JPH01228502A - Method for crystallizing fat and oil - Google Patents

Abstract

PURPOSE:To efficiently obtain high-purity pearl-like crystalline substance by heating and dissolving fats and oils having m.p. not lower than 30 deg.C which have been dispersed in a dispersion medium and thereafter lowering the temp. while making ultrasonic wave act on the dispersion medium and depositing crystalline fats and oils. CONSTITUTION:Fats and oils having m.p. not lower than 30 deg.C are dispersed in a dispersion medium and heated to dissolve them. Then the temp. is lowered while making ultrasonic wave act on this dispersion medium and crystalline fats and oils are deposited. As the above-mentioned fats and oils, higher alcohol, fatty acid, ester of fatty acid, ester of polyalcohol, fatty acid amide and acylated amino acid, etc., are utilized. As the dispersion medium, water, methanol, ethanol, glycerin, ethylene glycol, sorbitol, 1,3-butylene glycol, etc., are utilized. As the ultrasonic wave made to act, 1-100kHz is preferably utilized.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for crystallizing fats and oils, and more particularly to a method for crystallizing fats and oils using ultrasonic waves when precipitating fats and oils into crystals.

[Prior art and its problems] Oils and fats usually become amorphous solids when simply cooled after being melted, but such amorphous solids have few uses. However, when oils and fats crystallize, their purity improves,
Because it has a beautiful crowbar-like appearance, its uses are expanding. In particular, oils and fats have been used as pearlizing agents in cosmetics and cosmetics, and from the standpoint of high added value to products, it is becoming increasingly important to establish base materials that can produce such beautiful appearances and the technology for using them. It is coming.

Conventionally, the crystallization technology for such oils and fats involves dissolving oils and fats such as esters in a large amount of aqueous surfactant solution (almost the same amount), then heating to uniformly dissolve the whole, and then
Most of the methods involved gradually lowering the temperature to crystallize into a pearl state. Also, the oils and fats that can be used at this time are:
Most are polyhydric alcohol esters with 16 to 18 carbon atoms,
Other oils and fats are difficult to crystallize and are virtually unused.

Furthermore, according to the conventional method described above, it is essential to use a large amount of surfactant, so if the surfactant used at this time is anionic, the burl-shaped crystallized substance that is precipitated will also be anionic. The crystallized product obtained in this way can be used in product systems that have anionic active agents as the main ingredients, such as soyanpu, but cannot be used in products that have cationic or amphoteric active agents as main ingredients, such as rinses and treatments. The current situation was that there was no such thing.

Furthermore, in the conventional method described above, oils and fats exhibiting a pearl shape can only be obtained at a maximum concentration of about 30% of the surfactant solution, so it is difficult to efficiently obtain oils and fats exhibiting a pearl shape. was not possible.

As explained above, the conventional method of crystallizing pearly fats and oils has various limitations and cannot be called an excellent crystallization technique.

An object of the present invention is to provide a crystallization method that can efficiently precipitate highly pure pearl-like crystals and can be applied to many oils and fats.

[Means for solving problems]

As a result of intensive research, the present inventors have discovered that the above object can be achieved by precipitating fats and oils using ultrasonic waves.

The present invention is an ultrasonic crystallization method characterized by dispersing fats and oils having a melting point of 30° C. or higher in a dispersion medium, dissolving them by heating, and then applying ultrasonic waves to precipitate crystalline fats and oils. It provides: Although there are examples of ultrasonic irradiation technology being used for emulsification, dispersion, aggregation of fine particles, etc., it has never been applied to crystallization of fats and oils as in the present invention.

Next, the ultrasonic crystallization method of the present invention will be described in detail based on preferred embodiments.

First, a container equipped with an ultrasonic generator (preferably one with a simple stirring base for preliminary dispersion) is filled with a predetermined amount of dispersion medium, and the desired oil or fat with a melting point of 30°C or higher is poured into the container. and heat the dispersion medium to a predetermined temperature to dissolve the above-mentioned fats and oils.

The fats and oils used at this time are not limited to these, but are 5 to 50%, preferably 20 to 50%, based on the weight of the dispersion medium.
Dissolve 40% and completely dissolve below the boiling point of the dispersion medium. Therefore, the dispersion medium is appropriately selected depending on the melting point of the oil or fat used.

After the fats and oils are completely dissolved, the action of ultrasound is started under appropriate conditions and cooling begins. When cooling, if there is temperature unevenness in the solution, the crystallization state will become non-uniform.
In addition to stirring by ultrasonic action, it is desirable to stir the entire mixture using a simple stirrer such as the one described above, or to use a jacket-type container.

When cooling is continued while irradiating ultrasonic waves as described above,
Crystallization of fats and oils starts below the melting point of fats and oils in the dispersion medium. At the beginning of crystallization, the liquid is cloudy, but
As cooling continues, crystals gradually grow and the liquid takes on a burr-like appearance9.Normally, the temperature of the liquid is between 20 and 20°C.
Cool to 30°C. If the burr-shaped fats and oils crystallized in this way are left as they are, a portion of them will dissolve again, so the dispersion medium is removed by filtration or the like, and if necessary, the oil is dried. The oil and fat after drying also has a crowbar shape0
The crystalline fats and oils obtained according to the embodiment of the present invention described above exhibits needle-like, plate-like, etc. crystal shapes, but if a surfactant, which will be described later, coexists during crystallization, the crystals will not form due to the medicinal effect. It comes to show various shapes.

Furthermore, according to the method of the present invention, it is possible to produce crystalline fats and oils that have a burr shape and have a purity of 100% in a dry state. This can be said to be a significant technological improvement, considering that conventional products could only achieve purity of about 20% in surfactant solutions.

□As a practical method of using the crystalline fats and oils obtained by the method of the present invention, there is a method of imparting a crowbar-like appearance to the following products. This can be easily achieved by adding the above-mentioned crystalline fats and oils to each product and stirring.

For example, since it is possible to obtain a pearlizing agent that does not contain any impurities, products obtained by the same manufacturing method can be used simultaneously in an anionic shampoo agent and a cationic rinse agent. Dosage forms that can be used in this way include:
In addition to the above-mentioned shampoos, cleansing products that mainly use anionic activators such as facial cleansers, whole-body cleansers, soaps, etc., and in addition to the above-mentioned rinses, cationic activators such as treatments and conditioners are mainly used. An example is a finishing agent. In addition, dosage forms such as tonics, liquids, and blowing agents that contain large amounts of solvents, as well as various surfactants and oils,
Naturally, it can also be used in hair dyes, lipsticks, creams, foundations, etc. made by mixing powders, paints, etc.

Next, regarding the method of crystallizing oils and fats using ultrasound according to the present invention,
This will be explained in more detail.

The fats and oils to which the present invention is applied have a melting point of 30° C. or higher, and specific examples include higher alcohols, fatty acids, polyhydric alcohol esters, fatty acid amides, and acylated amino acids. The method of the present invention can be applied to one or more selected from the above oils and fats.

Specifically, the following compounds may be mentioned.

Higher alcohols: palmityl alcohol, stearyl alcohol, hehenyl alcohol, etc.

Fatty acids: palmitic acid, thearic acid, hehenic acid, etc.

Polyhydric alcohol esters: ethylene glycol distearate, diethylene glycol civalmitate, ethylene glycol monostearate, etc.

Fatty acid esters: myristyl myristate, cetyl palmitate, myristyl stearate, cholesteryl stearate, etc.

Fatty acid amides: palmitic acid monoethanolamide, stearic acid jetanolamide, hehenic acid monoethanolamide, etc.

Acylated amino acids: lauroylsarcosine, sodium lauroylsarcosine, sodium N-lauroylmethyltaurate, stearoylglycine, valmitoylalanine, etc.

There are no particular restrictions on the dispersion medium used in the present invention, but
One or more solvents selected from water and solvents such as methanol, ethanol, glycerin, ethylene glycol, sorbitol, 1,3-butylene glycol, and polyethylene glycol can be suitably used.

In addition, the above-mentioned dispersion medium has anionic properties as shown below,
Cationic, amphoteric or nonionic surfactants can be included. By including a surfactant in this way, it is possible to produce crystalline fats and oils with different properties such as pearl properties and dispersibility, so it is possible to use the crystalline fats and oils according to the dosage form.

The amount of surfactant used at this time is preferably in the range of 1 to 20%, more preferably 5 to 10%, based on the entire system.

Examples of preferred anionic surfactants include the following.

(2) A straight or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10-16.

■ Contains a linear or branched alkyl group or alkenyl group with an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide, propylene oxide, butylene oxide, ethylene oxide, toside, and propylene in one molecule. The ratio of oxide is 0.1/9.9 to 9.910.1 or ethylene oxide and butylene oxide are 0.1
/ alkyl or alkenyl ether sulfate added in a ratio of 9.9 to 9.910.1.

(2) Alkyl or alkenyl sulfate ester salts having an alkyl group or alkenyl group having an average carbon number of 10 to 20.

(2) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

(2) Alkanesulfonate having an average of lO to 20 carbon atoms in one molecule.

■ Ethylene oxide, propylene oxide, butylene oxide, having an alkyl group or alkenyl group with an average carbon number of 10 to 20, and an average of 0.5 to 8 moles per molecule;
Ethylene oxide and propylene oxide are 0.1/
The ratio of 9.9 to 9.910.1 or ethylene oxide and butylene oxide is 0.1/9.9 to 9.91.
Alkyl or alkenyl ether carboxylate added in a ratio of 0.1.

■R eye-CHCOOX.

C11, C00Y.

A succinic acid derivative represented by (wherein, R14 represents an alkyl group or alkenyl group having 6 to 20 carbon atoms, and X, Y each represents an ion).

Counter ions for these anionic surfactants include alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium and magnesium; ammonium ions; and 1 to 3 alkanol groups having 2 or 3 carbon atoms.
Specific examples include alkanolamines (eg, monoethanolamine, jetanolamine, triethanolamine, triisopropanolamine, etc.).

(2) α-Sulfone fatty acid salts or esters having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms.

(2) N-acylamino acid type surfactant having an acyl group having 8 to 24 carbon atoms and a free carboxylic acid residue.

[Phase] A phosphoric acid ester represented by the following general formula (1) or (II).

RI-(OCH! CHz), -0-P-OY ・
(1) represents a salt of an alkanolamine having a hydroxyalkyl group of 151. and represents a number from 0 to 10, respectively).

The above-mentioned phosphoric acid ester surfactant is preferably one in which the number of moles of ethylene oxide added is 0 to 3, particularly without ethylene oxide added, and with a carbon number of 12 to 3.
Preferably, those having 14 alkyl groups include sodium mono- or di-lauryl phosphate, potassium mono- or di-lauryl phosphate, mono- or di-lauryl phosphate,
or jetanolamine dilauryl phosphate, mono or triethanolamine dilauryl phosphate, mono or sodium similistyl phosphate, mono or potassium similistyl phosphate, jetanolamine mono or similistyl phosphate, mono or triethanol similistyl phosphate Examples include amines. This phosphate ester surfactant contains the compounds represented by the above formula (1) and formula (II) in a weight ratio of 10:0 to 5:5, particularly 10:O to 7.
Preferably, it is used as a mixture in a ratio of:

Examples of preferred cationic surfactants include the following.

A cationic surfactant represented by the following formulas (i) to (iii).

(In the formula, at least one of R2S, Ro, R2? and RZa represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, the others represent an alkyl group having 1 to 5 carbon atoms, and Xo represents a halogen atom. , ) (In the formula, Rzs, Ro, R2? and Xo have the above meanings.) (In the formula, nzs, Rlk and Xo have the above meanings, and R29 represents an alkylene group having 2 to 3 carbon atoms. and also
, means an integer from 1 to 20. ) Preferred nonionic surfactants include the following.

(2) Adducts of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and a total of 1 to 30 moles.

(The ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9.910.
1).

