JPS6230179A - Gelling agent - Google Patents

Abstract

PURPOSE:To provide a gelling agent capable of forming an oily gel having high structural viscosity and excellent temperature stability, durability and water-repellency when added to a wide variety of oils, by treating a water- swelling clay mineral with a quaternary ammonium salt-type cationic surfactant and a composite lipid. CONSTITUTION:The objective gelling agent can be produced by treating (A) a water-swelling clay mineral [e.g. the colloidal hydrous aluminum silicate of formula I (X is Al, Fe, Mn or Cr; Y is Mg, Fe, Ni, Zn or Li; Z is K, Na or Ca), etc.] with (B) a quaternary ammonium salt-type cationic surfactant [e.g. the compound of formula II (R1 is 10-22C alkyl or benzyl; R2 is methyl or 10-22C alkyl; R3 and R4 are 1-3C alkyl or hydroxyalkyl; X is halogen or methyl sulfate residue), e.g. dodecyl trimethyl ammonium chloride] and (C) a composite lipid (e.g. lecithin).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a gelling agent. More specifically, water-swellable clay minerals are treated with quaternary ammonium salt type cationic surfactants (
(hereinafter referred to as a cationic activator) and a complex lipid, which can be added to a wide range of oil components to achieve high structural viscosity.
The present invention relates to a gelling agent capable of producing an oily gel with excellent temperature stability, durability, and water repellency.

[Prior Art 1 and Problems to be Solved by the Invention] Conventionally, as an oil-swellable gelling agent, water or exchangeable cations interposed between the layers of water-swellable clay minerals (hereinafter simply referred to as clay minerals) have been used. Organically modified clay minerals obtained by cation exchange with quaternary ammonium salt type organic cations are known, but these organically modified clay minerals can be gelled with benzene, toluene, butyl acetate, ethyl acetate, etc. It has the disadvantage that it is difficult to swell or gel with nonpolar oils such as liquid paraffin and squalane, and polar oils such as isopropyl myristate and various ester oils.

One way to improve this drawback is to use methanol, ethanol, acetone,
One method is to add a small amount of a substance with a boiling point of 1°C, such as propylene carbonate. However, the oily gel obtained by these additions has a weak structural viscosity, especially in polar oils, so long-term storage at high or low temperatures may cause oil phase separation or aggregation of the gel phase. Since all boiling point substances have problems with human safety,
There were drawbacks such as the range of use of the obtained oil-based gel was limited.

Additionally, attempts have been made to construct gelling agents for non-polar oils by treating clay minerals with specific nonionic activators, but this method requires a large amount of nonionic activators to be blended. Because the nonionic active agent is not strongly adsorbed to clay minerals, when the gelling agent comes into contact with water, the nonionic active agent in the gelling agent may migrate into the water phase or partially emulsify. The disadvantage is that the gel structure is easily broken due to formation of water, and water resistance and water repellency are not necessarily sufficient.

As a result of intensive research to improve the shortcomings of the prior art, the present inventors added low-boiling substances such as methanol and ethanol by treating water-swellable clay minerals with a cationic activator and a complex lipid. We discovered that it is possible to obtain a gelling agent that can be added to various oils to produce oil-based gels that have high structural viscosity and excellent water resistance and water repellency.Based on this knowledge, we developed this book. The invention was completed.

[Means for Solving the Problems] That is, the present invention is an oil-swellable gelling agent obtained by treating a water-swellable clay mineral with a cationic activator and a complex lipid.

The configuration of the present invention will be described below.

The water-swellable clay mineral used in the present invention is a type of colloidal hydrated aluminum silicate having a three-layer structure, and is generally expressed by the following general formula %. Or synthesis (in this case, the (OH) group in the formula is substituted with fluorine) of the montmorillonite group (commercially available products include Veegum, Kunipia, Laponite, etc.) and sodium silicic mica and sodium or lithium taeniolite. Synthetic mica (commercially available products include Daimonite; available from Tobie Gyo Co., Ltd.), etc.

The quaternary ammonium salt type cationic surfactant used in the present invention has the following general formula (wherein R1 is an alkyl group having 10 to 22 carbon atoms or a benzyl group, R2 is a methyl group or an alkyl group having 10 to 22 carbon atoms, R3 and R4 are an alkyl group or a hydroxyalkyl group having 111 to 3 carbon atoms, and X is a halogen atom or a methyl sulfate residue.

For example, dodecyltrimethylammonium chloride, myristyltrimethylammonium cucoride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aracyltrimethylammonium chloride, behenyltrimethylammonium chloride,
Myristyldimethylethylammonium chloride, Cetyldimethylethylammonium chloride, Stearyldimethylethylammonium chloride, Arakyldimethylethylammonium chloride, Behenyldimethylethylammonium chloride, Myristyldiethylmethylammonium chloride, Cetyldiethylmethylammonium chloride, Stearyldiethylmethylammonium chloride, Araki diethylmethylammonium chloride,
Behenyldiethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylbehenylammonium chloride, benzylmethylethylcetylammonium chloride, benzylmethylethylstearylammonium chloride, dibehenyldihydroxyethyl Examples include ammonium chloride and corresponding bromides, as well as civalmitylpropylethylammonium methyl sulfate.

In carrying out the present invention, one or more of these may be arbitrarily selected.

Examples of the complex lipid used in the present invention include natural phospholipids such as lecithin, cephalin, sphybominilin, and plasmalogen; and/or synthetic phospholipids such as cimyristoyl lecithin, dipalmitoyl lecithin, and distearoyl lecithin, or non-naturally derived lecithin. Examples include hydrogenated lecithin in which a saturated carbon chain is saturated with hydrogen. In carrying out the present invention, one or more of these complex lipids may be arbitrarily selected and used.

The gelling agent of the present invention can be prepared, for example, by dispersing and stirring a clay mineral, a quaternary ammonium salt type cationic surfactant, and a complex lipid in a low boiling point solvent such as water, acetone, or a lower alcohol, or by dispersing and stirring a clay mineral, a quaternary ammonium salt type cationic surfactant, and a complex lipid in a low boiling point solvent such as water, acetone, or a lower alcohol, or It is obtained by treating a mineral and a quaternary ammonium salt type cationic surfactant in a low boiling point solvent to obtain a cationically modified clay mineral, then treating it with a complex lipid, and then removing the low boiling point solvent.

As the quaternary ammonium salt type cationic surfactant and the complex lipid enter between the layers, the interlayer spacing of the clay mineral becomes widened. The presence or absence of adsorption of ammonium salt-type cationic surfactants and complex lipids can be confirmed.

In addition, if the obtained gelling agent is subjected to Soxhlet extraction using chloroform, ether, etc., the cationic activator and complex lipids between the eyebrows will be washed away, so the extract can be analyzed by gas chromatography, thermal decomposition temperature measurement, or The presence of the cationic activator and complex lipid can be confirmed by measuring the amount (DTA-TG amount measurement, etc.).

The content of the quaternary ammonium salt type cationic surfactant in the gelling agent of the present invention is 60 to 100 g per 100 g of clay mineral.
It is preferably 140 meq (hereinafter abbreviated as meq). The content of the complex lipid in the present gelling agent is preferably 1 to 300 g, more preferably 5 to 200 g, per 100 g of clay mineral.

Although it is possible to directly produce an oily gel with excellent structural viscosity by mixing and stirring the clay mineral with the cationic activator, complex lipid, and oil, the treatment method of the present invention allows the gelling agent to It can be obtained in powder form and has the advantage of being extremely convenient for long-term storage and handling.

[Effects of the Invention] The gelling agent of the present invention exhibits higher structural viscosity than conventional organically modified clay minerals, which are called gelling agents, by being added to a wide range of oil components. It is possible to produce an oil-based gel composition that has excellent storage stability over a wide temperature range, and whose gel structure is not destroyed by contact with water and exhibits excellent water resistance and water repellency.

The oil in this oily gel composition can be any of the common oils used in cosmetics, pharmaceuticals, etc., and can be used in a wide range from polar oils to non-polar oils.

Examples of oils include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin, branched deposited light paraffin, isopropyl myristate, cetyl isooctanoate,
Examples include ester oils such as glyceryl trioctanoate, silicone oils such as decamethylpentasiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane. Also petrolatum, microcrystalline wax,
These include waxes such as lanolin and peace wax, higher alcohols such as cetyl alcohol and stearyl alcohol, and higher fatty acids such as palmitic acid and stearic acid, and one or more of these may be arbitrarily selected. The blending amount is 30 to 98% of the total amount of the oil-based gel composition.
%, preferably 60-95%.

In addition, this oil-based gel composition may contain antioxidants, humectants, ultraviolet absorbers, preservatives, fragrances, dyes, pigments,
It can also be manufactured by adding drugs and the like. Of course, these must be usable under qualitative and quantitative conditions that do not impair the purpose of the present invention.

