JPH0363426B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a metal soap that has excellent physical and chemical stability, such as dispersion stability against mechanical shock, stability over time due to temperature, and dispersion stability when repeatedly frozen and thawed, and does not deteriorate in water repellency. It relates to an aqueous dispersion. Fatty acid metal soaps, especially higher fatty acid metal soaps, have strong water repellency and are used in the building materials field as waterproofing agents for building materials based on cement, mortar, plaster, and calcium silicate. In the pulp field, it is used as an anti-dusting agent, a lubricant, and a viscosity modifier for color coating liquids during the production of coated paper. However, metal soap itself has strong water repellency, so
Since it hardly disperses in water, attempts have been made to make it easier to disperse in water by using surfactants. Recently, for example, in JP-A-57-84730, a method using a surfactant, a maleic anhydride copolymer salt, and a liquid oil, and in JP-A-57-77,642, the lipophilic group is nonylphenol or higher alcohol. Patent applications have been filed for methods of mechanically reducing particles to improve dispersibility in the presence of nonionic or anionic surfactants, which are residues of metal soaps obtained by these methods. The physical and chemical stability of aqueous dispersions is still not sufficient. That is,
When an aqueous dispersion of metal soap is pumped or circulated using a pump, the dispersion system is destroyed and separation or aggregation occurs. Or an increase in viscosity is observed during long-term storage. Foods that are frozen during storage in cold regions, etc. are thawed before use. While repeating this operation, the dispersion system breaks down and separation occurs, which poses a problem in workability. If a large amount of surfactant is used to improve these drawbacks, the water repellency, which is a characteristic of metal soaps, will be reduced, making it impossible to obtain a satisfactory result. Furthermore, the type of surfactant has an influence on various properties in use. In other words, when using a nonionic surfactant (A) to which ethylene oxide is added, stability at low temperatures is good, but stability is poor at high temperatures due to the clouding point, and the foaming is large. There are drawbacks. On the contrary, anionic surfactants (B) such as ABS and α-olefin sulfonic acid type have good stability at high temperatures, but have the drawbacks of poor stability at low temperatures and large foaming. Further, when soap (C) which is an alkali metal salt of a fatty acid is used, the stability and water repellency are good over time, but even if it is used alone, it does not have an emulsifying effect and is not suitable for use. Nonionic or anionic surfactants have emulsifying and dispersing performance even when used alone, but
It has the disadvantage of poor stability over time. The above surfactant (A), (B) alone, or (A+
Although an aqueous dispersion of metal soap can be obtained by using it as a mixed surfactant like B), (A+C), and (B+C), physical and chemical stability is poor in all cases. (A+B) When mixed surfactants of , (A+C), and (B+C) are used, the physical and chemical stability is slightly better than when each of (A) and (B) is used alone, but in either case. What is common to both is that the viscosity of an aqueous metal soap dispersion changes significantly over time, and the dispersion system becomes unstable and loses fluidity after 7 to 15 days. When mechanical impact is applied, the dispersion system becomes unstable and loses fluidity in 5 to 7 days, making it impractical. In order to improve the drawbacks of the conventional aqueous dispersions of metal salts, the present inventors conducted intensive research and found that the following (A), (B), (C) It has been discovered that by using a mixture of surfactants from the three groups described above, it is possible to obtain an aqueous dispersion of metal soap that has excellent physical and chemical stability and does not deteriorate in water repellency. Taking the composition as 100% by weight, 38 to 60% by weight of metal soap, 35 to 60% by weight of water, and as a surfactant (A) ethylene oxide added to alkylphenol, alkyldiol, higher alcohol, or castor oil. 0.5 to 2.5% by weight of at least one selected from the group of compounds obtained; (B) an alkali metal salt of dialkyl sulfosuccinic acid, an alkali metal salt of alkyl sulfonate;
(C) 0.5 to 2.5% by weight of at least one selected from the group consisting of an alkali metal salt of alpha olefin sulfonate and ABS; (C) 0.5 to 2.1% by weight of an alkali metal salt of a fatty acid; and (A) a surfactant. An aqueous dispersion of metal soap consisting of a total amount of +(B)+(C) of 1.6 to 6% by weight, of which the percentage of (A)+(B) is 60 to 80%. The body is physically
We have now completed the present invention by discovering that it is an aqueous dispersion of metal soap that has excellent chemical stability and no decrease in practical water repellency, and is improved in all aspects. The metal salts used in the present invention include Ca, Mg, Zn, Fe, Al, and Ag salts of fatty acids having 8 to 22 carbon atoms;
Fatty acids include caprylic acid, capric acid, lauric acid, oleic acid, myristic acid, palmitic acid, stearic acid, behenic acid, ricinoleic acid, 12
-Hydroxystearic acid, etc., and these fatty acids may be used alone or in combination of two or more.
