WO2019124050A1

WO2019124050A1 - Copper phthalocyanine pigment composition and ink composition containing same

Info

Publication number: WO2019124050A1
Application number: PCT/JP2018/044512
Authority: WO
Inventors: 晋吾斎藤; 太一橋口
Original assignee: Dic株式会社
Priority date: 2017-12-22
Filing date: 2018-12-04
Publication date: 2019-06-27
Also published as: JP6631764B2; JPWO2019124050A1

Abstract

The problem to be solved by the present invention is to provide a copper phthalocyanine pigment composition that exhibits an excellent redissolvability and a good viscosity (initial viscosity, viscosity with elapsed time) with glycol ether inks. This problem is solved by providing a copper phthalocyanine pigment composition characterized by comprising a β-form copper phthalocyanine pigment and a pigment derivative represented by formula (I) [in the formula, R¹, R², R³, and R⁴ each independently represent a hydrogen atom or a C₁ to C₂₀ alkyl group, and at least one of R¹, R², R³, and R⁴ is a C₆ to C₂₀ alkyl group].

Description

Copper phthalocyanine pigment composition and ink composition having the same

The present invention relates to a copper phthalocyanine pigment composition that can be used in a wide range of applications such as printing inks, paints, colored molded articles, and prints.

In general, pigments intended for coloring consist of fine particles. For example, in the case of dispersing a pigment, which is an aggregate of fine primary particles, in a medium, as in printing inks and paints such as gravure printing and flexo printing, for example, a strong force is applied for a long time to loosen the particles. It is devised such as dispersing or adding a dispersing agent.
Among them, copper phthalocyanine pigments are pigments used in various situations, but when used as a coloring agent in various applications, problems concerning fluidity are remarkable. Furthermore, in recent years, there is also a demand for an ink capable of reducing the environmental load and improving the leveling property of the surface of printed matter in general-purpose printing, and in order to achieve this, a low drying speed ink containing glycol ether as a main component And glycol ether-based inks are noted. The glycol ether-based ink has lower volatility than the conventional alcohol-based ink, and is expected to improve the leveling property (high definition) of the surface of the printed material as the drying speed is reduced. However, there is still little knowledge on the ink properties and printability of glycol ether inks. The ink properties of the glycol ether ink include viscosity (initial viscosity, viscosity over time), and printability includes resolubility.
For example, Patent Document 1 discloses a method of treating a copper phthalocyanine sulfonic acid ammonium salt (primary to quaternary) in printing ink and paint applications in order to improve the viscosity aptitude of the copper phthalocyanine pigment composition.

JP-A-7-53889

However, according to the method described in Patent Document 1, although a certain improvement in ink viscosity can be expected in the conventional ink composition, when used for a glycol ether-based ink which is required in recent years, the thickening when the ink is prepared is suppressed It was impossible. In addition, copper phthalocyanine pigment compositions capable of achieving such ink viscosity improvement and resolubility, which is an important printability in glycol ether-based inks, have not been known.
Under these circumstances, the problem to be solved by the present invention is to provide a copper phthalocyanine pigment composition having good viscosity (initial viscosity, temporal viscosity) and excellent resolubility in a glycol ether ink. It is in.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the viscosity of a glycol ether-based ink is obtained by using a plurality of specific copper phthalocyanine sulfonic acid derivatives in combination with a copper phthalocyanine pigment. It has been found that a pigment composition sufficiently low and compatible with the ink can be obtained, and the present invention has been completed.

That is, the present invention
"Item 1. β-type copper phthalocyanine pigment,
Formula (I):

Formula (I)

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a C ₁ to C ₂₀ alkyl group, and at least one of R ¹ , R ² , R ³ and R ⁴ is A pigment derivative represented by C ₆ -C ₂₀ alkyl group],
The copper phthalocyanine pigment composition (Hereinafter, it may be described with the pigment composition of this invention.) Characterized by the above-mentioned.

Item 2. β-type copper phthalocyanine pigment,
Formula (I):

Formula (I)

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a C ₁ to C ₂₀ alkyl group, and at least one of R ¹ , R ² , R ³ and R ⁴ is A pigment derivative represented by C ₆ -C ₂₀ alkyl group],
Formula (II):

Formula (II)

[Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C ₁ to C ₂₀ alkyl group, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is A copper phthalocyanine pigment composition (hereinafter sometimes referred to as a pigment composition of the present invention), which is a C ₆ to C ₂₀ alkyl group].

Item 3. The copper phthalocyanine pigment composition according to Item 1, wherein any ^{two of} R ¹ , R ² , R ³ and R ^{4 in} the formula (I) are a C ₆ to C ₂₀ alkyl group.
Item 4. In the above formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are a C ₆ to C ₂₀ alkyl group, and the above formulas (II): R ⁵ , R ⁶ , R ⁷ and The copper phthalocyanine pigment composition according to Item 2, wherein any two of R ⁸ are a C ₆ to C ₂₀ alkyl group.

