WO2021220497A1 - ハロゲン化亜鉛フタロシアニン顔料の製造方法 - Google Patents
ハロゲン化亜鉛フタロシアニン顔料の製造方法 Download PDFInfo
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- WO2021220497A1 WO2021220497A1 PCT/JP2020/018352 JP2020018352W WO2021220497A1 WO 2021220497 A1 WO2021220497 A1 WO 2021220497A1 JP 2020018352 W JP2020018352 W JP 2020018352W WO 2021220497 A1 WO2021220497 A1 WO 2021220497A1
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- pigment
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- zinc phthalocyanine
- halogenated zinc
- crude pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
Definitions
- the present invention relates to a method for producing a zinc halide phthalocyanine pigment.
- coloring compositions are used in various fields, and specific applications of the coloring compositions include printing inks, paints, resin colorants, fiber colorants, and IT information recording color materials (color filters). , Toner, inkjet) and the like.
- the dyes used in the coloring composition are mainly classified into pigments and dyes, and organic pigments, which are considered to be superior in terms of coloring power, are attracting attention.
- the organic compounds constituting the organic pigment exist in the state of aggregates called crudo, in which fine particles aggregate with each other after synthesis. Therefore, usually, the synthesized organic compound cannot be used as a pigment as it is, and a pigmentation step for adjusting the particle size is performed.
- the aggregate of the organic compounds pigmented in the pigmentation step is called a crude pigment, and a fine organic pigment can be obtained by grinding the crude pigment by kneading or the like.
- a zinc halide phthalocyanine pigment used for a green pixel portion of a color filter or the like is attracting attention (see, for example, Patent Document 1).
- An object of the present invention is to provide a novel method for producing a halogenated zinc phthalocyanine pigment, which enables further miniaturization of pigment particles.
- a method for synthesizing zinc halide phthalocyanine for example, a chlorosulfonic acid method, a melting method and the like are known.
- zinc halide phthalocyanine is synthesized using a compound that reacts with water to generate an acid.
- a crude pigment coarse pigment of zinc halide phthalocyanine
- an acid derived from a compound or the like that reacts with water to generate an acid usually adheres to the crude pigment. Therefore, the acid attached to the crude pigment is removed before the crude pigment is pigmented.
- one aspect of the present invention relates to a method for producing a halogenated zinc phthalocyanine pigment, which comprises a step of pigmentating the halogenated zinc phthalocyanine crude pigment.
- the halogenated zinc phthalocyanine crude pigment used in this method is obtained by precipitating halogenated zinc phthalocyanine synthesized using a compound that reacts with water to generate an acid, and the above step is the above-mentioned halogenation.
- a pretreatment step of heating a crude zinc phthalocyanine pigment in water to obtain a halogenated zinc phthalocyanine pre-pigment having a pH of 5.0 or higher is included.
- the acid contained in the zinc halide phthalocyanine crude pigment can be removed, whereby a fine halogenated zinc phthalocyanine pigment can be obtained.
- the temperature for heating the above-mentioned zinc halide phthalocyanine crude pigment in the pretreatment step may be 40 ° C. or higher.
- the time for heating the above-mentioned zinc halide phthalocyanine crude pigment in the pretreatment step may be 1 minute or more.
- the above-mentioned zinc halide phthalocyanine crude pigment may be heated in water, and then the heated zinc halide phthalocyanine crude pigment may be washed with water. Further, the operation of heating the halogenated zinc phthalocyanine crude pigment after washing in water and then washing with water may be repeated twice or more.
- the method for producing a halogenated zinc phthalocyanine pigment of one embodiment includes a first step of preparing a halogenated zinc phthalocyanine crude pigment and a second step of pigmenting the halogenated zinc phthalocyanine crude pigment.
- the second step includes a pretreatment step of heating the zinc halide phthalocyanine crude pigment in water to bring the pH of the halogenated zinc phthalocyanine crude pigment to 5.0 or more.
- the halogenated zinc phthalocyanine crude pigment is obtained by precipitating halogenated zinc phthalocyanine synthesized by using a compound that reacts with water to generate an acid
- the halogenated zinc phthalocyanine is obtained by the following formula ( It is a compound having a structure represented by 1).
- X 1 to X 16 each independently represent a hydrogen atom or a halogen atom.
- a halogenated zinc phthalocyanine crude pigment is prepared.
- the halogenated zinc phthalocyanine crude pigment contains one kind or a plurality of kinds of halogenated zinc phthalocyanines having different numbers of halogen atoms.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the halogenated zinc phthalocyanine preferably has at least one of a bromine atom and a chlorine atom as a halogen atom, and preferably has a bromine atom.
- the halogenated zinc phthalocyanine may have only one or both of a chlorine atom and a bromine atom as a halogen atom. That is, X 1 to X 16 in the above formula (1) may be a chlorine atom or a bromine atom.
- the average number of bromine atoms in one molecule of the compound represented by the formula (1) in the halogenated zinc phthalocyanine crude pigment is less than 13.
- the average number of bromine atoms may be 12 or less or 11 or less.
- the average number of bromine atoms may be 0.1 or more, 6 or more, or 8 or more.
- the above-mentioned upper limit value and lower limit value can be arbitrarily combined.
- the average number of bromine atoms may be 0.1 or more and less than 13, 8-12 or 8-11.
- the upper limit value and the lower limit value described individually can be arbitrarily combined.
- the average number of bromine atoms is less than 13
- the average number of halogen atoms in one molecule of the compound represented by the formula (1) in the halogenated zinc phthalocyanine crude pigment is 14 or less and 13 or less. , Less than 13 or less than 12.
- the average number of halogen atoms is 0.1 or more, and may be 8 or more or 10 or more.
- the average number of bromine atoms in one molecule of the compound represented by the formula (1) in the halogenated zinc phthalocyanine crude pigment is 5 or less and 3 or less. , 2.5 or less, or less than 2.
- the average number of chlorine atoms may be 0.1 or more, 0.3 or more, 0.6 or more, 0.8 or more, 1 or more, 1.3 or more, or 2 or more.
- the average number of bromine atoms in one molecule of the compound represented by the formula (1) in the halogenated zinc phthalocyanine crude pigment is 13 or more.
- the average number of bromine atoms may be 14 or more.
- the average number of bromine atoms may be 15 or less.
- the average number of bromine atoms is 13 or more
- the average number of halogen atoms in one molecule of the compound represented by the formula (1) in the halogenated zinc phthalocyanine crude pigment is 13 or more and 14 or more.