(2) Polyoxyethylene alkylphenyl ether having an alkyl group having an average carbon number of 8 to 12 and to which 3 to 12 moles of ethylene oxide is added.

■Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the following formula.

(In the formula, R36 represents H or cHl, and Rlt is an alkyl group or alkenyl group having 10 to 20 carbon atoms. 7 is an integer of 1 to 3. 5 is an integer of 0 to 3) ■ Average number of carbon atoms Fatty acid glycerin monoester consisting of 10-2o fatty acid and glycerin.

Examples of preferred amphoteric surfactants include the following.

■Alkylamine oxide represented by the formula below.

(In the formula, RIS is an alkyl group or alkenyl group having 10 to 2 carbon atoms, and R16 and R1'l are alkyl groups having 1 to 3 carbon atoms, and may be the same or different.) Preferably, RIS has 12 to 16 carbon atoms, and Rlk and R1ff are methyl groups.

■Quaternary ammonium salt represented by the formula below.

(In the formula, RI9 represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, R16 and Rlt are alkyl groups having 1 to 4 carbon atoms, 1. is an integer of 1 to 3, and X is C00- or -S.O.
, - group) Among these, RI9 has 12 to 16 carbon atoms, Rzo and Rl
Preferably, t is 1 or 3 methyl groups.

■ α-position addition type, secondary amide, or
A class amide type imidacillin amphoteric surfactant.

■Betaine type amphoteric surfactant represented by the following general formula.

(i) R11-N''-R2゜-000-■ R1 drop (wherein RII is an alkyl group, alkenyl group, β-hydroxyalkyl group, or β-hydroxyalkenyl group having 8 to 24 carbon atoms, R,9 represents an alkyl group having 1 to 4 carbon atoms, and R2゜ represents an alkylene group or hydroxyalkylene group having 1 to 6 carbon atoms.) (C, H, O)□11 (it) Rts N' R1゜-C00-
(CIH40) 1H (In the formula, Rts, Rz. and □ have the above meanings.) Rlt (if) Rts-N"-R,, -COO-ZI (In the formula, Rts and R2゜ have the above meanings. and R1
゜ represents a carboxyalkyl group or a hydroxyalkyl group.) Counter ions for the anionic residues of these surfactants include alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium and magnesium;
Ammonium ion; Alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (eg, monoethanolamine, jetanolamine, triethanolamine, triisopropanolamine, etc.) can be mentioned. Examples of counter ions for cationic residues include halogen ions such as chlorine, bromine, and iodine, and methosulfate and saracalinate ions.

Particularly preferred among the above surfactants are linear or branched alkyl sulfate salts having an average carbon number of 10 to 16, or polyoxyethylene alkyl sulfate salts having an alkyl group having an average carbon number of 8 to 20 ( anionic surfactants such as alkyl phosphoric acid esters having an average number of carbon atoms of 8 to 16, or olefin sulfonates having an average number of carbon atoms of 10 to 16, an average number of carbon atoms of 10
These include nonionic surfactants such as higher fatty acid mono- or dialkanolamides having an alkyl group of ~14, alkylamine oxides having the same average carbon number, alkyl betaines, and ionic surfactants derived from imidapurine.

The ultrasonic wave used in the present invention has a frequency of 1 to
100k11. It is preferably in the range of 10 to 6
A range of 0 kL is more preferable.

To explain the above ultrasonic waves in more detail, the oscillator type can be either a horn type or a bathtub type. There are two important conditions for ultrasonic processing: output and frequency.Of these, the frequency can be selected from the above range, and the output varies depending on the processing capacity, so it can be changed each time. Appropriate values are selected. As an example, for an experimental level (100-1000a+ff1), 100-300- can be given, and for a medium processing capacity (Equation 1), 300-1200- can be given.

If the processing capacity becomes larger than this, it can be implemented by using an oscillator with a large output or by combining multiple single oscillators. Moreover, in processing, it is possible to perform the processing in a batch manner, but it is also possible to perform the processing by continuously combining a plurality of oscillators. Moreover, the above-mentioned ultrasonic waves may be applied continuously until the fats and oils are completely cooled after heating and melting, or may be applied intermittently as necessary. Note that the method of ultrasonication varies depending on the type of oil and fat to be applied, the dispersion medium, surfactant, etc. used at that time, and specific differences will be illustrated in the following examples.

The present invention will be specifically explained below with reference to Examples.

Example-1 In a glass container with a volume of 1 liter, 300 g of ethylene glycol distearate and 500 g of ethanol (9
5 shi/shichi) was added and heated to 50°C to uniformly dissolve. After melting, the container was immersed in a 50°C water bath of an ultrasonic oscillator with an output of 100°C, and then an ultrasonic wave with a frequency of 25kHz was oscillated while maintaining the temperature at 50°C.
The water around the outer periphery of the container was started to be cooled down to 30° C. while the ultrasonic waves were being oscillated, thereby obtaining a crystalline oil and fat exhibiting a burr shape.

The crystals were separated by filtration and completely dried in a vacuum dryer. The crystalline fats and oils thus obtained were plate-like or hexagonal-shaped crystals of 10 to 20 μm.

Example-2 Put 100g of stearyl alcohol, 100g of ethylene glycol distearate, 10g of sodium lauryl sulfate, and 500g of ethanol (95v/νχ) into a glass container with a volume of 1 liter, and heat to 55°C to uniformly dissolve them. I let it happen. After melting, the container was immersed in a water tank at 55°C using an ultrasonic oscillator with an output of 100°C, and then, while maintaining the temperature at 55°C, an ultrasonic wave with a frequency of 19kl+ was oscillated. Cooling was started, and the mixture was cooled to 20° C. while the ultrasonic waves were being oscillated to obtain crystalline fats and oils exhibiting a pearl shape. The crystals were separated by filtration and completely dried in a vacuum dryer. The crystalline fats and oils thus obtained were needle-shaped crystals of 5 to 10μ.

Example-3 In a stainless steel container with a volume of 5 liters, 300 g of ethylene gelcol distearate, 200 g of stearoylglycine, and 3000 g of ethanol (95 v/vχ)
was added and heated to 55°C to uniformly dissolve. After dissolving,
The container was immersed in a 55°C water bath of an ultrasonic oscillator with an output of 120H, and then a frequency of 40°C was immersed while maintaining the temperature at 55°C.
kHz ultrasonic waves were oscillated. Next, the water around the outer periphery of the container began to be cooled, and was cooled to 20° C. while oscillating ultrasonic waves, to obtain pearl-like crystalline fats and oils. The crystals were separated by filtration and completely dried in a vacuum dryer.

The crystalline fats and oils obtained in this way are plate-shaped with a thickness of 10 to 30 μm.
It was a crystalline substance.

[Effects of the Invention] According to the method for crystallizing oils and fats of the present invention, it is possible to efficiently precipitate high-purity pearl-like crystals used as pearlizing agents in cosmetics and the like for a wide range of oils and fats.

Claims (6)

[Claims] (1) Oils and fats having a melting point of 30°C or higher are dispersed in a dispersion medium, heated and dissolved, and then cooled while applying ultrasonic waves to precipitate crystalline fats and oils. Crystallization method. (2) Crystalline fats and oils according to claim (1), wherein the fats and oils are one or more selected from higher alcohols, fatty acids, fatty acid esters, polyhydric alcohol esters, fatty acid amides, and acylated amino acids. Analysis method. (3) The dispersion medium is water, methanol, ethanol, glycerin, ethylene glycol, sorbitol, 1,3
- The method for crystallizing oils and fats according to claim 1, wherein the crystallization method is one or more selected from butylene glycol and polyethylene glycol. (4) Claim in which the dispersion medium contains a surfactant (
3) Crystallization method for oils and fats described above. (5) Claim (4) wherein the surfactant is one or more selected from anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.
) The crystallization method for oils and fats described in ). (6) The method for crystallizing fats and oils according to claim (1), wherein the ultrasonic wave has a frequency of 1 to 100 kHz.