JPS6026401B2 - Amphoteric hydroxyethylcellulose derivative, method for producing the same, and dispersion stabilizer for aqueous cosmetics containing the same as an active ingredient - Google Patents

Description

[Detailed Description of the Invention] The present invention provides a novel amphoteric hydroxyethyl cellulose mill conductor suitable for use in salmon ingredients, medicines, foods, etc., a method for producing the same, and an aqueous salmon product containing the same as an active ingredient. This invention relates to a dispersion stabilizer for materials.

Water-soluble polymer compounds can be classified as anionic, ionic, nonionic, and amphoteric, and can also be divided into natural polymers, modified polymers, and synthetic polymers.

These water-dropping polymer compounds exhibit high viscosity at low concentrations, and have many hydrophilic groups in one molecule, allowing them to form protective colloids.As they also have film-forming properties, they are used in pharmaceuticals and foods. It is widely used as a raw material for IQ shoryo, etc. The water-soluble polymer compounds used in medicines, foods, and IQ test materials are particularly required to be safe for the human body. In some cases, it is required that the effect on the skin be small.

For this reason, natural polymer compounds or their derivatives among water-dropping polymer compounds have conventionally been mainly used for these purposes. However, the water-soluble natural polymer compounds to date, except for those derived from proteins, are anionic,
Most of them are ionic and nonionic, and a satisfactory amphoteric one has not yet been developed.

Moreover, in protein-based compounds, the ionic moiety is a primary or tertiary fumi/group, and the isophyte point is on the acidic side, so they are not necessarily satisfactory as amphoteric water-soluble polymer compounds. Ta. The present inventors have conducted intensive research to overcome the drawbacks of conventional amphoteric water-soluble polymer compounds and develop a new amphoteric water-soluble polymer compound based on natural polymer compounds. Using hydroxyethyl cellulose, which is relatively inexpensive and readily available, the inventors found that a compound obtained by amphoterizing it is suitable for the purpose, and has thus completed the present invention.

That is, the present invention is based on the general formula [A in the formula is 40 naps per day for 2 days,
0chiqX2, nhakiC2day40narX3 (X in each formula,
, X2 and x3 are each a hydrogen atom or an amphoteric group represented by the general formula (wherein R and R2 are methyl or ethyl groups, m is an integer of 1 to 6, and n is an integer of 1 to 2) ,
p, q and r are integers of 0 or 1 or more], and the average number of moles of oxyethylene groups added per each structural unit is 0.5 to 3.
0 The average number of amphoteric groups per each constituent unit is 0.02 to 1.
The present invention provides an amphoteric hydroxyethyl cellulose derivative having a polyhydric acid of 0.

This amphoteric hydroxyethylcellulose mysterious conductor is made of hydroxyethylcellulose obtained by adding 0.5 to 30 moles of ethylene oxide per anhydroglucose unit to cellulose having an average degree of polymerization of at least 50, and the general formula (Y in the formula is a halogen atom, R and R2 are methyl or ethyl groups, and m is an integer of 1 to 6) is reacted in the presence of an alkali to etherify the reaction product It can be produced by reacting a monohalogen with acetic acid or acrylic acid in the presence of an alkali to make it amphoteric.

In this case, the raw material cellulose used has an average degree of polymerization of at least 50.

When the degree of polymerization is lower than this, it becomes difficult to exhibit properties as a water-soluble polymer. On the other hand, although there is no particular upper limit to the degree of polymerization, there is a natural limit to the degree of polymerization of naturally occurring cellulose; for example, wood cellulose has a degree of polymerization of 5,000 to 600 Fahrenheit. Further, the number of moles of ethylene oxide added to this cellulose needs to be on average 0.5 to 3.0 per anhydroglucose unit. If the number of moles added is less than this, it will not be possible to obtain a derivative that exhibits sufficient water-removal properties, and if it is more than this, water absorption will increase and it will become sticky immediately if left in the air. There are handling problems.

Next, since the reaction between this hydroxyethylcellulose and the dialkylaminoalkyl halide of general formula (0) is a dehydrohalogenation reaction, an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc. This is done by stirring in the presence of

This reaction is preferably carried out in a suitable solvent such as alcohols, nitriles, esters, or a mixed solvent of these and water. The general formula (0) used in this case
Examples of dialkylaminoalkyl halides represented by include dimethylaminoethyl chloride, dietylaminoethyl chloride, 3-dimethylamino/propyl chloride, 4-dimethylaminobutyl chloride, and corresponding bromides and bromides.

These dialkylaminoalkyl halides need to be reacted in a sufficient amount to substitute 0.02 to 1.0 units per anhydroglucose unit of the above-mentioned hydroxyethyl cellulose. If the degree of substitution is less than 0.02 mo, sufficient protective colloidal properties will not be exhibited;
If the amount is greater than 0, no improvement in effectiveness can be expected and it is economically disadvantageous. In this way, at least one
Hydroxyethylcellulose having 2 dialkylaminoalkyloxyethyl groups is obtained.

The amphoteric reaction of this reaction product is carried out, for example, by reacting it with monohalogenoacetic acid or acrylic acid in a suitable solvent in the presence of an alkali. As the solvent and alkali in this case, those exemplified as those used in the fable-forming reaction are used. Further, the monohalogenoacetic acid or acrylic acid used as the amphoteric agent may be a free one or a salt such as a sodium salt or a potassium salt. Particularly preferred amphoteric agents are sodium monochloroacetate and acrylic acid. The amphoteric agent must be used in an amount sufficient to substantially completely quaternize the dialkylamide/alkyl groups in the etherified hydroxyethyl cellulose. Usually, an excess of the amphoteric agent over the calculated amount is used to achieve this purpose. By this amphoteric reaction, an amphoteric group represented by the general formula (R, , R2, m and n in the formula have the same meanings as above) is introduced into the molecule of hydroxyethyl cellulose.

From the reaction mixture obtained in this way, the solvent and the reaction components of the reaction are removed according to a conventional method, and then purified by filtration, washing, reprecipitation as desired, and the composition of the general formula (1) is obtained. An amphoteric hydroxyethyl cellulose derivative consisting of units is obtained.

Unlike proteins, the amphoteric hydroxyethylcellulose derivative of the present invention has an isometric point on the neutral or alkaline side, and is highly safe for the human body, so it is suitable as a dispersion stabilizer for various aqueous IQ-hoko materials. .

In this case, it is blended in a proportion of 0.1 to 5% by weight with respect to known liquid products such as shampoos, conditioners, and lotions, and slurry cosmetics such as creams. . The thus prepared iQ-yellow material exhibits dispersion stability several to ten times higher than that without the compound of the present invention. The compound of the present invention also imitates water solubility, protective colloid-forming ability, film-forming property, antistatic property, etc., so it can be used not only as an ingredient but also in toiletries, pharmaceuticals, thickeners, papermaking aids, fiber treatment, etc. It is suitable as an agent, paint additive, etc. Next, the present invention will be explained in more detail with reference to Examples.

Example 1 A four-necked flask equipped with a stirrer, an air-cooled condenser, and a thermometer was charged with 16 parts by weight of 2-propanol, 2 parts by weight of water, and 2 parts by weight of sodium hydroxide, and stirred at room temperature for 10 minutes. .

Next, 7 parts by weight of hydroxyethyl cellulose (AH-15 (trade name) manufactured by Fuji Chemical Co., Ltd.) with an added mole of ethylene oxide (MB) of 1.70 per anhydroglucose unit were added, and the mixture was stirred for 30 minutes at room temperature. Later, hydrochloric acid 8-
Add 1 part by weight of dithylaminoethyl chloride, 25q
Stir and react for 3 hours while maintaining the temperature at o. After the reaction was completed, the reaction product was filtered by 8U and thoroughly washed with excess 2-propanol, and the washing liquid was suction filtered using a water jet pump using a Buchner funnel to obtain an etherified reaction product. A total of 7 parts of the obtained reaction product was charged again into the four-necked flask, and then 16 parts by weight of 2-propanol, 4 parts by weight of water, and 3 parts by weight of sodium monochloroacetate were added thereto. and raised the temperature to 50℃ for 6 hours.
The mixture was stirred and reacted.

After the reaction was completed, the reaction product was filtered and dried to obtain 7 parts by weight of crude amphoteric hydroxyethyl cellulose. Next, 2 parts by weight were taken and dissolved in 200 parts by weight of water, and this aqueous solution was poured into 100 parts by weight of acetone to reprecipitate the amphoteric hydroxyethyl cellulose. The same reprecipitation operation was repeated three times to purify the reaction product. After reprecipitation and purification, drying under reduced technique yields purified amphoteric hydroxyethyl cellulose 15
Parts by weight were obtained. It was confirmed as follows that this material was the desired amphoteric cellulose having a quaternary ammonium group. First, when you carefully add anthrone reagent 1' to the 2% aqueous solution 2, the mirror surface turns blue or green.

This indicates that this reaction product has a cellulose skeleton. Also, when measuring its amine value,
It is 0, and when the nitrogen content is measured by Kjeldahl method, it is 1. % by weight. These results revealed that the nitrogen contained in the reaction product was quaternary nitrogen. Furthermore, when an infrared absorption spectrum was measured, as shown in the attached drawing, absorption indicating the presence of a carboxylate group was observed at 1620-1. In view of these results, it is clear that the reaction product contains 2N
It was confirmed that the e-quantity of H2C was C2day5>2.

Further, the content of oxyethylene groups contained in this reaction product was measured according to the method of Mr. Morgan and was found to be 27.5% by weight. The average number of substitutions (DS) per anhydroglucose unit of the amphoteric hydroxyethylcellulose group obtained here was 0.19.
The average number of moles (MS) of ethylene oxide added per anhydroglucose unit was 1.70.

Example 2 14 parts by weight of acetonitrile, 1 part by weight of water, and 25 parts by weight of sodium hydroxide were placed in a four-necked flask similar to that in Example 1, and the mixture was stirred for 3 times at room temperature.

Next, hydroxyethylcellulose (MS) of 2.1 moles of ethylene oxide per anhydroglucose unit (
After adding 7 parts by weight of H-300 (trade name) manufactured by Hoechst and stirring at room temperature for 1 hour, 4 parts by weight of 3-jethylaminoethyl chloride hydrochloride was added and the temperature was kept at 2yo.
I stirred it for a while and reacted. After the reaction was completed, the same treatment as in Example 1 was carried out to take out the reaction product, and the total amount of 7 sparse portions was charged into the same four-necked flask as above. Next, 14 parts by weight of acetonitrile, 2 parts by weight of water, and 25 parts by weight of sodium monochloroacetate were added to the mixture, the temperature was raised to 5.0 mm, and the mixture was reacted with stirring for 8 hours. After completion of the reaction, the reaction product 55 was purified by post-treatment in the same manner as in Example 1.
I took out the part. The amphoteric hydroxyethylcellulose thus obtained has an amine value of 0, and a nitrogen content determined by Kjeldahl method of 0. The amount of oxyethylene groups was 28.5% by weight according to Morgan's method. The D. of the groups and ethylene oxide groups of this reaction product determined from these measured values. S. and M. S. are 0.
17, and 1.71.

Example 3 In a four-necked flask similar to Example 1, 1 part of 2-propanol was added.
6 parts by weight, 2 parts by weight of water, and 2 parts by weight of sodium hydroxide were added and stirred for 1 hour at room temperature.

Next, hydroxyethylcellulose (Natrosol 25 Misakicho (trade name) manufactured by Hercules) with an added mole of ethylene oxide (MS) of 2.5 per anhydroglucose unit was added.
) 7 by weight was added and stirred at room temperature for 30 minutes.
3 parts by weight of 8-jethylaminoethyl chloride hydrochloride was added, and the mixture was stirred and reacted for 3 hours while maintaining the temperature at 25 oo. After the reaction was completed, the same treatment as in Example 1 was carried out to take out the product, and the total amount of 7 base portions was charged into a four-necked flask similar to the above. Next, 16 parts by weight of 2-propanol, 4 parts by weight of water, and 27.2 parts by weight of sodium monochloroacetate were added thereto, the temperature was raised to 50:00, and the mixture was reacted for 4 hours with stirring. After the reaction was completed, weight parts of the two animals were taken and the same post-treatment as in Example 1 was carried out to obtain the purified reaction product 1.
5 parts (75% yield after purification) were taken out. The amine value of this product is 0, and the nitrogen content by Keltal method is 1. The content of oxyethylene groups according to Morgan's method was 35.6% by weight. The D. of the group in this reaction product is calculated from these values. S. is 0.23,
MS of oxyethylene group was 2.49.

Example 4 160 parts by weight of 2-propanol, 2 parts by weight of water, and 2 parts by weight of sodium hydroxide were charged into a four-loaf flask equipped with a stirrer, an air-cooled condenser, and a thermometer, and the mixture was stirred at room temperature for 10 minutes.

'Next, 7 parts by weight of hydroxyethyl cellulose (manufactured by Fuji Chemical Co., Ltd., AH-15 (trade name)) with an added mole of ethylene oxide (MS) of 1.7 per anhydroglucose unit was added, and 30 After stirring for a minute, add 3 ml of hydrochloric acid.
-Add 25 parts by weight of jethylaminoethyl chloride.
The reaction was allowed to take place while stirring for 3 hours while maintaining the qo. After the reaction was completed, the reaction product was neutralized, filtered 8U, thoroughly washed with excess 2-propanol, and further filtered by suctioning the washing liquid with a water pump using a Puchner funnel. A total of 7 parts obtained by drying the reaction product thus obtained was charged again into the four-necked flask, and 16 parts of 2-propanol was added to the four-necked flask.
Add 25 parts by weight of acrylic acid and 25 parts by weight of acrylic acid and raise the temperature to 75q.
The temperature was increased to 0, and the reaction was allowed to proceed with stirring for 6 hours. After the reaction is complete, filter the reaction product, take 2 parts by weight and add 20 parts by weight of water.
This aqueous solution was poured into 100 parts by weight of acetone to reprecipitate the reaction product. The same reprecipitation operation is repeated three times to purify the reaction product. The reaction product after reprecipitation and purification is dried under reduced pressure. When the amine value of the amphoteric hydroxyethylcellulose thus obtained was measured, it was 0, and when the nitrogen content was measured by the Kjeldahl method, it was 1. % by weight. Also, when the oxyethylene group contained in this reaction product was measured according to Mr. Morgan's method, it was 27. It was box weight%. The DS of the groups in amphoteric hydroxyethyl cellulose calculated from this nitrogen content and the content of oxyethylene groups is 0.1
9 MS of ethylene oxide is 1. It was hot with spots.

Example 5 Using the amphoteric hydroxyethyl cellulose obtained in Example 1, a shampoo composition having the following composition was prepared.

(Heavy leather %) Lauryl ether sulfate sodium salt (ethylene oxide P = 3) 13 Coconut fatty acid jetanolamide 3 Zinc pyridione 1 Amphoteric hydroxyethyl cellulose 1 Water The remainder contains this composition and amphoteric hydroxyethyl cellulose as a control substance Each of the compositions containing 100% of zinc pyridione was placed in a measuring cylinder of 50 and left in a constant temperature bath at 45°C for 1 month, and the separated and sedimented volume of zinc pyridione was measured. The material was separated and sedimented severely, and its volume was 5 mm, and the upper 45 mm was clear.

Example 6 A rinse composition having the following composition was prepared using the amphoteric hydroxyethylcellulose obtained in Example 1.

(% by weight) N-dialkyl-N-dimethylammonium chloride (Alucard is T, (trade name), manufactured by Lion Akzo Co., Ltd.) 3-Ampholytic hydroxyethyl cell.

-1 fish lymph pack
0.3 Water Balance This composition showed better dispersion stability compared to the control without amphoteric hydroxyethylcellulose. Example 7 A cream composition having the following composition was prepared using the amphoteric hydroxyethylcellulose obtained in Example 1.

(Weight%) Vaseline 10 Liquid paraffin 10 Glycerin monostearate 0.5 Isopropylene palmitate 2 Glycerin 3
Amphoteric hydroxyethyl cellulose 2 Purified water
The rest of the composition showed better dispersion stability compared to the control without amphoteric hydroxyethyl cellulose and showed no irritation to the skin.

[Brief explanation of the drawing]

The drawing shows an infrared absorption spectrum of the amphoteric hydroxyethylcellulose of the present invention.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A_1 in the formula is -(C_2H_4O)_p-X_1
, A_2 is -(C_2H_4O)_q-X_2, A_3
-(C_2H_4O)_r-X_3 (X_1 in each formula
, X_2 and X_3 are each a hydrogen atom or a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 and R_2 are methyl or ethyl groups, m is an integer from 1 to 6, and n is an integer from 1 to 2) an amphoteric group represented by ), p, q and r are integers of 0 or 1 or more],
and an amphoteric hydroxyethyl cellulose derivative having an average number of added moles of oxyethylene groups per each structural unit of 0.5 to 3.0 and an average conversion number of amphoteric groups per each structural unit of 0.02 to 1.0. 2 Hydroxyethyl cellulose obtained by adding 0.5 to 30 moles of ethylene oxide on average per anhydroglucose unit to cellulose with an average degree of polymerization of at least 50, and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Y in the formula is A dialkylaminoalkyl halide represented by a halogen atom, R_1 and R_2 are methyl or ethyl groups, and m is an integer from 1 to 6) is reacted in the presence of an alkali, and then this reaction product is mixed with monohalogen acetic acid or acrylic acid. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting in the presence of an alkali ▼
[A_1 in the formula is -(C_2H_4O)_p-X_1
, A_2 is -(C_2H_4O)_q-X_2, A_3
-(C_2H_4O)_r-X_3 (X_1 in each formula
, X_2 and X_3 each have a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 and R_2 are methyl or ethyl groups, m is an integer from 1 to 6, and n is an integer from 1 to 2) an amphoteric group represented by ), p, q and r are integers of 0 or 1 or more],
A method for producing an amphoteric hydroxyethyl cellulose derivative, wherein the average number of moles of oxyethylene groups added per each structural unit is 0.5 to 3.0, and the average conversion number of amphoteric groups per each structural unit is 0.02 to 1.0. 3 General formula [A_1 in the formula is -(C_2H_4O)_p-X_1,
A_2 is -(C_2H_4O)_q-X_2, A_3 is -(C_2H_4O)_r-X_3 (X_1 in each formula,
X_2 and X_3 are each a hydrogen atom or a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, R_1 and R_2 are methyl or ethyl groups, m is an integer from 1 to 6, and n is an integer from 1 to 2). consisting of at least 50 structural units represented by the following amphoteric group), p, q and r are integers of 0 or 1 or more],
and an amphoteric hydroxyethylcellulose derivative having an average number of added moles of oxyethylene groups per each structural unit of 0.5 to 3.0 and an average conversion number of amphoteric groups per each structural unit of 0.02 to 1.0 as an active ingredient. A dispersion stabilizer for water-based cosmetics.