- the number may be 15 or more.
- the average number of halogen atoms is 16 or less, and may be 15 or less.
- the average number of bromine atoms is 13 or more
- the average number of chlorine atoms in one molecule of the compound represented by the formula (1) in the halogenated zinc phthalocyanine crude pigment is 0.1 or more or 1 It may be more than one.
- the average number of chlorine atoms may be 3 or less or less than 2.
- the number of halogen atoms (for example, the number of bromine atoms and the number of chlorine atoms) is determined by halogenation using, for example, a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (JMS-S3000 manufactured by Nippon Denshi Co., Ltd.). It can be identified by mass spectrometry of zinc phthalocyanine crude pigments. Specifically, the number of each halogen atom can be calculated as a relative value per zinc atom from the mass ratio of the zinc atom and each halogen atom in the halogenated zinc phthalocyanine crude pigment.
- the first step is, for example, a step of synthesizing zinc halide phthalocyanine using a compound that reacts with water to generate an acid, and a step of precipitating the synthesized zinc halide phthalocyanine to obtain a halogenated zinc phthalocyanine crude pigment. And include.
- Examples of the method for synthesizing zinc halide phthalocyanine using a compound that reacts with water to generate an acid include a chlorosulfonic acid method and a melting method.
- Examples of the chlorosulfonic acid method include a method in which zinc phthalocyanine is dissolved in a sulfur oxide-based solvent such as chlorosulfonic acid, and chlorine gas and bromine are charged therein to halogenate the zinc phthalocyanine. The reaction at this time is carried out, for example, at a temperature of 20 to 120 ° C. and in the range of 3 to 20 hours.
- the chlorosulfonic acid method it is a compound in which a sulfur oxide-based solvent such as chlorosulfonic acid reacts with water to generate an acid.
- chlorosulfonic acid reacts with water to generate hydrochloric acid and sulfuric acid.
- Examples of the melting method include aluminum halides such as aluminum chloride and aluminum bromide, titanium halides such as titanium tetrachloride, alkali metal halides such as sodium chloride and sodium bromide, and alkaline earth metal halides (hereinafter, "alkali").
- Zinc phthalocyanine in a melt at about 10 to 170 ° C. consisting of one or a mixture of two or more compounds that serve as solvents during various halogenation, such as (earth) metal halides) and thionyl chloride. Examples thereof include a method of halogenating with a halogenating agent.
- a compound serving as a solvent during halogenation such as aluminum halide, titanium halide, alkali (earth) metal halide, and thionyl chloride, reacts with water to generate an acid.
- aluminum chloride reacts with water to generate hydrochloric acid.
- a suitable aluminum halide is aluminum chloride.
- the amount of aluminum halide added is usually 3 times or more, preferably 10 to 20 times by mole, based on zinc phthalocyanine.
- Aluminum halide may be used alone, but if an alkali (earth) metal halide is used in combination with aluminum halide, the melting temperature can be further lowered, which is advantageous in terms of operation.
- a suitable alkaline (earth) metal halide is sodium chloride.
- the amount of the alkali (earth) metal halide to be added is preferably 1 to 15 parts by mass of the alkali (earth) metal halide with respect to 10 parts by mass of aluminum halide within the range of producing a molten salt.
- halogenating agent examples include chlorine gas, sulfuryl chloride, bromine and the like.
- the halogenation temperature is preferably 10 to 170 ° C, more preferably 30 to 140 ° C. Further, it is possible to pressurize in order to increase the reaction rate.
- the reaction time may be 5 to 100 hours, preferably 30 to 45 hours.
- the ratio of chloride, bromide and iodide in the molten salt is adjusted, and the amount of chlorine gas, bromine, iodine, etc. introduced and the reaction time are changed. It is preferable because the content ratio of the halogenated zinc phthalocyanine having a specific halogen atomic composition in the produced halogenated zinc phthalocyanine can be arbitrarily controlled. Further, according to the melting method, the decomposition of the raw material during the reaction is small, the yield from the raw material is more excellent, and the reaction can be carried out by an inexpensive apparatus without using a strong acid.
- a halogenated zinc phthalocyanine having a halogen atomic composition different from that of the existing halogenated zinc phthalocyanine can be obtained by optimizing the raw material charging method, the catalyst species and the amount used thereof, the reaction temperature and the reaction time.
- the obtained mixture is put into an acidic aqueous solution such as water or hydrochloric acid to precipitate (precipitate) the produced zinc halide phthalocyanine.
- an acidic aqueous solution such as water or hydrochloric acid to precipitate (precipitate) the produced zinc halide phthalocyanine.
- the compound that reacts with the water to generate an acid generates an acid.
- the acid include hydrochloric acid, sulfuric acid and the like.
- the above-mentioned precipitate may be used as it is, but the above-mentioned precipitate is filtered and washed with water, sodium hydrogen sulfate water, sodium hydrogen carbonate water or sodium hydroxide water, and if necessary. Therefore, it is preferable to wash with an organic solvent such as acetone, toluene, methyl alcohol, ethyl alcohol, and dimethylformamide, and then post-treat such as drying to use as the halogenated zinc phthalocyanine crude pigment.
- an organic solvent such as acetone, toluene, methyl alcohol, ethyl alcohol, and dimethylformamide
- the precipitate or the precipitate after the post-treatment may be dry-ground in a crusher such as an attritor, a ball mill, a vibration mill, or a vibration ball mill, and used as a halogenated zinc phthalocyanine crude pigment.
- a crusher such as an attritor, a ball mill, a vibration mill, or a vibration ball mill, and used as a halogenated zinc phthalocyanine crude pigment.
- the arithmetic standard deviation of the particle size distribution of the zinc phthalocyanine halogenated crude pigment is, for example, 15 nm or more.
- the arithmetic standard deviation of the particle size distribution of the zinc phthalocyanine halogenated crude pigment is, for example, 1500 nm or less.
- the arithmetic standard deviation of the particle size distribution of the zinc halide phthalocyanine crude pigment can be measured using a dynamic light scattering type particle size distribution measuring device, and specifically, can be measured by the following methods and conditions.
- mm zircon beads disperse for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a dispersion. After removing the zircon beads with a nylon mesh, 0.02 g of the dispersion is diluted with 20 g of propylene glycol monomethyl ether acetate to obtain a dispersion for measuring the particle size distribution.
- -Measuring equipment Dynamic light scattering type particle size distribution measuring device LB-550 (manufactured by HORIBA, Ltd.) ⁇ Measurement temperature: 25 ° C -Measurement sample: Dispersion for particle size distribution measurement-Data analysis conditions: Particle size standard Scattered light intensity, dispersion medium refractive index 1.402
- the halogenated zinc phthalocyanine crude pigment obtained in the first step contains an acid (hydrochloride, sulfuric acid, etc.), and its pH is, for example, 4. It is 0.0 or less and may be 3.8 or less.
- the pH of the halogenated zinc phthalocyanine crude pigment is, for example, 1.5 or more, and may be 3.5 or more.
- the pH of the halogenated zinc phthalocyanine crude pigment is determined by mixing 5 g of the halogenated zinc phthalocyanine crude pigment with 5 g of methanol and then further mixing with 100 ml of ion-exchanged water, and heating the obtained mixture for 5 minutes to bring it to a boiling state. The mixture is further heated for 5 minutes to maintain the boiling state, the heated mixture is allowed to cool to 30 ° C. or lower, the total volume of the mixture is adjusted to 100 ml with ion-exchanged water, and the mixture is filtered to obtain 25 of the obtained filtrate. It can be confirmed by measuring the pH at ° C.
- the reason why the zinc halide phthalocyanine crude pigment obtained in the first step contains an acid is presumed as follows. That is, zinc halide phthalocyanine has a long distance between zinc, which is the central metal, and the nitrogen atom on the isoindolin unit, and has large pores around the central metal (zinc). Therefore, the phthalocyanine ring under acidic conditions. It is considered that the counter anion (for example, chloride ion) easily approaches the central metal (zinc) after the nitrogen is protonated, and the counter anion and the central metal (zinc) are likely to bond to form a stable structure.
- the counter anion for example, chloride ion
- the acid (water) contained in the precipitate is contained. It is presumed that the acid (such as the acid derived from the compound that generates the acid by reacting with) is difficult to remove, and the acid remains in the crude pigment.
- the second step is, for example, a pretreatment step of heating the halogenated zinc phthalocyanine crude pigment in water to bring the pH of the crude pigment to 5.0 or more, and a halogenated zinc phthalocyanine crude pigment after the pretreatment step (hereinafter, It includes a step (miniaturization step) of kneading and grinding a “halogenated zinc phthalocyanine pre-pigment” to make it finer.
- the kneading of the miniaturization step can be performed using, for example, a kneader, a mix muller, or the like.
- the halogenated zinc phthalocyanine crude pigment and water may be mixed and then heated, or the halogenated zinc phthalocyanine crude pigment may be added to the heated water to heat the crude pigment.
- the water used in the pretreatment step is not particularly limited as long as it can dissolve the acid contained in the halogenated zinc phthalocyanine crude pigment, and may be deionized water, ion-exchanged water, ultrapure water, or the like. good.
- the pH of water at 25 ° C. may be, for example, 5.5 to 8.5.
- the amount of water used may be, for example, 100 parts by mass or more and 10,000 parts by mass or less with respect to 100 parts by mass of the halogenated zinc phthalocyanine crude pigment.
- the amount of water used is equal to or higher than the above lower limit, the acid contained in the halogenated zinc phthalocyanine crude pigment tends to be more easily removed.
- An organic solvent (for example, an organic solvent that can be used in the miniaturization step described later) may be mixed in the water.
- the mixed amount of the organic solvent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less with respect to 100 parts by mass of water.
- the temperature (heating temperature) for heating the halogenated zinc phthalocyanine crude pigment is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint that the acid contained in the halogenated zinc phthalocyanine crude pigment is more easily removed. It is more preferably 70 ° C. or higher.
- the heating temperature may be the boiling point of water. That is, in the pretreatment step, the halogenated zinc phthalocyanine crude pigment may be boiled in water.
- the heating temperature is, for example, below the boiling point of water and may be below 100 ° C.
- the time (heating time) for heating the halogenated zinc phthalocyanine crude pigment may be appropriately adjusted according to the amount of the halogenated zinc phthalocyanine crude pigment and the like, and is, for example, 1 minute or more, 5 minutes or more, or 10 minutes or more. It may be 300 minutes or less, 200 minutes or less, or 100 minutes or less, and may be 1 to 300 minutes.
- the heating time may be referred to as the time for holding the halogenated zinc phthalocyanine crude pigment at the above heating temperature (for example, 40 to 100 ° C.). Therefore, when heating after mixing the halogenated zinc phthalocyanine crude pigment and water, the time required for raising the temperature (heating time) is not included in the heating time.
- the heating time may be, for example, 1 minute to 2 hours.
- halogen is used during or before the heat treatment in water (when the halogenated zinc phthalocyanine crude pigment is brought into contact with water or before). It is preferable to improve the wettability of the zinc phthalocyanine crude pigment to water.
- the method for improving the wettability of the halogenated zinc phthalocyanine crude pigment with water include a method of contacting the halogenated zinc phthalocyanine crude pigment with a water-soluble organic solvent such as methanol.
- the amount of the water-soluble organic solvent used may be, for example, 1 part by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the halogenated zinc phthalocyanine crude pigment.
- the halogenated zinc phthalocyanine crude pigment After the heat treatment in water, it is preferable to wash the halogenated zinc phthalocyanine crude pigment from the viewpoint of sufficiently removing the water containing acid.
- the washing either water washing (washing with water below 40 ° C.) or hot water washing (washing with water above 40 ° C.) can be adopted.
- the washing may be repeated a plurality of times (for example, 2 to 5 times). Specifically, it is preferable to perform cleaning until the pH of the filtrate becomes equal to the pH of water used for cleaning (for example, the difference between the two is 0.2 or less). After cleaning, operations such as filtration, drying, and pulverization may be performed, if necessary.
- the pretreatment step from the viewpoint of further removing the acid contained in the halogenated zinc phthalocyanine crude pigment, the crude pigment after cleaning is heated in water and then washed with water a plurality of times (preferably). It may be repeated (twice or more).
- the heating conditions and cleaning conditions at this time are the same as the above heating conditions and cleaning conditions. Therefore, the pretreatment step is a series of heating the halogenated phthalocyanine crude pigment in water (preferably at a heating temperature of 40 to 100 ° C. and a heating time of 1 to 300 minutes), and then washing the heated crude pigment with water. It can also be said that the above operation is repeated once or more (preferably three times or more) to bring the pH of the halogenated zinc phthalocyanine crude pigment to 5.0 or more.
- the pH of the zinc halide phthalocyanine pre-pigment is determined by mixing 5 g of the halogenated zinc phthalocyanine pre-pigment with 5 g of methanol and then further mixing with 100 ml of ion-exchanged water, and heating the obtained mixture for 5 minutes to bring it to a boiling state. The mixture is further heated for 5 minutes to maintain the boiling state, the heated mixture is allowed to cool to 30 ° C. or lower, the total amount of the mixture is adjusted to 100 ml with ion-exchanged water, and then filtered to obtain 25 of the filtrate. The pH at ° C.
- the pH of the halogenated zinc phthalocyanine pre-pigment is preferably 6.0 or more, more preferably 6.5 or more, from the viewpoint that finer pigment particles can be easily obtained.
- the pH of the halogenated zinc phthalocyanine pre-pigment may be, for example, 8.5 or less, or 7.0 or less.
- the miniaturization step may be a step of kneading the halogenated zinc phthalocyanine pre-pigment with an organic solvent, or may be a step of kneading with an inorganic salt and an organic solvent. It is preferable not to use water in the miniaturization step.
- the amount of water used may be, for example, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less with respect to 100 parts by mass of the organic solvent.
- the organic solvent one that does not dissolve the halogenated zinc phthalocyanine pre-pigment and the inorganic salt can be used.
- the organic solvent it is preferable to use an organic solvent capable of suppressing crystal growth.
- a water-soluble organic solvent can be preferably used.
- the organic solvent include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, and 2- (hexyl).
- Oxy) Ethanol, Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, Triethylene glycol, Triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Dipropylene glycol, Dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether and the like can be used.
- the amount of the organic solvent (for example, a water-soluble organic solvent) used is not particularly limited, but is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the halogenated zinc phthalocyanine pre-pigment.
- the halogenated zinc phthalocyanine pre-pigment may be kneaded while being heated.
- the heating temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, further preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher, from the viewpoint of facilitating the acquisition of finer pigment particles. be.
- the heating temperature may be, for example, 150 ° C. or lower.
- the kneading time of the miniaturization step may be, for example, 1 to 60 hours.
- the micronization step when an inorganic salt and an organic solvent are used, a mixture containing a halogenated zinc phthalocyanine pigment, an inorganic salt and an organic solvent is obtained. However, the organic solvent and the inorganic salt are removed from this mixture, and it is necessary. Depending on the situation, operations such as washing, filtering, drying, and pulverizing may be performed on a solid substance mainly composed of a halogenated zinc phthalocyanine pigment.
- both water washing and hot water washing can be adopted.
- the washing may be repeated in the range of 1 to 5 times.
- the organic solvent and the inorganic salt can be easily removed by washing with water. If necessary, acid cleaning, alkaline cleaning, and organic solvent cleaning may be performed.
- drying after the washing and filtration examples include batch type or continuous type drying in which the pigment is dehydrated and / or the solvent is removed by heating at 80 to 120 ° C. by a heating source installed in a dryer. ..
- the dryer generally include a box-type dryer, a band dryer, a spray dryer, and the like.
- spray-dry drying using a spray dryer is preferable because it is easy to disperse during paste preparation.
- the crushing after drying is not an operation for increasing the specific surface area or reducing the average particle size of the primary particles, but the pigment is used as in the case of drying using a box dryer or a band dryer, for example. This is done to dissolve the pigment and pulverize it when it becomes a lamp shape or the like. For example, crushing with a mortar, a hammer mill, a disc mill, a pin mill, a jet mill or the like can be mentioned.
- a fine halogenated zinc phthalocyanine pigment can be obtained.
- the present inventors infer the reason why such an effect is obtained as follows. First, when an acid is present at the time of pigmentation, the acid promotes the aggregation of the particles, so that the miniaturization of the pigment particles is hindered. On the other hand, in the above-mentioned production method, since the acid contained in the crude pigment is removed in the pretreatment step, the influence of the above-mentioned acid can be alleviated. Therefore, according to the above method, a fine halogenated zinc phthalocyanine pigment can be obtained.
- the zinc halide phthalocyanine pigment obtained by the above production method is preferably used as a green pigment for a color filter.
- the average particle size (average primary particle size) of the primary particles of the zinc halide phthalocyanine pigment obtained by the above method is, for example, 30 nm or less. According to the above method, for example, a zinc halide phthalocyanine pigment having an average primary particle size of 25 nm or less can be obtained.
- the average primary particle size of the zinc halide phthalocyanine pigment may be 10 nm or more.
- the average primary particle size is an average value of the major axis of the primary particle, and can be obtained by measuring the major axis of the primary particle in the same manner as the measurement of the average aspect ratio described later.
- the average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is, for example, 1.2 or more, 1.3 or more, 1.4 or more, or 1.5 or more.
- the average aspect ratio of the primary particles of the zinc halide phthalocyanine pigment is, for example, less than 2.0, 1.8 or less, 1.6 or less, or 1.4 or less. According to the zinc halide phthalocyanine pigment having such an average aspect ratio, a better contrast can be obtained.
- the zinc halide phthalocyanine pigment having an average aspect ratio of the primary particles in the range of 1.0 to 3.0 preferably does not contain primary particles having an aspect ratio of 5 or more, and contains primary particles having an aspect ratio of 4 or more. It is more preferable that there is no primary particle, and it is further preferable that the primary particle having an aspect ratio of more than 3 is not contained.
- the aspect ratio and average aspect ratio of the primary particles can be measured by the following methods. First, the particles in the field of view are photographed with a transmission electron microscope (for example, JEM-2010 manufactured by JEOL Ltd.). Then, the longer diameter (major axis) and the shorter diameter (minor axis) of the primary particles existing on the two-dimensional image are measured, and the ratio of the major axis to the minor axis is defined as the aspect ratio of the primary particles. Further, the average values of the major axis and the minor axis are obtained for 40 primary particles, and the ratio of the major axis to the minor axis is calculated using these values, and this is used as the average aspect ratio.
- a transmission electron microscope for example, JEM-2010 manufactured by JEOL Ltd.
- the halogenated zinc phthalocyanine pigment which is a sample, is ultrasonically dispersed in a solvent (for example, cyclohexane) and then photographed with a microscope. Further, a scanning electron microscope may be used instead of the transmission electron microscope.
- a solvent for example, cyclohexane
- the reaction mixture was taken out into water, filtered, washed with water, and dried to obtain a halogenated zinc phthalocyanine crude pigment (crude pigment A1).
