrylic.

Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used. As the carboxyl group-containing ethylenically unsaturated monomer, for example, acrylic acid, methacrylic acid, the ε-caprolactone moiety is acrylic acid, the ε-caprolactone moiety is methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like. One kind or two or more kinds can be selected.

In addition, a hydroxyl group-containing ethylenically unsaturated monomer can be used. As the hydroxyl group-containing ethylenically unsaturated monomer, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylates such as acrylate or cyclohexanedimethanol mono (meth) acrylate. Moreover, polyether mono (meth) acrylate which addition-polymerized ethylene oxide, propylene oxide, and / or butylene oxide with the said hydroxyalkyl (meth) acrylate, (poly) (gamma) -valerolactone (Poly) ester mono (meth) acrylate which added, (poly) (epsilon) -caprolactone, and / or (poly) 12-hydroxystearic acid, etc. can also be used.

Moreover, a phosphate ester group containing ethylenically unsaturated monomer can also be used. As the phosphate ester group-containing ethylenically unsaturated monomer, for example, the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer can be obtained by, for example, reacting a phosphate esterifying agent such as phosphorus pentaoxide or polyphosphoric acid.

Moreover, as monomers other than the said acryl-type monomer, For example, styrene or styrene, such as (alpha) -methylstyrene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl Vinyl ethers such as vinyl ether, or fatty acid vinyls such as vinyl acetate or vinyl propionate. The said monomers other than an acryl-type monomer can also be used together with the said acryl-type monomer.

As a method of obtaining suitable resin (A) in this invention, well-known methods, such as anion polymerization, a living anion polymerization, a cation polymerization, a living cation polymerization, a free radical polymerization, and a living radical polymerization, can be used. Among these, free radical polymerization or living radical polymerization is preferable.

In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl2,2'-azobis ( 2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2,2'-azobis [2- (2-imidazolin-2-yl) propane] etc. are mentioned. Examples of the organic peroxide include benzoyl peroxide, t-butylperbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butylperoxy neodecanoate, t-butylperoxybibarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide Can be. These polymerization initiators can be used individually or in combination of 2 or more types. The reaction temperature is preferably 40-150 ° C, more preferably 50-110 ° C, and the reaction time is preferably 3-30 hours, more preferably 5-20 hours.

In the living radical polymerization method, side reactions occurring in general radical polymerization are suppressed, and further, since polymerization growth occurs uniformly, a resin having a block polymer or a molecular weight can be easily synthesized.

Among these, the atom transfer radical polymerization method using an organic halide or a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and adopts a polymerization temperature adaptable to existing equipment. It is preferable in that it can be. The atomic transfer radical polymerization method can be carried out by the method described in References 1-8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329

(Ref. 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921

(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614

(Ref. 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866

(Ref. 5) WO96 / 030421

(Ref. 6) WO97 / 018247

(Reference 7) Japanese Patent Application Laid-Open No. 9-208616

(Reference 8) Japanese Patent Application Laid-open No. Hei 8-41117

It is preferable to use a solvent for the said superposition | polymerization. Although it does not specifically limit as a solvent, For example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, di Propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like. You may use these polymerization solvents in mixture of 2 or more types.

Moreover, in the resin (A) suitable for this invention, the manufacturing method of having a quaternary ammonium salt as a functional group not only copolymerized the ethylenically unsaturated monomer which has the said quaternary ammonium salt group as a monomer component, but has the said tertiary amino group After acryl-type resin which has the tertiary amino group which copolymerized ethylenic unsaturated monomer as a monomer component, you may obtain by making said quaternization agent react.

Although the quantity of the amino group and quaternary ammonium base group which exist in resin (A) suitable for this invention is not specifically limited, It is preferable that the sum total of the amine value and quaternary ammonium salt value of resin is 1-300 mg KOH / g, and it is 10-200 mg It is more preferable that it is KOH / g. When the sum of the amine value and the quaternary ammonium salt is 1 mg KOH / g or more, the expression of the effect becomes remarkable, and when it is 300 mgKOH / g or less, the compatibility in the fine organic pigment coloring composition is high and the viscosity is low. Furthermore, the structure of the amino group is not particularly limited, and can be used by substituting various functional groups.

Although the molecular weight of resin (A) used for this invention is not specifically limited, It is preferable that the converted weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000-500,000, and it is more preferable that it is 5,000-15,000. Do.

Moreover, it is preferable that resin (A) used by this invention has a characteristic which does not melt | dissolve in the solvent widely used for a fine organic pigment coloring composition. Thereby, a fine organic pigment coloring composition of high contrast ratio can be obtained. It is preferable that molecular weight (A) does not melt | dissolve in the ester solvent of 118-133, and it is more preferable not to melt | dissolve in propylene glycol monomethyl ether acetate of the molecular weight 132.16 among these.

In addition, the resin (A) used in the present invention can obtain fine organic pigments and fine organic pigment coloring compositions even when the resins obtained by block polymerization are used. A fine organic pigment and a fine organic pigment coloring composition can be obtained.

In block polymerization, only the monomer which exists previously is polymerized, and only another monomer is superposed | polymerized, and the block of each polymer is prepared beforehand, and this is reacted.

Although the quantity of resin (A) in a kneading composition is not specifically limited, It is preferable that it is 0.01-1.0 weight part with respect to 1 weight part of organic pigments, and it is more preferable that it is 0.03-0.3 weight part. When the amount of the resin (A) is 0.01 parts by weight or more, the miniaturization effect is easily obtained. When the amount of the resin (A) is 1.0 parts by weight or less, it becomes a preferable viscosity in the fine organic pigment coloring composition. Moreover, it is preferable to adjust the quantity of resin (A) by compatibility of resin (A) and a pigment carrier. In other words, when the compatibility is high, the amount of resin (A) is minimized to minimize the influence on the physical properties of the pigment carrier, while when the compatibility is low, the amount of resin (A) is increased to increase the dispersion effect. It is preferable to exhibit sufficiently.

In the kneading composition, additives such as various resins, dispersing aids, plasticizers, dispersing agents, surfactants, pigment derivatives present in compounds having substituents introduced into molecules of organic pigments, or calcium carbonate, barium sulfate, which are generally used as extender pigments, And inorganic pigments such as silica. Moreover, in order to adjust a hue, you may mix and process with another pigment.

In particular, the kneading composition contains at least one derivative selected from pigment derivatives, anthraquinone derivatives, acridon derivatives or triazine derivatives in order to prevent crystal growth and crystal transition of organic pigments and to efficiently produce fine organic pigments. It is preferable to make it. Each derivative is a compound having an organic pigment, anthraquinone, acridon or triazine, a basic substituent, an acidic substituent, or a phthalimide methyl group. The phthalimide methyl group may have a substituent. Among these, a pigment derivative, especially a pigment derivative having the same structure as the organic pigment to be micronized as a mother skeleton, is preferable because the effect of suppressing crystal growth of the pigment is particularly high.

A dye derivative is a compound which introduce | transduced the substituent into the organic pigment | dye here, and although it is preferable that it is close to the color of the pigment to be used, if there is little addition amount, you may use a thing with a different color. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalenes, which are generally not called dyes. As a dye derivative, Japanese Patent Laid-Open No. 63-305173, Japanese Patent Laid-Open No. 52-132031, Japanese Patent Laid-Open No. 54-062227, Japanese Patent Laid-Open No. 56-061461, or Japanese Patent Laid-Open No. 60 What is described in -088185 etc. can be used. In particular, the dye derivative having a basic group is suitably used because the pigment dispersing effect is large. These can be used individually or in mixture of 2 or more types.

A dye derivative is a compound represented by following General formula (4).

General formula (4):

A-B

(In general formula (4), A is an organic pigment residue and B is a basic substituent, an acidic substituent, or a phthalimide methyl group.)

In general formula (4), as an organic pigment which comprises the organic pigment residue of A, azo pigments, such as a diketopylopolo pyrrole pigment, azo, disazo, or polyazo, copper phthalocyanine, a copper halide phthalocyanine, or no Phthalocyanine-based pigments such as metal phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthrone, indanthrone, pyrantrone, or anthraquinone pigment such as bioanthrone, quinacridone Pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, benzimidazolone pigments, srenne pigments, or metal complexes System pigments; and the like.

In the general formula (4), examples of the basic substituent of B include a substituent represented by the following general formula (5), general formula (6), or general formula (7), and as the acidic substituent, general formula (8) , A substituent represented by General Formula (9) or General Formula (10).

Formula (5):

Formula (6):

Formula (7):

[In General Formula (5)-(7),

X is -SO _2- , -CO-, -CH _2- , -CH ₂ NHCOCH _2- , -CH ₂ NHSO ₂ CH _2- , or a direct bond,

Y is -NH-, -O-, or a direct bond,

n is an integer of 1-10,

Y ¹ is —NH—, —NR ²² —Z—NR ²³ —, or a direct bond,

R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, or a phenyl group which may have a substituent,

Z is an alkylene group which may have a substituent or an arylene group which may have a substituent,

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms that may have a substituent, or R ¹⁰ and R ¹¹ are integrated; Furthermore, it is a heterocyclic ring which may have a substituent containing nitrogen, oxygen, or a sulfur atom,

R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ may each independently have a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a substituent. It is a good C6-20 arylene group,

R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent,

R ¹⁷ is a substituent represented by general formula (5) or a substituent represented by general formula (6),

X is a hydroxyl group, an alkoxyl group, a substituent represented by the said General formula (5), or a substituent represented by the said General formula (6).]

As an amine component used in order to form the substituent represented by General formula (5)-(7), for example, dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N -Ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N , N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, Dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutyl Amine, N, N-diethylaminoethylamine, N, N- Ethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-di Butylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyllaurylaminopropylamine, N, N -Ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperizine, 2-pipecoline, 3-pipe Choline, 4-Pipecoline, 2,4-Lupentidine, 2,6-Lupentidine, 3,5-Lupentidine, 3-Piperizinmethanol, Pipecolinic Acid, Isonipecotinic Acid, Isonipecotinate, Miso Ethyl nifecotinate, 2-piperizine ethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperizine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-amino Propylpiperizine, N-aminopropyl-2- Pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino- 4-methyl piperazine, 1-cyclopentyl piperazine, etc. are mentioned.

Formula (8):

Formula (9):

Formula (10):

[In the said General Formula (8)-(10),

M is a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom,

i is the singer of M,

R ¹⁸ , R ¹⁹ , R ²⁰ , and R ²¹ may each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, or a substituent. A good phenyl group or polyoxyalkylene group.]

