JPH0248029A - Dispersant and dispersion liquid containing the dispersant - Google Patents

Abstract

PURPOSE:To prevent the flocculation of a pigment dispersed in a liq. by allowing a 1,2-epoxy compd. to react with polyethyleneimine, allowing the resulting product to react with polyester having a terminal carboxyl group and using the resulting product as a dispersant. CONSTITUTION:A 1,2-epoxy compd. represented by formula I (where R is H, alkyl, phenyl, etc.) and/or cycloalkene-1,2-epoxide represented by formula II (where n is an integer of 3-10) is allowed to react with polyethyleneimine. The resulting product is allowed to react with a compd. represented by formula III (where R2 is 7-38C alkyl, alkylene, etc., x is a number of 1-20 and y is a number of 0.1-10) and the resulting product is used as a dispersant. Fine solid powder and the dispersant are added to an org. liq. to prepare a dispersion liq.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to dispersing fine powder solids such as inorganic or organic pigments in an organic liquid, and of course when the organic liquid is polar. It is a dispersant that can impart excellent fluidity and dispersion stability to the dispersion system even when it is a non-polar system, and can be used in general coating compositions such as printing inks and paints. More specifically, it relates to a dispersant that has a high concentration, low viscosity, is stable over time, and can provide a pigment dispersion for coating that has satisfactory performance with a small amount of use, and the dispersant. The purpose of this is to provide a dispersion having excellent fluidity and dispersion stability.

[Conventional technology]

In general, useful pigments that can exhibit high tinting power, excellent gloss, and vivid color tone in color material compositions for various coatings such as printing inks and paints are composed of fine solid particles. There is.

However, fine particles, such as the known pigments, can be dispersed in nonpolar organic solvents containing vehicle polymers, such as in offset inks, gravure inks, flexographic inks, and paints, especially at high pigment concentrations. However, it is difficult to obtain a coloring material composition with excellent fluidity and storage stability, which often causes various problems that have a significant impact on the manufacturing process and the quality of the obtained product.

That is, a concentrated dispersion containing a pigment consisting of fine particles is
They often have a high viscosity, making them difficult to handle when stirring, mixing, removing the product from a disperser, or transporting the product, and sometimes thickening significantly during storage, making it difficult to use.
Undesirable phenomena such as flooding, 70-ting, reduction in coating film gloss, and discoloration over time occur.

Non-aqueous printing inks or coatings are pigment dispersions whose dispersion medium is an organic liquid containing a vehicle polymer and other auxiliaries; the rheological properties of these dispersions are essentially It depends on the nature of the pigment, which consists of fine particles.

In other words, in a dispersion system in which the fluidity of the dispersion liquid is extremely poor or the viscosity increases significantly over time, the aggregation of the pigment within the system is significant, and the coloring material in such a system is Not only does it have poor fluidity, but its coloring power during spreading is inferior to colorants that maintain a good dispersion state, and coarse aggregates create unevenness on the painted surface, causing it to lose its smoothness.
The gloss also tends to decrease significantly (6), thus impairing the commercial value of the object to be coated.

In other words, in the case of a dispersion having a commercial pigment concentration such as a printing ink, if an attempt is made to improve the viscosity or fluidity of the dispersion, the gloss of the coating film will be lost, and if an attempt is made to improve the gloss, the fluidity However, it has not been easy to produce coating colorants that satisfy both fluidity and gloss, such as poor storage stability.

Various methods have been proposed to prevent agglomeration of pigments in non-aqueous paints or printing inks.

For example, Japanese Patent Publication No. 54-34009, British Patent No. 1,342,746, U.S. Patent No. 3,778,
No. 282, etc., describes a dispersant comprising a polyester containing a terminal carboxyl group or a salt thereof obtained by dehydrating hydroxycaldic acid such as 12-hydroxystearic acid.

In addition, Japanese Patent Application Laid-Open No. 54-37082, British Patent Application Publication No. 2,001,083, and U.S. Patent No. 3.8
Specification No. 82,088, Specification No. 4,224,212, West German Patent Application No. 2,830,860, etc., describe the above-mentioned terminal carboxyl group-containing polyester and poly(lower alkylene)imide/and A dispersant consisting of an amine salt or amide obtained by reacting is described.

Furthermore, Japanese Patent Publication No. 57-25251, British Patent No. 1
, 373,660, the terminal carboxyl group of the above-mentioned terminal carboxyl group-containing polyester is esterified with dialkylamino alcohol or amidated by reacting with (dialkylamino)alkylamine, and then esterified with dimethyl sulfate. A dispersant in which the terminal tertiary amine group is a quaternary ammonium group is described.

[Problem that the invention attempts to solve]

Despite the various attempts described above, it has not yet been possible to obtain a dispersant that has sufficiently satisfactory performance in terms of fluidity and color development of the dispersion at high pigment concentrations.

Furthermore, although dispersants derived from dehydrated condensed polyesters of long-chain aliphatic hydroxycargenic acids such as 12-hydroxystearic acid have considerable versatility with respect to various pigments, they contain When used in dispersions such as metallic inks and baking paints, there is a problem in that the adhesion between the coating film and the metal is impaired, which limits its use.

In addition, for polyethyleneimine salt-type dispersants, such as those described in U.S. Pat. No. 4,224,212, the dispersant components include Since the content of polyethyleneimine in the composition is low, protons of the polyester terminal carboxyl group, which is a solubilizing group, are gradually withdrawn by the primary amine group of polyethyleneimine, which is a polar group component in such compositions, and ammonia gradually forms. It is said that by generating gas, the dispersant itself produces a pronounced ammonia odor, which is an unfavorable phenomenon in terms of environmental hygiene. It is clear that such a phenomenon is caused by the fact that the primary amine group in the polyethyleneimine constituting the anchor section of the dispersant is an extremely basic group. The mechanism of ammonia generation over time in such a dispersant composition can be expressed in an easy-to-understand manner using a reaction formula (N formula): (Polyethyleneimine) (Terminal carboxylic polyester) (Amine salt formation) Reaction) Equilibrium reaction (fast) (Polyethyleneimine salt type dispersant) The reaction that is generated is an equilibrium reaction accompanied by heat, and the higher the temperature of the reaction system, the more this equilibrium shifts to the left side. Therefore, in the dispersant manufacturing process, even if the two components, polyester carboxylic acid and polyethyleneimine, are mixed and heated, almost no ammonia elimination reaction occurs, but if the dispersant is kept at room temperature, When stored, the equilibrium shifts to the right-hand side, in the direction of amine salt formation, so that the nucleophilic attack of the caldexylate anion on the carbon atom bonded to the ammonium group causes
This can be explained by the fact that it gradually releases ammonia gas, causing a bad odor.

It is possible to confirm that this odor component is ammonia by, for example, gas chromatography mass spectrometry.

The problem to be solved by the present invention is to prevent the agglomeration of pigments in the dispersion when dispersing fine powdery solids, especially organic and inorganic pigments, in organic liquids, especially at high pigment concentrations. It is effective in imparting excellent fluidity and dispersion stability, and when used in thermosetting paints or inks,
It is an object of the present invention to provide a dispersant that does not reduce the adhesion between a coating film and a metal and does not generate bad odor due to ammonia, and a dispersion containing the dispersant.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention solves the above problems. (representing a substituted phenoxymethyl group, acyloxymethyl group) and/or (b) a compound represented by the general formula (in the formula, n represents an integer from 3 to 10) and polyethyleneimide/ product and (2) general formula % formula % () (wherein R2 is an alkyl group having 7 to 38 carbon atoms, an alkylene group, an alkyl diene group, a cycloalkyl group, a cycloalkylene group, a fused polycyclic group) represents a saturated hydrocarbon group, phenyl group, fused polycyclic aromatic hydrocarbon group, hydroxyl group-substituted polycyclic aromatic hydrocarbon group, X represents any numerical value between 1 and 20, and y/ri O , represents any numerical value between 1 and 10).

Furthermore, the present invention provides a dispersion agent for printing inks, paints, coloring bases thereof, etc., in which pigments and other finely powdered solids are dispersed in organic solvents or organic liquids such as organic solvent solutions of binder resins. A dispersion containing the above dispersant is provided.

Hereinafter, the configuration of the present invention will be explained in more detail. The reaction between the 1,2-epoxy compound of the general formula (1) and the active hydrogen in the polyethyleneimine molecule is expressed by the following formula (B) or (Q, H --NHcCH2CH2 or the cyclo of the general formula (I). The reaction between the alkene-1,2-epoxide and the active hydrogen in the polyethyleneimine molecule is represented by the following formula (b) or @) (where n is an integer from 3 to 10).

-NHCH2CH2 ＼ When preparing the dispersant according to the present invention, the feature is that at least one
The point is that polyethyleneimine to which [substituted alkyl] or hydroxycycloalkyl groups are bonded is used as a starting material; It becomes possible to reduce the content of primary amino groups in polyethyleneimine.

The reason for this is that primary amines are more reactive than secondary amines in the reaction between epoxides and amines. Therefore, it becomes possible to suppress or prevent the elimination reaction of ammonia as represented by the solidification, and it is possible to reduce or prevent the malodor of the amine salt type dispersant due to ammonia. In the present invention, a useful copolyester containing a terminal carboxyl group (hereinafter referred to as polyester (B)) represented by the general formula (to) 00C6H130 ... (to) in the average composition is reacted with the above starting material. The purpose is to prepare a dispersant.

Now, the hydroxyalkylated polyethyleneimine or hydroxycycloalkylated polyethyleneimine which is the starting material for preparing the dispersant of the present invention is a 1,2-epoxy compound represented by the general formula (1), such as evaporated ethylene oxide, 1. 2-f propylene oxide, 1,2-butylene oxide, styrene oxide, n-butyl glycidyl ether, phenyl glycidyl ether, 4-te
rt-butylphenyl glycidyl ether, 4-see
-Butylphenylglycidyl ether allyl glycidyl ether, persatic acid glycidyl ester, or cycloalkene-1,2-epoxides represented by general 2Q[), such as cyclotenthene oxide, cyclohexene oxide, cyclooctene oxide, etc. Each is obtained by reacting with polyethyleneimine.

The polyethyleneimine used in this reaction preferably has a number average molecular weight of 300 to 50,000, does not necessarily have to be highly branched, and the reaction temperature is 50 to 200°C, preferably 100 to 150°C. Apart from epoxides with extremely low boiling points,
This is carried out by slowly dropping epoxide into heated and stirred polyethyleneimine. Since the ring-opening addition reaction of epoxide is accompanied by heat generation, it is necessary to add the epoxide with care to maintain the reaction temperature of the system due to the reaction heat. The reaction between epoxide and polyethyleneimine may be performed before or after the neutralization reaction between polyester (B) and polyethyleneimine, which will be detailed later.
There is no particular problem in terms of performance as a dispersant.

The reason for this is that the number average molecular weight of polyester (B) is much lower than that of the monomer units constituting polyethyleneimine. This is because even if it is present in excess, the degree to which the reaction between the active hydrogen in polyethyleneimine and the epoxide is inhibited by the polyester (in the polyester) can be substantially ignored.

Now, next is polyester (B), that is, the terminal cal? The preparation of the xyl group-containing copolyester (general formula ([0)] will be explained.

(in the polyester) is represented by the general formula (IV) R2-C-OH...(IV) (wherein, R2 represents the same substituent as R2 of the compound represented by the general formula (2)). An adduct (hereinafter referred to as polyester) is prepared by ring-opening polymerization of ε-carrolactone to a monocarboxylic acid.

This reaction formula shows that in the presence of an oxide represented by formula (IV) and a Lewis acid catalyst such as boron trifluoride,
It is prepared by heating and stirring the monocarboxylic acid (5) and ε-casirolactone at 120 to 200°C, preferably 150 to 180°C, preferably in a nitrogen atmosphere.

Obtained in this way. i? IJ ester (A) is a waxy solid resin that is white to slightly yellowish at room temperature, but it is not necessary to extract it as an intermediate.
Continue to prepare 12-hydroxystearic acid and next dehydration? There is no problem in moving to the condensation type. This reaction is shown by equation 6).

00C6H15 Prieste Hamada Polyester (N...(IV) Formula (The ring-opening polymerization reaction of 0 is isopropyl orthotitanate, n-butyl orthotitanate, dibutyltin + yH20 Polyester (B)...(G) Formula In the reaction of (IV), monocarboxylic acid (IV) and ε
- The molar ratio of caprolactone is 1:1 to 20. Preferably it is 1:8-15.

Examples of monocarboxylic acids (IV) include n-octylic acid, 2-ethylhexanoic acid, lauric acid, myristic acid,
of? Lumitic acid, stearic acid, oleic acid, linoleic acid, lylunic acid, decanoic acid, nono-sactic acid, benzoic acid, p-hydroxybenzoic acid, salicylic acid, p-tert
-butylbenzoic acid, 2-hydroxy-3-naphthoic acid,
Examples include cyclohexenecarboxylic acid, neodic acid, abietic acid, etc., but it goes without saying that one type or a mixture of two or more of these acids may be used.

The dehydration polycondensation reaction of formula (G) can be carried out using known esterification catalysts such as phosphoric acid, p-)luenesulfonic acid, sulfuric acid, tetra-■-butyl titanate, tetra-1ao-propyl titanate, dibutyltin oxide, or Australian Patent No. 493,015, Japanese Unexamined Patent Publication No. 137, 1986
No. 67, No. 60-137,924, etc., the produced water is heated to 120 to 200°C, preferably 140 to 190°C, in the presence of methanesulfonic acid, etc. The dehydration and esterification reaction can be carried out by distilling off, preferably by passing an inert gas such as nitrogen through the reaction system, or the dehydration and esterification reaction can be carried out by distilling off aromatic hydrocarbons, e.g. It is advantageous to carry out the reaction in the presence of , toluene, or xylene, and to remove the produced water azeotropically from the reaction system. The degree of progress of the esterification reaction due to intermolecular dehydration is determined by measuring the amount of distilled water and the acid value of the reactant. The acid value of the polyester (B) thus obtained is 10 to 120, preferably 20 to 60.
This is practically advantageous. 1 which is usually easily available industrially
Since 2-hydroxystearic acid is produced by hydrolysis of hydrogenated castor oil, it contains small amounts of impurities such as
Although it contains stearic acid and palmitic acid, their presence does not cause any problems even if it is used for the production of polyester.

Next, a method for obtaining a novel dispersant, which is the object of the present invention, by reacting polyester (B) with hydroxyalkylated or hydroxycycloalkylated polyethynoneimine will be explained. The stoichiometric ratio in the reaction of the hydroxyalkylated polyethyleneimine (in the polyester) is less than one equivalent of carboxyl group per one amine nitrogen atom, producing an amine salt or amide depending on the reaction conditions. That is, when the reaction is carried out at a relatively low temperature, an amine salt is produced, and when heated and dehydrated at a relatively high temperature, an amide is produced, and these reactions can be judged from, for example, an infrared absorption spectrum chart.

The dispersant according to the present invention is used when dispersing an inorganic or organic pigment in a non-polar organic liquid.
00J, aromatic hydrocarbons such as "Tsurpetz 150" (alkylbenzene solvent manufactured by Esso Oil Co., Ltd.), petroleum hydrocarbons such as mineral spirit, mineral turpentine, light oil, chloroform, Tsuku-chloroethylene, doluchloroethylene, Carbon tetrachloride, chlorobenzene-like nahalodanized hydrocarbon, acetone, methyl ethyl ketone, methylinobutyl ketone, cyclohexanone, isophorone,
Chain or cyclic ketones such as, esters such as ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, carpitol acetate, but of course mixed solvents of two or more of these. Also good,
In addition, known alkyd resins, epoxy resins, epoxy ester resins, acrylic resins, vinyl acetate-acrylic copolymer resins, polyamide resins, polyester resins, polyurethane resins, acrylic urethane resins, vinyl resins, phenolic resins, nitrocellulose resins, etc. There is no problem even if it is a mixed system.

The powdery solids dispersed in the organic liquid by the dispersant of the present invention are usually fine solids with a particle size of 20 microns or less, such as rutile-type or anatase-type titanium white,
Red, colorless or yellow iron oxide, barium sulfate, zinc chromate, strontium chromate, lead chromate, aluminum oxide, calcium carbonate, Merck, clay silica, magnetic iron oxide, carpin black, aluminum, iron,
Various inorganic pigments, including coloring materials, fillers, conductive materials, magnetic materials, etc., such as brass, azo pigments, lakes, toners, phthalocyanine pigments, isoindolinone pigments, quinacridone pigments, indanthrene pigments, dioxanone pigments and organic pigments such as flavanthrone pigments.

The term "lake" as used herein refers to a water-insoluble salt or complex of an organic dye precipitated on a water-insoluble carrier such as alumina, and "toner" specifically refers to a water-insoluble salt or complex of an organic dye that is precipitated on a water-insoluble carrier such as alumina. It means an extremely poorly soluble calcium salt or complex.The relative proportion of the dispersant according to the present invention in the pigment dispersion is 0.1 to 100%, preferably 0. The content of the fine powder to be dispersed in the dispersion is 5 to 80%, preferably 10 to 70%. When producing paints and ink compositions, commonly used dispersing machines such as roll mills, tail mills,
Sand mill, planetary mixer, high speed disper
You can use an attritor or the like.

The dispersant of the present invention thus obtained is disclosed in Japanese Patent Application Laid-Open No. 54-3
No. 7,082 or as described in U.S. Pat. No. 4,415,705, the polyester chain of the solubilizing group consists essentially only of a dehydrated condensate of 12-hydroxystearic acid. Compared to conventional dispersants, when coating color materials such as inks and paints containing dispersants are used for painting or printing metals, they have the advantage of not impairing the adhesion between the paint film and metals. In addition, it is possible to prevent the bad odor resulting from ammonia generation, which is often pointed out in high-concentration polyethyleneimine-containing dispersants such as those described in the patent, and it is also more effective than conventional pigment dispersion compositions. It has the characteristic of being able to maintain a much higher pigment concentration. When performing a painting operation using a pigment dispersion for coating, the operation becomes difficult if the viscosity of the composition is too high.

In order to maintain a suitable viscosity for the operation, it is necessary to dilute with a considerable amount of solvent, resulting in a lower solids content and less effective coating.

In recent years, gray paint has been widely used in painting operations due to its efficiency, and this tendency is particularly noticeable when painting on a large scale.

Therefore, there is a strong demand for a pigment dispersion composition that has a high solid content percentage and has good fluidity to the extent that it does not interfere with the work. The pigment dispersion composition according to the present invention meets these demands, and improves coating efficiency,
It is also advantageous in that it can contribute to reducing the amount of organic solvent used. Further, the features and advantages of the dispersant of the present invention are as follows: (→ Savings in dispersion time and energy costs due to improved fluidity, increasing the amount charged to the dispersing machine, and reducing adhesion loss. Improved productivity by reducing the number of mill bases (→ Reducing the number of mill bases, storage base, and inventory interest rate (saving transportation costs by increasing the pigment concentration in the 3-lithographic ink flash base) Dispersion state in color material products Prevents abnormal agglomeration and color separation by stabilizing color, and improves quality such as color density and gloss.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
Needless to say, the gist of the present invention is not limited to these Examples. In addition, parts in the examples mean parts by weight.

(Example of Preparation of Dispersant) Example 1 (Preparation of Dispersant A) Into a 5 liter-4 turret flask equipped with a thermometer, nitrogen inlet tube, condenser and stirrer, 173.11I of 2-ethylhexanoic acid and 1369 I of 1-caprolactone were added. .7.9
．． n-butyl orthotitanate 1. Og was charged and kept at 160℃ for 3 hours while stirring in a nitrogen stream, and after 1
The temperature was raised to 80°C and stirred for 3 hours.

Next, the internal temperature was lowered to 100°C, and 540.9 II of industrial 12-human 0-oxystearic acid, 520.7 g of xylene,
Add 1.0 n-butyl orthotitanate and
After attaching a Stark trap, the mixture was refluxed at 162°C for 15 hours. The amount of water distilled into the trap was 21.3N.

The reaction product was cooled to obtain 2571 intermediate (polyester B). The acid value of this substance is 37.5 qKOH/,
? , the non-volatile content was 76%.

Next, xylene 112.5. Pr Epomin 5P-20
0J (Nippon Shokubai Kagaku Co., Ltd. group polyethyleneimine; average molecular weight 10,000) 30 g, xylene 112.
519 was mixed, 7.5 g of 1,2-butylene oxide was added while stirring, and the mixture was maintained at 110°C for 30 minutes.

The intermediate polyesters iso and oy were added to the mixture and heated under reflux at 138° C. for 2 hours in a nitrogen stream to distill 1.7 g of water into a Dean-Stark trap.

The contents were cooled to obtain a slightly viscous dispersant solution 292.3JF, which was light yellowish brown and transparent, having an acid value of 15.2 xyKoH/I, an amine value of 86.7 da KOVI, and a non-volatile content of 50.0%.

Example 2 (Preparation of Dispersant B) Xylene 79.5. lr epomi:y 5P-200J
20.5F was mixed, and 5.1 g of styrene oxide was added while stirring while maintaining the temperature at 100°C. 3 at 130℃
Heat and stir for 0 minutes, cool to 100°C, add the intermediate polyester 99.7F of Example 1, and heat at 138°C in a nitrogen stream for 30 minutes.
Heat to reflux for 1 hour in a Dean-Stark trap.
11! water was separated.

The contents were cooled to obtain a dispersant solution 203.6II having an acid value of 14.7 m9KOH/#, an amine value of 82.0119KOH/F, and a non-volatile content of 52.0%. This product had a viscosity of R-8 at 25 DEG C. by the Donner method, and a color number of 7 to 8 by the Gardner method.

Example 3 (Preparation of Dispersant C) Intermediate polyester of Example 1 100.0. P, r engineering I
Min 5P-0184 (polyethyleneimine manufactured by Nippon Shokubai Kagaku Co., Ltd.; average molecular weight 1800) 20.51 xylene 79.511 was mixed, and while stirring while maintaining the temperature at 120 tl, [Car Shella E-10J (Shell oil-based epoxy Made of lead: versatile acid glycisol ester) 5.1
．． 9 was added, and the mixture was heated and stirred at 138° C. for 3 hours in a nitrogen stream, and 1.5 g of water was separated in a Dean-Stark trap. Acid value 14.6QKOH/#, amine value 80
．． 9~KOH/l, non-volatile content 52.0%, viscosity N~0 (
Gardner method: 25℃), number of colors 7 to 8 (Gardner method)
A dispersant solution 204.3.9 was obtained.

Example 4 (Preparation of dispersant) Xylene 79.61/, [Epomin SP-012J (
Manufactured by Nippon Shokubai Kagaku Co., Ltd., J? IJ ethyleneimine; average molecular weight 1200) 20. ．． 5.1 g of cyclohexene oxide was added at 100° C. while stirring the mixture.

The internal temperature was raised to 120°C and maintained for 2 hours, then cooled to 100°C, the intermediate polyester 100ΩI of Example 1 was added, and the mixture was stirred and refluxed at 138°C for 3 hours.
1.39 of water was separated in the Stark trap. Acid value 1O
15 da KOH/#, amine value 81.7 ■ KOH/y,
Viscosity J-K (7!/- donor method; 25°C), number of colors 7-8
(Gardner method), non-volatile content 50.0% dispersant solution 2
06.8N was obtained.

Example 5 (Preparation of Dispersant E) Intermediate polyester of Example 1 100.0. f, xylene 79. sy, r Epomin 5P-200J20.5y
While stirring at 120℃,
BJ (manufactured by NOF Corporation; n-pterdalicidyl ether) 5.1. Added F. The mixture was heated to 138 ml in a nitrogen stream.
Heat to reflux for 2 hours at °C, Dean Starktra, 7″
1.311 of water was separated.

The yield of the product was 199.1F and its acid value was 14.
．． 1~KOH/,! i', amine value 82.7~KOH
/, 9. The nonvolatile content was 53.0%, the number of colors was 7 to 8 by Gardner method, and the viscosity was op (Gardner method, 25° C.).

Example 6 (Preparation of Dispersant F) Intermediate polyester of Example 1 100.0JiF, [Epomin 5P-006J (Nippon Shokubai Kagaku Co., Ltd. group polyethyleneimine; molecular weight 600) 20.5N, xylene 7
9.611 was mixed and stirred to dissolve. Mixture at 120℃
[Ebiol TBJ (manufactured by NOF Corporation)]
t-butylphenyl glycidyl ether) 5. I
11 was added and heated under reflux at 138°C for 2 hours in a nitrogen stream.
1.2I of water was separated in the Dean-Stark trap.

The reaction solution was cooled and the acid value was 13.5+11p KOH/, 9
, nonvolatile content 53%, number of colors 7 (Gardner method), viscosity Q
-R (Gardner method) dispersant solution 204.9 # was obtained.

In Examples 1 to 6, no malodor caused by ammonia was observed during the preparation of each dispersant. Also,
When each of the dispersants obtained in Examples 1 to 6 was stored in an 18-liter container in a sealed container for one week and the container was opened, no malodor due to ammonia was observed from any of the dispersants.

(Preparation example of dispersion liquid) Example 7 [Resin Red BH-IJ (product of Resin Color Co., Ltd.) Product name: C, 1, Pigment Red-48
-3) 15 parts, toluene 25 parts, and 2 parts of dispersant A to a diameter of 5
The mixture was shaken for 2 hours with a paint raker together with 100 parts of gourd glass peas to fully deflocculate and disperse. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and no aggregation or sedimentation was observed for at least one week.

Example 8 “Shimla Red 3014J (Dainippon Ink & Chemicals Co., Ltd. product) Product name: C, 1, Pigment Re
d-482), 25 parts of toluene, and 2 parts of dispersant B, together with 100 parts of glass beads having a diameter of 5 pieces, were shaken in a paint raker for 2 hours to fully peptize and disperse.

The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and no aggregation or sedimentation was observed even after standing for a long time.

Example 9 25 parts of Shimla Red 3014J, 40 parts of toluene, 20 parts of methyl ethyl ketone, 10 parts of ethyl acetate, 3 parts of "Vinyrite" VAGH (manufactured by U, C, C: vinyl chloride-vinyl acetate copolymer resin), dispersion 2 parts of agent C was shaken with 200 parts of glass beads having a diameter of 5 m for 3 hours using a paint shear force to fully peptize and disperse the dispersion.The dispersion showed good fluidity and was suitable for producing gravure printing ink. Even after standing for a long time, no agglomeration, sedimentation, or delification was observed, and the dispersion stability was good.

Example 10 “Shimla Red 3084J (Dainippon Ink & Chemicals @) Product Product Name: C, 1, Pigment Red
-48-3) 15 parts, toluene 20 parts, methyl ethyl ketone 5 parts, ethyl acetate 5 parts, [Vinylyl-VAGHJ
(Company U, C, C [: vinyl chloride-vinyl acetate copolymer resin)] 3 parts, dispersant D 2 parts, diameter 5ms + 1 lath beads
The mixture was shaken for 3 hours with a paint shake force of 0.00 parts to fully deflocculate and disperse. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and had good dispersion stability with no agglomeration, sedimentation, or caking observed even after standing for a long time.

Example 11 “Shimla Prilliant Carmine 6BJ233 (Dainippon Ink & Chemicals Co., Ltd. product) Product name: C, 1, P1
gm+snt Red 57) 20 parts, toluene 4
0 parts of methyl ethyl ketone, 20 parts of n-butyl acetate, 1 part of n-butyl acetate, 5 parts of isophorone, 3 parts of "Vinyrite" VAGH, and 82 parts of a dispersant, together with 200 parts of 5-diameter glass beads, were thoroughly deflocculated by shaking in a paint shaker for 3 hours. Dispersed. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and showed good dispersion stability with no agglomeration, sedimentation, or caking observed even after one month.

Example 12 “Shimla Red 4134AJ (Dainippon Ink & Chemicals Co., Ltd. product) Product name: C, 1, Pigment
R@d150) Part 18, “Nogu-Manent Carmine FB
B-02J (manufactured by Hoachat A, G: C,
1, Pigmsnt Rs+d 146) 2 parts, toluene 40fi, methyl ethyl ketone 20 parts, cyclohexanone 5 parts, isophorone 5 parts, cellosolve acetate 5 parts, 1 vinylite "VAGHJ part, dispersant F 2 parts diameter 5t
xm's paint shea force with 200 copies of russ beads.
The mixture was shaken for 3 hours to fully deflocculate and disperse. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and showed good dispersion stability with no aggregation, sedimentation, or gelation observed even after one month.

Example 13 “Fast Dan Green SJ (Dainippon Ink & Chemicals Co., Ltd. product) Product name: C, 1, Pigment Gr
een7) 20 parts, toluene 40 parts, methyl ethyl ketone 20 parts, ethyl acetate 10 parts, cyclohexanone 5 parts,
2 parts of "Vinyrite vAGH" and 03 parts of a dispersant were shaken together with 200 parts of 5-diameter glass beads in a paint shaker for 3 hours to fully peptize and disperse. The dispersion exhibited good fluidity and was suitable for image printing with gravure printing inks, and showed good dispersion stability with no agglomeration, sedimentation, or caking observed even after standing for a long time.

Example 14 “Shimla Red 3075J (Dainippon Ink & Chemicals @) M product Product name: C, 1, Pigmsnt Re
d-48-3], 32 parts of xylene, and 63 parts of a dispersant were shaken together with 100 parts of 51 alt diameter beads in a paint shaker for 3 hours to fully peptize and disperse.

The dispersion exhibits good fluidity and is suitable for the production of gravure printing ink, and shows good dispersion stability with no agglomeration, sedimentation, or gluing observed even after standing for a long time.

Example 15 “Carmine 6B) Nurer 750J (Daido Kasei Co., Ltd. product)”
Product name: C, 1, Pigment Red 57)
20 parts of toluene, 40 parts of toluene, 10 parts of ethyl acetate, 25 parts of methyl ethyl ketone, and 15 parts of a dispersant were shaken together with 100 parts of glass beads having a diameter of 5 mm for 3 hours in a paint shaker to fully peptize and disperse them. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and had good dispersion stability with no aggregation, sedimentation, or gluing observed for at least one week.

Example 16 “Shimla Fast Yellow 4090G” (Product of Inu Nippon Ink Chemical Industry Co., Ltd. Product name: C, I, Pi
gmentYellow 14) 20 parts, toluene 40 parts, ethyl acetate 10 parts, cyclohexanone 25 parts,
15 parts of the dispersant and 300 parts of 5-diameter glass beads were shaken in a paint shaker for 4 hours to fully peptize and disperse. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and had good dispersion stability with no agglomeration, sedimentation, or caking observed for at least one week.

Example 17 “Irgajin Yi,:co-2GLTEJ (CIB
A-Geigy product Group: C, 1, Pigme
nt Yellow 109) 20 parts, toluene 45
1, 25 parts of methyl ethyl ketone, 5 parts of ethyl acetate, and 55 parts of a dispersant were shaken together with 200 parts of glass beads having a diameter of 5 ml for 3 hours under a paint shear force to fully peptize and disperse. The dispersion exhibited good fluidity and was suitable for producing gravure printing ink, and had good dispersion stability with no aggregation, sedimentation, or gluing observed for at least one week.

Example 18 "Rapen 450J (carbon black manufactured by Columbia Carbon Co., Ltd.) 15 parts, xylene 34 parts, dispersant A1
The mixture was shaken in a paint shaker for 1 hour with 50 parts of glass beads having a diameter of 5 m to fully peptize and disperse the mixture. The dispersion exhibited good fluidity, and had good dispersion stability with no aggregation, sedimentation, or dulling observed for at least one week.

Example 19 “Fast Dan Blue FGF J (Inu Nippon Ink Chemical Industry Co., Ltd. product) Product name: C, 1, Pigment
15 parts of Blue15-3), 34 parts of xylene, and 1 part of dispersant A were added together with 50 parts of russian beads with a diameter of 5 m+n.
The solution was thoroughly dispersed by shaking with a shaker for 1 hour.

The dispersion exhibited good fluidity, and had good dispersion stability with no aggregation, sedimentation, or caking observed for at least one week.

Example 20 “Fast Can Blue Tori” (Inu Nippon Ink Chemical Industry Co., Ltd. product) Product name: C, 1, PIgment Bl
ue 15-3) Part 10, “Super Beckamin L
-1054 (Dainippon Ink & Chemicals Co., Ltd. product name) 3.5 parts, xylene 35.5 parts, dispersant A 1 part
The mixture was shaken for 1 hour in a paint shaker with 50 parts of fi glass peas to sufficiently peptize and disperse. Dispersion A
shall be.

On the other hand, “Dianaru 5650J (Mitsubishi Rayon (
Co., Ltd. Product Product name) 24 copies, ``Super Beckamine
L-1054 (Inu Nippon Ink Chemical Industry @) product product name) 6 copies, "Tie Bake CR-5N-2J (Gyosoku Sangyo (
Co., Ltd. Product Product Name) 20 parts to 50 glass beads with a diameter of 5 mm
The mixture was shaken with a paint shaker for 1 hour to fully deflocculate and disperse. This is called dispersion B.

Then, dispersion A and dispersion B were mixed at a ratio of ff 1:10, and stirred for 2 minutes at 200 ORPM using a homomixer to fully peptize and disperse. This will be referred to as dispersion C.

<Paint test> [Base grain peeling test] Dispersion C was applied onto a galvanized iron plate using a Ya40 bar coater and baked at 200°C for 90 seconds.

This coating film was cut with a cutter in a lattice pattern, with 11 lines lengthwise and widthwise, at intervals of 1 inch, cellophane tape was pasted on top of the cutters, and even when this was removed, no loss of the coating film was observed. Moreover, the gloss of the coating film was also good.

[Color separation test]

Similarly, Dispersion C was applied onto art paper using a Percoater of 40 mm, a portion of the paper was rubbed lightly with a finger, and a few drops of Dispersion C were dripped onto another portion. There was almost no difference in the color or gloss of each part, and there was no uneven color or pigment clumping.

Comparative Example 1 In place of the dispersant A blended into the dispersion A in the paint test of Example 20, [Solus Yasu 13240] (ICI
When using a surface product made by a company (name of surface product made by a company), most of the paint film was missing in the peel test with cellophane tape, and the color difference between the surface of the paint film spread on art paper and the area lightly rubbed with a finger. The gloss is different.

Comparative Example 2 In addition, in the paint test of Example 20, a coating containing only 12-hydroxystearic acid as a hydrophobic group instead of dispersant A (Patent Application No. 6) was used.
1-154190. % open area 63-12335), the coating film was 3 to 4 in the peel test with cellophane tape.
When using a material containing an epoxy compound in its hydrophilic group (Patent Application A 62-30768), the surface of the paint film spread on art paper and the area lightly rubbed with a finger are Different colors and luster.

〔Effect of the invention〕

Non-aqueous paints, printing inks, and their colored bases using the dispersant of the present invention as a pigment dispersant exhibit excellent fluidity and dispersion stability. Further, the dispersant of the present invention does not inhibit the adhesion between a coating film and a metal even when used in a paint for metal or a printing ink.

Furthermore, since the dispersant of the present invention does not generate any bad odor due to ammonia, the environment at the manufacturing site where the dispersant is used can be greatly improved.

Claims (1)

[Claims] 1. (1) (a) General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is H, alkyl group, phenyl group, alkoxymethyl group, alkenoxy methyl group, phenoxymethyl group, alkyl-substituted phenoxymethyl group, acyloxymethyl group) and/or (b) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n represents an integer from 3 to 10) and the reaction product of the compound represented by polyethyleneimine and (2) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2 is a carbon atom 7 to 38 alkyl groups, alkylene groups, alkyl diene groups, cycloalkyl groups, cycloalkylene groups, fused polycyclic saturated hydrocarbon groups, phenyl groups, fused polycyclic aromatic hydrocarbon groups, hydroxyl group-substituted polycyclic groups (represents an aromatic hydrocarbon group, x represents any numerical value between 1 and 20, and y represents any numerical value between 0.1 and 10.) A dispersant characterized in that it consists of a product. 2. A dispersion containing a finely powdered solid, an organic liquid as a dispersion medium, and a dispersant, in which the dispersion according to claim 1 is used as the dispersant. 3. The number average molecular weight of polyethyleneimine is 300 to 50
The dispersant according to claim 1 or the dispersion according to claim 2 in the range of . 4. Claim 1, wherein the amount of the compound represented by general formula (I) and/or the compound represented by general formula (II) is in the range of 0.01 to 100 parts by weight based on 100 parts by weight of polyethyleneimine. The dispersant according to claim 2 or the dispersion according to claim 2. 5. The compound represented by the general formula (III) is (1) (a) General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_2 is an alkyl group having 7 to 38 carbon atoms, alkylene group, alkylene diene group, cycloalkyl group,
Represents a cycloalkylene group, a polycyclic saturated hydrocarbon group, a phenyl group, a polycyclic aromatic hydrocarbon group, and a hydroxyl group-substituted polycyclic aromatic hydrocarbon group. ) The dispersant according to claim 1 or the dispersant according to claim 2, which is a compound obtained by dehydrating and condensing a reaction product of the compound represented by (b) ε-caprolactone and (2) 12-hydroxystearic acid. dispersion of. 6. The acid value of the compound represented by general formula (III) is 20~
The dispersant according to claim 1 or claim 2 in the range of 120
Dispersion as described. 7. The ratio of dispersant used is 0.1 to the fine powder solid.
3. A dispersion according to claim 2, in the range .about.100% by weight. 8. A paint comprising the dispersion according to claim 2. 9. A printing ink comprising the dispersion according to claim 2. 10. A colored base for paints having a high pigment concentration and comprising the dispersion according to claim 2. 11. A colored base for printing inks having a high pigment concentration and comprising the dispersion according to claim 2.