JPS63197529A - Dispersant and dispersion solution containing same - Google Patents

Abstract

PURPOSE:To enhance effect of dispersion to inorganic pigments by using, as a dispersant, a reaction product of polyester with acyl as an end hydroxyl group and containing esterified carboxyl and polyethylene-imine. CONSTITUTION:A dispersant is prepared by a reaction product comprising polyester with acyl as an end hydroxyl group shown by formula I (n shows 1-20, and m shows 0.1-10) and containing esterified carboxyl, and polyethylene- imine. As the reaction product of polyester with acyl end shown in formula I and polyethylene-imine, salt or amide or else a mixture of both, the preferred. The acid value of acyl end is preferably 10-120, while the average molecular weight of polyethylene-imine is preferably 300-10,000. The dispersant thus prepared is effective for giving damages to adhesiveness of a coating film with metal when used for coating metals with ink or coating material.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides an excellent method for dispersing a fine powder solid such as an inorganic or organic pigment in a non-polar organic liquid. The present invention relates to a dispersant that can provide good fluidity and dispersion stability, and its scope of application extends to the general field of various coating compositions such as printing inks and paints. In other words, the present invention provides a dispersant capable of providing a pigment dispersion liquid for coating that is highly concentrated, highly fluid, stable over time, and exhibits satisfactory performance with a small amount of use, and its dispersant. By containing various dispersants, it is intended 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 clear color tone in color material compositions for various coatings such as printing inks and paints are composed of fine solid particles. There is.

However, when fine particles such as the various known pigments are dispersed in non-polar organic solvents containing vehicle polymers such as in offset inks, gravure inks, flexo inks and paints, especially at high pigment concentrations, It is difficult to obtain a colorant composition with excellent fluidity and storage stability, and it often causes various problems that have an important effect on the manufacturing process and the quality of the obtained product.

That is, a concentrated dispersion containing a pigment consisting of fine particles is
The product is often non-flowing or has a high viscosity, making it difficult to handle when stirring, mixing, removing the product from the disperser, or transporting it, and sometimes thickens significantly during storage, making it difficult to use. , flooding, floating, m
Unfavorable phenomena such as a decrease in 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 hue in such a system is Not only does it have poor fluidity, but it also has inferior coloring power during spreading compared to colorants that maintain a good dispersion state, and coarse aggregates cause unevenness on the painted surface, causing it to lose its smoothness.
There is also a tendency for the gloss to decrease significantly, thus reducing the
Loss of product value.

In other words, for dispersions that require a high pigment concentration such as printing inks, if you try to improve the viscosity or fluidity of the dispersion, the gloss of the M film will be lost, and if you try to improve the gloss, It is difficult to produce coating coloring materials that satisfy both fluidity and gloss, as fluidity and storage stability are impaired.

Various methods have been proposed to prevent pigment agglomeration in non-aqueous paints or printing inks, and these methods have been shown to be effective to some extent.

For example, British Patent No. 949.739 states that (CuPe represents a copper phthalocyania group, R1 represents hydrogen or an aliphatic group, R2 represents an aliphatic group, or
1 and R2 together with the nitrogen atom to which they are bonded represent a heterocyclic group, and n represents 1-4. ) The use of anti-aggregating phthalocyanine derivatives represented by The resulting dispersant for phthalocyanine pigments is also described in British Patent No. 1.508,576.
Copper tetracyani/sulfonate and e.g. didodecyl,
There is a description that a quaternary ammonium salt of phthalocyanine sulfonic acid obtained by metathesis of a cationic activator such as dimethylammonium chloride is effective as a synergist for pigment dispersion, and US Pat. No. 4,313,766 In the specification, the following formula (wherein CuPa represents a copper phthalocyanine group, R1,
R.

represents an alkyl group or a heterocyclic group in which R1 and R7 together with the nitrogen atom to which they are bonded, and m and a represent 1 to 4. There is a description that the phthalocyanine derivative represented by ) has a phthalocyanine pigment dispersing effect. In addition, various amine salts of 7-talocyanine sulfonic acid are suitable for similar purposes in the specifications of Japanese Patent Publications No. 39-28884, No. 57-12067, and Japanese Patent Publication No. 52-33922. is stated.

However, these phthalocyanine derivative dispersion aids are
Needless to say, the applications are limited when the pigments treated therewith have similar color tones.

Next, as a dispersion aid for azo pigments, for example, in British Patent No. 1,139,294, a long chain alkyl group is used instead of the phenyl group of disazo yellow, as represented by the following formula %. It is stated that a compound having a disazo group is effective for dispersing a disazo yellow pigment, and US Pat. It has been reported that derivatives are effective as dispersion aids for disazo yellow pigments, but the use of these dispersion aids is limited to compounds with which the pigments treated with them have a similar color tone or similar structure. is the same as in the case of phthalocyanine pigment synergist.

Examples of practically colorless dispersants include JP-A-55-11
2273, British Patent No. 1,313,745 and West German Patent No. 2,041,033, and British Patent No. 1.445.
, No. 104 and Japanese Patent Publication No. 58-24463. Further, in British Patent No. 1,473,380, 12-
It is stated that an amide compound obtained by dehydrating droxystearic acid and 3-dimethylaminoglobilamine is effective as a pigment dispersant,
No. 9, British Patent No. 1,342.746, U.S. Patent No. 3
, 778, 282, etc., a dispersant related to a polyester containing a terminal carxyl group obtained by dehydrating a hydroxycarboxylic acid such as 12-hydroxystearic acid or a salt thereof is reported. Hey, are you coughing again? A dispersant useful for preparing a pigment dispersion for ink production, which is composed of a salt or amide obtained by reacting a polyester with a poly(lower alkylene)imine, is disclosed in Japanese Patent Application Laid-open No. Sho F14-3.
No. 7082, British Patent Application Publication No. 2.001,083, US Patent No. 4.224,212, West German Patent Application Publication Box 2. g3 o, s 60, or U.S. Pat. No. 3,88
This is stated in the specifications such as No. 2,088.

Furthermore, the polyester terminal cal? The xyl group is esterified with a dialkylamino alcohol or amidated by reacting with a (dialkylamino)alkylamine, and then the terminal tertiary amine group-1'24-ammonium group is converted using a quaternizing agent such as dimethyl sulfate. Regarding the dispersant, Japanese Patent Publication No. 57-25251, British Patent No. 1.373
, No. 660.

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.

In addition, dispersants derived from dehydrated condensed preesters of long chain aliphatic hydroxyl/I/&7 acids, such as 12-hydroxystearic acid, have considerable versatility with a variety of pigments. However, when a dispersion containing it is used in, for example, metal ink or baking paint, it has the disadvantage of impairing the adhesion between the paint film and the metal, so it is not recommended as a dispersion for base paint in metal coating materials. It was inappropriate and its use (there were restrictions).

[Problem that the invention seeks to solve]

In view of the above-mentioned problems of the prior art, the present inventors have conducted intensive research and found that when dispersing fine powdery solids, especially organic and inorganic pigments, in a non-polar organic liquid, prevent pigment agglomeration in the dispersion at a certain concentration;
It is possible to find a dispersant that is effective in forming a stable dispersion and does not reduce the adhesion between the coating film and the metal when it is mixed into a thermosetting paint or ink and used for coating metals such as iron. After thinking about it, I finally completed the present invention.

[Elaborate means to solve problems]

The first invention of the present invention is based on the general formula % (wherein R is a C7-C3° alkyl, alkylene,
A monocarbo/acid represented by cycloalkyl, fused cycloalkyl, phenyl, alkyl-substituted phenyl, hydroxy-substituted phenyl, fused polycyclic (unyl, hydroxy-substituted fused polycyclic aromatic group)) and 8-cablocktone. The compositional formula obtained by subjecting the reaction product to dehydrated polycondensation of 12-hydroxystearic acid/acid has the following average composition: A carfoxylic group-containing polyester (I) whose terminal hydroxyl group is esterified with an acyl group, represented by ? It is a dispersant obtained by reacting with lyethylenimine (It).

In the reaction between the monocarbo/acid and C-cablocktone, the reaction is carried out in the presence of a luyl acid catalyst such as n-butyl orthotitanate or diptyltin oxide to form a compound having an acyl group at one end and an acyl group at the other end. Synthesize a polyester having carmexyl groups. This is expressed as a reaction formula: (1
), and in this reaction, Nanatsuka A/citric acid and 6
- The molar ratio of caprolactone is between 1:1 and 20. Preferably, the ratio is 8 to 15 to 1, and the reaction temperature for lacto/ring-opening polymerization is 130 to 200°C, preferably 150 to 180°C, in an inert gas such as nitrogen gas.

Examples of monocarbo/acids are octylic acid, persatic acid, lauric acid, myristic acid, noglumitic acid, stearic acid, oleic acid, linoleic acid, lyluic acid, benzoic acid, 4-t@rtbutylbenzoic acid, salicylic acid. ,
2-hydrobasic 3-naphthoic acid, cyclohexene k
Contains phosphoric acid, neodic acid, abietic acid, etc., but of course one of these or a mixture of two or more of them may be used. There is no problem even if it is phosphoric acid. (The polyester containing one end acylated carboxyl group, which is a reaction product, is hereinafter referred to as polyester (1
). ) Next, in the second step, a monocarboxylic acid nocaderolactone adduct and 12-hydroxystearic acid are dehydrated and condensed to synthesize a mixed polyester containing terminal carmexyl groups. This can be expressed as a reaction formula (2).

C6H13 The molar ratio of polyester & (1), 12- and droxystearic acid in this reaction is 1:0.1 to 1:10, preferably l:l to 1:6, and (1) There is no need to take out the reaction product from the reactor, and the reaction (2) can be carried out in the same container.

This dehydration condensation reaction may be carried out in the presence of known esterification catalysts such as phosphoric acid, p-)luenesulfonic acid, tetra-n-butyl titanate, tetralso frovir titanium $-4, or Australian Patent No. 493. , 015 specification and JP-A-60-137967.

As described in the specification of No. 60-137924, it is carried out in the presence of methanesulfonic acid, etc., by distilling and removing the produced water from the system while heating to 120 to 200 °C, preferably 140 to 190 °C. Preferably, an inert gas such as nitrogen is passed through the reaction system, or the dehydration and esterification reaction is performed with aromatic hydrocarbons that form an azeotrope with water.
For example, it is advantageous to carry out the reaction in the presence of toluene or xylene, and remove the produced water azeotropically from the reaction system.

The degree of progress of the esterification reaction due to intermolecular dehydration can be determined by measuring the amount of distilled water and the acid value of the reactant.

The terminal lumexyl group-containing polyester obtained in this way is acylated at one end (hereinafter referred to as terminal acylated yj?).
The acid value of IJ ester (referred to as Ri) is suitably 10 to 120, and 20 to 60 is practically preferred.

Since 12- and droxystearic acid, which is usually easily available industrially, is produced by hydrolysis of hydrogenated castor oil, it contains small amounts of stearic acid and palmitic acid as impurities. This poses no particular problem when used in the production of dispersants.

Next, in the third step, the terminally acylated polyester is reacted with polyethyleneimine (II) to obtain the dispersant that is the object of the present invention.

The polyethyleneimide used in the present invention has a molecular weight of 300 to 50,000. Preferably 600-10,
000, polyethyleneimine and terminal acylation? Riester (1)? The stoichiometric ratio in the reaction is 1 atom of amine nitrogen to 1 equivalent of carxyl group or less, and an amine salt or amide is produced depending on the reaction conditions. Terminal acylated polyester (1
)and? When mixed with lyamine (10t), a calga/acid amine salt is produced, and when this is dehydrated by keeping it at a high temperature in the presence or absence of a catalyst, cardanamide is produced. This can be determined using, 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. Examples of the organic liquid used together include aromatic hydrocarbons such as toluene and xylene, and mineral spirits. , petroleum hydrocarbons such as mineral turpentine, halodanized hydrocarbons such as chloroform, perchlorethylene, trichloroethylene, chlorobenzene, linear or cyclic hydrocarbons such as acetone, methyl ethyl keto/, methyl isobutyl ketone, cyclohexanone, isophorone. Ketones, ethyl acetate.

Examples include esters such as butyl acetate, amyl acetate, and cellosolve acetate, but of course mixed solvents of two or more of these may also be used, and known alkyd resins, epoxy ester resins, nixy resins, Melamine resin, acrylic resin, polyamide resin, I-urethane resin, I-reester mMY1. Hini/Lll! J fat,
There is no problem even if it is a mixed system with phenol resin, nitrocellulose resin, etc.

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 μm or less, such as titanium dioxide, red and yellow iron oxides,
Colorants, fillers such as barium sulfate, aluminum oxide, calcium carbonate, talc, Fre+, silica, magnetic iron oxide, lead chromate, zinc chromate, strontium chromate, carmen black, aluminum, brass, iron, etc.
Examples include various inorganic pigments including conductive materials, magnetic materials, etc., azo pigments, lakes, toners, phthalocyanine pigments, isoindolinone pigments, quinacridone pigments, indanthrene pigments, dioxazine pigments, and organic pigments such as furapanthrone pigments. It will be done. Note that the term "Ruki" as used herein means a water-insoluble salt or complex of an organic dye precipitated on a water-insoluble inorganic carrier such as alumina, and 1 toner 1 refers to a water-insoluble salt or complex of an organic dye precipitated on a water-insoluble inorganic carrier such as alumina. means a calcium salt or complex that is insoluble or extremely sparingly soluble in

The relative proportion of the dispersant according to the invention in the pigment dispersion is advantageously used within the range of 0.1 to 100%, preferably 0.1 to 10%, based on the test dispersion. The content of the fine powder to be dispersed in the dispersion is 5 to 80%, preferably 10 to 70%.

〔Effect of the invention〕

The dispersant according to the present invention prepared as described above is described in Japanese Patent Application Laid-Open No. 54-37082 or US Patent No. 4,41
Compared to the case where the polyester chain is substantially only a dehydrated condensate of 12-hydroxystearic acid as described in No. 5,705, a coating coloring material containing a dispersant, For example, when used for painting or printing with ink, paint, gold, or metal, it has the excellent feature of not damaging the adhesion between the paint film and the metal, and is therefore advantageous in that its range of applications is wide. It is.

〔Example〕

The present invention will be explained in more detail below with reference to Examples, but it goes without saying that the gist and scope of the present invention are not limited by these Examples. Note that the part in the examples means a double note part.

<Preparation example of dispersant> Example 19 Dispersion rod JA 4-t@rt-Butylbenzoic acid 32.4.9 and diptyltin oxide 0.31 were mixed and heated and stirred in a nitrogen stream to 160~ e-caprolactone 228 at 170°C
．． 3. Fi was added dropwise over 2 hours. 170 minutes after completion of dripping
Stirred for an additional 2 hours at ~175°C.

This was cooled to Q100°C, and industrial 12-hydroxystearic acid (manufactured by Yoken Fine Chemicals, product name: Hydroxystearin 2 and below) was 90.2/! , Tetrainprovir Titanium) 0.21 and Tokx73ON were added and refluxed for 8 hours at 170-175°C in a nitrogen stream to separate 3.31i of water into a Dean-Stark drug.

When this is cooled to room temperature, the whole becomes a pale yellowish-brown wax-like substance containing toluene.
I got it. The acid value of this product was 35.9 Da KOH/1i, and the nonvolatile content was 91.0 Da.

Toluene-containing waxy polyester 1001 obtained as above and xylene-ingetaol 3:1
Mixed liquid 90I! , and “Ebomin ■” 5p-200 (
Product name Nippon Shokubai Kagaku Kogyo@ polyethyleneimine, average molecular weight 1lNo. 000 (hereinafter the same) mixed with ioy,
li! Dissolve and stir at 100°C for 1 hour. A pale yellow, transparent, slightly viscous dispersant solution was obtained in quantitative yield. The acid value of this solution is 19.519KOH/#, and the amine value is 5.
2.0■KOH/! , the content of non-volatile matter is 50.0%.

Example 22 Dispersant B Octylic acid (2-5thyl -h*xmnoic w
eld ) 28.89 and digyltin oxide 0.3
．． 160-17 while mixing Pt and stirring in a nitrogen:A stream.
At 0'C, g-caprolactone 228.3.9 was added dropwise over a period of 2 hours. After the dropwise addition was completed, stirring was continued for an additional 2 hours at 170-175°C.

This was cooled to 1ioo°C and melted in a mixed layer of industrial 12-hydroxystearic acid 90.2# and toluene 34.71° orthotitanate/L10.21'FrFr.
After refluxing for 15 hours at 170-175°C in a stream of zeta gas, 4.5 g of water was distilled into the Dean-Stark drug. When the reaction mixture is cooled to room temperature, the whole solidifies into a pale yellowish-brown wax. In this way, polyester containing toluene/l/370.0! ! The acid value of the J obtained was 36.5 KOH/7, and the nonvolatile content was 90.3.

The waxy polyester thus obtained 105.
01. -:r-yl'! i:y■'5P-2005,0
,9,*Mix silene 90Iiii, heat and melt, 100℃
Stir for 1 hour. Cool this to room temperature to obtain a pale yellowish-brown, transparent, slightly viscous dispersant solution in quantitative yield. The acid value of this product is 19.6 da KOH/#, and the amine value is 2.
4.7 da KOH/#, non-volatile content is 49.5% and 7
'2-O Example 31 Dispersant C Benzoic acid 22.4.9. Diptyltin oxide 0.3I
was heated to 165 to 168°C in a nitrogen stream and heated while stirring.
- Add 228.3 N of caprolactone dropwise at the same temperature over 1 hour. After completing the dropwise addition, stir at 168-170°C for 2 hours. To this reaction mixture were added 90.2.9 J' of industrial grade 12-hydroxystearic acid and 34 J' of toluene at 100°C, and the mixture was refluxed for 15 hours.
．． Just in case you let the 3I water drain out. 370.0I terminal carxyl polyester that solidifies into a waxy state when cooled to room temperature
Obtain I. The non-volatile content of this product is 91% and the acid value is 37.
It was 3ηKOH/l.

The above reaction product 98N and Epomine 5P-Zo.

10.9 and 92JF, a mixed solvent of xylene/imptarl 3/1, were mixed, stirred at 100° C. for 1 hour, and cooled to obtain a slightly viscous solution 200I, which was pale yellowish-brown and transparent. The acid value of this product is 22.3 WKOH/I, and the amine value is 53.
9ηKOH/11. Non-volatile content is 51.0 tatami and A.

Example 41 Dispersant D Persatic acid 34.4F, diptyltin oxide 0
．． 3f were mixed, and 228.31 ml of 1-caprolactone was added dropwise to the mixture over 1 hour while stirring at 168 to 170°C in a nitrogen stream. After the addition was completed, the mixture was stirred at 170°C for 2 hours, then cooled to 100°C, and 90.2.9% of industrial 12- and do4oxystearic acid and 0.2% of orthotitanic acid were added.
9. ) 34.81 ml of Rue was added, and the mixture was heated under reflux for 11 hours, and 4.5 II of water was collected in a Dean-Stark log.

When the product is cooled to room temperature, it solidifies into a pale yellowish-brown wax. Co-located with 377, OIl, acid value 38.4 da KO
H/, 9, and non-volatile content was 86.1 yen. This waxy polyester 105.011, "Technical/electronic p" 8P-
006 (Product name: Same as above, but average molecular weight 6.00)
10.0II,) Luene 85.0. Mix P, 100
The mixture was heated and stirred at ℃ for 1 hour and then cooled. Pale yellow-brown transparent,
Obtain a quantitative yield of dispersant solution. The acid value of this thing is 2
0.511PKOH/#, amine value is 55.9~KO
H/jl, the non-volatile content is 50.3 t, which is next.

Example 51 Dispersant E: 13.81 salicylic acid and 0.21 dipyltin oxide were mixed and heated to 165-170°C with stirring in a nitrogen stream.
Then e-caprolactyl 14.111 was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was stirred at 165-170°C for 2 hours, then cooled to 100°C, and 45% of hydroxystearic acid was added.
．． 1#, toluene 18.9g, methanesulfonic acid 0.
9. Add 21I and reflux at 160-165°C for 16 hours in a nitrogen stream. 2.31 of water was distilled into the Dean-Stark trap.

When the contents are cooled to room temperature, they solidify into a pale yellow-brown wax, and the secondary acid is 185.7N, acid value 33, 119K.
OH/11, non-volatile content is 88.4ch, 9.

This 10411, Epomin 5P-20010,9, and a mixture of xylene-isobutanol (3:1) (86IIt) were mixed and stirred at 100°C for 1 hour.

This was cooled to room temperature and quantitatively juxtaposed to obtain a dispersant solution.

This dispersant had an acid value of 21.2 Da KOH/Ii, an amine value of 49.2 apKOH/#, and a nonvolatile content of 51.4 Da.

Example 61 Dispersant F 0.11i n-butyl orthotitanate was added to 22.8N myristic acid, heated to 165-170°C in a nitrogen stream, and then gradually dropped into ε-caprolactone 171.2IIt over 1 hour. Next. After completion of the dropwise addition, the mixture was kept at 170° C. for 2 hours, and upon cooling, a pale yellow polyester solidified into a waxy state was obtained by quantitative co-positioning. The acid value of this product is 28.
6th next with 9 da KOH/II. This waxy product 10
3.3N 12-hydroxystearic acid 21.3I1
．． ) Mix 13.8N of toluene and 0.8I of n-butyl orthotitanate, and heat for 12 seconds at ~169°C in a nitrogen stream.
Refluxed for an hour. 0.8 Il of water distilled into the Dee/Stark trap.

The reaction solution was cooled to room temperature and the acid value was 25.2 da KOH/li.
A waxy product with a non-volatile content of 88% was obtained.

Cono product 1031 K-:t-d'! iy-5P-
200 log and 87 g'ir:m of a mixed solution of xylene-isobutanol (3:1) were combined and heated and stirred at 100° C. for 1 hour.

A dispersant solution was obtained by quantitative dispersion, and the acid value of this was 1.
8.1 Misaki KO! (/g, amine value is 50.OIll
KOH/#de9.

Example 71 Dispersant G 2-human oxygen 3-su7toic acid 18.8
114.1j' of caprolactone while stirring at ℃
I dripped it over an hour.

After the dropwise addition was completed, the same temperature was maintained for 2 hours to complete the reaction.

Next, this was cooled to 100°C, and 12-hydroquine stearic acid 45.11. To: X-719, 8φ, add methanesulfonic acid 0.21 to 170 to 17
The mixture was heated under reflux at 2° C. for 16 hours to distill 2.3 g of water into the Dee/Stark drug.

When the reaction product is cooled to room temperature, it solidifies into a white wax-like consistency. The acid value of this product was 42.6, the PKOH/IIs nonvolatile content was 90.0, and the yield was 191.6j'.

A mixture of 10 OI of this waxy reaction product and 90.5' of xylene-imbutanol (3:i) was added.

"Epomi/-5P-200101 was mixed and stirred at 100°C for 1 hour. After cooling to room temperature, a minato yellowish brown product with a slight cloudiness was obtained by quantitative deposition. The acid value of this product was was 21.91 IPKoa/y, the amine value was 51°59 KOH/y, and the nonvolatile content was 50.0 chi.

Example 8 Rutile to V Titanium White 5R-XA (Product name: Sakai Chemical) 7
0 parts 1 part Dispersant A 5 parts, "Super Parnock ■" DT
-1360-70 (trade name: Dainippon Ink & Chemicals ■ triazine-based ?Liau/l/: the same applies hereinafter) 5 parts, xylene 20 parts 3-diameter glass beads 200 parts 't- added,
The flocculation was dispersed by shaking for 3 hours using a paint conditioner manufactured by Red Devil Co., Ltd. The dispersion exhibited good flowability and no phenomena such as precipitation of the pigment were observed for at least one week. On the other hand, in the case of the system in which the dispersant f:f/# was not added, the mixture was a sticky coagulum and non-fluid.

Example 9 70 parts of Tyeek R-830 (trade name: rutile type detan white manufactured by Ishijin Dogyi ■), 5 parts of dispersant B, 5 parts of "Su・Quant-Parnock ■" DT-1160-705 parts Tsurupetz-150
10 parts, 10 parts of isophorone, 20 glass beads with a diameter of 3n
0 parts was added and shaken for 3 hours using a Red Devil paint shaker to deflocculate and disperse. The dispersion exhibited good fluidity and excellent storage stability.

Example 10 70 parts of TiOxide "R-CR-3 (trade name r, rutile titanium white coated type manufactured by BTP), 05 parts of dispersant,
'Super Parnock' DT-1140-705 parts, xylene 10 parts, and acetic acid-i-butyl 10 parts were mixed to make a diameter 311.
1 f-) Manufactured by Red Devil Co. with 200 copies of Subies.
The dispersion was deflocculated and dispersed by shaking for 3 hours with a 100% water solution and a 100% alcohol solution.The fluidity and storage stability of the dispersion were good.

Example 11 Shinkasha Red Y (product name: Clbm-G@lf)
Manufactured by ', C, [, F'tgrn@nt V-
19) Mix 20 parts, 1 Su-No-No-Knock-DT-1360-7010 parts, 010 parts of dispersant, and 60 parts of xylene together with 300 parts of steel/L/balls with a diameter of 3H, manufactured by Red Devil Co. It was dissolved or dispersed by shaking with Pei/Toko/Digi and Na for 3 hours.

The dispersion exhibited good fluidity and no phenomena such as sedimentation, thickening, or sludge formation were observed for at least one week.

Example 12 Sim 2-Fast Yellow 4192 (Product name Nippon Ink Chemical Industry @j!l!: C,!,!Jgm@nt
Tellow 154) 30 parts, 1 Super Parnock" DT-1360-7010 parts, dispersion l!li'1
1E10 parts, Nlupesso 10025 parts, Isophorone 2
Steel of diameter 311 by mixing 5 parts? The mixture was peptized and dispersed by shaking for 3 hours with 300 parts of 300 parts of the liquid in a Red'Devil Co., Ltd. Intoconditioner. The dispersion exhibited good fluidity and no phenomena such as thickening or sluggishing were observed even after standing for a long time.

Example 13 Fast l'7f FGF (Product name: manufactured by Nippon Ink & Chemicals, Inc.: C, 1, Pigment Dlve
15-3) ■- 20 copies, “Sol Snows 5000 (Product name:
t, c, r company, 7 talocyanine blue synergy)) 5 J"su-i-/4-/yri' DT-1
140-701 (1, Dispersant F2O parts, xylene 35 parts, cellosolve acetate 20 parts, φ3 foot snow steel pol 300 parts were added, Red Devil Co. 1!" Indian Condiji, shaken for 3 hours with a ner to peptize and disperse. The dispersion exhibited good fluidity and no phenomena such as pigment sedimentation, thickening, or dulling were observed for at least one week.

Example 14 ゛Fas) f 7' Green S (Product name Futari Nippon Ink Chemical Industry @l!j: CAL P1gm@nt G
r@en 7) 20 copies, 1 super paperback = D
10 parts of T-1360-70, 010 parts of a dispersant, and 60 parts of medium silane were mixed, 300 parts of φ3n steel mail was added, and the mixture was shaken for 3 hours using a paint container manufactured by Red Pill Co., Ltd. to peptize and disperse the mixture. . The dispersion exhibits good fluidity and, at least in the interstitial space, no phenomena such as sedimentation and thickening were observed.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. A product obtained by dehydrating and polycondensing 12-hydroxystearic acid with a reaction product of a monocarboxylic acid represented by phenyl, fused polycyclic phenyl, or a hydroxy-substituted fused polycyclic aromatic group, and ε-caprolactone. Its compositional formula, in terms of average composition, is represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, n represents 1 to 20, m represents 0.1 to 10) , a dispersant obtained by reacting a carboxyl group-containing polyester (I) whose terminal hydroxyl group is esterified with an acyl group and polyethyleneimine (II). 2. The dispersant according to claim 1, wherein the reaction product of the terminally acylated polyester (I) and polyethyleneimine (II) is a salt, an amide, or a mixture of both. 3. The acid value of the terminally acylated polyester (I) is 10~
120. The dispersant according to claim 1 or 2, which has a molecular weight of 120. 4. The average molecular weight of polyethyleneimine (II) is 300~
10,000. The dispersant according to claim 1, 2 or 3. 5. The dispersant according to claim 1, 2, 3 or 4, wherein the weight ratio of the terminally acylated polyester (I) to the polyethyleneimine (n) is from 1:0.001 to 1:1. 6. General formulas ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R is C_7 to C_3_0 alkyl, alkylene, cycloalkyl, fused cycloalkyl, phenyl, alkyl-substituted phenyl, hydroxy-substituted phenyl, fused polycyclic phenyl , representing a hydroxy-substituted condensed polycyclic aromatic group) and 1-caprolactone, and 12-hydroxystearic acid is dehydrated and polycondensed with the reaction product, and its composition formula is as follows: , in the average composition, ▲ There are mathematical formulas, chemical formulas, tables, etc. A pigment dispersion comprising a dispersant obtained by reacting a carboxyl group-containing polyester (I) esterified with polyethyleneimine (II).