JP3518300B2 - Pigment dispersant and pigment composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pigment dispersant having excellent suitability for use, particularly non-aggregation, non-crystallinity, and fluidity, and more specifically, a pigment dispersant effective for inks and paints. , And a pigment composition containing the same.

[0002]

2. Description of the Related Art Generally, in various coatings or ink compositions, practically useful pigments exhibiting a clear color tone and high tinting strength are composed of fine particles. When dispersed in non-aqueous vehicles such as offset inks, gravure inks and paints, it is difficult to obtain stable dispersions of fine pigment particles, and therefore pigment dispersants are used to improve the affinity between pigments and vehicles. It is known to improve the properties and stabilize the dispersion. Many proposals have been made for such pigment dispersants centering on copper phthalocyanine and quinacridone pigments.

For example, Japanese Patent Publication No. 41-2466 and USP
There is known a method of mixing a compound obtained by introducing a substituent such as a sulfonic acid, a sulfonamide group, an aminomethyl group or a phthalimidomethyl group into a side chain with an organic pigment as a base skeleton as represented by 2855403. However, although these compounds have a large effect on the non-aggregation property of the pigment, the crystal stability, etc., since the compound to be added is derived from a compound having the same chemical structure as the pigment, it has an inherently strong coloring and a different hue. When it is used as a pigment, it is significantly restricted. Therefore, it is necessary to prepare a corresponding compound for each individual pigment, which is a significant disadvantage in producing a pigment composition. Further, when introducing a substituent into the side chain of these compounds, it is necessary to dissolve the pigment in concentrated sulfuric acid, fuming sulfuric acid or the like, or to act chlorosulfonic acid or the like to introduce a reactive group into the pigment. Since concentrated sulfuric acid, fuming sulfuric acid, etc. are dangerous and extremely difficult to handle, they are disadvantageous in production due to restrictions on production equipment, production amount, etc.

[0004]

As a result of earnest research in view of the above problems, the present inventor has found that a specific compound which does not have a pigment skeleton and is colorless or slightly colored improves the above various problems. The inventors have found that the pigment can be dispersed well, and have completed the present invention.

[0005]

That is, the present invention is a pigment dispersant represented by the following general formula (1). General formula (1)

[0006]

[Chemical 8]

[0007] (wherein, X ₁ is -NR ₃ - represents or -O-, R ₁ represents an amino group, R ₂ is C androgenic atom, an amino group, a nitro group, a hydroxyl group, an alkoxy group, a carboxy group , A sulfone group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, and Y ₁ represents Represents any group represented by the general formulas (2) to (5), Y ₂ represents a hydroxyl group, an alkoxy group, Y ₁ or the following general formula (6), k represents an integer of 1 to 3, and 1 Represents an integer of 0 to 2.) General formula (2)

[0008]

[Chemical 9]

(In the formula, R ₄ and R ₅ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or the substituents are integrated together to form a further nitrogen atom, oxygen atom or sulfur atom. Represents a 5-membered ring or a 6-membered ring which may contain an atom, and n represents an integer of 1 to 6.) General formula (3)

[0010]

[Chemical 10]

(In the formula, R ₄ and R ₅ have the same meanings as in the general formula (2).) General formula (4)

[0012]

[Chemical 11]

(In the formula, R ₆ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group.) General formula (5)

[0014]

[Chemical 12]

(In the formula, R ₇ represents a group represented by the general formula (4) or a group represented by the following general formula (7), and p is 0 to
Represents an integer of 6, and m represents an integer of 1 to 2. ) General formula (6)

[0016]

[Chemical 13]

(In the formula, X ₁ , R ₁ , R ₂ , k and l have the same meanings as in the general formula (1).) General formula (7)

[0018]

[Chemical 14]

(In the formula, X ₂ represents a direct bond, —NH— or —O—, q represents an integer of 0 to 6, and R ₄ and R ₅ have the same meanings as in formula (2). ) Further, the present invention is a pigment composition comprising a pigment and the pigment dispersant of the above invention.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The pigment dispersant of the present invention has an aromatic amino group and an amino group represented by Y ₁ in the general formula (1) in the triazine ring. The alkoxy group contained in R ₂ and Y ₂ of the general formula (1) preferably has 1 to 20 carbon atoms, and a methoxy group,
Ethoxy group, n-propoxy group, isopropoxy group, n
-Butoxy group, isobutoxy group, pentoxy group, hexoxy group and the like can be mentioned.

The substituted or unsubstituted alkyl group or substituted or unsubstituted alkenyl group contained in R _{2 to} R ₆ in X ₁ and Y ₁ of the general formula (1) preferably has 1 to 20 carbon atoms. . As the unsubstituted alkyl group, a methyl group,
Examples thereof include an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group and hexyl group. Unsubstituted alkenyl groups include vinyl groups, 1
-Propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 2-pentenyl group, 2-methylallyl group and the like can be mentioned. The substituted alkyl group or alkenyl group is a group in which a hydrogen atom of the alkyl group or alkenyl group is substituted with a halogen group such as a fluorine atom, a chlorine atom or a bromine atom, a hydroxyl group or a mercapto group. Further, R ₄ and R ₅ may be a combination of alkyl groups which together form a 5-membered ring or a 6-membered ring which may further contain a nitrogen atom, an oxygen atom or a sulfur atom. Are as follows.

[0022]

[Chemical 15]

Of these, Y ₁ is preferably a group represented by the general formula (2), and R ₄ and R ₅ are preferably alkyl groups having 1 to 6 carbon atoms. The benzene ring in the pigment dispersant of the present invention may have the following substituents at other substitutable positions in addition to the amino group. That is, it may have a halogen atom, an amino group, a nitro group, a hydroxyl group, an alkoxy group, a carboxyl group, a sulfone group, or a substituted or unsubstituted alkyl group, and the kind of the substituent is not particularly limited. It is not something that will be done. Further, when a plurality of these substituents are included, the respective substituents may not be the same.

Although the structure of the pigment dispersant of the present invention has been described above, examples of the pigment dispersant of the present invention include the following.

[0025]

[Chemical 16]

[0026]

[Chemical 17]

[0027]

[Chemical 18]

[0028]

[Chemical 19]

[0029]

[Chemical 20]

The method for producing the pigment dispersant of the present invention is as follows by way of example. First, p-aminoacetanilide and cyanuric chloride are reacted in equimolar amounts in water, an aqueous solution of acetic acid, an alcohol, a mixed solvent of hydroalcohol, a general organic solvent such as xylol, and a compound represented by the following formula ( 8)
To manufacture.

[0031]

[Chemical 21]

Then, in order to introduce Y ₁ and Y ₂ , the compounds represented by the following general formulas (9) to (12) are reacted in water or a general organic solvent to obtain the general formula (13). ~ (1
The compound represented by 6) is produced. General formula (9)

[0033]

[Chemical formula 22]

General formula (10)

[0035]

[Chemical formula 23]

General formula (11)

[0037]

[Chemical formula 24]

General formula (12)

[0039]

[Chemical 25]

General formula (13)

[0041]

[Chemical formula 26]

General formula (14)

[0043]

[Chemical 27]

General formula (15)

[0045]

[Chemical 28]

General formula (16)

[0047]

[Chemical 29]

(Wherein R ₄ , R ₅ , R ₆ , R ₇ , m, n, p
Represents the same meaning as in general formula (1). ) Then, the general formula (1
The pigment dispersant of the present invention represented by the general formula (1) can be produced by hydrolyzing 3) to (16) with an aqueous hydrochloric acid solution or the like. Further, by using p-nitro-aniline instead of p-amino-acetanilide, a compound (17) represented by the following formula is produced and represented by general formulas (9) to (12). The compound of the general formula (1) can also be obtained by reducing the nitro group after reacting with the compound.
The pigment dispersant of the present invention represented by can be produced.

[0049]

[Chemical 30]

Even if one chlorine atom of the compound (8) or the compound (17) is hydrolyzed during the reaction to form a hydroxyl group or an alkoxy group, it can be used as the pigment dispersant of the present invention. . Examples of the compound represented by the general formula (9) of the present invention include N, N-dimethylaminoethylamine, N, N-diethylaminoethylamine, N, N
-Dibutylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminopropylamine, N, N-dibutylaminopropylamine, N, N
-Dimethylaminobutylamine, N, N-diethylaminobutylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminobutylamine, N, N-diethylaminohexylamine, N-aminomethylpiperidine, N-aminoethylpiperidine, N -Aminopropylpiperidine, N-aminoethylpyrrolidine, N-aminopropylpyrrolidine, N-aminomethyl-2-pipecoline, N-aminoethyl-4-pipecoline, N-aminopropyl-2-pipecoline, N-aminoethylmorpholine , N-aminopropylmorpholine, N, N-methyl-laurylaminopropylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine and the like.

Examples of the compound represented by the general formula (10) include N, N-dimethylaminomethanol, N,
N-dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibutylaminomethanol,
N, N-dibutylaminoethanol, N, N-dibutylaminopropanol, N, N-diethylaminobutanol, N, N-dioleylbutanol, N-hydroxyethylpiperidine, N-hydroxypropylpiperidine,
N-hydroxyethylpipecoline, N-hydroxypropylpipecoline, N-hydroxymethylpyrrolidine, N
-Hydroxybutylpyrrolidine, N-hydroxyethylmorpholine, N-hydroxybutylmorpholine and the like.

Examples of the compound represented by the general formula (11) include N-methylpiperazine, N-ethylpiperazine and N.
-Butylpiperazine, 1-cyclopentylpiperazine and the like. Examples of the compound represented by the general formula (12) include
1-amino-4-N, N-dimethylaminocyclohexane, 1-amino-4-N, N-diethylaminocyclohexane, 1-amino-4-N, N-dibutylaminocyclohexane, 1-aminomethyl-4-N, N-dimethylaminocyclohexane, 1-aminomethyl-4-N, N
-Diethylaminocyclohexane, 1-aminomethyl-
4-N, N-dibutylaminocyclohexane, 1-aminoethyl-4-N, N-dimethylaminocyclohexane, 1-aminoethyl-4-N, N-diethylaminocyclohexane, 1-aminoethyl-4-N, N- Dibutylaminocyclohexane, 1-amino-4-N, N-dimethylaminomethylcyclohexane, 1-amino-4-
N, N-diethylaminomethylcyclohexane, 1-amino-4-N, N-dibutylaminomethylcyclohexane, 1-amino-4-N, N-dimethylaminoethylaminocyclohexane, 1-amino-4-N, N-dimethyl Aminopropylaminocyclohexane, 1-amino-
4-N, N-diethylaminoethylaminocyclohexane, 1-amino-3,5-N, N-dimethylaminocyclohexane, 1-amino-3,5-N, N-diethylaminocyclohexane, 1-amino-3,5- N, N-dibutylaminocyclohexane, 1-amino-3,5-
N, N-dimethylaminomethylcyclohexane, 1-amino-3,5-N, N-diethylaminomethylcyclohexane, 1-amino-3,5-N, N-dibutylaminomethylcyclohexane, 1-amino-4-N- Methyl piperazine cyclohexane, 1-amino-4-N-ethyl piperazine cyclohexane, 1-amino-4-N-butyl piperazine cyclohexane and the like.

The pigment dispersant obtained in the present invention exhibits excellent effects on all pigments which are generally commercially available. For example, organic pigments such as phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene / perinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, benzimidazolone pigments, and azo pigments. And inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, red iron oxide, iron black, zinc white, navy blue, and ultramarine blue. Since the pigment dispersant of the present invention has a colorless or slightly colored hue, it is advantageous in that it has little change in hue even when added to various pigments and is excellent in versatility.

The pigment composition of the present invention comprises a pigment and a pigment dispersant represented by the general formula (1) added thereto. The amount of the pigment dispersant represented by the general formula (1) is 10
0.1 to 30 parts by weight is preferable with respect to 0 parts by weight. When the addition amount of the pigment dispersant represented by the general formula (1) is less than 0.1 parts by weight, the pigment dispersing effect is small, which is not preferable. Further, even if the amount is more than 30 parts by weight, the effect of the used amount cannot be obtained. Examples of the method of using the pigment dispersant according to the present invention include the following methods. 1. A pigment composition obtained by previously mixing a pigment and a pigment dispersant is added to and dispersed in a non-aqueous vehicle. 2. A pigment and a pigment dispersant are separately added to a non-aqueous vehicle and dispersed. 3. A pigment and a pigment dispersant are separately dispersed in advance in a non-aqueous vehicle, and the resulting dispersion is mixed. In this case, the pigment dispersant may be dispersed only with the solvent. 4. After dispersing the pigment in the non-aqueous vehicle, a pigment dispersant is added to the obtained pigment dispersion. Etc., and any of these can achieve the desired effect.

As a method for preparing the pigment composition, a sufficient dispersion effect can be obtained by simply mixing the pigment powder and the pigment dispersant of the present invention. However, a kneader, roll, attritor, super mill, various pulverizers, etc. By mechanical mixing, or by adding a solution containing the pigment dispersant of the present invention to the suspension system of the pigment in water or an organic solvent, depositing the pigment dispersant on the pigment surface, or having a strong dissolving power of sulfuric acid or the like. Even better results can be obtained by performing a careful mixing method such as co-dissolving an organic pigment and a pigment dispersant in a solvent and coprecipitating with a poor solvent such as water. In addition, for dispersing and mixing the pigment or the pigment dispersant in the non-aqueous vehicle or solvent, the pigment can be prepared by using a dissolver, a high speed mixer, a homomixer, a kneader, a roll mill, a sand mill, an attritor or the like as a dispersing machine. Can be well dispersed.

Therefore, according to the present invention, a gravure ink such as lime rosin varnish, polyamide resin varnish or vinyl chloride resin varnish, nitrocellulose lacquer,
In non-aqueous vehicles such as aminoalkyd resin air-drying or baking paints, acrylic lacquers, aminoacrylic resin baking paints, urethane resin paints, etc. At the same time, it shows good fluidity such as decrease, and at the same time has no problems such as color separation and crystal change, so that the gloss of the printed matter or the coating film is good and therefore a beautiful product can be obtained. The pigment dispersant and the pigment composition of the present invention are not limited to the non-aqueous vehicle, and also in the coloring of other printing inks and paints, as well as plastics, a coloring matter having an excellent dispersing effect and a coloring power can be obtained. .

[0057]

EXAMPLES The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”. Production Example 1 p-Aminoacetanilide 2 in 300 parts of methanol
0 parts and 25 parts of cyanuric chloride are charged and reacted at 20 ° C. or lower for 2 hours, then 46 parts of N, N-dibutylaminoethylamine are charged and heated under reflux for 2 hours. Next, after adding 100 parts of hydrochloric acid to hydrolyze, distilling off methanol, adding 40 parts of sodium hydroxide and 1000 parts of water, filtering, washing with water and drying, a pigment dispersant (a) having the following structure
64 parts were obtained.

Pigment dispersant (a)

[0059]

[Chemical 31]

Production Example 2 N, N-diethylaminopropylamine 35 of Production Example 1
Instead of parts, N, N-dibutylaminopropanol 5
The reaction was carried out in the same manner as in Production Example 1 using 0 part to obtain 76 parts of a pigment dispersant (b) having the following structure. Pigment dispersant (b)

[0061]

[Chemical 32]

Production Example 3 22 parts of 3-methyl-4-aminoacetanilide and 25 parts of cyanuric chloride were added to 300 parts of methanol to prepare 20 parts.
The reaction is carried out at a temperature of not more than 0 ° C. for 2 hours, then 12 parts of N, N-dimethylaminoethylamine are charged, and the mixture is heated under reflux for 2 hours.
Next, 100 parts of hydrochloric acid was added for hydrolysis, methanol was distilled off, 40 parts of sodium hydroxide and 1000 parts of water were added, and the mixture was filtered, washed with water and dried to obtain a pigment dispersant (c) 47 having the following structure. I got a part. Pigment dispersant (c)

[0063]

[Chemical 33]

Production Example 4 p-Aminoacetanilide 4 was added to 300 parts of methanol.
0 part and 25 parts of cyanuric chloride were charged and reacted at 30 ° C. for 2 hours, and then N, N-diethylaminoethylamine 1
Charge 4 parts and heat to reflux for 2 hours. Then, hydrochloric acid 10
After hydrolyzing by adding 0 part, 40 parts of sodium hydroxide and 1000 parts of water were added, followed by filtration, washing with water and drying to obtain 62 parts of a pigment dispersant (d) having the following structure. It was Pigment dispersant (d)

[0065]

[Chemical 34]

The pigment dispersants (e) to (l) shown in Table 1 were synthesized in the same manner as described below.

[0067]

[Table 1]

[0068]

Examples 1 to 21, Comparative Examples 1 to 15 Various pigments alone or various pigments having a pigment skeleton and pigment dispersants so that the pigment content in the amino alkyd resin varnish for baking paint is 6%. (A)-(l)
A pigment composition containing any of the above was dispersed to prepare a coating material. As the pigment dispersant having a pigment skeleton, the following compounds having a copper phthalocyanine skeleton and a quinacridone skeleton were used. Copper phthalocyanine skeleton pigment dispersant (m)

[0070]

[Chemical 35]

Quinacridone skeleton pigment dispersant (n)

[0072]

[Chemical 36]

When the viscosity of each paint was measured, as shown in Table 2, those using the pigment dispersant of the present invention showed low viscosity, small thixotropy (TI value) and excellent fluidity. . Also, the above coating composition was used in Ford Cup # 4 20
Viscosity is adjusted so that it becomes second (25 ° C.), and it is air-sprayed on an intermediately coated plate (steel plate coated with a primer coating in advance) so that the thickness of the dry coating film is about 30 μm.
After leaving it to stand for 10 minutes, it was baked at 140 ° C. for 30 minutes.
As shown in Table 2, those using the pigment dispersant of the present invention showed better coating film gloss than the comparative examples. The hue was the same as that of the pigment alone without staining the hue of the base pigment.

On the other hand, the non-aggregation property and the non-crystallinity were evaluated by the color-separation stability which is a problem in practical use.
The above coating composition is diluted with a titanium oxide base coating (titanium oxide is dispersed in an aminoalkyd resin varnish) so that the ratio of the pigment to the titanium oxide is 1/10 to prepare a light color coating. Then, after diluting with xylene and adjusting the viscosity with a Ford cup # 4 for 20 seconds (25 ° C.), it was injected into a test tube and observed for changes in the glass wall surface. The pigment dispersant according to the present invention was used. The color separation with time was smaller than that of the comparative example.

[0075]

[Table 2]

Further, the pigment composition containing the above-mentioned pigment dispersants (a) to (l) did not cause aggregation even when used in nitrocellulose lacquer acrylic resin paints and gravure inks, and showed good fluidity.

[0077]

EFFECT OF THE INVENTION By using the pigment dispersant of the present invention, not only excellent non-aggregating property, non-crystallinity and fluidity but also excellent
It is possible to obtain inks and paints having excellent gloss and hue of the coating film.

Front page continuation (51) Int.Cl. ⁷ identification code FI C09D 11/00 C09D 11/00 (58) Fields investigated (Int.Cl. ⁷ , DB name) C09C 3/08 C07D 251/46 C07D 251 / 52 C07D 251/70 C09D 7/12 C09D 11/00

Claims (5)

(57) [Claims] 1. A pigment dispersant represented by the following general formula (1). General formula (1) (Wherein, X ₁ is -NR ₃ - represents or -O- and, R ₁ represents an amino group, R ₂ is C androgenic atom, an amino group, a nitro group, a hydroxyl group, an alkoxy group, a carboxyl group, a sulfonic group Represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, and Y ₁ represents the following general formula ( 2) ~
Represents any group represented by (5), Y ₂ represents a hydroxyl group, an alkoxy group, Y ₁ or the following general formula (6), k represents an integer of 1 to 3, and 1 represents an integer of 0 to 2. Represents ) General formula (2) (In the formula, R ₄ and R ₅ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or the substituents are combined together to include a further nitrogen atom, oxygen atom or sulfur atom. May be a 5-membered ring or a 6-membered ring, and n represents an integer of 1 to 6.) General formula (3) (In the formula, R ₄ and R ₅ have the same meanings as in formula (2).)
General formula (4) (In the formula, R ₆ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group.) General formula (5) (In the formula, R ₇ represents a group represented by the general formula (4) or a group represented by the following general formula (7), p represents an integer of 0 to 6, and m represents an integer of 1 to 2. ) General formula (6) (In the formula, X ₁ , R ₁ , R ₂ , k and l have the same meanings as in the general formula (1).) General formula (7) (In the formula, X ₂ represents a direct bond, —NH— or —O—, q represents an integer of 0 to 6, and R ₄ and R ₅ represent the general formula (2).
Means the same as. ) 2. The pigment dispersant according to claim 1, wherein Y ₁ is a group represented by formula (2). 3. The pigment dispersant according to claim 2, wherein R ₄ and R ₅ are alkyl groups having 1 to 6 carbon atoms. 4. The method according to claim 1, wherein X ₁ is —NH—.
Any one of the pigment dispersants. 5. A pigment composition comprising a pigment and the pigment dispersant according to any one of claims 1 to 4.