Item 5. With respect to 100 parts by mass of β-type copper phthalocyanine pigment,
Item 4. The copper phthalocyanine pigment composition according to Item 1 or 3, wherein the pigment derivative represented by Formula (I) is contained in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less.
Item 6. With respect to 100 parts by mass of β-type copper phthalocyanine pigment,
The pigment derivative represented by the formula (I) is 0.1 parts by mass or more and 10.0 parts by mass or less,
The pigment derivative represented by the formula (II) is contained in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less, provided that the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) The total amount of with is 10.0 parts by mass or less,
Item 5. The copper phthalocyanine pigment composition according to item 2 or 4, wherein

Item 7. Furthermore, formula (III):

7. The copper phthalocyanine pigment composition according to any one of Items 1 to 6, which contains a pigment derivative represented by

Item 8. An ink composition comprising at least the pigment composition according to any one of Items 1 to 7, a nitrocellulose resin, and a glycol ether solvent. ].

According to the present invention, it is possible to provide a copper phthalocyanine pigment composition having good viscosity suitability (initial viscosity, temporal viscosity) and excellent re-solubility in a glycol ether ink.

Hereinafter, the present invention will be described in detail.
The present invention relates to a β-type copper phthalocyanine pigment,
Formula (I):

[Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a C ₁ to C ₂₀ alkyl group, and at least one of R ¹ , R ² , R ³ and R ⁴ is And a pigment derivative represented by the C ₆ -C ₂₀ alkyl group]. A copper phthalocyanine pigment composition comprising:

Such a pigment composition of the present invention exhibits excellent fluidity even when used as a printing ink or paint. Furthermore, the pigment composition of the present invention is excellent in viscosity suitability and excellent in re-solubility in the glycol ether-based ink which has recently been required.
In the present invention, viscosity suitability refers to the initial viscosity and the viscosity over time when the ink is prepared.
In the present invention, resolubility refers to the solubility of the pigment composition in the ink once it has become a dry substance in the solvent constituting the ink. For example, low resolubility (poor) means that the pigment composition is once again difficult to dissolve in a solvent once it becomes a dry product.
In the actual printing machine, the ink remaining on the printing plate after transfer (printing) to the medium is relatively easy to dry. Therefore, when it returns to the ink tank, it is considered preferable to dissolve again in its own ink. However, it is known that when the re-solubility is poor, the dried ink is stacked, which causes problems in printing, such as transfer failure to media and generation of printing streaks. From these points of view, resolubility is one of the important printability.

<Description of β-type copper phthalocyanine pigment>
The copper phthalocyanine pigment used in the present invention is a copper phthalocyanine crude (β) which is finely pulverized by dry grinding and then converted to a β type by solvent pigmentation, or copper phthalocyanine crude (β) is an inorganic salt together with a solvent Examples include β-type copper phthalocyanine obtained by heat-grinding treatment using crystals. A commercially available product (for example, FASTOGEN BLUE 5362K or FASTOGEN BLUE TGR manufactured by DIC, etc. may be used) may be used, or it may be manufactured and used by a known conventional method. In addition, an α-type copper phthalocyanine pigment or other structural pigment may be contained within a range not to adversely affect the performance as needed, such as hue adjustment. Of course, well-known processes may be added appropriately after production to be used in the present invention.

Even if it is beta-type copper phthalocyanine to which surface treatment with a resin and surface modification with a pigment derivative or a dispersing agent have been performed for the purpose of pigment crystal control and improvement of application suitability, it may be used as long as it does not adversely affect the performance. .

<Description of pigment derivative>
The pigment derivative used in the present invention is described in detail below.
1. Description of the pigment derivative represented by formula (I)

... Formula (I)

In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a C ₁ to C ₂₀ alkyl group, and at least one of R ¹ , R ² , R ³ and R ⁴ is C _The “C ₁ to C ₂₀ alkyl group” which is a ₆ to C ₂₀ alkyl group means a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n- group Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like.
The “C ₆ -C ₂₀ alkyl group” that can be taken by at least one of R ¹ , R ² , R ³ and R ⁴ is n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, An n-icosyl group and the like can be mentioned, but from the viewpoint of resolubility, a C ₈ to C ₁₈ alkyl group is preferable, and a C ₁₀ to C ₁₅ alkyl group is more preferable.
Furthermore, in order to obtain the excellent effects of the present invention, it is preferable that ^{two of} R ¹ , R ² , R ³ and R ⁴ be “C ₆ to C ₂₀ alkyl groups”, Examples of the C ₆ -C ₂₀ alkyl group "include those described above.
When one to three of R ¹ , R ² , R ³ and R ⁴ are “C ₆ to C ₂₀ alkyl group”, the remaining one to three are a hydrogen atom or C ₁ to C ₂₀ It is known that too many long-chain alkyl groups cause resistance in the ink and cause thickening of the ink. Further, a C ₁ to C ₃ alkyl group is preferable because the adsorption inhibition of the dispersion resin and the decrease in the compatibility with the ink solvent may be caused by the steric hindrance of the long chain alkyl group.
Of course, all of R ¹ , R ² , R ³ and R ⁴ may be “C ₆ -C ₂₀ alkyl group”.
In the pigment derivative represented by the formula (I), the copper phthalocyanine skeleton acts as an adsorption site to the copper phthalocyanine pigment, and the sulfonic acid quaternary ammonium salt moiety acts as a compatible group with the glycol ether solvent. Therefore, the dispersibility of the pigment and the pigment derivative represented by the formula (I) in the ink solvent is improved, and good resolubility can be expressed by appropriately inhibiting the film formation of the resin. On the other hand, when the sulfo group acts as an adsorption site for NC resin or the like, the resin can be adsorbed on the surface of the pigment and the pigment derivative represented by the formula (I). Therefore, the resin resistance in the ink solvent is reduced, and the effect of lowering the ink viscosity is obtained.

The present invention is based on the finding that the effect of the present invention can be obtained by using a pigment derivative having a specific structure with respect to copper phthalocyanine among trial derivatives by countless possible derivatives.
Since the present invention is found by trial and error, the mechanism of action is not clear, but the present inventors examined from the following viewpoints.
If the pigment or the pigment derivative does not quickly conform to the ink solvent, only the ink resin preferentially bonds and forms a film preferentially in the drying process, and the resolubility in the ink solvent is significantly reduced. Therefore, by treating the quaternary ammonium salt of copper phthalocyanine sulfonic acid which is compatible with glycol ether solvents, the pigment or the pigment derivative is uniformly dispersed between the coating films to obtain an appropriate coating film strength in which resolubility is expressed. It is believed that things will be possible. This effect can not be exhibited by the addition of derivatives such as those conventionally studied, such as monosubstituted copper phthalocyanine sulfonic acid primary ammonium salts.

2. Description of the pigment derivative represented by formula (II)

··· Formula (II)

In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a C ₁ to C ₂₀ alkyl group, and at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ is C ₆ is an alkyl group ~ _{C 20,} groups represented by the formula (II) in the two _{^{^{^{(SO 3 NR 5 R 6 R}}}} 7 R 8) may or may not be the same or different, are identical It is desirable from an industrial point of view.
The “C ₁ to C ₂₀ alkyl group” means methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-group -Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-octadecyl group And -nonadecyl group, n-icosyl group and the like.
The “C ₆ to C ₂₀ alkyl group” that at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ can take is n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -Decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-nonadecyl group -Icosyl group and the like can be mentioned, but from the viewpoint of resolubility, a C ₈ to C ₁₈ alkyl group is preferable, and a C ₁₀ to C ₁₅ alkyl group is more preferable.
Furthermore, in order to obtain the excellent effects of the present invention, it is preferable that two of R ⁵ , R ⁶ , R ⁷ and R ⁸ be “C ₆ to C ₂₀ alkyl groups”, Examples of the C ₆ -C ₂₀ alkyl group "include those described above.
When one to three of R ⁵ , R ⁶ , R ⁷ and R ⁸ are “C ₆ to C ₂₀ alkyl group”, the remaining one to three are a hydrogen atom or C ₁ to C ₂₀ It is known that too many long-chain alkyl groups cause resistance in the ink and cause thickening of the ink. Further, a C ₁ to C ₃ alkyl group is preferable because the adsorption inhibition of the dispersion resin and the decrease in the compatibility with the ink solvent may be caused by the steric hindrance of the long chain alkyl group.
Of course, all of R ⁵ , R ⁶ , R ⁷ and R ⁸ may be “C ₆ -C ₂₀ alkyl group”.

The pigment composition of the present invention can further obtain the effects of the present invention by further having a derivative of the formula (II). In the derivative, a copper phthalocyanine skeleton functions as an adsorption site to a copper phthalocyanine pigment, and a sulfonic acid quaternary ammonium salt portion functions as a compatible group with a glycol ether solvent. Therefore, the dispersibility of the pigment and the pigment derivative represented by the formula (I) in the ink solvent is improved, and good resolubility can be expressed by appropriately inhibiting the film formation of the resin. Moreover, since it is a disubstituted compound, the resolubility improvement effect is high compared with Formula (I).

3. Description of the pigment derivative represented by formula (III)

··· Formula (III)

The pigment composition of the present invention can further obtain the effects of the present invention by further having a derivative of the formula (III). Particularly in the ink composition using a nitrocellulose resin (hereinafter referred to as NC resin), the derivative has a copper phthalocyanine skeleton acting as an adsorption site to a copper phthalocyanine pigment while a sulfo group acts as an adsorption site such as NC resin. By working, the resin can be adsorbed on the surface of the pigment and the pigment derivative represented by the formula (III). Therefore, the resin resistance in the ink solvent is reduced, and the effect of lowering the ink viscosity is obtained.

<Description of compounding amount>
The pigment derivative represented by the formula (I) is 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the β-type copper phthalocyanine pigment, and the pigment derivative represented by the formula (II) is 0.1 The total amount of the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) is 10.0 parts by mass or less. By using it, it is possible to obtain preferable effects in terms of ink viscosity.

<Method of producing pigment derivative>
Here, the manufacturing method of each pigment derivative is shown. Either method may be adopted. As the di-substituted copper phthalocyanine pigment sulfonic acid derivative as a raw material, di-substituted copper phthalocyanine pigment sulfonic acid derivatives produced by a commercially available method or a commonly used method can be used, and as a commonly used method, for example, copper phthalocyanine Disubstituted copper phthalocyanine pigment sulfonic acid derivatives can be prepared by sulfonation of the pigment with concentrated sulfuric acid or oleum, or by sulfochlorination of the above starting material with chlorosulfonic acid followed by hydrolysis with water. The desired derivative is obtained by mixing the amine in the homogeneous or heterogeneous phase of the water or organic solvent of the disubstituted copper phthalocyanine pigment sulfonic acid derivative. Formula (I) can be obtained by using 0.5 mol of amine per mol of sulfo group of disubstituted copper phthalocyanine pigment sulfonic acid derivative, per mol of sulfo group of disubstituted copper phthalocyanine pigment sulfonic acid derivative By using 1 mole of amine, it is possible to produce a pigment derivative of the formula (III) by acid-precipitating the disubstituted copper phthalocyanine pigment sulfonic acid derivative and filtering off the disubstituted copper phthalocyanine pigment.

An example of a method for easily obtaining the pigment composition of the present invention is described below, but the present invention should not be construed as being limited thereto.
<Method of producing pigment composition>
The copper phthalocyanine crude is dry ground with an attritor to obtain a copper phthalocyanine ground product. Water, xylene, rosin and disubstituted copper phthalocyanine sulfonic acid are added to the copper phthalocyanine attrition to carry out pigmenting at 93 ° C. for 3 hours. After completion of the pigmentation, add disubstituted copper phthalocyanine sulfonic acid and additionally disperse at 93 ° C. for 1 hour. After completion of the dispersion, the temperature is raised to 100 ° C. to distill off xylene. After evaporation, a 9% aqueous acetic acid solution is added dropwise to adjust to pH = 3.5-4.0. The laurylamine acetic acid solution is added to this, and it stir-processes for 1 hour. Then filter and re-slurry the pigment press cake with water. After stirring, the product is dried by a spray dryer to obtain a powder pigment. The pigment composition of the present invention can be obtained by powder-blending a disubstituted copper phthalocyanine sulfonic acid quaternary ammonium salt with the obtained powder pigment composition.
A similar pigment composition can also be obtained by introducing the formulas (I), (II) and (III) into the kneader grinding pigmentation.
The same pigment composition can also be obtained by mixing the dried derivatives of Formula (I), Formula (II), and Formula (III) with the dried copper phthalocyanine pigment. It is also possible to combine two or more of the above manufacturing methods.

In addition, the pigment composition of the present invention can be further adjusted to be suitable for each application by further containing an additive, a dispersant and the like as long as the effect of the present invention is not adversely affected.
Moreover, the pigment composition of this invention can also be used together and used organic pigments other than (beta) -type copper phthalocyanine pigment as a coloring component.
Organic pigments that can be used in combination can be selected appropriately from among known organic pigments in accordance with various uses.

The pigment composition of the present invention thus obtained can be suitably used in any application requiring a coloring function. For example, it can be used in various conventional applications such as paints, printing inks, colored molded articles, toners for electrostatic charge image development, color filters for liquid crystal display devices, aqueous inks for inkjet recording, and the like.

The pigment composition of the present invention can provide a printing ink excellent in initial viscosity and storage stability. The printing ink can be prepared by mixing various known binder resins, various solvents, various additives and the like with the pigment composition of the present invention according to the conventional preparation method. Specifically, a liquid ink can be prepared by adjusting a base ink for liquid ink having a high pigment concentration and using various binders, various solvents, various additives, and the like.

The pigment composition of the present invention can produce PU ink and NC ink excellent in initial viscosity and storage stability, and is suitable as an organic pigment composition for gravure printing ink and flexographic printing ink. The PU ink comprises a PU resin, a pigment, a solvent and various additives, and the NC ink comprises an NC resin, a pigment, a solvent and various additives. The PU resin is not particularly limited as long as it has a urethane structure in the skeleton, and includes polyurethane, polyurethane polyurea and the like. As the solvent, aromatic organic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, Ester solvents such as methanol, ethanol, n-propanol, isopropanol, alcohol solvents such as n-butanol, isobutanol, t-butanol, propylene glycol monoethyl ether (herein, 1-ethoxy-2-propanol and the like) May be written), propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, (Poly) alkylene glycol monoalkyl ether solvents such as glycol mono-i-propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, ethylene glycol monomethyl ether (Poly) alkylene glycol monoalkyl ether acetate solvents such as acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol di Chirueteru, like other ether solvent such as diethylene glycol diethyl ether. In the present invention, glycol ether solvents refer to (poly) alkylene glycol monoalkyl ether solvents and (poly) alkylene glycol monoalkyl ether acetate solvents among the above solvents. Examples of glycol solvents include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, Propyl cellosolve and dipropylene glycol monomethyl ether are preferred. The solvents may be used alone or in combination of two or more. As various additives, surfactants such as anionic, nonionic, cationic and amphoteric surfactants, gum rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, hydrogenated rosin, hardened rosin, hardened rosin, alkyd phthalate resin, etc. Rosins, pigment derivatives, dispersants, wetting agents, adhesion aids, leveling agents, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components and the like can be used.

When the pigment composition of the present invention is used as a printing ink, the printing ink using the pigment composition of the present invention prepared as described above may be diluted in ethyl acetate, polyurethane varnish, or polyamide varnish. it can. A well-known and usual method can be employ | adopted for preparation of printing ink.

When the pigment composition of the present invention is used as a paint as a coloring agent, various resins such as acrylic resin, melamine resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin and phenol resin are used as the paint.

As solvents used for paints, aromatic solvents, acetic acid ester solvents, propionate solvents, alcohol solvents, ether solvents, ketone solvents, aliphatic hydrocarbon solvents, nitrogen compound solvents, lactone solvents Carbamates such as a 48: 52 mixture of methyl carbamate and ethyl carbamate, water, and the like. As the solvent, in particular, polar solvents such as propionate type, alcohol type, ether type, ketone type, nitrogen compound type, lactone type, water and the like and soluble in water are suitable.

In addition, when a pigment additive and / or a pigment composition is dispersed or mixed in a liquid resin to form a resin composition for a paint, conventional additives such as dispersants, fillers, and paints are prepared. Auxiliary agents, desiccants, plasticizers and / or auxiliary pigments can be used. This is accomplished by dispersing or mixing each component, alone or several together, collecting all the components, or adding all of them at once.

As a disperser for dispersing the composition containing the pigment composition prepared according to the application as described above, a disperser, homomixer, paint conditioner, scandex, bead mill, attritor, ball mill, two rolls, three rolls Although a known dispersing machine such as a roll and a pressure kneader can be mentioned, it is not limited thereto. In the dispersion of the pigment composition, a resin and a solvent are added and dispersed such that the viscosity of the pigment composition can be dispersed by the disperser. The high concentration paint base after dispersion has a solid content of 5 to 20%, to which a resin and a solvent are further mixed to be used as a paint.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. Unless otherwise noted in the following examples and comparative examples, “%” represents “mass%”.

Example 1
Dry grinding was performed on copper phthalocyanine crude manufactured by DIC Corporation using an attritor to obtain a copper phthalocyanine ground material. To 200 parts of this copper phthalocyanine ground product, 330 parts of a rosin solution and 450 parts of (1) copper phthalocyanine sulfonic acid solution were added. To this was added 220 parts of water and heated to 93 ° C. Immediately after completion of heating, 15 parts of xylene was added, and the mixture was stirred at 93 ° C. for 3 hours. After the completion of the stirring, (2) 330 parts of a copper phthalocyanine sulfonic acid solution was added and additionally dispersed at 93 ° C. for 1 hour. After completion of the dispersion, the temperature was raised to 100 ° C. to distill off xylene. Water was added until the total amount reached 4000 parts after evaporation, and a 9% aqueous acetic acid solution was added dropwise over 30 minutes to adjust to pH 3.9. To this, 500 parts of dimethyldialkyl (C = 12) acetic acid solution is added and stirred for 1 hour. Thereafter, the resultant was filtered, and the pigment press cake was reslurried with 250 parts of water and dried with a spray dryer to obtain a powdery pigment composition.

The following items used in Example 1 will be described below.
Rosin solution 4.6 parts of a 20% aqueous sodium hydroxide solution and 4.4 parts of hydrogenated rosin were added to 321 parts of water, and the hydrogenated rosin was dissolved by heating and stirring.
-About the above (1) copper phthalocyanine sulfonic acid solution, 7.4 parts of 20% aqueous sodium hydroxide solution and 8.2 parts of copper phthalocyanine sulfonic acid (number of substituents 2) are added to 434.4 parts of water, and the copper phthalocyanine is heated and stirred. A solution of sulfonic acid.
The solution of the above (2) copper phthalocyanine sulfonic acid is added to 323.1 parts of water, 4.3 parts of a 20% aqueous sodium hydroxide solution and 2.6 parts of copper phthalocyanine sulfonic acid (number of substituents) are added, and the copper phthalocyanine is heated and stirred. A solution of sulfonic acid.
-Dimethyldialkyl (C = 12) Acetic acid solution added to 471.8 parts of water with 22 parts of 99% dimethyldialkyl (C = 12) ammonium and 6.7 parts (6.1 parts as quaternary ammonium), dimethyl chloride A solution in which dialkyl (C = 12) ammonium is dissolved by heating and stirring.

Example 2
Dry grinding was performed on copper phthalocyanine crude manufactured by DIC Corporation using an attritor to obtain a copper phthalocyanine ground material. To 200 parts of this copper phthalocyanine ground product, 330 parts of a rosin solution and 450 parts of (1) copper phthalocyanine sulfonic acid solution were added. To this was added 220 parts of water and heated to 93 ° C. Immediately after completion of the heating, 15 parts of xylene is added and the mixture is stirred at 93 ° C. for 3 hours. Thereafter, the temperature was raised to 100 ° C. to distill off xylene. Water was added until the total amount reached 4000 parts after evaporation, and a 9% aqueous acetic acid solution was added dropwise over 30 minutes to adjust to pH 3.9. Thereafter, it was filtered and washed, and the pigment press cake was reslurried with 250 parts of water. Thereafter, it was dried by a spray drier to obtain a powdery pigment. 12.6 parts of copper phthalocyanine sulfonic-acid quaternary ammonium (dimethyl dialkyl (C = 12)) salt was powder-blended with respect to the obtained powder pigment composition whole quantity. Thus, a powdery pigment composition was obtained.

