JP6583586B1 - Dioxazine pigment composition and ink composition having the same - Google Patents

Abstract

The problem to be solved by the present invention is to provide a dioxazine pigment composition with significantly improved fluidity. Dioxazine pigment and the following formula (I) [wherein R1, R2, R3 and R4 each independently represent a hydrogen atom or a C1-C20 alkyl group, and at least one of R1, R2, R3 and R4 is C6. The above-mentioned problems are solved by providing a dioxazine pigment composition comprising a pigment derivative represented by the formula: ~ C20 alkyl group].

Description

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

In general, pigments for coloring purposes are composed of fine particles. For example, when a pigment, which is an aggregate of fine primary particles, is dispersed in a medium, such as printing inks and paints for gravure printing, flexographic printing, etc., a strong force is applied for a long time to loosen the particles. Some ideas have been made such as dispersing or adding a dispersing agent.
Especially, C.I. I. Although dioxazine pigments represented by Pigment Violet 23 are pigments used in various situations, they tend to cause structural stacking and tend to agglomerate strongly, so that they are fluid when used as colorants in various applications. Such a problem was remarkable. In view of this, techniques for using a dioxazine pigment derivative in combination for improving the fluidity have been studied. For example, Patent Document 1 describes that a certain dioxazine pigment sulfonic acid derivative is used in combination with a dioxazine pigment.

JP 2009-29858 A

  However, the method described in Patent Document 1 cannot be said to improve fluidity sufficiently.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a combination of a plurality of specific dioxazine pigment derivatives with respect to the dioxazine pigment, thereby improving the fluidity of the pigment composition over the prior art. Has been found, and the present invention has been completed.

That is, the present invention
[Section 1. A dioxazine pigment,
Formula (I):

[Where:
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a C ₁ -C ₂₀ alkyl group, and at least one of R ¹ , R ² , R ³ and R ⁴ is C ₆ -C a pigment derivative represented by a ₂₀ alkyl group,
A dioxazine pigment composition comprising:

Item 2. A dioxazine pigment,
A pigment derivative represented by the formula (I),
Formula (II):

[Where:
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 to} C a pigment derivative represented by a ₂₀ alkyl group,
Item 2. The dioxazine pigment composition according to Item 1, which contains

Item 3. The dioxazine pigment composition according to claim 1, wherein any ^{two of} R ¹ , R ² , R ³ and R ^{4 in} the formula (I) are C _{6 to} C ₂₀ alkyl groups.

Item 4. In the formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups, and the formula (II): R ⁵ , R ⁶ , R ⁷ and any two of R ^8, but dioxazine pigment composition according to claim 2, wherein the alkyl group of C ₆ -C _20.

Item 5. Item 2 is characterized in that, in the formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups, and any two are methyl groups. 2. The dioxazine pigment composition described in 1.

Item 6. In the formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups, and any two are methyl groups, and the formula (II): R ^{5, R} 6, any two of ^{R 7} and ^{R 8} is an alkyl group of _C 6 _{-C 20,} and dioxazine pigment composition according to claim 2, characterized in that any two of a methyl group .

Item 7. For 100 parts by mass of dioxazine pigment,
Item 2. The dioxazine pigment composition according to Item 1, 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.

Item 8. For 100 parts by mass of dioxazine 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 to 10.0 parts by mass, provided that the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) And the total amount is 10.0 parts by mass or less,
Item 3. The dioxazine pigment composition according to Item 2,

Item 9. Item 9. An ink composition comprising at least the dioxazine pigment composition according to any one of Items 1 to 8, a nitrocellulose resin, and a glycol ether solvent.

Item 10. The ink composition according to claim 9, wherein the glycol ether solvent is a monoether or diether of ethylene glycol or propylene glycol.

Item 11. The glycol ether solvent is at least one selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether. The ink composition according to claim 9, comprising: About].

  According to the present invention, a dioxazine pigment composition excellent in fluidity (initial viscosity, time-dependent viscosity) can be provided.

Hereinafter, the present invention will be described in detail.
The present invention comprises a dioxazine 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 A dioxazine pigment composition comprising: a pigment derivative represented by a C _{6 to} C ₂₀ alkyl group].

A dioxazine pigment;
A pigment derivative represented by the above formula (I);
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 dioxazine pigment composition comprising: a pigment derivative represented by a C _{6 to} C ₂₀ alkyl group].

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 exhibits excellent fluidity even in glycol ether-based inks that have been increasingly demanded from the market in recent years.
In the present invention, fluidity refers to the initial viscosity and the viscosity over time when an ink is prepared.

<Description of dioxazine pigment>
The dioxazine pigment used in the present invention is
C. I. Pigment violet 23, C.I. I. Pigment violet 37, C.I. I. And CI Pigment Blue 80. In particular, C.I. I. Pigment violet 23 (represented by the following chemical structural formula) is important. Such C.I. I. As the pigment violet 23, a commercially available product (for example, FASTOGEN SUPER VIOLET series (manufactured by DIC Corporation, specific surface area by BET method: 50 to 120 m ² / g, etc.) may be used, or a publicly known method. You may manufacture and use. As a known and commonly used method, for example, the method described in Wiley-VCH Verlag-GmbH Publishing (2002) High Performance Pigments, page 186, or the like can be used. Of course, you may use it after adding a well-known process suitably after manufacture. C. I. The specific surface area of the pigment violet 23 by the BET method is preferably in the range of 60 to 80 m ² / g from the viewpoint of preventing aggregation of excessively fine particles and accompanying thickening while maintaining transparency.

<Description of pigment derivative>
The pigment derivative used in the present invention is described in detail below.
1. Explanation of 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 ₆ is an alkyl group having -C _20.
“C ₁ -C ₂₀ alkyl group” means methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
“C ₆ -C ₂₀ alkyl group” which at least one of R ¹ , R ² , R ³ and R ⁴ can take is a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and the like. From the viewpoint of improving fluidity, a C _{8 to} C ₁₈ alkyl group is preferable, and C ₁₀ and more preferably an alkyl group having -C _15.
Furthermore, in order to obtain the excellent effect of the present invention, it is preferable that ^{two of} R ¹ , R ² , R ³ and R ⁴ are “C ₆ -C ₂₀ alkyl groups”. alkyl group of ₆ -C ₂₀ "include those described above.
When one to three Rs out of R ¹ , R ² , R ³ and R ⁴ are “C _{6 to} C ₂₀ alkyl groups”, the remaining one to three Rs are hydrogen atoms or C ₁ to is an alkyl group of C _20, it is preferable from the viewpoint of fluidity is further enhanced, is an alkyl group of C ₁ -C _3. In particular, when any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups and any two are methyl groups, a particularly excellent effect is obtained.
Of course, in the present invention, even if all of R ¹ , R ² , R ³ and R ⁴ are “C ₆ -C ₂₀ alkyl groups”, the effects of the present invention can be obtained.

2. Explanation of 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 having -C _20. The groups represented by two (SO ₃ NR ⁵ R ⁶ R ⁷ R ⁸ ) in formula (II) may be the same or different, but are preferably the same from an industrial viewpoint.
“C ₁ -C ₂₀ alkyl group” means methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
“C ₆ -C ₂₀ alkyl group” which at least one of R ⁵ , R ⁶ , R ⁷ and R ⁸ can take is hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, and the like. From the viewpoint of improving fluidity, a C _{8 to} C ₁₈ alkyl group is preferable, and C ₁₀ and more preferably an alkyl group having -C _15.
Further, in order to obtain the excellent effect of the present invention, it is preferable that two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are “C ₆ -C ₂₀ alkyl groups”. alkyl group of ₆ -C ₂₀ "include those described above.
When one to three Rs out of R ⁵ , R ⁶ , R ⁷ and R ⁸ are “C _{6 to} C ₂₀ alkyl groups”, the remaining one to three Rs are hydrogen atoms or C ₁ to is an alkyl group of C _20, it is preferable from the viewpoint of fluidity is further enhanced, is an alkyl group of C ₁ -C _3.
Of course, in the present invention, even when all of R ⁵ , R ⁶ , R ⁷ and R ⁸ are “C ₆ -C ₂₀ alkyl groups”, the effects of the present invention can be obtained.

