JP4747075B2 - Cosmetics and external preparations - Google Patents

Description

  The present invention relates to a nonionic surfactant containing a dimer diol and a derivative obtained by adding an alkylene oxide (C2 to C3) to dimer acid, and a cosmetic and an external preparation containing the nonionic surfactant. More specifically, a nonionic surfactant containing a dimer diol excellent in safety, stability, performance, etc. and a derivative obtained by adding an alkylene oxide to dimer acid, and safety containing this nonionic surfactant, The present invention relates to a cosmetic and an external preparation excellent in stability, feeling of use and the like.

  Conventionally, nonionic surfactants containing polyoxyalkylene / higher alcohol ethers and polyoxyalkylene higher fatty acid esters have been used in cosmetics and external preparations. For example, polyoxyethylene (hereinafter abbreviated as POE) -nonylphenol ether, POE-octylphenol ether, POE-stearyl ether, POE-oleyl ether, POE-oleate, POE-stearate, etc. are used (for example, (See Patent Documents 1 and 2).

JP 2006-76899 A JP 2006-182703 A

  However, these nonionic surfactants are not always satisfactory in terms of safety, stability, feeling of use and the like as raw materials for cosmetics and external preparations. Therefore, a raw material that is further excellent in safety, stability, feeling of use, pigment dispersibility, solubilization performance, odor and the like has been desired. As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a nonionic surfactant containing a dimer diol and a derivative obtained by adding an alkylene oxide (C2 to C3) to a dimer acid is a cosmetic or an external preparation. The present invention was completed by finding out that it is excellent in safety, stability, usability, etc.

The present invention provides a nonionic surfactant containing a derivative obtained by adding a single alkylene oxide ( any one of alkylene carbon number C2 or C3) to dimer diol and dimer acid. The present invention further provides cosmetics and external preparations that are excellent in safety, stability, feeling of use and the like, containing the nonionic surfactant.

(1) A nonionic surfactant composition obtained by addition polymerization of a single alkylene oxide (any one of alkylene carbon number C2 or C3) to dimer acid or dimer diol, having the structure shown below A cosmetic containing at least one selected from the group consisting of a polyoxyalkylene dimer diol ether addition polymer and a polyoxyalkylene dimer acid addition polymer.

(However, in the formula, a, b, c and d are integers of 1 or more and a + b + c + d = 12 to 40. Also, (RO) and (R′O) are attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer 10-90.)

(However, in the formula, e, f, g, and h are integers of 1 or more and in the range of e + f + g + h = 12 to 40. Also, (RO), (R′O) is attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.)

(2) A nonionic surfactant composition obtained by addition polymerization of a single alkylene oxide (any one of alkylene carbon number C2 or C3) to dimer acid or dimer diol, having the structure shown below It is an external preparation containing at least one selected from the group consisting of a polyoxyalkylene dimer diol ether addition polymer and a polyoxyalkylene dimer acid addition polymer.

(However, in the formula, a, b, c and d are integers of 1 or more and a + b + c + d = 12 to 40. Also, (RO) and (R′O) are attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.)

(However, in the formula, e, f, g, and h are integers of 1 or more and in the range of e + f + g + h = 12 to 40. Also, (RO), (R′O) is attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.)

  Cosmetics and external preparations containing the polyoxyalkylene dimer acid ester and the polyoxyalkylene dimer diol ether derivative according to the present invention as an active ingredient in one or more nonionic surfactant compositions are excellent in safety and functionally. It can be excellent.

  Hereinafter, the present invention will be described in detail.

  The dimer acid used in the polyoxyalkylene dimer acid ether represented by the above chemical formula 2 used in the present embodiment is a known dibasic acid obtained by an intermolecular polymerization reaction of an unsaturated fatty acid, and its industrial production The process is almost standardized in the industry. For example, dimer acid and its lower alcohol ester are obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms or its lower alcohol ester with a clay catalyst. The dimer acid obtained industrially is mainly composed of a dibasic acid having about 36 carbon atoms, but contains an arbitrary amount of trimer acid and monomer acid depending on the degree of purification. In general, dimer acid content of over 70% by weight and dimer acid content increased to 90% by weight or more by molecular distillation are in circulation. Although a double bond remains after the dimerization reaction, a hydrogen bond that has been further hydrogenated to improve oxidation stability is on the market. In the present invention, any dimer acid currently in circulation can be used.

  The dimer diol obtained industrially contains other components such as trimmer triol, monoalcohol and ether compound depending on the degree of purification of the above-mentioned dimer acid used as a raw material and its lower alcohol ester. In general, any dimer diol content exceeding about 70% by weight can be used in the present invention, but a high purity dimer diol, for example, a dimer diol content exceeding 90% by weight is preferred.

  The alkylene oxide used in the present invention is not particularly limited as long as it has C2 to C3 carbon atoms, but preferably has C2 carbon atoms. Examples of the alkylene oxide used in the present invention include ethylene oxide and propylene oxide.

  The synthesis conditions of the polyoxyalkylene dimer acid ester derivative and the polyoxyalkylene dimer diol ether derivative contained in the nonionic surfactant of the present invention were charged with dimer acid or dimer diol, and alkali such as sodium hydroxide or potassium hydroxide. A catalyst is added, and an arbitrary amount of alkylene oxide is added at a reaction temperature of 100 ° C to 200 ° C.

  The nonionic surfactant used in this embodiment in which alkylene oxide is addition-polymerized to dimer acid is used from a lipophilic substance to a hydrophilic substance, and from a liquid substance to a solid substance depending on the type and addition conditions of alkylene oxide. Can be manufactured in a wide range.

