JPH11323166A - Pigment composition and ink containing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment composition having excellent flowability and gloss by mixing a metal phthalocyanine and/or a halogenated metal phthalocyanine with a metal phthalocyaninesulfonic acid polyoxyalkyleneammonium and/or a halogenated metal phthalocyaninesulfonic acid polyoxyammonium. SOLUTION: There is provided a pigment composition comprising 100 pts.wt. metal phthalocyanine and/or halogenated metal phthalocyanine and 1-30 pts.wt. metal phthalocyaninesulfonic acid polyoxyalkyleneammonium and/or halogenated metal phthalocyaninesulfonic acid polyoxyalkyleneammonium represented by formula I or II. This composition is mixed with a liquid synthetic resin vehicle and a solvent to prepare a gravure ink. In the formulae, Me is a di- or tri-valent metal atom; Pc is a phthalocyanine ring; R1 to R3 are each H or a 1-5C alkyl; R4 is H or methyl; n is 2-100; and l+m=1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment composition and an ink containing the same.

[0002]

2. Description of the Related Art A wide variety of pigment compositions are known. For example, JP-A-57-120067 discloses a pigment composition containing a metal phthalocyanine and / or a halogenated metal phthalocyanine and a metal ammonium phthalocyanine sulfonate, which is not halogenated as the metal ammonium phthalocyanine sulfonate. And "A salt of a metal phthalocyanine sulfonic acid and a tertiary amine having an alkyl group" is described.

[0003] Japanese Patent Application Laid-Open No. 3-33166 discloses that
In a pigment composition containing a halogenated copper phthalocyanine and an ammonium halide phthalocyanine sulfonate, the ammonium copper phthalocyanine sulfonate may be a halogenated copper phthalocyanine sulfonic acid and a tertiary amine having an alkyl group. A pigment composition using a salt of is known.

[0004]

However, in any of the pigment compositions disclosed in the above publications, the tertiary amine forming the ammonium sulfonate is substantially composed of only an alkyl group. The fluidity of the pigment composition containing was high in viscosity and insufficient in fluidity. Moreover, the gravure ink prepared by mixing this with an ink vehicle had insufficient gloss.

[0005]

Means for Solving the Problems Accordingly, the present inventors have made intensive studies in view of the above practical use. As a result of including an oxyalkylene bond in the skeleton of the ammonium salt portion as ammonium metal phthalocyanine sulfonate,
The inventors have found that all of the above-mentioned problems can be solved, and have completed the present invention.

That is, the present invention provides the following invention.

[0007] 1. In a pigment composition containing a metal phthalocyanine and / or a metal halide phthalocyanine (A) and a metal ammonium phthalocyanine sulfonate (B), the metal ammonium phthalocyanine sulfonate (B) may be polyoxyalkylene ammonium metal phthalocyanine sulfonate. And / or a polyoxyalkylene ammonium halide metal phthalocyanine sulfonate.

[0008] 2. The composition according to claim 1, wherein the polyoxyalkylene ammonium metal phthalocyanine sulfonate is a polyoxypropylene ammonium metal phthalocyanine sulfonate or a polyoxypropylene ammonium halogenated metal phthalocyanine sulfonate.

3. 2. The composition according to the above 1, wherein the metal polyoxyalkylene ammonium phthalocyanine sulfonate is represented by the formula (I).

[0010]

Embedded image

In the general formula (I), Me represents a divalent or trivalent metal atom, and Pc represents a phthalocyanine ring in which a hydrogen atom on the ring may be substituted by a halogen atom. R ₁ ,
R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be the same or different. R ₄ represents a hydrogen atom or a methyl group. n is 2 to 100, (l +
m) is 1-4.

4. The composition according to the above 1, wherein the metal polyoxyalkylene ammonium phthalocyanine sulfonate is represented by the formula (II).

[0013]

Embedded image

In the general formula (II), Me represents a divalent or trivalent metal atom, and Pc represents a phthalocyanine ring in which a hydrogen atom on the ring may be substituted by a halogen atom.
R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be the same or different. R ₄ is
Shows a hydrogen atom or a methyl group. n is 1 to 100,
(L + m) is 1 to 4.