Further, the metal salt can be obtained by known methods such as double decomposition method and direct reaction method. The surfactants used in the present invention include (A) an ethylene oxide adduct of nonylphenol, dodecylphenol or octylphenol (3 to 20 moles of ethylene oxide), a castor oil ethylene oxide adduct (as an alkylphenol ethylene oxide adduct); 5 to 25 moles of ethylene oxide),
Examples of ethylene oxide adducts of higher alcohols include octyl alcohol, lauryl alcohol, oleyl alcohol, myristyl alcohol, and stearyl alcohol ethylene oxide adducts (number of moles added is 5 to 20). As an ethylene oxide adduct of linear glycol,

[Formula] (R=C _10-16 ) is used as a raw material and 10-40 moles of ethylene oxide is added thereto, and these can be used alone or in a mixture of two or more. (B) As the alkali metal salt of dialkylsulfosuccinic acid, Na and K salts of sulfosuccinic acid having an alkyl group of butyl, octyl, or lauryl can be used. Sulfates of higher alcohols include Na and K salts of sulfates of higher alcohols such as octyl alcohol, lauryl alcohol, oleyl alcohol, and stearyl alcohol, AOS (alpha olefin sulfonate), and ABS (alkylbenzene sulfonate). can be used alone or in combination of two or more. (C) Alkali metal salts of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid,
There are Na and K salts of fatty acids such as palmitic acid, stearic acid, oleic acid, and ricinoleic acid, and these can be used alone or in combination of two or more. The total amount of the above-mentioned surfactants (A) + (B) + (C) is 1.6 to 6% by weight based on 100% by weight of the aqueous dispersion of metal soap. If the total amount of surfactants is less than 1.6%, it is difficult to obtain an aqueous dispersion of metal soap, and there is almost no practical use.
Moreover, even if 6% or more is added, the physical and chemical stability and water repellency properties and performance of the aqueous dispersion of metal soap that the present inventors are aiming for cannot be obtained, but rather the water repellency is decreased, There are disadvantages such as easy foaming. In other words, if (B) is less than 0.5% or (C) is less than 0.5%, the resulting aqueous dispersion of metal soap will not have satisfactory physical and chemical stability;
If the content of (C) is 2.5% or more, or if (C) is 2.1% or more, the aqueous dispersion of metal soap will foam violently and the water repellency will decrease. When coated with an aqueous dispersion of metal soap, the strength of the dried film decreases and phenomena such as cracking are observed, which is not desirable. The amount of water contained in the aqueous dispersion of metal soap of the present invention is 35 to 60%, and if it is less than 35%, the resulting aqueous dispersion has a high viscosity and almost no fluidity, and is difficult to manufacture.
It is not desirable because it has problems in handling during use. In addition, if the water dispersion is above 60%, the intended performance and properties of the water dispersion can be obtained, but transportation costs will increase and costs will increase, and when used as a paper processing agent, paper processing manufacturers will not be able to save energy. From the point of view of speed-up, etc., there is a tendency to reduce the water concentration of the processing chemical adjustment bath in order to speed up drying. Therefore, from the viewpoint of the intended use, an aqueous dispersion of metal soap containing a large amount of water is not very preferable. To obtain the aqueous dispersion of metal soap of the present invention, a water-containing cake of metal soap obtained by double decomposition of a sodium salt of a fatty acid and a metal chloride or metal hydroxide by a known method, or a metal soap obtained by drying the metal soap itself. A method in which a powder or a powder of a metal soap obtained by directly reacting a fatty acid with a metal hydroxide or a metal chloride by a known method is added to an aqueous solution in which a surfactant is dissolved while stirring; There is a method in which fatty acids, surfactants, and water are heated and dissolved, and then metal hydroxide or chloride is added while stirring. Either method results in an aqueous dispersion of metal soap with particles of 10μ or less. However, if necessary, a homogenizer or the like may be used to make the particles even smaller. Examples of the homogenizer include TK homomixer, TK pipeline homomixer, super mycolloider, high-pressure homogenizer, and the like. The metal soap aqueous dispersion of the present invention is obtained by the following manufacturing method, which will be described below. [ ]: A fatty acid metal salt obtained from a fatty acid sodium salt and a metal chloride by a double decomposition method was thoroughly washed with water, and then centrifugally dehydrated to obtain a fatty acid metal salt with a water content of 35 to 40%. Separately, while stirring a mixed aqueous solution of water and a surfactant selected from each of Groups A, B, and C, the hydrated metal salt of fatty acid obtained above was gradually added to form an aqueous dispersion of metal soap. obtain. [ ]: Put a mixed aqueous solution of water and a surfactant selected from each of Groups A, B, and C into a reactor, and add 80 to 85
Add the fatty acids while stirring at °C. A metal hydroxide is gradually added to this and reacted. After addition,
Stirring was continued for 12 hours to complete the reaction and obtain an aqueous dispersion of metal soap. []: A commercially available fatty acid metal salt is replaced with the fatty acid metal salt of the method [], and the following is the same method as [] to obtain an aqueous dispersion of metal soap. An aqueous dispersion of metal soap can be obtained by the above methods [], [], and [], using a homogenizer if necessary. Using the aqueous dispersion of metal soap obtained by the above method, the following physical and chemical stability, foaming and water repellency tests were conducted. (1) Dispersion stability against mechanical impact The viscosity of the aqueous metal soap dispersion 3 was measured (using a B-type viscometer) after circulating it at 20° C. for 60 minutes using a 1/min gear pump. In addition, the temperature was 105℃ for the purpose of examining the degree of particle aggregation due to gelation, etc.
