JP2704211B2 - Dispersant and dispersion containing it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for dispersing a fine powdered solid such as an inorganic or organic pigment in an organic liquid, preferably a non-polar organic liquid. Dispersants that can impart excellent fluidity and dispersion stability to the system, especially polyesters,
The present invention relates to a dispersant having good compatibility with a vehicle polymer for paint such as an alkyd resin, and a dispersion liquid using the dispersant, and its application range is generally applied to coating compositions such as printing inks and paints. It is concerned.

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

[Conventional technology]

Generally, an organic or inorganic pigment which is a component of a coloring material composition for various coatings such as a printing ink or a paint is formed of a fine powder. When fine pigment particles are dispersed in a non-polar organic liquid containing a vehicle polymer as in printing inks and paints, especially at high pigment concentrations, color materials with excellent fluidity and storage stability Obtaining the composition is difficult and often raises various problems that have a significant effect on the manufacturing process as well as on the quality of the product obtained.

That is, a high-concentration dispersion of a pigment composed of fine particles generally has poor fluidity, and is difficult to handle, for example, when mixing, stirring, and kneading during the dispersion process, or when an attachment loss occurs during removal and transfer. It is known that undesired phenomena occur such as difficulty in color separation, floating, decrease in gloss, and change in viscosity and gloss with time when mixed and used with different kinds of pigments.

Non-aqueous printing inks or paints are pigment dispersions in which the dispersion medium is an organic liquid containing a vehicle polymer and other auxiliaries, but the basic part of the rheological properties of this dispersion is fine. It depends on the surface properties of the pigment composed of particles.

That is, in the system where the fluidity of the dispersion liquid is poor, color separation, floating phenomenon such as floating phenomenon,
The degree of aggregation of the pigment is large, and the color material using such a dispersion is inferior in color density, coloring power, sharpness, and coarse coagulation at the time of color development as compared with a color material that maintains a stable dispersion state. Due to the unevenness due to the aggregates, the coated surface tends to lose smoothness and the gloss also tends to be reduced, thus impairing the commercial value of the object to be coated.

Also, in a dispersion having a high pigment concentration, such as a printing ink or a paint, if the viscosity and fluidity of the dispersion are to be improved, the gloss of the coating film is lost, and if the gloss is to be improved, the fluidity is impaired. Thus, it was not easy to produce a coating coloring material that sufficiently satisfied various suitability.

Various methods have heretofore been proposed for the purpose of preventing the aggregation of pigments in non-aqueous printing inks or paints, and they have been recognized to some extent. For example, British Patent No. 949,739, U.S. Pat.No. 4,313,766 and the like include phthalocyanine derivative-based dispersing agents effective for dispersing phthalocyanine pigments, and British Patent No. 1,139,294, U.S. Pat. Publications disclose a dispersing aid effective for dispersing the disazo yellow pigment.

However, these dispersing aids have the disadvantage that the pigments treated with them have a limited application to pigments having a similar color or a similar skeleton.

Examples of the substantially colorless dispersant include JP-A-55-111.
No. 2273, UK Patent No. 1,313,745, US Patent No. 4,294,620
Urea derivatives as described in the specifications of West German Patent No. 2,041,033, British Patent No. 1,445,104, JP-B-58
No. 24433, urethane derivatives described in each specification such as JP-A-60-166,318, or U.S. Pat.
The amide derivative described in the specification of Japanese Patent No. 682 is known.

Further, British Patent No. 1,473,380 discloses that an amide compound obtained by dehydration of 12-hydroxystearic acid and 3-dimethylaminopropylamine is effective as a pigment dispersant, Japanese Patent Publication No. 54-34009, UK Patent No. 1,34
No. 2,746 and U.S. Pat.
Dispersants relating to polyesters having a terminal carboxyl group obtained by dehydrating a hydroxycarboxylic acid such as hydroxystearic acid or salts thereof are disclosed in JP-A-54-37082.
No., UK Patent Application Publication No. 2,001,083, U.S. Pat.No. 4,22
No. 4,212, West German Patent Publication No. 2,830,860, U.S. Pat.
In each specification such as 3,882,088, terminal carboxyl groups such as poly (lower alkyleneimine) and poly (12-hydroxystearic acid) are used as dispersants useful for preparing pigment dispersions for printing ink production. No. 4,415,705 discloses a rosin-modified polyester carboxylic acid blended with tall oil rosin in a dehydration condensation process of hydroxystearic acid. Have been reported, respectively.

