CN113302241A

CN113302241A - Blue pigment composition

Info

Publication number: CN113302241A
Application number: CN201980088972.1A
Authority: CN
Inventors: 柴野隆; 河村彩香; 胜部浩史
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2019-01-18
Filing date: 2019-11-28
Publication date: 2021-08-24
Also published as: JP6852839B2; WO2020149024A1; JPWO2020149024A1

Abstract

A blue pigment composition which gives a greenish shade when used as a coloring material for paints and is excellent in transparency. The present inventors have found that when a blue pigment composition containing a copper chloride phthalocyanine having a specific average number of chlorine substitutions and a specific copper phthalocyanine pigment derivative is used as a coloring material for a coating material, a coated sheet having a greenish hue and a shaded hue, good dispersibility and high transparency can be obtained, and have completed the present invention.

Description

Blue pigment composition

Technical Field

The present invention relates to a blue pigment composition containing a copper phthalocyanine chloride pigment or a pigment derivative and suitably usable mainly as an automotive coating material, and a coating material containing the same.

Background

Conventionally, as a blue organic pigment having excellent fastness, phthalocyanine compounds having a phthalocyanine structure represented by copper phthalocyanine have been widely used as coloring materials in various applications represented by paints, plastics, toners, and inkjet inks.

Further, it is known that the color tone of copper phthalocyanine varies depending on the number of chlorine atoms present in the molecule, and as the number of chlorine increases, the color shifts from reddish blue to green through greenish blue. In particular, as a blue pigment for an automobile paint, a chlorinated copper phthalocyanine having a chlorine number of 1 to 4 is frequently used, and in the automobile industry of japan, a reddish blue color using a monochloro copper phthalocyanine having a chlorine number of 1 is preferred.

Further, the hue of the monochloro copper phthalocyanine pigment is observed to vary depending on the angle of vision, and particularly, there is a problem that the red color is excessively strong in a region called a shadow. In addition to the hue, the characteristics of the pigment such as transparency and dispersibility are also important as a pigment for an automobile coating material.

Cited document 1 proposes a pigment composition containing unsubstituted copper phthalocyanine and a pigment derivative of copper phthalocyanine, but the pigment composition has different hues and is also poor in transparency and dispersibility.

In the cited document 2, a chlorinated copper phthalocyanine pigment composition in which monochloro copper phthalocyanine and copper phthalocyanine are mixed is proposed, but transparency and dispersibility are not good.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 1-70568

Patent document 2: japanese laid-open patent publication No. 9-59531

Disclosure of Invention

Problems to be solved by the invention

The invention aims to provide a blue pigment composition which has greenish shade hue and excellent transparency when used as a coloring material of a coating.

Means for solving the problems

The present inventors have conducted intensive studies on copper chloride phthalocyanine and as a result, have found that when a pigment composition containing copper chloride phthalocyanine having a specific average number of chlorine substitution and a specific copper phthalocyanine pigment derivative is used as a coloring material for coating materials, the shade hue is greenish and a coated plate having excellent transparency can be obtained, and have completed the present invention.

Namely, the present invention provides:

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

[ solution 1]

[ solution 2]

[ solution 3]

-SO₃R₅(4)

[ solution 4]

[ in formulas (1) to (5), a and b are each independently an integer of 1 to 10, R₁、R₂、R₃、R₄、R₅、R₆And R₇Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and X₁And X₂Each independently represents a single bond, arylene, -NH-, -O-or-S-.]

[2] The blue pigment composition according to the above [1], wherein the pigment derivative is contained in an amount of more than 1 part by weight and 15 parts by weight or less per 100 parts by weight of the copper phthalocyanine chloride.

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

[4] A paint which is characterized by containing the blue pigment composition according to any one of the above-mentioned [1] to [3 ].

Effects of the invention

The content of unsubstituted copper phthalocyanine is reduced by setting the average number of chlorine substitution of the chlorinated copper phthalocyanine to 0.3 to 2.2, and the crystal growth of pigment particles can be relatively easily suppressed without being greatly affected by the pigmentation method by using a specific pigment derivative in combination. As a result, primary particles having an aspect ratio of approximately 1 can be obtained, and excellent pigments can be obtained in that transparency having better characteristics can be obtained as the aspect ratio is smaller. Further, when the average number of chlorine substitution of the copper chloride phthalocyanine is 0.3 to 2.2, the color development of the pigment itself is greenish, and the shade hue becomes greenish.

As a result, a pigment having excellent hue and transparency of a shade, which are important characteristics of a pigment composition for an automobile coating material, can be produced.

When the blue pigment composition of the present invention is used as a coloring material for coating, a coated plate with green shading and excellent transparency can be obtained.

Detailed Description

The present invention is most characterized by containing a copper phthalocyanine chloride having a specific average number of chlorine substitution and a specific copper phthalocyanine pigment derivative.

< chlorinated copper phthalocyanine >

The copper phthalocyanine chloride used in the present invention can be obtained by a known and customary method. Examples thereof are as follows.

First, copper phthalocyanine chloride can be produced by the following method: the Wyler method in which chlorinated phthalic anhydride in which a part of hydrogen atoms in an aromatic ring of phthalic anhydride is substituted with chlorine is reacted with urea and a copper or copper compound, and the phthalonitrile method in which chlorinated phthalonitrile in which a part of hydrogen atoms in an aromatic ring is substituted with chlorine is reacted with copper or a copper compound in a high boiling solvent.

As another production method, a chlorination method using a chlorosulfonic acid method is known. Examples thereof include a method of dissolving copper phthalocyanine in a sulfur oxide-based solvent such as chlorosulfonic acid, and adding chlorine gas thereto to perform halogenation. The reaction is carried out at a temperature of 20 to 120 ℃ for 3 to 20 hours.

Further, as a chlorination method, a melting method is known. The melting method includes a method of chlorinating copper phthalocyanine with a chlorinating agent in a melt of about 10 to 170 ℃ composed of one or a mixture of two or more compounds as a solvent in chlorination, such as titanium halide such as aluminum chloride and titanium tetrachloride, alkali metal chloride or alkaline earth metal chloride such as sodium chloride, thionyl chloride, and the like.

