JPS63305173A - Pigment dispersant - Google Patents

Abstract

PURPOSE:To obtain a pigment dispersant which is excellent in non-agglomerating property and noncrystallizability and can give a paint excellent in dispersion stability and free of problems, such as gelation during storage, color non- uniformity of a colored object and loss of tinting power, due to, e.g., floatation, sedimentation or decrease of pigment due to agglomeration, having a specified structural formula. CONSTITUTION:A compound of formula I [wherein A and B are each -CO-, -NH-, -S- or -O-, W is H, a galogen, nitro, methoxy, ethoxy, phenoxy, sulfamoyl, carbamoyl, (substituted)alkyl or (methyl-, nitro- or halogen-substituted) phenylcarbamoyl or phenylsulfamoyl, and l is 0-2] is chlorosulfonated to obtain a pigment dispersant of formula II [wherein X is -CO- or -SO2-, Y1 is a group of formula III or IV, Z is a (substituted)alkylene or arylene, Y2 is a group of any one of formulas V-VII, Y3 is Y2, OH or alkoxy, R1-2 each H or a (substituted)alkyl, R3-5 are each a (substituted)alkyl and R3 and R4 may be combined together to form a nitrogenous heterocyclic ring, M is 1-6 and n is 1-2].

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a pigment dispersant that is suitable for use, particularly excellent in non-aggregation and non-crystallinity.

(Prior Art) Practically useful pigments that exhibit clear color tones and high tinting power in various coating compositions are composed of fine particles. However, fine particles of pigments make it difficult to obtain stable dispersions when dispersed in non-aqueous vehicles such as gravure inks and paints, and there are various problems that have an important impact on manufacturing operations and the value of the resulting products. This often causes problems.

For example, dispersions containing pigments made up of fine particles often have a low viscosity, making it difficult to remove them from the product dispersion and transport them, and even worse, they gel during storage, making them difficult to use. It may become. Furthermore, when different types of pigments are mixed and used, color separation due to aggregation and decreased sedimentation may result in color unevenness and a significant decrease in coloring power in the mixed color mixture. Furthermore, e of the mixed color
Regarding the 119 surface, poor conditions such as reduced gloss and poor leveling may occur. Although not directly related to the dispersion of the pigment, some mechanical pigments experience a decrease accompanied by a change in the crystalline state of the pigment.

In other words, pigment crystal particles, which are energetically unstable in non-aqueous vehicles such as gravure inks and paints, change their size and morphology and shift to a stable state, resulting in significant hue changes in color mixtures.2.Coloring power The product value may be impaired due to a decrease in the amount of carbon dioxide, generation of coarse particles, etc.

In order to improve the non-aggregation properties and crystal stability of the above-mentioned pigments, numerous proposals have been made, mainly copper phthalocyanine and quinacridone pigments.

For example, Special Publication No. 41-2466 and USP28554
As represented by 03, the base skeleton is an organic pigment, and the side chain has a sulfone group, a sulfonamide group, an aminomethyl group,
A method of mixing compounds obtained by introducing substituents such as phthalimidomethyl groups is known, but although these compounds have great effects on the non-aggregation property and crystal stability of pigments, Because it is derived from a compound with the same chemical structure as , it has strong inherent coloring, and there are significant restrictions when using it for pigments of different hues.

Therefore, it is necessary to prepare corresponding compounds for each pigment, which is extremely disadvantageous in the production of pigment compositions.

[Problem that the invention seeks to solve]

The present invention provides a practically excellent pigment dispersant for solving various problems occurring in non-aqueous vehicles such as gravure inks and paints.

[Structure of the invention]

(Means for Solving the Problem) As a result of extensive research, the present inventors have discovered that all of the compounds represented by the general formula (I) are colorless or slightly colored compounds, and that they are different from pigments of various hues. The present inventors have discovered that even if they are mixed arbitrarily, there is no problem with hue, and furthermore, significant effects can be obtained in terms of non-aggregation properties, crystal stability, etc. of pigments in non-aqueous vehicles, leading to the present invention.

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

In the formula, A and B each independently represent -CO-, -NH-9-
3- or 10-. W is a hydroxyl group, a halogen atom,
Nitro group, methoxy group, ethoxy group, phenoxy group, sulfamoyl group, carbamoyl group.

HtA or $A-substituted alkyl group 3, or phenyl erbamo substituted or unsubstituted with a methyl group, nitro group, or halogen atom. " is a group or a phenylsulfamoyl group. X is -CO- or -SOR,, R1
are each independently a hydrogen atom or a substituted or unsubstituted alkyl group.

R3, R4, and R% each independently represent a substituted or unsubstituted alkyl group, and +Rff and R4 may form a heterocycle containing a nitrogen atom.

l is an integer from 0 to 2.

m is an integer from 1 to 6.

n is an integer of 1-2.

More specifically, 1, for example, the following general formulas (It) to (V)
It is expressed as

(In the formula W, R3, R4, Rs, !!, m, n
The compound represented by the general formula (!, is the same as the general formula (I)) is chlorosulfonated according to a conventional method, or (Vl) is preliminarily substituted with a sulfonic group or a carboxyl group (if Vl is substituted with a sulfonic group), the compound represented by the general formula (!, is the same as the general formula (I)) is Thionyl chloride according to the law.

After chloride with phosphorus pentachloride, the following general formula (■)
The pigment dispersant of the present invention can be obtained by reacting with amines represented by:

(In the formula, R++Rz, Z, Yt, and Ys are the same as in general formula (I)) For these dehydrochlorination reactions, common organic solvents such as water, methanol, ethanol, acetone, dioxane, toluene, xylene, and dimethylformamide are used. can be used. As the acid binding side, pyridine.

Triethylamine, sodium hydroxide, sodium carbonate, etc. can be used.

For example, the amines represented by the general symbol (■) are 1.

Equimolar amounts of P-amino-7cetanilide and cyanuric chloride in a mixed solvent of water, alcohol, and hydroalcohol.

Compound 91 (-7) represented by the linear formula is produced by reacting in a common organic solvent such as quijirol.

Then, in order to introduce Y or Y, it is reacted with amines or alcohols represented by the 5th order general formula (■), (X), or (XI) in water or a general organic solvent to obtain the general formula (Xn), (XI[I).

A compound represented by (XIV) is produced.

/R(O-(CHz)m-N (X)\R4 (in the formula, Ra, Ra, R1, m are the same as in general formula (I))
Then (Xfl), (XI), (XrV)
The amines represented by the general formula (■) can be produced by hydrolyzing with a hydrochloric acid/water mixture.

Note that even if one chlorine atom in the general formula (■) undergoes hydrolysis during the reaction and becomes a hydroxyl group or an alkoxy group, it can be used as a raw material for the pigment dispersant of the present invention.

By using P-nitro-aniline in place of P-amino-acedoanilide, a compound (XV) represented by the following formula is prepared: (IX), (X).

The compound represented by general formula (■) can also be produced by reacting with amines or alcohols represented by (XI) and then reducing the nitro group. Using, for example, N-acetylethylenediamine instead of P-amino-acedoanilide, the general formula (, The represented amines can be prepared.

(In the formula, R, Rn, and m are the general formula (same as eyes) or the compound represented by the general formula (V[) is chlorosulfonated, and P
-Amino-acedoanilide and then hydrolyzed according to a conventional method to produce a compound represented by the general formula (X). [X), (X)
The pigment dispersant of the present invention represented by general formula (I) can also be produced by reacting with amines or alcohols represented by (XI).

(In the formula, A and B are the same as in the general formula (I)) Examples of the amines represented by the general formula (■) of the present invention include 1, for example, 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-7minoethylpyrrolidine, N-aminopropylpyrrolidine, N-aminoethylmorpholine, N-aminopropylmorpholine, N,N-methyl-lauryl Aminopropylamine, N
, N-aoleylaminoethylamine, N,N-distearylaminobutylamine, and the like.

Alcohols represented by general formula (X) include:

For example, N,N-dimethylaminomethanol, N,N
-dimethylaminoethanol, N,N-diethylaminoethanol, N,N-dibutylaminoethanol, N,
N-dibutylaminoethanol, N,N-dibutylamitubrobanol, N,N-diethylaminobutanol,
N,N-dioleylbutanol.

N-hydroxymethylpiperidine, N-hydroxyethylpiperidine, N-hydroxypropylpiperidine, N
-Hydroxyethylpipecoline, N-hydroxypropylpipecoline, N-hydroxymethylpyrrolidine, N-
These include hydroxybutylpyrrolidine, N-hydroxyethylmorpholine, N-hydroxybutylbutylmorpholine, and the like.

Examples of the amine represented by the general formula (XI) include N-methylbiperazine, N-ethylpiperazine, N-butylpiperazine, and l-cyclopentylpiperazine.

The pigment dispersant obtained in the present invention exhibits an excellent dispersion effect on all pigments that are generally commercially available.

For example, soluble and insoluble azo pigments, azo pigments such as condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene/perinone pigments, dioxazine pigments, vat dye pigments, and basic dye pigments. Machine pigments such as pigments and carbon blanks, titanium oxide, yellow lead, cadmium yellow.

It can be used for inorganic pigments such as cadmium red, Bengara, iron black, zinc white, navy blue, and ultramarine blue.

The content of the pigment dispersant obtained in the present invention in the pigment is preferably 0.1 to 30 parts by weight per 100 parts by weight of the pigment. If the amount is less than 0.1 part by weight, the effect of the pigment dispersant obtained in the present invention cannot be obtained, and even if it is used in an amount greater than 30 parts by weight, the effect of the amount used cannot be obtained.

The method of using the pigment dispersant according to the present invention is as follows.

For example, there are the following methods.

1. A pigment composition obtained by pre-mixing a pigment and a pigment dispersant is added to a non-aqueous vehicle and dispersed.

2. Add pigment and pigment dispersant separately to a non-aqueous vehicle and dissolve.

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 a solvent.

4. After dispersing the pigment in a non-aqueous vehicle, a pigment dispersant is added to the resulting dispersion.

There are four methods, and any of these methods can achieve the desired effect.

Regarding the method for preparing the pigment composition shown in 1 above, the desired effect can be obtained by simply mixing the pigment powder and the powder of the pigment dispersant related to the present invention, but a kneader is used.

Mix mechanically using a roll, attritor, super mill, various types of pulverizers, etc., or add a solution containing the pigment dispersant according to the present invention to a pigment suspension system of water or an organic solvent, and apply the pigment dispersant to the surface of the pigment. or deposit
Even better results can be obtained by performing an intimate mixing method such as co-dissolving the organic pigment and pigment dispersant in a solvent with strong dissolving power such as sulfuric acid and co-precipitating with a poor solvent such as water.

Further, as shown in 2 to 4 above. When using pigments and pigment dispersants, dispersion machines for dispersing pigments or pigment dispersants in non-aqueous vehicles or solvents, mixing them, etc. are used as dispersion machines such as Tisilver, high speed mixer, homomixer, kneader, roll mill, etc. Good dispersion of the pigment can be achieved by using a sand mill, attritor, etc.

According to the invention, therefore, a lime rosin varnish.

Gravure inks such as polyamide resin varnish or vinyl chloride resin varnish, nitrocellulose lacquer.

Air drying or baking of amino alkyd resin is a paint.

Acrylic lacquer and amino acrylic resin baking are paints.

In non-aqueous vehicles such as urethane resin paints.

Compared to when a pigment is used alone, the dispersion exhibits good fluidity such as lower viscosity and structural viscosity, and at the same time, there are no problems such as color separation or crystal changes, and the gloss of printed matter or coatings is good. You can get beautiful products. especially,
Conventional pigment dispersants showed dispersion effects in oil-modified aminoalkyd resin paints, but did not show excellent dispersing effects in oil-free aminoalkyd resin paints.1 The pigment dispersant of the present invention shows dispersion effects in oil-modified aminoalkyd resin paints It has an extremely excellent dispersion effect not only in paints but also in oil-free alkyd resin paints.

The pigment dispersant of the present invention is not limited to non-aqueous vehicles, but can also be used to color other printing inks, paints, and even plastics, providing a colored product with an excellent 1-dispersion effect and 2-coloring strength.

The outline of the method for synthesizing the pigment dispersant of the present invention will be described below as a manufacturing example. In the example 0, "part" means "part by weight."

[Production Example 1] A product having the following structural formula obtained by reacting equimolar amounts of P-aminoacedoanilide and cyanuric chloride, further reacting with twice the mole of N,N-dimethylaminoethylamine, and then hydrolyzing the product. 40 parts of amine and anthraquinone-2-carboxylic acid were added according to a conventional method.

27 parts of anthraquinone-2-carbochloride obtained by chlorination with thionyl chloride and 300 parts of methanol are heated under reflux for 3 hours.

1,500 parts of reaction-completed activated water and 8 parts of sodium hydroxide were added, filtered, washed with water, and dried to obtain a pigment dispersant having a 9-order structure (
a) 58 parts were obtained.

[Production Example 2] The following t1 is obtained in place of anthraquinone-2'-carbochloride in Production Example 1 according to a conventional method! The same amine as in Production Example 1 was reacted using 29.5 parts of cafridone-2-sulfochloride having the following structure.

62 parts of a pigment dispersant (b) having the following structure was obtained.

[Production Example 3] After reacting N-acetylethylenediamine and cyanuric chloride in equimolar amounts, and then reacting with N,N-diethylaminoethanol and N,N-dibutylaminoprobylamine,
44 parts of an amine having the following structure obtained by hydrolysis and a conventional method. Phenoki + having the following structure
'y −+,
°-"7 Heat and stir 38 parts of chlorosulfonated sazine in dimethylformamide at 90-100"C for 3 hours. After the reaction is complete, add 2500 parts of water and 20 parts of sodium hydroxide, filter, wash with water, and dry. 113 parts of a pigment dispersant (C) having the following structure was obtained.

(Hereinafter, blank spaces) Table 1 Next, examples and comparative examples will be given and explained. The chemical structure of each pigment dispersant shown in alphabetical order corresponds to that shown on the manufacturer's side.

Example 1 The above pigment dispersant (al 1.8 parts, C, 1, Pigme
nt B1ue60 16.2 copies and a9. A7.
The viscosity at 25°C during kneading of a paint prepared by kneading 382 parts of Ya71 resin varnish in an 1E ball mill was measured using a BM type rotational viscosity.
Paints containing a) showed no structural viscosity.

The results of measurement using the same BM type viscometer after leaving these paints for one week are shown below, and the paints containing the pigment dispersant showed little increase in viscosity.

I made a 1/10 Kaft light color paint using a white coating material adjusted with titanium white, adjusted the viscosity to 4.20 to 22 seconds under a Ford cup, and observed the state of aggregation in a test tube, but even after a month, the color separated. , no sedimentation was observed.

Furthermore, the mixed pigment containing the pigment dispersant (al) did not agglomerate even in nitrocellulose lacquer acrylic resin paints and gravure inks, and exhibited good fluidity.

Examples 2 to 8 C, 1, Pigment B1 (Ie
A paint was prepared in the same manner as in Example 1, using the H material in Table 2 instead of 60, and each pigment dispersant shown in (bl to (g) instead of al). The viscosity was measured.

The results are shown in Table 2. When using inorganic pigments, use the face! '4
Adjust the paint by setting the amount to 25%.

(Hereinafter, blank space) After the paints were left for one week, the viscosity was further measured, and the paints containing the pigment dispersant showed a small increase in viscosity.

In addition, we observed the agglomeration state of light-colored paint, but compared to the comparative example,
The mixed pigment containing the pigment dispersant had excellent color separation and sedimentation properties. This mixture pigment can also be used for nitrocellulose lacquer,
Even in acrylic resin paints and gravure inks, it showed good fluidity without causing ali.

(Effects of the Invention) According to the present invention, it is possible to obtain paints and gravure inks with excellent dispersion stability, and gelation during storage due to color separation due to aggregation of pigments and decrease in sedimentation, This prevents color unevenness and significant deterioration of coloring power, and provides a colored product with excellent gloss.

Claims (1)

[Claims] 1. A pigment dispersant represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In the formula, A and B are each independently -CO-, -NH-, -
S- or -O-. W is a hydrogen group, a halogen atom,
Nitro group, methoxy group, ethoxy group, phenoxy group, sulfamoyl group, carbamoyl group, substituted or unsubstituted alkyl group, or phenylcarbamoyl group or phenylsulfamoyl group substituted or unsubstituted with methyl group, nitro group, or halogen atom. It is. X is -C
O- or -SO_2-. Y_1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Z is an alkylene group or an arylene group which may have a substituent. Y_2 is ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. Y_3 is a hydroxyl group, an alkoxy group, or Y_2. R_1 and R_2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group. R_3, R_
4 and R_5 each independently represent a substituted or unsubstituted alkyl group, and R_3 and R_4 may form a heterocycle containing a nitrogen atom. l is an integer from 0 to 2. m is an integer from 1 to 6. n is an integer of 1-2.