Furthermore, after the terminal carboxyl group of the polyester obtained by dehydration of the hydroxycarboxylic acid is esterified with a dialkylamino alcohol or reacted with a dialkylaminoalkylamine and amidated, the terminal tertiary amine group is changed to dimethyl sulfate. Dispersants converted to quaternary ammonium salts by treatment with a suitable quaternizing agent are described in JP-B-57-25251 and British Patent 1,373,660.

[Problems to be solved by the invention]

Of these, the above-mentioned amine salts of polyestercarboxylic acid and / or amide-based dispersants are particularly effective fluidizers for a wide range of pigments, but are not sufficient with respect to the dispersion stability of the dispersion. Difficult to say, so-called non-resin-based dispersions consisting of pigment / non-polar organic solvent / dispersant have a pigment sedimentation during storage, so-called solvent shock upon dilution with solvents or foreign vehicles. Many improvements were required, such as generation of aggregated particles.

[Means for solving the problem]

In view of the problems of the prior art, the present inventors have conducted intensive studies and, as a result, dispersed a fine powdery solid, particularly an organic or inorganic pigment, in an organic liquid, preferably a non-polar organic liquid. In this case, when a specific modified polyester type compound is used as a dispersant, it is effective to prevent pigment aggregation in the dispersion at a high pigment concentration and to form a stable dispersion which does not cause solvent shock. Find out,
The present invention has been completed.

That is, the present invention relates to a product obtained by esterifying 1 mol of tris (hydroxyethyl) isocyanurate 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, It consists of a modified polyester type compound obtained by subjecting 0.1 to 1 equivalent of higher monocarboxylic acid glycidyl ester to ring-opening addition to 1 equivalent of hydroxyl group in the product and then introducing an acidic group and / or a basic group. And a dispersion comprising the dispersant, a powdered solid, and an organic liquid.

As the hydroxyl group-containing higher monocarboxylic acid (hereinafter, referred to as hydroxycarboxylic acid) used in this reaction, 12-hydroxystearic acid, ricinoleic acid and the like are particularly preferable. Normally, 12-hydroxystearic acid, which is industrially available, is produced by hydrolysis of hydrogenated castor oil, and thus contains small amounts of palmitic acid, stearic acid, and the like as impurities. It does not hinder the production of the dispersant.

Examples of the hydroxycarboxylic acid include a chain monocarboxylic acid having 8 to 22 carbon atoms, a branched monocarboxylic acid, and a cyclic monocarboxylic acid, each of which is used alone or in combination of two or more.

Specific examples include octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid,
Linoleic acid, linolenic acid, coconut oil fatty acid, soybean oil fatty acid, tallow oil fatty acid, linseed oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, abietic acid, 4-tert-butylbenzoic acid and the like can be mentioned.

Further, as the higher monocarboxylic acid glycidyl ester, for example, glycidyl stearate, glycidyl palmitate, glycidyl myristate, glycidyl laurate, glycidyl octylate, glycidyl neodecanoate, and the like, among which neodecanoate Glycidyl esters (trade name: Kadura E, glycidyl versatate manufactured by Shell Chemical Co., Ltd.) are preferred.

The esterification reaction of THEIC with a hydroxycarboxylic acid and a hydroxyl-free higher monocarboxylic acid can be carried out by a known acid catalyst such as phosphoric acid, P-toluenesulfonic acid, tetra-n-butyl titanate, tetra-iso-propyl titanate or an Australian patent. No. 493,015, in the presence of methanesulfonic acid or the like, preferably by passing an inert gas such as nitrogen, or an aromatic hydrocarbon which forms an azeotrope with water, for example, toluene,
It is advantageous to azeotropically remove water generated by heating and refluxing in the presence of xylene or the like to the outside of the reaction system. The reaction temperature of the esterification is 120 to 200 ° C, preferably 140 to 180 ° C, and the degree of progress of the reaction can be judged by measuring the amount of distilled water and the acid value of the product.

The amount of hydroxycarboxylic acid used in this esterification reaction is usually 0.5 to 20 mol per 1 mol of THEIC, and when the amount of hydroxycarboxylic acid is excessive, the amount of hydroxycarboxylic acid bonded to the side chain of THEIC by esterification is increased. The hydroxyl group of the acid further dehydrates and condenses with unreacted hydroxycarboxylic acid to form a polyester chain,
Among them, 0.8 to 3.5 mol is preferable, since the formation of polyester chains is small and the adhesion of the coating film is excellent. In addition, the amount of the hydroxyl group-free higher monocarboxylic acid used is determined by THEIC 1
It is generally 0 to 2 mol, preferably 0.8 to 2.0 mol, per mol.

In carrying out this esterification reaction, THEIC, hydroxycarboxylic acid and hydroxyl group-free higher monocarboxylic acid may be simultaneously charged, mixed and dehydrated and esterified, or THEIC and hydroxycarboxylic acid may be dehydrated and esterified. Then, a higher monocarboxylic acid containing no hydroxyl group may be added, followed by dehydration esterification.

The reaction for ring-opening addition of a higher monocarboxylic acid glycidyl ester to the product thus obtained is carried out, for example, by using a Lewis acid such as dibutyltin trifluoride borate or tetra-n-butyl titanate, or a quaternary ammonium such as tetrabutylammonium bromide. In the presence of a salt catalyst, while heating and stirring, 0.1 to 1 equivalent of higher monocarboxylic acid glycidyl ester to 1 equivalent of hydroxyl group in the above product,
Preferably, it is carried out by gradually adding 0.8 to 1 equivalent. The temperature condition of this ring-opening addition reaction is 160-180 ° C.
The progress of the reaction can be determined by, for example, gel permeation chromatography, and the reaction time is usually 1 to 4 hours.

Although the terminal hydroxyl group-containing polyester thus obtained can be used as a pigment dispersant by itself,
Since surface characteristics vary depending on the type of pigment, in the present invention, in order to obtain a stable pigment dispersion, an appropriate acidic group and / or basic group is introduced into the dispersant.

As the reagent for introducing an acidic group, dibasic acids or anhydrides thereof are preferably used. Examples thereof include phthalic anhydride, maleic anhydride, eis-Δ4-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydride. Hymic acid,
Examples of succinic anhydride, glutaric anhydride, heptic acid, isophthalic acid, terephthalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, dimer acid, etc. Examples of the reagent include isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, and polycondensates thereof, polyethylene imine, piperazine, N-alkyl piperazine, 4-diazabicyclo (2,2,2) octane, 1,8-diazabicyclo (5,4,0) undecene (7), various alkanolamines, ω-dialkylaminoalkylamines such as dimethylaminopropylamine and others It can be mentioned amines.

Since the dispersing agent of the present invention has an acidic and / or basic polar group at the terminal of the solubilizing group having a structurally high steric hindrance, it has a large steric protection effect on the particles to be dispersed. It has the characteristic that it is suitable for obtaining a stable pigment dispersion, and there is almost no sedimentation and separation of the pigment after storage for a long time, and there is almost no change in viscosity with time. Such a phenomenon is not observed, and the compatibility with various solvents and vehicles is excellent, so that it is extremely suitable as a dispersant for producing a multi-use mill base for paints and inks.

Further, the dispersant of the present invention is a polyesteramine salt having a terminal carboxyl group and / or an amide type dispersant, for example, JP-A-61-234919, JP-A-62-4433, JP-A-63-12355.
, US Pat. No. 4,224,212 or US Pat. No. 4,415,705, in combination with dispersant, Solstars 13240 (polyethyleneimine salt of polyhydroxystearic acid and amine) manufactured by ICI of the United Kingdom, etc. As a result, the dispersing effect is further increased, and it is possible to obtain a general-purpose mill base for paints or inks that exhibits excellent fluidity even at a high pigment concentration and has good storage stability.

Examples of the organic liquid used in the dispersion according to the present invention include aromatic hydrocarbons such as toluene, xylene, “Solvesso” 100, and “Solvesso” 150; mineral spirits;
Petroleum hydrocarbons such as mineral terpenes; halogenated hydrocarbons such as chloroform, perchlorethylene, trichloroethylene and chlorobenzene; linear or cyclic ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone isophorone; acetic acid Esters such as ethyl, butyl acetate, amyl acetate, cellosolve acetate, carbitol acetate; isopropyl alcohol, isobutyl alcohol, n-butyl alcohol;
Examples thereof include alcohols such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, and butyl carbitol. Of course, a mixed solvent of two or more of these may be used, or a known alkyd resin, polyester resin, epoxy resin, epoxy resin, or the like. A mixed system with an ester resin, a polyurethane resin, an acrylic resin, an acrylic urethane resin, a vinyl resin, a phenol resin, a melamine resin, a nitrocellulose resin, or the like may be used.

The powdery solid dispersed in the organic liquid by the dispersant of the present invention is usually a fine solid having an average particle size of 20 μm or less, for example, titanium dioxide, red and yellow or black iron oxide, barium sulfate, and water. Coloring agents such as aluminum oxide, calcium carbonate, talc, clay, silica, magnetic iron oxide, lead chromate, zinc chromate, strontium chromate, carbon black, aluminum, brass, iron, fillers, conductive materials, magnetic And organic pigments such as various inorganic pigments including materials, azo pigments, lakes, toners, phthalocyanine pigments, isoindolinone pigments, benzimidazolone pigments, quinacridone pigments, indanthrene pigments, dioxazine pigments and the like. Above all, bengara / titanium white, phthalocyanine blue / titanium white,
It is effective for preventing color separation (flooding) and floating which often occur in a mixed pigment system such as carbon black / titanium white.

The relative proportion of the dispersant in the present invention in the pigment dispersion, 0.1 to 200 parts by weight, preferably 1 to 50 parts by weight per 100 parts by weight of the powder to be dispersed, it is advantageous to use the dispersion The content of the powder to be dispersed is 5 to 80% by weight, preferably
10-70% by weight.

The pigment-dispersed color paste or mill base is prepared by using a commonly known dispersing machine such as a ball mill, a sand mill, a roll mill, and an attritor.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the gist of the present invention is, of course, not limited by these Examples. The parts and percentages in the examples are on a weight basis.

<Preparation Example of Dispersant of the Present Invention> Example 1 (Dispersant A) 130.6 g of THEIC, 15-hydroxystearic acid for industrial use 15
0.3 g, 139.6 g of dehydrated castor oil fatty acid, 0.2 g of tetraisopropyl titanate and 42 g of toluene were mixed and heated under reflux in a nitrogen stream to separate 18 g of water in a Dean-Stark trap. After refluxing for 6 hours, almost no water distilling was observed. The temperature of the reaction solution was 162 ° to 182 ° C. Next, 0.3 g of dibutyltin oxide was added, and 245 g of glycidyl versatate was added dropwise at 160 to 165 ° C over 1.5 hours. After dropping, stir at 180 ° C for 3 hours,
Then, 37.0 g of phthalic anhydride was added, the temperature was raised to 160 ° C., and the mixture was stirred for 2 hours, and cooled to give a pale brown transparent, slightly viscous resinous substance with a nonvolatile content of 95% (dispersant A). 711.4 g were obtained. This dispersant A had an acid value of 18 mg KOH / g, a color number of 6 (Gardner method), and a viscosity at 25 ° C. of Z ₂ (Gardner method). As a result of measuring the infrared absorption spectrum of the solid component, 1605
And amide 1620 cm ^-1, the ether bond 1160 cm ^-1,
The carboxylic acid carbonyl 1720 cm ^-1, respectively group Nuisance absorption band in the ester carbonyl was observed at further 1760 cm ^-1. The result of molecular weight measurement by gel permeation chromatography was _Mn = 1,698 and _Mw = 1855.

Example 2 (Dispersant B) THEIC 130.6 g, 2-ethylhexanoic acid 72.1 g, industrial 1
150.3 g of 2-hydroxystearic acid, 35.3 g of toluene and 0.2 g of n-butyl orthotitanate were mixed, and mixed in a nitrogen stream.
Reflux at 0-182 ° C. for 10 hours and separate 16 g of water in the Dean Stark trap. Next, 0.4 g of methanesulfonic acid
Was added thereto, and 245 g of glycidyl versatate was added dropwise at 160 to 165 ° C over 1 hour. After dropping, 180
After stirring at 4 ° C for 4 hours and cooling to 160 ° C, phthalic anhydride 3
After adding 7.0 g, the mixture was stirred at 160 to 165 ° C. for 2 hours, and cooled to obtain 650 g of a pale yellowish brown, slightly viscous resinous substance (dispersant B) having a nonvolatile content of 95% (dispersant B). The acid value of this dispersant B is 19.9mg KOH
/ g, the viscosity by the Gardner method was Z _{2 to} Z ₃ (25 ° C.), and the color number was 4 to 5.

Example 3 (Dispersant C) THEIC 65.3 g, 2-ethylhexanoic acid 36.1 g, dehydrated castor oil fatty acid 69.8 g, industrial 12-hydroxystearic acid 7
5.2 g, n-butyl nult titanate 0.2 g, toluene 24.6 g
Was refluxed in a nitrogen stream at 160-182 ° C. for 10 hours to separate 12.5 g of water in a Dean-Stark trap.
0.3 g of boron trifluoride etherate was added thereto, and 61.3 g of glycidyl versatate was added dropwise at 160 ° C. over 30 minutes. After dropping, stir at 180 ° C for 3 hours,
After cooling to ℃, 18.5 g of phthalic anhydride was added, and 160-165
The mixture was stirred at 2 ° C. for 2 hours and cooled to obtain 335 g of a pale yellowish brown, slightly transparent, slightly viscous resinous substance (dispersant C) having a nonvolatile content of 95%.
The acid value of this dispersant C was 17.3 mgKOH / g, the viscosity V to W (25 ° C.) according to the Gardner method, and the color number according to the Gardner method was 5.

Example 4 (Dispersant D) THEIC 52.2 g, industrial 12-hydroxystearic acid 18
0.3 g, n-butyl orthotitanate 0.2 g, toluene 25.9 g
And heated to reflux in a nitrogen stream to separate 10.8 g of water in a Dean-Stark trap. After 4 and a half hours of reflux, almost no water distilling was observed. The temperature of the reaction solution was 169-173 ° C. Next, 0.6 g of tetrabutylammonium bromide was added, and 147.0 g of glycidyl versatate was added dropwise at 140 ° C. over 1 hour. After completion of the dropwise addition, the mixture was stirred at 160 to 165 ° C for 3 hours, cooled to 100 ° C, and added with 14.8 g of phthalic anhydride. Nonvolatile content 84
% Resinous material (dispersant D) was obtained. The acid value of the dispersant D is 0.7 mg KOH / g, viscosity (Gardner) is ▲ Z ² ₁
▼ to Z _2, color number (Gardner) was 4 ^2-5.

Example 5 (Dispersant E) 52.2 g of THEIC, 12-hydroxystearic acid for industrial use 60.
1 g, tall oil fatty acid 57.8 g, n-butyl orthotitanate
0.2 g, mixed with 18.9 g of toluene, 160-165 in a nitrogen stream
Reflux at 7 ° C. for 7 hours in a Dean-Stark trap.
2 g of water were separated. Next, tetrabutyl ammonium bromide
Add 0.2g of Mide and add "Kajura" at 132-142 ℃ "E10 9
After dropping 8g over 50 minutes, stir at 150-160 ° C for 2 hours
After cooling to 100 ° C, 7.4 g of phthalic anhydride was added,
Stir at 158 ° C for 2 hours, cool to light yellow-brown transparent, slightly viscous
285.3 g of a resinous substance (dispersant E) having a dense non-volatile content of 91% was obtained.
Was. This dispersant E has an acid value of 0.6 mg KOH / g and a viscosity (Guard
Gnar) is XY_TwoThe number of colors (Gardner) was 8.

Example 6 (Dispersant F) THEIC 52.2 g, ricinoleic acid 59.7 g, linseed oil fatty acid 5
5.8 g, n-butyl orthotitanate 0.2 g, toluene 18.7 g
And refluxed at 158 ° C. for 6 hours in a nitrogen stream.
6.7 g of water was separated in the Stark trap. Next,
Add 0.2 g of trabutylammonium bromide, add 140-1
At 45 ° C "Drop 98g of E10 over 35 minutes,
The temperature was raised to 155 to 160 ° C., and the mixture was stirred for 3 hours. Cool to 100 ° C
After that, 14.8 g of phthalic anhydride was added, and 155 to 160 ° C again.
And stirred for 2 hours, then cooled to clear light brown
287.5 g of a resinous material (dispersant F) was obtained. This dispersant F
Has an acid value of 0.9 mg KOH / g and a nonvolatile content of 86%. Also sticky
The degree (Gardner) is P ~ Q, the number of colors (Gardner) is 8.
there were.

<Dispersion of terminal amine carboxyl group-containing polyesteramine salt
Preparation Example of Dispersant> Reference Example (Dispersant G) “Epomin "SP-006 [Pos made by Nippon Shokubai Chemical Industry Co., Ltd.
1,2-butyrate in 30 g of ethylenedimine: average molecular weight 600]
The mixture was stirred at 80 ° C. for 1 hour. This
Poly (12-hydroxystearic acid) toluene mixture
(Non-volatile content 92.1%, Non-volatile acid value 25.6mg KOH / g) 119g
And 146.8 g of toluene, and heated at 112-113 ° C for 2 hours under reflux
The water was collected in a Dean Stark trap. 0.6g
Water has collected. The pale yellow transparent product (min.
Powder G) 300.5 g were obtained.

The amine value was 98.2 mg KOH / g and the acid value was 8.2 mg KOH / g.
g, tertiary amine nitrogen content in total amine nitrogen is 14.3%
And the content of non-volatile components was 49.5%.

Reference Example 2 (Dispersant H) 30 g of Epomin SP-200 [polyethyleneimine manufactured by Nippon Shokubai Chemical Industry Co., Ltd .: average molecular weight 10,000] in 150 g of toluene
The mixture was mixed with 3.6 g of 1,2-butylene oxide and stirred at 100 ° C. for 1 hour. To this was added 116.4 g of poly (12-hydroxystearic acid) (acid value: 36.7 mg KOH / g), and the mixture was heated under reflux at 114 to 116 ° C. for 2 hours. Thus, the acid value of 12.5 mg KOH /
g, 300.6 g of a dispersant (dispersant H) solution having an amine value of 90.6 mg KOH / g and a non-volatile content of 49.5%.

<Dispersion liquid preparation example and red down stability test> Example 7 Red iron oxide 140M (manufactured by Baruel Corporation) 52.5 parts, dispersant A7.
Five parts, 1.0 part of Dispersant G and 14 parts of xylene were peptized and dispersed together with 100 parts of glass beads having a diameter of 5 mm using a paint conditioner manufactured by Red Devil for 1 hour. The dispersion has good flowability and a viscosity at 25 ° C of 145 cps
(B-type viscometer, 6 rotation viscosities, the same applies hereinafter). Also,
No sedimentation or separation of the pigment was observed after storage for 10 days.

Next, a room temperature drying type acrylic resin (Acrydic FL-121, manufactured by Dainippon Ink and Chemicals, Inc.), vinyl acetate-
White enamel (titanium oxide / resin solid) prepared from an acrylic copolymer resin (Nippon Synthetic Chemical Industry Co., Ltd., Coponyl 9503) and an acrylic polyol resin (Dainippon Ink Chemical Industry Co., Ltd., Acridic A-801) Min / thinna weight ratio = 20/30/50) Take 20 parts each, add 2 parts each of the dispersion prepared above, and add 2 parts with TK homodisper.
Mix vigorously for minutes. 100 of each mixed enamel
Apply on art paper with a micron doctor blade, 30
After 秒 60 seconds, the finger was rubbed lightly with a finger to observe the state of color separation (color difference between the surface and the bottom) (red down stability test). As a result, no color separation was observed in any of the mixed enamels, and the gloss of the coating film was good.

Example 8 Red iron oxide 160M (manufactured by Bayer AG) 60 parts, dispersant B 8
Parts, 1 part of dispersant H and 11 parts of xylene were peptized and dispersed together with 100 parts of glass beads having a diameter of 5 mm using a paint conditioner manufactured by Red Devil for 1 hour. The dispersion exhibited good fluidity, no sedimentation or separation of the pigment was observed even after storage for 10 days, and the viscosity at 25 ° C was 665 cps.

Next, a red down stability test was performed in the same manner as in Example 7 except that this dispersion was used. As a result, no color separation was observed and the gloss of the coating film was good.

Comparative Example 1 "Beccosol" was used instead of 7.5 parts of dispersant A. "J-524-IM6
0 [Short oil alkyd tree manufactured by Dainippon Ink and Chemicals, Inc.
Butter] was dispersed in the same manner as in Example 7 except that 7.5 parts was used.
I tried to prepare a liquid, but the beads did not move at all,
A good dispersion could not be obtained.

Comparative Example 2 "Beccosol" instead of 8 parts of dispersant B "J-524-IM60
A dispersion was prepared in the same manner as in Example 8 except that 8 parts were used.
But the beads did not move at all and the dispersion was good.
A good dispersion could not be obtained.

Comparative Example 3 Dispersant A 8.5 parts and Dispersant G 8.5 instead of Dispersant G 1 part
A dispersion was obtained in the same manner as in Example 7 except that the above-mentioned parts were used. Then, a mixed enamel was obtained in the same manner as in Example 7 except that this dispersion was used. Generation of aggregated particles was observed.

Comparative Example 4 A dispersion was obtained in the same manner as in Example 8 except that 9 parts of the dispersant H was used instead of 8 parts of the dispersant B and 1 part of the dispersant H, and then the example was performed except that this dispersion was used. In the same manner as in Example 8, mixed enamels were obtained, but generation of agglomerated particles was observed in all of the mixed enamels.

Example 9 Dispersant A 8.5 instead of 7.5 parts Dispersant A and 1 part Dispersant G
A dispersion was obtained in the same manner as in Example 7, except that the parts were used.
This dispersion showed good fluidity, and no sedimentation or separation of the pigment was observed even after storage for 10 days.

Next, a red down stability test was performed in the same manner as in Example 7 except that this dispersion was used. As a result, no color separation was observed and the gloss of the coating film was good.

Example 10 A dispersion liquid was obtained in the same manner as in Example 8, except that 9 parts of the dispersant B was used instead of 8 parts of the dispersant B and 1 part of the dispersant H. This dispersion showed good fluidity, and no sedimentation or separation of the pigment was observed even after storage for 10 days.

Next, a red down stability test was performed in the same manner as in Example 8 except that this dispersion was used. As a result, no color separation was observed and the gloss of the coating film was good.

Example 11 20 parts of carbon black Raven 14 (manufactured by Columbia Carbon Co.), 5 parts of dispersant C, 2 parts of dispersant G, and 33 parts of xylene were mixed with 100 parts of glass beads having a diameter of 3 mm in a paint conditioner manufactured by Red Devil for 1 hour. The mixture was shaken and peptized and dispersed.

The dispersion has good flowability and a viscosity at 25 ° C. of 10
5 cps. No sedimentation or separation of the pigment was observed after storage for 10 days.

Next, a red down stability test was performed in the same manner as in Example 7 except that this dispersion was used. As a result, no color separation was observed and the gloss of the coating film was good.

