Blue pigment composition

Abstract

The invention provides a blue pigment composition. The blue pigment composition is characterized by comprising a blue pigment, the present invention is a pigment derivative containing a copper chloride phthalocyanine having an average chlorine substitution number of 0.3-2.2, and a pigment derivative in which at least one hydrogen atom in the benzene ring of the copper phthalocyanine is substituted by at least one of a group represented by general formula (1), a group represented by general formula (2), a group represented by general formula (3), a group represented by general formula (4), or a group represented by general formula (5). The average aspect ratio of primary particles of the copper chloride phthalocyanine is 1.0-3.5.

Description

[0001] This application is a divisional application of the Chinese patent application with the application date of November 28, 2019, application number 201980088972.1, and invention name “Blue Pigment Composition”. Technical Field

[0002] The present invention relates to a blue pigment composition containing a copper chlorinated phthalocyanine pigment and a pigment derivative, which can be preferably used mainly as a paint for automobiles, and a paint containing the same. Background Art

[0003] Phthalocyanine compounds having a phthalocyanine structure, typified by copper phthalocyanine, have been widely used as coloring materials in various applications, typified by coatings, plastics, toners, and inkjet inks, as blue organic pigments with excellent fastness.

[0004] In addition, it is known that the color tone of copper phthalocyanine changes depending on the number of chlorine atoms present in the molecule, and changes from reddish blue to greenish blue via greenish blue as the number of chlorine atoms increases. In particular, as a blue pigment for automotive coatings, copper chloride phthalocyanine with 1 to 4 chlorine atoms is often used, and the Japanese automotive industry prefers monochlorocopper phthalocyanine with 1 chlorine atom, which produces a reddish blue color.

[0005] Furthermore, it was observed that the hue of the monochlorocopper phthalocyanine pigment changes depending on the viewing angle, and there is a problem that the red color is too strong in the area called the shadow. In addition to the hue, the transparency and dispersibility of the pigment are also important as a pigment for automotive coatings.

[0006] Citation 1 proposes a pigment composition containing unsubstituted copper phthalocyanine and a pigment derivative of copper phthalocyanine, but the hue is different and the transparency and dispersibility are not good.

[0007] Reference 2 proposes a copper phthalocyanine chloride pigment composition in which monochlorocopper phthalocyanine and copper phthalocyanine are mixed, but the transparency and dispersibility are also poor.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 1-70568

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 9-59531 Summary of the invention

[0012] Problems to be solved by the invention

[0013] An object of the present invention is to provide a blue pigment composition which has a greenish hue when used as a coloring material for a coating material and has excellent transparency.

[0014] Methods for solving problems

[0015] The present inventors have conducted intensive research on copper phthalocyanine chloride and found that when a pigment composition containing copper phthalocyanine chloride with a specific average chlorine substitution number and a specific copper phthalocyanine pigment derivative is used as a coloring material for a coating, the hue of the shadow is green and a coating plate with excellent transparency can be obtained, thereby completing the present invention.

[0016] That is, the present invention provides:

[0017] [1] A blue pigment composition characterized by comprising copper phthalocyanine chloride having an average chlorine substitution number of 0.3 to 2.2, and a pigment derivative in which at least one hydrogen atom in the benzene ring of the copper phthalocyanine is substituted with at least one of a group represented by the following general formula (1), a group represented by the following general formula (2), a group represented by the following general formula (3), a group represented by the following general formula (4), or a group represented by the following general formula (5), wherein the average aspect ratio of the primary particles of the copper phthalocyanine chloride is 1.0 to 3.5.

[0018] [Chemistry 1]

[0019]

[0020] [Chemistry 2]

[0021]

[0022] [Chemistry 3]

[0023]

[0024] -SO 3 R 5 (4)

[0025] [Chemistry 4]

[0026]

[0027] [In formulas (1) to (5), a and b are each independently an integer of 1 to 10, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and X 1 and X 2 Each independently represents a single bond, an arylene group, -NH-, -O- or -S-.]

[0028] [2] The blue pigment composition according to [1], characterized in that the composition contains more than 1 part and less than 15 parts of the pigment derivative per 100 parts of the copper phthalocyanine chloride on a weight basis.

[0029] [3] The blue pigment composition according to [1] or [2] above, characterized in that the average primary particle size is 20 to 60 nm.

[0030] [4] A coating material comprising the blue pigment composition according to any one of [1] to [3].

[0031] Effects of the Invention

[0032] By setting the average chlorine substitution number of copper phthalocyanine chloride to 0.3 to 2.2, the content of unsubstituted copper phthalocyanine is reduced, and by using a specific pigment derivative in combination, the crystal growth of the pigment particles can be relatively easily suppressed without being greatly affected by the pigmentation method. As a result, primary particles with an aspect ratio close to 1 can be obtained, and the smaller the aspect ratio, the better the transparency of the characteristics can be obtained, and an excellent pigment can be obtained. In addition, if the average chlorine substitution number of copper phthalocyanine chloride is 0.3 to 2.2, the color of the pigment itself tends to be green, and the hue of the shadow also becomes green.

[0033] As a result, a pigment having excellent hue and transparency of the shade, which are important characteristics of the pigment composition for automobile coatings, can be produced.

[0034] By using the blue pigment composition of the present invention as a coloring material for coating materials, a coating plate having a greenish tint and excellent transparency can be obtained. DETAILED DESCRIPTION

[0035] The greatest feature of the present invention is that it contains copper phthalocyanine chloride having a specific average chlorine substitution number and a specific copper phthalocyanine pigment derivative.

[0036] <Copper phthalocyanine chloride>

[0037] The copper phthalocyanine chloride used in the present invention can be obtained by a known conventional method. Examples thereof are as follows.

[0038] First, copper phthalocyanine chloride can be produced by the following methods: the Wyler method in which chlorinated phthalic anhydride in which a part of the hydrogen atoms in the aromatic ring of phthalic anhydride are replaced by chlorine is reacted with urea and copper or a copper compound; the phthalonitrile method in which chlorinated phthalonitrile in which a part of the hydrogen atoms in the aromatic ring are replaced by chlorine is reacted with copper or a copper compound in a high boiling point solvent.

[0039] In addition, as another production method, there is a chlorination method using a chlorosulfonic acid method. For example, copper phthalocyanine is dissolved in a sulfur oxide solvent such as chlorosulfonic acid, and chlorine gas is added thereto for halogenation. The reaction is carried out at a temperature of 20 to 120° C. and within a range of 3 to 20 hours.

[0040] Furthermore, a melting method is known as a chlorination method. As a melting method, there is a method of chlorinating copper phthalocyanine with a chlorinating agent in a melt at about 10 to 170° C. composed of one or a mixture of two or more compounds serving as solvents during chlorination, such as aluminum chloride, titanium halides such as titanium tetrachloride, alkali metal chlorides or alkaline earth metal chlorides such as sodium chloride, and thionyl chloride.

[0041] The present invention uses copper chlorinated phthalocyanine synthesized by the Wyler method. Representative production conditions are described below.

[0042] The Wyler method is a method for synthesizing phthalocyanine by reacting phthalic anhydride or its derivatives with urea or its derivatives in the presence of a metal source and a catalyst at 90°C to 300°C. It is the most widely used method in industry as a method for synthesizing phthalocyanine. During the synthesis, a solvent may be used for the purpose of temperature control in the system, improving stirring efficiency, etc. In addition, the reaction may be carried out under a pressurized condition of 0.2 to 0.7 MPa for the purpose of improving yield and purity, etc.

[0043] As the phthalic acids used when synthesized by the Wyler method, there are substances known in various documents, such as phthalic anhydride, phthalic acid and its salts, its esters, phthalimide, phthalamide, etc. In addition, phthalic acids having substituents such as alkyl, aryl, nitro, sulfo, sulfonamide, cyano, amino, hydroxyl, carboxyl, sulfenyl, acyl, siloxy, silyl, halogen, or substituents derived from them on the aromatic rings of these compounds may also be contained. In the present invention, by mixing these phthalic acids with chlorinated phthalic acids in any proportion and synthesizing by the Wyler method, copper chlorinated phthalocyanine with an average chlorine substitution number in any proportion is synthesized. When manufacturing copper chlorinated phthalocyanine of the present invention, it is preferred to use 3-chloro sodium hydrogen phthalate, 4-chloro sodium hydrogen phthalate, 3-chlorophthalic anhydride, and 4-chlorophthalic anhydride as part of the raw materials.

[0044] As urea or its derivatives used in the synthesis of phthalocyanines using the Wyler method, there are urea, ammonia, biuret, triuret, etc. The amount used is about 1 mol to 10 mol relative to 1 mol of phthalic anhydride or its derivatives. Metal sources can use metal powder, chloride, bromide, iodide, sulfate, sulfide, acetate, oxide, hydroxide, carbonate, phosphate, etc. Although the valence of the metal has an effect on the reaction, it can generally be used for phthalocyanine synthesis. Regarding the amount of metal source used, relative to phthalic acid or its derivatives, it is preferably used in the range of 0.15 to 0.40 in terms of molar ratio. As a catalyst, all known catalysts in the Wyler method can be used. For example, there are molybdenum oxide compounds such as ammonium molybdate, ammonium oxide, phosphomolybdic acid, titanium compounds such as titanium tetrachloride, titanate, antimony oxide, arsenic oxide, boric acid, etc. There is no particular limitation on the amount used, and relative to phthalic acid or its derivatives, it is preferably used in the range of 0.0001 to 0.3 in terms of weight ratio. In addition, for the purpose of improving reactivity, improving product purity and clarity, or the like, orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, polymetaphosphoric acid, sulfuric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide and their metal salts and ammonium salts may be added in a molar ratio of 0.05 mol to 1 mol relative to phthalic acid or its derivatives.

[0045] As the solvent that can be used, any substance known as the synthetic solvent of the Wyler method can be used. For example, aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene, tetralin, alicyclic hydrocarbons such as alkylcyclohexane, decalin, alkyldecalin, decane, dodecane, nitrobenzene, o-nitrotoluene, halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene, chloronaphthalene, hexachlorobutadiene, sulfide compounds such as sulfolane, dimethyl sulfolane, dimethyl sulfoxide, heterocyclic compounds such as quinoline, etc. can be used. It is also acceptable that these organic solvents are mixtures of more than two kinds.

[0046] After the reaction is completed, it is preferably washed with water or an organic solvent after separation from the reaction solvent by solvent filtration or solvent distillation. Acids or alkalis can be used for washing. If further purification is necessary, impurities can be removed by sublimation, acid gelatinization, acid pulping, reprecipitation, recrystallization, extraction, and the like, which are known purification techniques.

[0047] In addition, the copper phthalocyanine chloride of the present invention is a mixture of copper phthalocyanine chloride having 1 to 5 chlorine substitutions in one molecule and unsubstituted copper phthalocyanine having no chlorine substitution. The average chlorine substitution number of copper phthalocyanine chloride is identified by a fluorescent X-ray analyzer or a mass spectrometer (FD-MS, TOF-MS). In the production method of copper phthalocyanine chloride, the average chlorine substitution number distribution of copper phthalocyanine chloride obtained by the Wyler method or the nitrile method is narrow. On the other hand, the average chlorine substitution number distribution of copper phthalocyanine chloride obtained by a synthesis method such as melting copper phthalocyanine and chlorinating with chlorosulfonic acid is affected by the source of the chlorination starting raw material and the reaction conditions, and generally tends to become larger.

[0048] The average chlorine substitution number of the copper phthalocyanine chloride of the present invention is preferably 0.3 to 2.0, and more preferably 0.5 to 1.6. If the average chlorine substitution number is too high, the hue is excessively green, exceeding the desired hue; on the contrary, if the average chlorine substitution number is too low, the hue is reddish, not only exceeding the desired hue, but also increasing the average aspect ratio of the primary particles and reducing transparency as described below.

[0049] The average primary particle size of the copper phthalocyanine chloride of the present invention is preferably 20 to 60 nm. If the average primary particle size is too small, the dispersibility during the coating preparation will be poor and the copper phthalocyanine chloride will not be fully dispersed in the coating. If the average primary particle size is too large, the properties such as transparency and coloring power will be poor.

[0050] The average aspect ratio is preferably 1.0 to 3.5, and the hue, transparency, and dispersibility are all good. If the average aspect ratio is too large, the transparency, dispersibility, tinting power, and other characteristics will deteriorate.

[0051] In the present invention, the color measurement of the highlight area using the multi-angle spectrophotometer is the color measurement at the light receiving angle near the regular reflection light (specifically, -15° when the regular reflection light is set to 0°), and the color measurement of the shadow area using the multi-angle spectrophotometer is the color measurement at the light receiving angle far from the regular reflection light with a small intensity (specifically, 110° when the regular reflection light is set to 0°). As a method for making the hue of the shadow greenish, there are methods such as reducing the average primary particle size of the pigment, reducing the reddish scattered light, and increasing the average chlorine substitution number of copper phthalocyanine chloride to make the color of the pigment itself greenish.

[0052] <Copper phthalocyanine pigment derivatives>

[0053] Next, the copper phthalocyanine pigment derivative of the present invention is described. The copper phthalocyanine pigment derivative used in the present invention is a pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted by at least one of the groups represented by the general formula (1), the group represented by the general formula (2), the group represented by the general formula (3), the group represented by the general formula (4), or the group represented by the general formula (5), and is synthesized by a well-known and commonly used method.

[0054] The pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted with a substituent represented by the general formula (1) is a basic pigment derivative. When used in a pigmentation process, excessive crystal growth of the pigment is suppressed. In addition, it is often used in a pigment composition for coatings to improve the viscosity stability of the coating.