Used in the present invention is copper chloride phthalocyanine synthesized by the Wyler method. Typical production conditions are described below.

The Wyler method is a phthalocyanine synthesis method in which phthalic anhydride or a derivative thereof and urea or a derivative thereof are reacted at 90 to 300 ℃ in the presence of a metal source and a catalyst, and is the most industrially used method as a phthalocyanine synthesis method. In the synthesis, a solvent may be used for the purpose of controlling the temperature in the system, improving the stirring efficiency, and the like. In addition, the reaction may be carried out under a pressure of about 0.2 to 0.7MPa for the purpose of improving the yield, improving the purity, and the like.

Examples of phthalic acids used in the synthesis by the Wyler method include phthalic anhydride, phthalic acid and salts thereof, esters thereof, phthalimide, and phthalic acid amide. Furthermore, phthalic acids having a substituent such as an alkyl group, an aryl group, a nitro group, a sulfo group, a sulfonamide group, a cyano group, an amino group, a hydroxyl group, a carboxyl group, a thio group, an acyl group, a siloxy group, a silyl group, a halogen group, or a substituent derived therefrom may be contained in the aromatic ring of these compounds. In the present invention, these phthalic acids and chlorinated phthalic acids are mixed at an arbitrary ratio and synthesized by the Wyler method, whereby copper chloride phthalocyanine having an average number of chlorine substitution at an arbitrary ratio is synthesized. In the production of the copper chloride phthalocyanine of the present invention, it is preferable to use sodium 3-chlorophthalic acid, sodium 4-chlorophthalic acid, 3-chlorophthalic anhydride, or 4-chlorophthalic anhydride as a part of the raw material.

Examples of urea or its derivative used for synthesizing phthalocyanines by the Wyler method include urea, ammonia, biuret, and triurea. The amount of the compound to be used is about 1 to 10 moles based on 1 mole of phthalic anhydride or a derivative thereof. As the metal source, metal powder, chloride, bromide, iodide, sulfate, sulfide, acetate, oxide, hydroxide, carbonate, phosphate, or the like can be used. The valence number of the metal, although it affects the reaction, can be generally used for phthalocyanine synthesis. As for the amount of the metal source used, it is preferably used in the range of 0.15 to 0.40 in terms of a molar ratio relative to phthalic acid or a derivative thereof. As the catalyst, any of the catalysts known in the Wyler method can be used. Examples of the inorganic filler include molybdenum oxide compounds such as ammonium molybdate, ammonium oxide and phosphomolybdic acid, titanium compounds such as titanium tetrachloride and titanate, antimony oxide, arsenic oxide and boric acid. The amount of the phthalic acid derivative is not particularly limited, and is preferably in the range of 0.0001 to 0.3 in terms of a weight ratio to the phthalic acid derivative. For the purpose of improving reactivity, product purity, clarity, etc., orthophosphoric acid, metaphosphoric acid, polyphosphoric acid, polymetaphosphoric acid, sulfuric acid, hydrochloric acid, hydrogen bromide, hydrogen iodide, and metal salts and ammonium salts thereof may be added in a molar ratio of 0.05 to 1 mole relative to phthalic acid or a derivative thereof.

As the solvent to be used, any known solvent for the Wyler method can be used. For example, aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene, and tetralin, alicyclic hydrocarbons such as alkylcyclohexane, decalin, and alkyldecalin, aliphatic hydrocarbons such as decane and dodecane, nitro compounds such as nitrobenzene and o-nitrotoluene, halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene, chloronaphthalene, and hexachlorobutadiene, sulfur compounds such as sulfolane, dimethylsulfolane, and dimethylsulfoxide, and heterocyclic compounds such as quinoline can be used. These organic solvents may be a mixture of 2 or more kinds.

After the reaction is completed, it is preferable to perform a treatment such as solvent filtration or solvent distillation for separation from the reaction solvent, and then wash the reaction product with water or an organic solvent. For washing, an acid or a base may be used. If further purification is necessary, impurities can be removed by sublimation, acid gelatinization (アシッドペースト), slurrying (アシッドスラリー), reprecipitation, recrystallization, extraction, and the like, which are known purification techniques.

In addition, the copper chloride phthalocyanine of the present invention is a mixture of 1 to 5 chlorine-substituted copper chloride phthalocyanines in 1 molecule and unsubstituted copper phthalocyanines without chlorine substitution. The average number of chlorine substitutions of the copper phthalocyanine chloride was identified by a fluorescent X-ray analyzer or a mass spectrometer (FD-MS, TOF-MS). In the method for producing a copper chloride phthalocyanine, the average chlorine substitution number distribution of the copper chloride phthalocyanine obtained by the Wyler method or the nitrile method is narrow. On the other hand, the average chlorine substitution number distribution of chlorinated copper phthalocyanine obtained by a synthetic method such as chlorosulfonic acid in which copper phthalocyanine is melted and chlorinated tends to be generally large due to the origin of the chlorination starting material and the reaction conditions.

The average number of chlorine substitutions of the copper chloride phthalocyanine of the present invention is preferably 0.3 to 2.0, and more preferably 0.5 to 1.6. If the average number of chlorine substitutions is too high, the hue becomes excessively green and exceeds the desired hue; on the other hand, if the average number of chlorine substitution is too low, the hue becomes reddish, and not only does it exceed the desired hue, but also the average aspect ratio of the primary particles becomes large as described below, and transparency is lowered.

The average primary particle diameter of the copper chloride phthalocyanine of the present invention is preferably 20 to 60nm, and if the average primary particle diameter is too small, dispersibility of the coating material is poor and the coating material cannot be sufficiently dispersed. When the average primary particle size is too large, the properties such as transparency and coloring power are deteriorated.

The average aspect ratio is preferably 1.0 to 3.5, and the color, transparency and dispersibility are good. When the average aspect ratio is too large, the characteristics such as transparency, dispersibility, and coloring power are deteriorated.

In the present invention, the color measurement in the highlight region by the multi-angle spectrocolorimeter is a color measurement at a light receiving angle near the regular reflection light (specifically, -15 ° when the regular reflection light is set to 0 °), and the color measurement in the shadow region by the multi-angle spectrocolorimeter is a color measurement at a light receiving angle at which the intensity of the reflection light away from the regular reflection light is small (specifically, 110 ° when the regular reflection light is set to 0 °). As a method for making the shade hue greenish, there is a method of making the pigment itself develop a green color by reducing the average primary particle diameter of the pigment, reducing reddish scattered light, and increasing the average number of chlorine substitutions of copper chloride phthalocyanine.

< copper phthalocyanine pigment derivative >

Next, the copper phthalocyanine pigment derivative of the present invention will be explained. 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 with at least one group selected from the group 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) and the group represented by the general formula (5), and is synthesized by a known and publicly known method.

The pigment derivative in which at least one hydrogen atom in the benzene ring of the copper phthalocyanine is substituted with a substituent represented by the general formula (1) is a basic pigment derivative. By using the pigment in the pigmentation treatment, excessive crystal growth of the pigment is suppressed. In addition, they are frequently used in pigment compositions for coatings to improve the viscosity stability of the coatings.

[ solution 5]

[ in the general formula (1), a is independently an integer of 1 to 10, R₁、R₂Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.]

The pigment derivative in which at least one hydrogen atom in the benzene ring of the copper phthalocyanine is substituted with a substituent represented by the general formula (2) is a basic pigment derivative. By using the pigment in the pigmentation treatment, excessive crystal growth of the pigment is suppressed. In addition, they are frequently used in pigment compositions for coatings to improve the viscosity stability of the coatings.

[ solution 6]

[ in the general formula (2), b is independently an integer of 1 to 10, R₃、R₄Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.]

The pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted by a substituent represented by the general formula (3) is known to have an effect as a crystal growth inhibitor for copper phthalocyanine, and is often contained in a phthalocyanine pigment for color filter and a phthalocyanine pigment for toner which require a small particle diameter. It is presumed that, in the present invention, not only the effect of reducing the particle size and suppressing the crystal growth is obtained in the same manner as the above-mentioned effects, but also the non-uniform distribution of the primary particle size of the pigment is suppressed to suppress scattered light, thereby making the shade green.

[ solution 7]

The pigment derivative in which at least one hydrogen atom in the benzene ring of the copper phthalocyanine is substituted with a substituent represented by the general formula (4) is used in the pigmenting treatment, thereby suppressing excessive crystal growth of the pigment. In addition, it is commonly used in pigment compositions for plastics, and has an effect of improving dispersibility. It is presumed that, in the present invention, not only the effect of reducing the particle size and suppressing the crystal growth is obtained as in the above-mentioned effects, but also the uneven distribution of the primary particle size of the pigment is suppressed to suppress scattered light, thereby making the shade green.

-SO₃R₅ (4)

[ in the general formula (4), R₅Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent.]

The pigment derivative in which at least one hydrogen atom in the benzene ring of copper phthalocyanine is substituted by a substituent represented by the general formula (5) is known to have an effect as a crystal growth inhibitor for copper phthalocyanine, and is often contained in a phthalocyanine pigment for color filter and a phthalocyanine pigment for toner which require a small particle diameter. It is presumed that, in the present invention, not only the effect of reducing the particle size and suppressing the crystal growth is obtained as in the above-mentioned effects, but also the uneven distribution of the primary particle size of the pigment is suppressed to suppress scattered light, thereby making the shade green.

[ solution 8]

[ in the general formula (5), R₆And R₇Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and X₁And X₂Each independently represents a single bond, arylene, -NH-, -O-or-S-.]

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

Further, a plurality of copper phthalocyanine pigment derivatives may be used in combination.

Examples of the copper phthalocyanine pigment derivative used in the present invention include compounds represented by the following formulae (4-1) to (4-7), but it is needless to say that the compounds are not limited thereto.

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

[ solution 13]

[ solution 14]

[ solution 15]

Since the pigment derivative has a large substituent structure, the number of substituents in 1 molecule is at most 5 in a general synthesis method. The average number of substituents of the substituents represented by the general formulae (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.

In the blue pigment composition of the present invention, the amount of the pigment derivative added to the copper chloride phthalocyanine is preferably more than 1 part by weight and 15 parts by weight or less based on 100 parts by weight of the copper chloride phthalocyanine, and more preferably 1 to 10 parts by weight, in order to control the shade hue so that the color change due to the pigment derivative does not occur as much as possible.

It is known that the growth rate of pigment particles is generally the fastest for unsubstituted copper phthalocyanine and slower for chlorinated copper phthalocyanine as the number of chlorine substitutions increases. The copper chloride phthalocyanine of the present invention is a mixture of 1 molecule of copper chloride phthalocyanine having 1 to 5 chlorine substitutions and non-substituted copper phthalocyanine having no chlorine substitution, and therefore, in the process of producing a pigment, the growth rate of pigment particles is different in each compound, and pigment particles having particles of different sizes are easily formed, which is presumed to be one of the causes of poor scattering depending on the visual angle and reddening of the shaded region. In this connection, it is presumed that the specific copper phthalocyanine pigment derivative used in the present invention has a particularly high crystal growth inhibitory effect, and therefore, even in copper chloride phthalocyanine composed of a plurality of compounds having different growth rates, pigment composition particles having a narrow particle size distribution and a small number of coarse particles can be obtained, and as a result, when used as a coloring material for coating materials, a coated sheet having a green shade and excellent transparency can be obtained.

The blue pigment composition of the present invention can be controlled in hue and dispersibility simply by mixing the copper phthalocyanine chloride and the copper phthalocyanine pigment derivative, but in order to make both substances uniform on a molecular level, the both substances are once mixed, dissolved and precipitated, whereby a pigment composition uniform on a molecular level can be produced.

The particle diameter of the blue pigment composition of the present invention is obtained by taking a picture of particles in a field of view with a Transmission Electron Microscope (TEM), and then determining the longest length (maximum length) and the shortest length (minimum length) of each particle based on 50 primary particles constituting an aggregate on a two-dimensional image. The average of the maximum lengths of the respective particles was defined as an average primary particle diameter. The maximum length/minimum length of each particle is determined, and the average value of the maximum length/minimum length is defined as the average aspect ratio of the primary particles.

The average primary particle size of the blue pigment composition of the present invention is preferably 20 to 60nm, and when the average primary particle size is too small, dispersibility in a paint is poor and the paint cannot be sufficiently dispersed. When the average primary particle size is too large, the properties such as transparency and coloring power are deteriorated.

< method for producing blue pigment composition of the present invention >

As an example, a method of obtaining the blue pigment composition of the present invention is described. In the following, a more suitable pigment composition is described, but the method for obtaining the blue pigment composition of the present invention is not to be construed in a limiting manner.

For example, a blue pigment composition can be obtained by the following steps: a first step of dissolving a pigment in a good solvent, and then bringing the solution into contact with a poor solvent to precipitate the pigment, thereby micronizing the pigment particles; and a second step of heating the pigment obtained in the first step in an organic solvent or a mixed solution of an organic solvent and water to granulate the pigment.

The first step is a step of dissolving the pigment in a good solvent, and then bringing the solution into contact with a poor solvent to precipitate the pigment, thereby micronizing the pigment particles. The pigment is prepared by dissolving the copper phthalocyanine chloride in 50 to 10000 parts by weight of a strong acid at 0 to 90 ℃ completely or partially (acid gelatinization, acid slurrying, and acid swelling depending on the acid concentration), and then mixing the resulting solution with a poor solvent to precipitate pigment particles.

As the strong acid, sulfuric acid, hydrochloric acid, nitric acid may be used. Among them, sulfuric acid is preferable in view of cost, handling property, and mass productivity. The acid concentration of sulfuric acid is 70% to 100% (anhydrous sulfuric acid) at which the phthalocyanine pigment is soluble. Among them, the concentration at which the pigment can be completely dissolved is preferably 90% or more.

When the pigment strong acid solution is mixed with the poor solvent, the amount of the poor solvent is required to sufficiently precipitate the pigment, and 50 to 10000 parts by weight per 100 parts by weight of the strong acid solution is used.

The poor solvent may be any solvent as long as the pigment precipitates due to a decrease in the acid concentration, and in the present invention, water or a mixed solvent of water and 1 to 300 parts by weight of an organic solvent with respect to 100 parts by weight of water may be used. As the organic solvent, either water-soluble or water-insoluble organic solvents can be used. In the case of water-insoluble solvents such as alcohols, glycols, ketones, hydrocarbons, etc., the water-insoluble solvents can be mixed with water by stirring at high speed or emulsifying by adding an emulsifier or a surfactant.

The method for mixing the pigment strong acid solution and the poor solvent may be a known and commonly used method, and the strong acid solution may be taken out into the poor solvent, or vice versa. For example, there are a method of adding a strongly acidic solution of a pigment slowly to a large amount of a poor solvent solution, and a mixing method of a so-called microreactor system in which a strongly acidic solution of a pigment is precipitated by being constantly brought into contact with a poor solvent. For example, the mixing method using an ejector is more preferable because the strong acid concentration at the time of contact is uniform because the strong acid solution of the pigment and the poor solvent are always brought into contact and precipitated as in the case of the microreactor, and because the particles are precipitated at a constant temperature, the particles having a narrow particle size distribution can be obtained.

The second step is a step of heating the pigment obtained in the first step in an organic solvent or a mixed solution of an organic solvent and water to granulate the pigment.

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

The organic solvent used may be a single solvent, a mixture of a plurality of kinds of solvents, or a mixture of various organic solvents and water. The mixing ratio thereof may be appropriately set according to the kind of the organic solvent.

Further, a mixed solution of an organic solvent and water may be used in the form of an emulsion. Any commercially available surfactant can be used as the surfactant used in the emulsion preparation. Any surfactant of nonionic, anionic, cationic and amphoteric systems may be used as long as water forms an emulsion with the organic solvent. In the present invention, it is preferable to use an anionic surfactant as the surfactant, particularly in view of having an ability to emulsify methyl benzoate and water and not adversely affecting the coating suitability.

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 depend on the type of the liquid medium used. Generally, the temperature is in the range of 30-150 ℃ and the time is in the range of 30 minutes-6 hours.

A representative use of the blue pigment compositions of the present invention is in coatings. A resin composition for coating materials can be easily prepared by adding a liquid resin and the pigment composition of the present invention.

The liquid resin used in the resin composition for coating to be colored by the present invention may be natural or synthetic. The liquid resin is preferably a resin capable of forming a coating film. Examples of the resin include varnish, shellac varnish, raw lacquer, phthalic acid resin, alkyd resin, melamine alkyd resin, epoxy resin, vinyl resin, polyurethane resin, unsaturated polyester resin, acrylic melamine resin, fluorine resin, silicone resin, and chlorinated rubber resin. In the present invention, two or more of these liquid resins may be used in combination.

In addition, when the pigment composition is dispersed or mixed in a liquid resin to prepare a resin composition for coating, usual additives such as dispersants, fillers, coating aids, desiccants, plasticizers and/or auxiliary pigments can be used. This is achieved by: dispersing or mixing the ingredients individually or several together and collecting all the ingredients, or adding all of them at once.

Examples of the dispersing machine for dispersing the pigment composition include known dispersing machines such as a disperser, a homomixer, a paint conditioner, a Scandex, a bead mill, a ball mill, a double roll, a triple roll, and a pressure kneader, but are not limited thereto.

As the additives, known and commonly used 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, Solsperse 3000, Solspeser 6000, Solspeser 17000, Solspeser 20000 and the like, which are manufactured by WLWLN, FLOWLDOPA-22, FLOWLEN A-17, FLOEN-15, FLOEN AF-205, FLOEN-405, FLOEN AF-1000 and the like, which are manufactured by BYK Chemie.

The amount of the additive to the organic pigment varies depending on the requirements of the end-use coating material, and is added in an arbitrary amount as specified. The additive is usually 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the organic pigment.

The amount of the additive to the liquid resin varies depending on the requirements of the end-use coating material, and is added in an arbitrary amount as specified. Generally, the additive is 0.001 to 4 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight of the liquid resin.

The amount of the pigment composition to the liquid resin varies depending on the requirements of the end-use coating material, and is added in an arbitrary amount as specified. Generally, the pigment composition is 0.01 to 40 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the liquid resin.

The blue pigment composition of the present invention is used for a resin composition for coating, and exhibits good dispersibility in a wide range of dispersion resin systems. Further, the obtained resin composition for coating is excellent in fluidity, high in definition and tinting strength, excellent in color mixing stability, and further excellent in storage stability, and thus can provide excellent coating in a coating for building/construction material, a coating for structure, a coating for ship, a coating for road vehicle, a coating for electric/mechanical equipment, a coating for metal product, a coating for wood product, a coating for household use, and the like.

Examples

The present invention will be described in further detail below with reference to examples, reference examples and comparative examples.

In the following examples, "part" and "%" represent "part by weight" and "% by weight", respectively, unless otherwise specified.

(method of calculating the number of average chlorine substitution of copper chloride phthalocyanine)

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

the powder of chlorinated copper phthalocyanine was measured with a fluorescent X-ray analyzer (epsilon 5, product of PANALYTICAL CO., LTD.). Then, the obtained measurement value was used to calculate as the average number of chlorine substitution of copper chloride phthalocyanine as follows.

The average number of substitution with chlorine of copper chloride phthalocyanine ═ chlorine atom measurement value (%)/chlorine atom amount)/(copper atom measurement value (%)/copper atom amount)

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

(method of measuring average particle diameter and average aspect ratio of Primary particles)

The particle diameter of the blue pigment composition was photographed by a transmission electron microscope using particles in a visual field, and then the longest length (maximum length) and the shortest length (minimum length) of each particle were determined based on 50 primary particles constituting the aggregate on the two-dimensional image. The average of the maximum lengths of the respective particles was defined as an average primary particle diameter. The maximum length/minimum length of each particle is determined, and the average value of the maximum length/minimum length is defined as the average aspect ratio of the primary particles.

(lightness L)^*Method of measuring (1)

On coated paper on which a black band was printed, the blue coating composition was subjected to color development by an applicator to obtain a blue coated sheet. The color spread portion on the black band of the coated plate was measured with a spectrophotometer (DataColor 650, Deta corporation) to calculate the lightness L^*. The more transparent the pigment, the more reflective the substrate black band, L^*The smaller.

(method of measuring hue at highlight/shadow)

On the transparent film, the blue coating composition was subjected to color development by an applicator to obtain a blue coated plate. The coated sheet was placed on a black paper with the developed surface facing upward, and measured with a multi-angle spectrophotometer (MA 98, manufactured by X-rite Co., Ltd.) to calculate the hue angle h and chroma C^*. The apparatus has a light source at an angle of 45 ° with respect to the sample, and color evaluation was performed at light receiving angles of six angles of-15 ° to 110 ° with regular reflection set to 0 °. The smaller the difference (Δ h) between the hue angle h of-15 ° (highlight) and 110 ° (shade), the more excellent the flip-flop property.

(Synthesis example 1)

400ml 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 (Fuji film and Wako pure chemical industries, Ltd.), 153.9 parts of urea (Fuji film and Wako pure chemical industries, Ltd.), 19.8 parts of copper (I) chloride (Fuji film and Wako pure chemical industries, Ltd.), and 0.45 part of hexaammonium heptamolybdate tetrahydrate (Fuji and Wako pure chemical industries, Ltd.) were placed in a 1-liter autoclave, and the temperature was raised to 195 ℃ while stirring, and the mixture was stirred at 195 ℃ under 3.5 atmospheres for 2 hours.

And naturally standing the reaction solution, cooling to normal temperature, and removing the solvent by using an evaporator to obtain a crude product of the copper chloride phthalocyanine. The crude product and 2000 parts of an aqueous solution of sulfuric acid (5%) were put in a 3L glass separable flask equipped with a reflux tube, and the mixture was heated to 70 ℃ and stirred at 70 ℃ for 1 hour. Then, the filtrate was filtered through a suction filter, and water washing was repeated until the filtrate had a pH of 6 or more. Then, the mixture was dried at 90 ℃ for 20 hours and pulverized to obtain 109 parts of copper phthalocyanine chloride (1).

The average number of chlorine substitution of copper chloride phthalocyanine (1) was 1.48 as measured by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine contained in the copper chloride phthalocyanine (1) was 20%.

(Synthesis example 2)

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

The average number of chlorine substitution of copper chloride phthalocyanine (2) was 1.12 as measured by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine contained in the copper chloride phthalocyanine (2) was 34%.

(Synthesis example 3)

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

The average number of chlorine substitution of copper chloride phthalocyanine (3) was measured to be 0.90 by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine contained in the copper chloride phthalocyanine (3) was 38%.

(Synthesis example 4)

101 parts of copper phthalocyanine chloride (4) was obtained in the same manner as in Synthesis example 1, except that 26.7 parts of sodium 4-chlorophthalate and 115.5 parts of phthalic anhydride were used in Synthesis example 1.

The average number of chlorine substitution of copper chloride phthalocyanine (4) was measured to be 0.60 by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine contained in the copper chloride phthalocyanine (4) was 57%.

(Synthesis example 5)

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

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

(Synthesis example 6)

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

The chlorine number of the copper phthalocyanine chloride (6) was 0.30 by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine contained in the copper chloride phthalocyanine (6) was 67%.

(Synthesis example 7)

110 parts of copper phthalocyanine chloride (7) was obtained in the same manner as in Synthesis example 1, except that 89.1 parts of sodium 4-chlorophthalate and 59.4 parts of phthalic anhydride were used in Synthesis example 1.

The chlorine number of the copper chloride phthalocyanine (7) was measured to be 2.01 by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine was contained in the chlorinated copper phthalocyanine (7) in an amount of 5.1%.

(Synthesis example 8)

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

(Synthesis example 9)

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

The chlorine number of the copper chloride phthalocyanine (9) was measured to be 3.20 by fluorescent X-ray analysis. The FD-MS analysis showed that the unsubstituted copper phthalocyanine was contained in the chlorinated copper phthalocyanine (9) in an amount of 0.6%.