Example 12 Monoazo red pigment Nova Palm Red F5RK (manufactured by Hoechst) 25 parts, dispersant F 3 parts, dispersant G 2 parts, xylene 43
The portion was shaken with a paint conditioner manufactured by Red Devil for 1 hour together with 100 parts of glass beads having a diameter of 3 mm for deflocculation and dispersion.

The dispersion shows good flowability and has a viscosity at 25 ° C. of 52
5 cps. No sedimentation or separation of the pigment was observed after storage for 10 days.

Next, a red down stability test was performed in the same manner as in Example 7 except that this dispersion was used. As a result, no color separation was observed and the gloss of the coating film was good.

Example 13 Phthalocyanine Blue Pigment Fastogen Blue TRG
[Dai Nippon Ink Chemical Industry Co., Ltd.] 25 parts, dispersant E12
And 45 parts of toluene together with 100 parts of glass beads having a diameter of 3 mm were shaken for 1 hour with a paint conditioner manufactured by Red Devil to disperse and peptize.

The dispersion has good flowability and a viscosity at 25 ° C. of 10
5 cps. No sedimentation or separation of the pigment was observed after storage for 10 days.

Next, a varnish for gravure ink [nitrified cotton (H-20:
Asahi Kasei Co., Ltd.) / Polyamide resin (S-1510: Sanyo Kasei Co., Ltd.) / Amide wax / Thinner weight ratio = 10/12/3/50], and take 75 parts of the above dispersion.
32 parts were added, and the mixture was vigorously stirred with a TK homodisper for 2 minutes.
The obtained ink did not show any agglomerated particles, and had good gloss, good adhesion, and good printability.

〔The invention's effect〕

The dispersant of the present invention has excellent fluidity and dispersion stability, and is suitable for obtaining a powdery solid dispersion.

Further, the dispersion of the present invention comprising the dispersant, the powdered solid, and the organic liquid has good compatibility with the vehicle polymer, and can be suitably used for various applications of paints and inks.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08G 63/685 C08G 63/685 C09C 3/10 C09C 3/10 C09D 167/00 C09D 167/00 ( 72) Inventor Masaru Tamura 2-5-7 Senrien, Toyonaka-shi, Osaka (56) References JP-A-61-163977 (JP, A) JP-T-62-501013 (JP, A)

Claims (6)

(57) [Claims] 1. A higher monocarboxylic acid containing a hydroxyl group, comprising 1 mol of tris (hydroxyethyl) isocyanurate.
To a product obtained by esterification with 0.5 to 20 mol and 0 to 2 mol of a hydroxyl group-free higher monocarboxylic acid, 0.1 to 1 equivalent of a higher monocarboxylic acid glycidyl ester per 1 equivalent of a hydroxyl group in the product is added. A dispersant comprising a modified polyester type compound obtained by ring-opening addition and then introducing an acidic group and / or a basic group. 2. The dispersant according to claim 1, wherein the hydroxyl group-containing higher monocarboxylic acid is ricinoleic acid or 12-hydroxystearic acid. 3. The dispersant according to claim 1, wherein the higher monocarboxylic acid glycidyl ester is neodecanoic acid glycidyl ester. 4. The dispersant according to claim 1, wherein the hydroxyl-free higher monocarboxylic acid is a chain monocarboxylic acid having 8 to 22 carbon atoms, a branched monocarboxylic acid and / or a cyclic monocarboxylic acid. 5. A hydroxyl group-containing higher monocarboxylic acid containing 1 mol of tris (hydroxyethyl) isocyanurate.
To a product obtained by esterification with 0.5 to 20 mol and 0 to 2 mol of a hydroxyl group-free higher monocarboxylic acid, 0.1 to 1 equivalent of a higher monocarboxylic acid glycidyl ester per 1 equivalent of a hydroxyl group in the product is added. A dispersion comprising a dispersant comprising a modified polyester type compound obtained by ring-opening addition and then introducing an acidic group and / or a basic group, a powdery solid and an organic liquid. 6. The dispersion according to claim 5, wherein the powdery solid is an organic or inorganic pigment having a particle size of 20 μm or less.