JPS59142834A - Manufacture of nonaqueous dispersion liquid of ultrafine carbonate particles - Google Patents

Abstract

PURPOSE:To manufacture quickly the titled nonaqueous dispersion liquid by blowing CO2 in the phase incorporating four components consisting of water, polyoxyethylene-type nonionic surface-active agent, metallic hydroxide and nonpolar org. liquid, or five components obtained by adding alkanol in addition to said components. CONSTITUTION:Carbon dioxide is blown in the W/O microemulsion phase incorporating four components consisting of water, polyoxyethylene-type nonionic surface-active agent, metallic hydroxide (e.g. barium hydroxide), nonpolar org. liquid (e.g. kerosene) or five components consisting of water, polyoxyethylene- type nonionic surface-active agent, metal hydroxide, nonpolar org. liquid and alkanol. By this method, the larger reaction rate compared with the conventional method is attained and ultrafine carbonate particles which have not been obtained by any conventional method can be obtained.

Description

Detailed Description of the Invention Technical Field The present invention relates to a method for producing a non-aqueous dispersion of ultrafine carbonate particles useful as fillers, colorants, etc. or the attached ultrafine particulate carbonate is dispersed in a water-insoluble non-aqueous solvent (containing the surfactant).

Prior Art Conventionally, carbonate inorganic pigments used as fillers in rubber, plastics, etc., or coloring agents in printing inks, paints, etc., are generally produced by blowing carbon dioxide into an aqueous solution of metal hydroxide, or by injecting carbon dioxide into an aqueous solution of metal hydroxide. - Surfactant - It is carried out by reacting two types of electrolytes, namely CaCl2 and Na2 COB or CO, in an O/W emulsion phase of a non-polar organic liquid (water-insoluble non-aqueous solvent) system. However, the reaction rate of the former method is slow, and the carbonate obtained by either method is amorphous or coarse particles, so it is impossible to maintain a stable dispersion state in a non-aqueous solvent containing a surfactant. For example, when used as a coloring agent in printing ink for inkjet recording, it clogs jet nozzles.

Objective The first objective of the present invention is to provide a method for rapidly producing a non-aqueous dispersion in which carbonate is extremely stably dispersed in a non-aqueous solvent containing a surfactant.

A second object of the present invention is to provide carbonate inorganic pigments that are ultrafine and therefore do not clog inkjet nozzles.

Structure The method for producing a non-aqueous dispersion of ultrafine carbonate particles according to the present invention uses four components: water, polyoxyethylene type nonionic surfactant, metal hydroxide, and non-polar organic liquid, or water-polyoxyethylene type non-ionic surfactant. It is characterized by blowing carbon dioxide into a W10 microemulsion/phase containing five components: ionic surfactant - gold maple hydroxide - non-polar organic liquid - alkanol.

The method of the present invention thus includes W containing the four or five components.
10 by simply bubbling carbon dioxide into the microemulsion phase. The temperature of the reaction system is -30 to +80
The temperature is preferably about 0.degree. C., and more preferably room temperature.

The metal hydroxide used in the present invention may be any compound that can become a water-insoluble carbonate by reaction with carbon dioxide, such as BIL(oH)t
+ Mg (OH) 2 * Ca (OH) 2 and the like.

Examples of polyoxyethylene type nonionic surfactants include the following.

(1) R' building 0 ÷ CH, CH, O large H (however, R1
is an alkyl group having 1 to 20 carbon atoms, preferably 6 to 20 carbon atoms, and is particularly preferably an unsaturated alkyl group or a side chain alkyl group. n is 1 to 20, preferably 1 to 6 to io. ) (2) R'0(-CH2CH20+n, H (however,
R1 is the same as in general formula (1) above.

n' is preferably 1 to 20 degrees or preferably 4 to 1 degrees. )(31C
HOCO-R2 HOH TomiH20 (However, R2 is an alkyl group having 8 to 20 carbon atoms, preferably an unsaturated alkyl group, (li11 chain alkyl group.) (41R3C0+CH,CH,0-)HOH (however, ,R
11 is an alkyl group having 4 to 2 carbon atoms, preferably 8 to 18 carbon atoms, particularly preferably an unsaturated alkyl group or a side chain alkyl group. n is the same as in general formula (1) above. )(5) ++ OH (R2 is the same as the general formula (3) above.) f6
J HO(C2H40)n-'(CsHsO)m-(
Ct)I40). -H (However, n is 1 to 10, preferably 1 to 3, and m is 5 to 20, preferably 5 to 10.) The above nonionic surfactants may be used alone or in combination of two or more. used.

The non-polar organic liquid serves as a dispersion medium for the non-aqueous dispersion together with water, and various water-insoluble non-aqueous solvents can be used. Specifically, petroleum hydrocarbons such as kerosene and Isopar H (trade name, manufactured by Esso Standard Oil Co., Ltd.); other hydrocarbons such as hexane, octane, cyclopentane, benzene, toluene, and xylene; carbon tetrachloride, trichloroethylene, Halogenated hydrocarbons such as tetrachloroethane and Schiff's benzene; ethers such as diethyl ether and isoprogyl ether; esters such as ether acetate, propyl acetate, and phenyl acetate;
Examples include alcohols such as octyl alcohol, nonyl alcohol, tepyl alcohol, and benzyl alcohol. These can be used alone or in combination of two or more.

The alkanol has the general formula ROH (where R is 1 carbon number).
-20, preferably 1-1o alkyl group, unsaturated alkyl group or side chain alkyl group).