Any amine of primary, secondary, tertiary and quaternary may be sufficient as the amine component used in order to form the sulfonate amine salt of General formula (10).

Examples of the primary amine include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, and penta. Saturated amines, such as a decylamine, an octadecylamine, a nonadecylamine, or an eicosyl amine, or the unsaturated amine corresponding to carbon number of the said saturated amine is mentioned.

Examples of the secondary amines include dioleylamine, distearylamine, and the like.

Examples of the tertiary amines include dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilauryl monomethylamine, trioctylamine, and the like.

As quaternary amines, dimethyldidodecylammonium chloride, dimethyldioleylammonium chloride, dimethyldidecylammonium chloride, dimethyldioctylammonium chloride, trimethylstearylammonium chloride, dimethyldistearylammonium chloride, trimethyldecyl Ammonium chloride, trimethylhexadecyl ammonium chloride, trimethyloctadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride, or dimethyl hexadecyl octadecyl ammonium chloride, etc. are mentioned.

Moreover, when any of R <^18> , R <^19> , R <^20> , and R <^21> represents a polyoxyalkylene group in General formula (10), a polyoxyethylene group, a polyoxypropylene group, etc. are mentioned as the example. .

The compounding quantity of the pigment derivative in a kneading composition is 1-30 weight part with respect to 100 weight part of organic pigments, More preferably, it is 5-20 weight part. When the compounding quantity of a derivative is 1 weight part or more, the added effect is easy to be acquired, and when it is 30 weight part or less, an excess derivative does not affect dispersion.

In particular, the amount of the dye derivative added during the miniaturization of the quinophthalone-based yellow pigment is preferably 0.005-0.1 parts by weight, more preferably 0.01-0.02 parts by weight with respect to 1 part by weight of the total organic pigment.

As a device for mechanically kneading the kneaded mixture, a kneader, a planetary mixer, a trimix (manufactured by Inoue Co., Ltd.), two rolls, three bone rolls, a multi-axis roll, an extruder, and a KRC kneader (Kurimoto) Iron Works Co., Ltd., or Miracle KCK (manufactured by Asada Iron Works, Inc.) may be used, but is not particularly limited and can be used regardless of batch type and continuous type, provided that the kneaded material is provided with an efficient mechanical shearing force.

Although the temperature at the time of kneading a kneaded mixture mechanically is not specifically limited, It is preferable to process at 20-80 degreeC, and it is more preferable to process at 30-65 degreeC. Under kneading conditions of 20 ° C or more and 80 ° C or less, the speed of grinding and miniaturizing organic pigment particles without reducing the kneaded material throughput or reducing the viscosity of the kneaded mixture, or using these behaviors in combination. It is easy to control the crystal growth rate of the organic pigment particles, and a predetermined degree of refinement can be obtained.

The fine organic pigment after kneading is processed by a conventional method. That is, the kneading composition is treated with water or an aqueous mineral solution, filtered and washed with water to remove the water-soluble inorganic salts and the water-soluble organic liquid and to isolate the fine organic pigment. Specifically, the fine organic pigment after kneading is introduced into water, stirred to form a slurry, and then the slurry is filtered and washed to remove the water-soluble inorganic salt and the water-soluble organic solvent, thereby producing a fine organic pigment. . You may repeat these processes multiple times. Although it does not specifically limit as aqueous mineral solution, The aqueous solution containing inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, is mentioned. As stirring, you may use a high speed mixer, for example. As the filtration, for example, a filter press may be used. The fine pigment may be used as it is in a wet state, or may be used in a powder state by drying and grinding.

It is preferable that the average primary particle diameter of the fine organic pigment obtained is 40 nm or less, More preferably, it is 30 nm or less, More preferably, it is 20 nm or less. Moreover, it is preferable that average primary particle diameter is 5 nm or more. When the average primary particle diameter of a pigment is larger than an upper limit, transparency of a coloring film etc. fall. Moreover, when smaller than a lower limit, pigment dispersion becomes difficult, it becomes difficult to maintain stability as a coloring composition and to ensure fluidity. In addition, the following are mentioned as a calculation method of a primary particle diameter. By image-processing the image of the micronized organic pigment image | photographed with the transmission electron microscope (TEM), the projection area of each particle is calculated | required, and the diameter of the circle | round | yen corresponded to the projection area is computed. It is possible to use the value which divided the total of the diameter of the circle | round | yen of each calculated particle | grain by the number as an average primary particle diameter.

It can be set as a fine organic coloring composition using the obtained fine organic pigment. The microorganism coloring composition contains a fine organic pigment and a pigment carrier.

The pigment carrier contained in the fine organic pigment coloring composition of the present invention is obtained by dispersing a fine organic pigment and is composed of a resin, a precursor thereof, or a mixture thereof. The resin has a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400-700 nm in the visible light region. The resin includes a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin, and the precursor includes monomers or oligomers that are cured by active energy ray irradiation to produce a resin, and these alone or in combination thereof. It can mix and use species.

The pigment carrier may be used in an amount of 30-700 parts by weight, preferably 60-450 parts by weight with respect to 100 parts by weight of the fine organic pigment in the microorganic coloring composition. In the case where a mixture of a resin and its precursor is used as the pigment carrier, the resin is in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the fine organic pigment in the microorganic coloring composition. Can be used. The precursor of the resin may be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the fine organic pigment in the microorganic 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, polyester resin, and acrylic resin. 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.

As active energy ray curable resin, the (meth) acryl compound which has reactive substituents, such as an isocyanate group, an aldehyde group, or an epoxy group, and capic acid, is made to react with the polymer which has reactive substituents, such as a hydroxyl group, a carboxyl group, or an amino group, The thing which introduce | transduced photocrosslinkable groups, such as a (meth) acryloyl group or a styryl group, is used. Moreover, half-esterification of the linear polymer containing acid anhydrides, such as a styrene maleic anhydride copolymer and an alpha olefin maleic anhydride copolymer, with (meth) acryl compounds which have hydroxyl groups, such as hydroxyalkyl (meth) acrylate, One is used.

As a monomer and oligomer which are precursors of resin,

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate , Isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl Such as (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyl steel (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate Linear or branched alkyl (meth) acrylates;

Cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dish Cyclic alkyl (meth) acrylates such as clofentenyloxyethyl (meth) acrylate or isobonyl (meth) acrylate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate Rates;

(Meth) acryloxy-modified polydimethylsiloxane (silicone macroma);

(Meth) acrylates having heterocycles such as tetrahydroprryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracutylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or (Meth) acrylates having aromatic rings such as nonylphenoxy polyethylene glycol (meth) acrylate;

2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (Meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethyl Hexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyethylene glycol monostearyl ether ( (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as meta) acrylate;

(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth (Meth) which has carboxyl groups, such as acryloyloxypropyl hexahydrophthalate, ethylene oxide modified zucchini (meth) acrylate, (beta) -carboxyethyl (meth) acrylate, or (omega) -carboxypolycaprolactone (meth) acrylate. Acrylates;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxy Ethyl-2-hydroxyethyl (meth) phthalate,

Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetra Methylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (Meth) acrylates having hydroxyl groups such as (meth) acrylate or glycerol (meth) acrylate;

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol ) Di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polytetramethylene glycoldi (meth) acrylate, 1,3-butanedioldi (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, or 2-ethyl-2-butyl-propanedioldi (meth ) Acrylate of (poly) alkylene glycol di (meth) acrylate;

Dimethyrol dicyclopentanedi (meth) acrylate, hydroxypivaline neopentylglycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, Propylene oxide modified bisphenol A di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetra Di (meth) acrylates such as methylene oxide-modified bisphenol F di (meth) acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, or glycerol di (meth) acrylate;

(Meth) acrylate which has tertiary amino groups, such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or diethylaminopropyl (meth) acrylate Ryu;

Glycerol tri (meth) acrylate, trimetholpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipenta Trifunctional or higher polyfunctional (meth) acrylates such as erythritol hexa (meth) acrylate;

Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycid Dil ether, alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenylglycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) acrylic acid addition Water, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic acid adduct, Epichlorohydrin-modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diggle Cedyl ether- (meth) acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolak type epoxy resin-(meta Epoxy (meth) acrylates such as acrylic acid adduct, cresol novolac-type epoxy resin- (meth) acrylic acid adduct, or other epoxy resin- (meth) acrylic acid adduct;

(Meth) acryloyl modified silicone, (meth) acryloyl modified polyurethane, (meth) acryloyl modified polyester, (meth) acryloyl modified melamine, (meth) acryloyl modified silicone, (Meth) acryloyl modified resin oligomers, such as (meth) acryloyl modified polybutadiene or (meth) acryloyl modified rosin;

Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;

Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;

Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or,

Acrylonitrile etc. are mentioned. These can be used individually or in mixture of 2 or more types.

When curing the said composition by ultraviolet irradiation, the photoinitiator etc. are added to the organic pigment coloring composition of this invention.

As a photoinitiator,

4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydrate Oxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, or 2-methyl-1- [4- (methylthio) phenyl] -2 -Acetophenone series photoinitiators such as morpholino propane-1-one;

Benzoin photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal;

Benzophenone photoinitiators such as benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenylsulfide;

Thioxane-based photopolymerization initiators such as thioxanthone, 2-chlorothioxone, 2-methylthioxone, isopropyl thioxane, or 2,4-diisopropylthioxone;

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-tril) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine photoinitiators such as 6-triazine or 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine;

Borate photopolymerization initiator; Carbazole-based photopolymerization initiator; Or imidazole series photoinitiators etc. are used.

The photopolymerization initiator may be used in an amount of 5-200 parts by weight, preferably 10-150 parts by weight with respect to 100 parts by weight of the organic micropigment in the colored composition.

The photoinitiator is used alone or in mixture of two or more, or as a sensitizer, α-acyloxy ester, acyl phosphine oxide, methylphenylglyoxylate, benzyl-9, 10-phenan srenquinone, camphor quinone, ethyl anthra Such as quinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, or 4,4'-diethylaminobenzophenone You may use a compound together. A sensitizer can be used in the quantity of 0.1-60 weight part with respect to 100 weight part of photoinitiators in a coloring composition.

The fine organic pigment coloring composition of this invention can be adjusted in the form of a solvent developing type or an alkali developing type coloring resist. The coloring resist is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or an active energy ray-curable resin, and a monomer. In a carrier, it can manufacture using various dispersion means, such as a three roll mill, a two roll mill, a sand mill, a kneader, or an atrider. In addition, the fine organic pigment coloring composition of the present invention may be prepared by mixing a plurality of fine organic pigments dispersed in a pigment carrier separately.

When disperse | distributing a fine organic pigment in a pigment carrier, dispersion adjuvant, such as a resin pigment dispersant, surfactant, and a dye derivative, can be used suitably. Since the dispersing aid is excellent in dispersing the pigment and has a great effect of preventing reaggregation of the pigment after dispersing, when the colored film is produced using a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersing aid, Excellent transparency The dispersing aid can be used in an amount of 0.1-40 parts by weight, preferably 0.1-30 parts by weight with respect to 100 parts by weight of the pigment in the colored composition.

Among these, the pigment derivative is excellent in the role of preventing aggregation of fine organic pigments and maintaining a state in which organic pigments are finely dispersed, and by using a fine organic coloring composition containing these derivatives, the color purity is high at a high contrast ratio. Since a highly colored film can be manufactured, it is suitable as a dispersing aid.

The resinous pigment dispersant to be added in the fine organic pigment coloring composition of the present invention has a pigment affinity site having a property of adsorbing to the pigment and a site compatible with the pigment carrier, adsorbed onto the pigment to form a pigment carrier of the pigment. This is to stabilize the dispersion of the furnace.

Resin-type pigment dispersants include polyvinyl-based, polyurethane-based, polyester-based, polyether-based, formalin condensed-based, silicone-based, or a composite polymer thereof,

As a pigment affinity site | part, polar groups, such as a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphate ester group, a sulfonic acid group, a hydroxyl group, an amino group, a quaternary ammonium base group, or an amide group, and polyethylene oxide, a polypropylene oxide, or these Hydrophilic polymer chains, such as a complex type, etc.,

As a site | part compatible with a pigment carrier, a long chain alkyl chain, a polyvinyl chain, a polyether chain, or a polyester chain is mentioned.

Specifically as a resin pigment dispersant,

Styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly (meth) acrylate, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, (meth) acrylic acid-poly Vinyl macrocopolymer, phosphate ester group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide- (meth) acrylic acid copolymer, carboxymethyl cellulose, polyurethane having a carboxyl group, formalin condensate of naphthalene sulfonate, Or anionic resin pigment dispersants such as sodium alginate;

Nonionic resin type pigment dispersants such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; or,

Polyethylenimine, aminoalkyl (meth) acrylate copolymer, polyvinylimidazoline, polyurethane having amino group, reactant of poly (lower alkyleneimine) with polyester having free carboxyl group, or cationic system such as chitosan A resin pigment dispersant is mentioned, These can be used individually or in mixture of 2 or more types.

As a commercial resin type pigment dispersant,

Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2090, 2091, 2164, or 2163, or, Anti-Terra-U, 203, or 204, or BYK-P104, P104S, or 220S, or, Lactimon, or Lactimon- Resin type pigment dispersants made by BIC Chem Corporation, such as WS or Bykumen;

SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090, or 53095 Nippon Lubrizol resin type pigment dispersant; or,

EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, or 1503 Although a resin type pigment dispersant made by Chiba Specialty Chemicals Co., Ltd., etc. may be mentioned, but not limited to these, any resin type pigment dispersant may be used, and these may be used alone or in combination of two or more thereof.

As a surfactant,

Polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanol Anionic surfactants such as amine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, or polyoxyethylene alkyl ether phosphate ester;

Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, or polyethylene glycol monolaurate ;

Chaotic surfactants such as alkyl quaternary ammonium salts or ethylene oxide adducts thereof;

Alkyl betaines such as alkyl dimethylamino acetic acid betaine; or,

Amphoteric surfactants, such as alkylimidazoline, are mentioned, These can be used individually or in mixture of 2 or more types.

The fine organic pigment coloring composition of this invention can be made to contain a non-aqueous solvent. As a result, the fine organic pigment is sufficiently dispersed in the pigment carrier, and the coating film is formed on a transparent substrate such as a glass substrate so as to have a dry film thickness of 0.2-5 탆, thereby facilitating formation of a colored film.

As the non-aqueous solvent, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-pentanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexanone-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxypropionic acid Ethyl, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 3-methoxybutanol, 3-methoxybutylacetate, 4 -Pentanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetoamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate , n-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, e Tylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol mono Hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether a Tate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or dibasic acid ester Can, These are used individually or in mixture. The solvent can be used in an amount of 800-4000 parts by weight, preferably 1000-2500 parts by weight, based on 100 parts by weight of the pigment in the pigment dispersion and the colored composition.

In addition, the fine organic pigment coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity over time of the composition. As a storage stabilizer, For example, quaternary ammonium chlorides, such as benzyl trimethylammonium chloride or diethylhydroxyamine; Organic acids such as lactic acid or oxalic acid; Methyl esters of the organic acids; catechols such as t-butyl pyrocatechol; Organic phosphines such as triphenylphosphine, tetraethylphosphine, or tetraphenylphosphine; Or a phosphite etc. are mentioned. The storage stabilizer can be used in an amount of 0.1-10 parts by weight based on 100 parts by weight of the fine organic pigment in the fine organic pigment coloring composition.

The fine organic pigment coloring composition of the present invention can be adjusted in the form of gravure offset printing ink, anhydrous offset printing ink, silk screen printing ink, solvent developing type or alkali developing coloring resist.

The alkali developing colored resist is obtained by dispersing the fine organic pigment of the present invention in a composition containing a binder resin, a monomer and / or oligomer, a photopolymerization initiator, and an organic solvent. The binder resin is at least one resin selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and is a resin containing at least an alkali-soluble resin.

As a fine organic pigment coloring composition, when adjusting an alkali developable coloring resist,

The fine organic pigment of this invention is disperse | distributed in the composition containing binder resin, a monomer and / or oligomer, a photoinitiator, and an organic solvent, or

It can prepare by mixing previously the fine organic pigment dispersion which disperse | distributed and adjusted the fine organic pigment of this invention, the monomer and / or oligomer, and a photoinitiator in the composition containing binder resin and the organic solvent.

From the viewpoints of color characteristics of the coating film, dispersion stability of the pigment, and simplicity of prescription adjustment, the latter adjustment method is preferable, but is not limited thereto.

The fine organic pigment dispersion is itself a fine organic pigment coloring composition of the present invention and, if necessary, may contain a part of monomers and / or oligomers, and a part of the binder resin and / or the organic solvent may be used to adjust the color resist. At the time of mixing, you may mix.

The fine organic pigment is preferably contained in a proportion of 5-70% by weight based on the total solid content of the fine organic pigment coloring composition (100% by weight). It is more preferable that it is the ratio of 20-50 weight%.

In addition, the fine organic pigment coloring composition of the present invention can be made to contain a dye within the range of not lowering the heat resistance for coloring.

The fine organic pigment coloring composition of the present invention is a coarse particle of 5 μm or more, preferably 1 μm or more of coarse particles, more preferably 0.5 μm or more of coarse particles and mixed by means of centrifugation, sintering filter, membrane filter, or the like. It is preferable to remove dust.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not impose any limitation on the scope of the present invention. In addition, "part" and "%" in an Example represent "weight part" and "weight%", respectively.

(Measurement)

<Particle diameter of pigment>

First, the image which image | photographed the primary particle of a pigment was obtained using the transmission electron microscope (made by Japan Electronics Corporation). Furthermore, by using the image analysis type particle size distribution measurement software (manufactured by Mountain Tech Co., Ltd.), the projection area of each particle of the obtained image is obtained, and the number of particles is divided from the total of the projection area of the particles, thereby obtaining the average particle diameter of the pigment particles. Calculated.

<Amine value of resin>

The amine number of resin was calculated | required by the potentiometric titration method using 0.1N aqueous hydrochloric acid solution, and it converted into the equivalent of potassium hydroxide. The amine number of the following resin solution shows the amine value of solid content.

<Quarter ammonium cheapness of resin>

The quaternary ammonium salt of the resin was obtained by titrating with a 5% aqueous potassium chromate solution as an indicator, titrating with 0.1 N silver nitrate aqueous solution, and converting it to the equivalent of potassium hydroxide. The quaternary ammonium salt of the following resin solution represents the quaternary ammonium salt of solid content.

<Acid value of resin>

The acid value of resin was calculated | required by the potentiometric titration method using 0.1N potassium hydroxide ethanol solution. The acid value of the following resin solution represents the acid value of solid content.

<Weight Average Molecular Weight of Resin (A)>

The weight average molecular weight of the resin (A) was measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation). When measured by GPC, when the resin having an amino group was dissolved in tetrahydrofuran, TSK gel supermultipoa HZ-M manufactured by Tosoh was used as a column using triethylamine added to tetrahydrofuran as the elution solvent. Measured by standard polystyrene using consecutive times, and not dissolved in tetrahydrofuran and dissolved in 50/50 mixed solvents of methanol / water. Standard polyethylene was prepared using TSK gel G5000PWxl-CP manufactured by Tosoh as a column using the same. It measured by oxide conversion.

<Weight Average Molecular Weight of Acrylic Resin>

The weight average molecular weight (Mw) of the acrylic resin used as binder resin was measured by the gel permeation chromatography (GPC) (made by Tosoh Corporation) equipped with the RI detector. When measuring by GPC, it measured by the polystyrene conversion measured using TSK gel column (made by Tosoh Corporation) and using THF as a developing solvent.

<Method of Forming Colored Film>

The colored film was produced by using a fine organic pigment colored composition, using a spin coater to arbitrarily change the number of revolutions, and making the dry film thickness 2.0 m. After coating, the mixture was dried in a hot air oven at 80 ° C. for 30 minutes.

<Contrast ratio>

The polarizing plates were superposed on both surfaces of the substrate on which the colored film was formed so that the polarization axes of both polarizing plates were parallel to each other, the backlight was incident from one polarizing plate side, and the luminance Lp of the light transmitted through the other polarizing plate was measured as a luminance meter. Next, the polarizing plates superposed on both surfaces of the board | substrate were arrange | positioned so that the polarization axes of both polarizing plates may mutually orthogonally cross, the backlight was made to enter from one polarizing plate side, and the brightness Lc of the light which permeate | transmitted the other polarizing plate was measured with the luminance meter. The contrast ratio Lp / Lc was computed using the obtained measured luminance value. The measurement was performed with respect to the normal direction of the board | substrate. Moreover, "NPF-SEG1224DU" (made by Nito Denko) was used as both polarizing plates. As a luminance meter, "BM-5A" (made by Topcon Co., Ltd.) was used and the brightness | luminance was measured on the conditions of a 2 degree visual field. The higher the contrast ratio, the better the transparency of the colored film (colored composition).

<Half width>

The dried pigment was pulverized with 80 mesh of gold steel and then subjected to X-ray measurement. X-ray diffraction spectol was measured under the following conditions.

Device: Rigaku Ultima 2001

X-ray source: CuKα

Voltage: 40kV

Current: 40 mA

Measuring range: 5.0 ° -35.0 °

Step angle: 0.01 °

From this measurement result, data processing was performed on condition of the following, and half width ((DELTA) 2 (theta) degree) was calculated | required. Here, half width | variety is a black angle value defined by the peak width in the intensity | strength position used as 1/2 intensity | strength of the X-ray-diffraction intensity in arbitrary 2 (theta) degrees peak.

2θ ° 11.0-13.7 °, 24.5-27.0 °, 27.0-29.3 ° for quinophthalone pigments, 2θ ° 4.0-7.0 °, 8.0-12.0 °, 15.5-18.5 °, 24.5-27.5 °, phthalocyanine In the pigment, 5.0-12.0 °, in the copper halide phthalocyanine pigment, a straight line connecting 15.5-18.3 ° and 21.6-22.7 ° was used as the base line, and the background was removed. After this data processing, the maximum intensity in each range was selected and the half width was calculated | required. When having a peak in several places, the average value was computed and it was set as half width. The half width determined here is considered to correspond to the size of the particles. In other words, when the half width is large, the particles are small.

<Recognition>

Elliptical polarized light is incident from the normal direction and 45 ° inclination direction of the substrate on which the colored film is formed. In the wavelength range of 535-560 nm, 410-520 nm for a blue substrate, 535-635 nm for a yellow substrate, and 410-520 nm for a purple substrate, Δ (unit nm) was measured every 1 nm. In this case the Δ = 0 and the area of a region formed of the respective specifications of the toll of the wavelength range Δ were obtained by calculating (in nm ²⁾ of the. Since the retardation shows that a retardation will arise in transmitted light and a viewing angle characteristic will worsen when a value increases, it is preferable that it is 30 or less, Furthermore, it is more preferable that it is 20 or less.

<Synthesis method of resin>

Synthesis Example 1

62.4 parts of methyl ethyl ketone was injected into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Filtration, dropping lotto 19.5 parts of methyl methacrylate, 11.7 parts of n-butyl methacrylate, 11.7 parts of 2-ethylhexyl methacrylate, a diethylene glycol monomethacrylate (NOF make, brand name: Brenma) PE90 '), 7.8 parts of dimethylaminoethyl methacrylate, 27.3 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 4.7 parts of methyl ethyl ketone were injected and homogenized. It was attached to a four-neck separable flask and dripped for 2 hours. After 2 hours of completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, and the weight average molecular weight (Mw) was 7130, and the mixture was cooled to 50 ° C. 22.0 parts of benzyl chloride and 22.0 parts of ethanol were added here, after making it react at 50 degreeC for 2 hours, it heated up to 80 degreeC for 1 hour, and also made it react for 2 hours. Then, 150 parts of diethylene glycol was added, ethanol and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 1 whose resin component is 40 weight% was obtained (amine value 3 mgKOH / g, quaternary ammonium salt 97 mgKOH / g).

Synthesis Example 2

80 parts of methyl ethyl ketones were injected into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Filtration, 20 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, 5 parts of 2-ethylhexyl methacrylate, 16 parts of Brenma PE90 to a dropping lot, Kayama PM-21 (made by Nippon Kayaku Co., Ltd.) 1 part of caprolactone) 10 parts of 2-hydroxyethyl methacrylate), 25 parts of dimethylaminoethyl methacrylate, 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) After injecting 20 parts of methyl ethyl ketone to make it uniform, it was attached to a four-neck separable flask and dripped for 2 hours. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7320, and the mixture was cooled to 50 ° C. 13.8 parts of benzyl chloride and 13.8 parts of ethanol were added here, and after making it react at 50 degreeC for 2 hours, it heated up to 80 degreeC for 1 hour, and made it react for 2 hours again. Furthermore, the resin solution was concentrated and the solvent was replaced with ethylene glycol monomethyl ether acetate to obtain a resin solution 2 having a solid content of 50% by weight (amine value of 29 mgKOH / g, quaternary ammonium salt 62 mgKOH / g).

Synthesis Example 3

Into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 80 parts of methyl ethyl ketone, 92.0 parts of butyl acrylate, 2.8 parts of spartane, and 1.9 parts of ethyl bromoisolactate were injected into a 40 degreeC under nitrogen stream. It heated up as. 1.1 parts of cuprous chloride chlorides were thrown in, and it heated up to 75 degreeC, and started superposition | polymerization. After the polymerization for 3 hours, the polymerization solution was sampled to confirm that the polymerization yield was 95% or more from the solid content of the polymerization, and the weight average molecular weight (Mw) was 6860. 8.0 parts of dimethylaminoethyl methacrylate and 20.0 parts of MEK were added. And it superposed | polymerized again. After 2 hours, the polymerization yield was confirmed to be 97% or more from the solid content of the polymerization solution, and the mixture was cooled to room temperature to terminate the polymerization. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resins "Diion® PK228LH (made by Mitsubishi Chemical Corporation)" were added, and it stirred at room temperature for 1 hour, and again it was made into Kyowa 500 SN (Kyowa Chemical Co., Ltd.) as a neutralizing agent. 6 parts) was added and stirred for 30 minutes. The residue of the polymerization catalyst was removed by removing the cation exchange resin and the adsorbent by filtration. Furthermore, the resin solution was concentrated and the solvent was substituted with ethylene glycol monomethyl ether acetate to obtain a resin solution 3 having a solid content of 50% by weight (amine value of 29 mgKOH / g, quaternary ammonium salt 0 mgKOH / g).

Synthesis Example 4

80 parts of ethylene glycol monomethyl ether acetates were poured into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 90 degreeC under nitrogen stream. Filtration, dropping lot 40 parts of methyl methacrylate, 37 parts of n-butyl methacrylate, 10 parts of methacrylic acid, fraxel FM5 (made by Daicel Chemical Industry: 5 mol addition of ε-caprolactone 2-hydroxyethyl methacrylate) 10 parts) of dimethylaminoethyl methacrylate, 6 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), 20 parts of ethylene glycol monomethyl ether acetate, It was attached to a four-neck separable flask and dripped for 2 hours. After continuing stirring at the same temperature for 2 hours, it was confirmed that the polymerization yield was 98% or more from the solid content, the weight average molecular weight (Mw) was 6790, and thereafter, an appropriate amount of ethylene glycol monomethyl ether acetate was added to thereby obtain a solid content ratio. A 50% by weight resin solution 4 was obtained (amine value 11 mgKOH / g, quaternary ammonium salt 0 mgKOH / g).

Synthesis Example 5

80 parts of ethylene glycol monomethyl ether acetates were poured into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 90 degreeC under nitrogen stream. Filtration, dropping lot 40 parts methyl methacrylate, 20 parts n-butyl methacrylate, 10 parts methacrylic acid, 30 parts 2-hydroxyethyl methacrylate, 2,2'- azobis (2,4- 6 parts of dimethylvaleronitrile) and 20 parts of ethylene glycol monomethyl ether acetate were injected to make it uniform, and then it was attached to a four-neck separable flask and dripped for 2 hours. After continuing stirring at the same temperature for 2 hours after completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, the weight average molecular weight (Mw) was 7050, and thereafter, an appropriate amount of ethylene glycol monomethyl ether acetate was added to thereby add a solid content. A resin solution 5 having a rate of 50% by weight was obtained (amine value 0 mg KOH / g, quaternary ammonium salt 0 mg KOH / g).

Synthesis Example 6

62.4 parts of methyl ethyl ketone was injected into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Filtration and dropping lot 19.5 parts of methyl methacrylate, 15.6 parts of n-butyl methacrylate, 15.6 parts of 2-ethylhexyl methacrylate, 27.3 parts of dimethylaminoethyl methacrylate, 2,2'-azobis (2, 4.7 parts of 4-dimethylvaleronitrile) and 15.6 parts of methyl ethyl ketone were injected | poured, it was made uniform, it was attached to the four neck separable flask, and it was dripped for 2 hours. After 2 hours of completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7380, and the mixture was cooled to 50 ° C. 22.0 parts of benzyl chloride and 22.0 parts of ethanol were added here, and after making it react at 50 degreeC for 2 hours, it heated up to 80 degreeC for 1 hour, and made it react for 2 hours again. Then, 150 parts of diethylene glycol was added, ethanol and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 6 whose resin component is 40 weight% was obtained (amine value 3 mgKOH / g, quaternary ammonium salt 97 mgKOH / g).

Synthesis Example 7

57.0 parts of methyl ethyl ketone were injected into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Filtration, dropping lot 14.3 parts of methyl methacrylate, 10.7 parts of n-butyl methacrylate, 10.7 parts of 2-ethylhexyl methacrylate, 35.6 parts of dimethylaminoethyl methacrylate, 2,2'- azobis (2, 4.7 parts of 4-dimethylvaleronitrile) and 14.3 parts of methyl ethyl ketone were injected | poured, it was made uniform, it was attached to the four neck separable flask, and it was dripped for 2 hours. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7090, and the mixture was cooled to 50 ° C. 28.7 parts of benzyl chloride and 28.7 parts of ethanol were added here, after making it react at 50 degreeC for 2 hours, it heated up to 80 degreeC for 1 hour, and made it react for 2 hours again. Then, 150 parts of diethylene glycol was added, ethanol and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 7 whose resin component is 40 weight% was obtained (amine value 5 mgKOH / g, quaternary ammonium salt 127 mgKOH / g).

Synthesis Example 8

62.4 parts of methyl ethyl ketone was injected into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Filtration, dropping lot 9.8 parts of methyl methacrylate, 6.6 parts of n-butyl methacrylate, 6.6 parts of 2-ethylhexyl methacrylate, 42.7 parts of dimethylaminoethyl methacrylate, 2,2'- azobis (2, 4.7 parts of 4-dimethylvaleronitrile) and 13.1 parts of methyl ethyl ketone were injected | poured, it was made uniform, it was attached to the four neck separable flask, and it was dripped for 2 hours. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content, the weight average molecular weight (Mw) was 6480, and cooled to 50 ° C. 34.4 parts of benzyl chloride and 22.0 parts of ethanol were added here, and after making it react at 50 degreeC for 2 hours, it heated up to 80 degreeC for 1 hour, and made it react for 2 hours again. Then, 150 parts of diethylene glycol was added, ethanol and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 8 whose resin component is 40 weight% was obtained (amine value 3 mgKOH / g, quaternary ammonium salt 152 mgKOH / g).

Synthesis Example 9

62.4 parts of methyl ethyl ketone was injected into the four neck separable flask provided with the thermometer, the stirrer, the distillation tube, and the cooler, and it heated up at 75 degreeC under nitrogen stream. Filtration, dropping lot, methyl methacrylate 6.1 parts, n-butyl methacrylate 3.0 parts, 2-ethylhexyl methacrylate 3.0 parts, dimethylaminoethyl methacrylate 48.7 parts, 2,2'-azobis (2, 4.7 parts of 4-dimethylvaleronitrile) and 12.2 parts of methyl ethyl ketone were injected | poured, it was made uniform, it was attached to the four neck separable flask, and it was dripped for 2 hours. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7140, and the mixture was cooled to 50 ° C. 39.2 parts of benzyl chloride and 39.2 parts of ethanol were added here, after making it react at 50 degreeC for 2 hours, it heated up to 80 degreeC for 1 hour, and made it react for 2 hours again. Then, 150 parts of diethylene glycol was added, ethanol and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 9 whose resin component is 40 weight% was obtained (amine value 3 mgKOH / g, quaternary ammonium salt 174 mgKOH / g).

Synthesis Example 10

108.9 parts of four-neck separable flasks equipped with a thermometer, a stirrer, a distillation tube, and a cooler were injected with isopropanol, and the temperature was raised to 75 ° C under a nitrogen stream. In another vessel, an initiator solution in which 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 20 parts of methyl ethyl ketone was prepared. Thereafter, 19.5 parts of methyl methacrylate, 15.6 parts of n-butyl methacrylate, 15.6 parts of 2-ethylhexyl methacrylate, 49.3 parts of methacryloyloxyethyldimethylbenzyl ammonium chloride, and 21.1 parts of methanol were injected into the dropping lot. It was made uniform, the dropping lot was attached to a four-neck separable flask, and it was dripped for 2 hours. At the same time as dropping, an amount of 1/13 of the initiator solution was added 13 times to the flask over 10 times. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content. 150 parts of diethylene glycol was added here, methanol, isopropanol, and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 10 whose resin component is 40 weight% was obtained (amine value 0 mgKOH / g, quaternary ammonium salt 97 mgKOH / g).

Synthesis Example 11

93.9 parts of four-neck separable flasks equipped with a thermometer, a stirrer, a distillation tube, and a cooler were injected with isopropanol, and the temperature was raised to 75 ° C. under a nitrogen stream. In another vessel, an initiator solution in which 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 20 parts of methyl ethyl ketone was prepared. Thereafter, 11.1 parts of methyl methacrylate, 11.1 parts of n-butyl methacrylate, 11.1 parts of 2-ethylhexyl methacrylate, 30.6 parts of benzyl methacrylate, methacryloyloxytrimethylammonium chloride 36.1 and methanol were added to the dropping lot. 36.1 parts were injected | poured, it was made uniform, the dripping lot was attached to the four neck separable flask, and it was dripped for 2 hours. At the same time as dropping, an amount of 1/13 of the initiator solution was added 13 times to the flask over 10 times. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content. 150 parts of diethylene glycol was added here, methanol, isopropanol, and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 11 whose resin component is 40 weight% was obtained (amine value 0 mgKOH / g, quaternary ammonium salt 97 mgKOH / g).

Synthesis Example 12

93.9 parts of four-neck separable flasks with isopropanol equipped with a thermometer, a stirrer, a distillation tube, and a cooler were injected and heated to 75 ° C. under a nitrogen stream. In another vessel, an initiator solution in which 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 20 parts of methyl ethyl ketone was prepared. Thereafter, 24.6 parts of methyl methacrylate, 19.7 parts of n-butyl methacrylate, 19.7 parts of 2-ethylhexyl methacrylate, 36.0 parts of methacryloyloxytrimethylammonium chloride, and 36.0 parts of methanol were injected into the dropping lot, It was made uniform, the dropping lot was attached to the four neck separable flask, and it was dripped for 2 hours. At the same time as dropping, an amount of 1/13 of the initiator solution was added 13 times to the flask over 10 times. 2 hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content. 150 parts of diethylene glycol was added here, methanol, isopropanol, and methyl ethyl ketone were distilled off under reduced pressure at 100 degreeC, and the solvent was substituted by diethylene glycol. Thus, the resin solution 12 whose resin component is 40 weight% was obtained (amine value 0 mgKOH / g, quaternary ammonium salt 97 mgKOH / g).

<Preparation of acrylic resin solution>

800 parts of propylene glycol monoethyl ether acetate were placed in a reaction vessel, heated to 100 DEG C while injecting nitrogen gas into the vessel, and at the same temperature, 80.0 parts of methacrylic acid, 85.0 parts of methyl methacrylate, 85.0 parts of butyl methacrylate, And 10.0 parts of 2,2'-azobisisobutyronitrile were added dropwise for 1 hour to conduct a polymerization reaction. After dripping, after making it react again at 100 degreeC for 3 hours, the thing which melt | dissolved 2.0 parts of azobisisobutyronitrile in 50 parts of propylene glycol monoethyl ether acetate was added, and also the reaction was continued at 100 degreeC for 1 hour, and weight average An acrylic resin solution having a molecular weight (Mw) of 40,000 was obtained.

<Color Derivative>

As the dye derivative used in the examples, a dye derivative represented by the following General Formulas (11) to (15) was used.

Diketopyrrolopyrrole pigment derivative

Formula (11):

Quinophthalone pigment derivative

Formula (12):

Benzimidazolone pigment derivatives

Formula (13):

Copper phthalocyanine pigment derivative

Formula (14):

Cu-Pc: copper phthalocyanine residues

Dioxane dye derivatives

Formula (15):

Example 1

The kneaded material of the following composition was put into a 15,000 volumetric trimix, and the rotation speed was kneaded for 8 hours at 19 rpm by revolution, 57 rpm by rotation, and 40 degreeC of processing temperature.

450 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red 254, `` IRGAFOR RED B-CF '' made by Chiba Specialty Chemicals)

Resin solution 1 141 parts

4500 parts of sodium chloride

Diethylene glycol (DEG) 714 parts

The kneaded material obtained here was taken out in 30000 parts of 1% sulfuric acid solutions at 70 degreeC, and after 1-hour warm-stirring, it filtered, washed with water, dried, and grind | pulverized, and obtained the fine diketopylopiro pyrrole pigment 1.

Next, the mixture of the following composition containing the obtained fine diketophyllopyrrole pigment was uniformly stirred, and then dispersed with a bead mill for 5 hours using zirconia beads having a diameter of 1 mm, followed by filtration with a 5 μm filter. , Red fine organic pigment dispersion 1 was prepared.

Fine Diketophyllopyrrole Pigment 19.0 parts

Diketopyrrolopyrrole pigment derivative 1.0 parts

Acrylic resin solution 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAc) 50.0 parts

Furthermore, after stirring and mixing the mixture of the following composition containing the obtained red fine organic pigment dispersion 1 to be uniform, it filtered with a 1 micrometer filter, and red fine organic pigment composition 1 (red alkali developing resist material 1) Prepared.

Red fine organic pigment dispersion 1 45.0 parts

Acrylic resin solution 15.0 parts

9.0 parts of trimetholpropane triacrylate (NK ester ATMPT manufactured by Shin-Nakamura Chemical Co., Ltd.)

Photoinitiator 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1-one ("Irucure 907" by Chiba Specialty Chemicals) 2.0 parts

0.2 parts of sensitizer 4,4'-bis (diethylamino) benzophenone ("EAB-F" by Hodogaya Chemical Corporation)

Propylene glycol monomethyl ether acetate 28.8 parts

Example 2

The kneaded material of the following composition was put into a 15,000-capacity trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation and for 35 hours at a treatment temperature of 35 ° C.

450 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red 254, `` IRGAFOR RED B-CF '' made by Chiba Specialty Chemicals)

Resin solution 2 90 parts

4500 parts of sodium chloride

Ethylene glycol 720 parts

By treating the kneaded product obtained in the same manner as in Example 1, fine diketophyllopyrrole pigment 2 was obtained. Next, a red fine organic pigment dispersion 2 was prepared in the same manner as in Example 1 except that the fine diketophyllopyrrolopyrrole pigment 1 was replaced with the fine diketophyllopyrrole pigment 2, and again, the red fine organic Except having replaced the pigment dispersion 1 with the red fine organic pigment dispersion 2, it carried out similarly to Example 1, and produced the red fine organic pigment composition 2 (alkali-type resist material 2).

Example 3

A fine diketophyllopyrrole pigment 3 was obtained in the same manner as in Example 2, except that the amount of the resin solution 2 was changed to 45 parts. Next, the red fine organic pigment dispersion 3 was manufactured like Example 1 except having replaced the fine diketophyllopyrrole pigment 1 with the fine diketophyllopyrrole pigment 3, and again, red fine organic A red fine organic pigment composition 3 (red alkali developing resist material 3) was prepared in the same manner as in Example 1, except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 3.

Example 4

A fine diketophyllopyrrole pigment 4 was obtained in the same manner as in Example 2 except that the amount of the resin solution 2 was changed to 180 parts. Next, a red fine organic pigment dispersion 4 was prepared in the same manner as in Example 1 except that the fine diketopyrrolopyrrole pigment 1 was replaced with the fine diketophyllopyrrole pigment 4, and again, the red fine organic A red fine organic pigment composition 4 (red alkali developing resist material 4) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 4.

Example 5

The kneaded material of the following composition was put into a 15,000 volumetric trimix, and the rotation speed was kneaded for 6 hours at 19 rpm by revolution, 57 rpm by rotation, and 35 degreeC of processing temperature.