- the washing with water was carried out until the difference between the pH of the filtrate and the pH of the water used for washing became ⁇ 0.2.
- Mass spectrometry of crude pigment A1 by JMS-S3000 manufactured by JEOL Ltd. was performed, and it was confirmed that the crude pigment A1 was a halogenated zinc phthalocyanine having an average chlorine number of 1.8 and an average bromine number of 13.2.
- the Delay Time was 500 ns
- the Laser Intensity was 44%
- the reaction mixture was taken out into water, filtered, washed with water, and dried to obtain a halogenated zinc phthalocyanine crude pigment (crude pigment A2).
- the washing with water was carried out until the pH of the filtrate became the same as the pH of the water used for washing.
- Mass spectrometry of crude pigment A2 by JMS-S3000 manufactured by JEOL Ltd. was carried out, and it was confirmed that the zinc phthalocyanine halide had an average chlorine number of 2.9 and an average bromine number of 9.3.
- the Delay Time was 510 ns
- the Laser Intensity was 40%
- PH measurement of crude pigment A1 and crude pigment A2 In a 300 ml beaker, 5 g of a crude pigment (crude pigment A1 or crude pigment A2) and 5 g of methanol are weighed and mixed, then 100 ml of ion-exchanged water is further sprinkled, and the mixture is boiled in a hot stirrer for 5 minutes, and then boiled for another 5 minutes. Continued boiling. Then, after allowing to cool to 30 ° C. or lower, the mixture was transferred to a 100 ml graduated cylinder, the total volume was adjusted to 100 ml with ion-exchanged water, and then filtered. The pH and specific conductivity of the filtrate were measured. The pH of the crude pigment A1 at 25 ° C.
- the pH of the crude pigment A2 at 25 ° C. was 3.4, and the specific conductivity was 193 ⁇ S / cm. From this, the crude pigment A1 and the crude pigment A2 contain an acid, and the acid cannot be removed even if the filtrate is washed with water until the pH becomes equal to that of the water used for washing. confirmed.
- the pH was measured with a PH71 personal pH meter manufactured by Yokogawa Electric Corporation, and the specific conductivity was measured with a Seven Easy S30 manufactured by METTLER TOLEDO Co., Ltd.
- Example 1> (Pretreatment process) 50 g of crude pigment A1, 50 g of methanol, and 1 L of ion-exchanged water were placed in a 3 L beaker, the temperature was raised to 90 ° C. over 20 minutes with a hot stirrer, and heating was continued at 90 ° C. for 10 minutes. Then, it was filtered and washed with water. The washing with water was carried out until the pH of the filtrate became the same pH as the water used for washing.
- the crude pigment after washing with water (hydrous crude pigment 1) is transferred to a 3 L beaker, 1 L of ion-exchanged water is weighed in, the temperature is raised to 90 ° C. over 20 minutes with a hot stirrer, and the mixture is further heated at 90 ° C. for 10 minutes. Continued. Then, it was filtered and washed with water to obtain a water-containing crude pigment 2. The washing with water was carried out until the pH of the filtrate became the same pH as the water used for washing. The above series of operations (heating and washing in water) were repeated once more for the obtained water-containing crude pigment 2.
- the water-containing crude pigment 2 is transferred to a 3 L beaker, 1 L of ion-exchanged water is weighed in, the temperature is raised to 90 ° C. over 20 minutes with a hot stirrer, heating is continued at 90 ° C. for 10 minutes, and then filtration is performed. , Washed with water. The washing with water was carried out until the pH of the filtrate became the same pH as the water used for washing. As a result, a water-containing crude pigment 3 was obtained. The obtained hydrous crude pigment 3 was dried and pulverized to obtain a halogenated zinc phthalocyanine pre-pigment (pre-pigment B1).
- pre-pigment B1 halogenated zinc phthalocyanine pre-pigment
- PH measurement of pre-pigment B1 In a 300 ml beaker, 5 g of pre-pigment B1 and 5 g of methanol were weighed and mixed, and then 100 ml of ion-exchanged water was weighed in and boiled in a hot stirrer for 5 minutes, and boiling was continued for another 5 minutes. Then, after allowing to cool to 30 ° C. or lower, the mixture was transferred to a 100 ml graduated cylinder, the total volume was adjusted to 100 ml with ion-exchanged water, and then filtered. When the pH and specific conductivity of the filtrate were measured, the pH at 25 ° C. was 6.0, and the specific conductivity was 51 ⁇ S / cm. From this, it was confirmed that at least a part of the contained acid was removed from the pre-pigment B1.
- the green pigment G1 was ultrasonically dispersed in cyclohexane and then photographed with a microscope, and the average particle size of the primary particles was calculated from the average value of 40 primary particles constituting the aggregates on the two-dimensional image.
- the average particle size of the primary particles was 29 nm.
- Pigment Yellow 138 (Chromofine Yellow 6206EC manufactured by Dainichiseika Co., Ltd.) 1.65 g, DISPERBYK-161 (manufactured by Big Chemie) 3.85 g, propylene glycol monomethyl ether acetate 11.00 g and 0.3 to 0.4 mm zircon Using beads, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a dispersion.
- Example 2 0.3 with 2.48 g of the green pigment G1 obtained in Example 1 together with 1.24 g of BYK-LPN6919 manufactured by Big Chemie, 1.86 g of Unidic ZL-295 manufactured by DIC Corporation, and 10.92 g of propylene glycol monomethyl ether acetate. Using zircon beads of ⁇ 0.4 mm, the mixture was dispersed for 2 hours with a paint shaker manufactured by Toyo Seiki Co., Ltd. to obtain a pigment dispersion (MG1) for a color filter.
- MG1 pigment dispersion
- the evaluation composition (CG1) was spin-coated on a soda glass substrate, dried at 90 ° C. for 3 minutes, and then heated at 230 ° C. for 1 hour. As a result, a glass substrate for contrast evaluation having a colored film on the soda glass substrate was produced. By adjusting the spin rotation speed at the time of spin coating, the thickness of the colored film obtained by heating at 230 ° C. for 1 hour was set to 1.8 ⁇ m.
- the coating liquid obtained by mixing the yellow composition for toning (TY1) prepared above and the composition for evaluation (CG1) is spin-coated on a soda glass substrate and dried at 90 ° C. for 3 minutes. , 230 ° C. for 1 hour.