  The substance obtained by addition-polymerizing only ethylene oxide as an alkylene oxide to dimer acid is preferably ethylene oxide (1 mol to 200 mol) with respect to dimer acid (1 mol), more preferably (5 mol to 100 mol). . The obtained polyoxyethylene (hereinafter abbreviated as “POE”) (n mol) dimer acid ester compound is an oil-soluble nonionic surfactant in which n = 10 mol or less is an adduct and n = 10 mol or more is an adduct. It was a hydrophilic nonionic surfactant.

  The material obtained by addition polymerization of only propylene oxide as alkylene oxide to dimer acid is preferably propylene oxide (1 mol to 200 mol), more preferably (2 mol to 100 mol), relative to dimer acid (1 mol). It is. The obtained polyoxypropylene (hereinafter abbreviated as “POP”) dimer acid ester compounds were all oil-soluble nonionic surfactants.

  The material obtained by blocking and random addition polymerization of ethylene oxide and propylene oxide as alkylene oxide to dimer acid is preferably propylene oxide (1 mol to 50 mol) and ethylene oxide (2 mol to 100 mol) with respect to dimer acid (1 mol). More preferably, it is in the range of propylene oxide (1 mol to 10 mol) and ethylene oxide (2 mol to 100 mol). The obtained POP + POE dimer acid ester compound could be developed in a wide variety from a liquid appearance to a solid one, a strong emulsification and solubilization performance to a weak one.

  The substance obtained by addition-polymerizing only ethylene oxide as alkylene oxide to dimer diol is preferably ethylene oxide (1 mol to 200 mol) with respect to dimer diol (1 mol), more preferably in the range of (5 mol to 100 mol). . The obtained polyoxyethylene (n mole) dimer diol ether compound is an oil-soluble nonionic surfactant with an adduct of n = 10 mol or less, and a hydrophilic nonionic surfactant with an adduct of n = 10 mol or more. there were.

  The material obtained by addition polymerization of only propylene oxide as alkylene oxide to dimer diol is preferably propylene oxide (1 mol to 200 mol), more preferably (2 mol to 100 mol), relative to dimer diol (1 mol). It is. All of the obtained POP (nmol) dimer acid ester compounds were oil-soluble nonionic surfactants.

  A material obtained by blocking and random addition polymerization of ethylene oxide and propylene oxide as alkylene oxide to dimer diol is preferably propylene oxide (1 mol to 50 mol) and ethylene oxide (2 mol to 100 mol) with respect to dimer diol (1 mol). More preferably, it is in the range of propylene oxide (1 mol to 10 mol) and ethylene oxide (2 mol to 100 mol). The obtained POP + POE dimer diol ether compound could be developed in a wide variety from a liquid appearance to a solid appearance, a strong emulsification and solubilization performance to a weakness.

  Dimer acid and dimer diol have a molecular weight twice that of conventional higher fatty acids and higher alcohols, and their alkylene oxide adducts are excellent in safety, stability, touch, etc. It is possible to provide cosmetics and external preparations that have no stability, good stability, and excellent usability.

  Although the compounding quantity of the nonionic surfactant of this invention to cosmetics and a skin external preparation is not specifically limited, About 0.1 to 50% is desirable, More preferably, it is 0.5 to 30%.

  One or more polyoxyalkylene dimer acid ester or polyoxyalkylene dimer diol ether derivative used in the present embodiment is a cleansing oil, a facial cleansing foam, a cleansing cream, a cleansing gel, a massage cream, a cold cream, an emollient cream. , Moisture cream, Hand cream, Emollient milk, Moisture milk, Hand milk, Lotion, Pack, Foundation, Lipstick, Press powder, Eye shadow, Chick, Hair kit, Set lotion, Permanent wave liquid, Hair cream, Hair lotion, Hair mousse , Shampoo, hair rinse, hair conditioner, body shampoo, solid detergent, liquid detergent, antiperspirant, after shave cream, sunscreen Over arm, sunscreen oils, hair tonics, hair tonic, bath agents, can be used as a nonionic surfactant upon adjustment of cosmetics and external preparations such as external pharmaceutical composition. There are no particular restrictions on the dosage forms of cosmetics and external preparations, and any emulsification system, solubilization system, solution system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, etc. It may be a dosage form.

  The cosmetics and external preparations of the present embodiment include, as oil phase materials, saturated or unsaturated fatty acids and higher alcohols obtained therefrom, squalane, castor oil and derivatives thereof, lanolins including beeswax, liquid and refined lanolin, and Derivatives, cholesterol and derivatives thereof, macadamia nut oil, jojoba oil, carnauba wax, sesame oil, cacao oil, palm oil, mink oil, tree wax, candelilla wax, whale wax and other oil-phase raw materials, paraffin, microcrystalline wax Oil phase raw materials such as liquid paraffin, petrolatum, ceresin and other petroleum and minerals, methylpolysiloxane, polyoxyethylene / methylpolysiloxane, polyoxypropylene / methylpolysiloxane, poly (oxyethylene / oxypropylene) / methylpoly Siloxa Silicone polymers such as silicone polymers such as methylphenyl polysiloxane, fatty acid-modified polysiloxane, aliphatic alcohol-modified polysiloxane, amino acid-modified polysiloxane, resin acids, esters, ketones, oily components For example, the polyoxyalkylene dimer acid ester or polyoxyalkylene dimer diol ether adduct of the present invention can be used in combination as long as the effect of the nonionic surfactant is not impaired.

  In addition, the cosmetics and external preparations of the present embodiment include the polyoxyalkylene dimer acid ester and the polyoxyalkylene dimer diol ether or the nonionic surfactant composition used in the present embodiment as long as the effects of the composition are not impaired. Other surfactants include N-long chain acyl amino acid salts such as N-long chain acyl acidic amino acid salts and N-long chain acyl neutral amino acid salts; N-long chain fatty acid acyl-N-methyl taurine salts, alkyls Sulfates and alkylene oxide adducts, fatty acid amide ether sulfates, fatty acid metal salts and weak bases, sulfosuccinic acid surfactants, alkyl phosphates and their alkylene oxide adducts, anionic surfactants such as alkyl ether carboxylic acids; higher alcohols And its alkylene oxide adducts Type nonionic surfactants, ether ester type nonionic surfactants such as glycerin esters and sorbitan esters adducts thereof, polyoxyalkylene fatty acid esters, glycerin esters, fatty acid polyglycerin esters, N-long chain acyl peptide polyglycerin Ester surfactants such as esters, sorbitan esters, sucrose fatty acid esters, alkylglycosides, hydrogenated castor oil pyroglutamic acid diester and its ethylene oxide adducts, and nitrogen-containing nonionic surfactants such as fatty acid alkanolamides Aliphatic amine salts such as alkyl ammonium chloride and dialkyl ammonium chloride, quaternary ammonium salts thereof, aromatic quaternary ammonium salts such as benzalkonium salt, fatty acids Various surfactants such as cationic surfactants such as silarginine esters; amphoteric surfactants such as betaine type surfactants such as carboxybetaine, aminocarboxylic acid type surfactants, and imidazoline type surfactants; In addition to the polyoxyalkylene dimer acid ester and polyoxyalkylene dimer diol ether of the present invention or a nonionic surfactant composition thereof, they can be blended.

  Furthermore, the cosmetic and the external preparation of the present embodiment include, as an aqueous phase component, amino acids such as glycine, alanine, serine, threonine, arginine, glutamic acid, aspartic acid, leucine, and valine; glycerin, ethylene glycol, 1, Polyhydric alcohols such as 3-butylene glycol, propylene glycol and dipropylene glycol; polyamino acids including polyglutamic acid and polyaspartic acid and salts thereof, polyethylene glycol, gum arabic, alginate, xanthan gum, hyaluronic acid, hyaluronic acid salt, Chitin, chitosan, water-soluble chitin, carboxyvinyl polymer, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyltrimethylammonium chloride, polydimethylmethylenepiperide , Quaternary ammonium, polyvinylpyrrolidone derivatives, cationized proteins, collagen degradation products and derivatives thereof, acylated proteins, polyglycerols, amino acid polyglycerol esters, and other water-soluble polymers; sugar alcohols such as mannitol and alkylene oxide adducts thereof As well as lower alcohols such as ethanol and propanol.

  Furthermore, examples of additives and medicines that are blended in the cosmetics and external preparations of the present embodiment include those that are usually blended in cosmetics and external preparations. For example, preservatives such as paraben derivatives, fragrances, pigments, pearlizing agents, antibacterial agents, antibacterial agents, anti-inflammatory agents, analgesics, antifungal agents, keratin softening and release agents, UV protection agents, hair restorers, whitening agents, Antiperspirants, sweat deodorants, vitamins, pH adjusters, hormone agents, viscosity adjusters, herbal medicines and the like can be blended.

  Nonionic containing the above POE (n) dimer acid ester and POE (n) dimer diol ether or one or more thereof as an active ingredient, to be blended in cosmetics and external preparations prepared by appropriately blending the above ingredients The amount of the surfactant used varies depending on the product form, but is usually 0.01 to 100% by weight (the nonionic surfactant composition of the present invention is used as it is, for example, as a makeup remover without adding other components. Can be used), preferably 0.1 to 50% by weight.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Example 1: Synthesis of POE (5 mol) dimer diol ether;
Dimer diol ("Pripol 2033" manufactured by Unikema, in Examples 1-11, 23, 25-28, this product was used as a dimer diol for synthesis) was charged with 800 g, stirred, and nitrogen was introduced. While raising the temperature. When the temperature is raised to 80 ° C., 1.6 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 328 g of ethylene oxide was added in a reaction time of 2 hours and 20 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Precoat filtration was performed using diatomaceous earth to obtain 1072 g of the product (yield: about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.10, a hydroxyl value of 144.21 (theoretical value 148.2), and an HLB value = 5.2.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3450cm < ^-1 > (hydroxyl group) and 1120cm < ^-1 > (ether).

Example 2: Synthesis of POE (10 mol) dimer diol ether;
650 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 2.6 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 533 g of ethylene oxide was added in a reaction time of 2 hours and 05 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 7.5 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration was performed to obtain 1124 g (yield: about 95%) of the product.

  As a result of analysis of this product, it was a compound having an acid value of 0.15, a hydroxyl value of 114.45 (theoretical value: 114.9), and an HLB value = 7.6.

As a result of measuring the infrared absorption spectrum of this compound, characteristic absorption was observed at wavelengths of 3477 cm ⁻¹ (hydroxyl group) and 1118 cm ⁻¹ (ether).

Example 3: Synthesis of POE (20 mol) dimer diol ether;
Charge 600 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 984 g of ethylene oxide was added in a reaction time of 2 hours and 20 minutes, it was cooled with water and neutralized with 7.5 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Using diatomaceous earth, precoat filtration was performed to obtain 1505 g of product (yield: about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.11, a hydroxyl value of 79.77 (theoretical value: 79.2), and an HLB value = 10.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3485cm < ^-1 > (hydroxyl group) and 1119cm < ^-1 > (ether).

Example 4: Synthesis of POE (30 mol) dimer diol ether;
Charge 350 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 2.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 861 g of ethylene oxide was added in a reaction time of 2 hours and 20 minutes, the reaction solution was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration was performed to obtain 1150 g (yield: about 95%) of the product.

  As a result of analysis of this product, it was a compound having an acid value of 0.18, a hydroxyl value of 60.15 (theoretical value: 60.4), and an HLB value = 12.0.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3491cm < ^-1 > (hydroxyl group) and 1113cm < ^-1 > (ether).

Example 5: Synthesis of POE (40 mol) dimer diol ether;
Charge 350 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1148 g of ethylene oxide was added in a reaction time of 2 hours and 40 minutes, it was cooled with water and neutralized with 110 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Using diatomaceous earth, precoat filtration was performed to obtain 1423 g (yield: about 95%) of the product.

  As a result of analysis of this product, it was a compound having an acid value of 0.17, a hydroxyl value of 47.1 (theoretical value 48.9), and an HLB value = 13.4.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3487cm < ^-1 > (hydroxyl group) and 1111cm < ^-1 > (ether).

Example 6: Synthesis of POE (50 mol) dimer diol ether;
280 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 2.8 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1148 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized with 10 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Using diatomaceous earth, precoat filtration gave 1328 g of product (yield about 93%).

  As a result of analysis of this product, it was a compound having an acid value of 0.21, a hydroxyl value of 41.36 (theoretical value: 41.0), and an HLB value = 14.2.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3499cm < ^-1 > (hydroxyl group) and 1119cm < ^-1 > (ether).

Example 7: Synthesis of POE (60 mol) dimer diol ether;
200 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 2.4 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 984 g of ethylene oxide was added in 2 hours and 20 minutes, the reaction was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration was performed to obtain 1101 g of product (yield: about 93%).

  As a result of analysis of this product, it was a compound having an acid value of 0.35, a hydroxyl value of 41.36 (theoretical value 41.0), and an HLB value = 14.7.

Per present compounds, as a result of infrared absorption spectrum measurement, wavelength 3500 cm ^-1 (hydroxyl group), and 1111cm revealed a characteristic absorption to ^-1 (ether).

Example 8: Synthesis of POE (70 mol) dimer diol ether;
Charge 250 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.8 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1435 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized with 10 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Precoat filtration using diatomaceous earth gave 1567 g of product (yield about 93%).

  As a result of analysis of this product, it was a compound having an acid value of 0.33, a hydroxyl value of 31.41 (theoretical value 31.0), and an HLB value = 15.2.

Per present compounds, as a result of infrared absorption spectrum measurement, wavelength 3500 cm ^-1 (hydroxyl group), and 1115cm revealed a characteristic absorption to ^-1 (ether).

Example 9: Synthesis of POE (80 mol) dimer diol ether;
Charge 240 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.6 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1572 g of ethylene oxide was added in a reaction time of 2 hours and 40 minutes, it was cooled with water and neutralized with 10 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Using diatomaceous earth, precoat filtration was performed to obtain 1631 g (yield: about 90%) of the product.

  As a result of analysis of this product, it was a compound having an acid value of 0.23, a hydroxyl value of 28.41 (theoretical value 27.7), and an HLB value = 15.6.

As a result of measuring the infrared absorption spectrum of this compound, characteristic absorption was observed at wavelengths of 3487 cm ⁻¹ (hydroxyl group) and 1115 cm ⁻¹ (ether).

Example 10: Synthesis of POE (90 mol) dimer diol ether;
200 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 4.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. After 1474 g of ethylene oxide was added in a reaction time of 2 hours and 40 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 8 cc of a 50% aqueous citric acid solution. Precoat filtration was performed using diatomaceous earth to obtain 1507 g (yield: about 90%) of the product.

  As a result of analysis of this product, it was a compound having an acid value of 0.25, a hydroxyl value of 26, 23 (theoretical value: 25.00), and an HLB value = 15.9.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3287cm < ^-1 > (hydroxyl group) and 1115cm < ^-1 > (ether).

Example 11: Synthesis of POE (100 mol) dimer diol ether;
200 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 4.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1,638 g of ethylene oxide was added in a reaction time of 2 hours and 40 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 8 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 11654 g of product (yield about 90%).

  As a result of analysis of this product, it was a compound having an acid value of 0.28, a hydroxyl value of 23.45 (theoretical value 22.00), and HLB = 16.1.

As a result of measuring the infrared absorption spectrum of this compound, characteristic absorption was observed at wavelengths of 3487 cm ⁻¹ (hydroxyl group) and 1115 cm ⁻¹ (ether).

Example 12: Synthesis of POE (5 mol) dimer acid ester;
Dimer acid ("Pripol 1009" manufactured by Unikema, in Examples 12-22, 24, 29-32, this product was used for synthesis as dimer acid) was charged with 1000 g, stirred, and nitrogen was introduced. While raising the temperature. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 390 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration was performed to obtain 1321 g of product (yield: about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.95, a hydroxyl value of 135.04 (theoretical value 143), a saponification value of 141.45 (theoretical value 143), and an HLB value = 6.1.

As a result of measuring the infrared absorption spectrum of this compound, characteristic absorption was observed at wavelengths of 3451 cm ⁻¹ (hydroxyl group), 1738 cm ⁻¹ (ester) and 1128 cm ⁻¹ (ether).

Example 13: Synthesis of POE (10 mol) dimer acid ester;
750 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while flowing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. After adding 585 g of ethylene oxide in a reaction time of about 2 hours, the mixture was cooled with water and neutralized at 110 to 120 ° C. with 6 cc of a 50% aqueous citric acid solution. Precoat filtration using diatomaceous earth gave 1268 g of product (yield about 95%).

  As a result of analysis of this product, a compound having an acid value of 0.51, a hydroxyl value of 111.75 (theoretical value 111.7), a saponification value of 115.34 (theoretical value 111.7), and an HLB value = 8.3 was obtained. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3469.94cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1122.57cm < ^-1 > (ether).

Example 14: Synthesis of POE (20 mol) dimer acid ester;
Charge 500 g of dimer acid (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 780 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 6 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1216 g of product (yield about 95%).

  As a result of analysis of this product, a compound having an acid value of 0.65, a hydroxyl value of 78.5 (theoretical value: 77.7), a saponification value of 77.0 (theoretical value: 77.7), and an HLB value = 11.1. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3469.94cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1122.57cm < ^-1 > (ether).

Example 15: Synthesis of POE (30 mol) dimer acid ester;
Charge 400 g of dimer acid (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 2.8 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 936 g of ethylene oxide was added in a reaction time of 2 hours and 20 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 6 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1269 g of product (yield about 95%).

  As a result of analysis of the product, the product was found to be a compound having an acid value of 0.72, a hydroxyl value of 64.2 (theoretical value 59.5), a saponification value of 59.42 (theoretical value 59.5), and an HLB value = 12.7. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 16: Synthesis of POE (40 mol) dimer acid ester;
Charge 350 g of dimer acid (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1092 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 6 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1370 g of product (yield about 95%).

  As a result of analysis of this product, a compound having an acid value of 0.80, a hydroxyl value of 53.3 (theoretical value 48.3), a saponification value of 48.10 (theoretical value 48.3), and an HLB value = 13.7 was obtained. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 17: Synthesis of POE (50 mol) dimer acid ester;
Charge 300 g of dimer acid (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1167 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Precoat filtration was performed using diatomaceous earth to obtain 1364 g (yield: about 93%) of the product.

  As a result of analysis of the product, the product was a compound having an acid value of 0.76, a hydroxyl value of 45.2 (theoretical value 40.6), a saponification value of 41.0 (theoretical value 40.6), and an HLB value = 14.5. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 18: Synthesis of POE (60 mol) dimer acid ester;
250 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1168 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1319 g of product (yield about 93%).

  As a result of analysis of this product, it was found that the compound had an acid value of 0.86, a hydroxyl value of 39.42 (theoretical value 35.00), a saponification value of 35.96 (theoretical value 35.00), and an HLB value = 15.0. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3487cm < ^-1 > (hydroxyl group), 1738cm < ^-1 > (ester), and 1119cm < ^-1 > (ether).

Example 19: Synthesis of POE (70 mol) dimer acid ester;
200 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1090 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 6 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration was performed to obtain 1199 g (yield: about 93%) of the product.

  As a result of analysis of this product, a compound having an acid value of 0.83, a hydroxyl value of 34.35 (theoretical value 30.80), a saponification value of 30.12 (theoretical value 30.80), and an HLB value = 15.4 was obtained. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 20: Synthesis of POE (80 mol) dimer acid ester;
180 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 2.7 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1121 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized at 110 to 120 ° C. with 6 cc of a 50% aqueous citric acid solution. Precoat filtration was performed using diatomaceous earth to obtain 1170 g (yield: about 90%) of the product.

  As a result of analysis of this product, a compound having an acid value of 1.01, a hydroxyl value of 33.82 (theoretical value 27.5), a saponification value of 27.67 (theoretical value 27.5), and an HLB value = 15.8 was obtained. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3485cm < ^-1 > (hydroxyl group), 1738cm < ^-1 > (ester), and 1115cm < ^-1 > (ether).

Example 21: Synthesis of POE (90 mol) dimer acid ester;
200 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 4.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1402 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized with 10 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Pre-coated filtration using diatomaceous earth gave 1442 g of product (yield: about 90%).

  As a result of analysis of this product, it was found that the compound had an acid value of 0.90, a hydroxyl value of 29.3 (theoretical value 24.8), a saponification value of 24.5 (theoretical value 24.8), and an HLB value = 16.0. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3485.37cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 22: Synthesis of POE (100 mol) dimer acid ester;
200 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 4.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1558 g of ethylene oxide was added in a reaction time of 2 hours and 30 minutes, it was cooled with water and neutralized with 10 cc of 50% aqueous citric acid solution at 110 to 120 ° C. Using diatomaceous earth, precoat filtration was performed to obtain 1582 g (yield: about 90%) of the product.

  As a result of analysis of this product, it was found that the compound had an acid value of 0.98, a hydroxyl value of 26.0 (theoretical value 22.6), a saponification value of 22 and 2 (theoretical value 22.6), and an HLB value = 16.3. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3485.37cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Reference Example 1 : Synthesis of POP (10 mol) + POE (60 mol) dimer diol ether;
200 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 216 g of propylene oxide is added in a reaction time of about 1 hour, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 ° C to 165 ° C. When 984 g of ethylene oxide was added in 2 hours and 30 minutes, the reaction was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1330 g of product (yield about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.35, a hydroxyl value of 31.2 (theoretical value 29.9), and an HLB value = 13.3.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3485.37cm < ^-1 > (hydroxyl group) and 1114.86cm < ^-1 > (ether).

