JPH0449249A - Liquid oil gelling agent and its production - Google Patents

Abstract

PURPOSE:To obtain a gelling agent, composed of a dextrin ester of a fatty acid prepared by a specific method and having a gel-forming ability in both a nonpolar oil and a polar oil and capable of forming stable gels for a long period without losing transparency at or below ordinary temperature. CONSTITUTION:A liquid oil gelling agent is obtained by reacting one or more of dextrin or reduced dextrin having 3-100, especially 10-50 average polymerization degree of glucose with an 8-14C saturated fatty acid in the presence of a tertiary amine as a catalyst and water or an alcohol (preferably a 1-3C alcohol) in an amount of 3.0-50.0% based on the total amount of the dextrin or reduced dextrin so as to provide 1.2-2.4 substitution degree of the fatty acid based on glucose unit of the dextrin, esterifying the fatty acid, washing the resultant product with water and an alcohol. The aforementioned gelling agent is composed of the dextrin ester of the fatty acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a highly versatile liquid oil gelling agent and a method for producing the same. More specifically, the present invention has gel-forming ability in both non-polar oil and polar oil,
In addition, even at room temperature or below room temperature, especially at temperatures as low as around 0°C, if the temperature is above the freezing point of the target liquid oil, the liquid oil does not lose its transparency and can form an excellent gel that is stable for a long period of time. It traps the oil gelling agent.

[Prior Art] As is well known, liquid oil gelling agents (hereinafter referred to as "gelling agents") used in the production of ointments, herbal medicines, eye shadows, foundations, lipsticks, blushers, etc., include:
Conventionally, metal soaps, lipophilic sucrose fatty acid esters, organic bentonite fatty acid esters, dextrin fatty acid esters, and the like have been used.

However, metal soap has poor solubility in liquid oil and requires a high temperature of about 100°C to dissolve, which leads to a decline in the quality of other mixed oils and pigments, and the resulting gel may crack or Changes over time such as oil seepage or sweating are likely to occur, and in addition, there are many unsatisfactory points regarding gloss and spreadability. If the amount added is suppressed to satisfy luster and elongation, changes over time such as cracking and oil seepage will become more severe.

Lipophilic sucrose fatty acid esters have poor gelling properties and transparency, and lack stability at low temperatures.

Although organic bentonite fatty acid esters have thickening properties, they have poor gelling properties and are not thixotropic, so they have drawbacks such as high viscosity at high temperatures and difficulty in blending with other substances. has a lanolin or greasy, heavy feel and is sensitive to pH fluctuations.

Dextrin fatty acid ester is an esterification of dextrin, which is a starch decomposition product, and a fatty acid, and is structurally stable and has excellent functionality as a gelling agent (see Japanese Patent Publication No. 19834/1983). but,
It is difficult for the dextrin fatty acid ester to form a transparent gel in polar oil such as ester oil;
It is particularly poor in low-temperature stability, which is required in cold regions.

On the other hand, conventionally, in the synthetic reaction of dextrin fatty acid ester, the base and catalyst involved in the reaction have generally been used as anhydrides, and the dextrin undergoing the reaction has also been used in the reaction system. The coexistence of more active substances such as alcohols is avoided.

[Problem to be solved by the invention]

As mentioned above, existing gelling agents for liquid oils all have various problems in use and have many restrictions in terms of use. In other words, existing gelling agents have drawbacks such as poor transparency and lack of stability at low temperatures when used with polar oils, so they are only used for gelling or thickening functions. could not. Furthermore, even when utilizing these two functionalities, it is difficult to use them alone or simply combine them, so it is necessary to compensate for the drawbacks by using other substances in combination, which makes the formulation complicated. It has the ability to form gels in both polar and non-polar oils, and loses transparency even at temperatures below room temperature, especially around 0°C, if the temperature is above the freezing point of the target liquid oil. Moreover, there is a long-awaited development of a highly versatile gelling agent that can form a gel that is stable for a long period of time, and a method for producing the same.

[Means and actions to solve the problem]

The present invention combines glucose with one or more dextrins having an average degree of polymerization of 3 to 100 or reduced dextrins and having 8 to 8 carbon atoms.
14 saturated fatty acids in the presence of 3.0 to 50.0% of water or alcohol based on the total amount of dextrin while using a tertiary amine as a catalyst. 1 per glucose unit
．． A gelling agent consisting of a dextrin fatty acid ester obtained by reacting and esterifying 2 to 2.4,
and one or more types of dextrin or reduced dextrin having an average degree of polymerization of glucose from 3 to 100 (hereinafter referred to as "dextrin") and a saturated fatty acid having 8 to 14 carbon atoms (hereinafter referred to as "saturated fatty acid"). , tertiary amine (
(hereinafter referred to as "pyridine etc.") as a catalyst and in the presence of 30 to 50.0% water or alcohol based on the total amount of the dextrin or reduced dextrin, the degree of substitution of the fatty acid per glucose unit of the dextrin is This is a method for producing a liquid oil gelling agent made of a texttrin fatty acid ester, which is characterized by washing the product obtained by esterification by reacting so as to give a ratio of 1.2 to 2.4 with water and alcohol.

First, the dextrin used in the present invention preferably has an average degree of polymerization of 3 to 100, particularly 10 to 50. If the average degree of polymerization is 2 or less, it becomes wax-like and a smooth gel cannot be obtained, and the degree of substitution becomes high, making it impossible to obtain transparency.

Moreover, if it is 100 or more, the molecular weight becomes high, and the viscosity of the reaction system increases, so that an excessive amount of catalyst such as pyridine is required, resulting in poor reaction efficiency.

Further, the saturated fatty acid used in the present invention, for example, the saturated fatty acid halide or the saturated fatty acid anhydride, needs to have 8 to 14 carbon atoms. If the number of carbon atoms is less than 8 or 15 or more, a gel having high transparency not only at room temperature but also at low temperature cannot be obtained in polar oil such as ester oil.

Next, the most important technical means in the present invention are to allow water or alcohol to exist in an amount of 3.0 to 50.0%, which was required to be eliminated as much as possible in the conventional technology, and to replace fatty acids per unit glucose. It is to specify the degree as 1.2 to 2.4.

Here, the specific method for adding water or alcohol is to adjust the amount of water contained in dextrin to the required amount by adjusting the drying temperature and time, or to add water or alcohol to the required amount in a dispersion of dry dextrin and pyridine. The insufficient amount of water or alcohol may be added. In this case, the catalyst such as pyridine also contains a trace amount of water (0.01% with special grade reagent).
(below), but since the amount is constant, only the water content in dextrin may be used as the standard.

In the reaction, various solvents are sometimes used as diluents in the reaction system, such as formamide-based solvents such as dimethylformamide, acetamide-based solvents, ketone-based solvents, dioxane, or toluene. Instead of adding water or alcohol to the dispersion of dry dextrin and pyridine etc., the required amount of water or alcohol can also be added to this solvent.

Note that, as the alcohol, an alcohol having 1 to 3 carbon atoms is preferable among primary alcohols such as methyl alcohol and ethyl alcohol, and polyhydric alcohols such as glycerin. When these alcohols are used together with water, they are separately measured and added before the reaction so that the total amount with water is 3.0 to 50.0%.

The amount of water or alcohol to dextrin is 3.0
If the amount of water or alcohol is less than 50.0%, the obtained dextrin fatty acid ester will have unfavorable quality phenomena such as off-odor and coloring, and if the amount of water or alcohol is more than 50.0%,
A large amount of saturated fatty acids, which are highly reactive with water, is decomposed, resulting in not only poor reaction efficiency, but also complicated removal of generated free fatty acids and fatty acid esters, which are reaction products with alcohol. Therefore, the amount of saturated fatty acid added in this case is adjusted as appropriate in order to obtain a product with the targeted degree of substitution.

Here, if the degree of fatty acid substitution is less than 1.2, the introduction rate of fatty acids is low, resulting in poor solubility and gel-forming ability, resulting in poor functionality. Furthermore, when the degree of substitution is 2.4 or more, although the solubility is improved, the gelation ability in polar oil and the stability at room temperature or below room temperature are significantly reduced.

The gelling agent according to the present invention allows water or alcohol to be present during its production process, so compared to conventional products,
This operation significantly enhances the quality characteristics, as it is easily purified by cleaning agents such as water and alcohol.

That is, from the product of the esterification reaction in the present invention, pyridine and the like are easily removed by washing with water, and free fatty acids are easily removed by washing with alcohol. The order of washing with water and alcohol is not particularly limited, and may be water and alcohol in that order, or alcohol and water in that order.

The gelling agent according to the present invention is liquid paraffin (hereinafter referred to as LP).
That's what it means. ) and squalane (hereinafter referred to as SQ), and 2-octyldodecanol (
Hereinafter referred to as HA. ) and higher alcohols such as 2-hexyldecanol, and polar oils such as triglycerin isooctanate (hereinafter referred to as GTO) and 2-ethylhexanoic acid triglyceride (hereinafter referred to as ODO). to form a transparent gel.

For example, the present inventor blended the gelling agent according to the present invention into cold HA at a concentration of 10 wt/wt%, heated it to 80°C to 120°C with stirring to dissolve it, and transferred it into a 1 cm x lam cell. The resulting gel is maintained at 20°C or 5°C for 24 to 72 hours, and the transmittance of visible light at 600 nm is determined for each temperature. Using this as an index, the transmittance of the gel that is judged to be transparent by visual inspection is determined. Since the rate is 40% or more when the air transmittance is 100%, this value was evaluated as the transparency standard, and as a result, the polar oil gel sample was 10°C or less, Even in harsh low temperatures like winter, it maintained its transparency for a long time as long as the temperature was above the freezing point of the polar oil used, and it was extremely stable with no cracks or oil seepage.f! I agree.

The present invention will be explained in more detail with reference to Examples below.

〔Example〕

Example 1 439 g of caprylic acid chloride (8 carbon atoms), 615 g of lauric acid chloride (12 carbon atoms), 718 g of myristic acid chloride (14 carbon atoms), and 859 g of palmitic acid chloride (16 carbon atoms) Using 165.5 g of 2.1% water dextrin with an average degree of polymerization of 20, 650 g of pyridine catalyst (moisture 0.01
%), 10.5 g of water was added and the ratio of water to the amount of dextrin was 8.6% to carry out the reaction and esterification. The reaction temperature at that time was 90°C and the reaction time was 5 hours. The reaction product obtained here was a homogeneous paste containing the base and catalyst involved in the reaction. 2.51 degrees of water was added to this reaction product, and the mixture was stirred at 50°C for 30 minutes to separate the solid and the liquid containing pyridine. After that, the solid matter was filtered and 3. methanol was added at 50°C. After stirring and cleaning with ON for 10 minutes and further removing methanol as the cleaning liquid, repeat 3. The product was purified by stirring and washing with methanol at 50° C. for 10 minutes.

As a result, dextrin fatty acid esters of caprylic acid, lauric acid, myristic acid, and palmitic acid each having a free fatty acid content of 1% or less and having different fatty acid chain lengths were obtained. At this time, the respective yields (g) and yields (%) relative to the theoretical yields were as follows. Dextrin caprylic acid ester (hereinafter referred to as CLDE).

) 400g, 93.6%: Dextrin laurate ester (hereinafter referred to as LDE) 584g, 86.5%:
Dextrin myristate ester (hereinafter referred to as MDE) 687g, 88.9%: Dextrin palmitate ester (hereinafter referred to as PDE) 811g, 89°0%.

In addition, using 602 g of myristic acid chloride as a control, MDE was prepared using the same amounts of dextrin and pyridine according to the production method of the present invention described in this example without adding water to the reaction system. 636g
(Yield 88.5%) samples were obtained, and each was used as a gelling agent.

Using these gelling agents, set the concentration to 10 svt/wt% for various polar oils and non-polar oils, heat and dissolve to form a gel, and then heat to 20°C (normal temperature) and 5°C (low temperature). It was held for 24 hours. The transparency of the gel obtained here was measured using visible light at a wavelength of 600 nm while maintaining the respective temperature, i.e., 20°C or 5°C, and was expressed as the transmittance when the transmittance of air was taken as 100%. These are shown in Tables 1 and 2 below, respectively.

In addition to the above, the abbreviations used in the table and the following description are as follows.

Neopentyl glycol decanate: NPGD. Cetylisooctanate: CIO, Isotridecyl myristate: MI TD, Octyldodecyl myristate: MOD.

As shown in Tables 1 and 2, the dextrin fatty acid ester of the present invention is effective against all polar oils, not only at room temperature (Table 1) but also at a low temperature of 5°C (Table 2).
Table), which showed transparency with a transmittance of 40% or more,
Even at room temperature, DE, especially GTOIODO
8.4% and 4.8%, respectively, as seen for
The transmittance was extremely low.

Furthermore, for SQ, which is a non-polar oil, the PDE transmittance tends to be high at both 20°C and 5°C. However, L.P.
At room temperature, PDE also showed a high transmittance similar to the product of the present invention, but PDE became cloudy at 5°C. The dextrin fatty acid ester, which is a product of the present invention, exhibited a transmittance of 60% or more in all cases and maintained high transparency.

On the other hand, MDE used as a control was unable to maintain transparency at low temperatures.

The polar oil gel obtained using the product of the present invention maintains its transparency even below 5°C, and in particular, as is clear from Table 3 below, even when maintained at -35°C, for example, LDE showed a high transmittance of 73.8% with GTO.

Example 2 Using 503 g of lauric acid chloride, the average degree of polymerization was 2.
30.5 g of methanol was added to 1655 g of dextrin with 2.1% water content of 0.0 and 650 g of pyridine catalyst (moisture 0.01%) adjusted to have a degree of substitution of 1.6, and the ratio of water to dextrin was The total amount of methanol was adjusted to 21.0%, and esterification was carried out at 92° C. for 4 hours. Thereafter, 2.5 liters of water was added to the pasty reaction product and stirred at 70° C. for 30 minutes to separate the solid from the pyridine-containing liquid. The obtained solid substance was filtered, and the process of stirring for 10 minutes, washing and filtration with 70°C water 3.01 minutes was repeated twice, and finally 3.
LDE was obtained by stirring for 10 minutes using methanol at 50° C., washing and purification. The yield at that time is 5
15 g, yield was 88%.

Using the LDE obtained here, gels of various liquid oils were prepared in the same manner as in Example 1, and the results regarding the transmittance of the gels are shown in Table 4 below. As is clear from the wood surface, the DE prepared by adding methanol maintained its polar oil gel transparency at room temperature and low temperature, as in Example 1 in which water was added. At the same time, the stability was also satisfactory.

Example 3゜Under the same conditions as in Example 2, using lauric acid chloride, a pyridine catalyst (water content 0.0
1%), 55 g of ethanol was added, and the total amount of water and ethanol relative to the amount of dextrin was set at 36.1%, and the reaction was carried out at 92° C. for 4 hours to esterify. After that, 2.01 methanol was added to the pasty reaction product and 3.
Solid-liquid separation was performed by stirring for 0 minutes, and then the solid obtained by filtration was stirred and washed for 10 minutes with methanol 2.51 at 50 °C, and then washed again with methanol 2.51 at 50 °C Wash for 70 minutes and then wash for 70 minutes.
Stir for 15 min with water at 3.01 °C, wash and purify the LDE.
I got it. The yield was 510 g, and the yield was 87%.

Gels of various liquid oils were created using the LDE obtained by adding this ethanol. The transmittance results of the gel are also shown in Table 4 along with those of the methanol LDE of Example 2. It was determined that LDE prepared from the wood surface by adding ethanol was also extremely effective and gave satisfactory results.

Example 4 Using 590 g of lauric acid chloride, the average degree of polymerization was 2.
5. To 1657 g of dextrin with a moisture content of 2.2%, 7.5 g of glycerin was added under 650 g of pyridine catalyst (water content 0.01%) adjusted to have a degree of substitution of 2.0, and the amount of water relative to the amount of dextrin was and glycerin in a total amount of 6.8%, and esterification was carried out by reaction at 90° C. for 6 hours.

Thereafter, for the cleaning solution of Example 3, 60°C ethanol was used instead of methanol, and the L was washed in the same manner as in Example 3.
DE was obtained in an amount of 584 g and a yield of 88%.

Using this LDE, gels of various liquid oils were prepared in the same manner as in Example 2 or 3, and the results regarding the transmittance of the gels were also shown in Table 4. The DE prepared by adding this polar oil gel also maintained high transparency at room temperature and low temperature. At the same time, it was highly stable, with no changes such as cracking or oil seepage, and it maintained its transparency for a long period of time.

Example 5 Using 870 g of lauric acid chloride, the average degree of polymerization was 2.
64.5 g of ethanol was added to 1634 g of 0.8% water dextrin under 325 g of pyridine catalyst (moisture 0.01%) adjusted to have a degree of substitution of 2.2.
(equivalent to 39.5%) was added to make the total amount of water and ethanol to dextrin 40.2%, and the mixture was heated at 92°C.
The mixture was reacted for 4 hours to effect esterification. Thereafter, LDE was obtained by washing using the same method as in Example 1. The yield at that time was 625 g, and the yield was 926%.

Using the LDE obtained here, gels of various liquid oils were prepared in the same manner as in Example 1, and the results regarding the transmittance of the gels are shown in Table 5 below, along with the results of the LED gel produced with the addition of 23% ethanol. It was shown to. As is clear from the wood surface, LDE prepared by adding a large amount of ethanol also maintained its polar oil gel transparency at room temperature and low temperature, as in Example 1 where water was added. Ta. At the same time, the stability was also satisfactory.

Example 6 Dextrin 16 with an average degree of polymerization of 20.0.8% water and 924 g of lauric acid chloride was used in the same manner as in Example 5.
3 adjusted to have a degree of substitution of 2.2 for 3.4g
73.5g of ethanol (equivalent to 45.0%) was added to 25g of pyridine catalyst (moisture 0.01%) to make the total amount of water and ethanol to dextrin 45.8%, and then heated at 92°C for 4 hours. After the reaction and esterification, this was also washed in the same manner as in Example 1 to obtain LDE.

The yield at that time was 622.3 g, and the yield was 92.2%.

Using the LDE obtained here, GTO as a representative polar oil
When a gel was prepared and the transmittance of the gel was measured, it was found to be 723% at a holding temperature of 20°C and 69.8% at 5°C. In addition, it was determined that this gel has sufficient stability even after long-term storage without cracking or oil leaching. .

T% 600nlL.

T% Transmittance at 35℃ 600nw+.

T% LL) hCv direct pressure of chrycerin removal is Z.

U.

600 na.

T% [Effect of the invention] The gelling agent according to the present invention, that is, the dextrin fatty acid ester produced by the new manufacturing method, can be used in the production of cosmetics and pharmaceuticals.
In gelation of liquid oil, which was difficult with conventional technology,
For a wide range of base materials, regardless of whether they are polar or non-polar oils,
It provides transparency and also maintains low temperature stability and stability over time. As a result, LDE has greatly contributed to the cosmetics and pharmaceutical industries, not only by simplifying the usage of liquid oil gelling agents but also by expanding the scope of their application.
The substitution degree of is

Claims (2)

[Claims] (1) One or more types of dextrin or reduced dextrin with an average degree of polymerization of glucose of 3 to 100 and carbon atoms of 8 to 14
of saturated fatty acids in the presence of 3.0 to 50.0% of water or alcohol based on the total amount of the dextrin or reduced dextrin while using a tertiary amine as a catalyst, the degree of substitution of the fatty acids is adjusted to the glucose level of the dextrin. A liquid oil gelling agent characterized by comprising a dextrin fatty acid ester obtained by reacting and esterifying the dextrin fatty acid ester so as to have a ratio of 1.2 to 2.4 per unit. (2) One or more types of dextrin or reduced dextrin with an average degree of polymerization of glucose of 3 to 100 and carbon atoms of 8 to 14
of saturated fatty acids in the presence of 3.0 to 50.0% of water or alcohol based on the total amount of the dextrin or reduced dextrin while using a tertiary amine as a catalyst, the degree of substitution of the fatty acids is adjusted to the glucose level of the dextrin. 1. A method for producing a liquid oil gelling agent made of dextrin fatty acid ester, which comprises washing the product obtained by reacting and esterifying the dextrin fatty acid ester with water and alcohol so that the number of dextrin fatty acid esters is 1.2 to 2.4 per unit.