- a glass substrate for luminance evaluation having a colored film on the soda glass substrate was produced.
- a colored film having a chromaticity (x, y) of (0.275, 0.570) in the C light source was prepared.
- the contrast of the colored film on the glass substrate for contrast evaluation was measured with a contrast tester CT-1 manufactured by Tsubosaka Electric Co., Ltd., and the brightness of the colored film on the glass substrate for luminance evaluation was measured with U-3900 manufactured by Hitachi High-Tech Science. The results are shown in Table 1.
- the contrast and brightness shown in Table 1 are values based on the contrast and brightness of Comparative Example 1.
- Example 2 In the pretreatment step, the pre-pigment B2 was obtained in the same manner as in Example 1 except that the above series of operations (heating and washing in water) were repeated 9 times for the water-containing crude pigment 1. Further, the pH and specific conductivity of the pre-pigment B2 were measured in the same manner as in Example 1. The results are shown in Table 1.
- a green pigment G2 was obtained in the same manner as in Example 1 except that the pre-pigment B2 was used instead of the pre-pigment B1. Further, in the same manner as in Example 1, the average primary particle size, pH and specific conductivity of the green pigment G2 were measured. Further, a glass substrate for contrast evaluation and a glass substrate for luminance evaluation were produced and the contrast and luminance were measured in the same manner as in Example 1 except that the green pigment G2 was used instead of the green pigment G1. The results are shown in Table 1.
- Examples 3 and 4 Pre-pigments B3 and B4 were obtained in the same manner as in Example 1 except that the heating time or heating temperature in water in the pretreatment step was changed as shown in Table 1. Further, the pH and specific conductivity of the pre-pigments B3 and B4 were measured in the same manner as in Example 1. The results are shown in Table 1.
- Green pigments G3 and G4 were obtained in the same manner as in Example 1 except that the pre-pigment B3 or B4 was used instead of the pre-pigment B1. Further, in the same manner as in Example 1, the average primary particle size, pH and specific conductivity of the green pigments G3 and G4 were measured. Further, a glass substrate for contrast evaluation and a glass substrate for luminance evaluation were produced and the contrast and luminance were measured in the same manner as in Example 1 except that the green pigment G3 or G4 was used instead of the green pigment G1. The results are shown in Table 1.
- Examples 5 and 6 The green pigments G5 and G6 were obtained in the same manner as in Example 1 except that the heating temperature and / or the kneading time at the time of kneading in the miniaturization step was changed as shown in Table 1. Further, in the same manner as in Example 1, the average primary particle size, pH and specific conductivity of the green pigments G5 and G6 were measured. Further, a glass substrate for contrast evaluation and a glass substrate for luminance evaluation were produced and the contrast and luminance were measured in the same manner as in Example 1 except that the green pigment G5 or G6 was used instead of the green pigment G1. The results are shown in Table 1.
- ⁇ Comparative example 1> A miniaturization step was carried out in the same manner as in Example 1 except that the crude pigment A1 was used instead of the pre-pigment B1 to obtain a green pigment G7. That is, in Comparative Example 1, the pretreatment step in Example 1 was not performed. Further, in the same manner as in Example 1, the average primary particle size, pH and specific conductivity of the green pigment G7 were measured. Further, a glass substrate for contrast evaluation and a glass substrate for luminance evaluation were produced and the contrast and luminance were measured in the same manner as in Example 1 except that the green pigment G7 was used instead of the green pigment G1. The results are shown in Table 1.
- a green pigment G8 was obtained in the same manner as in Example 1 except that the pre-pigment B8 was used instead of the pre-pigment B1. Further, in the same manner as in Example 1, the average primary particle size, pH and specific conductivity of the green pigment G8 were measured. Further, a glass substrate for contrast evaluation and a glass substrate for luminance evaluation were produced and the contrast and luminance were measured in the same manner as in Example 1 except that the green pigment G8 was used instead of the green pigment G1. The results are shown in Table 1.
- Example 7 The crude pigment was pretreated in the same manner as in Example 1 except that the crude pigment A2 was used instead of the crude pigment A1 to obtain a pre-pigment B9. Further, the pH and specific conductivity of the pre-pigment B9 were measured in the same manner as in Example 1. The results are shown in Table 2.
- a green pigment G9 was obtained in the same manner as in Example 1 except that the pre-pigment B9 was used instead of the pre-pigment B1. Further, in the same manner as in Example 1, the average primary particle size, pH and specific conductivity of the green pigment G9 were measured.
- Pigment Yellow 185 Pigment Yellow D1155 manufactured by BASF
- Pigment Yellow 138 Chromofine Yellow 6206EC manufactured by Dainichi Seika Co., Ltd.
- Green pigment G9 was used in place of green pigment G1
- a glass substrate for contrast evaluation and a glass substrate for brightness evaluation were produced in the same manner as in Example 1 except that the chromaticity (x, y) of the colored film was adjusted to (0.230, 0.670). , Contrast and brightness were measured. The results are shown in Table 2.
- ⁇ Comparative example 3> A miniaturization step was carried out in the same manner as in Example 7 except that the crude pigment A2 was used instead of the pre-pigment B9 to obtain a green pigment G10. That is, in Comparative Example 3, the pretreatment step in Example 7 was not performed. Further, in the same manner as in Example 7, the average primary particle size, pH and specific conductivity of the green pigment G10 were measured. Further, a glass substrate for contrast evaluation and a glass substrate for luminance evaluation were produced and the contrast and luminance were measured in the same manner as in Example 7 except that the green pigment G10 was used instead of the green pigment G9. The results are shown in Table 2.