The oil-based gel composition can be produced by directly mixing the gelling agent of the present invention and an oil component. Mixing can be done with a weak mixing force such as hand stirring, but it can be done using a disper, homogenizer, roller, TK mill, Huber muller, kneader, etc.
It is preferable to use a general-purpose mixer such as a ball mill.
Furthermore, if you want to directly obtain the desired oil-based gel composition without dilution, use a mixer such as a disper or homogenizer, or use a storable high-temperature gel composition to obtain the desired oil-based gel by diluting it as needed. When it is desired to obtain a viscous oil-based gel composition, it is preferable to use a mixer having a strong combined force, such as a roller.

Since the gelling agent of the present invention is in powder form, it is very easy to handle and store. The gelling agent of the present invention, which has such great advantages, can be used in a wide range of fields such as pharmaceuticals, cosmetics, and paints by taking advantage of its characteristics.

[Example] Next, in order to further understand the present invention, the present invention will be described in more detail by giving examples. The present invention is not limited thereby. In examples, all parts and % are by weight.
It is.

Example 1 Benzyldimethylstearylammonium chloride 45
g (equivalent to about 100 meq) and 30 g of hydrogenated lecithin.
Veegum (trade name of Panderbilt, USA), which is a water-swellable clay mineral, was added to 500 ml of an aqueous solution dissolved at 0°C.
g, and thoroughly dispersed and mixed with a disper for about 30 minutes.

Next, water was removed using a filter, and the mixture was dried for about 24 hours to obtain the desired gelling agent.

Benzyldimethylstearylammonium chloride (
Abbreviated as (A). ) and hydrogenated lecithin (abbreviated as (B)) was determined by X-ray diffraction and by measuring the amount of thermal decomposition of the cationic activator and complex lipid using the DTA-TG method. ).

The results are shown in Table 1.

*The amount of hail per 100g of clay minerals.

As is clear from Table 1, the gelling agent of Example 1 has a significantly wider interlayer spacing than the clay mineral before treatment. As is clear from the DTA-TO measurement results, it can be seen that this is caused by the combination of benzyldimethylstearylammonium chloride and hydrogenated lecithin.

Example 2 20 g of dipalmitoyl lecithin (hereinafter abbreviated as (C))
100 g of bentone-38 [montmorillonite], an organically modified clay mineral, was dissolved in 500 ml of ethanol.
Thoroughly disperse and mix 100 g of an organically modified clay mineral treated with 0 meq of distearyldimethylammonium chloride (hereinafter abbreviated as (D)), a trade name manufactured by National Red Company, USA, using a lab homogenizer.

Next, after removing ethanol with an evaporator,
The desired gelling agent was obtained by drying at 0° C. for about one day and one night.

As in Example 1, the presence or absence of surface modification was evaluated from X-ray diffraction and the amounts of the cation activator and complex lipid in the Soxhlet extract with chloroform.

The results are shown in Table 2.

Table 2 As is clear from Table 2, even if the organically modified clay mineral (Bentone-38) previously treated with the quaternary ammonium salt type cationic surfactant (D) was used, the complex lipid of (C) It was found that the interlayer spacing was further increased by treatment. Similar to Example 1, this is thought to be caused by the binding of complex lipids. The amount of quaternary ammonium salt type cationic surfactant extracted by Soxhlet extraction is the amount of quaternary ammonium salt type cationic surfactant physically adsorbed in the organically modified clay mineral (Bentone-38) that has been organically modified by cation exchange reaction. D
As shown in Example 1, the amount of all quaternary ammonium salt type cationic surfactants can be determined by the TA-TG method.

Example 3 4 parts of the gelling agent obtained in Example 1 were dispersed and mixed with 96 parts of liquid paraffin in a disper to obtain an oil-based gel composition.

Example 4 An oily gel was obtained in the same manner as in Example 3, except that the gelling agent obtained in Example 2 was used instead of the gelling agent obtained in Example 1.

Comparative Example 1 384 parts of bentone, 95 parts of liquid paraffin, and 1 part of ethanol were dispersed and mixed using a disperser to obtain an oily gel.

Comparative Example 2 Bentone-2 was used instead of Bentone-38 in Comparative Example 1.
An oily gel was obtained in the same manner as in Comparative Example 1, except that Comparative Example 7 was used.

Comparative Example 3 384 parts of bentone and 96 parts of liquid paraffin were dispersed and mixed using a disperser to obtain an oily gel.

Oily gel composition obtained in Example 3.4 and Comparative Examples 1 to 4
Table 3 shows the viscosity of the oily gel obtained and the results of the stability test in a 50 part tank. The viscosity is expressed as a value at a shear rate of 1700 sce using a cone plate viscometer, and the stability test in a 50° C. constant temperature bath was evaluated based on the appearance after being left for 2 weeks using the following evaluation criteria.

0: No separation observed at all.

Δ: Separation of liquid phase (oil) was observed.

X: Significant liquid phase separation was observed.

Table 3 As is clear from Table 3, the gelling agent of the present invention has excellent structural viscosity in a non-polar oil system and can produce an oil-based gel composition with excellent temperature stability.

Example 5 4 parts of the gelling agent obtained in Example 1 and 16 parts of liquid paraffin were combined twice using a roller with a pressure of 15 kg/cm, and then 80 parts of liquid paraffin was added and diluted and dispersed with a disper to form an oil-based mixture. A gel composition was obtained.

Comparative Example 5 Clay mineral (high purity montmorillonite) 4 parts, polyoxyethylene (16 mol) 2-octyldodecyl ether 4 parts
After pre-stirring and mixing 12 parts of liquid paraffin and 12 parts of liquid paraffin, they were combined twice using a roller with a pressing force of 15 kg/cm, and then diluted and dispersed with 80 parts of liquid paraffin using a disper to obtain an oil-based gel composition.

Viscosity of the oily gel compositions obtained in Example 5 and Comparative Example 5,
Table 4 shows the evaluation results of stability and water repellency in a 50°C constant temperature bath. The viscosity and stability were evaluated using the same method as described above, and the water repellency was evaluated by measuring the contact angle (Note 2).

Table 4 (Note 2) To measure the contact angle, apply the oil-based gel composition uniformly onto a glass plate, place a 1 μl water droplet on it, and measure the angle at which the water droplet contacts the oil-based gel composition using a contact angle measuring device. I asked for it. The higher the value, the higher the water repellency.

Although both the Examples and Comparative Examples have excellent gelling ability and stability, it can be seen that in terms of water repellency, the gel composition prepared using the gelling agent of the present invention is significantly degraded.

(Left below) Example 6 Sunscreen (1) Oily gel composition 54.9 (
2) Liquid paraffin 22.0 (3
) Vaseline 5.0 (4)
Silicone 5.0 (5) Titanium oxide 5.0 (6) p-dimethylaminoamine, ρ isooctyl fragrant 3.0 (7) Fragrance appropriate amount (8) Inorganic powder pigment appropriate amount Oil-based gel composition according to Example 4 Manufactured in advance. Vaseline is melted in liquid paraffin, and silicone and isooctyl p-dimethylaminobenzoate are sequentially added, mixed and dissolved. After adding titanium oxide and inorganic powder pigment, they are dispersed using a homomixer. Next, the oil-based gel composition was added and mixed uniformly using a homomixer, and then a fragrance was added and further mixed to obtain the desired sunscreen.

Example 7 Suntan gel (1) oil-based gel composition 60.0 (
2) Liquid paraffin 32.5 (3
) Cetyl isooctate 5.0 (4) p-dimethylaminobenzoic acid 1°5 (
5) Perfume (appropriate amount) (6) Pigment (appropriate amount) According to Example 5, a suntan gel for suntan use was produced.

Example 8 Oily ointment (1) Oily gel composition 50.0 (
2) Liquid paraffin 45.0 (3
) Castor oil 5.0 (4)
Chemicals Appropriate amounts of liquid paraffin, microcrystalline wax vaseline, and α-tocopherol are heated and mixed, and after cooling, a gelling agent prepared by treating glycerin and organically modified clay mineral (bentone-38) with distearoyl lecithin is added and premixed. After standing for 1 hour, roller kneading is performed twice to obtain an oil-based gel composition. The oily gel composition was added to a mixed oil phase of liquid paraffin and castor oil in which the drug had been dissolved, and the mixture was diluted and mixed with a disper to obtain the desired oily ointment.

Claims (3)

[Claims] (1) A gelling agent obtained by treating a water-swellable clay mineral with a quaternary ammonium salt type cationic surfactant and a complex lipid. (2) The content of quaternary ammonium salt type cationic surfactant is 60 to 140 per 100 g of water-swellable clay mineral.
The gelling agent according to claim 1, which is milliequivalent. (3) The gelling agent according to claim 1, wherein the content of the complex lipid is 1 to 300 g per 100 g of water-swellable clay mineral.