[0015] 5. 5. The composition according to the above 1, 2, 3 or 4, wherein the polyoxyalkylene ammonium metal phthalocyanine sulfonate has only one metal phthalocyanine residue.

6. Per 100 parts by weight of metal phthalocyanine and / or halogenated metal phthalocyanine (A),
Polyoxyalkylene ammonium metal phthalocyanine sulfonate and / or polyoxyalkylene ammonium halogenated metal phthalocyanine sulfonate (B)
6. The composition according to the above 1, 2, 3, 4 or 5, containing ３０30 parts by weight.

[7] A gravure ink in which the composition of the above 1, 2, 3, 4, 5, or 6 is dispersed as a colorant in a liquid synthetic resin vehicle (C).

The component (A) used in the present invention is a metal phthalocyanine (A) which may be halogenated. As such a material, any of those known and used can be used, but a metal phthalocyanine or a halogenated metal phthalocyanine is used. In the present invention, the metal phthalocyanine refers to a metal that is not halogenated.

More specifically, as the component (A), for example, copper, nickel, cobalt, titanium,
Examples include metal phthalocyanine containing a metal such as aluminum, and halogenated metal phthalocyanine corresponding to the metal phthalocyanine containing a halogen atom such as a chlorine atom or a bromine atom. The content of halogen atoms contained in the halogenated metal phthalocyanine is not particularly limited, and any of low-chlorinated, low-brominated, high-chlorinated, high-brominated, and mixed halogenated metal phthalocyanines can be used. .

These metal phthalocyanines and halogenated metal phthalocyanines can be used alone or in combination of two or more different types.

The component (A) may be subjected to a surface treatment such as a rosin treatment or a surfactant treatment, if necessary. The component (A) can be used in any form, such as a slurry, a wet cake, and a dry powder.

The ammonium metal phthalocyanine sulfonate (B) used in the present invention is an unhalogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate and / or a halogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate. These are characterized in that the molecule contains a skeleton based on repeating oxyalkylene bonds.

Here, the oxyalkylene bond may be, for example, oxyethylene, oxypropylene, oxytetramethylene, oxytetramethylene having a lower alkyl group on a carbon atom, or a skeleton such as a block copolymer of two or more of these, or a random bond. Copolymerized skeletons are exemplified. Even if the terminal of the oxyalkylene is a hydroxyl group,
For example, it may be blocked with an alkoxy group such as a methoxy group.

Unhalogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate and / or
Alternatively, the halogenated metal polyoxyalkylene ammonium phthalocyanine sulfonate can be used alone, or two or more different metal phthalocyanine sulfonates can be used in combination.

Unhalogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate and / or
Alternatively, as the halogenated metal polyoxyalkylene ammonium phthalocyanine sulfonate, a substance having only one phthalocyanine residue based on a phthalocyanine ring in one molecule is preferable in that the fluidity becomes better.

A non-halogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate is preferred over a halogenated metal polyoxyalkylene ammonium phthalocyanine sulfonate because of its excellent bleed resistance.

If the preferred polyoxyalkylene ammonium metal phthalocyanine sulfonate which may be halogenated used in the present invention is represented by the general formula, one of the polyoxyalkylene ammonium metal phthalocyanine sulfonates represented by the following general formula (I) is: Oxyalkylene ammonium is preferred.

[0028]

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In the general formula (I), Me represents a divalent or trivalent metal atom, and Pc represents a phthalocyanine ring in which a hydrogen atom on the ring may be substituted with a halogen atom. R
₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be the same or different. R ₄ represents a hydrogen atom or a methyl group. n is 2 to 100, (l
+ M) is 1 to 4.

In the above general formula (I), Me is C
u, Pc is a phthalocyanine ring in which a hydrogen atom on the ring is not substituted with a halogen atom, R ₁ , R ₂ , and R ₃ are
Hydrogen atom or carbon number 1-4 which may be the same or different
In particular, a metal phthalocyanine sulfonate polyoxyalkylene ammonium, wherein R ₄ is an alkyl group having 1 to ₄ carbon atoms, n is 20 to 50, and l + m is 1 to 4, is preferred.

If the preferred polyoxyalkylene ammonium metal phthalocyanine sulfonate, which may be halogenated, used in the present invention is represented by the general formula, other than those described above, the following general formula (II) may be used. Metal phthalocyanine sulfonate polyoxyalkylene ammonium is preferred.

[0032]

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In the general formula (II), Me represents a divalent or trivalent metal atom, and Pc represents a phthalocyanine ring in which a hydrogen atom on the ring may be substituted by a halogen atom.
R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be the same or different. R ₄ is
Shows a hydrogen atom or a methyl group. n is 1 to 100,
(L + m) is 1 to 4.

Among them, in the above general formula (II), Me is Cu, Pc is a phthalocyanine ring in which a hydrogen atom on the ring is not substituted with a halogen atom, R ₁ , R ₂ , and R
₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be the same or different, R ₄ is an alkyl group having 1 to ₄ carbon atoms, n is 20 to 50, and l + m is 1 to 4; Polyoxyalkylene ammonium sulfonates are particularly preferred.

The component (B) used in the present invention, ie, a non-halogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate or a halogenated polyoxyalkylene ammonium metal phthalocyanine sulfonate can be obtained by a known and conventional method. I can do it.

The component (B) of the present invention is obtained, for example, by reacting the component (A) with, for example, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or the like in the first step to obtain an unhalogenated metal phthalocyanine sulfonic acid. Alternatively, after obtaining a halogenated metal phthalocyanine sulfonic acid or a metal salt thereof, 1 mol thereof is combined with an organic acid salt or quaternary ammonium salt of the corresponding primary, secondary or tertiary amine.
The compound can be produced by a second step in which a mole is used to carry out a heat reaction in water, an organic solvent or a mixed solvent with water by a conventional method. Of course, the substances of the above general formulas can be obtained in the same manner.

As the organic amine used in the heating reaction, those having a polyoxyalkylene bond can be used. Specifically, primary amines such as polyoxypropylene amine, secondary amines such as polyoxypropylene methylamine and polyoxypropylene ethylamine, tertiary amines such as polyoxydimethylamine and polyoxymethylethylamine, polyamines Quaternary ammonium salts such as oxypropylene dimethylethylammonium chloride, polyoxytrimethylammonium chloride and polyoxypropylenemethyldiethylammonium chloride are used.

The component (B) thus obtained can be used as it is, but it can be used in any form such as a wet cake or a dry powder after filtration, dehydration and drying.

The pigment composition of the present invention contains both the above components (A) and (B) as essential components, and the component (B) per 100 parts by weight of the above component (A) Is 1 to 30 parts by weight, preferably 1 to 15 parts by weight.

Such a pigment composition can be easily obtained by sufficiently mixing the components (A) and (B) by any known and conventional means so as to be uniform. Can be.

The mixing method at this time may be mixing in a powder state, adding as a wet cake, a slurry or a solution, or adding the component (A), ie, a non-halogenated metal phthalocyanine or a halogenated metal. In the presence of the phthalocyanine pigment, the component (B), that is, an ammonium salt of a metal phthalocyanine sulfonate which may be halogenated, may be used by being formed by a reaction.

Further, the component (B) may be added in the step of pulverizing the crude pigment of the component (A), or in preparing an ink, the components (A) and (B) may be mixed in advance to form a composition. After that, not only can it be used as an ink by using it, but also the ink obtained by dispersing the component (B) in the ink in which the pigment of the component (A) is dispersed.

The gravure ink of the present invention is typically
The pigment composition of the present invention as a coloring agent and a solvent are mixed with the liquid synthetic resin vehicle (C), and the mixture can be obtained by ball milling.

In the present invention, the liquid synthetic resin vehicle (C) used for preparing the gravure ink includes, for example, tall oil rosin, gum rosin, wood rosin, lime rosin, rosin ester, maleic acid resin, vinyl resin,
Polyamide resin, nitrocellulose, cellulose acetate,
Either a resin such as ethyl cellulose, an ethylene-vinyl acetate copolymer, a urethane resin, a polyester resin, an alkyd resin, an acrylic resin, a Gilsonite, a dammar, or a shellac, alone or in a mixture.

The gravure ink of the present invention comprises, for example, 10 to 50 parts by weight of a liquid synthetic resin vehicle (C), a solvent alone such as hydrocarbons, alcohols, esters, ketones, ether alcohols, ethers and water, or a mixture of two or more solvents. It can be composed of 30 to 80 parts by weight.

[0046]

Next, the present invention will be described with reference to Examples and Comparative Examples. All parts in the examples are parts by weight.

Example 1 Non-halogenated copper phthalocyanine sulfonic acid acidic water-containing cake (containing 3.5 parts of pure copper phthalocyanine sulfonic acid) represented by the following formula (III): A water-containing phthalocyanine cake (containing 46.5 parts of pure copper phthalocyanine) was dispersed in 3000 parts of water, and the pH was adjusted to 8.0 to 8.0 with an aqueous sodium hydroxide solution.
Adjusted to 8.5.

[0048]

Embedded image Me-Pc- (SO ₃ H) _x (III)

In the formula (III), Me and Pc have the same meanings as described above, and x is 1 to 4, and the average is 1.0.

Then, 8.41 parts of polyoxypropylene ammonium chloride (Adecacol CC36, manufactured by Adeka Corporation) having a repeating unit of oxypropylene bond represented by the following formula (IV) of 25 (n = 25) was added, and
After stirring at 0 to 90 ° C. for 1 hour, the mixture was filtered.

[0051]

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However, in the formula (IV), R ₁ and R ₂ are an alkyl group having 2 carbon atoms, and R _{3 and} R ₄ are a methyl group.

Next, the filtrate was washed with water until it was free from salts, dried at 90 to 100 ° C., and a powder mixture of non-halogenated copper phthalocyanine and non-halogenated copper phthalocyanine sulfonate polyoxypropylene ammonium salt. (Weight ratio of the former / the latter = 46.5 /
11.7) 58.2 parts were obtained.

The non-halogenated polyoxypropylene ammonium salt of copper phthalocyanine sulfonic acid obtained here is represented by the formula (I): Me = Cu,
R ₁ and R ₂ are an alkyl group having 2 carbon atoms, R _{3 and} R ₄ are methyl groups, 1 = 0, m = 1, and n = 25.

To 10 parts of this pigment composition, 13 parts of isopropyl alcohol, 13 parts of ethanol, 7 parts of ethyl acetate and 30 parts of nitrocellulose resin varnish were added and ball-milled to produce 73 parts of nitrocellulose gravure ink. Next, fluidity and gloss were measured as follows. Table 1 shows the measurement results.

Fluidity: Brookfield viscometer (N
o. No. 2 rotor or No. 2 3 rotors)
The viscosity of the gravure ink was measured at 0 ° C. and 60 rpm. Gloss: The gravure ink was applied to a polyethylene film using a 0.15 mm bar coater. This was measured for gloss.

Example 2 The same non-halogenated copper phthalocyanine sulfonic acid acidic wet cake (containing 3.5 parts of pure copper phthalocyanine sulfonic acid) and the same non-halogenated copper phthalocyanine wet cake (as in Example 1) Copper phthalocyanine (46.5 parts in pure content) was dispersed in 3000 parts of water, and the pH was adjusted to 8.0 to 8.5 with an aqueous sodium hydroxide solution.

Next, a polyoxypropylene ammonium having a molecular weight of 2,000 represented by the following formula (V) (HUN
TSMAN Jeffamine M-2005) 10.69
To this part, 0.36 part of 90% acetic acid was added to make 11.05 parts of polyoxypropylene ammonium acetate []. The mixture was stirred at 80 to 90 ° C. for 1 hour, and then filtered.

[0059]

Embedded image

However, in the formula (V), R represents a hydrogen atom or a methyl group, and the molar ratio is 3/32. Also, n = 30.2.

Next, the filtrate was washed with water until it was free from salts, dried at 90 to 100 ° C., and used to prepare non-halogenated copper phthalocyanine and non-halogenated copper phthalocyanine sulfonate polyoxypropylene ammonium salt (the former / the latter). (Weight ratio = 46.5 / 14.1) was obtained.

The thus obtained non-halogenated polyoxypropylene ammonium salt of copper phthalocyanine sulfonic acid is represented by the formula (II): Me = Cu, R
₁ , R ₂ and R ₃ are a hydrogen atom, R ₄ is a hydrogen atom or a methyl group and the molar ratio is 3/32, l = 0, m = 1, n = 3
0.2.

A nitrocellulose gravure ink was produced in the same manner as in Example 1 except that the same amount of the pigment composition was used. Then, in the same manner as in Example 1,
The gloss was measured. Table 1 also shows the measurement results.

Comparative Example 1 The procedure of Example 1 was repeated, except that 1.31 parts of dodecylammonium acetate was used in place of the non-halogenated polyoxypropylene ammonium hydrochloride of the above formula (IV). Cellulose-based gravure inks were manufactured and the fluidity and gloss were measured. Table 1 shows the measurement results.

COMPARATIVE EXAMPLE 2 Except that 1.45 parts of hexadecyl ammonium acetate was used in place of the non-halogenated polyoxypropylene ammonium hydrochloride represented by the above formula (IV),
A nitrocellulose-based gravure ink was produced in the same manner as in Example 1, and the fluidity and gloss were measured. Table 1 shows the measurement results.

[0066]

[Table 1]

As can be seen from Table 1, since the pigment composition of the present invention includes those having a polyoxyalkylene bond, it has superior fluidity to the conventional pigment compositions including those having no polyoxyalkylene bond. It shows that it shows. Moreover, the gravure ink containing this pigment composition can be used for high-speed printing,
It can be seen that a printed matter having excellent gloss was provided.

[0068]

The pigment composition provided by the present invention has a polyoxyalkylene bond in the molecule of a metal alkylammonium phthalocyanine sulfonate in which a hydrogen atom of the phthalocyanine ring may be substituted by a halogen atom. Therefore, the fluidity and gloss are more excellent, and the fluidity and gloss, which could not be improved by the conventional pigment composition containing the same containing no polyoxyalkylene bond, are greatly improved. To play.

Claims (7)

[Claims] 1. A pigment composition containing a metal phthalocyanine and / or a metal halide phthalocyanine (A) and a metal ammonium phthalocyanine sulfonate (B), wherein the metal phthalocyanine sulfonate (B) is a metal phthalocyanine sulfonate. A pigment composition using a polyoxyalkylene ammonium ammonium acid and / or a polyoxyalkylene ammonium halide metal phthalocyanine sulfonate. 2. The composition according to claim 1, wherein the polyoxyalkylene ammonium metal phthalocyanine sulfonate is a polyoxypropylene ammonium metal phthalocyanine sulfonate or a polyoxypropylene ammonium halogenated metal phthalocyanine sulfonate. 3. The composition according to claim 1, wherein the polyoxyalkylene ammonium metal phthalocyanine sulfonate is represented by the formula (I). Embedded image In the general formula (I), Me is a divalent or trivalent metal atom,
Pc represents a phthalocyanine ring in which a hydrogen atom on the ring may be substituted with a halogen atom. R ₁ , R ₂ and R ₃ are
1 hydrogen atom or 1 carbon atom which may be the same or different
5 to 5 alkyl groups. R ₄ represents a hydrogen atom or a methyl group. n is 2 to 100, and (l + m) is 1 to 4. 4. The composition according to claim 1, wherein the polyoxyalkylene ammonium metal phthalocyanine sulfonate is represented by the formula (II). Embedded image In the general formula (II), Me represents a divalent or trivalent metal atom, and Pc represents a phthalocyanine ring in which a hydrogen atom on the ring may be substituted with a halogen atom. R ₁ , R ₂ , R ₃
Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may be the same or different. R ₄ represents a hydrogen atom or a methyl group. n is 1 to 100, (l + m) is 1 to
4. 5. The composition according to claim 1, wherein the polyoxyalkylene ammonium metal phthalocyanine sulfonate has only one metal phthalocyanine residue. 6. A metal phthalocyanine and / or a halogenated metal phthalocyanine (A) per 100 parts by weight of a metal phthalocyanine sulfonate polyoxyalkylene ammonium and / or a metal phthalocyanine sulfonate polyoxyalkylene ammonium (B) of 1 to 30 parts by weight.
2. The composition of claim 1 containing parts by weight. 7. A gravure ink in which the composition of claim 1 is dispersed as a colorant in a liquid synthetic resin vehicle (C).