Reference Example 2 : Synthesis of POP (10 mol) + POE (60 mol) dimer acid ester;
200 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 206 g of propylene oxide is added in a reaction time of about 1 hour, ethylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 934 g of ethylene oxide was added in 2 hours and 30 minutes, the reaction was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration was performed to obtain 1273 g (yield: about 95%) of the product.

  As a result of analysis of this product, a compound having an acid value of 0.75, a hydroxyl value of 32.0 (theoretical value 29.6), a saponification value of 29.0 (theoretical value 29.6), and an HLB value = 13.6 was obtained. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3485.37cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 25: Synthesis of POP (10 mol) dimer diol ether;
Charge 700 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 721 g of propylene oxide was added in a reaction time of about 1 hour and 30 minutes, the mixture was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Precoated filtration using diatomaceous earth gave 1383 g of product (yield about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.10, a hydroxyl value of 105.50 (theoretical value: 100.5), and an HLB value = 3.4.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3450.37 cm < ^-1 > (hydroxyl group) and 1114.86 cm < ^-1 > (ether).

Example 26: Synthesis of POP (30 mol) dimer diol ether;
Charge 350 g of dimer diol (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1134 g of propylene oxide was added in about 2 hours and 30 minutes, the reaction mixture was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of a 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1410 g of product (yield about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.20, a hydroxyl value of 51.85 (theoretical value 49.3), and an HLB value = 3.6.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3450.37 cm < ^-1 > (hydroxyl group) and 1114.86 cm < ^-1 > (ether).

Example 27: Synthesis of POP (60 mol) dimer diol ether;
200 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1296 g of propylene oxide was added in about 2 hours and 30 minutes, the reaction mixture was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1421 g of product (yield about 95%).

  As a result of analysis of this product, it was a compound having an acid value of 0.30, a hydroxyl value of 29.0 (theoretical value 27.9), and an HLB value = 3.8.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3450.37 cm < ^-1 > (hydroxyl group) and 1114.86 cm < ^-1 > (ether).

Example 28: Synthesis of POP (90 mol) dimer diol ether;
150 g of dimer diol (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1458 g of propylene oxide was added in about 2 hours and 30 minutes, the reaction was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Precoat filtration was performed using diatomaceous earth to obtain 1447 g (yield: about 90%) of the product.

  As a result of analysis of this product, it was a compound having an acid value of 0.27, a hydroxyl value of 20.8 (theoretical value 19.5), and an HLB value = 3.9.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3450.37 cm < ^-1 > (hydroxyl group) and 1114.86 cm < ^-1 > (ether).

Example 29: Synthesis of POP (10 mol) dimer acid ester;
700 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 721 g of propylene oxide was added in a reaction time of about 2 hours, it was cooled with water and neutralized at 110-120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1350 g of product (yield about 95%).

  As a result of analysis of this product, it was found to be a compound having an acid value of 0.56, a hydroxyl value of 100.3 (theoretical value 98.0), a saponification value of 99.7 (theoretical value 98.0), and an HLB value = 3.9. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 30: Synthesis of POP (30 mol) dimer acid ester;
Charge 350 g of dimer acid (manufactured by Unikema), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 80 ° C., 3.5 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1078 g of propylene oxide was added in about 2 hours and 30 minutes, the reaction mixture was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1357 g of product (yield about 95%).

  As a result of analysis of this product, it was found to be a compound having an acid value of 0.45, a hydroxyl value of 50.4 (theoretical value 48.7), a saponification value of 49.3 (theoretical value 48.7), and an HLB value = 4.0. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 31: Synthesis of POP (60 mol) dimer acid ester;
200 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1232 g of propylene oxide was added in about 2 hours and 30 minutes, the reaction was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1360 g of product (yield about 95%).

  As a result of analysis of this product, it was found to be a compound having an acid value of 0.35, a hydroxyl value of 30.1 (theoretical value 27.7), a saponification value of 28.3 (theoretical value 27.7), and an HLB value = 4.0. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

Example 32: Synthesis of POP (90 mol) dimer acid ester;
150 g of dimer acid (manufactured by Unikema) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 80 ° C., 3.0 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C., propylene oxide addition starts, and the reaction is carried out at a reaction temperature of 160 to 165 ° C. When 1386 g of propylene oxide was added in about 2 hours and 30 minutes, the reaction was cooled with water and neutralized at 110 to 120 ° C. with 7 cc of 50% aqueous citric acid solution. Using diatomaceous earth, precoat filtration gave 1382 g of product (yield about 90%).

  As a result of analysis of this product, it was found to be a compound having an acid value of 0.27, a hydroxyl value of 21.1 (theoretical value 19.4), a saponification value of 20.3 (theoretical value 19.4), and an HLB value = 4.0. there were.

As a result of carrying out an infrared absorption spectrum measurement about this compound, characteristic absorption was recognized by wavelength 3477.66cm < ^-1 > (hydroxyl group), 1737.86cm < ^-1 > (ester), and 1114.86cm < ^-1 > (ether).

  Hereinafter, the results of evaluating the effects of the nonionic surfactant composition using the POE (n) dimer acid ester and the POE (n) dimer diol ether of the present invention or one or more of them as active ingredients according to the blending examples will be specifically described below. Show.

Examples 33-34 and Comparative Examples 1-3 (milky lotion)
The formulations shown in Table 1 below were prepared using the POE (n) dimer acid ester and POE (n) dimer diol ether obtained in Examples, or a nonionic surfactant containing one or more thereof as an active ingredient.

  Using the fatty acid polyethylene glycol derivatives and POE-oleyl ether derivatives, which are the nonionic surfactants of Examples 7 and 18 and Comparative Examples, emulsions having the formulations shown in Table 1 below were prepared. In these emulsion preparation methods, Component A and Component B were each heated to 70 ° C., Component B was gradually added to Component A, and the mixture was emulsified with a homomixer.

  The emulsion stability of these emulsions was evaluated by the following method. That is, each adjusted emulsion was left in a constant temperature room at 40 ° C., and the state of the emulsion was observed after one month. The evaluation criteria for the emulsion stability were ○ if it was stable at 40 ° C. for 1 month, and × if it was separated in 1 month. The results are shown in Table 3. Expressed by weight percent.

Example 35: (W / O-emollient cream)
W / O-emulsions having the compositions shown in Table 2 below were prepared by a conventional method. That is, component 1 and component 2 were dissolved, and component 2 was mixed while stirring component 1. The W / O-emollient cream prepared in this manner exhibited a stable, sleeky and moist sensation.

Example 36: W / O-foundation A W / O-foundation having the composition shown in Table 3 below was prepared as follows. That is, component 1 and component 2 were each heated to 60 ° C., and component 2 was gradually added while stirring component 1. Next, component 3 was added and cooled to 30 ° C. This W / O-foundation exhibited a sensuality that was excellent in spreading, familiarity and emollient.

Example 37 (cream face washing)
A cream face-wash with the composition shown in Table 4 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 2 was gradually added while stirring component 1. Next, the mixture was stirred while cooling with water, and Component 3 was added at 50 ° C. to cool to 30 ° C. This cream face-wash has a good feeling of use, an excellent emollient effect, and good foaming and stability.

Example 38 (Liquid face wash)
A liquid face wash having the composition shown in Table 5 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, the mixture was stirred while cooling with water, and Component 3 was added at 50 ° C. to cool to 30 ° C. This liquid face wash showed good sensation of spreading and creamy foaming.

Example 39 (body shampoo)
A body shampoo having the composition shown in Table 6 below was prepared as follows. That is, component 1 was heated to 70 ° C. with stirring to dissolve each component uniformly. Next, the mixture was stirred while cooling with water, and Component 3 was added at 50 ° C. to cool to 30 ° C. This liquid face wash showed good sensation of spreading and creamy foaming.

Example 40 (cleansing oil)
A cleansing oil having the composition shown in Table 7 below was prepared as follows. That is, component 1 is heated to 40 ° C. to make it transparent and uniform. Next, it is cooled to 30 ° C., and component 2 is added while stirring to make a product. Since this cleansing oil is excellent in pigment dispersibility, it is well suited to foundations, makeup, etc., and has a sensuality excellent in cleansing performance.

Example 41 (cleansing rekit)
A cleansing rekit having the composition shown in Table 8 below was prepared as follows. That is, component 1 and component 2 were each heated to 60 ° C., and component 2 was gradually added while stirring component 1. Next, it cooled with water and added the component 3 at 40 degreeC, and cooled to 30 degreeC. This cleansing rekit has the characteristics of being transparent, viscous, and difficult to sag during use, has excellent cleansing performance, and has a refreshing sensation after use.

Example 42 (cleansing gel)
A cleansing gel having the composition shown in Table 9 below was prepared as follows. That is, component 1 and component 2 are each stirred and dissolved at room temperature, and component 3 is added to component 2 and stirred and dissolved. Component 1 was gradually added while stirring component 2 + component 3. Since this cleansing gel was excellent in pigment dispersibility, it was well suited to foundations, makeup, etc., and exhibited excellent cleansing performance.

Example 43 (skin lotion)
A lotion having the composition shown in Table 10 below was prepared as follows. That is, components 1 and 2 were each heated to 40 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This lotion showed an excellent sensuality such as good spread and familiarity.

Example 44 (Treatment Lotion)
Treatment lotions having the compositions shown in Table 11 below were prepared as follows. That is, component 1 and component 2 were each heated to 40 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This treatment lotion was a sensuality excellent in flexibility, slipperiness and moistness.

Example 45 (Milky Lotion)
The milky lotion having the composition shown in Table 12 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This milky lotion exhibited an excellent sensory stability, spreadability and tight feeling.

Example 46 (moisture cream)
A moisture cream having the composition shown in Table 13 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This moisture cream was glossy, gave emollient properties and exhibited excellent sensuality.

Example 47 (mud pack)
A hair shampoo having the composition shown in Table 14 below was prepared as follows. That is, component 2 was gradually added while stirring component 1. Next, component 3 and component 4 were added and mixed uniformly. This mud pack showed an excellent sensation of good spread and tight feeling.

Example 48 (hair shampoo)
A hair shampoo having the composition shown in Table 15 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This hair shampoo imparted moist feeling and gloss to the hair and exhibited excellent sensuality as a smooth finger.

Example 49 (conditioning shampoo)
A conditioning shampoo having the composition shown in Table 16 below was prepared as follows. That is, component 1 was heated to 60 ° C. with stirring, and then component 2 was added and cooled to 30 ° C. This conditioning shampoo preserved the moisture of the hair, imparted gloss and moist feeling, and exhibited excellent sensuality in a smooth finger.

Example 50 (Rinse In Shampoo)
A rinse-in shampoo having the composition shown in Table 17 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This rinse-in shampoo imparted moist feeling and gloss to the hair and exhibited excellent sensuality as a smooth finger.

Example 51 (hair treatment)
A hair treatment having the composition shown in Table 18 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, component 3 was added and cooled to 30 ° C. This hair treatment preserved the moisture of the hair, was supple and moist, and showed a superior sensuality with a smooth feel.

Example 52 (hair wax)
A hair wax having the composition shown in Table 19 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 2 was gradually added while stirring component 1. Next, component 3 was added and cooled to 30 ° C. This hair wax was glossy, non-sticky, did not disperse even when moved, and exhibited an excellent sensuality in hairstyle retention.

Example 53 (washable pomade)
Washable pomades having the compositions shown in Table 20 below were prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 2 was gradually added while stirring component 1. Next, component 3 was added and cooled to 30 ° C. This washable pomade was glossy, non-sticky and showed excellent styling retention.

Example 54 (liquid hair conditioner)
A liquid hair styling composition having the composition shown in Table 21 below was prepared as follows. That is, while stirring Component 1, Component 2 was gradually added and mixed uniformly. This liquid hair styling material is glossy, non-sticky, has high adhesion, does not move even if it moves, and exhibits excellent sensuality in hairstyle retention.

Example 55 (lipstick)
Lipsticks having the compositions shown in Table 22 below were prepared as follows. That is, component 1 was dissolved by heating, component 2 was added thereto, kneaded with a roll mill, uniformly dispersed, defoamed, poured into a mold, rapidly cooled, and formed into a stick shape. This lipstick was well-familiar with the skin and excellent in spreading.

Example 56 (massage cream)
A massage cream having the composition shown in Table 23 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 2 was gradually added while stirring component 1. Next, component 3 was added and cooled to 30 ° C. This massa cream exhibited a sensuality that was glossy, stretchy and moist.

Example 57 (Suntan cream)
A suntan cream having the composition shown in Table 24 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 2 was gradually added while stirring component 1. Next, component 3 was added and cooled to 30 ° C. This suntan cream has excellent sensory properties because it suppresses breakage caused by sweat and has excellent pigment dispersibility.

Example 58 (hair treatment oil)
A hair treatment oil having the composition shown in Table 25 below was prepared as follows. That is, component 1 was heated to 55 ° C., and component 1 was uniformly dissolved while stirring. Next, it was cooled and component 2 was added at 40 ° C. and cooled to 30 ° C. This hair cream oil kept moisture in the hair and showed excellent sensation that was supple, moist and smooth.

Example 59 (hair conditioner)
A hair conditioner having the composition shown in Table 26 below was prepared as follows. That is, component 1 and component 2 were each heated to 75 ° C., and component 1 was gradually added while stirring component 2. Next, it cooled and added the component 3 at 50 degreeC, and cooled to 30 degreeC. This hair conditioner kept the moisture of the hair, imparted gloss and moist feeling, and exhibited excellent sensuality as a smooth finger.

Example 60 (fiber wax)
A fiber wax having the composition shown in Table 27 below was prepared as follows. That is, component 1 and component 2 were each heated to 80 ° C., component 3 was heated to 60 ° C., and component 2 was gradually added while stirring component 1. Next, the mixture was cooled and stirred, and components 3 and 4 were added at 45 ° C. and cooled to 30 ° C. This fiber wax was glossy, non-sticky, did not dislodge even when moved, and exhibited an excellent sensuality for maintaining hairstyles.

Example 61 (hair cream)
A hair cream having the composition shown in Table 28 below was prepared as follows. That is, component 1 and component 2 were each heated to 70 ° C., and component 1 was gradually added while stirring component 2. Next, it cooled and added the component 3 at 50 degreeC, and cooled to 30 degreeC. This hair cream was glossy, non-sticky and exhibited an excellent sensation for maintaining styling.

  Application examples of the present invention include application to cosmetics and external preparations.

Claims (2)

A nonionic surfactant composition obtained by addition polymerization of a single alkylene oxide (any one of alkylene carbon number C2 or C3) to dimer acid or dimer diol,
A cosmetic comprising at least one selected from the group consisting of a polyoxyalkylene dimer diol ether addition polymer and a polyoxyalkylene dimer acid addition polymer having the structure shown below.

(However, in the formula, a, b, c and d are integers of 1 or more and a + b + c + d = 12 to 40. Also, (RO) and (R′O) are attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.)

(However, in the formula, e, f, g, and h are integers of 1 or more and in the range of e + f + g + h = 12 to 40. Also, (RO), (R′O) is attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.) A nonionic surfactant composition obtained by addition polymerization of a single alkylene oxide (any one of alkylene carbon number C2 or C3) to dimer acid or dimer diol,
An external preparation comprising at least one selected from the group consisting of a polyoxyalkylene dimer diol ether addition polymer and a polyoxyalkylene dimer acid addition polymer having the structure shown below.

(However, in the formula, a, b, c and d are integers of 1 or more and a + b + c + d = 12 to 40. Also, (RO) and (R′O) are attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.)

(However, in the formula, e, f, g, and h are integers of 1 or more and in the range of e + f + g + h = 12 to 40. Also, (RO), (R′O) is attached with a single alkylene oxide of C2 or C3. N ₁ + n ₂ when ( RO) and (R′O) is C2 is an integer of 5 to 200, and n ₁ + when (RO) and (R′O) is C3 n ₂ is an integer of 10 to 90.)