The following items used in Example 2 will be described below.
Regarding a rosin solution: 4.6 parts of a 20% aqueous sodium hydroxide solution and 4.4 parts of hydrogenated rosin were added to 321 parts of water, and the hydrogenated rosin was dissolved by heating and stirring.
-About the above (1) copper phthalocyanine sulfonic acid solution, add 7.4 parts of a 20% aqueous sodium hydroxide solution and 5.0 parts of copper phthalocyanine sulfonic acid (number of substituents 2) to 432 parts of water, and heat stir to give copper phthalocyanine sulfonic acid Dissolved.
-About the powder production method of (2) copper phthalocyanine sulfonic acid quaternary ammonium (dimethyl dialkyl (C = 12)) salt 3.6 parts of 20% sodium hydroxide aqueous solution and copper phthalocyanine sulfonic acid (number of substituents 2) in 441 parts of water 5.9 parts are added and dissolved by heating and stirring. Thereto, 22 parts of 99% acetic acid and 5.3 parts of dimethyldialkyl (C = 12) ammonium chloride (4.8 parts as quaternary ammonium) were added to 471.8 parts of water and dissolved by heating and stirring. . The pH was adjusted to 6.8 to 7.5, and filtration was performed to obtain a presscake of copper phthalocyanine sulfonic acid quaternary ammonium salt. This is dried and pulverized to obtain a powdered copper phthalocyanine sulfonic acid quaternary ammonium salt.

Example 3
(First step) Copper phthalocyanine crude manufactured by DIC Co. was dry-ground with an attritor to obtain a copper phthalocyanine-ground product.
(Second step) To 200 parts of this copper phthalocyanine ground product, 330 parts of a rosin solution and (1) 450 parts of a copper phthalocyanine sulfonic acid solution were added. To this was added 220 parts of water and heated to 93 ° C. Immediately after completion of heating, 15 parts of xylene was added, and the mixture was stirred at 93 ° C. for 3 hours. After the completion of the stirring, (2) 330 parts of a copper phthalocyanine sulfonic acid solution was added and additionally dispersed at 93 ° C. for 1 hour. After completion of the dispersion, the temperature was raised to 100 ° C. to distill off xylene. Water was added until the total amount reached 4000 parts after evaporation, and a 9% aqueous acetic acid solution was added dropwise over 30 minutes to adjust to pH 3.9. To this, 500 parts of laurylamine (primary ammonium (monoalkyl)) acetic acid solution was added and stirred for 1 hour. Thereafter, the resultant was filtered, and the pigment press cake was reslurried with 250 parts of deionized water. After completion of the stirring treatment, it was dried by a spray drier to obtain a powdery pigment composition.

The following items used in Example 3 will be described below.
Rosin solution 15 parts of a 20% aqueous sodium hydroxide solution and 15.0 parts of hydrogenated rosin are added to 321 parts of water, and the hydrogenated rosin is dissolved by heating and stirring.
-About the above (1) copper phthalocyanine sulfonic acid solution, 7.4 parts of 20% aqueous sodium hydroxide solution and 8.3 parts of copper phthalocyanine sulfonic acid (number of substituents 2) are added to 434.4 parts of water, and the copper phthalocyanine is heated and stirred. A solution of sulfonic acid.
· With regard to (2) copper phthalocyanine sulfonic acid solution, 4.3 parts of 20% aqueous sodium hydroxide solution and 4.5 parts of copper phthalocyanine sulfonic acid (number of substituents 2) were added to 323.1 parts of water, and copper phthalocyanine was heated and stirred. A solution of sulfonic acid.
A solution obtained by adding 22 parts of 99% acetic acid and 6.2 parts of laurylamine to 471.8 parts of water with respect to a laurylamine (primary ammonium (monoalkyl)) acetic acid solution and dissolving the laurylamine by heating and stirring.

Example 4
Dry grinding was performed on copper phthalocyanine crude manufactured by DIC Corporation using an attritor to obtain a copper phthalocyanine ground material. To 200 parts of this copper phthalocyanine ground product, 330 parts of a rosin solution and 450 parts of (1) copper phthalocyanine sulfonic acid solution were added. To this was added 220 parts of water and heated to 93 ° C. Immediately after completion of heating, 15 parts of xylene was added, and the mixture was stirred at 93 ° C. for 3 hours. After the completion of the stirring, (2) 330 parts of a copper phthalocyanine sulfonic acid solution was added and additionally dispersed at 93 ° C. for 1 hour. After completion of the dispersion, the temperature was raised to 100 ° C. to distill off xylene. Water was added until the total amount reached 4000 parts after evaporation, and a 9% aqueous acetic acid solution was added dropwise over 30 minutes to adjust to pH 3.9. To this, 500 parts of a dimethyldialkyl (C = 12) acetic acid solution was added and stirred for 1 hour. Thereafter, the resultant was filtered, and the pigment press cake was reslurried with 700 parts of water and dried with a spray dryer to obtain a powdery pigment composition.

The following items used in Example 4 will be described below.
Regarding a rosin solution: 4.6 parts of a 20% aqueous sodium hydroxide solution and 4.4 parts of hydrogenated rosin were added to 321 parts of water, and the hydrogenated rosin was dissolved by heating and stirring.
-About the above (1) copper phthalocyanine sulfonic acid solution, 7.4 parts of 20% aqueous sodium hydroxide solution and 8.2 parts of copper phthalocyanine sulfonic acid (number of substituents 2) are added to 434.4 parts of water, and the copper phthalocyanine is heated and stirred. A solution of sulfonic acid.
The solution of the above (2) copper phthalocyanine sulfonic acid is added to 323.1 parts of water, 4.3 parts of a 20% aqueous sodium hydroxide solution and 2.6 parts of copper phthalocyanine sulfonic acid (number of substituents) are added, and the copper phthalocyanine is heated and stirred. A solution of sulfonic acid.
Add dimethyldialkyl (C = 12) acetic acid solution to 471.8 parts of water, add 22 parts of 99% acetic acid, 6.2 parts of dimethyldialkyl chloride (C = 12) ammonium (5.6 parts as quaternary ammonium), A solution in which dimethyldialkyl chloride (C = 12) ammonium is dissolved by heating and stirring.

Comparative Example 1
Dry grinding was performed on copper phthalocyanine crude manufactured by DIC Corporation using an attritor to obtain a copper phthalocyanine ground material. 3960 parts of isobutanol and 8040 parts of water were added to 1350 parts of the copper phthalocyanine attrition. After heating to 89 ° C. and reflux pigmenting for 1 hour, isobutanol was distilled off. Water was then added until the total amount was 12000 parts. It was dried by a spray dryer to obtain a powder pigment. To 200.0 parts of this copper phthalocyanine powder pigment, 14.0 parts of copper phthalocyanine sulfonic acid quaternary dimethyl dialkyl (C = 18) ammonium salt was powder blended. Thus, a powdery pigment composition was obtained.

-Powder preparation method of copper phthalocyanine sulfonic acid quaternary dimethyl dialkyl (C = 18) salt 3.6 parts of 20% sodium hydroxide aqueous solution and 17.3 parts of copper phthalocyanine sulfonic acid (number of substituents 2) are added to water of 440 parts and heated. It was dissolved by stirring. Thereto, 22 parts of 99% acetic acid and 27.5 parts of dimethyldialkyl chloride (C = 18) ammonium were added to 471.8 parts of water, and those dissolved by heating and stirring were dropped. The pH was adjusted to a weak alkali of 7 to 8, and filtration was performed to obtain a presscake of copper phthalocyanine sulfonic acid quaternary dimethyldialkyl (C = 18) ammonium salt. This was dried and pulverized to obtain a powdery copper phthalocyanine sulfonic acid quaternary dimethyl dialkyl (C = 18) ammonium salt.

Comparative example 2
Dry grinding was performed on copper phthalocyanine crude manufactured by DIC Corporation using an attritor to obtain a copper phthalocyanine ground material. 3960 parts of isobutanol and 8040 parts of water were added to 1350 parts of the copper phthalocyanine attrition. After heating to 89 ° C. and reflux pigmenting for 1 hour, isobutanol was distilled off. Water was then added until the total amount was 12000 parts. It was dried by a spray dryer to obtain a powder pigment. To 200.0 parts of this copper phthalocyanine powder pigment, 14.0 parts of copper phthalocyanine sulfonic acid (number of substituents: 2) was powder blended. Thus, a powdery pigment composition was obtained.

Preparation of Evaluation Ink (1) Preparation of Evaluation Ink 17.3 parts of pigment, 8.9 parts of NC resin, 48.7 parts of propylene glycol monoethyl ether (manufactured by Kanto Chemical Co., Ltd.), n-propyl alcohol (Kanto Chemical Co., Ltd.) 8.0 parts, ethanol (Kanto Chemical Co., Ltd.) 11.0 parts, ethyl acetate (Kanto Chemical Co., Ltd.) 6.1 parts, SAZ beads (Tokyo Glass Instruments Co., Ltd. zirconia YTZ ball 1.25φ) One hundred and fifty (150) parts were placed in a 200 mL glass bottle and dispersed for 2 hours with Shaker Skandex SK550 (manufactured by Fast & Fluid Management B. V. Company) to obtain an evaluation ink.

(2) Ink viscosity adjustment Ethanol (made by Kanto Chemical Co., Ltd.) was added as needed, and the viscosity was adjusted. The viscosity is determined by using It adjusted to 23 seconds using 2 (made by Meisei Co., Ltd.).

(3) Hue evaluation method The ink whose viscosity was adjusted in (2) was used for the bar coater No. 2 (manufactured by RK Print Coat Instruments) was used to develop a color paper or acetate film, and the hue was visually determined.

(4) Viscosity evaluation method The viscosity was measured at 6 to 120 RPM using a Brookfield viscometer (model: DV3TRVTJO).

(5) Re-dissolving test method The ink prepared in (2) was spread on a re-dissolving evaluation plate. After that, it was dried with a dryer for 1 minute. Thereafter, ethanol (manufactured by Kanto Chemical Co., Ltd.) was poured on the ink-coated surface dried from the top of the resolubility evaluation plate. If the dried ink coating surface fell, it was judged that the resolubility was good, and if it did not fall, it was defective. When it was not possible to make a judgment alone, it was displayed side-by-side with the target ink coating surface, and the superiority was judged by comparison.

Glycol Ether Ink Evaluation <Viscosity>
:: good at a measured viscosity of 1500 mPa · s or less ○: good at a measured viscosity of 1500 to 2000 mPa · s ×: defective at a measured viscosity of 2000 mPa · s or more

<Resolubility>
:: All the ink runs down and re-dissolution is good. :: Some ink remains but re-dissolution is good. X: Ink does not run out and re-dissolution is poor

<Hue>
:: Color development and transparency good by visual judgment O: Color development and transparency within the use range by visual judgment ×: Color development and poor transparency

Example 1 contains Formula (I) and Formula (II), and low viscosity-ization can be achieved because Formula (I) works as a resin adsorption site. Moreover, Formula (I) and Formula (II) are highly compatible with the glycol ether solvent, and good resolubility is expressed. The resolubility improving effect is higher in the formula (II) than in the formula (I).

Example 2 contains Formula (I), Formula (II), and Formula (III), and a low viscosity-ization can be achieved because Formula (I) and Formula (III) work as a resin adsorption site. In addition, the formula (I) and the formula (II) are highly compatible with the glycol ether solvent, and good resolubility is expressed. Formula (III) shows a better resin adsorption effect than Formula (I). The resolubility improving effect is higher in the formula (II) than in the formula (I).

Example 3 contains Formula (I) and Formula (III), and low viscosity-ization can be achieved by each acting as a resin adsorption site. Further, the formula (I) is highly compatible with the glycol ether solvent, and resolubility is developed. Formula (III) shows a better resin adsorption effect than Formula (I).

Since Example 4 contains only Formula (I), coexistence of low viscosity-ization and resolubility improvement effect can be achieved. However, since the formula (II) and the formula (III) are not contained, the effect is low.

Since Comparative Example 1 contains only the formula (II), the compatibility with the glycol ether solvent is high, and good resolubility is exhibited. However, the viscosity is extremely high because it does not contain the formula (I) or the formula (III), which is not a range that can be used industrially.

Since Comparative Example 2 contains only the formula (III), it works as a resin adsorption site and can achieve viscosity reduction. However, it does not contain formula (I) and formula (II), it is significantly inferior to resolubility and can not be used industrially.

Claims

β-type copper phthalocyanine pigment,
Formula (I):

Formula (I)
[Wherein, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a C 1 to C 20 alkyl group, and at least one of R 1 , R 2 , R 3 and R 4 is A pigment derivative represented by the formula: C 6 -C 20 alkyl group], and a copper phthalocyanine pigment composition comprising
β-type copper phthalocyanine pigment,
Formula (I):

Formula (I)
[Wherein, R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a C 1 to C 20 alkyl group, and at least one of R 1 , R 2 , R 3 and R 4 is A pigment derivative represented by C 6 -C 20 alkyl group],
Formula (II):

Formula (II)
[Wherein, R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or a C 1 to C 20 alkyl group, and at least one of R 5 , R 6 , R 7 and R 8 is A pigment derivative represented by the formula: C 6 -C 20 alkyl group], and a copper phthalocyanine pigment composition comprising
The copper phthalocyanine pigment composition according to claim 1, wherein any two of R 1 , R 2 , R 3 and R 4 in the formula (I) are a C 6 to C 20 alkyl group. .
In the above formula (I), any two of R 1 , R 2 , R 3 and R 4 are a C 6 to C 20 alkyl group, and in the above formula (II), R 5 , R 6 , R 7 and The copper phthalocyanine pigment composition according to claim 2, wherein any two of R 8 are a C 6 to C 20 alkyl group.
With respect to 100 parts by mass of β-type copper phthalocyanine pigment,
The copper phthalocyanine pigment composition according to claim 1 or 3, wherein the pigment derivative represented by the formula (I) is contained in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less.
With respect to 100 parts by mass of β-type copper phthalocyanine pigment,
The pigment derivative represented by the formula (I) is 0.1 parts by mass or more and 10.0 parts by mass or less,
The pigment derivative represented by the formula (II) is contained in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less, provided that the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) The total amount of with is 10.0 parts by mass or less,
The copper phthalocyanine pigment composition according to claim 2 or 4, characterized in that
Furthermore, formula (III):

Formula (III)
The copper phthalocyanine pigment composition according to any one of claims 1 to 6, which contains a pigment derivative represented by
An ink composition comprising at least the copper phthalocyanine pigment composition according to any one of claims 1 to 7, a nitrocellulose resin, and a glycol ether solvent.