300 g of the aqueous dispersion of the metal soap was filtered under reduced pressure using a 300 mesh standard sieve that had been dried to a constant weight at After cooling to room temperature, the weight was measured, and the filtration residue was determined using the following formula. Filtration residue (%) = (weight after filtration and drying)
- (Weight before filtration) / 300 g × (concentration of aqueous dispersion of metal soap / 100) × 100 (2) Dispersion stability over time Using Coolnics, each at 5°C and 25
The viscosity (using a B-type viscometer) of an aqueous dispersion of metal soap was measured when it was left at 40°C for 6 months. Using the sample, the filtration residue was measured in the same manner as in (1). (3) Dispersion stability when repeatedly frozen and thawed An aqueous dispersion of metal soap is left to freeze at -15°C for 30 hours, taken out, and left to stand in an atmosphere at 25°C to thaw. This was counted as one time, and the viscosity when this was repeated five times (using a B-type viscometer) and the filtration residue were measured using the sample by the method described in (1). (4) High temperature stability The aqueous dispersion of metal soap was placed in a second flask equipped with a water cooler, thermometer, and stirrer, and heated to 80°C.
After stirring at 300 RPM for 4 hours, the viscosity of the sample was naturally cooled to 25°C (using a B-type viscometer) and the filtration residue was measured using the method described in (1). (5) Foaming test Add water to an aqueous dispersion of metal soap to make a dispersion with a metal soap concentration of 2%. Pour 50ml of this liquid into a 250ml stoppered graduated cylinder and use a shaker (YAMATO Shaker Model SA-31) for 3 minutes.
It was shaken for a minute and the amount of foam was measured. (6) Water repellency Water dispersion of metal soap (solid content concentration 30%)
A glass plate measuring cm x 20 cm was coated with a thickness of 0.25 mm, dried at 110°C for 60 minutes, and then heated at 20°C for 40 minutes.
After 24 hours under %RH condition, apply 0.01ml to the coated surface using a micro cylinder.
Water droplets were placed on five locations, and the spread of the water droplets was visually judged. The criteria for determining water repellency are as follows: ○: Water droplets hardly spread △: Water droplets spread slightly ×: Water droplets spread quickly The present invention will be explained below with reference to measurement examples. Tables 1 to 3 show the compositions of the metal soap aqueous dispersions used in the measurement examples, the types of metal soaps used therein, and the types of surfactants used therein. Table 4 shows the viscosity (25℃, CPS) before the test and after each of the following tests (dispersion stability against mechanical shock, dispersion stability after repeated freezing and thawing, high temperature stability).
Also, the results of measurement of filtration residue (%), foaming test (cc), and water repellency are shown. In addition, Table 5 shows the temperature immediately after production (0 day), 15 days, 30 days, 90 days, and 180 days under three conditions of temperature 5, 25, and 40℃.
Table 5 shows the results of measuring the viscosity (25°C, cps) and filtration residue (%) of the metal soap aqueous dispersion after a day of aging.

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[Table] (c) High temperature stability test

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Claims (1)

[Claims] 1 Composition: 38-60% by weight of metal soap, 35-60% by weight of water
60% by weight, and as a surfactant, (A) 0.5 to 2.5% of at least one selected from the group of compounds obtained by adding ethylene oxide to one selected from alkyl phenols, alkyl diols, higher alcohols, and castor oil. % by weight, (B) alkali metal salt of dialkyl sulfosuccinic acid, alkali metal salt of alkyl sulfonate,
(C) 0.5 to 2.5% by weight of at least one selected from the group consisting of an alkali metal salt of alpha olefin sulfonate and ABS; (C) 0.5 to 2.1% by weight of an alkali metal salt of a fatty acid; and (A) a surfactant. The total amount of + (B) + (C) is 1.6 to 6% by weight, and of that (A) + (B)
An aqueous dispersion of metal soap in which the percentage of the amount of is 60 to 80%.