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Abstract
Description
<方法>
ハロゲン化亜鉛フタロシアニン粗顔料2.48gを、ビックケミー社製BYK-LPN6919 1.24g、DIC株式会社製ユニディックZL-295 1.86g、プロピレングリコールモノメチルエーテルアセテート10.92gと共に0.3~0.4 mmのジルコンビーズを用いて、東洋精機株式会社製ペイントシェーカーで2時間分散して分散体を得る。ジルコンビーズをナイロンメッシュで取り除いた後の分散体0.02gをプロピレングリコールモノメチルエーテルアセテート20gで希釈して粒度分布測定用分散体を得る。
<条件>
・測定機器:動的光散乱式粒子径分布測定装置LB-550(株式会社堀場製作所製)
・測定温度:25℃
・測定試料:粒度分布測定用分散体
・データ解析条件:粒子径基準 散乱光強度、分散媒屈折率 1.402
(粗顔料A1の合成)
300mlフラスコに、塩化スルフリル(富士フイルム和光純薬工業株式会社製) 91g、塩化アルミニウム(関東化学株式会社製) 109g、塩化ナトリウム(東京化成工業株式会社製) 15g、亜鉛フタロシアニン(DIC株式会社製) 30g、臭素(富士フイルム和光純薬工業株式会社製) 230gを仕込んだ。130℃まで昇温し、130℃で40時間保持した。反応混合物を水に取り出した後、ろ過し、水洗し、乾燥することによりハロゲン化亜鉛フタロシアニン粗顔料(粗顔料A1)を得た。なお、水洗は、ろ液のpHと洗浄に用いられる水のpHの差が±0.2になるまで行った。
300mlフラスコに、塩化スルフリル(富士フイルム和光純薬工業株式会社製) 90g、塩化アルミニウム(関東化学株式会社製) 105g、塩化ナトリウム(東京化成工業株式会社製) 14g、亜鉛フタロシアニン(DIC株式会社製) 27g、臭素(富士フイルム和光純薬工業株式会社製) 55gを仕込んだ。130℃まで昇温し、130℃で40時間保持した。反応混合物を水に取り出した後、ろ過し、水洗し、乾燥することによりハロゲン化亜鉛フタロシアニン粗顔料(粗顔料A2)を得た。なお、水洗は、ろ液のpHが洗浄に用いられる水と同等のpHになるまで行った。
300mlビーカーに、粗顔料(粗顔料A1又は粗顔料A2) 5gとメタノール 5gとをはかりこみ混合した後、さらにイオン交換水 100mlをはかりこみ、ホットスターラーで5分かけて煮沸状態とし、さらに5分間煮沸を続けた。次いで、30℃以下に放冷した後、100mlのメスシリンダーへ移し、イオン交換水で全量を100mlに調整してからろ過した。ろ液のpHと比電導度を測定した。粗顔料A1の25℃でのpHは3.7であり、比電導度は163μS/cm(マイクロジーメンス・パー・センチメートル)であった。粗顔料A2の25℃でのpHは3.4であり、比電導度は193μS/cmであった。このことから、粗顔料A1及び粗顔料A2には酸が内包されており、ろ液のpHが洗浄に用いられる水と同等のpHになるまで水洗を行ったとしても、酸を除去できないことが確認された。なお、pHは、横河電機株式会社製のPH71 パーソナルpHメータで測定し、比電導度はメトラー・トレド株式会社製のセブンイージーS30で測定した。
(前処理工程)
3Lビーカーに、粗顔料A1 50gと、メタノール 50gと、イオン交換水 1Lとをはかりこみ、ホットスターラーで20分かけて90℃に昇温し、さらに90℃で10分間加熱を続けた。その後、ろ過し、水洗した。水洗は、ろ液のpHが洗浄に用いられる水と同等のpHになるまで行った。
300mlビーカーに、プレ顔料B1 5gとメタノール 5gとをはかりこみ混合した後、さらにイオン交換水 100mlをはかりこみ、ホットスターラーで5分かけて煮沸状態とし、さらに5分間煮沸を続けた。次いで、30℃以下に放冷した後、100mlのメスシリンダーへ移し、イオン交換水で全量を100mlに調整してからろ過した。ろ液のpHと比電導度を測定したところ、25℃でのpHは6.0であり、比電導度は51μS/cmであった。このことから、プレ顔料B1では、内包されていた酸の少なくとも一部が除去されていることが確認された。
プレ顔料B1 40g、粉砕した塩化ナトリウム 400g及びジエチレングリコール 63gを双腕型ニーダーに仕込み、80℃で8時間混練した。混練後の混合物を80℃の水2kgに取り出し、1時間攪拌した。その後、ろ過し、湯洗し、乾燥し、粉砕することにより、緑色顔料G1を得た。
緑色顔料G1をシクロヘキサンに超音波分散させてから顕微鏡で撮影し、二次元画像上の凝集体を構成する一次粒子40個の平均値から、一次粒子の平均粒子径を算出した。一次粒子の平均粒子径は29nmであった。
300mlビーカーに、緑色顔料G1 5gとメタノール 5gとをはかりこみ混合した後、さらにイオン交換水 100mlをはかりこみ、ホットスターラーで5分かけて煮沸状態とし、さらに5分間煮沸を続けた。次いで、30℃以下に放冷した後、100mlのメスシリンダーへ移し、イオン交換水で全量を100mlに調整してからろ過した。ろ液のpHと比電導度を測定したところ、25℃でのpHは6.1であり、比電導度は46μS/cmであった。
ピグメントイエロー138(大日精化社製クロモファインイエロー6206EC) 1.65gを、DISPERBYK-161(ビックケミー社製) 3.85g、プロピレングリコールモノメチルエーテルアセテート 11.00gと共に0.3~0.4 mmのジルコンビーズを用いて、東洋精機株式会社製ペイントシェーカーで2時間分散して分散体を得た。
前処理工程において、含水粗顔料1に対して、上記一連の操作(水中での加熱及び洗浄)を9回繰り返し行ったこと以外は、実施例1と同様にして、プレ顔料B2を得た。また、実施例1と同様にして、プレ顔料B2のpH及び比電導度を測定した。結果を表1に示す。
前処理工程における、水中での加熱時間又は加熱温度を、表1に示すように変更したこと以外は、実施例1と同様にして、プレ顔料B3及びB4を得た。また、実施例1と同様にして、プレ顔料B3及びB4のpH及び比電導度を測定した。結果を表1に示す。
微細化工程における、混練時の加熱温度及び/又は混練時間を、表1に示すように変更したこと以外は、実施例1と同様にして、緑色顔料G5及びG6をそれぞれ得た。また、実施例1と同様にして、緑色顔料G5及びG6の平均一次粒子径、pH及び比電導度を測定した。また、緑色顔料G1に代えて緑色顔料G5又はG6を用いたこと以外は、実施例1と同様にして、コントラスト評価用ガラス基板及び輝度評価用ガラス基板を作製し、コントラスト及び輝度を測定した。結果を表1に示す。
プレ顔料B1に代えて粗顔料A1を用いたこと以外は、実施例1と同様にして、微細化工程を行い、緑色顔料G7を得た。すなわち、比較例1では、実施例1における前処理工程を行わなかった。また、実施例1と同様にして、緑色顔料G7の平均一次粒子径、pH及び比電導度を測定した。また、緑色顔料G1に代えて緑色顔料G7を用いたこと以外は、実施例1と同様にして、コントラスト評価用ガラス基板及び輝度評価用ガラス基板を作製し、コントラスト及び輝度を測定した。結果を表1に示す。