[0055] [Chemistry 5]

[0056]

[0057] [In the general formula (1), a is independently an integer from 1 to 10, R 1 , R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.]

[0058] The pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted with a substituent represented by the general formula (2) is a basic pigment derivative. By using it in the pigmentation process, excessive crystal growth of the pigment is suppressed. In addition, it is often used in a pigment composition for coatings to improve the viscosity stability of the coating.

[0059] [Chemistry 6]

[0060]

[0061] [In the general formula (2), b is independently an integer from 1 to 10, R 3 , R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.]

[0062] Pigment derivatives in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted with a substituent represented by the general formula (3) are widely known to be effective as crystal growth inhibitors of copper phthalocyanine, and are often contained in phthalocyanine pigments for color filters and phthalocyanine pigments for toners that require small particle sizes. It is presumed that in the present invention, not only are there effects of reducing particle size and inhibiting crystal growth similar to these effects, but also scattered light can be suppressed by suppressing uneven distribution of primary particle size of the pigment, making the hue of the shadow green.

[0063] [Chemistry 7]

[0064]

[0065] The pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted with a substituent represented by the general formula (4) can suppress excessive crystal growth of the pigment by using it in the pigmentation process. In addition, it is often used in a pigment composition for plastics and has the effect of improving dispersibility. It is speculated that in the present invention, not only the effects of reducing the particle size and suppressing crystal growth are similar to these effects, but also the scattered light can be suppressed by suppressing the uneven distribution of the primary particle size of the pigment, making the hue of the shadow green.

[0066] -SO 3 R 5 (4)

[0067] [In general formula (4), R 5 A hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.]

[0068] Pigment derivatives in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted with a substituent represented by the general formula (5) are widely known to be effective as crystal growth inhibitors of copper phthalocyanine, and are often contained in phthalocyanine pigments for color filters and phthalocyanine pigments for toners that require small particle sizes. It is presumed that in the present invention, not only are there effects of reducing particle size and inhibiting crystal growth similar to these effects, but also scattered light can be suppressed by suppressing uneven distribution of primary particle size of the pigment, making the hue of the shadow green.

[0069] [Chemistry 8]

[0070]

[0071] [In general formula (5), R 6 and R 7 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and X 1 and X 2 Each independently represents a single bond, an arylene group, -NH-, -O- or -S-.]

[0072] The copper phthalocyanine pigment derivative used in the present invention may be any pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted by at least one of the substituents represented by the above-mentioned general formulae (1) to (5), and may be a pigment derivative substituted by the same or different substituents represented by multiple general formulae (1) to (5).

[0073] Furthermore, a plurality of copper phthalocyanine pigment derivatives may be used in combination.

[0074] Examples of the copper phthalocyanine pigment derivative used in the present invention include compounds of the following formulae (4-1) to (4-7), but the invention is not limited to these compounds.

[0075] [Chemistry 9]

[0076]

[0077] [Chemistry 10]

[0078]

[0079] [Chemistry 11]

[0080]

[0081] [Chemistry 12]

[0082]

[0083] [Chemistry 13]

[0084]

[0085] [Chemistry 14]

[0086]

[0087] [Chemistry 15]

[0088]

[0089] The substituent structure of the above-mentioned pigment derivative is large, and therefore, in a conventional synthesis method, the maximum number of substituents in one molecule is 5. The average number of substituents represented by the above-mentioned general formulas (1) to (5) in the pigment derivative of the present invention is 0.5 to 5.0, and preferably 1.0 to 1.7 from the viewpoint of heat resistance and light resistance.

[0090] In the blue pigment composition of the present invention, the amount of the pigment derivative added to copper phthalocyanine chloride is preferably more than 1 part by weight and less than 15 parts by weight relative to 100 parts by weight of copper phthalocyanine chloride, and is more preferably 1 to 10 parts by weight in order to control the hue of the shadow and minimize the color change caused by the pigment derivative.

[0091] It is known that the growth rate of pigment particles is generally the fastest for unsubstituted copper phthalocyanine, and the slower for copper phthalocyanine chloride as the number of chlorine substitutions increases. The copper phthalocyanine chloride of the present invention is a mixture of copper phthalocyanine chloride having 1 to 5 chlorine substitutions in one molecule and unsubstituted copper phthalocyanine without chlorine substitution. Therefore, the growth rate of pigment particles of each compound is different in the process of manufacturing the pigment, and pigment particles with inconsistent particle sizes are easily formed. It is speculated that this is one of the reasons for the scattering difference that exists depending on the visual angle and the reddish shadow area. In this regard, it is speculated that the specific copper phthalocyanine pigment derivative used in the present invention has a particularly high crystal growth inhibition effect, so it is possible to obtain pigment composition particles with a narrow particle size distribution and few coarse particles even in copper phthalocyanine chloride composed of a plurality of compounds with different growth rates. As a result, when used as a coloring material for coatings, a coating plate with a greenish shadow and excellent transparency is obtained.

[0092] The blue pigment composition of the present invention can control the hue and dispersibility simply by mixing the aforementioned copper phthalocyanine chloride and the aforementioned copper phthalocyanine pigment derivative. However, in order to make the two substances uniform at the molecular level, the two substances are temporarily mixed, dissolved, and precipitated to produce a pigment composition uniform at the molecular level.

[0093] Regarding the particle size of the blue pigment composition of the present invention, the particles in the field of view are photographed using a transmission electron microscope (TEM), and then, based on the 50 primary particles constituting the agglomerate on the two-dimensional image, the longest length (maximum length) and the shortest length (minimum length) of each particle are obtained. The average value of the maximum length of each particle is used as the average primary particle size. In addition, the maximum length / minimum length in each particle is obtained, and their average value is used as the average aspect ratio of the primary particle.

[0094] The average primary particle size of the blue pigment composition of the present invention is preferably 20 to 60 nm. If the average primary particle size is too small, the dispersibility when made into a coating material will be poor and it will not be fully dispersed in the coating material. In addition, if the average primary particle size is too large, the properties such as transparency and coloring power will be poor.

[0095] <Method for producing the blue pigment composition of the present invention>

[0096] As an example, a method for obtaining the blue pigment composition of the present invention is described. Hereinafter, a method for obtaining a more suitable pigment composition is described, but it is not intended to be a limitative interpretation of the method for obtaining the blue pigment composition of the present invention.

[0097] For example, a blue pigment composition can be obtained by using the following steps: a first step of dissolving the pigment in a good solvent and then contacting it with a poor solvent to precipitate the pigment to refine the pigment particles; and a second step of heating the pigment obtained in the first step in an organic solvent or a mixture of an organic solvent and water to granulate the pigment.

[0098] The first step is to dissolve the pigment in a good solvent and then contact it with a poor solvent to precipitate it and refine the pigment particles. After 100 parts by weight of copper phthalocyanine chloride is completely or partially dissolved in 50 to 10,000 parts by weight of a strong acid at 0 to 90°C (according to the acid concentration, acid gelatinization, acid slurrying, or acid swelling is performed), it is mixed with a poor solvent to precipitate the pigment particles.

[0099] As the above-mentioned strong acid, sulfuric acid, hydrochloric acid, and nitric acid can be used. Among them, sulfuric acid is preferred in consideration of cost, handling, and mass production. In addition, the acid concentration of sulfuric acid is 70% to 100% (anhydrous sulfuric acid) at which phthalocyanine pigments can be dissolved. Among them, as a concentration at which the pigment can be completely dissolved, it is preferably 90% or more.

[0100] When a strong acid solution of a pigment is mixed with a poor solvent, the amount of the poor solvent is necessary to allow sufficient precipitation of the pigment, and 50 to 10,000 parts by weight is used with respect to 100 parts by weight of the strong acid solution.

[0101] As the above-mentioned poor solvent, any solvent can be used as long as the pigment is precipitated due to the reduction of the acid concentration. In the present invention, water or a mixed solvent consisting of water and 1 to 300 parts by weight of an organic solvent relative to 100 parts by weight of water can be used. As the organic solvent, any water-soluble or water-insoluble organic solvent can be used. In the case of water-insoluble solvents such as alcohols, glycols, ketones, hydrocarbons, etc., they can be emulsified by high-speed stirring or adding an emulsifier or a surfactant to prepare a mixed solvent with water.

[0102] The mixing method of the strong acid solution of the pigment and the poor solvent can be a known and commonly used method, and the strong acid solution can be taken out into the poor solvent, or vice versa. For example, there is also a method of slowly adding the strong acid solution of the pigment to a large amount of poor solvent solution, and a mixing method of the so-called microreactor method in which the strong acid solution of the pigment is kept in contact with the poor solvent to precipitate. For example, as for the mixing method using an ejector, it is similar to the microreactor, in that the strong acid solution of the pigment is kept in contact with the poor solvent to precipitate, so the strong acid concentration during contact is uniform, and because the particles are precipitated at a certain temperature, particles with a narrow particle size distribution can be obtained, and therefore, it is a more preferred mixing method.

[0103] The second step is a step of granulating the pigment obtained in the first step by heating it in an organic solvent or a mixed solution of an organic solvent and water.

[0104] The liquid medium used in the heat treatment is selected to control the blue pigment composition to a target particle size and a narrow particle size distribution. As the liquid medium, an organic solvent or a mixture of an organic solvent and water can be used. As an organic solvent, for example: aromatic compounds such as benzene, toluene, xylene, nitrobenzene, benzoic acid, methyl benzoate, aliphatic hydrocarbon compounds such as heptane, hexane, petroleum ether, mineral spirits, kerosene, alcohols such as isopropyl alcohol, butanol, isobutyl alcohol, heptanol, isoheptanol, diethylene glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, ethers such as tetrahydrofuran, N-methylpyrrolidone, γ-butyrolactone, dimethylformamide, etc. Among them, tetrahydrofuran, methyl benzoate, N-methylpyrrolidone, and γ-butyrolactone with high affinity to copper chloride phthalocyanine are preferred.

[0105] The organic solvent used may be a single organic solvent, a mixed solvent of several organic solvents, or a mixed solution of various organic solvents and water. The mixing ratio may be appropriately set according to the type of organic solvent.

[0106] In addition, the mixed solution of organic solvent and water can also be used in the form of emulsion. The surfactant that can be used in the preparation of emulsion can use any commercially available surfactant. As long as water and organic solvent form an emulsion, any surfactant in nonionic, anionic, cationic, and amphoteric systems can be used. In the present invention, in particular, in terms of having the ability to emulsify methyl benzoate and water and not having an adverse effect on the film suitability, it is preferred to use anionic surfactants as surfactants.

[0107] The temperature and time of the heat treatment are not particularly limited as long as the time is suitable for controlling the particle size distribution to be narrow at the target particle size, and it depends on the type of liquid medium used. Generally, the temperature range is 30 to 150° C. and the time range is 30 minutes to 6 hours.

[0108] A typical application of the blue pigment composition of the present invention is coatings. A resin composition for coatings can be easily prepared if it contains a liquid resin and the pigment composition of the present invention.

[0109] The liquid resin used in the coating resin composition to be colored by the present invention may be natural or synthetic. As the liquid resin, a resin that can form a film is preferred. For example, there are oil varnish, shellac varnish, lacquer, phthalic acid resin, alkyd resin, melamine alkyd resin, epoxy resin, vinyl resin, polyurethane resin, unsaturated polyester resin, acrylic resin, acrylic melamine resin, fluororesin, silicone resin, chlorinated rubber resin, etc. In the present invention, these liquid resins may also be used in combination of two or more.

[0110] In addition, when the pigment composition is dispersed or mixed in a liquid resin to prepare a coating resin composition, conventional additives such as dispersants, fillers, coating additives, desiccants, plasticizers and / or auxiliary pigments may be used. This is achieved by dispersing or mixing each component individually or by adding several components together or all of them at once.

[0111] Examples of the disperser for dispersing the pigment composition include, but are not limited to, known dispersers such as disperser, homomixer, paint conditioner, Scandex, bead mill, attritor, ball mill, double roll, triple roll, and pressure kneader.

[0112] As the additives, known and commonly used ones include Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-170, Disperbyk-171, Disperbyk-174, Disperbyk-180, Disperbyk-182, Disperbyk-183, Disperbyk-185, Disperbyk-2000, Disperbyk-2001 and the like manufactured by BYK Chemie, Solsperse 3000, Solsperse 6000, Solsperse 17000, Solsperse 20000 and the like manufactured by Zeneca, and Flowlen DOPA-22, Flowlen DOPA-17, Flowlen DOPA-28, Flowlen DOPA-30, Flowlen DOPA-31, Flowlen DOPA-32, Flowlen DOPA-33, Flowlen DOPA-34, Flowlen DOPA-35, Flowlen DOPA-36, Flowlen DOPA-37, Flowlen DOPA-38, Flowlen DOPA-39, Flowlen DOPA-40, Flowlen DOPA-41, Flowlen DOPA-42, Flowlen DOPA-43, Flowlen DOPA-44, Flowlen DOPA-45, Flowlen DOPA-46, Flowlen DOPA-47, Flowlen DOPA-48, Flowlen DOPA-49, Flowlen DOPA-50, Flowlen DOPA-51, Flowlen DOPA-52, Flowlen DOPA-53, Flowlen DOPA-54, Flowlen DOPA-55 DOPA-15, FLOWLEN AF-205, FLOWLEN AF-405, FLOWLEN AF-1000, etc.

[0113] The amount of additives relative to the organic pigment varies depending on the requirements of the final coating and is added in a predetermined arbitrary amount. Usually, the additive is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of the organic pigment.

[0114] The amount of additives relative to the liquid resin varies depending on the requirements of the final coating and is added in a predetermined arbitrary amount. Usually, the additive is 0.001 to 4 parts by weight, preferably 0.01 to 2 parts by weight, relative to 100 parts by weight of the liquid resin.