The preferred composition for carrying out the method of the present invention is as follows. First, the concentration of nonionic surfactant is 0.05 to 0.3.
The concentration of the metal hydroxide is in the range of 9 to 9 mol/l, and the concentration of the metal hydroxide is below the saturation concentration of the water used. The concentration of water depends on the type and amount of nonionic surfactant used, but is within a range that can be solubilized in the composition liquid. The concentration of alkanol is θ~
The range is 0.2 mol/9. It goes without saying that the concentration of carbon dioxide should be no higher than 7.0 to bring the pH of the composition liquid to 7.0.

As described above, according to the method of the present invention, particles having a specific nonionic surfactant adsorbed or attached to the surface have a diameter of 30 to 100
(In case of uphill diameter, 30~200X, length 200~t
0, ooo

Effects The method of the present invention not only has a faster reaction rate than conventional methods using an aqueous medium, but also makes it possible to easily obtain ultrafine particulate carbonate by a simple blowing method, which could not be obtained by conventional methods. can. Therefore, this carbonate has extremely good dispersibility in surfactant-containing non-aqueous solvents, in addition to the fact that the surface is coated with a surfactant. Furthermore, since it is in the form of ultrafine particles, it does not clog jet nozzles even when used as a coloring agent in printing ink for inkjet recording, making it highly reliable. Therefore, the carbonate or its non-aqueous dispersion obtained by the method of the present invention can be used as a coloring agent for printing ink (for IP!J and inkjet recording), paint, toner of electrophotographic liquid developer, etc. It is extremely useful as a filler for rubber, plastics, etc., which require high transparency, as a coating agent for plastics, glass, etc., and as an ultrafine powder for various uses.

Example 1 After solubilizing an aqueous solution of Ba(OH)2 in a 0.1 mol/Kg cyclohexane solution of polyoxyethylene nonylphenyl ether (average number of ethylene oxide groups: 6), carbon dioxide was added into the solution at 25°C. was blown through a glass filter until the pH of the solution reached 70 to produce a non-aqueous dispersion of B a CO3. The reaction was stopped by injecting nitrogen gas and gold.

Next, BaCO3 was precipitated from this BaCO, non-aqueous dispersion using an ultracentrifuge, washed several times with ethanol to remove the activator, and then dried to obtain BaCO3 of the same shape. The conversion rate was 99%.

Further, the same 13aCO3 nonaqueous dispersion was passed through a cellophane dialysis membrane, and the resulting BaCO3 was washed with ethanol using a Soxhlet extractor to remove the activator, and then dried to obtain solid BaCO3.

On the other hand, for comparison, a cyclohexane solution of polyoxyethylene nonylphenyl ether was prepared using Ba(
B was prepared using the same method as in this example except that B was solubilized.
A (Co,) aqueous dispersion was prepared.

Thereafter, Ba(CO3) was separated using an ultracentrifuge in the same manner as described above, and the activator was removed to obtain solid BaCO3.

The relationship between the BaCO5 production rate and the carbon dioxide blowing time in the above Examples and Comparative Examples is shown in the accompanying diagram.

The non-aqueous dispersion of the present invention did not cause sedimentation or aggregation even when left at room temperature for 6 months.

Example 2 Ba(Co3) was prepared in the same manner as in Example 1 except that methanol was further solubilized in addition to water and Ba(OH) in a cyclohexane solution of polyoxyethylene nonylphenyl ether, and the following component concentrations were used. A non-aqueous dispersion was prepared. The concentrations of each component at this time are as follows.

Polyoxyethylene nonylphenyl ether degree 20.
9 to 1 mol/Water concentration: 0.1 to 720 mol/Kq range Ba(oH)
Concentration (as an aqueous solution): 0.2 mol/Kg methanol 2005 mol/9 As a result, BaCO3 particles with a particle size of 30 to 50X were obtained. The conversion rate was 99%. The dispersion stability of the non-aqueous dispersion of this example was as good as that of Example 1.

Example 3 BaC was prepared in the same manner as in Example 1 except that the following component concentrations were used.
A non-aqueous dispersion of O3 was prepared.

Polyoxyethylene nonylphenyl ether concentration:
0.10-eA-/Kq water concentration 20.1-720 mol/
Range of garlic BIL(OH)2 concentration (as aqueous solution):
In this reaction system, 9°Ba (OR
)z6 degrees (as an aqueous solution) 0.2 mol/Kq(7)
In the system, Ba(CO3) particles have a diameter of 30X and a length of 3000
It was obtained in the shape of a rod. Similarly, at a water concentration of 720 m/L7/, 9° Ba(OH), (as an aqueous solution) a concentration of 02 m)v
/ In the K9 system, BaCO3 particles have a diameter tooX,
It was obtained in the form of a rod with a length of zoooX. In addition, in a system with a water concentration of 90 mol/Ky rBa (OH) concentration of 0.1 mol/Kg, 13acO3 has a diameter of 30X and a length of 30.0OOX.
It was obtained in the form of a line. The dispersion stability of the non-aqueous dispersion of this example was as good as that of Example 1.

[Brief explanation of the drawing]

The figure is a diagram showing the relationship between the production rate of B a CO3 and the amount of carbon dioxide blown in Example 1 and Comparative Example. Curve a...Example 1 Curve b...Comparative example co2o'K if (mff/rr 50 to 12B (OH)2 y'<Name (company)

Claims (1)

[Claims] 1. Water - polyoxyethylene type nonionic surfactant -
Blowing carbon dioxide into the W10 microemulsion phase containing metal hydroxide-non-polar organic liquid, or water-polyoxyethylene-type nonionic surfactant-metal hydroxide-non-polar organic liquid-Alkatsuru'nol. A method for producing a non-aqueous dispersion of ultrafine carbonate particles, characterized by: