阅读说明：本技术 酞菁颜料组合物及其制造方法、油墨 (Phthalocyanine pigment composition, method for producing same, and ink ) 是由 大竹英弘 小林永年 桥口太一 于 2014-03-27 设计创作，主要内容包括：本发明涉及酞菁颜料组合物及其制造方法、油墨。所述酞菁铜颜料组合物,其特征在于,包含酞菁铜、松香化合物、磺酸酞菁铜或其盐以及月桂胺,该颜料组合物中的钙含量为200ppm以下。(The present invention relates to a phthalocyanine pigment composition, a method for producing the same, and an ink. The copper phthalocyanine pigment composition is characterized by comprising copper phthalocyanine, a rosin compound, copper phthalocyanine sulfonate or a salt thereof and laurylamine, wherein the calcium content in the pigment composition is 200ppm or less.)

1. A copper phthalocyanine pigment composition comprising copper phthalocyanine, a rosin compound, copper phthalocyanine sulfonate or a salt thereof, and laurylamine, wherein the calcium content in the pigment composition is 200ppm or less.

2. The method of manufacturing a copper phthalocyanine pigment composition according to claim 1, comprising: a first step of obtaining a pre-pigment by dry-pulverizing crude copper phthalocyanine; and a second step of mixing the pre-pigment obtained in the first step with an organic solvent or a mixed solution of an organic solvent and water in the presence of copper phthalocyanine sulfonate or a salt thereof.

3. The method for producing a copper phthalocyanine pigment composition according to claim 2, wherein the calcium content of the process water used in the second step is 10ppm or less.

4. The method for producing a copper phthalocyanine pigment composition according to claim 2 or 3, wherein in the second step, the mixed liquid of the organic solvent and water is an emulsion prepared together with the rosin compound.

5. A base ink for liquid ink, comprising 20% or more of the copper phthalocyanine pigment composition according to claim 1.

6. A base ink for liquid ink, characterized by containing 20% or more of the copper phthalocyanine pigment composition obtained by the method for producing a copper phthalocyanine pigment composition according to claims 2 to 4.

7. The base ink for liquid ink according to claim 5 or 6, comprising a nitrocellulose resin.

Technical Field

The present invention relates to a phthalocyanine pigment composition and a method for producing the same, and further relates to a liquid ink containing the phthalocyanine pigment composition.

Background

As important characteristics of a copper phthalocyanine blue pigment used for liquid ink applications, viscosity characteristics as an index of lowering viscosity and dispersion stability of a base ink for the purpose of improving productivity are required. An ink using a pigment having poor dispersion stability has a high initial viscosity, and even when the initial viscosity is low, the viscosity increases with the passage of time. Such pigments are produced with importance placed on productivity, and are not suitable for producing a high-concentration base ink which is diluted and prepared as a liquid ink. Therefore, in order to improve dispersion stability, the primary particles are controlled and the surface treatment method is optimized.

The cited document 1 proposes the following method: the crude phthalocyanine pigment is formed into a pre-pigment by any one of dry pulverization, wet pulverization, salt kneading, acid pasting and acid swelling, and the pre-pigment is treated together with the phthalocyanine derivative in a mixture of water and an organic solvent. Citation 2 proposes a method in which crude copper phthalocyanine is pulverized and separated together with a resin and a pulverization aid in a dry or aqueous manner, and then subjected to conditioning treatment. Further, cited document 3 proposes a pigment dispersant in which a phthalocyanine sulfonic acid and a rosin amine form a salt, and a pigment composition containing the pigment dispersant and phthalocyanine.

However, in the production methods and pigment compositions of cited documents 1 to 3, the copper phthalocyanine sulfonate is bound to calcium contained in the pigment or the process water before interacting with the organic amine or the like to be added later, and as a result, the effect of treating the pigment surface is insufficient, and the stability of the ink over time cannot be ensured.