[0115] The amount of the pigment composition relative to the liquid resin varies depending on the requirements of the final coating and is added in a predetermined amount. Generally, the pigment composition is 0.01 to 40 parts by weight, preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of the liquid resin.

[0116] The blue pigment composition of the present invention is used for a coating resin composition, and shows good dispersibility for a wide range of dispersed resin systems. In addition, the obtained coating resin composition has good fluidity, high clarity / high tinting strength, good color mixing stability, and further shows good storage stability, so that it can provide excellent coating in coatings for buildings / building materials, coatings for structures, coatings for ships, coatings for road vehicles, coatings for electrical / mechanical coatings, coatings for metal products, coatings for wood products, coatings for household use, etc.

[0117] Example

[0118] Hereinafter, the present invention will be described in further detail using Examples, Reference Examples, and Comparative Examples.

[0119] In the following examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

[0120] (Calculation method of average chlorine substitution number of copper phthalocyanine chloride)

[0121] As a method for calculating the average chlorine substitution number of copper phthalocyanine chloride,

[0122] The powder of copper chlorophthalocyanine was measured using a fluorescent X-ray analyzer (epsilon 5 manufactured by PANalytical Co., Ltd.) and the average chlorine substitution number of copper chlorophthalocyanine was calculated as follows using the obtained measured value.

[0123] Average chlorine substitution number of copper phthalocyanine chloride = (measured value of chlorine atoms (%) / atomic weight of chlorine) / (measured value of copper atoms (%) / atomic weight of copper)

[0124] In addition to the fluorescent X-ray analysis, the average chlorine substitution number can be calculated by a common measurement method using a mass spectrometer such as FD-MS or TOF-MS, and the same result as that of the fluorescent X-ray analysis can be obtained.

[0125] (Method for measuring average particle size and average aspect ratio of primary particles)

[0126] Regarding the particle size of the blue pigment composition, the particles in the field of view are photographed using a transmission electron microscope, and then the longest length (maximum length) and the shortest length (minimum length) of each particle are obtained based on the 50 primary particles constituting the agglomerate on the two-dimensional image. The average value of the maximum length of each particle is used as the average primary particle size. In addition, the maximum length / minimum length in each particle is obtained, and their average value is used as the average aspect ratio of the primary particle.

[0127] (Brightness L * Determination method of

[0128] On the coated paper printed with black stripes, the blue coating composition was spread with an applicator to obtain a blue coated plate. The color development part on the black stripes of the coated plate was measured using a spectrophotometer (DataColor 650 manufactured by Data Corporation) to calculate the lightness L * The more transparent the pigment is, the more it can reflect the black band of the base. * The smaller.

[0129] (Method for measuring hue of highlights and shadows)

[0130] On a transparent film, the blue coating composition was spread with an applicator to obtain a blue coated plate. The coated plate was placed on black paper with the color development side facing up and measured using a multi-angle spectrophotometer (MA98 manufactured by X-rite Corporation) to calculate the color angle h, chroma C * The device has a light source at an angle of 45° relative to the sample, and when regular reflection is set to 0°, hue evaluation is performed at six light receiving angles of -15° to 110°. The smaller the difference (Δh) between the hue angles h at the light receiving angles of -15° (highlight) and 110° (shadow), the better the angular flop.

[0131] (Synthesis example 1)

[0132] In a 1 L autoclave, 400 ml of T-SOL150 (manufactured by JXTG Energy Co., Ltd.), 66.8 parts of sodium hydrogen 4-chlorophthalate (Tokyo Chemical Industry Co., Ltd.), 74.1 parts of phthalic anhydride (Fujifilm Wako Pure Chemical Industries, Ltd.), 153.9 parts of urea (Fujifilm Wako Pure Chemical Industries, Ltd.), 19.8 parts of copper (I) chloride (Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.45 parts of hexaammonium heptamolybdate tetrahydrate (Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the temperature was raised to 195° C. while stirring, and stirred at 195° C. and 3.5 atmospheres for 2 hours.

[0133] After the reaction solution is naturally cooled to room temperature, the solvent is removed by an evaporator to obtain a crude copper phthalocyanine chloride. In a 3L glass separable flask with a reflux tube, the crude product and 2000 parts of a sulfuric acid (5%) aqueous solution are added, the temperature is raised to 70°C, and stirred at 70°C for 1 hour. Then, it is filtered with a suction filter and repeatedly washed with water until the pH of the filtrate is above 6. Then, it is dried at 90°C for 20 hours and crushed to obtain 109 parts of copper phthalocyanine chloride (1).

[0134] The average number of chlorine substitutions in chlorocopper phthalocyanine (1) was measured by fluorescent X-ray analysis to be 1.48. The proportion of unsubstituted copper phthalocyanine contained in chlorocopper phthalocyanine (1) was measured by FD-MS analysis to be 20%.

[0135] (Synthesis example 2)

[0136] 102 parts of copper phthalocyanine chloride (2) were obtained in the same manner as in Synthesis Example 1 except that 49.0 parts of sodium hydrogen 4-chlorophthalate and 85.9 parts of phthalic anhydride were used.

[0137] The average number of chlorine substitutions in chlorocopper phthalocyanine (2) was 1.12 as determined by fluorescent X-ray analysis, and the proportion of unsubstituted copper phthalocyanine in chlorocopper phthalocyanine (2) was 34% as determined by FD-MS analysis.

[0138] (Synthesis example 3)

[0139] 103 parts of copper phthalocyanine chloride (3) were obtained in the same manner as in Synthesis Example 1 except that 40.1 parts of sodium hydrogen 4-chlorophthalate and 91.8 parts of phthalic anhydride were used.

[0140] The average number of chlorine substitutions in chlorocopper phthalocyanine (3) was measured by fluorescent X-ray analysis to be 0.90. The proportion of unsubstituted copper phthalocyanine contained in chlorocopper phthalocyanine (3) was measured by FD-MS analysis to be 38%.

[0141] (Synthesis Example 4)

[0142] 101 parts of copper phthalocyanine chloride (4) were obtained in the same manner as in Synthesis Example 1 except that 26.7 parts of sodium hydrogen 4-chlorophthalate and 115.5 parts of phthalic anhydride were used.

[0143] The average number of chlorine substitutions in chlorocopper phthalocyanine (4) was measured by fluorescent X-ray analysis to be 0.60. The proportion of unsubstituted copper phthalocyanine contained in chlorocopper phthalocyanine (4) was measured by FD-MS analysis to be 57%.

[0144] (Synthesis Example 5)

[0145] 101 parts of copper phthalocyanine chloride (5) were obtained in the same manner as in Synthesis Example 1 except that 22.3 parts of sodium hydrogen 4-chlorophthalate and 103.7 parts of phthalic anhydride were used.

[0146] The number of chlorine in copper phthalocyanine chloride (5) was measured by fluorescent X-ray analysis to be 0.51. The ratio of unsubstituted copper phthalocyanine contained in copper phthalocyanine chloride (5) was measured by FD-MS analysis to be 68%.

[0147] (Synthesis Example 6)

[0148] 102 parts of copper phthalocyanine chloride (6) were obtained in the same manner as in Synthesis Example 1 except that 13.4 parts of sodium hydrogen 4-chlorophthalate and 109.6 parts of phthalic anhydride were used.

[0149] The number of chlorine in copper phthalocyanine chloride (6) was measured by fluorescent X-ray analysis to be 0.30. The ratio of unsubstituted copper phthalocyanine in copper phthalocyanine chloride (6) was measured by FD-MS analysis to be 67%.

[0150] (Synthesis Example 7)

[0151] 110 parts of copper phthalocyanine chloride (7) were obtained in the same manner as in Synthesis Example 1 except that 89.1 parts of sodium hydrogen 4-chlorophthalate and 59.4 parts of phthalic anhydride were used.

[0152] The number of chlorine in copper phthalocyanine chloride (7) was measured by fluorescent X-ray analysis and was 2.01. The ratio of unsubstituted copper phthalocyanine in copper phthalocyanine chloride (7) was measured by FD-MS analysis and was 5.1%.

[0153] (Synthesis Example 8)

[0154] 100 parts of copper phthalocyanine (8) were obtained in the same manner as in Synthesis Example 1 except that 0 parts of sodium hydrogen 4-chlorophthalate and 118.5 parts of phthalic anhydride were used.

[0155] (Synthesis Example 9)

[0156] 115 parts of copper phthalocyanine chloride (9) were obtained in the same manner as in Synthesis Example 1 except that 142.4 parts of sodium hydrogen 4-chlorophthalate and 23.7 parts of phthalic anhydride were used.

[0157] The number of chlorine in copper phthalocyanine chloride (9) was measured by fluorescent X-ray analysis to be 3.20. The ratio of unsubstituted copper phthalocyanine in copper phthalocyanine chloride (9) was measured by FD-MS analysis to be 0.6%.

[0158] (Production Example 1)

[0159] In a 1L glass separable flask with a reflux tube, 28.5 parts of copper phthalocyanine chloride (1) synthesized in Synthesis Example 1 and 257 parts of sulfuric acid (95%) were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 1 hour. After being cooled to 45°C by natural cooling, the mixture was mixed with 2300 parts of water at 45°C while being sucked with an ejector (resin aspirator) to obtain a sulfuric acid slurry. In a 3L glass separable flask with a reflux tube, the sulfuric acid slurry was added, the temperature was raised to 70°C, the mixture was stirred at 70°C for 1 hour, and then filtered with a suction filter. The mixture was repeatedly washed with water until the pH of the filtrate was 6 or more to obtain a wet cake of copper phthalocyanine chloride (1) (non-volatile content 12%).

[0160] In a 1L glass separable flask with a reflux tube, the entire amount of the wet cake, 1.5 parts of the following pigment derivative (1), and 100 parts of tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) were added, the temperature was raised to 55°C, and the mixture was stirred at 55°C for 2 hours. Then, 19 parts of an aqueous sodium hydroxide solution (25%) (Fujifilm Wako Pure Chemical Industries, Ltd.) and 180 parts of water were added, and the mixture was stirred for 30 minutes. Then, the reflux tube was removed, a Leighton condenser was installed, the temperature was raised to 100°C, and the mixture was stirred at 100°C for 30 minutes to remove the tetrahydrofuran from the pigment slurry.

[0161] After being naturally cooled to room temperature, the mixture was filtered with a suction filter and repeatedly washed with water until the pH of the filtrate was 8 or less. The mixture was then dried at 90° C. for 20 hours and pulverized to obtain 29 parts of a blue pigment composition (1).

[0162] [Chemistry 16]

[0163]

[0164] (Production Example 2)

[0165] 29 parts of a blue pigment composition (2) were obtained in the same manner as in Production Example 1 except that the copper phthalocyanine chloride (1) in Production Example 1 was replaced by copper phthalocyanine chloride (2).

[0166] (Production Example 3)

[0167] 29 parts of a blue pigment composition (3) were obtained in the same manner as in Production Example 1 except that the copper phthalocyanine chloride (1) in Production Example 1 was replaced by copper phthalocyanine chloride (3).

[0168] (Production Example 4)

[0169] 29 parts of a blue pigment composition (4) were obtained in the same manner as in Production Example 3 except that the pigment derivative (1) in Production Example 3 was replaced by the pigment derivative (2).

[0170] [Chemistry 17]

[0171]

[0172] (Production Example 5)

[0173] 29 parts of a blue pigment composition (5) were obtained in the same manner as in Production Example 3 except that the pigment derivative (1) in Production Example 3 was replaced by the pigment derivative (3).

[0174] [Chemistry 18]

[0175]

[0176] (Production Example 6)

[0177] 29 parts of a blue pigment composition (6) were obtained in the same manner as in Production Example 3 except that 1.5 parts of the pigment derivative (1) in Production Example 3 was replaced by 1.0 part of the pigment derivative (1) and 0.5 part of the pigment derivative (2).

[0178] (Production Example 7)

[0179] In a 1L glass separable flask with a reflux tube, 28.5 parts of copper phthalocyanine chloride (3) and 257 parts of sulfuric acid (95%) were added, the temperature was raised to 70°C, and the mixture was stirred at 70°C for 1 hour. After being cooled to 45°C by natural cooling, the mixture was mixed with 2300 parts of water at 45°C while being sucked with an ejector (resin aspirator) to obtain a sulfuric acid slurry. In a 3L glass separable flask with a reflux tube, the sulfuric acid slurry was added, the temperature was raised to 70°C, the mixture was stirred at 70°C for 1 hour, and then filtered with a suction filter. The mixture was repeatedly washed with water until the pH of the filtrate was 6 or more to obtain a wet cake of copper phthalocyanine chloride (3) (non-volatile content 12%).

[0180] 303 parts of water, 15.3 parts of methyl benzoate (Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.46 parts of sodium dioctyl sulfosuccinate (Tokyo Chemical Industry Co., Ltd.) were placed in a 1 L glass beaker and stirred at 10,000 rpm for 10 minutes using a TK homomixer MARKII (manufactured by Primix Co., Ltd.) to prepare an emulsion (1).

[0181] In a 1L glass separable flask with a reflux tube, add the entire amount of the wet cake of the copper phthalocyanine chloride (3), 1.5 parts of the pigment derivative (1), and 500 parts of water, and heat to 85°C. Further, add 64 parts of the emulsion (1), and stir at 85°C for 2 hours. After cooling naturally to room temperature, add 10 parts of an aqueous sodium hydroxide solution (25%), heat to 85°C, and stir at 85°C for 2 hours. Then, confirm that the pH is above 10, cool naturally to room temperature, filter with a suction filter, and repeatedly wash with water until the pH of the filtrate is below 8. Then dry at 90°C for 20 hours and crush to obtain 29 parts of a blue pigment composition (7).