The present invention is represented by a group represented by (SO ₃ H) and (SO ₃ NR ¹ R ² R ³ R ⁴ ) with respect to a dioxazine pigment residue by trial and error among a myriad of possible derivatives. Wherein R ¹ , R ² , R ³ and R ⁴ are as described above, and at least one R is a C _{6 to} C ₂₀ alkyl group, one by one. This is because it has been found that the effect of the present invention can be obtained by using the pigment derivative represented by (I) for the dioxazine pigment. Furthermore, the pigment derivative represented by the aforementioned formula (I),
The group (R ⁵ , R ⁶ , R ⁷ and R ⁸ ) represented by (SO ₃ NR ⁵ R ⁶ R ⁷ R ⁸ ) for the dioxazine pigment residue is as described above, and at least one of these When both of the pigment derivatives represented by the formula (II) in which two R are C _{6 to} C ₂₀ alkyl groups are combined with the dioxazine pigment, exceptional fluidity is achieved compared to the conventional case. Pigment composition can be obtained.
Since the present invention has been found by trial and error, the mechanism of action is not clear, but the group represented by (SO ₃ H) in the pigment derivative represented by formula (I) has wettability. It is estimated that the pigment derivative acting in the improving direction and the pigment derivative represented by the formula (II) contributes to an increase in steric hindrance between the pigments.
In particular, the stability after ink preparation in nitrocellulose ink (hereinafter sometimes referred to as NC ink) is improved, and a low viscosity is maintained even after a storage stability test.
Since the glycol ether solvents such as ethoxypropanol constituting the NC ink are more hydrophobic than ethanol constituting the ink that has been conventionally used, the pigment derivative represented by the formula (I) and the formula The alkyl chain portion of the pigment derivative represented by (II) is more spread out in the glycol ether solvent, and is considered to have a large repulsive effect due to steric hindrance. Therefore, it is considered that a higher effect is exhibited in glycol ether-based inks for which market demand has been increasing in recent years.
In the present invention, it is important that the pigment derivative represented by the formula (I) exists, and the sulfonic acid derivative (alkyl ammonium salt) of the dioxazine pigment as in the technique described in Patent Document 1 described above. In the case of using only, there is no remarkable effect as much as the present invention exhibits. The present invention is an invention that differs from the prior art such as Patent Document 1 in that a pigment derivative having a sulfo group in part is also used.

3. Explanation of pigment derivative represented by formula (III)

・・・式（ＩＩＩ）

... Formula (III)

The pigment composition of the present invention can further obtain the effects of the present invention by having a derivative of the formula (III) in addition to the above two pigment derivatives. Due to the combined effect of the three pigment derivatives described so far, particularly in an ink composition using a nitrocellulose resin (sometimes referred to as NC resin in the present specification), an effect of further reducing the ink viscosity can be expected. Conceivable.

<Description of blending amount>
The pigment derivative represented by the formula (I) can be contained in an amount of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the dioxazine pigment. Further, when the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) are used in combination, the pigment derivative represented by the formula (I) is added to 100 parts by mass of the dioxazine pigment. The pigment derivative represented by the formula (II) can be contained in an amount of 0.1 to 10.0 parts by mass (provided that the formula (I) The total amount of the pigment derivative represented by formula (II) and the pigment derivative represented by formula (II) is 10.0 parts by mass or less). By setting it as such a compounding quantity, it is thought that the ink viscosity reduction effect increases more.