Production example 1

28.5 parts of copper phthalocyanine chloride (1) synthesized in Synthesis example 1 and 257 parts of sulfuric acid (95%) were charged into a 1L separable flask made of glass equipped with a reflux tube, and the mixture was heated to 70 ℃ and stirred at 70 ℃ for 1 hour. After naturally left to cool to 45 ℃, 2300 parts of water having a temperature of 45 ℃ was mixed with the mixture while sucking the mixture by an ejector (resin aspirator) to obtain a sulfuric acid slurry. The sulfuric acid slurry was added to a 3L separable glass flask equipped with a reflux tube, the temperature was raised to 70 ℃ and the mixture was stirred at 70 ℃ for 1 hour, and then the mixture was filtered through a suction filter and washed with water repeatedly until the pH of the filtrate became 6 or more, whereby a wet cake of copper phthalocyanine chloride (1) (12% of non-volatile matter) was obtained.

A1L separable glass flask equipped with a reflux tube was charged with the total amount of the wet cake, 1.5 parts of the following pigment derivative (1), and 100 parts of tetrahydrofuran (Fuji film and Wako pure chemical industries, Ltd.), and the mixture was stirred at 55 ℃ for 2 hours. Then, 19 parts of an aqueous sodium hydroxide solution (25%) (Fuji film and Wako pure chemical industries, Ltd.) and 180 parts of water were added thereto, and the mixture was stirred for 30 minutes. Then, the reflux pipe was removed, a Lishi condenser was installed, the temperature was raised to 100 ℃ and stirred at 100 ℃ for 30 minutes, and tetrahydrofuran was removed from the pigment slurry.

Naturally standing, cooling to room temperature, filtering with suction filter, and repeatedly washing with water until the pH of the filtrate is below 8. Then, dried at 90 ℃ for 20 hours and pulverized to obtain 29 parts of a blue pigment composition (1).

[ solution 16]

Pigment derivative (1)

Production example 2

29 parts of a blue pigment composition (2) was obtained in the same manner as in production example 1, except that the copper chloride phthalocyanine (1) in production example 1 was changed to the copper chloride phthalocyanine (2).

(production example 3)

29 parts of a blue pigment composition (3) was obtained in the same manner as in production example 1, except that the copper chloride phthalocyanine (1) in production example 1 was changed to the copper chloride phthalocyanine (3).

Production example 4

29 parts of a blue pigment composition (4) was obtained in the same manner as in production example 3, except that the pigment derivative (1) in production example 3 was changed to the pigment derivative (2).

[ solution 17]

Pigment derivative (2)

Production example 5

29 parts of a blue pigment composition (5) was obtained in the same manner as in production example 3, except that the pigment derivative (1) in production example 3 was changed to the pigment derivative (3).

[ solution 18]

Pigment derivative (3)

(production example 6)

29 parts of a blue pigment composition (6) was 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 changed to 1.0 part of the pigment derivative (1) and 0.5 part of the pigment derivative (2).

Production example 7

In a 1L glass separable flask equipped with a reflux tube, 28.5 parts of copper phthalocyanine chloride (3) and 257 parts of sulfuric acid (95%) were added, and the mixture was heated to 70 ℃ and stirred at 70 ℃ for 1 hour. After naturally left to cool to 45 ℃, 2300 parts of water having a temperature of 45 ℃ was mixed with the mixture while sucking the mixture by an ejector (resin aspirator) to obtain a sulfuric acid slurry. The sulfuric acid slurry was added to a 3L separable glass flask equipped with a reflux tube, the temperature was raised to 70 ℃ and the mixture was stirred at 70 ℃ for 1 hour, and then the mixture was filtered through a suction filter and washed with water repeatedly until the pH of the filtrate became 6 or more, whereby a wet cake of copper phthalocyanine chloride (3) (12% of non-volatile matter) was obtained.

In a 1L glass beaker were added 303 parts of water, 15.3 parts of methyl benzoate (Fuji film and Wako pure chemical industries, Ltd.), and 0.46 part of dioctyl sodium sulfosuccinate (Tokyo Kaisha chemical industries, Ltd.), and the mixture was stirred at 10000rpm for 10 minutes by a T.K. homomixer MARKII (Primix Kaisha) to prepare an emulsion (1).

Into a 1L separable glass flask equipped with a reflux tube, the whole amount of the wet cake of copper phthalocyanine chloride (3), 1.5 parts of the pigment derivative (1) and 500 parts of water were charged, the temperature was raised to 85 ℃ and 64 parts of the emulsion (1) was further charged and stirred at 85 ℃ for 2 hours. After naturally standing and cooling to normal temperature, 10 parts of sodium hydroxide aqueous solution (25%) was added, and the mixture was heated to 85 ℃ and stirred at 85 ℃ for 2 hours. Then, the pH was confirmed to be 10 or more, and after naturally standing and cooling to room temperature, the filtrate was filtered through a suction filter, and washing with water was repeated until the pH of the filtrate was 8 or less. Then, dried at 90 ℃ for 20 hours and pulverized to obtain 29 parts of a blue pigment composition (7).

Production example 8

29 parts of a blue pigment composition (8) was obtained in the same manner as in production example 1, except that the copper chloride phthalocyanine (1) in production example 1 was changed to the copper chloride phthalocyanine (4).

Production example 9

95 parts of copper phthalocyanine chloride (4), 5 parts of pigment derivative (1), 700 parts of sodium chloride and 130 parts of diethylene glycol (Fuji photo film and Wako pure chemical industries, Ltd.) were placed in a stainless steel double-arm kneader (2L) and kneaded at 90 ℃ for 6 hours. Then, 4000 parts of an aqueous solution of 70 ℃ hydrochloric acid (0.5%) was added to the mixture, and the mixture was stirred for 1 hour to prepare a slurry, which was filtered through a suction filter, and washed repeatedly with water until the filtrate had a pH of 6 or more and an electric conductivity of 200. mu.S/cm or less, to remove sodium chloride and diethylene glycol. Then, dried at 90 ℃ for 20 hours and pulverized to obtain 95 parts of a blue pigment composition (9).

Production example 10

29 parts of a blue pigment composition (10) was obtained in the same manner as in production example 6, except that the copper chloride phthalocyanine (3) in production example 6 was changed to the copper chloride phthalocyanine (5).

Production example 11

28 parts of a blue pigment composition (11) was obtained in the same manner as in production example 6, except that the copper chloride phthalocyanine (3) in production example 6 was changed to the copper chloride phthalocyanine (6).

Production example 12

28 parts of a blue pigment composition (12) was obtained in the same manner as in production example 6, except that the copper chloride phthalocyanine (3) in production example 6 was changed to the copper chloride phthalocyanine (7).

Production example 13

27 parts of a blue pigment composition (13) was obtained in the same manner as in production example 12, except that the pigment derivative (1) in production example 12 was changed to the pigment derivative (4).

[ solution 19]

Pigment derivative (4)

Production example 14

26 parts of a blue pigment composition (14) was obtained in the same manner as in production example 12, except that the pigment derivative (1) in production example 12 was changed to the pigment derivative (5).

[ solution 20]

Pigment derivative (5)

Production example 15

29 parts of a blue pigment composition (15) was obtained in the same manner as in production example 6, except that the copper phthalocyanine chloride (3) in production example 6 was changed to the copper phthalocyanine (8).

Production example 16

28 parts of a blue pigment composition (16) was obtained in the same manner as in production example 6, except that the copper chloride phthalocyanine (3) in production example 6 was changed to the copper chloride phthalocyanine (9).

[ Table 1]

(example 1)

(preparation of blue coating composition)

3.50 parts of the blue pigment composition (1) obtained in production example 1, 17.5 parts of ACRYDIC47-712(DIC Co., Ltd.), 19.3 parts of xylene and 6.4 parts of n-butanol were mixed and dispersed for 4 hours by Scandex (FAST & FLUID). Thereafter, 41.5 parts of ACRYDIC47-712, 12.3 parts of Super Beckamine L-117-60 (available from DIC Co., Ltd.), 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).

(preparation of coated sheet)

The obtained blue coating composition (1) was spread on coated paper printed with black stripes by a 6mil applicator, and dried for 15 minutes by a constant temperature dryer adjusted to 130 ℃ to obtain a blue coated sheet (1-1). The obtained blue coating composition (1) was applied to a transparent film with a 4mil applicator, and dried for 15 minutes in a constant temperature dryer adjusted to 130 ℃ to obtain a blue coated plate (1-2).

L of the blue-coated sheet (1-1) obtained in example 1^*1.8, h at a light-receiving angle of-15 ℃ of the blue coated plate (1-2) was 272.7, C^*30.7, h is 290.7 at a light receiving angle of 110 DEG, C^*21.7, and the difference Δ h between the hue angles h of-15 ° and 110 ° was 18.0.

(example 2)

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 changed to the blue pigment composition (2).

L of blue-coated sheet (2-1) obtained in example 2^*1.9, h of 272.7 at a light-receiving angle of-15 ℃ of the blue coated plate (2-2), C^*30.7, h is 291.5 at a light receiving angle of 110 DEG, C^*It was 22.0, and the difference Δ h between the hue angles h of-15 ° and 110 ° was 18.8.

(example 3)

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 changed to the blue pigment composition (3).

L of blue-coated sheet (3-1) obtained in example 3^*2.0, h of 275.9 at a light-receiving angle of-15 ℃ of the blue coated plate (3-2), C^*30.2, and a light receiving angle of 110 DEG h of 292.6, C^*At 23.9, the difference Δ h between the hue angles h of-15 ° and 110 ° was 16.7.

(example 4)

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 changed to the blue pigment composition (4).

L of blue-coated sheet (4-1) obtained in example 4^*2.2, h at a light-receiving angle of-15 ℃ of the blue coated plate (4-2) was 278.4, C^*31.3, and a light receiving angle of 110 DEG h of 292.9, C^*24.6, and the difference Δ h between the hue angles h of-15 ° and 110 ° was 14.6.

(example 5)

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 changed to the blue pigment composition (5).

L of blue-coated sheet (5-1) obtained in example 5^*2.1, h of 281.2 at a light-receiving angle of-15 ℃ of the blue coated plate (5-2), C^*Is 29.4, and h at a light receiving angle of 110 DEG is 292.5, C^*It was 26.0, and the difference Δ h between the hue angles h of-15 ° and 110 ° in light reception angle was 11.4.

(example 6)

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 changed to the blue pigment composition (6).

L of blue-coated sheet (6-1) obtained in example 6^*2.1, h at a light-receiving angle of-15 ℃ of the blue coated plate (6-2) was 277.0, C^*30.7, h is 292.7 at a light receiving angle of 110 DEG, C^*24.0, and a difference Δ h between hue angles h of-15 ° and 110 ° in light receiving angle was 15.7.

(example 7)

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 changed to the blue pigment composition (7).

L of blue-coated sheet (7-1) obtained in example 7^*1.7, h at a light-receiving angle of-15 ℃ of the blue coated plate (7-2) was 268.4, C^*31.0, and a light receiving angle of 110 DEG h of 292.4, C^*21.6, and the difference Δ h between the hue angles h of-15 ° and 110 ° was 24.0.

(example 8)

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 changed to the blue pigment composition (8).

L of blue-coated sheet (8-1) obtained in example 8^*1.7, h at a light-receiving angle of-15 ℃ of the blue coated plate (8-2) is 276.9, C^*31.9, h at a light receiving angle of 110 DEG is 294.4, C^*At 25.1, the difference Δ h between the hue angles h of-15 ° and 110 ° was 17.5.

(example 9)

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 changed to the blue pigment composition (9).

L of blue-coated sheet (9-1) obtained in example 9^*1.5, h at a light-receiving angle of-15 ℃ of the blue coated plate (9-2) was 277.4, C^*27.7, h at a light-receiving angle of 110 DEG is 295.5, C^*At 25.9, the difference Δ h between the hue angles h of-15 ° and 110 ° was 18.1.

(example 10)

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 changed to the blue pigment composition (10).

L of blue-coated sheet (10-1) obtained in example 10^*1.9, h of 270.4 at a light-receiving angle of-15 ℃ of the blue coated plate (10-2), C^*30.9, h at a light receiving angle of 110 DEG is 294.5, C^*At 25.6, the difference Δ h between the hue angles h of-15 ° and 110 ° was 24.1.

(example 11)

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 changed to the blue pigment composition (11).

L of blue-coated sheet (11-1) obtained in example 11^*1.7, h at a light-receiving angle of-15 ℃ of the blue coated plate (11-2) is 271.0, C^*40.7, h at a light-receiving angle of 110 DEG is 295.0, C^*At 27.1, the difference Δ h between the hue angles h of-15 ° and 110 ° was 24.0.

(example 12)

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 changed to the blue pigment composition (12).

L of blue-coated sheet (12-1) obtained in example 12^*2.0, h of 265.6 at a light-receiving angle of-15 ℃ of the blue coated plate (12-2), C^*30.5, h is 291.6 at a light receiving angle of 110 DEG, C^*It was 23.9, and the difference Δ h between the hue angles h of-15 ° and 110 ° in light reception angle was 25.9.

(example 13)

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 changed to the blue pigment composition (13).

L of blue-coated sheet (13-1) obtained in example 13^*2.0, 263.4 for a light receiving angle of-15 DEG of the blue coated plate (13-2), and C^*29.3, h at a light receiving angle of 110 DEG is 290.1, C^*24.4, and the difference Δ h between the hue angles h of-15 ° and 110 ° was 25.7.

(example 14)

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 changed to the blue pigment composition (14).

L of blue-coated sheet (14-1) obtained in example 14^*Is 2.0, and h is 2665.0 at a light-receiving angle of-15 DEG of the blue coated plate (14-2), C^*29.4, h at a light receiving angle of 110 DEG is 290.3, C^*24.0, and 25.3 for the difference Δ h between the hue angles h of-15 ° and 110 °.

Comparative example 1

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 changed to the blue pigment composition (15).

L of the blue-coated sheet (15-1) obtained in comparative example 1^*2.3, h at a light-receiving angle of-15 ℃ of the blue coated plate (15-2) is 262.6, C^*42.7, h at a light-receiving angle of 110 DEG is 298.2, C^*31.7, and the difference Δ h between the hue angles h of-15 ° and 110 ° was 35.6.

Comparative example 2

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 changed to the blue pigment composition (16).

L of the blue-coated sheet (16-1) obtained in comparative example 2^*2.3, h of 255.0 at a light-receiving angle of-15 ℃ of the blue coated plate (16-2), C^*25.8, h at a light receiving angle of 110 DEG is 291.7, C^*At 22.4, the difference Δ h between the hue angles h of-15 ° and 110 ° was 36.7.

[ Table 2]

Although the pigment derivative (1) was used in examples 1, 2, 3, 8, 10, 11 and 12 and comparative example 1, the average number of chlorine substitution of copper phthalocyanine was different. In examples 1, 2, 3, 8, 10, 11 and 12 having an average number of chlorine substitution of 0.3 to 2.0, the pigment particles were hardly grown by containing copper phthalocyanine chlorideThe aspect ratio and the average particle diameter are small. Thus, h, L of the shadow^*Are small and suitable as pigments for automotive coatings.

In contrast, comparative example 1, which is an unsubstituted copper phthalocyanine having an average number of chlorine substitutions of 0, is reddish in shade compared with examples 1, 2, 3, 8, 10, 11 and 12. Further, since copper phthalocyanine is not substituted with chlorine at all, the pigment particles easily grow. Therefore, the aspect ratio and the average particle diameter are both increased, Δ h and L^*Both become larger. Therefore, comparative example 1 is not suitable for a blue pigment for an automobile paint.

Examples 7, 10, 11 and 12 and comparative example 2 were prepared under the same conditions, but the average number of chlorine substitutions of copper phthalocyanine was different. In examples 7, 10, 11 and 12 in which the average number of chlorine substitutions was 0.3 to 2.0, the inclusion of copper chloride phthalocyanine made it difficult for the pigment particles to grow, and the aspect ratio and the average particle diameter were small, so that the reddening of the shade due to scattered light from coarse pigment particles could be suppressed.

In comparative example 2, the average number of chlorine substituents in the copper phthalocyanine was as high as 3.2, and therefore, the highlight and shade h were small, and the color development of the pigment itself was greenish. Therefore, comparative example 2 is not suitable for a blue pigment for automobile paint.

Examples 3, 4 and 5 and examples 12, 13 and 14 were samples prepared under the same conditions except that the type of pigment derivative was different. H, L in shade in any pigment derivative^*Are small and suitable as pigments for automotive coatings.

Example 6 is a sample prepared under the same conditions as examples 3 and 4 except that a pigment derivative is used in combination. The same applies to the combination of pigment derivatives, shaded h, L^*Are small and suitable as pigments for automotive coatings.

Examples 12, 13 and 14 were samples prepared under the same conditions except that the pigment derivatives were different in type. H, L in shade in any pigment derivative^*Are small and suitable as pigments for automotive coatings.

Examples 3 and 7 were prepared under the same conditions except that the pigmentation method was differentAnd (3) sampling. H, L of shade in any pigmentation method^*Are small and suitable as pigments for automotive coatings.

Claims

1. A blue pigment composition, characterized in that,

the copper phthalocyanine dye comprises a copper phthalocyanine chloride having an average number of chlorine substitutions 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 group selected from 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) and a group represented by the following general formula (5), wherein the average aspect ratio of primary particles of the copper phthalocyanine chloride is 1.0 to 3.5,

[ solution 1]

[ solution 2]

[ solution 3]

-SO₃R₅(4)

[ solution 4]

In the formulas (1) to (5), a and b are each independently an integer of 1 to 10, R₁、R₂、R₃、R₄、R₅、R₆And R₇Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, and X₁And X₂Each independently represents a single bond, arylene, -NH-, -O-or-S-.

2. The blue pigment composition according to claim 1, wherein the pigment derivative is contained in an amount of more than 1 part by weight and not more than 15 parts by weight per 100 parts by weight of the copper chloride phthalocyanine.

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

4. A paint comprising the blue pigment composition according to any one of claims 1 to 3.