JP2567954B2 - Cleaning composition - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel polyglycerin monofatty acid ester-containing cleaning composition, and more specifically, it is obtained by subjecting polyglycerin having a low content of low polymers to an esterification reaction with a fatty acid. A polyglycerin monofatty acid ester-containing cleaning composition containing a polyglycerin monoester as an active ingredient, which has a high foaming power and is excellent in safety, and is sometimes suitable for oral use, food / tableware, and body washing It is about things.

BACKGROUND ART Conventionally, as a cleaning composition used in contact with the mucous membranes and skin of the human body, for example, an oral composition such as toothpaste, hair and scalp shampoo, body shampoo, facial cleanser, shaving foam, Food and tableware cleaners, residential cleaners, clothes and textile cleaners, selective finishing aids such as bleaching / softening agents, various industrial cleaners, etc. are known, but in these compositions In addition to surface properties such as surface tension, emulsifying / solubilizing power, and foaming power of the surfactant used, safety such as toxicity and skin irritation becomes a problem. Among the above-mentioned compositions, in particular, oral compositions, cleaning agents for food and tableware, and body cleaning agents such as shampoos require a highly safe surfactant, and fatty acid alkylolamides derived from animal and vegetable oils and fats are used. Various surfactants such as and higher alcohol-based nonionic surfactants, amino acid-based surfactants and castor oil-based surfactants have been developed and used.

On the other hand, polyglycerin fatty acid ester is known as a highly safe surfactant approved as a food additive and is mainly used as an emulsifying agent and a solubilizing agent for food, but it is also used for cosmetics, food and tableware. Detergent (JP-A-59-187096, JP-A-60-53599, JP-A-60-149)
699, 62-27493), oral compositions (JP-A-62-45513, 63-60917) and the like have been tried.

By the way, in order to obtain a polyglycerin fatty acid ester having a high foaming power, it is sufficient to use polyglycerin having an average degree of polymerization of 6 or more (JP-A-62-45513), HLB.
In order to obtain high polyglycerin fatty acid ester,
It is sufficient to use polyglycerin having an average degree of polymerization of 2 to 30 and a reaction molar ratio with a fatty acid of 1 or less (JP-A-63-23837
No. publication) is known. In addition, in order to increase the foaming power of the polyglycerin fatty acid ester and eliminate the bitterness and astringency during use, it is effective to react polyglycerin having an average degree of polymerization of 6 or more with a fatty acid having 10 to 20 carbon atoms. It is also known that there is (Japanese Patent Laid-Open No. 63-60917).

However, these polyglycerin fatty acid esters are comparable to monoglycerides, sugar esters, sorbitan esters, etc. as emulsifying and solubilizing agents, but their foaming power is not always sufficient and foaming power is required. When used in various cleaning compositions, improvement of foaming power has been desired.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention responds to such a demand, is excellent in safety,
In addition, the purpose of the present invention is to provide a cleaning composition containing a polyglycerin fatty acid ester having a high foaming power, which is particularly suitable for oral cavity, food / tableware, and body cleaning.

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on improving the foaming power of polyglycerin fatty acid ester, and as a result, low molecular weight polyglycerin, that is, polyglycerin having a low content of diglycerin and triglycerin. It was found that a polyglycerin monofatty acid ester obtained by reacting glycerin and a fatty acid at a predetermined ratio has excellent safety and high foaming power, and based on this finding, the present invention has been completed.

That is, the present invention is a polycondensation product of glycerin, wherein the total amount of glycerin, diglycerin and triglycerin is 20 wt% or less, polyglycerin mono obtained by reacting less than equimolar amount of fatty acid The present invention provides a cleaning composition containing a fatty acid ester mixture as an active ingredient.

 The present invention will be described in detail below.

Polyglycerin, which is one of the raw materials for the polyglycerin monofatty acid ester used in the composition of the present invention, is
It is usually produced by adding a small amount of a catalyst such as sodium hydroxide to glycerin and subjecting this to polycondensation in an atmosphere of an inert gas such as nitrogen or carbon dioxide at a high temperature of 180 ° C. or higher while removing generated water.

The polyglycerin thus obtained is not a single component, but is a linear polyglycerin condensed at the α-position, a branched polyglycerin partially condensed at the β-position, and a cyclic condensed inside the molecule. It is a mixture having an extremely complicated composition that contains polyglycerin, and these linear, branched, and cyclic polyglycerins each have a degree of polymerization distribution. Therefore, the degree of polymerization of this polyglycerin is usually represented by the average degree of polymerization obtained from the hydroxyl value. The degree of polymerization distribution of polyglycerin can be determined by gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC), etc. For example, commercially available decaglycerin having an average degree of polymerization of 10 is available. Exists from a monomer (glycerin) to a decamer or more, and the content of the monomer to the trimer is about 30% by weight. Here, the dimer and trimer are linear, branched,
It includes cyclic diglycerin and triglycerin.

In the present invention, as the polyglycerin, the total amount of monomers and trimers is 20% by weight or less, preferably 15% by weight.
It is used in an amount of not more than 10% by weight, and its average degree of polymerization is 6
The above are preferred. If the total amount of monomers or trimers exceeds 20% by weight or if the average degree of polymerization is less than 6, the foaming power is insufficient. Such polyglycerin can be produced, for example, by removing the monomer or trimer from the polyglycerin obtained by the above method, such as by molecular distillation or vacuum distillation.
Of course, the method is not limited to this.

As the fatty acid which is the other raw material of the polyglycerin monofatty acid ester used in the composition of the present invention, for example, a saturated or unsaturated fatty acid having 10 to 18 carbon atoms can be used. These fatty acids may be linear or branched, and may be used alone or in combination of two or more. Examples of the fatty acid include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid.

In the composition of the present invention, it is necessary to use a polyglycerin monofatty acid ester in order to increase the foaming ability.
It can be produced by reacting less than mol.
When the amount of the fatty acid used is 1 mol or more, the obtained polyglycerin fatty acid ester contains polyesters such as diesters and triesters, and the foaming power of the polyglycerin fatty acid ester decreases.

The method of this esterification reaction is not particularly limited, and any method such as chemical synthesis or enzymatic method may be used, but in the case of the chemical synthesis method, usually in the presence of an alkali catalyst such as sodium hydroxide, React at a high temperature of 180 ℃ or higher.

Various known components can be added to the composition of the present invention depending on the application. For use in the oral cavity, for example, an abrasive such as calcium carbonate or dicalcium phosphate, a thickener such as sorbid, a binder such as carboxymethyl cellulose, a sweetener, a flavoring agent and the like are added. In this case, the content of polyglycerin monofatty acid ester is usually selected in the range of 0.5 to 10% by weight. When used as a detergent for food and tableware, other anionic or nonionic surfactants, stabilizers such as ethanol, colorants and the like can be added.

EFFECTS OF THE INVENTION The composition of the present invention contains polyglycerin monofatty acid ester, is excellent in safety, and has high foaming power, and thus is used in contact with human mucous membranes or skin, particularly It is suitable for oral use, food and tableware, and body wash.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

 The foaming power was determined as follows.

That is, 3.5 wt% sample in 100 ml Epton tube
Add 20 ml of 3 ° DH hard aqueous solution containing 25 ° C for 15 seconds.
The mixture was shaken up and down 30 times, and the volume of the foam after 1 minute was measured and used as the foaming force.

Reference Example 1 150 g of commercially available polyglycerin having an average degree of polymerization of 10 was added to pyridine 10
It was dissolved in 00 ml, 610 ml of trimethylchlorosilane was gradually added thereto, and the mixture was stirred in an oil bath at about 60 ° C for 2 hours. After cooling the reaction solution, water was added and the mixture was extracted with diethyl ether, the extract was dehydrated with anhydrous sodium sulfate, and the diethyl ether was distilled off to obtain 203 g of a trimethylsilyl ether compound.

Next, this was distilled under reduced pressure to remove a low boiling point trimethylsilyl ether compound (180 to 210 ° C., 1 mmHg) to obtain 150 g of polyglycerin trimethylsilyl ether having a low content of monomer or trimer. Then, add diluted hydrochloric acid and 800 ml of methanol to this to adjust the pH to 3 to 4, hydrolyze and concentrate, and then treat with an ion exchange resin to obtain polyglycerin (average polymerization of 10% by weight of total amount of glycerin, diglycerin and triglycerin). 16) 80g was obtained.

80g (0.067mol) of this polyglycerin, lauric acid
5.4 (0.027 mol) and 0.08 g of sodium hydroxide were added, and the esterification reaction was carried out at 240 ° C. for 2 hours in a nitrogen atmosphere to obtain 84 g of pale yellow polyglycerol monolaurate.

The foaming power of this polyglycerin monolaurate is shown in Table 1.

Reference Example 2 2 g of sodium hydroxide was added to 204 g of diglycerin, and a dehydration condensation reaction was carried out at 240 ° C. for 2 hours in a nitrogen atmosphere. After cooling the reaction product, it was converted to trimethylsilyl ether in the same manner as in Reference Example 1, then distilled and then hydrolyzed to give polyglycerin (average degree of polymerization: 8) having a total amount of glycerin, diglycerin and triglycerin of 13% by weight. Obtained.

Next, to 100 g (0.164 mol) of this polyglycerin, 16.4 g (0.082 mol) of lauric acid and 1.2 g of sodium hydroxide
Was added and the esterification reaction was carried out at 240 ° C. for 2 hours in a nitrogen atmosphere to give 113 g of pale yellow polyglycerol monolaurate.
I got

The foaming power of this polyglycerin monolaurate is shown in Table 1.

Reference Example 3 Based on Reference Example 1, polyglycerol having an average degree of polymerization of 11, and a total amount of glycerin, diglycerin and triglycerin of 25% by weight was obtained, and then monolaurate thereof was produced.

The foaming power of this polyglycerin monolaurate is shown in Table 1. For comparison, the foaming power of commercially available decaglycerin monolaurate and hexaglycerin monolaurate is also shown in Table 1.

From Table 1, the polyglycerin monolaurate of Reference Examples 1 and 2 according to the present invention is more foamed than the polyglycerin monolaurate, the commercially available decaglycerin monolaurate and the commercially available hexaglycerin monolaurate of Reference Example 3. You can see that the power is high.

Example 1 Polyglycerin monolaurate obtained in Reference Example 1 and commercially available decaglycerin monolaurate were used as foaming agents, respectively, to prepare a dentifrice composition having the following composition, and the foaming thereof was conducted by seven general panelists. A pair of comparative sensory evaluations were carried out. Table 2 shows the results.

Toothpaste composition Dibasic calcium phosphate 45.0% by weight Cuic acid anhydride 3.0% by weight Carboxymethyl cellulose sodium 0.8% by weight Carrageenan 0.2% by weight Sorbit solution 26.0% by weight Propylene glycol 3.0% by weight Saccharin sodium 0.2% by weight Fragrance 1.0% by weight Foaming agent 6.0% by weight % Preservative 0.1% by weight Purified water balance 100.0 Example 2 1 mol of polyglycerin obtained in Reference Example 1 and 0.1% lauric acid
Polyglycerin monolaurate obtained by reacting with 8 mol and commercially available decaglycerin monolaurate were used as surfactants to prepare a kitchen cleaning composition having the following composition.

Kitchen cleaning composition Surfactant 30% by weight Ethanol 5% by weight Sodium toluenesulfonate 3% by weight Perfume 0.1% by weight Purified water balance 100.0 Dissolving 1.5 g of the cleaning composition in tap water 3 at 25 ° C. After compressing the sponge 10 times to generate bubbles with air, a dish contaminated with commercial salad oil was rubbed and washed, and the foaming was evaluated by 5 panelists. The result is the third
Shown in the table.

Claims (2)

(57) [Claims] 1. A polycondensation product of glycerin, wherein the total amount of glycerin, diglycerin and triglycerin is 20.
A cleaning composition containing, as an active ingredient, a polyglycerin monofatty acid ester mixture obtained by reacting less than or equal to wt% with an equimolar amount of a fatty acid. 2. The composition for oral cavity according to claim 1, which contains 0.5 to 10% by weight of a mixture of polyglycerin monofatty acid esters.