450 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red 254, `` IRGAFOR RED B-CF '' made by Chiba Specialty Chemicals)

Resin solution 3 71 parts

4500 parts of sodium chloride

Ethylene glycol 765 parts

By treating the kneaded product obtained in the same manner as in Example 1, fine diketopyrrolopyrrole pigment 5 was obtained. Next, the red fine organic pigment dispersion 5 was manufactured like Example 1 except having replaced the fine diketophyllopyrrole pigment 1 with the fine diketophyllopyrrole pigment 5, and again, red fine organic A red fine organic pigment composition 5 (red alkali developing resist material 5) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 5.

Comparative Example 1

The kneaded material of the following composition was put into a 15,000 volumetric trimix, and the rotation speed was kneaded for 6 hours at 19 rpm by revolution, 57 rpm by rotation, and 35 degreeC of processing temperature.

450 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red 254, `` IRGAFOR RED B-CF '' made by Chiba Specialty Chemicals)

Resin solution 4 90 parts

4500 parts of sodium chloride

Ethylene glycol 810 parts

By treating the kneaded product obtained in the same manner as in Example 1, fine diketophyllopyrrole pigment 6 was obtained. Next, a red fine organic pigment dispersion 6 was prepared in the same manner as in Example 1 except that the fine diketophyllopyrrolopyrrole pigment 1 was replaced with the fine diketophyllopyrrolopyrrole pigment 6, and again, the red fine organic A red fine organic pigment composition 6 (red alkali developing resist material 6) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 6.

Comparative Example 2

The kneaded material of the following composition was put into a 15,000 volumetric trimix, and the rotation speed was kneaded for 6 hours at 19 rpm by revolution, 57 rpm by rotation, and 40 degreeC of processing temperature.

450 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red 254, `` IRGAFOR RED B-CF '' made by Chiba Specialty Chemicals)

Resin solution 5 90 parts

4500 parts of sodium chloride

Diethylene glycol 800 parts

By treating the kneaded product obtained in the same manner as in Example 1, fine diketophyllopyrrole pigment 7 was obtained. Next, a red fine organic pigment dispersion 7 was prepared in the same manner as in Example 1 except that the fine diketopyrrolopyrrole pigment 1 was replaced with the fine diketophyllopyrrole pigment 7, and again, the red fine organic A red fine organic pigment composition 7 (red alkali developing resist material 7) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 7.

Comparative Example 3

The kneaded material of the following composition was thrown into the double arm type kneader of 20000 volume parts, and it knead | mixed for 6 hours at the rotation speed of 30 rpm and the processing temperature of 35 degreeC.

810 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red # 254, Chiba Specialty Chemicals company "IRGAFOR RED B-CF")

90 parts of diketopyrrolopyrrole pigment derivative

Sodium chloride 9000 parts

Ethylene Glycol 1980 parts

By treating the kneaded product obtained in the same manner as in Example 1, fine diketophyllopyrrole pigment 8 was obtained. Next, the red fine organic pigment dispersion 8 was produced like Example 1 except having replaced the fine diketophyllopyrrole pigment 1 with the fine diketophyllopyrrole pigment 8, and again, red fine organic A red fine organic pigment composition 8 (red alkali developing resist material 8) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 8.

[Comparative Example 4]

The kneaded material of the following composition was thrown into the double arm type kneader of 20000 volume parts, and it knead | mixed for 6 hours at the rotation speed of 30 rpm and the processing temperature of 35 degreeC.

900 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red # 254, "IRGAFOR RED B-CF" made by Chiba Specialty Chemicals)

Sodium chloride 9000 parts

1800 parts of ethylene glycol

By treating the kneaded product obtained here in the same manner as in Example 1, fine diketophyllopyrrole pigment 9 was obtained. Next, the red fine organic pigment dispersion 9 was produced in the same manner as in Example 1 except that the fine diketophyllopyrrolopyrrole pigment 1 was replaced with the fine diketophyllopyrrole pigment 9, and again, the red fine organic A red fine organic pigment composition 9 (red alkali developing resist material 9) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 9.

[Comparative Example 5]

After uniformly stirring the following composition mixture containing fine diketophyllopyrrole pigment 8 obtained in Comparative Example 3, using a zirconia beads of diameter 1mm, dispersed with a bead mill for 5 hours, and then filter of 5㎛ Filtration was carried out to prepare a red fine organic pigment dispersion 10.

Fine Diketopyrrolopyrrole Pigment 8 9.0 parts

Diketopyrrolopyrrole pigment derivative 1.0 parts

Resin solution 1 1.0 part

Acrylic resin solution 39.0 parts

Propylene glycol monomethyl ether acetate (PGMAc) 50.0 parts

Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the red fine organic pigment dispersion 10, a red fine organic pigment composition 10 (red alkali developing resist material 10) was prepared in the same manner as in Example 1.

Comparative Example 6

The kneaded material of the following composition was put into a 15,000 volumetric trimix, and the rotation speed was kneaded for 6 hours at 19 rpm by revolution, 57 rpm by rotation, and 35 degreeC of processing temperature.

450 parts of diketopyrrolopyrrole pigment (C.I.Pigment Red 254, `` IRGAFOR RED B-CF '' made by Chiba Specialty Chemicals)

Addisper PB821 (manufactured by Ajinomoto Finetech, Co., Ltd., polycaprolactone basic functional group-containing copolymer, amine number 10 mgKOH / g, acid value 17 mgKOH / g)

4500 parts of sodium chloride

Ethylene glycol 810 parts

By treating the kneaded product obtained here in the same manner as in Example 1, fine diketophyllopyrrole pigment 10 was obtained. Next, a red fine organic pigment dispersion 11 was prepared in the same manner as in Example 1 except that the fine diketopyrrolopyrrole pigment 1 was replaced with the fine diketophyllopyrrole pigment 10, and again, the red fine organic A red fine organic pigment composition 11 (red alkali developing resist material 11) was prepared in the same manner as in Example 1 except that the pigment dispersion 1 was replaced with the red fine organic pigment dispersion 11.

With respect to the fine diketopyrrolopyrrole pigment 1-10 and the red fine organic pigment composition 1-11 (red alkali developing resist material 1-11) prepared by the method of the above example, the average particle diameter, contrast ratio, Retardation is measured and shown in Table 1.

Example 6

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C for 12 hours.

Quinophthalone Pigment (C.I.Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 1 126 parts

4500 parts of sodium chloride

Diethylene glycol 1246 parts

The kneaded material obtained here was taken out in 32000 parts of 1% sulfuric acid solutions at 70 degreeC, and after stirring and warming for 1 hour, it filtered, washed with water, dried and pulverized, and obtained the fine quinophthalone pigment 1. Next, after stirring the mixture of the following composition containing the obtained fine quinophthalone pigment 1 uniformly, using zirconia beads of diameter 1mm, it disperse | distributed with a bead mill for 5 hours, and filtered with a 5 micrometer filter, and yellow Fine organic pigment dispersion 1 was prepared.

Fine quinophthalone pigment 1 5.3 parts

Quinophthalone pigment derivative 1.0 part

7.0 parts of acrylic resin solution

Propylene Glycol Monomethyl Ether Acetate

Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the yellow fine organic pigment dispersion 1, a yellow fine organic pigment composition 1 (yellow alkali developing resist material 1) was prepared in the same manner as in Example 1.

Example 7

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I.Pigment Yellow 138, (BASF's `` Pariotoruero K0961HD '') 441

Benzimidazolone-based pigment derivative 9 parts

Resin solution 6 123 parts

4500 parts of sodium chloride

Diethylene glycol 1241 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 2 was obtained. Next, a yellow fine organic pigment dispersion 2 was prepared in the same manner as in Example 6 except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 2. Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the yellow fine organic pigment dispersion 2, a yellow fine organic pigment composition 2 (yellow alkali developing resist material 2) was prepared in the same manner as in Example 1.

Example 8

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and 60 ° C treatment temperature for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 7 123 parts

4500 parts of sodium chloride

Diethylene glycol 1217 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 3 was obtained. Next, a yellow fine organic pigment dispersion 3 was prepared in the same manner as in Example 6 except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 3. Furthermore, except that the red fine pigment dispersion 1 was replaced with the yellow fine pigment dispersion 3, the yellow fine organic pigment composition 3 (yellow alkali developing resist material 3) was prepared in the same manner as in Example 1.

Example 9

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 8 124 parts

4500 parts of sodium chloride

Diethylene glycol 1268 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 4 was obtained. Next, a yellow fine organic pigment dispersion 4 was prepared in the same manner as in Example 6 except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 4. Furthermore, except that the red fine pigment dispersion 1 was replaced with the yellow fine pigment dispersion 4, in the same manner as in Example 1, a yellow fine organic pigment composition 4 (yellow alkali developing resist material 4) was prepared.

Example 10

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 9 125 parts

4500 parts of sodium chloride

Diethylene glycol 1166 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 5 was obtained. Next, a yellow fine organic pigment dispersion 5 was prepared in the same manner as in Example 6 except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 5. Furthermore, except that the red fine pigment dispersion 1 was replaced with the yellow fine pigment dispersion 5, a yellow fine organic pigment composition 5 (yellow alkali developing resist material 5) was prepared in the same manner as in Example 1.

Example 11

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 10 110 parts

4500 parts of sodium chloride

Diethylene glycol 1102 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 6 was obtained. Next, a yellow fine organic pigment dispersion 6 was prepared in the same manner as in Example 6 except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 6. Furthermore, except that the red fine pigment dispersion 1 was replaced with the yellow fine pigment dispersion 6, a yellow fine organic pigment composition 6 (yellow alkali developing resist material 6) was prepared in the same manner as in Example 1.

Example 12

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 11 110 parts

4500 parts of sodium chloride

Diethylene glycol 1054 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 7 was obtained. Next, the yellow fine organic pigment dispersion 7 was produced like Example 6 except having replaced the fine quinophthalone pigment 1 with the fine quinophthalone pigment 7. Furthermore, except that the red fine pigment dispersion 1 was replaced with the yellow fine pigment dispersion 7, the yellow fine organic pigment composition 7 (yellow alkali developing resist material 7) was prepared in the same manner as in Example 1.

Example 13

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

Resin solution 12 110 parts

4500 parts of sodium chloride

Diethylene glycol 1053 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 8 was obtained. Next, the yellow fine organic pigment dispersion 8 was produced like Example 6 except having replaced the fine quinophthalone pigment 1 with the fine quinophthalone pigment 8. Furthermore, except that the red fine pigment dispersion 1 was replaced with the yellow fine pigment dispersion 8, in the same manner as in Example 1, a yellow fine organic pigment composition 8 (yellow alkali developing resist material 8) was prepared.

Example 14

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero 루 K0961HD '') 405 parts

Benzimidazolone pigment derivative 8 parts

110 parts of Disperbyk-2000 (made by Big Chemie Japan, modified acrylic block copolymer, amine number 4mgKOH / g, quaternary ammonium salt 90mgKOH / g)

4500 parts of sodium chloride

Diethylene glycol 1035 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 9 was obtained. Next, a yellow fine organic pigment dispersion 9 was prepared in the same manner as in Example 6 except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 9. Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the yellow fine organic pigment dispersion 9, a yellow fine organic pigment composition 9 (yellow alkali developing resist material 9) was prepared in the same manner as in Example 1.

Comparative Example 7

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

4500 parts of sodium chloride

Diethylene glycol 1305 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 10 was obtained. Next, the yellow fine organic pigment dispersion 10 was produced like Example 6 except having replaced the fine quinophthalone pigment 1 with the fine quinophthalone pigment 10. Further, except that the red fine organic pigment dispersion 1 was replaced with a yellow fine organic pigment dispersion 10, in the same manner as in Example 1, a yellow fine organic pigment composition 10 (yellow alkali developing resist material 10) was prepared.

Comparative Example 8

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

Quinophthalone Pigment (C.I. Pigment Yellow 138, (BASF's `` Pariotorero K0961HD '') 441 copies

Benzimidazolone-based pigment derivative 9 parts

112 parts of john creel 682 (BASF Japan styrene-acrylic copolymer, acid value 238mgKOH / g)

4500 parts of sodium chloride

Diethylene glycol 1305 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine quinophthalone pigment 11 was obtained. Next, a yellow fine organic pigment dispersion 11 was prepared in the same manner as in Example 6, except that the fine quinophthalone pigment 1 was replaced with the fine quinophthalone pigment 11. Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the yellow fine organic pigment dispersion 11, a yellow fine organic pigment composition 11 (yellow alkali developing resist material 11) was prepared in the same manner as in Example 1.

The half width of the fine quinophthalone pigment 1-11 manufactured by the method of the said example, the contrast ratio of the yellow alkali developing resist material 1-11, and retardation were measured, and it is shown in Table 2.

Example 15

 The kneaded material of the following composition was put into a 15,000-capacity trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and at a treatment temperature of 100 ° C. for 6 hours.

Copper halide phthalocyanine pigment (C.I. Pigment Green 36, `` Rionol Green 6YK '' manufactured by Toyo Ink Co.)

Resin solution 1 51 parts

Sodium chloride 4280 parts

Diethylene glycol 902 parts

The kneaded material obtained here was taken out in 32000 parts of 1% aqueous sulfuric acid solutions at 70 degreeC, and after 1-hour warm-stirring, it filtered, washed with water, dried, and grind | pulverized, and obtained the fine copper halide phthaloline pigment 1. The obtained pigment was a copper halide phthaloline pigment having a peak at black angle 2θ (acceptable range ± 0.2 degrees) = 22.3 degrees by X-ray diffraction measurement (CuKα 1 line).

Next, the mixture of the following composition containing the obtained fine copper halide phthaloline pigment 1 was uniformly stirred, and then dispersed in a bead mill for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , Green fine organic pigment dispersion 1 was prepared.

Fine copper halide phthalocyanine pigment 9 parts

1 part copper phthalocyanine pigment derivative

15 parts of acrylic resin solution

Propylene glycol monomethyl ether acetate 49 parts

Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the green fine organic pigment dispersion 1, a green fine organic pigment composition 1 (green alkali developing resist material 1) was prepared in the same manner as in Example 1.

Example 16

The kneaded material of the following composition was put into a 15,000-capacity trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and at a treatment temperature of 100 ° C. for 6 hours.

Copper halide phthalocyanine pigment (C.I.Pigment Green 36, `` Rionol Green 6YK '' manufactured by Toyo Ink, Japan)

Resin solution 1 203 parts

4500 parts of sodium chloride

Diethylene glycol 635 parts

By treating the kneaded product obtained in the same manner as in Example 15, fine copper halide phthaloline pigment 2 was obtained. The obtained pigment was a copper halide phthaloline pigment having a characteristic peak at black angle 2θ (acceptable range ± 0.2 degrees) = 22.3 degrees by X-ray diffraction measurement (CuKα1 ray).

Next, the green fine organic pigment dispersion 2 was manufactured like Example 15 except having replaced the fine copper halide phthaloline pigment 1 with the fine copper halide phthaloline pigment 2. Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the green fine organic pigment dispersion 2, in the same manner as in Example 1, a green fine organic pigment composition 2 (green alkali developing resist material 2) was prepared.

Comparative Example 9

The kneaded material of the following composition was put into a 15,000-volume trimix (manufactured by Inoue Co., Ltd.), and the kneading speed was kneaded at 19 rpm for revolution, 57 rpm for rotation, and treatment temperature of 60 ° C. for 12 hours.

450 parts of copper halide phthalocyanine pigment (C.I.Pigment® Green 36, Toyo Ink Co., Ltd. `` Rionol Green 6YK '')

4500 parts of sodium chloride

Diethylene glycol 675 parts

By treating the kneaded product obtained in the same manner as in Example 15, fine copper halide phthaloline pigment 3 was obtained. The obtained pigment was a copper halide phthaloline pigment having a peak at black angle 2θ (acceptable range ± 0.2 degrees) = 22.3 degrees by X-ray diffraction measurement (CuKα1 line).

Next, the green fine organic pigment dispersion 3 was produced like Example 15 except having replaced the fine copper halide phthaloline pigment 1 with the fine copper halide phthaloline pigment 3. Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the green fine organic pigment dispersion 3, a green fine organic pigment composition 3 (green alkali developing resist material 3) was prepared in the same manner as in Example 1.

The half width of each green pigment manufactured by the method of the said example, the contrast ratio, and the retardation of a green alkali developing resist material are measured, and it is shown in Table 2.

Example 17

The kneaded material of the following composition was thrown into a kneader (manufactured by Inoue Co., Ltd.) at 3000 parts by volume, and kneaded for 6 hours at a rotation speed of 24.5 rpm and a treatment temperature of 70 ° C.

ε-type copper phthalocyanine pigment (C.I. Pigment 15: 6, Toyo Ink Co., Ltd. `` Lion Norble E '') 123 parts

Resin solution 1 27 parts

Sodium chloride1364part

Diethylene glycol 213 parts

The kneaded material obtained here was taken out in 8700 parts of 1% sulfuric acid aqueous solution at 70 degreeC, and after stirring and warming for 1 hour, it filtered, washed with water, dried and pulverized, and obtained the fine phthalocyanine pigment 1. The obtained pigment was (epsilon) copper phthalocyanine pigment which has the strongest peak at black angle 2 (theta) (acceptable range +/- 0.2 degree | times) = 9.1 degree by X-ray diffraction measurement (CuK alpha 1 line).

Next, after stirring the mixture of the following composition containing the obtained fine (epsilon) copper phthalocyanine pigment 1 uniformly, using zirconia beads of diameter 1mm, it disperse | distributed with a bead mill for 5 hours, and it filtered with a 5 micrometer filter, A blue fine organic pigment dispersion 1 was prepared.

Fine epsilon copper phthalocyanine pigment 1 part 5

1 part copper phthalocyanine pigment derivative

10 parts of acrylic resin solution

Propylene glycol monomethyl ether acetate 31 parts

Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the blue fine organic pigment dispersion 1, a blue fine organic pigment composition 1 (blue alkali developing resist material 1) was prepared in the same manner as in Example 1.

Comparative Example 10

The kneaded material of the following composition was thrown into a kneader (manufactured by Inoue Co., Ltd.) at 3000 parts by volume, and kneaded for 6 hours at a rotation speed of 24.5 rpm and a treatment temperature of 70 ° C.

ε-type copper phthalocyanine pigment (C.I. Pigmentable 15: 6, Toyo Ink Manufacturing Co., Ltd. `` Lion Norble E '') 136 parts

Sodium chloride1364part

Diethylene glycol 224 parts

The kneaded material obtained here was taken out in 8600 parts of 1% sulfuric acid aqueous solution at 70 degreeC, and after stirring and warming for 1 hour, it filtered, washed with water, dried and pulverized, and obtained the fine phthalocyanine pigment 2. The obtained pigment was (epsilon) copper phthalocyanine pigment which has the strongest peak at black angle 2 (theta) (acceptable range +/- 0.2 degree | times) = 9.1 degree by X-ray diffraction measurement (CuK alpha 1 line).

Next, the blue fine organic pigment dispersion 2 was produced like Example 17 except having replaced the fine copper phthaloline pigment 1 with the fine copper phthaloline pigment 2. Furthermore, except that the red fine organic pigment dispersion 1 was replaced with the blue fine organic pigment dispersion 2, a blue fine organic pigment composition 2 (blue alkali developing resist material 2) was prepared in the same manner as in Example 1.

The half width of the fine copper phthalocyanine pigments 1 and 2 manufactured by the method of the said example, the contrast ratio of the blue alkali developing resist materials 1 and 2, and retardation are measured, and it is shown in Table 2.

Example 18

The kneaded material of the following composition was thrown into a kneader (manufactured by Inoue Co., Ltd.) at 3000 volume parts, and kneaded for 6 hours at a rotational speed of 24.5 rpm and a treatment temperature of 60 ° C.

Dioxazine Violet Pigment (C.I.Pigment®Violet®23, Sumitomo Chemical Co., Ltd. `` Sumiton Paste Violet RL Base '')

Resin solution 1 (solid content rate: 50% by weight) 27 parts

Sodium chloride1364part

Diethylene glycol 249 parts

The kneaded material obtained here was taken out in 8800 parts of 1% sulfuric acid aqueous solution at 70 degreeC, and after stirring and warming for 1 hour, it filtered, washed with water, dried, and grind | pulverized, and obtained the fine dioxazine violet pigment 1.

Next, after uniformly stirring the mixture of the following composition containing the obtained fine dioxazine violet pigment 1, using a 1 mm diameter zirconia beads, dispersed for 5 hours in a bead mill, and then filtered through a 5 μm filter, A purple fine organic pigment dispersion 1 was prepared.

Fine Dioxazine Violet Pigment 1 part 10

Dioxazine pigment derivative 1 part

40 parts of acrylic resin solution

Propylene glycol monomethyl ether acetate 48 parts

Furthermore, except for replacing the red fine organic pigment dispersion 1 with the purple fine organic pigment dispersion 1, in the same manner as in Example 1, a purple fine organic pigment composition 1 (purple alkali developing resist material 1) was prepared.

Comparative Example 11

The kneaded material of the following composition was thrown into a kneader (manufactured by Inoue Co., Ltd.) at 3000 volume parts, and kneaded for 6 hours at a rotational speed of 24.5 rpm and a treatment temperature of 60 ° C.

Dioxazine violet pigment (C.I.Pigment®Violet®23, Sumitomo Chemical Co., Ltd. `` Sumiton Paste Violet RL Base '')

Sodium chloride1364part

Diethylene glycol 259 parts

By treating the kneaded product obtained in the same manner as in Example 6, fine dioxazine violet pigment 2 was obtained. Next, a purple fine organic pigment dispersion 2 was prepared in the same manner as in Example 18 except that the fine dioxazine violet pigment 1 was replaced with the fine dioxazine violet pigment 2. Furthermore, except for replacing the red fine organic pigment dispersion 1 with the purple fine organic pigment dispersion 2, in the same manner as in Example 1, a purple fine organic pigment composition 2 (purple alkali developing resist material 2) was prepared.

The half width of the fine dioxazine violet pigments 1 and 2 manufactured by the method of the said example, the contrast ratio of the violet alkali developing resist materials 1 and 2, and retardation are measured, and it is shown in Table 2.

Table 3 shows the aggregation of the solubility of propylene glycol monomethyl ether acetate or diethylene glycol of the resin used in the pigment miniaturization in the methods of the examples and comparative examples.

Resin (A) of this application is resin solutions 1-3, 6-12, and a commercial item Disperbyk-2000.

<Solubility of Resin in Organic Solvents>

Resin solution 1-12 evaporated ethanol and methyl ethyl ketone, reducing the solution before substituting with diethylene glycol at the time of synthesis at 100 degreeC, and obtained solid resin. As for the commercial resin, in the case of the solid resin, in the case of the organic solvent solution, the organic solvent was evaporated in the same manner to obtain the solid resin. An organic solvent (propylene glycol monomethyl ether acetate or diethylene glycol) was added to collect 1 part of each solid part resin, and it was made into 10 parts as a whole, and after processing for 5 minutes with a shaker, it was set in the oven set to 100 degreeC. Stored for 10 minutes, taken out, cooled to 25 ° C, and used as a Spectrawave® S1200 (Diotoray Visible Spectrophotometer) manufactured by Biochrom, for a wavelength of 600 nm for each solution placed in a Disposable Cell. The light transmittance was measured to evaluate the solubility of the resin.

Melting ○: Light transmittance of 90% or more

Insoluble "x": Less than 90% of light transmittance or undissolved resin exists

Resin Solution Fine Pigment Presence or absence of resin at the time of miniaturization Particle diameter (nm) Half width (-) Pigment Composition Resist Materials Contrast Ratio (-) Retardation (nm ² ) Example 1 Resin solution 1 DP 1 U 24 0.84 Red 1 6050 18 Example 2 Resin solution 2 DP 2 U 26 0.81 Red 2 5820 8 Example 3 Resin solution 2 DP 3 U 25 0.79 Red 3 5440 14 Example 4 Resin solution 2 DP 4 U 24 0.83 Red 4 6340 17 Example 5 Resin solution 3 DP 5 U 26 0.78 Red 5 5020 14 Comparative Example 1 Resin solution 4 DP 6 U 29 0.80 Red 6 4890 66 Comparative Example 2 Resin Solution 5 DP 7 U 29 0.80 Red 7 4250 35 Comparative Example 3 - DP 8 radish 23 0.88 Red 8 6740 80 Comparative Example 4 - DP 9 radish 33 0.76 Red 9 3670 50 Comparative Example 5 Resin solution 1 DP 8 radish 23 0.88 Red 10 6510 69 Comparative Example 6 Yamoussoukro-pb821 DP 10 U 28 0.79 Red 11 4140 16

DP: fine diketopyrropyrrole pigment

Red: Red fine organic pigment composition (red alkali developing resist material)

Resin Solution Fine Pigment Presence or absence of resin at the time of miniaturization Half width (-) Pigment Composition Resist Contrast Ratio (-) Retardation (nm ² ) Example 6 Resin solution 1 XP1 U 0.97 Yellow 1 9200 480 Example 7 Resin Solution XP2 U 0.97 Yellow 2 9560 -510 Example 8 Resin Solution XP3 U 1.03 Yellow 3 8880 -390 Example 9 Resin Solution XP4 U 1.03 Yellow 4 8220 -470 Example 10 Resin Solution XP5 U 1.07 Yellow 5 9530 -470 Example 11 Resin Solution XP6 U 0.96 Yellow 6 9480 -500 Example 12 Resin Solution XP7 U 0.95 Yellow 7 9670 -480 Example 13 Resin Solution XP8 U 0.95 Yellow 8 9620 -530 Example 14 Disperbyk-2000 XP9 U 1.01 Yellow 9 9380 -490 Comparative Example 7 - XP10 radish 0.94 Yellow 10 8050 -390 Comparative Example 8 John Krill 682 XP11 U 0.90 Yellow 11 7300 -450 Example 15 Resin Solution PG1 U 0.57 Green 1 8440 -20 Example 16 Resin Solution PG2 U 0.71 Green 2 8670 -110 Comparative Example 9 - PG3 radish 0.51 Green 3 7670 30 Example 17 Resin Solution PB1 U 0.60 Blue 1 8590 20 Comparative Example 10 - PB2 radish 0.52 Blue 2 7880 90 Example 18 Resin Solution DV1 U 0.83 Purple 1 3310 -850 Comparative Example 11 - DV2 radish 0.78 Purple 2 3110 -770

XP: fine quinophthalone pigment; GP: copper microhalogenated phthalocyanine green;

PB: fine epsilon copper phthalocyanine blue; DV: Fine Dioxazine Violet Pigment

Yellow: Yellow fine organic pigment composition (yellow alkali developing resist material)

Green: Green fine organic pigment composition (green alkali developing resist material)

Blue: Blue fine organic pigment composition (blue alkali developing resist material)

Purple: Purple fine organic pigment composition (purple alkali developing resist material)

Resin Resin structure Amine number Quaternary Ammonium Cheap Amine + Ammonium Cheap Acid Solubility Acrylic system Random system MgKOH / g MgKOH / g MgKOH / g MgKOH / g PGMAc DEG Resin solution 1 ○ ○ 3 97 100 0 × ○ Resin solution 2 ○ ○ 29 62 91 18 × ○ Resin solution 3 ○ Block system 29 0 29 0 × ○ Resin solution 4 ○ ○ 11 0 11 85 ○ × Resin Solution 5 ○ ○ 0 0 0 85 ○ ○ Resin Solution 6 ○ ○ 3 97 100 0 × ○ Resin Solution 7 ○ ○ 5 127 132 0 × ○ Resin Solution 8 ○ ○ 3 152 155 0 × ○ Resin Solution 9 ○ ○ 3 174 177 0 × ○ Resin Solution 10 ○ ○ 0 97 97 0 × ○ Resin Solution 11 ○ ○ 0 97 97 0 × ○ Resin Solution 12 ○ ○ 0 97 97 0 × ○ Disperbyk-2000 ○ Block system 4 90 94 0 × ○ Yamoussoukro-pb821 × Graft system 10 0 10 17 ○ × John Krill 682 ○ ○ 0 0 0 238 ○ ○

PGMAc: Propylene Glycol Monomethyl Ether Acetate

DEG: diethylene glycol

In Table 1, the fine organic pigment of Example 1-5 which is a pigment refine | purified using the resin which does not melt | dissolve in the propylene glycol monomethyl ether acetate which is the fine organic pigment composition solvent shown in Table 3 is comparative example 1, Compared with 2, and 6, it was found that the particle diameter was smaller, and further refinement proceeded. The fine organic pigment compositions of Examples 1-5 have a high contrast ratio, and a low tendency of retardation, as compared to Comparative Examples 1, 2, and 4. Moreover, although Comparative Examples 3 and 5 have a high contrast ratio, the retardation shows a large value compared with Example 1-5, and the viewing angle dependence is bad. By producing a pigment by adding a resin having the structure and properties of the substrate of the fine organic pigment composition of the present invention as in Example 1-5, fine diketophyllopy with excellent display angle dependence and high contrast ratio and good display characteristics It is found that a roll-based pigment and a red fine organic pigment composition can be provided.

In Table 2, Example 6-14, 15-16, 17, and 18 which consists of a pigment refine | purified using resin which does not melt | dissolve in the propylene glycol monomethyl ether acetate which are the dispersion solvents shown in Table 3 are Comparative Examples 7 Compared with -8, 9, 10, and 11, the half width is larger, so the particle diameter is fine, the contrast ratio is high, and the retardation is low. It is found that, as in Example 6-18, a resin having a structure and properties of the substrate of the present invention may be used to provide a fine organic pigment and an organic pigment coloring composition having good microscopic properties.

Claims (8)

Preparation of micronized organic pigments comprising mechanically kneading an organic pigment, a water-soluble inorganic salt, a water-soluble organic solvent, and a resin (A) to obtain a kneading composition, and then removing the water-soluble inorganic salt and the water-soluble organic solvent from water. In the method, the resin (A) has a solubility per 100 parts by weight of the water-soluble organic solvent at 25 ° C of 1 part by weight or more, and has a group selected from an amino group and a quaternary ammonium base group. Method for producing a pigment. The method for producing a fine organic pigment according to claim 1, wherein the resin (A) is an acrylic resin. The method for producing a fine organic pigment according to claim 2, wherein the acrylic resin is an acrylic resin synthesized by random polymerization. The method for producing a fine organic pigment according to claim 1, wherein the resin (A) is not dissolved in propylene glycol monomethyl ether acetate. The organic pigment according to any one of claims 1 to 4, wherein the organic pigment is selected from the group consisting of diketopyloporopyrrole organic pigments, quinophthalone organic pigments, dioxazine organic pigments, and phthalocyanine organic pigments. Method for producing a fine organic pigment, characterized in that at least one kind of pigment. It is obtained by the manufacturing method in any one of Claims 1-5, The fine organic pigment characterized by the above-mentioned. A fine organic pigment coloring composition comprising the fine organic pigment according to claim 6 and a pigment carrier. 8. The fine organic pigment coloring composition according to claim 7, further comprising a non-aqueous solvent.