実施例1と同様にして含水粗顔料1を得た後、得られた含水粗顔料1を乾燥し、粉砕することにより、ハロゲン化亜鉛フタロシアニンプレ顔料(プレ顔料B8)を得た。すなわち、比較例2では、含水粗顔料1に対し、更なる水中での加熱及び洗浄を行わなかった。また、実施例1と同様にして、プレ顔料B8のpH及び比電導度を測定した。結果を表1に示す。
粗顔料A1に代えて粗顔料A2を用いたこと以外は、実施例1と同様にして、粗顔料の前処理を行い、プレ顔料B9を得た。また、実施例1と同様にして、プレ顔料B9のpH及び比電導度を測定した。結果を表2に示す。
プレ顔料B9に代えて粗顔料A2を用いたこと以外は、実施例7と同様にして、微細化工程を行い、緑色顔料G10を得た。すなわち、比較例3では、実施例7における前処理工程を行わなかった。また、実施例7と同様にして、緑色顔料G10の平均一次粒子径、pH及び比電導度を測定した。また、緑色顔料G9に代えて緑色顔料G10を用いたこと以外は、実施例7と同様にして、コントラスト評価用ガラス基板及び輝度評価用ガラス基板を作製し、コントラスト及び輝度を測定した。結果を表2に示す。
Claims (5)
- ハロゲン化亜鉛フタロシアニン粗顔料を顔料化する工程を有する、ハロゲン化亜鉛フタロシアニン顔料の製造方法であって、
前記ハロゲン化亜鉛フタロシアニン粗顔料は、水と反応して酸を発生する化合物を用いて合成したハロゲン化亜鉛フタロシアニンを析出させて得られたものであり、
前記工程は、前記ハロゲン化亜鉛フタロシアニン粗顔料を水中で加熱し、pHが5.0以上であるハロゲン化亜鉛フタロシアニンプレ顔料を得る前処理工程を含む、ハロゲン化亜鉛フタロシアニン顔料の製造方法。 - 前記前処理工程における前記ハロゲン化亜鉛フタロシアニン粗顔料を加熱する温度は40℃以上である、請求項1に記載の製造方法。
- 前記前処理工程における前記ハロゲン化亜鉛フタロシアニン粗顔料を加熱する時間は1分間以上である、請求項1又は2に記載の製造方法。
- 前記前処理工程では、前記ハロゲン化亜鉛フタロシアニン粗顔料を水中で加熱した後、加熱後のハロゲン化亜鉛フタロシアニン粗顔料を水で洗浄する、請求項1~3のいずれか一項に記載の製造方法。
- 前記前処理工程では、洗浄後のハロゲン化亜鉛フタロシアニン粗顔料に対し、水中で加熱した後水で洗浄する操作を2回以上繰り返し行う、請求項4に記載の製造方法。
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US17/296,656 US20230144572A1 (en) | 2020-04-30 | 2020-04-30 | Method for producing halogenated zinc phthalocyanine pigment |
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JP2006083368A (ja) * | 2004-09-18 | 2006-03-30 | Clariant Produkte (Deutschland) Gmbh | マイクロ波加熱による顔料仕上げ |
JP2007284590A (ja) * | 2006-04-18 | 2007-11-01 | Dainippon Ink & Chem Inc | ポリハロゲン化金属フタロシアニン粗製顔料、同顔料及び同顔料を緑色画素部に含有させてなるカラーフィルタ |
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JP2006184427A (ja) * | 2004-12-27 | 2006-07-13 | Dainippon Ink & Chem Inc | カラーフィルター用緑色セミクルードの製造方法、緑色顔料組成物、およびそれらを緑色画素部に含有してなるカラーフィルター |
JP5141939B2 (ja) | 2006-04-18 | 2013-02-13 | Dic株式会社 | ポリハロゲン化亜鉛フタロシアニン顔料組成物及びカラーフィルタ |
JP4882515B2 (ja) * | 2006-05-30 | 2012-02-22 | Dic株式会社 | ポリハロゲン化亜鉛フタロシアニン顔料組成物及びカラーフィルタ |
JP2009221376A (ja) * | 2008-03-17 | 2009-10-01 | Fujifilm Corp | 加工顔料、顔料分散組成物、感光性組成物、カラーフィルタおよびその製造方法 |
JP2014181321A (ja) * | 2013-03-21 | 2014-09-29 | Dic Corp | インクジェット記録用水性インク調製のための水性顔料分散液及びインクジェット記録水性インク |
WO2014185471A1 (ja) | 2013-05-14 | 2014-11-20 | 花王株式会社 | 微細有機顔料の製造方法 |
KR102475159B1 (ko) * | 2016-09-13 | 2022-12-08 | 디아이씨 가부시끼가이샤 | 폴리할로겐화아연프탈로시아닌, 폴리할로겐화아연프탈로시아닌 안료 및 이것을 화소부에 갖는 컬러필터 |
KR102558140B1 (ko) | 2016-10-20 | 2023-07-21 | 이경환 | 모션 침대 제어를 위한 단말장치 및 그 동작 방법 |
KR20220101044A (ko) * | 2019-12-09 | 2022-07-19 | 디아이씨 가부시끼가이샤 | 컬러 필터용 할로겐화아연프탈로시아닌 안료 및 컬러 필터용 할로겐화아연프탈로시아닌 안료의 제조 방법 |
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JP2006083368A (ja) * | 2004-09-18 | 2006-03-30 | Clariant Produkte (Deutschland) Gmbh | マイクロ波加熱による顔料仕上げ |
JP2007284590A (ja) * | 2006-04-18 | 2007-11-01 | Dainippon Ink & Chem Inc | ポリハロゲン化金属フタロシアニン粗製顔料、同顔料及び同顔料を緑色画素部に含有させてなるカラーフィルタ |
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TW202115198A (zh) | 2021-04-16 |
CN112334547A (zh) | 2021-02-05 |
US20230144572A1 (en) | 2023-05-11 |
JP6819825B1 (ja) | 2021-01-27 |
KR102527027B1 (ko) | 2023-04-28 |
JPWO2021220497A1 (ja) | 2021-11-04 |
KR20200128612A (ko) | 2020-11-13 |
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