JPH0753859B2 - Gelling agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a gelling agent. More specifically, it relates to a gelling agent obtained by treating a water-swellable clay mineral with an ammonium salt-modified organopolysiloxane (hereinafter also referred to as "polysiloxane ammonium").

The gelling agent of the present invention is particularly preferably used for gelling silicone oil. In this use, if this gelling agent is added to silicone oil and mixed, the structural viscosity is high,
An oily gel composition of a silicone-based oil having excellent temperature stability, water resistance and water repellency can be obtained. The oily gel composition can be used in a wide range of fields such as cosmetics, pharmaceuticals, and paints.

[Conventional technology and problems]

Conventionally well-known oil-swelling gelling agents are organically modified clay minerals obtained by cation-exchanging water or exchangeable cations existing between layers of water-swellable clay minerals with quaternary ammonium salt type organic cations. Has been. Further, for the purpose of improving the swelling ability and the gelling ability, a small amount of a low boiling point polar substance such as methanol, ethanol, acetone, or propylene carbonate is added when the organically modified clay mineral is mixed, or a water-swellable clay mineral is added. There is a method of treating with a specific nonionic activator. However, in such a method, the gellable oil is limited to the oil having a hydrocarbon chain or a benzene ring, and thus it has been difficult to gel the silicone oil.

The present inventors have conducted intensive studies in view of these circumstances, and as a result, when a water-swellable clay mineral is treated with polysiloxane ammonium, it has high structural viscosity and excellent temperature stability, water resistance and water repellency. It was found that a gelling agent capable of forming an oily gel of a silicone-based oil having the above is obtained, and the present invention has been completed based on this finding.

[Means for solving problems]

That is, the present invention is a gelling agent obtained by treating a water-swellable clay mineral with an ammonium salt-modified organopolysiloxane.

The configuration of the present invention will be described below.

The water-swellable clay mineral in the present invention is usually one kind of colloidal hydrous aluminum silicate having a three-layer structure and represented by the following general formula.

(X, Y) ₂₃ (Si, Al) ₄ O ₁₀ (OH) ₂ Z · nH ₂ O where X is Al, Fe, Mn, Cr, Y is Mg, Fe, Ni, Zn, Li,
Z represents K, Na and Ca.

Specifically, natural or synthetic montmorillonites such as montmorillonite, saponite, smectite, or hectorite (commercially available products include beegum, kripia, laponite, etc.), sodium silicic mica, sodium teniolite, lithium teniolite, etc. Synthetic mica group [commercially available products include Dimonite and Topy Industries, Ltd. ] And so on.

In the present invention, one or more of these are arbitrarily selected.

The ammonium salt-modified organopolysiloxane of the present invention contains at least one ammonium base in one molecule because the functional group capable of exchanging with the exchangeable cation between the clay mineral layers is a quaternary ammonium salt type organic cation. Organopolysiloxane, a typical example of which is
It is represented by the following general formula.

R ¹ _a R ² _b SiO _{(4-ab) / 2} [wherein R ¹ is a monovalent hydrocarbon having 1 to 6 carbon atoms, and R ² is the following formula: (Here, R ³ is a divalent hydrocarbon group, a divalent organic group consisting of carbon, nitrogen and hydrogen or a divalent organic group consisting of carbon, oxygen and hydrogen, and R ⁴ , R ⁵ and R ⁶ are hydrogen or carbon. Is a monovalent hydrocarbon group of number 1 to 30), a is an average of 0 <a <3, b is an average of 0 <b <3,
a + b is a number of 1.8 <a + b <3 on average. ] Further, a methyl group, an ethyl group and a phenyl group are exemplified as R ¹ , and a divalent hydrocarbon group of R ³ is an ethylene group, a propylene group, an n-butylene group, And the following groups are exemplified as the organic group composed of divalent carbon, nitrogen and hydrogen.

The following groups are exemplified as the hydrocarbon group composed of divalent carbon, oxygen and hydrogen.

Further, as the monovalent hydrocarbon group constituting R ⁴ , R ⁵ and R ⁶ , an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a lauryl group, a stearyl group and a misilyl group, or a vinyl group. Examples thereof include alkenyl groups such as groups, allyl groups and oleyl groups, and aralkyl groups such as benzyl groups.

The molecular structure of this organopolysiloxane may be linear, branched, cyclic or network, but is linear or branched from the viewpoint of compatibility with water, alcohols and other organic solvents. Alternatively, it is preferably a ring. The following are specific examples of the ammonium salt-modified organopolysiloxane in the present invention.

The ammonium salt-modified organopolysiloxane of the present invention can be produced, for example, by the following synthetic method.

Synthesis method (1) (In the formula, R ¹ , R ³ , R ⁴ , and R ⁵ are as described above, and x and y are positive numbers satisfying the above-mentioned a and b), and an amino group-containing organopolysiloxane represented by R ⁶ Cl ( In the formula, R ⁶ is as described above) and a chlorinated hydrocarbon, in the presence or absence of a solvent such as isopropanol, in a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer. 150 ° C, 5
Allow to react for ~ 20 hours.

