JPH02245231A - Polymer dispersant and dispersion containing the same dispersant - Google Patents

Abstract

PURPOSE:To prevent the flocculation of pigment even in a dispersion having a high content of pigment and to form a dispersion without causing a solvent shock by using a specified modified polyester type compd. as a dispersant. CONSTITUTION:One mol of tetrakis(2-hydroxyalkyl)ethyelenediamine shown by the general formula I (R is H, alkyl, etc.) is esterified by 0.2-20mols of a hydroxyl group-contg. higher monocarboxylic acid and 0-2mols of a higher monocarboxylic acid free of a hydroxyl group. To the product, 0.1-1 equivalent of a glycidyl ester of a higher monocarboxylic acid based on one equivalent of a hydroxyl group in the product is ring-opened and added. An acidic group or a basic group or both are then introduced into the material. The polymer dispersant thus obtained is used for stably dispersing pigment or powdery solid in a nonpolar liq. in high concn. for a long period, and the dispersant has low viscosity and high fluidity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a dispersion system in which fine powdery solids such as inorganic or organic liquids are dispersed in an organic liquid, preferably a non-polar organic liquid. Dispersants that can provide excellent fluidity and dispersion stability to paints, particularly those that have good compatibility with paint vehicle polymers such as polyester and alkyd resins, and dispersions made using these dispersants. The scope of application is related to coating compositions such as printing inks and paints in general.

In other words, a dispersant that can provide a stable coating dispersion that exhibits excellent fluidity at a high pigment concentration and also prevents solvent shock during letdown.
and a dispersion using this dispersant.

[Conventional technology]

Organic or inorganic pigments, which are constituent components of color material compositions for various coatings such as printing inks and paints, generally consist of fine powders. When pigment particles are dispersed in a non-polar organic liquid containing a vehicle polymer, such as in printing inks and paints, the colorant composition has excellent fluidity and storage stability, especially at high pigment concentrations. are difficult to obtain and often cause various problems that seriously affect the manufacturing process and the quality of the resulting products.

In other words, highly concentrated dispersions of pigments made up of fine particles generally have poor fluidity, and when mixed, stirred, or kneaded during the dispersion process, or when taken out from a dispersion machine or transferred from a container, etc. However, there are various undesirable problems such as considerable adhesion loss, color separation when different pigments are mixed, floating, reduced gloss, color differences due to different painting methods, and changes in viscosity and gloss over time. This phenomenon is known to 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 due to fine particles. It depends on the surface properties of the pigment particles.

In other words, in systems where the fluidity of the dispersion is poor or where phenomena related to abnormal dispersion such as color separation or floating occur, the degree of pigment aggregation may be large, and colorants using such dispersions may be unstable. Compared to colorants that maintain a dispersed state, color density, tinting power, hiding power, and sharpness during color development are inferior, and the painted surface loses smoothness and gloss due to unevenness caused by coarse aggregates. tend to damage the commercial value of the object to be coated.

In addition, in dispersions with high pigment concentrations such as printing inks and paints, if you try to improve the concentration or fluidity of the dispersion, the gloss of the coating will be lost, and if you try to improve the gloss, the fluidity will be impaired. It has not been easy to produce coating coloring materials that fully satisfy various suitability requirements. Various methods have been proposed in the past for the purpose of preventing aggregation of pigments in non-aqueous printing inks or paints, and these methods have been recognized to be effective to some extent.

For example, British Patent No. 949.739, U.S. Patent No. 4,
No. 313.766, Japanese Patent Publication No. 39-2.884, Japanese Patent Application Publication No. 33.922-1982, Japanese Patent Application Publication No. 1987-12.0
67 and other specifications describe phthalocyanine derivative dispersion aids effective for dispersing phthalocyanine pigments, as well as British Patent No. 1.139.294 and U.S. Patent No. 3.532.
The specifications of No. 520 and the like list dispersion aids that are effective in dispersing disazo yellow pigments. However, these dispersion aids have the disadvantage that their use is limited to pigments that have a similar color tone or similar skeleton to the pigments treated with them. Examples of substantially colorless dispersants include JP-A-55-112.273 and British Patent No. 1,313.
745, U.S. Patent No. 4.294.620, West German Patent No. 2.041.033, British Patent No. 1.445.104, Japanese Patent Publication No. 1983- 24, No. 433, JP-A-60-166, 318
Urethane derivatives described in US Pat. No. 4,317,682 and amide derivatives are known.

In general, in the process of manufacturing pigment dispersions, fine particles are mixed into a dispersion medium (vehicle) through three processes: wetting the pigment particle surface, grinding with strong shear force, and stabilizing the dispersion by adsorbing the vehicle polymer. However, it has been well known to use a dispersant for the purpose of improving the wetting of the pigment and vehicle polymer and improving their affinity.

These are generally surface-active substances and are classified into cations, anions, nonionic active pillars, etc., depending on the type of polar group. Methods such as treating with these substances during the pigment manufacturing process or adding relatively small amounts to the system during the dispersion manufacturing process have been known, and it is possible to save dispersion energy. becomes.

In particular, examples of wetting and dispersing agents having considerable versatility include Japanese Patent Publication No. 54-34.009 and British Patent Nos. 1 and 3.
42.746 and U.S. Pat. No. 3.778.282, a dispersion consisting of a polyester containing a terminal carboxyl group or a salt thereof obtained by dehydrating a hydroxycarboxylic acid such as 12-hydroxystearic acid. There are also JP-A No. 54-37.082 and JP-A No. 6
3-30.057, British Patent Application Publication No. 2.001.
No. 083, U.S. Patent No. 3.882.088, U.S. Patent No. 4.
No. 224.212, No. 4, 415.705, and West German Patent Application No. 2.830.860 disclose that the above-mentioned terminal carboxyl group-containing polyester is reacted with poly(lower alkylene imine). Dispersants are described which consist of amine salts and/or amides obtained in the following manner. Also, in British Patent No. 1,473.380, 12-
An amide dispersant obtained by dehydrating hydroxystearic acid and 3-dimethylaminopropylamine has been reported, and is disclosed in Japanese Patent Publication No. 57-25.251 and British Patent No. 1.37.
According to the specifications of No. 3.660, an ester or amide derivative obtained by reacting a poly(12-hydroxystearic acid) polyester having a carboxyl group at the end with a dialkylamino alcohol or a dialkylaminoalkylaminoylamine. A quaternary ammonium salt type dispersant obtained by reacting a terminal tertiary amine group with a quaternizing agent such as dimethyl sulfate has been reported.

[Problems to be solved by the present invention]

Among these, the above-mentioned polyestercarboxylic acid amine salt and/or amide dispersant are quite effective thinning and fluidizing agents for a wide range of pigments, but the dispersion stability of the dispersion liquid is It is difficult to say that there is enough pigment/
So-called non-resin based dispersions consisting of non-polar organic solvents/dispersants may suffer from pigment settling during storage or agglomerated particles known as solvent shock upon dilution with solvents or foreign vehicles. There were many points that required improvement, such as the occurrence of

[Means to solve the problem]

In view of the above-mentioned problems with the prior art, the present inventors have conducted extensive research, and as a result, have discovered a method for dispersing fine powdery solids, particularly organic and inorganic pigments, in an organic liquid, preferably a non-polar organic liquid. In some cases, the use of certain modified polyester-type compounds as dispersants has been shown to be effective in preventing pigment aggregation in the dispersion at high pigment concentrations and forming stable dispersions that do not cause solvent shock. This discovery led to the completion of the present invention. That is, in the present invention, 1 mole of tetrakid(2-hydroxyalkyl)ethylenediaminekoxymethyl, phenoxymethyl, alkenoxymethyl, alkyl-substituted phenoxymethyl represented by the general formula (1),
A product obtained by esterification with 0.5 to 20 mol of a hydroxyl group-containing higher monocarboxylic acid and 0 to 2 mol of a hydroxyl group-free higher monocarboxylic acid is added to a higher monocarboxylic acid per equivalent of hydroxyl group in the product. A polymeric dispersant characterized by comprising a modified polyester type compound obtained by ring-opening addition of 01 to 1 equivalent of acid glycidyl ester and then introducing an acidic group, a basic group, or both, and this dispersant. The present invention provides a dispersion liquid characterized by comprising a powdery solid and an organic liquid.

Examples of the tetra-wound (2-hydroxyalkyl)ethylenediamine represented by the general formula (I) include tetra-wound (2-hydroxyethyl)ethylenediamine, tetra-wound (2-hydroxyfurobyl)ethylenediamine, tetra-wound (2-hydroxybutyl)ethylenediamine, and tetra-wound (2-hydroxybutyl)ethylenediamine. (2-hydroquine-3-n-butoxdipropyl) ethylenediamine, tetra-scratch (2-hydroxy-3
-phenoxypropyl) ethylenediamine and the like. Moreover, as the hydroxyl group-containing higher monocarboxylic acid (hereinafter referred to as hydroxycarboxylic acid) used in this reaction, 12-hydroxystearic acid, ricinoleic acid, etc. are particularly suitable. 12-Hydroxystearic acid, which is usually commercially available, is produced by hydrolysis of hydrogenated castor oil and contains small amounts of stearic acid and palmitic acid as impurities (7). This does not cause any trouble in producing the dispersant of the present invention. Examples of the hydroxyl group-free higher monocarboxylic acids include chain, branched, and cyclic monocarboxylic acids having 8 to 22 carbon atoms, each of which is used singly or in combination of two or more. As a specific example,
n-octylic acid, 2-ethyl bovine acid, lauric acid,
Myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, lilunic acid, palm fatty acid, soybean oil fatty acid, beef tallow fatty acid, linseed oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, abietic acid, 4-terL, - Butylbenzoic acid can be mentioned. Further, higher monocarboxylic acid glycidyl esters include, for example, stearic acid glycidyl ester, palmitic acid glycidyl ester, lauric acid glycidyl ester, octylic acid glycidyl ester, neodecanoic acid glinodyl ester (trade name: "Cardura" E, shell oil). Versatic acid glycidyl ester (manufactured by Kaepogushi Co., Ltd.) is preferred. Tetra-wound (2-hydroxyalkyl)ethylenediamine (I)
The esterification reaction with a hydroxycarboxylic acid and a hydroxyl-free higher mono/carphonic acid can be carried out using a known catalyst, such as m-acid, p-toluenesulfonic acid tetra-n-butyl titanate, tetra-1so-propyl titanate, or , Australia, US Pat. No. 493,015, preferably by passing an inert gas such as nitrogen or forming an azeotrope with water in the presence of methanesulfonic acid or the like. It is advantageous to azeotropically remove the water produced by heating under reflux in the presence of aromatic hydrocarbons such as toluene, xylene, etc., out of the reaction system. The reaction temperature for esterification is 120-200°C, preferably 140-18°C.
0°C, and the degree of progress of the reaction can be judged by measuring the acid value of the distilled water. The amount of hydroxycarboxylic acid used in this esterification reaction is
I) It is usually 0.5 to 20 mol per 1 mol, and if the hydroxycarboxylic acid is in excess, by esterification (
The hydroxyl group of the hydroxycarboxylic acid bonded to the side chain of I) further dehydrates and condenses with unreacted hydroxycarboxylic acid to form a polyester chain, but the formation of polyester chains is small and the adhesion of the coating film is excellent. , particularly preferably 0.8 to 35 mol. Further, the amount of the hydroxyl group-free higher monocarboxylic acid used is usually 0 to 2.0 mol per 1 mol of formula (■). In carrying out this esterification reaction, (I), a hydroxycarboxylic acid, and a hydroxyl group-free higher monocarboxylic acid may be charged simultaneously to form a mixed dehydrated ester, or (I) and a hydroxycarboxylic acid may be combined into a dehydrated ester. After that, a hydroxyl group-free higher monocarboxylic acid may be added to further dehydrate and esterify. The ring-opening addition reaction of a higher monocarboxylic acid glycidyl ester to the thus obtained intermediate product can be carried out, for example, with fluorine trifluoride, dibutyltin oxide, tetra-n-butyl titanate, tetra-1so-
Propyl titanate, aluminum isofropoxide,
While heating and stirring in the presence of a quaternary ammonium salt catalyst such as a carboxylic acid, or a quaternary ammonium salt catalyst such as te)-n-butylammonium bromide, a higher monocarphonic acid is added per equivalent of hydroxyl group in the above intermediate product. This is carried out by gradually adding 0.1 to 1.0 parts, preferably 0.8 to 1 part, of the glycidyl ester. The temperature conditions for this ring-opening addition reaction are preferably from 160 to 180'C, and the degree of progress of the reaction can be determined, for example, by gel permeability chromatography, but a reaction time of from 1 to 4 hours is usually sufficient.

The polyester containing a terminal hydroxyl group obtained in this way can be used as a pigment dispersant by itself, but since the surface characteristics differ depending on the type of pigment, in the present invention, in order to obtain a stable pigment dispersant, A suitable acidic group, basic group, or both are introduced into the dispersant.

As the agent for introducing acidic groups, dibasic acids or their anhydrides are preferably used, examples of which include phthalic anhydride, maleic anhydride, cis-Δ4-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydride. Examples include hymic acid, succinic anhydride, geltaric anhydride, het acid, isophthalic acid, terephthalic acid, fumaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sepatic acid, dodecanedioic acid, dimer acid, etc. .

Examples of agents for introducing salt-navigating groups include incyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, inlon diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, and polycondensates thereof, polyethyleneimine, and piperazine. , N-
Alkylpiperazine, 1,4-diazabicyclo (2,
2,2) Octane, 1,8-diazabicyclo (5,4
, 0) undecene (7), various alkanolamines, dialkylaminopropylamine and other amines.

The dispersing agent of the present invention has an acidic or basic polar group or both at the end of the solubilizing group that has a high degree of structural steric hindrance, so it has a steric protective effect on the particles to be dispersed. It has the characteristics that it is suitable for obtaining a stable pigment dispersion, and there is almost no sedimentation and separation of pigments even after long-term storage, and there is almost no change in viscosity over time, and there is no color separation when different pigments are mixed. No phenomena such as lifting or loss of gloss were observed.
In addition, it has excellent compatibility with various solvents and vehicles, so it is suitable as a dispersant for producing a versatile mill base for paints and inks.

Furthermore, the dispersant of the present invention can be used in conjunction with existing polyester amine salt and/or amide type dispersants, such as Japanese Patent Application No.
．． No. 369, JP-A-63-12.335, JP-A-63
-30,057, or U.S. Patent No. 4,41
Dispersants such as those described in No. 5,705, etc.
Sols Bars 13,240 manufactured by IC1 in the UK (product name;
When used in combination with polyethyleneimine salts and amides of polyhydroxystearic acid, etc., the dispersion effect is further increased, and a versatile mill base for paints or inks that exhibits excellent fluidity even at high pigment concentrations and has good storage stability. You can get it.

Examples of the organic liquid used in the dispersion according to the present invention include aromatic hydrocarbons such as toluene, xylene, and "Tsurupets" 100 and "Tsurupets" 150 (both trade names);
Halogenated hydrocarbons such as chloroform, perchloroethylene, trichloroethylene, and chlorobenzene; linear or cyclic ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone;
Esters such as ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, carpitol acetate; alcohols such as isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, ethyl cellosolve, butyl cellosolve, ethyl calpitol, and butyl carpitol. However, it is of course possible to use a mixed solvent of two or more of these, and also known alkyd resins, polyester resins, epoxy resins, epoxy ester resins, polyurethane resins, acrylic resins, acrylic urethane resins, vinyl resins, phenol resins, and melamine resins. , nitrocellulose resin, etc. may be used.

The powdery solids dispersed in the organic liquid by the dispersant of the present invention are usually fine solids with an average particle size of 20 μm or less, such as titanium dioxide, red, yellow or black iron oxide, barium sulfate, water, etc. Colorants, fillers, conductive agents, magnetic materials such as aluminum oxide, calcium carbonate, talc, clay, silica, magnetic iron oxide, lead chromate, zinc chromate, strontium chromate, carbon black, aluminum, brass, iron, etc. various inorganic pigments, including pigments, ablation pigments, lakes, toners, phthalocyanine pigments, isoindolinone pigments, benzimidasilone pigments,
Examples include organic pigments such as quinacridone pigments, indanthrene pigments, and dioxazine pigments. In particular, it is effective in preventing color separation (flooding) and floating that often occur in mixed pigment systems such as red iron/titanium white, phthalocyanine blue/titanium white, and carbon black/titanium white.

The relative proportion of the dispersant of the present invention in the pigment dispersion is advantageously 0.1 to 200 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the powder to be dispersed. The content of the dispersed powder in the dispersion is 5 to 80%, preferably 1
It is 0 to 70% by weight.

Pigment-dispersed color pastes or millbases are prepared using commonly known dispersing machines such as ball mills, sand mills, roll mills, and attritors.

〔Example〕

The present invention will be explained in more detail below with reference to Examples and Test Examples, but the gist of the present invention is of course not limited to these Examples. Note that parts and percentages in the examples are based on weight.

Example 1 Intermediate <1) THEEA (N, N) was placed in 11 4-cone flasks equipped with a thermometer, nitrogen inlet tube, condenser and stirrer.

N', N'-tetrakiz(2-hydroxyethyl)ethylenediamine>118.2 g (0.5 mol)
, 12-HS A (12-hydroxystearic acid)
150.3 g (0.5 mol), dehydrated castor oil fatty acid (acid value 201.0 mgKOH/g) 279.2 g (1,
After adding 50 g of toluene as a solvent and 0.2 g of n-butyl orthotitanate as a catalyst, and attaching a Dean-Stark trap, the mixture was refluxed at 132 to 173 °C for 5 hours while stirring in a nitrogen stream. did.

The I of water distilled into the trap was 26.1 g.

Then, aluminum isopropoxide 0 was used as a catalyst.
．． Add 3g of “Cardura” through the dropping funnel.
E-10 (trade name; manufactured by Shell Yuka Epoxy Co., Ltd.; hersatic acid glycidyl ester) 245 g (1.0 equim
) was added dropwise over a period of about 1 hour and 30 minutes while maintaining the internal temperature at about 160°C. After dropping, the temperature is further increased to 180°.
It was kept at C for 3 hours. After that, the volatile components were concentrated under reduced pressure using a suction pump and a vacuum pump, and the reaction product was cooled to 751
．． 2 g of intermediate (I) as a dark brown oil was obtained. The nonvolatile content of this product is 98%, and the hydroxyl value is 74.1mgKOH/
It was g.

Example 2 Intermediate (II) In the same apparatus as in Example 1, THPEA (N, N.

N', N'-tetra-kiz (2-hydroxypropyl)ethylenediamine 146.2g (0.5mol), 12-H3A 150Jg (0.5mol), dehydrated castor oil fatty acid 279.2g (1.0 equivalent!t) , 50 g of toluene and 0.2 g of n-butyl orthotitanate were charged, and the mixture was refluxed at 150 to 188°C for about 7 hours. The total amount of water captured was 25.9 g.

Next, after adding 03 g of aluminum isopropoxide in the same manner as in Example 1, 245 g (1.0 kg) of "Cardura" E-10 was added for about 1 hour while keeping the temperature at about 160°C.
dripped over a period of minutes. After that, increase the temperature and bring the internal temperature to 180°
It was kept at C for 3 hours.

The volatile components were then concentrated under reduced pressure to obtain 5 g of intermediate (If) as a pale reddish brown transparent oil.

The nonvolatile content of this product is 90%, and the hydroxyl value is 71.4 mg.
KOH/g.

Example 3 Intermediate (m) Into the same apparatus as in Example 1, 146.2 g of THPEA (
0.5 mol), 12-HS A 150.3 g
((1.5 mol), linseed oil fatty acid acid value 201.4 m
gKOII/g) 278.6 g (1.0 equivalent)
, toluene 50g and n-butyl orthotitanate 0,
2 g was charged and refluxed at 142 to 188°C for about 10 hours. The amount of distilled water was 26.3g. After adding 0.3g of aluminum isopropoxide, the internal temperature was about 16.
Keep it at 0°C and add “Cardura” Elo 245g (
1.0 equivalents) was added dropwise over about 1 hour and 25 minutes. The temperature was increased and the internal temperature was maintained at approximately 180°C for 3 hours.

The volatile components were removed by concentration under reduced pressure to obtain 709.8 g of intermediate (III) as a reddish brown oil.

The non-volatile content of this product is 97%, and the hydroxyl value is 71.6 mg.
Kon/g.

Example 4 Intermediate (IV) In an apparatus similar to Example 1, T HP E A 146.
2g (0.5 mol), 12-HS A 150.3
g (0.5 mol), tall oil fatty acid (acid value 194.
OmgKO1l/g) 289.2g (1,0
(equivalent), 50 g of toluene, and 0.2 g of -0-phthyl orthotitanate were charged, and the mixture was refluxed at 145 to 177°C for about 11 hours to obtain 26.1 g of distilled water.

Similar to Example 1, aluminum isopropoxide 0
．． After that, while keeping the internal temperature at about 160°C, add about 1.5 g of Cardura "E-10245 g (1.0 equivalent).
It was added dropwise over a period of 20 minutes. Raise the temperature to bring the internal temperature to about ia
It was kept at 0°C for 3 hours.

660.4 g of a reddish brown oily intermediate (■
) was obtained.

The nonvolatile content of this product is 99%, and the hydroxyl value is 70.4 mg.
KOR/g.

Example 5 Intermediate (V) In the same apparatus as in Example 1, 118.2 g of TREEA (
0.5 mol) 12-ISA 150.3 g (0.5 mol), linseed oil fatty acid acid value 201.4 mg KOII/
g) 278.4 g (1.0 equivalent), toluene 50
g and 0.2 g of -butyl orthotitanate, and refluxed at 143 to 186°C for about 9 hours to produce 25.9 g.
of water was captured in the trap.

In the same manner as in Example 1, 0.3 g of aluminum isopropoxide was added and the internal temperature was maintained at 155 to 160°C.
0 equim) was added dropwise over about 1 hour and 30 minutes. Thereafter, the internal temperature was maintained at about 180°C for 3 hours.

Working up as in Example 4, 738.3 g of a reddish-brown oil was obtained.

The nonvolatile content of this product is 98%, and the hydroxyl value is 74.2mg.
KOH/g.

Example 6 Dispersant A 757.2 g (0.5 mol) of the intermediate (1) obtained in Example 1 and 38.5 g (0.25 mol; l/4 equivalent) of hexahydrophthalic anhydride (HHPA, trade name: Rikazid HH, manufactured by Shinnihon Chemical Co., Ltd.) was charged, and the mixture was heated and stirred at 160 to 164°C for 3 hours. It becomes a dark brown transparent oil.

Analyzed after cooling, non-volatile content 99%, acid value 12.2mgKO
A value of 1 l/g was obtained.

Example 7 Dispersant B Into the same apparatus as in Example 6, the intermediate obtained in Example 2 (
II) 758.9 g <0.5 mol) and 38.5 g hexahydrophthalic anhydride (0.25 mol; 17
4 equivalents) and heated and stirred at 160 to 166°C for 3 hours. It became a reddish-brown transparent oil.

This product has a non-volatile content of 98% and an acid value of 0.6mgKOH/
It was g.

In addition, the viscosity (25℃) according to the Gardner method is Q~R2
, color number is 11-12, weight average molecular weight by GPC is 2
106, and the number average molecular weight was 1996.

Example 8 Dispersant C The intermediate obtained in Example 3 (
m ) 783.7 g (0.5 mol) and 38.5 g (0.25 mol; l/4 equivalent It) of hexahydrofuranhydride were heated at 160-165°C for 3 hours and 20 minutes, and stirred. A reddish-brown oily clear liquid was obtained.

This product has a non-volatile content of 100% and an acid value of 1.2mg KOI.
l/g.

Example 9 Dispersant D Into the same apparatus as in Example 6, the intermediate obtained in Example 4 (
rV)79? , Og (0,5 mol) and 38.5 g of hexahydrophthalic anhydride (0,25 mol; 1
/4 tm) and heated at 160 to 164°C for 3 hours 10
After heating and stirring for a minute, a reddish-brown transparent oily liquid was obtained.

This product has a non-volatile content of 99% and an acid value of 1.1mgKOH/
It was g.

Example 10 Dispersant E Into the same apparatus as in Example 6, the intermediate obtained in Example 2 (
n) 758.9 g (0.5 mol) and tetrahydrophthalic anhydride (THPA: trade name Rikazid TH manufactured by Shin Nihon Rika) 38.0 g (0.25 mol; l
/4 equivalent) and heated and stirred at 160 to 162°C for 3 hours and 15 minutes.

A reddish-brown transparent oily liquid was obtained.

The nonvolatile content of this product is 97.5%, and the acid value is 0.8 mgK.
It was OH/g.

Example 11 Dispersant F The intermediate obtained in Example 2 (
II) 758.9 g (0.5 mol) and 37.0 g (0.25 mol) of phthalic anhydride were charged, and 160
The mixture was heated and stirred at ~165°C for 3 hours. A reddish-brown transparent oily liquid was obtained.

This product has a non-volatile content of 99.5% and an acid value of 1. Omg
KOH/g.

Test Example 1 45 parts of red iron oxide 140M (made by Bayer), 88 parts of the dispersant of Example 7, 22 parts of xylene and 150 parts of glass beads with a diameter of 3 mm were mixed, and a paint conditioner made by Red Devil was used. A pigment dispersion was prepared by shaking for 1 hour and peptizing the mixture. The viscosity of the dispersion was measured at 25°C using a B-type viscometer, and the following results were obtained.

*Thixotropic index 26 rotational viscosity 60
The value divided by the degree of rotation.

'Beccosol' J 524-I instead of dispersant B
When M 60 (trade name; alkyd resin manufactured by Dainippon Ink Chemical Co., Ltd.) was used, the beads did not move and the resulting composition was non-fluid.

Test Example 2 When dispersant C and D of Examples 8 and 9 were used in the same amount in place of dispersant B of Test Example 1, the viscosity of the dispersion liquid was as follows.

All of the dispersions exhibited good fluidity, and no hard cake formation due to pigment sedimentation was observed even after storage for one month.

Test Example 3 49 parts of rutile type titanium white JR-701 (manufactured by Teikoku Kako),
A pigment dispersion was prepared by shaking and peptizing 8 parts of the dispersant D of Example 9 and 18 parts of xylene together with 150 parts of glass beads having a diameter of 3 mm for 1 hour using a paint conditioner manufactured by Red Devil. When the viscosity of the dispersion was measured at 25°C, the following results were obtained. When "Beccosol" J-524-IM-60 was used under the same conditions in place of the dispersant, the beads did not move. The composition was non-flowing.

〔Effect of the invention〕

Since the present invention is as described above, the dispersant of the present invention includes:
The dispersion of the present invention is capable of stably dispersing powdered solids such as various organic and inorganic pigments and fillers at a high content rate over a long period of time in non-polar organic liquids such as printing inks and paints. has the excellent characteristics of significantly lower viscosity and higher fluidity than conventional products of this type, even when the content of non-dispersed fine powder is high.

In addition, the dispersant of the present invention has various polar groups in its molecule or chemical structure, and since many types of molecules are mixed together, it has wide applicability to non-dispersed particles such as pigments. Moreover, it has excellent compatibility with a wide range of organic liquids. Therefore, the dispersant of the present invention prevents color separation, floating, and loss of gloss when different types of pigments are mixed and used, and prevents solvent shock when mixed with different types of solvents or vehicles or diluted with them. Effectively prevents the generation of agglomerated particles.

The characteristics and advantages of the dispersant of the present invention are listed below.

(b) Improved productivity by reducing dispersion time, energy and cost by improving fluidity, increasing the amount charged to the dispersing machine, and reducing adhesion loss.

(b) Reducing the number of mills and bases, reducing the number of times the meat is processed, storage space, and inventory interest.

(c) Savings on transportation costs due to increased pigment concentration in the mill base.

(d) Prevention of abnormal agglomeration and color separation of mixed pigments and improvement of quality such as color density and gloss of paint films based on stabilization of the dispersion state in colorant products.

Claims (1)

[Scope of Claims] 1. Tetra-wound (2-hydroxyalkyl)ethylenediamine represented by the general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (R is H, alkyl, phenyl, alkoxymethyl ,
(representing phenoxymethyl, alkenoxymethyl, alkyl-substituted phenoxymethyl) is esterified with 0.2 to 20 moles of a hydroxyl group-containing higher monocarboxylic acid and 0 to 2 moles of a hydroxyl group-free higher monocarboxylic acid. The hydroxyl group 1 in the product is
Higher monocarboxylic acid glycidyl ester 0 per equivalent weight
．． A polymeric dispersant characterized by comprising a modified polyester type compound obtained by ring-opening addition of 1 to 1 equivalent and then introducing an acidic group, a basic group, or both. 2. The polymeric dispersant according to claim 1, wherein the hydroxyl group-containing higher monocarboxylic acid is ricinoleic acid or 12-hydroxystearic acid. 3. The polymer dispersant according to claim 1, wherein the higher monocarboxylic acid glycidyl ester is neodecanoic acid glycidyl ester. 4. Hydroxyl group-free higher monocarboxylic acid has 8 carbon atoms
2. The polymer dispersant according to claim 1, which is at least one selected from chain, branched, and cyclic monocarboxylic acids. 5. A dispersion liquid comprising the polymer dispersant according to claim 1, a powdery solid, and an organic liquid. 6. The dispersion according to claim 5, wherein the powdery solid is an organic or inorganic pigment with a particle size of 20 μm or less.