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide a phthalocyanine pigment composition which has excellent transparency, gloss, and initial viscosity suitability during production, and also has remarkably excellent stability over time in the application to liquid inks. Among others, an object of the present invention is to provide a phthalocyanine pigment composition which exhibits remarkably excellent viscosity stability with time in a base ink for liquid ink having a high pigment concentration.

Means for solving the problems

The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that: a copper phthalocyanine pigment composition which is used in a liquid ink and has remarkably excellent stability over time in addition to excellent transparency, gloss, and initial viscosity suitability for production, characterized by containing copper phthalocyanine, a rosin compound, copper phthalocyanine sulfonate or a salt thereof, and an aliphatic amine, and has a calcium content of 200ppm or less.

Further, there is provided a method for producing a copper phthalocyanine pigment composition, comprising: a first step of obtaining a pre-pigment by dry-pulverizing crude copper phthalocyanine; and a second step of mixing the pre-pigment obtained in the first step with an organic solvent or a mixed solution of an organic solvent and water in the presence of copper phthalocyanine sulfonate or a salt thereof.

Further, there is provided a method for producing a copper phthalocyanine pigment composition, wherein the calcium content of the process water used in the second step is 10ppm or less.

Further, there is provided a method for producing a copper phthalocyanine pigment composition, wherein in the second step, a mixed solution of an organic solvent and water is an emulsion prepared together with a rosin compound.

Further, there is provided a base ink for liquid ink, characterized by containing the copper phthalocyanine pigment composition in an amount of 20% or more.

Further, there is provided a base ink for liquid ink, characterized by containing 20% or more of the copper phthalocyanine pigment composition obtained by the method for producing a copper phthalocyanine pigment composition.

Further, a base ink for liquid ink is provided, which comprises a nitrocellulose resin.

Effects of the invention

The liquid ink composition is characterized by comprising copper phthalocyanine, a rosin compound, copper phthalocyanine sulfonate or a salt thereof, and an aliphatic amine, and has a calcium content of 200ppm or less, and thus has remarkably excellent stability over time in addition to excellent transparency, gloss, and initial viscosity suitability for production.

Detailed Description

The present invention will be described in detail below.

In the present invention, a target pigment composition can be obtained by subjecting a pre-pigment obtained in the first step to a treatment of mixing the pre-pigment with an organic solvent or a mixed solution of an organic solvent and water in the presence of copper phthalocyanine sulfonate or a salt thereof, wherein the pigment composition comprises copper phthalocyanine, a rosin compound, copper phthalocyanine sulfonate or a salt thereof, and an aliphatic amine, and the calcium content in the pigment composition is 200ppm or less.

The crude copper phthalocyanine used in the present invention can be obtained by, for example, reacting phthalic anhydride or a derivative thereof, urea or a derivative thereof, and a copper metal source, or reacting phthalodinitrile and a copper metal source.

In this case, examples of the phthalic acid derivative include phthalate, phthalic anhydride, phthalimide, a salt thereof or an ester thereof, phthalonitrile, and the like; examples of the urea derivative include urea, ammonia, and the like; examples of the metal source include metallic copper, cuprous metal, or a halide of copper, cupric oxide, cupric sulfate, cupric sulfide, and cupric hydroxide; examples of the catalyst include molybdenum compounds such as ammonium molybdate and molybdenum oxide, titanium compounds such as titanium tetrachloride and titanate, zirconium compounds such as zirconium chloride and zirconium carbonate, antimony oxide and boric acid; examples of the organic solvent include aromatic hydrocarbons such as alkylbenzenes and alkylnaphthalenes, alicyclic hydrocarbons such as alkylcyclohexane and decalin, aliphatic hydrocarbons such as decane and dodecane, aromatic nitro compounds such as nitrobenzene and nitrotoluene, and aromatic halogenated hydrocarbons such as trichlorobenzene and chloronaphthalene.

In the production of a crude phthalocyanine by the above production method, a catalyst is added to each raw material as necessary, and the mixture is heated, for example, at 180 to 300 ℃ for 1 to 5 hours in the presence or absence of an organic solvent.

The crude copper phthalocyanine obtained in the above synthesis step can be appropriately purified. The salts formed by the synthesis step and derivatives derived from the raw materials can be removed by washing with an alkaline and/or acidic aqueous solution and/or an organic solvent. In the method of the present invention, both of the crude copper phthalocyanine containing the salt and the derivative derived from the raw material and the crude copper phthalocyanine purified by removing the salt and the derivative derived from the raw material can be used. The crude copper phthalocyanine used in the present invention is β -type crystal, and the purity is preferably 97%, and more preferably 98% or more.

Further, the calcium content of the crude copper phthalocyanine can be reduced by purifying the crude copper phthalocyanine with process water having a calcium content of 10ppm or less, preferably 1ppm or less. As the process water having a calcium content of 1ppm or less, distilled water, ion-exchanged water, water-softened treated water, reverse osmosis membrane treated water, and the like, and treated water obtained by combining these can be used as the process water. By purifying with such process water, a crude copper phthalocyanine having a calcium content of 150ppm or less, particularly preferably 100ppm or less, can be obtained.

The first step of obtaining a prepigment by dry-pulverizing the crude copper phthalocyanine pigment obtained above will be described.

In the present invention, the temperature for pulverizing the crude copper phthalocyanine is usually 200 ℃ or lower, preferably 60 to 130 ℃. As the pulverizing method of the present invention, a conventional dry method can be used. For the pulverization, a pulverizer having a medium such as beads or rods built therein may be used. Here, a medium made of glass or metal is generally used. Furthermore, a pulverizer capable of controlling the pulverization state by temperature control is preferable, and the pulverization temperature can be controlled by controlling the rotation speed of the medium to be pulverized.

As the pulverizer, an attritor, a vibration mill, a ball mill, or the like can be used. Among them, the attritor is more preferably an attritor in consideration of productivity and easiness of control of the pulverization temperature.

The conditions for dry grinding are not particularly limited, and for example, in the case of using the above-mentioned attritor, the dry grinding is carried out at a rotational peripheral speed of the stirring blade of 1 to 20 m/sec, more preferably in a range of 1.2 to 10 m/sec. The time required for the pulverization is not particularly limited, and is usually in the range of several minutes to several hours.

Dry pulverization is performed by utilizing, for example, pulverization force or breaking force between media or between media and walls. Examples of the pulverizing apparatus include an attritor, a ball mill, and a vibration mill, which are known methods. If necessary, the reaction may be carried out in an inert gas atmosphere such as nitrogen or argon in the pulverizer. As the dispersing machine, a bead MILL such as a horizontal sand MILL (DYNO-MILL), a dry MILL, or a sand MILL, which is a known method, can be used. The prepigment thus obtained is a mixed crystal of α -type crystals and β -type crystals, and the ratio of α -type crystals to β -type crystals (α/β ratio) determined by an X-ray diffraction method is not particularly limited, but is preferably in the range of 30/70 to 80/20, and more preferably in the range of 50/50 to 65/35.

Next, a second step of treating the prepigment of the present invention by mixing it with an organic solvent or a mixed solution of an organic solvent and water in the presence of copper phthalocyanine sulfonate or a salt thereof will be described.

As the copper phthalocyanine sulfonate or a salt thereof used in the second step, at least one selected from the group consisting of copper phthalocyanine sulfonate, an alkali metal salt of copper phthalocyanine sulfonate, an aliphatic primary amine salt of copper phthalocyanine sulfonate, an aliphatic secondary amine salt of copper phthalocyanine sulfonate, an aliphatic tertiary amine salt of copper phthalocyanine sulfonate, and a quaternary ammonium salt of copper phthalocyanine sulfonate or a salt thereof can be used. Among them, alkali metal salts of copper phthalocyanine sulfonate are more preferable.

The number of substituents of the sulfonic acid residue in the copper phthalocyanine sulfonate or the salt thereof is not particularly limited, but if the number of substituents is too large, the solubility in water or an organic solvent becomes high, insolubilization becomes difficult, and the expected treatment effect cannot be obtained, and therefore the number of substituents is preferably in the range of 1 to 3.

The copper phthalocyanine sulfonate or a salt thereof may be dissolved in water and/or an organic solvent. Among them, when used in a dissolved state, alkali metal salts of copper phthalocyanine sulfonate having a property of being easily dissolved in water are preferable from the viewpoint of obtaining a copper phthalocyanine composition having high uniformity. The method for producing the alkali metal salt of copper phthalocyanine sulfonate is preferably used by dispersing copper phthalocyanine sulfonate in 10 to 100 times of water and adjusting the pH of the dispersion to an alkaline atmosphere of 8 to 12 with an alkali such as sodium hydroxide or potassium hydroxide. Further, if the basicity is strong, the solubility of the alkali metal salt of copper phthalocyanine sulfonate tends to be low, and therefore, from the viewpoint of uniform treatment, the pH is most preferably in the range of 8 to 10.8.

If the amount of the copper phthalocyanine sulfonate or the salt thereof added is too small, the dispersibility of the obtained pigment is insufficient, and if it is too large, the crystallinity is insufficient. In order to exhibit excellent properties of viscosity, transparency and tinting strength while having sufficient crystallinity, the content of the prepigment is preferably in the range of 2 to 20%, and more preferably 3 to 11%.

When the pre-pigment is mixed with an organic solvent or a mixed solution of an organic solvent and water, the pre-pigment may be in any form, such as Dry powder (Dry), wet cake containing water, or slurry suspended in water. It can be appropriately selected in consideration of productivity and operability.

In addition, as for the time of charging the prepigment, a predetermined prepigment may be charged into the reactor at one time in an initial stage to a liquid medium heated in advance to have a certain temperature; the reactor can be put into the second procedure for two to more times; can be continuously fed in small portions at a time by using a feeder. Among them, it is preferable to add the ink in two or more portions from the viewpoint of obtaining an ink having a lower initial viscosity and a lower viscosity with time.

In the present invention, the heat treatment of the prepigment is carried out at a temperature in the range of 60 to 150 ℃ at which the prepigment, which is a mixed crystal of α -type crystals and β -type crystals, is easily crystallized and converted into β -type crystals. Further preferably, the heat treatment may be performed at a temperature of 80 to 110 ℃. Particularly, it is preferable to convert a prepigment, which is a mixed crystal of α -type crystals and β -type crystals, into a pigment form of β -type crystals in a temperature range of 80 to 97 ℃, and to control the size of the crystals to be formed to 50 to 150 nm, which is a copper phthalocyanine pigment composition for liquid ink excellent in transparency and coloring power. The time of the heat treatment is not particularly limited as long as it is a time suitable for converting the prepigment into β -type crystals and capable of controlling the size of the target crystals, and is in the range of several minutes to several hours.

As the liquid medium used in the second step, an organic solvent or a mixed liquid of an organic solvent and water may be used.

Examples of the organic solvent include aromatic compounds such as benzene, toluene, xylene, and nitrobenzene; 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 cellulose and the like; ethers such as tetrahydrofuran. Among them, xylene is preferable from the viewpoint of obtaining the following pigment particles: 1) the effect of converting the pre-pigment into a pigment form of beta-type crystals is high; 2) when used as a liquid ink, the ink has low thixotropy and a small aspect ratio suitable for exhibiting excellent printing suitability. The organic solvent used may be a single solvent or a mixture of a plurality of solvents.

In the mixed liquid of the organic solvent and water, the organic solvent and water may be mixed at any ratio as long as they are effective for crystal growth and particle uniformity treatment, but in order to obtain crystallinity and crystal size excellent in transparency and coloring power, it is preferable to carry out the mixing at a mass ratio of the organic solvent to the water within a range of 0.5:99.5 to 3: 97.

Further, a mixed solution of an organic solvent and water may be used as an emulsion. Any commercially available surfactant can be used as the surfactant that can be used for the emulsion preparation. Any surfactant of nonionic, anionic, cationic and both surfactants may be used as long as water and an organic solvent form an emulsion, and the surfactant has the ability to emulsify an organic solvent, particularly xylene, with water; from the viewpoint of not adversely affecting the printability or the suitability for a coating film as a printed matter, a rosin compound is preferably used as the surfactant.

The method for producing the emulsion using the rosin compound is not particularly limited, and for example, first, the rosin compound is dissolved in an alkali atmosphere with 10 to 100 times of water at 60 to 100 ℃ by heating with an alkali such as sodium hydroxide or potassium hydroxide to prepare a rosin aqueous solution. Next, an organic solvent such as xylene is added to the rosin aqueous solution to obtain an organic solvent emulsion solution. The pH value of the rosin solution is preferably in the range of 8-10.8 to prevent alkaline precipitation of rosin, and the heating temperature is more preferably in the range of 70-94 ℃.

As the rosin compound that can be used, rosin, disproportionated rosin, hydrogenated rosin, polymerized rosin, and rosin soap resin can be used. Among them, disproportionated rosin and hydrogenated rosin are preferable.

The amount of the rosin compound added is 2 to 20% based on the pre-pigment, and is preferably 3 to 10% from the viewpoint that the pre-pigment can be well dispersed and uniformly treated in the aqueous slurry in the second step.

The ratio of the prepigment to the liquid medium is 2 to 100 in terms of mass ratio of the liquid medium/the prepigment to the prepigment, and is preferably 2 to 20, more preferably 3 to 10, in consideration of good stirring state which affects production efficiency, production cost, transparency of the obtained pigment, and coloring power.

Further, as the aliphatic amine used in the present invention, an aliphatic primary amine (R) can be used₁NH₂：R₁Alkyl with 8-18 carbon atoms) and aliphatic secondary amine (R)₁R₂NH：R₁、R₂Alkyl group having 8 to 18 carbon atoms), and aliphatic tertiary amine (R)₁R₂R₃N：R₁、R₂Is methyl, R₃Alkyl with 8-22 carbon atoms, quaternary ammonium salt (R)₁R₂R₃R₄N⁺Cl^-：R₁、R₂Is methyl, R₃、R₄An alkyl group having 8 to 18 carbon atoms).

The amount of the aliphatic amine added is preferably in the range of 0.1 to 10%, more preferably 0.1 to 3%, relative to the pre-pigment. The amount of the aliphatic amine to be added can be determined by the degree of neutralization by hydrogen bonds with respect to the number of sulfonic acid residues in the copper phthalocyanine sulfonate or its salt to be used. In order to obtain a pigment having desired transparency, coloring power and dispersion stability by surely forming a hydrogen bond between the aliphatic amine and the sulfonic acid residue, the ratio of the number of moles of the aliphatic amine to the number of moles of the sulfonic acid residue (neutralization degree) is preferably in the range of 0.2 to 0.8, more preferably in the range of 0.4 to 0.7.

The process water used in the present invention is required to have a small calcium content, and the calcium content in the process water is preferably 10ppm or less, more preferably 1ppm or less. The process water having a low calcium content is preferably pure water, soft water, ion-exchanged water, distilled water, reverse osmosis membrane treated water, or the like.

As a result of intensive studies, the inventors have found that removal of factors inhibiting hydrogen bonding or chemical bonding between copper phthalocyanine sulfonate and aliphatic amine is important for the viscosity of ink, particularly viscosity stability with time. The following description will be made in detail.

In the surface treatment of copper phthalocyanine pigments, the formation of hydrogen bonds or chemical bonds between copper phthalocyanine sulfonate and aliphatic amine is very important for the viscosity, particularly viscosity stability over time, of the ink. That is, copper phthalocyanine sulfonate is hydrogen-bonded or ion-bonded to an aliphatic amine as in the case of using an aliphatic primary amine (formula 1), the case of using an aliphatic secondary amine (formula 2), the case of using an aliphatic tertiary amine (formula 3), and the case of using an aliphatic quaternary amine (formula 4).

[ general formula 1]

CuPc-SO₃H+NH₂R₁→CuPc-SO₃H·NH₂R₁

[ general formula 2]

CuPc-SO₃H+NHR₁R₂→CuPc-SO₃H·NHR₁R₂

[ general formula 3]

CuPc-SO₃H+NR₁R₂R₃→CuPc-SO₃H·NR₁R₂R₃

[ general formula 4]

CuPc-SO₃ ^-+〔NR₁R₂R₃R₄〕⁺→CuPc-SO₃〔NR₁R₂R₃R₄〕

Here, CuPc represents a copper phthalocyanine residue, R₁～R₄Represents an alkyl group.

In this case, if calcium ions are present in the system, the copper phthalocyanine sulfonate is chemically bonded to the calcium ions to form a salt, which inhibits the copper phthalocyanine sulfonate from forming a hydrogen bond or a chemical bond with the aliphatic amine. Therefore, the calcium salt of copper phthalocyanine sulfonate deteriorates the viscosity, particularly the viscosity stability with time, of the ink. Hereinafter, formula 5 shows an example of using an aliphatic primary amine.

[ general formula 5]

CuPc-SO₃ ^-+Ca²⁺+NH₂R→CuPc-SO₃-Ca+NH₂R

The inventors have conducted extensive studies based on the above-mentioned findings, and as a result, have found that the calcium content in the copper phthalocyanine pigment composition derived from calcium contained in crude copper phthalocyanine, copper phthalocyanine sulfonate or a salt thereof, and process water used in production is preferably 200ppm or less, more preferably 150ppm or less, and particularly preferably 100ppm or less.

The calcium content can be measured by fluorescent X-ray analysis of the copper phthalocyanine pigment composition and ICP emission spectrometry of the process water.

The copper phthalocyanine pigment composition thus obtained can be used for various printing inks, paints, colored resin moldings, and the like. Further, the toner can be used for applications such as toners for electrostatic development and inks for inkjet recording.

The copper phthalocyanine pigment composition of the present invention and the copper phthalocyanine pigment composition obtained by the method for producing a copper phthalocyanine pigment composition of the present invention can provide a liquid ink having excellent stability over time in addition to initial viscosity, hue, and tinting strength. The liquid ink can be prepared by mixing the copper phthalocyanine composition obtained by the production method of the present invention with various known and conventional binder resins, various solvents, various additives, and the like according to a conventional preparation method. Specifically, a liquid ink can be prepared by preparing a base ink for a liquid ink having a high pigment concentration, and using various binders, various solvents, various additives, and the like.

The copper phthalocyanine pigment composition of the present invention can produce a base ink for a low-viscosity nitrocellulose resin-based liquid ink having excellent fluidity, and is suitable as an organic pigment composition for gravure ink and flexographic ink. A base ink for nitrocellulose resin-based liquid ink contains a nitrocellulose resin (nitrogen component: 10.7 to 12.2), a solvent, and a pigment, and has a pigment concentration of 20% or more. To the nitrocellulose resin-based base ink for liquid ink, various binder resins, solvents, and various additives can be added to produce a liquid ink. For the binder, for example, nitrocellulose resin, polyamide resin, polyurethane resin can be used, and for the solvent, for example, methanol, ethanol, isopropanol, propanol, butanol, ethyl acetate, toluene, methyl ethyl ketone can be used.