<Manufacturing method>
Here, the manufacturing method of each pigment derivative is shown. Any method may be adopted. As the dioxazine pigment sulfonic acid derivative used as a raw material, a dioxazine pigment sulfonic acid derivative (CI Direct Blue 108) which is commercially available or manufactured by a known and conventional method can be used. Examples of the known and conventional method include dioxazine. The dioxazine pigment sulfonic acid derivative can be prepared by sulfonating the pigment with concentrated sulfuric acid or fuming sulfuric acid, or by sulfochlorinating the starting material with chlorosulfonic acid and then hydrolyzing with water. The desired derivative can be obtained by mixing an amine in the homogeneous or heterogeneous phase of the dioxazine pigment sulfonic acid derivative in water or an organic solvent. When the dioxazine pigment sulfonic acid derivative having only two substituents of the sulfo group is used as a raw material, by using 1 mol or less of amine with respect to 2 mol of the sulfo group of the dioxazine pigment sulfonic acid derivative, the formula (I) The represented pigment derivatives can be produced. Moreover, the pigment derivative represented by Formula (I) and Formula (II) can be manufactured simultaneously by using 1-2 mol amine. Furthermore, the pigment derivative of the formula (II) can be produced by using 2 mol or more of amine with respect to 2 mol of the sulfo group of the dioxazine pigment sulfonic acid derivative.
As a raw material, a dioxazine pigment sulfonic acid derivative having a distribution in which the number of substituents of the sulfo group is 1 to 5 can be used for producing each pigment derivative. For example, when an amine is added to a dioxazine pigment sulfonic acid derivative having a distribution of 1 to 3 substituents of the sulfo group, first, the sulfo group of the derivative having 1 substituent and the 1 sulfo group of the derivative having 2 substituents are firstly added. The group and one sulfo group of the derivative having 3 substituents become an ammonium salt (that is, a pigment derivative represented by the formula (I) is synthesized). Next, the second sulfo group of the derivative having 2 substituents and the second sulfo group of the derivative having 3 substituents become ammonium salts (that is, a pigment derivative represented by the formula (II) is synthesized). Finally, the third sulfo group of the derivative having 3 substituents becomes an ammonium salt. By adjusting the amount of amine added to the dioxazine pigment sulfonic acid derivative, the ratio of the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) can be set to a desired value. it can. The substituent distribution of the dioxazine pigment sulfonic acid derivative sulfo group can be analyzed by, for example, liquid chromatography mass spectrometry or field desorption mass spectrometry.

One 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.
A dry powder or wet cake of dioxazine pigment is added to water or an organic solvent and stirred to prepare a dioxazine pigment slurry. To the dioxazine pigment slurry, a dioxazine pigment sulfonic acid derivative dry powder or wet cake, or a dioxazine pigment sulfonic acid derivative slurry dissolved in water / organic solvent is added. Subsequently, a dry powder or wet cake of dioxazine pigment sulfonic acid derivative or an amine solution dissolved in water / organic solvent is added. This is appropriately filtered, dried and pulverized to obtain the pigment composition of the present invention.
The pigment composition of the present invention can also be prepared by mixing a dry powder of a pigment derivative and a dry powder of a dioxazine pigment. That is, mixing the pigment derivative produced by the above-mentioned pigment derivative production method with a suitable ratio so as to obtain the desired ratio of the pigment derivative represented by the formulas (I) to (II) to the dry powder of the dioxazine pigment. Thus, the pigment composition of the present invention can be easily produced.

In addition, the pigment composition of the present invention can be adjusted so as 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 in combination with organic pigments other than a dioxazine pigment as a coloring component.
Organic pigments that can be used in combination can be appropriately selected from known organic pigments according to various uses.

  The pigment composition of the present invention thus obtained can be suitably used for any application that requires a coloring function. For example, it can be used for various known and commonly used applications such as paints, printing inks, colored molded articles, toners for developing electrostatic images, color filters for liquid crystal display devices, and water-based inks for inkjet recording.

  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 commonly known binder resins, various solvents, various additives, and the like with the pigment composition of the present invention according to a conventional preparation method. Specifically, liquid ink can be adjusted 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. PU ink consists of PU resin, pigment, solvent and various additives, and NC ink consists of NC resin, pigment, 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 each solvent,
Aromatic organic solvents such as toluene and xylene,
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone,
Ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate,
Alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, ethylene glycol mono-t -Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i-butyl ether, propylene glycol Mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol Diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol di-i-propyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-i-butyl ether, ethylene glycol di-t-butyl ether, propylene glycol dimethyl ether, propylene Glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol di-i-propyl ether, propylene glycol di-n-butyl ether, propylene glycol di-i-butyl ether, propylene glycol di-t-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, die Lenglycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-i-butyl ether, diethylene glycol mono-t-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-i- Propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-i-butyl ether, diethylene glycol di-t-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol Mono-i-propyl ether, di Propylene glycol mono-n-butyl ether, dipropylene glycol mono-i-butyl ether, dipropylene glycol mono-t-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol Di-i-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol di-i-butyl ether, dipropylene glycol di-t-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol Monomethyl ether acetate, and the like glycol ether solvents such as diethylene glycol monoethyl ether acetate.

  The pigment composition of the present invention exhibits excellent fluidity with respect to inks composed of any solvent, but in order to describe the applicability to glycol ether inks, which have recently increased market demand, To do.

  In recent years, in the general-purpose printing field, there has been a demand for an ink that has a low environmental load and can improve the leveling of the surface of a printed material. In order to achieve this, a low drying speed ink (hereinafter referred to as a glycol ether ink) mainly composed of a glycol ether solvent has attracted attention. Glycol ether-based inks are less volatile than conventional alcohol-based inks, and are expected to improve the leveling properties (higher definition) of the printed surface as the drying speed decreases. However, there is still little knowledge about the ink properties and printability of glycol ether inks. Under these circumstances, the viscosity (initial viscosity, viscosity over time) is known to be an important characteristic of glycol ether inks, but the fluidity of dioxazine pigments is the same as that of conventional alcohol inks. Even if the technology is used, it has become clear that sufficient fluidity cannot be secured.

  If it mentions from a viewpoint which is a solvent which comprises such a recently calculated | required ink, it is preferable that the ink composition of this invention contains the pigment composition of this invention, and a glycol ether solvent at least.

  Among these glycol ether solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether are preferred, and propylene glycol monoethyl ether Ether is more preferred.

  In addition, a solvent may be used independently or 2 or more types may be used together. Various additives include anionic, nonionic, cationic, amphoteric surfactants, gum rosin, polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, cured rosin, phthalic acid alkyd resin, etc. Rosin, pigment derivative, dispersant, wetting agent, adhesion aid, leveling agent, antifoaming agent, antistatic agent, trapping agent, antiblocking agent, wax component and the like can be used.

  The pigment composition of the present invention exhibits excellent fluidity with respect to inks composed of any resin, but is useful in nitrocellulose. Nitrocellulose, also called nitrified cotton, is a resin in which the hydroxyl groups of cellulose are nitrified with a mixed acid of sulfuric acid and nitric acid. The solubility of nitrocellulose in a solvent varies depending on the degree of nitrification, and those having a high degree of nitrification are used for hydrocarbon solvents and ester solvents, and those having a low degree of nitrification are used for alcohol solvents. Nitrocellulose has a high glass transition point, and there is almost no blocking at the time of winding the printed matter. Furthermore, since nitrocellulose-based gravure ink has good printability, nitrocellulose is widely used as a binder resin for printing ink.

  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 with ethyl acetate, polyurethane varnish, or polyamide varnish. it can. The printing ink can be prepared by a known and commonly used method.

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

  Solvents used in the paint include aromatic solvents, acetate solvents, propionate solvents, alcohol solvents, ether solvents, ketone solvents, aliphatic hydrocarbon solvents, nitrogen compound solvents, lactone solvents. Carbamic acid esters such as a 48:52 mixture of methyl carbamate and ethyl carbamate, water, and the like. As the solvent, polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, lactone-based, water and the like that are water-soluble are particularly suitable.

  In addition, when a pigment additive and / or pigment composition is dispersed or mixed in a liquid resin to obtain a resin composition for paints, conventional additives such as dispersants, fillers, paints, etc. Adjuvants, desiccants, plasticizers and / or auxiliary pigments can be used. This is accomplished by dispersing or mixing each component, alone or in combination, collecting all the components, or adding them all at once.

  Dispersers that disperse the composition containing the pigment composition prepared for the application as described above include dispersers, homomixers, paint conditioners, scandex, bead mills, attritors, ball mills, two rolls, and three. Although well-known dispersers, such as a roll and a pressure kneader, are mentioned, it is not limited to these. In the dispersion of the pigment composition, a resin and a solvent are added and dispersed so that the viscosity can be dispersed by these dispersers. The high-concentration paint base after dispersion has a solid content of 5 to 20%, and is further mixed with a resin and a solvent for use as a paint.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “%” represents “% by mass” unless otherwise specified.

[Example 1]
1) C.I. I. 171.9 parts of pigment violet 23 (manufactured by DIC Corporation) (60 parts of pigment) and 828.1 parts of ion-exchanged water were placed in a 2 L stainless steel cup and homodisper 2.5 type (primics) with a rotation speed of 500 rpm. For 30 minutes, C.I. I. A slurry of Pigment Violet 23 was prepared.
2) Separately, a C.I. having a sulfo group average substituent number of 2.4 (the main component is 2 substituents). I. Ion-exchanged water is added to a wet cake of pigment violet 23 sulfonic acid derivative (manufactured by DIC Corporation) (3.0 parts of dye) to make a total of 50 parts, and a magnetic stirrer is used at 60 ° C. in a 100 mL glass beaker. C. for 1 hour with stirring. I. A sulfonic acid derivative slurry of Pigment Violet 23 was prepared.
3) Also, 6.0 parts of acetic acid (Wako Pure Chemical Industries, Ltd.), 100 parts of water, ARCARD 2HT-75 (manufactured by Lion Akzo, dialkyldimethylammonium chloride, alkyl chain = C14 to C18, ammonium salt component 75) %) 4.5 parts in a 200 mL glass beaker were heated and stirred at 60 ° C. for 1 hour using a magnetic stirrer to prepare a dialkyldimethylammonium solution.
4) C.I obtained in 1). I. C. obtained in 2) while stirring the slurry of Pigment Violet 23 with a vertical stirring blade. I. The entire amount of the sulfonic acid derivative slurry of Pigment Violet 23 was added and stirred for 1 hour. Subsequently, the entire amount of the dialkyldimethylammonium solution obtained in 3) was added, and the mixture was further stirred for 1 hour. Next, the reaction solution was subjected to Nutsche filtration, and the filtrate was washed with 3000 parts of water. The filtered material was blown dry (98 ° C., 18 hours) and pulverized to obtain 63.1 parts of a dioxazine pigment composition (1). The ratio of the pigment derivative represented by formula (I) to the pigment derivative represented by formula (II) in the dioxazine pigment composition (1) is estimated to be formula (I): formula (II) = 66: 34 The
[Example 2]
1) C.I. I. 171.9 parts of pigment violet 23 (manufactured by DIC Corporation) (60 parts of pigment) and 828.1 parts of ion-exchanged water were placed in a 2 L stainless steel cup and homodisper 2.5 type (primics) with a rotation speed of 500 rpm. For 30 minutes, C.I. I. A slurry of Pigment Violet 23 was prepared.
2) Separately, a C.I. having a sulfo group average substituent number of 2.4 (the main component is 2 substituents). I. Ion-exchanged water is added to a wet cake of pigment violet 23 sulfonic acid derivative (manufactured by DIC Corporation) (3.0 parts of dye) to make a total of 50 parts, and a magnetic stirrer is used at 60 ° C. in a 100 mL glass beaker. C. for 1 hour with stirring. I. A sulfonic acid derivative slurry of Pigment Violet 23 was prepared.
3) Also, 6.0 parts of acetic acid (Wako Pure Chemical Industries, Ltd.), 100 parts of water, ARCARD 2HT-75 (manufactured by Lion Akzo, dialkyldimethylammonium chloride, alkyl chain = C14 to C18, ammonium salt component 75) %) In a 200 mL glass beaker, 2.1 parts were heated and stirred using a magnetic stirrer at 60 ° C. for 1 hour to prepare a dialkyldimethylammonium solution.
4) C.I obtained in 1). I. C. obtained in 2) while stirring the slurry of Pigment Violet 23 with a vertical stirring blade. I. The entire amount of the sulfonic acid derivative slurry of Pigment Violet 23 was added and stirred for 1 hour. Subsequently, the entire amount of the dialkyldimethylammonium solution obtained in 3) was added, and the mixture was further stirred for 1 hour. Next, the reaction solution was subjected to Nutsche filtration, and the filtrate was washed with 3000 parts of water. The filtrate was blown and dried (98 ° C., 18 hours) and pulverized to obtain 60.9 parts of a dioxazine pigment composition (2). The ratio of the pigment derivative represented by formula (I) to the pigment derivative represented by formula (II) in the dioxazine pigment composition (2) is estimated to be formula (I): formula (II) = 100: 0. The
[Comparative Example 1]
1) C.I. I. 171.9 parts of pigment violet 23 (manufactured by DIC Corporation) (60 parts of pigment) and 828.1 parts of ion-exchanged water were placed in a 2 L stainless steel cup and homodisper 2.5 type (primics) with a rotation speed of 500 rpm. For 30 minutes, C.I. I. A slurry of Pigment Violet 23 was prepared.
2) Separately, C.I. having a sulfo group average substituent number of 2.4. I. Ion-exchanged water is added to a wet cake of pigment violet 23 sulfonic acid derivative (manufactured by DIC Corporation) (3.0 parts of dye) to make a total of 50 parts, and a magnetic stirrer is used at 60 ° C. in a 100 mL glass beaker. C. for 1 hour with stirring. I. A sulfonic acid derivative slurry of Pigment Violet 23 was prepared.
3) Further, 10.0 parts of acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 100 parts of water, ARCARD 2HT-75 (dialkyldimethylammonium chloride, manufactured by Lion Akzo Co., Ltd.), alkyl chain = C14 to C18, ammonium salt component 75% ) 7.8 parts were heated and stirred in a 200 mL glass beaker using a magnetic stirrer at 60 ° C. for 1 hour to prepare a dialkyldimethylammonium solution.
4) C.I obtained in 1). I. C. obtained in 2) while stirring the slurry of Pigment Violet 23 with a vertical stirring blade. I. The entire amount of the sulfonic acid derivative slurry of Pigment Violet 23 was added and stirred for 1 hour. Subsequently, the entire amount of the dialkyldimethylammonium solution obtained in 3) was added, and the mixture was further stirred for 1 hour. Next, the reaction solution was subjected to Nutsche filtration, and the filtrate was washed with 3000 parts of water. The filtrate was blown and dried (98 ° C., 18 hours) and pulverized to obtain 65.2 parts of a comparative dioxazine pigment composition (3 ′). The ratio of the pigment derivative represented by the formula (I) to the pigment derivative represented by the formula (II) in the comparative dioxazine pigment composition (3 ′) is as follows: Formula (I): Formula (II) = 0: 100 Presumed.
[Preparation Example 1]
(Preparation of NC glycol ether varnish)
Nitrocellulose resin (nitrogen content: 10.7-12.2, non-volatile content 70%, volatile content isopropanol) 164.5 parts, propylene glycol monoethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 335.5 parts 1L poly It was placed in a bottle and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 2 hours to obtain NC glycol ether varnish.
[Preparation Example 2]
(Preparation of NC ethanol varnish)
Nitrocellulose resin (nitrogen content: 10.7-12.2, non-volatile content 70%, volatile content ethanol) 164.5 parts, ethanol (Wako Pure Chemical Industries, Ltd.) 436.5 parts, ethyl acetate (Wako Pure Chemical Industries) 13.5 parts (manufactured by Kogyo Co., Ltd.) was placed in a 1 L plastic bottle and dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.) for 2 hours to obtain NC ethanol varnish.
[Example 2]
Dioxazine pigment composition (1) 18.2 parts, NC glycol ether varnish 32.5 parts, propylene glycol monoethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 40.3 parts, n-propanol (Wako Pure Chemical Industries, Ltd.) 9.0 parts, 150 parts of SAZ beads (Zirconia YTZ ball 1.25φ, manufactured by Tokyo Glass Instruments Co., Ltd.) 150 parts are placed in a 200 mL glass bottle and 2 by Shaker Skandex SK550 (Fast & Fluid Management BV Company). The ink composition (1) was obtained by time dispersion.
[Example 2]
Dioxazine pigment composition (2) 18.2 parts, NC glycol ether varnish 32.5 parts, propylene glycol monoethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 40.3 parts, n-propanol (Wako Pure Chemical Industries, Ltd.) 9.0 parts, 150 parts of SAZ beads (Zirconia YTZ ball 1.25φ, manufactured by Tokyo Glass Instruments Co., Ltd.) 150 parts are placed in a 200 mL glass bottle and 2 by Shaker Skandex SK550 (Fast & Fluid Management BV Company). The ink composition (2) was obtained by time dispersion.
[Example 4]
Dioxazine pigment composition (1) 22.0 parts, NC ethanol varnish 36.9 parts, ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 36.9 parts, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts , 150 parts of SAZ beads (Zirconia YTZ ball 1.25φ, manufactured by Tokyo Glass Instrument Co., Ltd.) are placed in a 200 mL glass bottle and dispersed with Shaker Skandex SK550 (manufactured by Fast & Fluid Management BV Company) for 2 hours. A product (3) was obtained.
[Comparative Example 2]
Untreated C.I. I. Pigment Violet 23 (manufactured by DIC Corporation) 18.2 parts, NC ethoxypropanol varnish 32.5 parts, propylene glycol monoethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 40.3 parts, n-propanol (Wako Pure Chemical Industries, Ltd.) 9.0 parts, 150 parts of SAZ beads (Zirconia YTZ ball 1.25φ, manufactured by Tokyo Glass Instruments Co., Ltd.) 150 parts are placed in a 200 mL glass bottle and placed in Shaker Skandex SK550 (Fast & Fluid Management BV Company). For 2 hours to obtain a comparative ink composition (1 ′).
[Comparative Example 3]
Comparative dioxazine pigment composition (3 ') 22.0 parts, NC ethanol varnish 36.9 parts, ethanol (Wako Pure Chemical Industries, Ltd.) 36.9 parts, ethyl acetate (Wako Pure Chemical Industries, Ltd.) 1 part, 150 parts of SAZ beads (Zirconia YTZ ball 1.25φ, manufactured by Tokyo Glass Instrument Co., Ltd.) are placed in a 200 mL glass bottle, and dispersed for 2 hours with Shaker Skandex SK550 (Fast & Fluid Management BV Company). A comparative ink composition (2 ′) was obtained.
[Comparative Example 4]
Untreated C.I. I. Pigment Violet 23 (manufactured by DIC Corporation) 22.0 parts, NC ethanol varnish 36.9 parts, ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 36.9 parts, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 1. 1 part, 150 parts of SAZ beads (Zirconia YTZ ball 1.25φ, manufactured by Tokyo Glass Instrument Co., Ltd.) are placed in a 200 mL glass bottle, and dispersed for 2 hours with Shaker Skandex SK550 (Fast & Fluid Management BV Company). A comparative ink composition (3 ′) was obtained.
[Results of measuring initial viscosity of purple ink composition]
The obtained ink composition was allowed to stand for 1 hour or more in a 20 ° C. constant temperature bath, and the viscosity was measured with an R85 viscometer RB85L (manufactured by Toki Sangyo Co., Ltd.). The evaluation results are shown in Table 1. The lower the viscosity, the better.

[Viscosity measurement result after storage stability test of purple ink composition]
The obtained ink composition was allowed to stand at room temperature for 24 hours, and then allowed to stand for 1 hour or longer in a thermostatic bath at 20 ° C., and the viscosity was measured with an R85 type viscometer RB85L (manufactured by Toki Sangyo Co., Ltd.). The evaluation results are shown in Table 2. The lower the viscosity, the better.

Claims (11)

C. I. A dioxazine pigment which is CI Pigment Violet 23 ;
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 dioxazine pigment composition characterized by containing a pigment derivative represented by C ₆ alkyl group -C _20]. A dioxazine pigment, a pigment derivative represented by the formula (I), and a 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 dioxazine pigment composition according to claim 1, wherein the dioxazine pigment composition is a C ₆ -C ₂₀ alkyl group]. ^2. The dioxazine pigment composition according to claim 1, wherein any ^{two of} R ¹ , R ² , R ^3, and R ^{4 in} the formula (I) are C _{6 to} C ₂₀ alkyl groups. In the formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups, and the formula (II): R ⁵ , R ⁶ , R ⁷ and any two of R ^8, but dioxazine pigment composition according to claim 2, wherein an alkyl group of C ₆ -C _20. In the formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups, and any two are methyl groups. Item 10. The dioxazine pigment composition according to Item 1. In the formula (I), any ^{two of} R ¹ , R ² , R ³ and R ⁴ are C _{6 to} C ₂₀ alkyl groups, and any two are methyl groups, and the formula (II): 3. The dioxazine pigment according to claim 2, wherein any two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are C _{6 to} C ₂₀ alkyl groups, and any two are methyl groups. Composition. For 100 parts by mass of dioxazine pigment,
The dioxazine pigment composition according to claim 1, 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. For 100 parts by mass of dioxazine 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 to 10.0 parts by mass, provided that the pigment derivative represented by the formula (I) and the pigment derivative represented by the formula (II) The dioxazine pigment composition according to claim 2, wherein the total amount of the dioxazine pigment is 10.0 parts by mass or less. An ink composition comprising at least the dioxazine pigment composition according to any one of claims 1 to 8, a nitrocellulose resin, and a glycol ether solvent. The ink composition according to claim 9, wherein the glycol ether solvent is a monoether or diether of ethylene glycol or propylene glycol. The glycol ether solvent is at least one selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether. The ink composition according to claim 9, comprising: