JPS6228761B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel cosmetic. In general, the ideal properties that cosmetic oils should have include: minimal skin irritation, no color or odor, no discoloration or deterioration over time, good texture, and good compatibility with other ingredients. Examples include having a viscosity suitable for the purpose and not interfering with the physiological functions of the skin. The purpose of the present invention is to provide an oil agent having the above-mentioned properties, which is viscous and has various physical properties ranging from water-solubility to oil-solubility. The aim is to obtain cosmetics for use. As conventional oils for cosmetics and ointments, glycerides and waxes obtained from animal and vegetable oils, and hydrocarbons such as vaseline and paraffin obtained from mineral oils are mainly used. Each of these oils has advantages and disadvantages, and in general, animal and vegetable oils and fats have drawbacks such as large fluctuations in quality and price, poor stability against oxidation, and quality deterioration over time. In addition, widely used hydrocarbon oils do not have polar groups in their molecules, so they have relatively good storage stability, but on the other hand, they do not have the desired feel due to the lack of polar groups. It has disadvantages such as poor compatibility with other ingredients, and is not necessarily suitable for use in cosmetics. In view of the current situation, the present inventors conducted extensive research and found that the following esterified composition satisfies the above object, and completed the present invention. That is, the present invention provides (1) a synthetic nitrogen polymer polyol represented by the following general formula, in which propylene oxide or (and) ethylene oxide is added and modified to the four active hydrogen atoms of ethylenediamine. (However, in the formula, n ₁ , n ₂ , n ₃ , n ₄ are 1 to 20, m ₁ , m ₂ ,
m ₃ and m ₄ are 0 to 15) and (2) an esterified composition obtained by esterifying a saturated aliphatic dicarboxylic acid or (and) an oxydylcarboxylic acid, or one or more salts thereof. It is a cosmetic that is characterized by the fact that it is formulated with The nitrogen-containing polymer polyol in the present invention is a product obtained by adding propylene oxide or (and) ethylene oxide to the four active hydrogens of ethylenediamine, and is generally used as a polyol raw material for various urethane resins and polyester resins, and as a surfactant. Commercially available products can be used. Known product names include Adeka Quadrol, Adeka Polyether EDP Series (Asahi Denka Kogyo Co., Ltd.), and Tetronik (W&D Chemical Co., Ltd. and Asahi Denka Kogyo Co., Ltd.). The general chemical formula of these polymer polyols is as shown in (1) below, which contains two tertiary amine nitrogen atoms in one molecule, exhibits weak basicity, and has an ether bond.
It is a nitrogen-containing polyether polyol having a secondary hydroxyl group or a primary hydroxyl group at the end of the molecule. (However, in the formula, n ₁ , n ₂ , n ₃ , n ₄ are 1 to 20, m ₁ , m ₂ ,
(m ₃ and m ₄ are 0 to 15) When both ethylene oxide and propylene oxide are added, either block polymerization or random polymerization may be used. Saturated aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, and these acids with saturated alkyl side chain groups can be used, and for esterification, they can be used singly or in combination of two or more, or mixed with the following oxydicarboxylic acids. use Malic acid and tartaric acid are used as the oxydicarboxylic acids, and in the esterification, they are used singly or as a mixture of two types. For the esterification, a conventional method such as an esterification reaction without a catalyst or in the presence of a catalyst under normal pressure or reduced pressure can be adopted. When reacting with excess acid in esterification, a product with a high acid value is obtained, but part or all of this acid value may be converted into an alkali metal salt such as sodium or potassium salt, or an amine salt such as triethanolamine or morpholine. Since the esterified composition in the present invention is an esterified product of a nitrogen-containing polyether polyol and an aliphatic dicarboxylic acid, so-called oligoesterified products with various physical properties can be produced by changing the alcohol excess rate or acid excess rate. is obtained. Furthermore, oil agents with various physical properties can be obtained by combining the number of moles of ethylene oxide or (and) propylene oxide added in the nitrogen-containing polyether polyol and the type of aliphatic dibasic acid. That is, ethylene oxide or (and)
By varying the number of moles of propylene oxide added, the desired performance can be obtained, from water-soluble to oil-soluble, and the type of aliphatic dibasic acid or excess rate during the reaction can be changed. This allows the viscosity and hydrophilicity to be adjusted freely. The esterified composition of the present invention has a higher viscosity than the original polymeric polyol and has an excellent texture. In this way, the esterified composition of the present invention is an oligoesterified product, which is a compound that has the properties of both a monomer and a polymer, which is different from conventional oil agents, and has low viscosity, hydrophilicity, and molecular weight. It is possible to arbitrarily change the cosmetics from high to high, and to produce distinctive cosmetics corresponding to each type. In addition, since the esterified composition of the present invention has an ether, an ester, and a terminal hydroxyl group introduced into one molecule, intermolecular association can be expected, and furthermore, since a polyether polyol of a tetrahydric alcohol is used, The oligoesterified product has a three-dimensional structure, and the intermolecular association becomes stronger, making it possible to obtain sufficient viscosity compared to an oil agent of the same molecular weight. Furthermore, the esterified composition of the present invention contains two tertiary amine nitrogen atoms in the polyether polyol used, exhibits weak basicity, and therefore has good adsorption and texture to the hair. Since there are ether groups and ester groups in the same molecule, these characteristics combine to create an extremely soft finish on hair. Furthermore, this esterified composition is not irritating to the human body. From the above, the esterified composition of the present invention has functions as a gelling agent, a dispersing agent, a solubilizing agent, and a moisturizing agent, so cosmetics containing it can be used as creams, lotions, etc. for the skin. is also suitable. Furthermore, due to the above characteristics, the esterified composition of the present invention is useful as a fatliquoring agent for shampoos and rinses, and is also suitable for aerosol applications for hair. That is, the cosmetic of the present invention contains the above-mentioned esterified composition as an essential component, and during production, commonly used components and optional components are appropriately blended. That is, cosmetics may be produced by conventional methods by replacing all or part of conventional oils, gelling agents, etc. with the above-mentioned esterified composition. Next, the present invention will be explained in more detail based on examples. [] Preparation of esterified composition Esterified compositions having the compositions shown in Table 1 were prepared in the following manner (Samples Nos. 11 and 12 are control examples). In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a water separator, 541 g of a nitrogen-containing polymer polyol (trade name: Tetronic 701 (Asahi Denka Kogyo Co., Ltd.)) and 16.2 g of succinic anhydride were placed in a four-neck flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a water separator. g. As an esterification catalyst, tin chloride is 0.5% of the total amount charged, and xylene is 5% of the total amount charged.
The mixture was added, stirred well, and reacted at 160 to 230°C for 8 hours. After the reaction is completed, the catalyst is filtered off, dried under reduced pressure, then decolorized under reduced pressure with 2% white clay and 0.4% activated carbon, filtered off the white clay and activated carbon, and deodorized with steam under reduced pressure. Yellow-brown odorless Tetronik
701 succinic acid oligoester (sample No. 5) was obtained. Esterified compositions of samples Nos. 1 to 4 and 6 to 10 were obtained in the same manner. [] Properties of Esterified Compositions The acid value, solubility in aqueous ethanol, and viscosity of these esterified compositions were examined, and the results shown in Table 1 were obtained. That is, these esterified compositions have a higher viscosity than the corresponding original polymeric polyol and also have a better hand. On the other hand, the presence or absence of irritation of the esterified composition to the human body and the presence or absence of odor were also investigated. First, the primary irritation to the human body was investigated using an occlusion patch test as follows. Specifically, keratin and sebum were removed from the epidermis of the anterior or flexor side of the upper arm of 20 healthy people, and a 1-inch square lint cloth coated with the sample was applied to the surface of the skin, covered with oiled paper, and then covered with a paper bandage. It is fastened on four sides with parallel strings, and is then held down with a bandage from above. When the presence or absence of irritation was determined in this state after 24 hours, 48 hours, and one week, almost no irritation was observed in the esterified compositions (Nos. 1 to 10) that met the conditions of the present invention. , was found to be useful as an oil for cosmetics. In addition, 0.2g was applied to the skin surface of the anterior groin area of 20 healthy people.
Apply the sample over a 2-inch square, and after 10 minutes, 20 minutes, 30 minutes, 1 hour, 4 hours, and 8 minutes.
When the odor was evaluated by sense of smell after a period of time, all of the esterified compositions (Nos. 1 to 10) that met the conditions of the present invention had no odor at all. [] Preparation of cosmetics Cosmetics are prepared by mixing commonly used ingredients in addition to the essential esterified composition. Any of Sample Nos. 1 to 10 can be used as the esterified composition, and formulation examples using some of them are shown below. Formulation example 1 (Liquid hair conditioner) Esterified composition No. 8 20% by weight Ethanol 40 Purified water 40 Perfumes and pigments Trace amounts Formulation example 2 (Liquid hair conditioner) Esterified composition No. 9 15% by weight Glycerin 1 Ethanol 45 Purified water 39 Fragrances and pigments Trace amount Formulation example 3 (Water-soluble pasty hair conditioner) Esterified composition of No. 5 50% by weight Polypropylene glycol (Average molecular weight 1000) 25 Polypropylene glycol (Average Molecular weight 2000) 25 〃 Fragrances and pigments Trace amount Formulation example 4 (Hand cream) Stearic acid 4.0% by weight Liquid paraffin 10.0 〃 Paraffin 8.0 〃 Esterified composition of No. 5 4.0 〃 Stearyl alcohol 4.3 〃 Silicone oil 1.0 〃 Polyoxyethylene Cetyl ether (2EO)
1.5 〃 Triethanolamine 1.0 〃 Preservative Appropriate amount Purified water Total amount 100.0% Formulation example 5 (Transparent oil shampoo)

[Table] 〓

Claims (1)

[Claims] 1. A nitrogen-containing polymeric polyol represented by the following general formula, in which propylene oxide or (and) ethylene oxide is added and modified to the four active hydrogens of ethylenediamine. (However, in the formula, n ₁ , n ₂ , n ₃ , n ₄ are 1 to 20, m ₁ , m ₂ ,
m ₃ , m ₄ is 0 to 15) and (2) saturated aliphatic dicarboxylic acid or (and) oxydylcamboxylic acid, or one or more esterified compositions or salts thereof. Cosmetics characterized by being formulated with