Synthesis method (2) (Wherein R ¹ and R ³ are as described above, and x and y are positive numbers satisfying the above-mentioned a and b), and a chlorinated alkyl group-containing organopolysiloxane represented by the following formula: (Wherein R ⁴ , R ⁵ and R ⁶ are as described above) and a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer in the presence or absence of a solvent such as isopropanol. The reaction is carried out at 50 to 150 ° C for 5 to 20 hours.

In the above two synthetic methods, a trace amount of an alkali metal hydroxide such as sodium hydroxide may be added as a catalyst. The type of ammonium base produced varies depending on the type of raw material and the amount charged, and is a secondary, tertiary or quaternary ammonium base.

The gelling agent of the present invention is obtained, for example, by subjecting a water-swelling clay mineral and polysiloxane ammonium to a dispersion stirring treatment in a low boiling point solvent such as water, acetone or a lower alcohol, and then removing the low boiling point solvent. .

Since the layer spacing of the water-swelling clay mineral is widened by the intercalation of polysiloxane ammonium, the presence or absence of incorporation of polysiloxane ammonium can be confirmed by measuring the long plane spacing by X-ray diffraction.

The presence of polysiloxane ammonium can be confirmed by subjecting the gelling agent to thermal decomposition temperature measurement or thermal decomposition amount measurement (DTA-TG measurement).

The content of polysiloxane ammonium in the gelling agent of the present invention is preferably 60 to 140 milliequivalents as the nitrogen (N ⁺ ) content with respect to 100 g of the water-swelling clay mineral.

〔The invention's effect〕

The gelling agent of the present invention, when added to a silicone-based oil, shows a high structural viscosity which cannot be obtained by a conventional organically modified clay mineral called a gelling agent, and
It has excellent storage stability over a wide temperature range, and the gel structure is not easily destroyed by contact with water,
An oily gel composition of a silicone oil exhibiting excellent water resistance and water repellency is produced.

Further, the gelling agent of the present invention is obtained as a powder, and has the advantage of being extremely convenient for long-term storage and handling.

[Application of invention]

The oily gel composition of the silicone-based oil produced here is used, for example, in the fields of cosmetics and pharmaceuticals. As the silicone-based oil to be gelled, those usually used in the fields of cosmetics and pharmaceuticals are mentioned. To be Examples thereof include dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher fatty acid-modified organopolysiloxane, higher alcohol-modified organopolysiloxane, and trimethylsiloxysilicate. One or three or more types are arbitrarily selected from these. The silicone oil is contained in an amount of 30 to 98% by weight, preferably 60 to 95% by weight, based on the total amount of the oily gel composition.

If necessary, an antioxidant, a moisturizer, an ultraviolet absorber, an antiseptic, a fragrance, a dye, a pigment, a drug (antibacterial agent, etc.) and the like may be added to the oily gel composition.

The production of the oily gel composition can be achieved by directly mixing the gelling agent of the present invention with the silicone oil. The mixing can be performed with a weak mixing force such as hand stirring, but it is preferable to use a general-purpose mixer such as a disper, homogenizer, roller, TK mill, Hoover Mahler, kneader, ball mill, or ultrasonic disperser. In this case, when it is desired to obtain an oily gel composition to be directly used without dilution, it is preferable to use a mixer such as a disper and a homogenizer, and it is appropriately diluted before use. When obtaining an oily gel composition, in other words, when obtaining a storable high viscosity oily gel composition, it is preferable to use a mixer having a strong kneading force such as a roller. .

〔Example〕

Next, for further understanding of the present invention, the present invention will be described in more detail with reference to Examples. The case where there is one quaternary ammonium salt type organic cation will be described as an example.
It is obvious that (h) also exhibits the same reaction since it has the same quaternary ammonium salt type organic cation. The present invention is not limited to this. All parts and percentages in the examples are by weight.

Example 1 Among the specific examples of the ammonium salt-modified organopolysiloxane, the polysiloxane ammonium shown in “Example (a)”
To 500 ml of an aqueous solution in which 5 g was dissolved, 10 g of synthetic smectite (manufactured by Kunimine Industries), which is a water-swelling clay mineral, was added, and about 3
It was thoroughly dispersed and mixed with a disper for 0 minutes. Then
After removing water with a filter, it was dried uniformly for 24 hours to obtain the desired gelling agent.

Whether or not the polysiloxane ammonium is taken in,
It was evaluated from the results of the X-ray diffraction of the clay mineral before and after the treatment and the thermal decomposition amount measurement of polysiloxane ammonium by the DTA-TG method. The results are shown in Table 1.

The results in Table 1 show that the layer spacing of smectite treated with polysiloxane ammonium increased by about 8Å compared to before treatment, and the thermal decomposition amount increased from 0 to 0.48 g / g. From the results, it can be seen that the uptake of polysiloxane ammonium has occurred.

Example 2 Polysiloxane ammonium shown in “Example (b)” in the specific examples of the ammonium salt-modified organopolysiloxane
10 g of natural montmorillonite, which is a water-swelling clay mineral, was sufficiently dispersed and mixed in 100 ml of an ethanol solution in which 5 g was dissolved by a lab homogenizer. Then, after removing ethanol with an evaporator, it was dried at 50 ° C. for about 24 hours to obtain a desired gelling agent.

The results of obtaining the layer spacing value and the amount of thermal decomposition in the same manner as in Example 1 are as shown in Table 2.

As is clear from the results shown in Table 2, it is understood that the incorporation of polysiloxane ammonium occurs in the treated montmorillonite as in Example 1.

[Application example and comparative application example]

 All parts and percentages in the examples are by weight.

Application Example 1 5 parts of the gelling agent obtained in Example 1 was replaced with octamethylsiloxane.
An oily gel composition was obtained by dispersing and mixing with 95 parts by a disper.

Application Example 2 5 parts of the gelling agent obtained in Example 2 was dispersed and mixed with 95 parts of decamethylcyclopentasiloxane with a disper to obtain an oily gel composition.

Comparative Application Example 1 (without gelling agent of the present invention) 5 parts Benton 38 (montmorillonite treated with dimethyl ammonium chloride) and octamethylsiloxane 95
Parts were dispersed and mixed with a disper to obtain an oily gel composition.

Comparative Application Example 2 (same as above) 5 parts of Benton 27 (montmorillonite treated with benzyldimethylstearyl ammonium chloride) and 95 parts of decamethylcyclopentasiloxane were dispersed and mixed with a disper to obtain an oily gel.

(Viscosity Measurement and Stability Test) The results of viscosity measurement of the oily gel compositions obtained in Application Examples 1 and 2 and the oily gel compositions obtained in Comparative Application Examples 1 and 2 and in a 50 ° C. constant temperature bath The results of the stability test are shown in Table 3. Viscosity is represented by a value obtained by using a Bruchfield viscometer at 30 revolutions and using rotor No. 3. In the stability test in a 50 ° C constant temperature bath, the appearance after standing for 2 weeks was judged by the following evaluation criteria. .

◯: No separation is observed.

X: Significant liquid phase separation is observed.

As is apparent from Table 3, in the case of using the gelling agent of the present invention, a dimethylpolysiloxane-based oil component, that is, a silicone-based oil having excellent structural viscosity in a silicone-based oil and excellent in temperature stability. It can be seen that the oily gel composition of

Application Example 3 A sunscreen was prepared as follows.

(1) Oily gel composition 55.0% (2) Liquid paraffin 22.0 (3) Vaseline 5.0 (4) Microcrystalline wax 5.0 (5) Titanium oxide 5.0 (6) Isooctyl p-dimethylamitobenzoate 3.0 (7) Perfume proper amount (8) Inorganic powder pigment proper amount above oiliness The gel composition was manufactured in advance according to Application Example 1. Vaseline and microcrystalline wax were melted in liquid paraffin, and isooctyl p-dimethylaminobenzoate, titanium oxide, and an inorganic powder pigment were sequentially added, and then dispersed by a homomixer. Next, a pre-made oily gel composition was added and uniformly mixed with a homomixer, then a fragrance was added and further mixed to produce an intended sunscreen.

Application Example 4 A sunburn suntan gel was prepared as follows.

(1) Oily gel composition 60.0% (2) Decamethylcyclopentane 20.0 (3) Squalane 12.5 (4) Cetylisooctanolate 5.0 (5) p-Dimethylaminobenzoic acid 1.5 (6) Perfume Suitable amount (7) Dye Suitable amount Using the above method of Application Example 3 The desired suntan gel for sunburn was produced according to the above.

Application 5 An oily ointment was prepared as follows.

(1) Oily gel composition 50.0 (2) Octamethylsiloxane 25.0 (3) Liquid paraffin 20.0 (4) Isopropyl adipate 5.0 (5) Drug (antibacterial agent) Appropriate amount Octamethylsiloxane, microcrystalline wax, petrolatum, α-tocopherol are heated and mixed, and after cooling, glycerin And a gelling agent were added and mixed. After standing for 1 hour, roller kneading was performed twice to obtain an oily gel composition. The above components (2) to (4) in which a drug is dissolved
The mixed oil component of the formulation was added, and the mixture was diluted and mixed with a disper to produce the target oily ointment.

Claims (2)

[Claims] 1. A gelling agent obtained by treating a water-swellable clay mineral with an ammonium salt-modified organopolysiloxane. 2. The gel according to claim 1, wherein the ammonium salt-modified organopolysiloxane is contained in a nitrogen (N ⁺ ) content of 60 to 140 milliequivalents per 100 g of the water-swelling clay mineral. Agent.