[0182] (Production Example 8)

[0183] 29 parts of a blue pigment composition (8) were obtained in the same manner as in Production Example 1 except that the copper phthalocyanine chloride (1) in Production Example 1 was replaced by the copper phthalocyanine chloride (4).

[0184] (Production Example 9)

[0185] 95 parts of copper phthalocyanine chloride (4), 5 parts of the pigment derivative (1), 700 parts of sodium chloride and 130 parts of diethylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a stainless steel double-arm kneader (2L) and kneaded at 90°C for 6 hours. Then, the mixture was added to 4000 parts of a 70°C hydrochloric acid (0.5%) aqueous solution, stirred for 1 hour to make a slurry, filtered with a suction filter, and repeatedly washed with water until the pH of the filtrate was 6 or more and the conductivity was 200 μS / cm or less, and the sodium chloride and diethylene glycol were removed. Then, it was dried at 90°C for 20 hours and pulverized to obtain 95 parts of a blue pigment composition (9).

[0186] (Production Example 10)

[0187] 29 parts of a blue pigment composition (10) were obtained in the same manner as in Production Example 6 except that the copper phthalocyanine chloride (3) in Production Example 6 was replaced by the copper phthalocyanine chloride (5).

[0188] (Production Example 11)

[0189] 28 parts of a blue pigment composition (11) were obtained in the same manner as in Production Example 6 except that the copper phthalocyanine chloride (3) in Production Example 6 was replaced by the copper phthalocyanine chloride (6).

[0190] (Production Example 12)

[0191] 28 parts of a blue pigment composition (12) were obtained in the same manner as in Production Example 6 except that the copper phthalocyanine chloride (3) in Production Example 6 was replaced by copper phthalocyanine chloride (7).

[0192] (Production Example 13)

[0193] 27 parts of a blue pigment composition (13) were obtained in the same manner as in Production Example 12 except that the pigment derivative (1) in Production Example 12 was replaced by the pigment derivative (4).

[0194] [Chemistry 19]

[0195]

[0196] (Production Example 14)

[0197] 26 parts of a blue pigment composition (14) were obtained in the same manner as in Production Example 12 except that the pigment derivative (1) in Production Example 12 was replaced by the pigment derivative (5).

[0198] [Chemistry 20]

[0199]

[0200] (Production Example 15)

[0201] 29 parts of a blue pigment composition (15) were obtained in the same manner as in Production Example 6 except that copper phthalocyanine (8) was used instead of copper phthalocyanine (3).

[0202] (Production Example 16)

[0203] 28 parts of a blue pigment composition (16) were obtained in the same manner as in Production Example 6 except that the copper phthalocyanine chloride (3) in Production Example 6 was replaced by copper phthalocyanine chloride (9).

[0204] [Table 1]

[0205]

[0206] (Example 1)

[0207] (Preparation of blue coating composition)

[0208] 3.50 parts of the blue pigment composition (1) obtained in Production Example 1, 17.5 parts of ACRYDIC 47-712 (manufactured by DIC Corporation), 19.3 parts of xylene, and 6.4 parts of n-butanol were mixed and dispersed in Scandex (manufactured by FAST & FLUID Co., Ltd.) for 4 hours. Then, 41.5 parts of ACRYDIC 47-712, 12.3 parts of Super Beckamine L-117-60 (manufactured by DIC Corporation), 9.8 parts of xylene, and 3.2 parts of n-butanol were mixed and dispersed in Scandex for 10 minutes to prepare a blue coating composition (1).

[0209] (Production of coated boards)

[0210] The obtained blue coating composition (1) was applied on coated paper printed with black stripes using a 6 mil applicator, and dried in a constant temperature dryer adjusted to 130° C. for 15 minutes to obtain a blue coated plate (1-1). In addition, the obtained blue coating composition (1) was applied on a transparent film using a 4 mil applicator, and dried in a constant temperature dryer adjusted to 130° C. for 15 minutes to obtain a blue coated plate (1-2).

[0211] The L of the blue coated plate (1-1) obtained in Example 1 * is 1.8, and the blue coated plate (1-2) has a light receiving angle of -15° of 272.7. * is 30.7, and h is 290.7 when the light receiving angle is 110°. * is 21.7, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 18.0.

[0212] (Example 2)

[0213] A blue coated plate (2-1) and a blue coated plate (2-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (2).

[0214] The L of the blue coated plate (2-1) obtained in Example 2 * is 1.9, and the blue coated plate (2-2) has a light receiving angle of -15° of h of 272.7, C * is 30.7, h is 291.5 when the light receiving angle is 110°, C * is 22.0, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 18.8.

[0215] (Example 3)

[0216] A blue coated plate (3-1) and a blue coated plate (3-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (3).

[0217] The L of the blue coated plate (3-1) obtained in Example 3 * is 2.0, and the blue coated plate (3-2) has a light receiving angle of -15° of 275.9, C * is 30.2, h is 292.6 when the light receiving angle is 110°, C * It is 23.9, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 16.7.

[0218] (Example 4)

[0219] A blue coated plate (4-1) and a blue coated plate (4-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (4).

[0220] The L of the blue coated plate (4-1) obtained in Example 4 * is 2.2, and the blue coated plate (4-2) has a light receiving angle of -15° of 278.4. * is 31.3, h is 292.9 when the light receiving angle is 110°, C * It is 24.6, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 14.6.

[0221] (Example 5)

[0222] A blue coated plate (5-1) and a blue coated plate (5-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (5).

[0223] The L of the blue coated plate (5-1) obtained in Example 5 * is 2.1, and the blue coated plate (5-2) has a light receiving angle of -15° of 281.2. * is 29.4, h is 292.5 when the light receiving angle is 110°, C * is 26.0, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 11.4.

[0224] (Example 6)

[0225] A blue coated plate (6-1) and a blue coated plate (6-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (6).

[0226] The L of the blue coated plate (6-1) obtained in Example 6 * is 2.1, and the blue coated plate (6-2) has a light receiving angle of -15° of 277.0, C * is 30.7, h is 292.7 when the light receiving angle is 110°, C * is 24.0, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 15.7.

[0227] (Example 7)

[0228] A blue coated plate (7-1) and a blue coated plate (7-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (7).

[0229] The L of the blue coated plate (7-1) obtained in Example 7 * is 1.7, and the blue coated plate (7-2) has a light receiving angle of -15° of 268.4. * is 31.0, h is 292.4 when the light receiving angle is 110°, C * is 21.6, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 24.0.

[0230] (Example 8)

[0231] A blue coated plate (8-1) and a blue coated plate (8-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (8).

[0232] The L of the blue coated plate (8-1) obtained in Example 8 * is 1.7, and the blue coated plate (8-2) has a light receiving angle of -15° of 276.9, C * is 31.9, h is 294.4 when the light receiving angle is 110°, C * is 25.1, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 17.5.

[0233] (Example 9)

[0234] A blue coated plate (9-1) and a blue coated plate (9-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (9).

