HU201345B - Process for preparing shape-proof carrier gel - Google Patents

Abstract

Product is made of a high molecular weight polyethylene glycol (PEG, M at least 4000) and/or sodium stereate or palminate soap prepared with alcohol and that is liquid at 60 deg.C. By altering the proportions of PEG and soap, the solidifying point may be altered as well as its viscosity, volume and pourability. By add. of various ingredients this basic gel may be applied in many household, health and cosmetic products. The gel may be freely poured or stored under pressure.

Description

The present invention relates to a process for the production of a molded carrier gel.

The gel of the present invention can be used in household chemicals (e.g. deodorant, stain remover, polishing bar), cosmetic (e.g. deodorant, antiperspirant stick, solid perfume, solid tooth soap, solid foam bath), adhesives, insect repellents, repellents.

Various formulations containing a gel-like carrier are widely available and are well known in the art.

A composition comprising sodium stearate or sodium palmitate is also disclosed in Hungarian Patent Specification 160 419 and German Patent Specification 1 265 344.

U.S. Patent No. 4,322,400 discloses a solid, bar-shaped cosmetic composition comprising a polyhydroxy compound such as polyglycol, sodium stearate and water, and an active ingredient.

European Patent Publication No. 107,330 describes a transparent soap gel. The gel is used in cosmetic formulations and is prepared from sodium salts of fatty acids, polyethylene glycol, water and monohydroxy alcohol.

The carrier gels described have the disadvantage that they have poor gel stability, do not completely eliminate tackiness after casting and gelling, and have insufficient storage and pH stability.

Attempts have been made to formulate a carrier carrier gel that is free of the above disadvantages.

It has been found that the addition of an alkali or ammonium salt of an oligomer of a saturated fatty acid sodium or ammonium salt and water to a C16-C18 unsaturated fatty acid, and addition of monovalent or polyhydric alcohol and polymeric glycol, a shelf life longer, a pH-less sensitive gel is obtained which separates better from the mold after gelling, a surface which is less sensitive to gel after release, a less sticky surface.

The oligomer added according to the invention increases the gel density and stabilizes the gel by its increased solvating effect.

The oligomer is prepared by reacting 1 mole of unsaturated fatty acid with 1-3 moles of vinyl compound at 30-60 ° C in the presence of a catalyst, preferably benzoyl peroxide.

Preferably, the vinyl compound is vinyl ester, vinyl pyrrolidone or styrene.

The oligomer used has a molecular weight of 320-800.

The gelling agent of the present invention is prepared by preparing 99.5-87 parts by weight of an oligomer of C15-20 saturated aliphatic monocarboxylic acid and 0.5-13 parts by weight of C15-18 unsaturated aliphatic monocarboxylic acid with a vinyl compound; To a mixture of 20 parts by weight and 1-60 parts by weight of water are added 0-25 parts by weight of monovalent aliphatic alcohol and 0-40 parts by weight of polyvalent aliphatic alcohol, and the mixture is heated to 60-90 ° C with 0.3-50 parts by weight polyethylene glycol or polypropylene glycol and homogenize the mass.

Suitably, the saturated aliphatic carboxylic acid is palmitic or stearic acid.

The unsaturated carboxylic acid is linoleic, linolenic or ricinolic acid.

The monohydric alcohol is preferably ethyl alcohol, the monohydric alcohol being glycerol, ethylene glycol or propylene glycol.

Formulations of the carrier gel of the present invention are prepared by incorporating the active ingredients and additives into the molten gel, then pouring the mixture into a mold and allowing it to solidify.

The formulations contain 98.5 to 25 parts by weight of carrier gel and 1.5 to 75 parts by weight of active ingredient.

Household chemical compositions, preferably deodorant, stain remover, polishing compositions, contain 25-60 parts by weight of carrier gel and 75-40 parts by weight of active ingredient and additives.

The deodorant composition preferably contains from 60 to 70 parts by weight of active ingredient and additive: a mixture of surfactant, sodium sulfate, formaldehyde or glyoxane, phenol, fragrance and, if desired, dye, in an amount of 40 to 30 parts by weight of gel.

The spot-cleaning composition preferably contains 75-65 parts by weight of a mixture of solvent, ammonium hydroxide and elain as active ingredient and 25-35 parts by weight of carrier gel.

The polishing composition is preferably comprised of 40-50 parts by weight of a mixture of surfactant, filler, ammonium carbonate and ammonium hydroxide as active ingredient and 60-50 parts by weight of gel.

Cosmetic and therapeutic cosmetic products are deodorant, antiperspirant, solid perfume, tooth soap, solid foam bath composition, headache and migraine sticks: from 98.5 to 55 parts by weight of gel and

1.5-45 parts by weight of active ingredient and additive.

The deodorant composition preferably comprises 98.5 parts by weight of a gel and 1.5 parts by weight of a mixture of bactericidal fragrances and other additives.

The antiperspirant composition preferably contains 5 parts by weight of urea, hexamethylene tetrarain, ZnO, aluminum 3 as active ingredient and additive.

HU 201345 um-stearate, a fragrance mixture containing 95 parts by weight of gel.

The solid perfume contains 5 parts by weight of active ingredient and excipient: 95% by weight of a fragrance and a fragrance fixer.

The headache migraine stick is preferably composed of 69 parts by weight of gel and 31 parts by weight of a mixture of methyl, camphor and fragrance.

The solid foam bath composition preferably comprises 41 parts by weight of gel and 59 parts by weight of a mixture of surfactant, sodium sulfate, sodium bicarbonate, sodium bitartrate, sodium chloride, starch and fragrance.

Preferably, the solid tooth soap comprises 47 parts by weight of a mixture of gel and surfactant, calcium carbonate, magnesium oxide and carbonate, calcium phosphate, perfume and sugar.

The adhesive composition preferably comprises 70-80 parts by weight of a gel and 20-30 parts by weight of a natural adhesive, preferably a glue or polymeric adhesive and optionally a preservative.

The insect repellent or repellent composition consists of 80-90 parts by weight of a gel and 10-20 parts by weight of camphor menthol, fragrance and other additives.

Advantages of the compositions comprising the carrier gel of the invention are as follows:

- have greater storage stability,

- they also have greater gel stability,

- less crumbling than the known preparations,

- when the body is solidified, it is easily separable from the mold and does not stick to the surface.

The following examples illustrate the preparation of the gel of the present invention and the composition thereof.

Example 1 A mixture of parts by weight of stearic acid and 2 parts by weight of a linoleic acid vinyl acetate oligomer (1: 2 molar ratio of linoleic acid and vinyl acetate in the presence of 0.1% by weight of besoyl peroxide at 50 ° C, 452.4). It is dispersed in 250 parts by weight of water and saponified with 25 parts by weight of 35% by weight NaOH.

369 parts by weight of a 1: 1 mixture of glycerol and propylene glycol and 150 parts by weight of ethyl alcohol are then added.

The material was then blended with 125% by weight polyethylene glycol 4000 at a temperature of 60 ° C and homogenized. The homogeneous mixture is used to make a cosmetic composition.

EXAMPLE 2 0.15 parts by weight of an oligomer of ricinoleic acid in vinylpyrrolidone (molecular weight: 399) was added to a portion of palmitic acid.

The oligomer was prepared from a 1: 1 molar mixture of ricinoleic acid and vinylpyrrolidone in the presence of 0.1% by weight benzoyl peroxide at 60 ° C.

The mixture is then saponified with 11.4 parts by weight of 30% NH 4 OH. 75.7 parts of water, 201.8 parts of ethyl alcohol are added, and at 50 ° C, 378.5 parts of 4,000 molecular weight polyethylene glycol are mixed and the mass is homogenized.

EXAMPLE 3 Stearic acid, by weight, was mixed with 0.96 parts by weight of a styrene linoleic acid oligomer.

The oligomer was prepared from a 1: 3 molar mixture of linolenic acid and styrene in the presence of 0.2 mass% benzoyl peroxide at 50 ° C. (Molecular weight: 590.)

The mixture was saponified with 3.2 parts by weight of 35% NaOH in the presence of 24.2 parts by weight of water.

71.6 parts by weight of ethylene glycol are added to the mixture, and the mixture is mixed at 60 ° C with polypropylene glycol having a molecular weight of 6000 and homogenized.

Example 4 Stearic acid and 6 parts of the oligomer of Example 1 were blended.

To the mixture was added 14.2 parts by weight of 35% NaOH and saponified in the presence of 587 parts by weight of water. 53.1 parts by weight of ethylene glycol are added. 4.4 parts by weight of 20,000 molecular weight polyethylene glycol are then added and the mixture is blended at 50 ° C.

The mass is then homogenized.

Example 5 A mixture of part by weight of palmitic acid and 3 parts by weight of the oligomer of Example 2 was mixed with 12.5 parts by weight of water. 12.5 parts by weight of 35% NaOH are added and the mixture is saponified. The soap mixture was mixed with 31.2 parts by weight of ethyl alcohol and 156 parts by weight of propylene glycol. 15.6 parts by weight of 8000 molecular weight β-ethylene glycol are added and the mixture is blended at 60 ° C. The mass is then homogenized.

HU 201345 Β

Example 6

Production of deodorant bars

98.15 parts by weight of the gel of Example 1 are mixed with 0.2 parts by weight of bactericide, 1.6 parts by weight of lavender essential oil and 0.05 parts by weight of dimethylene glycol methyl ether fragrance at 40 ° C.

The mixture was homogenized and then poured into a mold and cooled to room temperature. The frozen bars are removed from the molds and removed.

Example 7

Manufacture of rods for headache

69.26 parts by weight of the gel of Example 2 were mixed with 25.26 parts by weight of menthol, 5.04 parts by weight of camphor and 0.21 parts by weight of eucalyptus oil as a fragrance. In the following, the procedure of Example 6 is followed.

Example 8

Production of toilet deodorant molds

The 3.40 g gel of Example 3 was mixed with 34.89 parts by weight

6.45 parts fatty acid diethanolamide, 16.12 parts sodium sulfate, 40.32 parts fatty alcohol sulfate Na salt, 2.01 parts 37% formaldehyde, 0.15 parts lemon oil fragrance and 0, 06 parts by weight of dye. The homogeneous mass is filled into a polymeric gut, allowed to freeze, then cut into 65 mm bars and disassembled.

Example 9

Preparation of antiperspirant composition

84.19 parts by weight of the gel of Example 1 with 3.42 parts by weight of urea at 40 ° C,

2.62 parts by weight of hexamethylenetetramine, 2.14 parts by weight of ZnO, 5.63 parts by weight of aluminum stearate. An additional 1.9 parts by volume of perfume and 0.1 parts by weight of 3,4,4'trichlorocarbanilide bactericide. From the homogenized mixture, as in Example 6, rods were cast and disassembled.

Example 10

Production of insect sticks

The 45 ° C gel of Example 2 was mixed with 82.35 parts by weight

9.63 parts by weight of Ν, Ν-diethyl-m-toluamide, 6.42 parts by weight of menthol, 0.96 parts by weight of camphor, in a -10% by weight ethanol solution.

An additional 0.64 parts by weight of lavender oil fragrance is added to the homogeneous mixture. In the following, the procedure of Example 6 is followed.

Example 11

Preparation of a solid perfume composition

The 40 ° C gel of Example 1 was mixed with 95.1 parts by weight

4.85 parts by weight of rose oil and 0.05 parts by weight of perfume. In the following, the procedure of Example 6 is followed.

Example 12

Preparation of a bubble bath composition

To 41.34 parts by weight of the gel of Example 3, 1.16 parts by weight of sodium sulfate, 28.98 parts by weight of fatty alcohol sulfate, 9.66 parts by weight of sodium bicarbonate, 9.66 parts by weight of sodium are added at 40 ° C. bitartrate, 0.97 parts sodium chloride, 4.84 parts starch,

3.39 parts by weight of lavender oil fragrance.

The mixture is homogenized and the composition is filled into a plastic gut. The mixture is allowed to freeze, then cut into bars and disassembled.

Example 13

Manufacture of adhesive rods

To the 74.78 parts by weight of the gel prepared in Example 4, 24.78 parts by weight of glue and 0.44 parts of preservative are mixed at 45 ° C. The mixture was homogenized and then proceeded as in Example 6 below.

Example 14

Manufacture of adhesive rods

Each was prepared as in Example 13, but 25.22 parts by weight of 3,000 molar polyvinyl acetate) were mixed with the 74.78 parts by weight of gel at 40 ° C.

Example 15

Preparation of a polishing composition

9.51 parts by weight of fatty alcohol sulphonate are added to 56.92 parts by weight of the gel of Example 1 at 56 ° C.

HU 201345 Β

16.30 parts by weight of chalk, 12.33 parts by weight of kaolin, 2.19 parts by weight of ammonium carbonate and 2.85 parts by weight of 25% by weight of ammonium hydroxide.

From the homogenized mixture rods were prepared as described in Example 6.

Example 16

Preparation of stain remover

To 29.02 parts by weight of the gel of Example 5 was added 31.20 trichlorethylene, 15.6 parts by weight of benzene, 6.24 parts by weight of methylcyclohexanol, 15.6 parts by weight of elaine, 2.34 parts by weight at 35 ° C. by weight of ammonium hydroxide.

The mixture was homogenized, placed in a pod and allowed to freeze.

Example 17

Production of solid toothpaste

To 47.27 parts by weight of the gel of Example 2 was added 5.06 parts by weight of stearylsulfate sodium salt, 17.56 parts by weight of calcium carbonate, 12.15 parts by weight of magnesium carbonate, 9.45 parts at 50 ° C. tricalcium phosphate, 4.05 parts by weight of sugar, 1.08 parts by weight of menthol.

The mixture was homogenized and allowed to freeze in a vial.

Example 18 (Comparative)

By way of a comparative example, it is intended to demonstrate that the presence of the oligomeric soap of the present invention in the gel results in more advantageous applications with improved shelf life.

Samples 1, 2, and 3 were prepared as in Example 6. Sample 1 contains a gel 10 in which 2 parts by weight of the oligomer of the invention are replaced by sodium stearate. Sample 2 contains a gel containing 2 parts by weight of a 1: 2 molar mixture of linoleic acid and vinyl acetate. Thus, the monomer mixture is used instead of the oligomer. Sample 3 is a product prepared according to Example 6 of the invention, wherein the gel contains 2 parts by weight of an oligomer of the invention prepared from linoleic acid and vi20 nyl acetate as in Example 1.

The softening temperature of the samples was measured by the Kramer-Sarnow method.

The softening point of samples stored at + 25 ° C for 48 hours and stored at -18 ° C for 48 hours was also measured by the above method.

The test results are summarized in Table 1 (rate of temperature rise: 1 ° C / min).

Table I

Softening temperature range (° C)

Sample storage for 48 hours without heat treatment at + 25 ° C to -18 ° C

First

Second

Third

39-40

27-29

58-60

38-40 40-43

29-32 Liquid. kiizzadós'

55-80 63-65

It can be seen from the table that sample 3, produced according to the invention, has the highest softening point and thus has the lowest pressure sensitivity.

In this sample, no change in structure occurred during storage at different temperatures, no irreversible change in gel structure was observed after warm storage in cold - .swell.

Example 19 (Comparative)

The weight loss of the three samples in Example 18 was measured at temperatures corresponding to extreme storage conditions, such as -10 ° C and + 35 ° C, respectively.

Measurement of the loss of capital shows the extent of fluid loss and dehydration.

The study interval was 60 days.

HU 201345 Β

In each case, the differences that occur when the samples are stored freely or in sealed form in the usual commercial presentation are also examined. The cumulative results represent the masses obtained at the start of the study and at the end of the study (after 60 days) and the resulting weight loss X.

The results show that at both temperatures the smallest weight loss occurs in sample 3 (according to the invention), which is about one-half that of the other two samples.

The amount of weight loss during storage is shown in Table II. are summarized in Table.

The pH sensitivity of the samples is shown in Table III. is shown in Table.

The test results show that the samples have a soft ointment at pH below 7 and gradually become more stable as the pH is raised. However, samples 1 and 2 become brittle at higher pH, while the sample of the invention retains elasticity even at extreme pH (around pH 9).

II. spreadsheet

Initial and final weight (in g) of gel samples and weight loss (liquid / evaporation) of X after 60 days at extreme storage temperatures

-10 ° C + 35 ° C

Sample Tested --- Open Closed Open Closed Sign Quality —— ------- - —— - ^- Beginner Final Beginner Final Beginner Final Beginner Final

First weight (g) 37.52 36.34 40.21 39.89 41.91 35.12 39.69 38.81 crowd- loss (X) 3.15 0.80 16,20 2.22 Second weight (g) 41.38 39.91 39.12 38.83 40.71 33.63 38.92 37.92 crowd- loss (X) 3.55 0.74 17.39 2.57 weight (g) 38.93 38.52 39,71 39.61 40.60 36.71 41.48 41.11

Third weight loss (X) 1.05 0.25 9.58 0.89

III. spreadsheet

Sample sign Sensitivity of pH, change in stock depending on pH 6.5 6.8 7.1 7.4 7.7 pH values 8.0 8.3 8.6 8.9 9.2 First soft ointment solid ointment form-keeping gel rigid gel Second soft ointment ointment is solid ointment form-keeping gel brittle gel Third ointment solid ointment dimensionally stable elastic gel

-611

HU 201345 Β

Example 20 (Comparative)

The rheological properties of the three samples in Example 18 were measured with a Rotovisco RV-1 rotary viscometer. The shear stress variation as a function of rotational viscometer revolutions was measured and flow curves were recorded.

From these, the Bigham yield point values are calculated, which is plotted in Figure 1 as a function of temperature.

Figure 2 shows the change in dynamic viscosity values as a function of temperature.

It can be seen from Figure 1 that the temperature dependence of the yield point 15 of the samples is very different.

Sample 3 has a relatively high structural strength even at 60 ° C and, with increasing temperature, gradually becomes fluid, but even at higher temperatures (80 ° C) it is difficult to flow and has very good gel properties.

Samples 1 and 2 behave roughly similar to each other, both measuring at low temperatures and softening their advantageous gel properties. This difference is further illustrated by the data shown in Figure 2, which represents the temperature dependence of the dynamic viscosity. As can be seen in Figure 30, the dynamic viscosity value (reciprocity of liquidity) of sample 3 at each temperature is nearly three times that of the other high sample.

The exceptionally high dynamic viscosity 35 of Sample 3 has no effect on the value of the inflection point, as it has been found to gradually soften to approx. Up to 60 ° C, it can be stored well without the risk of liquefaction or permanent deformation. 40

This pattern is most resistant to temperature increase. Sample 2 is undoubtedly of the softest consistency.

Thus, sample 3 exhibits a very good elastic deformation, suggesting that this sample also exhibits good shape retention when casting into gel (whereas it does not occur in the other two samples).

For sample 3, therefore, no gel sticking is expected. 50

Claims (2)

PATENT CLAIMS A process for the preparation of a carrier carrier gel, preferably from alkali or ammonium salts of fatty acids saturated with household chemical, cosmetic, adhesive, insecticidal compositions, mono-or di-alcohol, polyalkylene glycol and water, characterized in that: 99.5-87 parts by weight of an alkali or ammonium salt of 15-20 aromatic saturated aliphatic monocarboxylic acid and 0.5-13 parts by weight of a 320-800 molar weight of the oligomer of a oligomer of a C15-18 saturated aliphatic monocarboxylic acid with a vinyl compound. Disperse -20 parts by weight with 1-60 parts by weight of water, then add 0-25 parts by weight of monovalent C2-C4 aliphatic alcohol, 0-40 parts by weight of polyvalent aliphatic alcohol, and add 0.3-50 parts by weight at 60-90 ° C. It is blended with polyethylene glycol or polypropylene glycol having a molecular weight of -20,000 and homogenizing the mass. (Priority: 11/11/1988) The process according to claim 1, wherein the saturated aliphatic monocarboxylic acid is stearic acid or palmitic acid.