[0235] The L of the blue coated plate (9-1) obtained in Example 9 * is 1.5, and the blue coated plate (9-2) has a light receiving angle of -15° of 277.4, C * is 27.7, h is 295.5 when the light receiving angle is 110°, C * is 25.9, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 18.1.

[0236] (Example 10)

[0237] A blue coated plate (10-1) and a blue coated plate (10-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (10).

[0238] The L of the blue coated plate (10-1) obtained in Example 10 * is 1.9, and the blue coated plate (10-2) has a light receiving angle of -15° of 270.4, C * is 30.9, h is 294.5 when the light receiving angle is 110°, C * is 25.6, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 24.1.

[0239] (Example 11)

[0240] A blue coated plate (11-1) and a blue coated plate (11-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (11).

[0241] The L of the blue coated plate (11-1) obtained in Example 11 * is 1.7, and the blue coated plate (11-2) has a light receiving angle of -15° of 271.0, C * is 40.7, h is 295.0 when the light receiving angle is 110°, C * is 27.1, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 24.0.

[0242] (Example 12)

[0243] A blue coated plate (12-1) and a blue coated plate (12-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (12).

[0244] The L of the blue coated plate (12-1) obtained in Example 12 * is 2.0, and the blue coated plate (12-2) has a light receiving angle of -15° of 265.6, C * is 30.5, h is 291.6 when the light receiving angle is 110°, C * is 23.9, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 25.9.

[0245] (Example 13)

[0246] A blue coated plate (13-1) and a blue coated plate (13-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (13).

[0247] The L of the blue coated plate (13-1) obtained in Example 13* is 2.0, and the blue coated plate (13-2) has a light receiving angle of -15° of 263.4, C * is 29.3, h is 290.1 ​​when the light receiving angle is 110°, C * is 24.4, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 25.7.

[0248] (Example 14)

[0249] A blue coated plate (14-1) and a blue coated plate (14-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (14).

[0250] The L of the blue coated plate (14-1) obtained in Example 14 * is 2.0, and the blue coated plate (14-2) has a light receiving angle of -15° of 265.0, C * is 29.4, h is 290.3 when the light receiving angle is 110°, C * is 24.0, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 25.3.

[0251] (Comparative Example 1)

[0252] A blue coated plate (15-1) and a blue coated plate (15-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (15).

[0253] The L of the blue coated plate (15-1) obtained in Comparative Example 1 * is 2.3, the blue coated plate (15-2) has a light receiving angle of -15° and h is 262.6, C * is 42.7, h is 298.2 when the light receiving angle is 110°, C * It is 31.7, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 35.6.

[0254] (Comparative Example 2)

[0255] A blue coated plate (16-1) and a blue coated plate (16-2) were obtained in the same manner as in Example 1 except that the blue pigment composition (1) in Example 1 was replaced by the blue pigment composition (16).

[0256] The L of the blue coated plate (16-1) obtained in Comparative Example 2 * is 2.3, and the blue coated plate (16-2) has a light receiving angle of -15° of 255.0, C* is 25.8, h is 291.7 when the light receiving angle is 110°, C * is 22.4, and the difference Δh between the hue angles h at the light receiving angles of -15° and 110° is 36.7.

[0257] [Table 2]

[0258]

[0259] Although Examples 1, 2, 3, 8, 10, 11 and 12 and Comparative Example 1 used the pigment derivative (1), the average chlorine substitution number of copper phthalocyanine was different. In Examples 1, 2, 3, 8, 10, 11 and 12, where the average chlorine substitution number was 0.3 to 2.0, the pigment particles were difficult to grow due to the presence of copper phthalocyanine chloride, and the aspect ratio and average particle size were very small. Therefore, the h and L of the shadow were * They are all very small and are suitable as pigments for automotive coatings.

[0260] The shadow of Comparative Example 1, in which the average number of chlorine substitutions is 0, is redder than that of Examples 1, 2, 3, 8, 10, 11, and 12. In addition, since there is no chlorine substitution in the copper phthalocyanine, the pigment particles grow easily. Therefore, the aspect ratio and average particle size are increased, and Δh and L * Therefore, Comparative Example 1 is not suitable for a blue pigment for automotive coatings.

[0261] Although Examples 7, 10, 11 and 12 and Comparative Example 2 were prepared under the same conditions, the average chlorine substitution number of copper phthalocyanine was different. In Examples 7, 10, 11 and 12, where the average chlorine substitution number was 0.3 to 2.0, the pigment particles were difficult to grow due to the inclusion of copper phthalocyanine chloride, and the aspect ratio and average particle size were very small, so that the reddish shadow caused by the scattered light of the coarse pigment particles could be suppressed.

[0262] In Comparative Example 2, the average number of chlorine substituents of copper phthalocyanine is as high as 3.2, so the h of highlights and shadows is very small, and the color of the pigment itself is green. Therefore, Comparative Example 2 is not suitable for blue pigments for automotive coatings.

[0263] Examples 3, 4, 5 and Examples 12, 13, and 14 are samples prepared under the same conditions except that the types of pigment derivatives are different. * They are all very small and are suitable as pigments for automotive coatings.

[0264] Example 6 is a sample produced under the same conditions as Examples 3 and 4 except that a pigment derivative is used in combination. * They are all very small and are suitable as pigments for automotive coatings.

[0265] Examples 12, 13, and 14 are samples prepared under the same conditions except that the types of pigment derivatives are different. * They are all very small and are suitable as pigments for automotive coatings.

[0266] Examples 3 and 7 are samples made under the same conditions except for the different pigmentation methods. * They are all very small and are suitable as pigments for automotive coatings.

Claims

1. A blue pigment composition, characterized in that A pigment derivative comprising copper phthalocyanine chloride having an average chlorine substitution number of 0.3 to 2.2, and at least one hydrogen atom in the benzene ring of the copper phthalocyanine is substituted with at least one of a group represented by the following general formula (1), a group represented by the following general formula (2), a group represented by the following general formula (3), a group represented by the following general formula (4), or a group represented by the following general formula (5), wherein the average aspect ratio of the primary particles of the copper phthalocyanine chloride is 1.0 to 3.5, [Chemistry 1] [Chemistry 2] [Chemistry 3] -SO3R5(4) [Chemistry 4] In formulae (1) to (5), a and b are each independently an integer of 1 to 10, R1, R2, R3, R4, R5, R6 and R7 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and X1 and X2 are each independently a single bond, an arylene group, -NH-, -O- or -S-.

2. The blue pigment composition according to claim 1, characterized in that When converted by weight, the pigment derivative is contained in an amount of more than 1 part and 15 parts or less per 100 parts of the copper phthalocyanine chloride.

3. The blue pigment composition according to claim 1 or 2, characterized in that: The average primary particle size of the copper phthalocyanine chloride is 20 to 60 nm.

4. A coating, characterized in that: A blue pigment composition comprising the blue pigment composition according to any one of claims 1 to 3.

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