JP2010209018A - Nonionic surfactant composition, and cosmetic and external preparation using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonionic surfactant other than a silicone series, having performances analogous to a polyoxyalkylene-modified organopolysiloxane, as a raw material excellent even in safety, stability, feeling of use, pigment dispersibility, solubilization performance, odor, and the like. <P>SOLUTION: The present invention provides at least one nonionic surfactant selected from the group consisting of derivatives obtained by esterification reaction of carboxylic acid groups or hydroxyl groups of both ends of a dimer acid and a dimer diol, a polyoxyalkylene dimer acid and polyalkylene dimer diol (2-4C alkylene) with a fatty acid and its alkylene oxide adduct, an amino acid selected from the group consisting of an acylamino acid and pyroglutamic acid and the like, and a cosmetic and an external preparation containing the same. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a nonionic surfactant composition, a cosmetic using the same, and an external preparation.

  Water-in-oil emulsified cosmetics are highly effective in protecting the skin from drying by covering the skin surface with an oil film, protecting the skin from drying, and imparting emollient and moisturizing effects to the skin. It is applied to various cosmetics and external preparations because of its wide area, and various bases are blended in order to obtain desired quality characteristics.

  Conventionally, the water-in-oil emulsifier shaping technology is highly dependent on the surfactant used, and various oil agents such as volatile silicones can be used as the oil agent, such as polyoxyalkylene-modified organopolysiloxanes and sorbitan stears. Nonionic surfactants such as rate and polyethylene glycol 1500 dihydroxystearate have been used (see, for example, Patent Documents 1 and 2).

  On the other hand, in order to obtain the moisturizing effect of water-in-oil cosmetics and external preparations, dimer linoleic acid di (phytosteryl, isostearyl, cetyl, stearyl, behenyl) and oligomeric esters of dimer acid and dimer diol and isostearic acid Dimer acid and dimer diol oligomer ester and isostearyl alcohol ester compound are incorporated as a component for improving the adhesion between the coating compound and the skin (see, for example, Patent Documents 3 and 4). Technology (see, for example, Patent Document 5) has been known.

  Regardless of the dosage form, ester oils mainly composed of dimer acid or / and dimer diol are used as an oily base material in cosmetics and external preparations in general and have excellent compatibility with silicone oil (for example, Patent Document 6), and it has been known to impart high emollient properties to cosmetics and external preparations (for example, refer to Patent Document 7) due to high water retention, but dimer acid or / and dimer diol ester It was not known that the derivatives function as nonionic surfactants.

JP-A-11-279020 JP 2005-506333 A JP 2005-104854 A JP 2007-291095 A JP 2008-297239 A JP 2004-256515 A JP 2005-132729 A

  However, these surfactants, as raw materials for cosmetics and external preparations, have problems such as safety, stability, stickiness of use due to excessive blending, compatibility with oil phase base materials, etc., and are always satisfactory. It was not a thing. When designing silicone-free cosmetics and external preparations, polyoxyalkylene-modified organopolysiloxane is a silicone surfactant and cannot be used as an emulsifier. Therefore, it is a raw material that is further excellent in safety, stability, feeling of use, pigment dispersibility, solubilization performance, odor, etc., and has a nonionic interface other than a silicone system that retains performance similar to polyoxyalkylene-modified organopolysiloxane. An activator is desired.

  Under such circumstances, the present inventors have conducted extensive studies to solve the above problems, and as a result, dimer acid, dimer diol, polyoxyalkylene dimer acid, and polyoxyalkylene dimer diol were used as raw materials, and fatty acid and alkylene oxide addition thereof were performed. Nonionic surfactants containing compounds, alcohols and their alkylene oxide adducts, new derivatives esterified with amino acids such as acylamino acids and pyroglutamic acids, and compounds that have traditionally been used only as oily substrates or emollients The agent was found to be excellent as a raw material for water-in-oil cosmetics and external preparations in terms of safety, stability, and feeling of use, and the present invention was completed.

  The present invention relates to dimer acid and dimer diol, polyoxyalkylene dimer acid and polyoxyalkylene dimer diol (an alkylene oxide of 2 to 4 carbon atoms (hereinafter referred to as “C2 to C4 carbon atoms”)). The esterification reaction of carboxylic acid groups or hydroxyl groups at both ends of the compound) with fatty acids and their alkylene oxide adducts, alcohols and their alkylene oxide adducts, amino acids such as acylamino acids and pyroglutamic acids, etc. Provided is a nonionic surfactant containing a new derivative obtained and a compound conventionally used only as an oily substrate or an emollient. The present invention further provides a water-in-oil cosmetic and an external preparation containing the nonionic surfactant and having excellent safety, stability, feeling of use and the like.

  The present invention is as follows.

（但し、式中、Ｒ，Ｒ’は水素またはエステル化反応に用いた化合物残基であるが、Ｒ，Ｒ’のどちらか一方が水素の場合、もう一方はエステル化反応に用いた化合物残基となる。ａ，ｂ，ｃ，ｄは１以上の整数でａ＋ｂ＋ｃ＋ｄ＝１２〜４０の範囲である。また、ＲＯ、Ｒ’Ｏはエステル化度によりモノエステル化合物、セスキエステル化合物、ジエステル化合物となる。） (1) A nonionic surfactant containing a new derivative obtained by esterifying a carboxylic acid group at both ends of a dimer acid with an alcohol and its alkylene oxide adduct and an alkylene oxide adduct of a fatty acid, A nonionic surfactant composition containing at least one selected from the group consisting of dimer acid ester derivatives having the structure shown below.

(However, in the formula, R and R ′ are hydrogen or a compound residue used in the esterification reaction. However, when either R or R ′ is hydrogen, the other is the residue of the compound used in the esterification reaction. A, b, c, d are integers of 1 or more and a + b + c + d = 12 to 40. RO and R′O are monoester compounds, sesquiester compounds, diester compounds depending on the degree of esterification. Become.)

（但し、式中、Ｒ，Ｒ’は水素またはエステル化に用いた脂肪酸及びアミノ酸残基であるが、Ｒ，Ｒ’のどちらか一方が水素の場合、もう一方はエステル化反応に用いた脂肪酸及びアミノ酸残基となる。ｅ，ｆ，ｇ，ｈは１以上の整数でｅ＋ｆ＋ｇ＋ｈ＝１２〜４０の範囲である。また、ＲＯ、Ｒ’Ｏはエステル化度によりモノエステル化合物、セスキエステル化合物、ジエステル化合物となる。） (2) A nonionic surfactant composition obtained by esterifying a hydroxyl group at both ends of dimer diol with a fatty acid and / or a fatty acid and an amino acid such as acylamino acid or pyroglutamic acid, having the structure shown below A nonionic surfactant composition containing at least one selected from the group consisting of dimer diol ester derivatives.

(However, in the formula, R and R ′ are hydrogen or the fatty acid and amino acid residue used for esterification, but when either R or R ′ is hydrogen, the other is the fatty acid used for esterification. E, f, g, and h are integers of 1 or more and in the range of e + f + g + h = 12 to 40. In addition, RO and R′O are monoester compounds, sesquiester compounds, It becomes a diester compound.)

（但し、式中、Ｒ，Ｒ’は水素またはエステル化に用いた脂肪酸及びアミノ酸残基であるが、Ｒ，Ｒ’のどちらか一方が水素の場合、もう一方はエステル化反応に用いた脂肪酸及びアミノ酸残基となる。ｉ，ｊ，ｋ，ｌは１以上の整数でｉ＋ｊ＋ｋ＋ｌ＝１２〜４０の範囲である。また、（ＡＯ）、（ＡＯ）’がＣ２、Ｃ３またはＣ４の単一アルキレンオキシドの付加重合体である。また、（ＡＯ）、（ＡＯ）’がＣ２〜Ｃ４のアルキレンオキシドのブロックまたはランダム付加重合体である。ｎ＋ｎ’はアルキレンオキシドの平均付加モル数を示し、１〜４０の整数である。また、アルキレンオキシドの種類、付加モル数により乳化特性が異なる。ＲＯ、Ｒ’Ｏはエステル化度によりモノエステル化合物、セスキエステル化合物、ジエステル化合物となる。） (3) Obtained by esterifying the hydroxyl groups at both ends of polyoxyalkylene dimer acid (alkylene carbon number C2-4) with an amino acid selected from the group consisting of fatty acid and / or fatty acid and acylamino acid and pyroglutamic acid. A nonionic surfactant composition containing at least one selected from the group consisting of polyoxyalkylene dimer acid ester derivatives having the structure shown below.

(However, in the formula, R and R ′ are hydrogen or the fatty acid and amino acid residue used for esterification, but when either R or R ′ is hydrogen, the other is the fatty acid used for esterification. I, j, k, l is an integer of 1 or more and i + j + k + 1 = 12-40, and (AO), (AO) ′ is a single alkylene of C2, C3 or C4 (AO), (AO) ′ is a C2-C4 alkylene oxide block or random addition polymer, n + n ′ represents the average number of moles of alkylene oxide added, It is an integer of 40. Also, the emulsification characteristics vary depending on the type of alkylene oxide and the number of moles added.RO and R'O are monoester compounds, sesquiester compounds, diester compounds depending on the degree of esterification. It becomes.)

（但し、式中、Ｒ，Ｒ’は水素またはエステル化に用いた脂肪酸及びアミノ酸残基であるが、Ｒ，Ｒ’のどちらか一方が水素の場合、もう一方はエステル化反応に用いた脂肪酸及びアミノ酸残基となる。ｍ，ｏ，ｐ，ｑは１以上の整数でｍ＋ｏ＋ｐ＋ｑ＝１２〜４０の範囲である。また、（ＡＯ）、（ＡＯ）’がＣ２、Ｃ３またはＣ４の単一アルキレンオキシドの付加重合体である。また、（ＡＯ）、（ＡＯ）’がＣ２〜Ｃ４のアルキレンオキシドのブロックまたはランダム付加重合体である。ｎ＋ｎ’はアルキレンオキシドの平均付加モル数を示し、１〜４０の整数である。また、アルキレンオキシドの種類、付加モル数により乳化特性が異なる。ＲＯ、Ｒ’Ｏはエステル化度によりモノエステル化合物、セスキエステル化合物、ジエステル化合物となる。） (4) Obtained by esterifying the hydroxyl groups at both ends of polyoxyalkylene dimer diol (alkylene carbon number C2-4) with an amino acid selected from the group consisting of fatty acids and / or fatty acids and acylamino acids and pyroglutamic acids. A nonionic surfactant composition comprising at least one selected from the group consisting of polyoxyalkylene dimer diol ester derivatives having the structure shown below.

(However, in the formula, R and R ′ are hydrogen or the fatty acid and amino acid residue used for esterification, but when either R or R ′ is hydrogen, the other is the fatty acid used for esterification. M, o, p, q are integers of 1 or more and m + o + p + q = 12 to 40. Also, (AO), (AO) ′ is a single alkylene of C2, C3 or C4 (AO), (AO) ′ is a C2-C4 alkylene oxide block or random addition polymer, n + n ′ represents the average number of moles of alkylene oxide added, It is an integer of 40. Also, the emulsification characteristics vary depending on the type of alkylene oxide and the number of moles added.RO and R'O are monoester compounds, sesquiester compounds, diester compounds depending on the degree of esterification. It becomes.)

  (5) Dimer acid, dimer diol, polyoxyalkylene dimer acid, polyoxyalkylene dimer diol (alkylene carbon number C2 to C4), the carboxylic acid group or hydroxyl group at both ends of the fatty acid and its alkylene oxide adduct, alcohol and A nonionic surfactant composition obtained by an esterification reaction with an amino acid selected from the group consisting of an alkylene oxide adduct, an acylamino acid and pyroglutamic acid, and a dimer having the structure shown in Chemical Formulas 1 to 4 above A cosmetic comprising a nonionic surfactant composition comprising at least one selected from the group consisting of acid ester derivatives and dimer diol ester derivatives.

  (6) Dimer acid, dimer diol, polyoxyalkylene dimer acid, polyoxyalkylene dimer diol (alkylene carbon number C2 to C4) of carboxylic acid groups or hydroxyl groups at both ends are converted to fatty acid and its alkylene oxide adduct, alcohol and A nonionic surfactant composition obtained by an esterification reaction with an amino acid selected from the group consisting of an alkylene oxide adduct, an acylamino acid and pyroglutamic acid, and a dimer having the structure shown in Chemical Formulas 1 to 4 above An external preparation containing a nonionic surfactant composition comprising at least one selected from the group consisting of acid ester derivatives and dimer diol ester derivatives.

  One or more nonionic surfactant compositions of dimer acid, dimer diol, polyoxyalkylene dimer acid and polyoxyalkylene dimer diol derivative according to the present invention are more stable in emulsion than conventional nonionic surfactants. In addition, even when used in combination with a silicone surfactant, further stability and excellent usability can be obtained.

  Cosmetics containing 1 or more nonionic surfactant compositions of dimer acid, dimer diol and polyoxyalkylene dimer acid, polyoxyalkylene dimer diol derivative as an active ingredient according to the present invention, and external preparations are excellent in safety, Furthermore, it can also be made excellent in terms of functionality, such as a slip feeling.

  Hereinafter, the present invention will be described in detail.

  The dimer acid used in the dimer acid ester derivative represented by the above chemical formula 1 used in the present embodiment is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids.

  The polyoxyalkylene dimer acid used in the polyoxyalkylene dimer acid ester derivative represented by the above chemical formula 3 used in the present embodiment is a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids with a carbon number of C2. ˜C4 alkylene oxide (that is, ethylene oxide, propylene oxide or butylene oxide) is subjected to addition polymerization.

  Dimer acid, which is a known dibasic acid, is a dibasic acid obtained by an intermolecular polymerization reaction of unsaturated fatty acids. In general, a compound obtained by dimerizing an unsaturated fatty acid having 11 to 22 carbon atoms with a clay catalyst or the like is preferable. For example, if the unsaturated fatty acid to be dimerized is mentioned, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid and the like are preferred examples. 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 mass and dimer acid content increased to 90% by mass or more by molecular distillation are in circulation. In addition, double bonds remain after the dimerization reaction, but there are also products in which a double bond existing in a dimer acid residue is reduced to a saturated aliphatic dibasic acid by hydrogenation reduction. Any dimer acid currently in circulation can be used in the present invention, but hydrogenated dimer acid is more preferable from the viewpoint of oxidation stability. In addition, those derived from animal oils and fats and vegetable oils are distributed among these dimer acids, but those derived from vegetable oils and fats are more preferable. As such dimer acid, for example, PRIPOL 1006, 1009, 1013, 1098, and EMPOL 1012 of Cognis Japan, available from Croda Japan, are commercially available.

  The dimer diol used in the dimer diol ester derivative represented by the chemical formula 2 used in the present embodiment is obtained by reducing a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids. .

  The polyoxyalkylene dimer diol used in the polyoxyalkylene dimer diol ester derivative represented by Chemical Formula 4 used in the present embodiment reduces a known dibasic acid obtained by intermolecular polymerization of unsaturated fatty acids. Is obtained by addition polymerization of a C2-C4 alkylene oxide (that is, ethylene oxide, propylene oxide or butylene oxide) to the compound obtained by the above.

  In the present invention, the dimer diol is one in which the carboxyl group portion of the dimer acid is a hydroxyl group. For example, dimer acid or a lower alcohol ester thereof is preferably hydrogenated in the presence of a catalyst to convert the carboxyl group portion of dimer acid to a hydroxyl group. The dimer diol is a substance mainly composed of a diol having usually 22 to 44 carbon atoms, preferably 24 to 40 carbon atoms, and more preferably about 36 carbon atoms. Examples of the lower alcohol ester of dimer acid include esters derived from alcohol having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. The dimer diol obtained industrially may contain, for example, a trimer triol, a monomer alcohol and an ether compound depending on the degree of purification of the dimer acid used as a raw material and its lower alcohol ester, and generally contains dimer diol. Since those having an amount of 70 to 100% by weight and those having a dimer diol content of 90 to 100% by weight after further purification have been distributed, these can be used. Any of the present invention can be used. As dimer diol, those derived from animal fats and oils and vegetable fats and oils are distributed, but those derived from vegetable fats and oils are desirable. As such a dimer diol, PRIDOL 2033 of Croda Japan Co., Sovermol 908 of Cognis Japan Co., Ltd., etc. are commercially available.

  The alkylene oxide is not particularly limited as long as it has C2 to C4 carbon atoms, but preferably has C2 carbon atoms. Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, butylene oxide and the like.

  In addition, in the formula (the above-mentioned chemical formula 1 to chemical formula 4), the addition form in the case where two or more AOs are present may be random or block form, but is preferably a block form. In that case, C3 and C4 alkylene oxides It is desirable to add ethylene oxide after either or both of these have been added first.

  The dimer acid ester derivative contained in the nonionic surfactant of the present invention comprises dicarboxylic acids having carboxylic acid groups at both ends of the alcohol and its alkylene oxide adduct, fatty acid alkylene oxide adduct, acylamino acid and pyroglutamic acid alkylene. It is a compound esterified with an oxide adduct.

  The dimer diol ester derivative contained in the nonionic surfactant of the present invention is a compound obtained by esterifying the hydroxyl groups at both ends of the dimer diol with a fatty acid and / or a fatty acid and an amino acid such as acylamino acid or pyroglutamic acid.

  The polyoxyalkylene dimer acid ester contained in the nonionic surfactant of the present invention is a fatty acid and / or a fatty acid and an amino acid such as an acyl amino acid or pyroglutamic acid at both ends of the compound obtained by adding an alkylene oxide to the dimer acid. And the esterification reaction compound.

  The polyoxyalkylene dimer diol ester contained in the nonionic surfactant of the present invention is a fatty acid and / or a fatty acid and an amino acid such as an acyl amino acid or pyroglutamic acid at both ends of a compound obtained by adding an alkylene oxide to a dimer diol. And the esterification reaction compound.

  As the fatty acid used for the production of the ester contained in the nonionic surfactant of the present invention, any fatty acid can be used as long as it is usually used in cosmetics and the like. Specifically, linear saturated fatty acids such as acetic acid, butanoic acid, hexanoic acid, octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid, and linear chains such as linoleic acid, linolenic acid and oleic acid Unsaturated fatty acids, branched fatty acids such as isostearic acid, isooleic acid, lanolin fatty acid and neopentanoic acid, ring-containing fatty acids such as paramethoxycinnamic acid and salicylic acid, divalent fatty acids such as succinic acid, glutaric acid and dimer acid, citric acid, A divalent or higher fatty acid such as trimer acid contained as a by-product in dimer acid can be used, and one or more of these are used. In this study, higher fatty acids such as isostearic acid are particularly preferably used.

  As the polyoxyalkylene fatty acid used for the production of the ester contained in the nonionic surfactant of the present invention, any polyoxyalkylene fatty acid can be used as long as it is usually used in cosmetics and the like as a nonionic surfactant. Specifically, ether / ester compounds in which alkylene oxide is added to capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, lanolin fatty acid, linoleic acid, linolenic acid, oleic acid, etc. 1 type or 2 types or more of these are used. In this study, polyethylene glycol monoisostearate is particularly preferably used.

  As the alcohol used for the production of the ester contained in the nonionic surfactant of the present invention, any alcohol can be used as long as it is usually used in cosmetics and the like. Specifically, lower alcohols such as ethanol, isopropanol, butanol, polyhydric alcohols such as 1,3-butanediol, glycerin, polyglycerin, ethylene glycol, polyethylene glycol, polypropylene glycol, castor oil, hardened castor oil, Saccharides such as sorbitol, mannitol, glucose, sucrose, xylitol, lactose, trehalose, sterols such as cholesterol and phytosterol, higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, and oleyl alcohol One or more of these are used. In this study, higher alcohols such as isostearyl alcohol and 2-octyldodecanol are particularly preferably used.

  As the polyoxyalkylene alcohol used for the production of the ester contained in the nonionic surfactant of the present invention, any polyoxyalkylene alcohol can be used as long as it is usually used in cosmetics and the like as a nonionic surfactant. Specifically, capryl alcohol, lauryl alcohol, myristyl alcohol, isostearyl alcohol, cetyl alcohol, cholesterol, phytosterol, stearyl alcohol, oleyl alcohol, cetostearyl alcohol, batyl alcohol, behenyl alcohol, decyl alcohol, 2-octyldodecanol, Examples include etherified products obtained by adding alkylene oxide to glycerin, polyglycerin, ethylene glycol, propylene glycol, castor oil, hydrogenated castor oil, glycerin, sorbitol, phytosterol, and the like, and one or more of these are used. In this study, polyoxyethylene isostearyl ether and polyoxyethylene oleyl ether are particularly preferably used.

  The sterols used in the production of the ester contained in the nonionic surfactant of the present invention are sitosterol, campesterol, stigmasterol, brassicasterol, ergosterol and a mixture thereof, phytosterol, and hydrogenated phytosterol, Cholesterol, dihydrocholesterol, desmosterol, lanosterol, dihydrolanosterol, agnosterol, latosterol and the like can be used.

  Although there is no special restriction | limiting in the kind of amino acid of the acylamino acid part used for manufacture of ester contained in the nonionic surfactant of this invention, A neutral amino acid and an acidic amino acid are preferable. Examples of suitable amino acids include glycine, alanine, threonine, β-alanine, sarcosine, N-methyl-β-alanine, aminobutyric acid, glutamic acid, and aspartic acid.

  The polyglycerol used for manufacture of ester contained in the nonionic surfactant of this invention is a polyglycerol of 2-15 by the average degree of polymerization computed from the hydroxyl group.

  The synthesis conditions of the dimer acid ester derivative contained in the nonionic surfactant of the present invention are not particularly limited, and are carried out by a commonly used method. For example, a method in which dimer acid, an arbitrary amount of alcohol and its alkylene oxide adduct, and an alkylene oxide adduct of a fatty acid are charged, and an esterification reaction is performed in a nitrogen atmosphere at 230 ° C. to 260 ° C., preferably 250 ° C. In this method, an esterification reaction is performed using sulfonic acid or sulfuric acid as a catalyst. Moreover, the esterification degree of the ester derivative obtained can be arbitrarily adjusted between monoester and diester by changing the charging ratio of dimer acid and alcohol and its alkylene oxide adduct and fatty acid alkylene oxide adduct. .

  The conditions for synthesizing the dimer diol ester derivative contained in the nonionic surfactant of the present invention are not particularly limited and are performed by a commonly used method. For example, dimer diol and an arbitrary amount of fatty acid and / or fatty acid and an amino acid such as acylamino acid or pyroglutamic acid are charged, and esterification is performed at 230 ° C. to 260 ° C., preferably 250 ° C. (130 ° C. in the case of an amino acid) in a nitrogen atmosphere. It is a method of performing a reaction, or a method of performing an esterification reaction using paratoluenesulfonic acid or sulfuric acid as a catalyst. Moreover, the esterification degree of the ester derivative obtained can be arbitrarily adjusted between monoester and diester by changing the charging ratio of dimer diol and fatty acid and / or fatty acid and amino acid such as acylamino acid and pyroglutamic acid. .

  The conditions for synthesizing the polyoxyalkylene dimer acid ester derivative contained in the nonionic surfactant of the present invention are not particularly limited and are carried out by a commonly used method. For example, polyoxyalkylene dimer acid and an arbitrary amount of fatty acid and / or fatty acid and an amino acid such as acylamino acid or pyroglutamic acid are charged, 230 ° C. to 260 ° C., preferably 250 ° C. (130 ° C. in the case of amino acid), under nitrogen atmosphere And a method of performing an esterification reaction using paratoluenesulfonic acid or sulfuric acid as a catalyst. Moreover, the esterification degree of the obtained ester derivative is arbitrarily adjusted between monoester to diester by changing the charging ratio of polyoxyalkylene dimer acid and fatty acid and / or fatty acid and amino acid such as acylamino acid and pyroglutamic acid. be able to.

  The conditions for synthesizing the polyoxyalkylene dimer diol ester derivative contained in the nonionic surfactant of the present invention are not particularly limited, and are carried out by a commonly used method. For example, polyoxyalkylene dimer diol and an arbitrary amount of fatty acid and / or fatty acid and an amino acid such as acylamino acid or pyroglutamic acid are charged, and 230 ° C. to 260 ° C., preferably 250 ° C. (130 ° C. in the case of an amino acid), under a nitrogen atmosphere And a method of performing an esterification reaction using paratoluenesulfonic acid or sulfuric acid as a catalyst. Moreover, the esterification degree of the obtained ester derivative is arbitrarily adjusted between monoester and diester by changing the charging ratio of polyoxyalkylene dimer diol and fatty acid and / or fatty acid and amino acid such as acylamino acid and pyroglutamic acid. be able to.

  The dimer acid ester derivative, dimer diol derivative, polyoxyalkylene dimer acid ester derivative, and polyoxyalkylene dimer diol derivative of the present invention can be made into various types of ester compounds depending on the purpose of development. That is, the desired properties are selected depending on the choice of fatty acid and its alkylene oxide adduct, alcohol and its alkylene oxide adduct, selection of amino acid type, combination of two or more different types, selection of added alkylene oxide and its addition amount. Esters having can be obtained.

  Dimer acid, dimer diol and polyoxyalkylene dimer acid, polyoxyalkylene dimer diol and fatty acid and its alkylene oxide adduct, alcohol and its alkylene oxide adduct, amino acid such as acylamino acid and pyroglutamic acid and its alkylene oxide adduct Esters can be selected for their viscosity, state (solid, soft wax, liquid, etc.), IOB value (= inorganic value / organic value), compatibility with other components (compatibility, etc.) by appropriately selecting the raw materials. It can be arbitrarily adjusted, and can provide cosmetics and external preparations excellent in usability and stability.

  Dimer acids and dimer diols have molecular weights twice that of conventional higher fatty acids and higher alcohols, and their alkylene oxide addition polymers, as well as fatty acids and their alkylene oxide adducts, alcohols and their alkylene oxide adducts, A compound obtained by an esterification reaction with an amino acid is excellent in safety, stability, touch and the like, and by blending it, a cosmetic and an external preparation excellent in safety and use feeling are obtained. Can be provided.

  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 mass%-50 mass% are desirable, More preferably, 0.5 mass%-30 % By mass.

  Dimer acid ester derivative, dimer diol ester derivative, polyoxyalkylene dimer acid derivative, and polyoxyalkylene dimer diol derivative used in the present embodiment are one or more of these, cleansing oil, facial cleansing foam, cleansing cream, cleansing gel, massage Cream, cold cream, emollient cream, moisture cream, hand cream, emollient emulsion, moisture emulsion, hand emulsion, lotion, pack, foundation, lipstick, press powder, eye shadow, tic, hair liquid, set lotion, permanent wave solution, Hair cream, hair lotion, hair mousse, hair wax, hair gel, shampoo, hair rinse, hair conditioner, body sham -Non-ionic surface activity in preparation of cosmetics and external preparations such as solid detergent, liquid detergent, antiperspirant, after shave cream, sunscreen cream, sunscreen oil, hair restorer, hair nourishing agent, bath preparation, external pharmaceutical composition It can be used as an agent. 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 raw 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 thereof, cholesterol and derivatives thereof, macadamia nut oil, jojoba oil, carnauba wax, sesame oil, cacao oil, palm oil, mink oil, owl, candelilla wax, whale wax and other oil phase raw materials, paraffin, microcrystalline wax, Oil phase raw materials derived from petroleum and minerals such as liquid paraffin, petrolatum, ceresin, methylpolysiloxane, polyoxyethylene / methylpolysiloxane, polyoxypropylene / methylpolysiloxane, poly (oxyethylene / oxypropylene) / methylpolysiloxane S , Silicones 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, The dimer acid ester, dimer diol ester, polyoxyalkylene dimer acid ester, and polyoxyalkylene dimer diol ester of the present invention can be used in combination as long as the effects of the nonionic surfactant are not impaired.

  In addition, the cosmetics and external preparations of the present embodiment include dimer acid esters, dimer diol esters and polyoxyalkylene dimer acid esters, polyoxyalkylene dimer diol esters or nonionic surfactant compositions used in the present embodiment. N-long chain acyl amino acid salts such as N-long chain acyl acidic amino acid salts and N-acyl neutral amino acid salts as other surfactants as long as they do not inhibit the effect of the product; N-long chain fatty acid acyl-N -Anions such as methyl taurine salts, alkyl 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, alkyl ether carboxylic acids, etc. Surfactants; higher alcohols and Ether type nonionic surfactants such as alkylene oxide adducts of the above; ether ester type nonionic surfactants such as glycerin esters and their alkylene oxide adducts, sorbitan esters and their alkylene oxide adducts; fatty acid esters, glycerin esters, fatty acids Ester-type nonionic surfactants such as polyglycerin ester, N-long chain acyl peptide polyglycerin ester, sorbitan ester, sucrose fatty acid ester; alkyl glucosides, hydrogenated castor oil pyroglutamic acid diester and its alkylene oxide adduct, and fatty acid Nitrogen-containing nonionic surfactants such as alkanolamides; aliphatic amine salts such as alkylammonium chloride and dialkylammonium chloride, and their quaternary ammonia Cation surfactants such as aromatic quaternary ammonium salts, fatty acid acyl arginine esters, etc .; and betaine surfactants such as carboxybetaine; aminocarboxylic acid type surfactants; imidazoline type surfactants, etc. Various surfactants such as amphoteric surfactants are also added to the dimer acid ester, dimer diol ester and polyoxyalkylene dimer acid ester, polyoxyalkylene dimer diol ester of the present invention or a nonionic surfactant composition thereof. Can be blended.

  Furthermore, the cosmetics and external preparations 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, polydimethylmethylenepiperidi , Quaternary ammonium of polyvinylpyrrolidone derivatives, cationized protein, collagen degradation product and derivatives thereof, water-soluble polymers such as acylated protein, polyglycerol, amino acid polyglycerol ester; sugar alcohols such as mannitol and alkylene oxide adducts thereof; In addition, lower alcohols such as ethanol and propanol can be blended.

  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, antioxidants, bactericides, anti-inflammatory agents, analgesics, antifungal agents, keratin softening release agents, UV absorbers, UV scattering agents, hair restorers , Whitening agents, antiperspirants, sweat deodorants, vitamins, pH adjusters, hormone agents, viscosity adjusters, herbal medicines and the like can be blended.

  The above-mentioned dimer acid ester, dimer diol ester, polyoxyalkylene dimer acid ester, polyoxyalkylene dimer diol ester or one or more of these should be blended in cosmetics and external preparations prepared by appropriately blending the above components The amount of the nonionic surfactant contained as a component varies depending on the product form, but is usually 0.01 to 100% by mass (the nonionic surfactant of the present invention is added with other components as a makeup remover, for example) And can be used as it is, preferably 0.1 to 50% by mass.

  One embodiment of the present invention will be described below, but the present invention is not limited thereto. In the examples, unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.

Example 1: Synthesis of dimer acid diisostearyl alcohol ester compound;
Each of dimer acid “Pripol 1009” (manufactured by Croda Japan) is charged with 1 mol (663 g) of isostearyl alcohol “Risonol 18SP” (manufactured by Higher Alcohol Industry) to a ratio of 2 mol (637 g), and nitrogen. The esterification reaction was conducted for 6 hours at a reaction temperature of 250 ° C. while flowing in, and in the nonionic surfactant (1) 1227 g (yield 94.4%) of the present invention, that is, in the above [Chemical Formula 1], R = isostearyl A dimer acid diisostearyl alcohol ester compound having an alcohol ester group and R ′ = isostearyl alcohol ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 7.12, a hydroxyl value of 7.56, a saponification value of 99.42, and an HLB value of 0.92.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid diisostearyl alcohol ester compound showed characteristic absorption at wavelengths of 1738.90 cm ⁻¹ (ester) and 1170.84 cm ⁻¹ (ether).

Example 2: Synthesis of dimer acid distearyl alcohol ester compound;
To 1 mol (519 g) of dimer acid “Pripol 1009” (manufactured by Croda Japan), stearyl alcohol “calcol 8688” (manufactured by Kao) was charged at a ratio of 2 mol (481 g), and nitrogen was introduced. Then, the esterification reaction was carried out at a reaction temperature of 250 ° C. for 7 hours and 30 minutes, and 942 g (yield 94.2%) of the nonionic surfactant (1) of the present invention, that is, in the above [Chemical Formula 1], R = stearyl alcohol ester Dimer acid distearyl alcohol ester compound in which R ′ = stearyl alcohol ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 7.99, a saponification value of 107.55, and an HLB value of 0.90.

The compound per, as a result of infrared absorption spectrum measurement, dimer acid distearyl alcohol ester compound, the characteristic absorption was observed at wavelengths 1739.87cm ^-1 (ester) and 1170.84cm ^-1 (ether).

Example 3 Synthesis of dimer acid dihexadecyl alcohol ester compound;
Hexadecyl alcohol “Lisonol 16SP” (manufactured by Higher Alcohol Industry) is charged in a ratio of 2 mol (459 g) to 1 mol (541 g) of dimer acid “Pripol 1009” (manufactured by Croda Japan), respectively. The esterification reaction was conducted for 7 hours and 30 minutes at a reaction temperature of 250 ° C. while flowing in, and 924 g (yield 92.4%) of the nonionic surfactant (1) of the present invention, that is, in the above [Chemical Formula 1], R = A dihexadecyl alcohol ester compound having a hexadecyl alcohol ester group and R ′ = hexadecyl alcohol ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 7.68, a saponification value of 96.92, and an HLB value of 0.95.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid hexadecyl alcohol ester compound showed characteristic absorption at wavelengths of 1738.90 cm ⁻¹ (ester) and 1100.84 cm ⁻¹ (ether).

Example 4: Synthesis of dimer acid dibehenyl alcohol ester compound;
To 1 mol (470 g) of dimer acid “Pripol 1009” (made by Croda Japan), behenyl alcohol “Calcol 220-80” (made by Kao) was charged in a ratio of 2 mol (530 g), and nitrogen was introduced. The reaction was conducted for 6 hours and 30 minutes at a reaction temperature of 250 ° C., and 946 g (yield 94.6%) of the nonionic surfactant (1) of the present invention, that is, in the above [Chemical Formula 1], R = behenyl alcohol ester Dimer acid dibehenyl alcohol ester compound in which R ′ = behenyl alcohol ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 7.5, a saponification value of 97.45, and an HLB value of 0.81.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid dibehenyl alcohol ester compound showed characteristic absorption at wavelengths of 1738.90 cm ⁻¹ (ester) and 1173.73 cm ⁻¹ (ether).

Example 5: Synthesis of dimer acid di (octyldodecyl alcohol / phytosterol) ester compound;
1 mol (200 g) of octyldodecyl alcohol “Risonol 20SP” (manufactured by Higher Alcohol Industry) and 1 mol (200 g) of phytosterol “Phytosterol SP” (Tama Biochemical Co., Ltd.) Manufactured at a reaction temperature of 250 ° C. for 9 hours and 30 minutes, and 742 g of the nonionic surfactant (1) of the present invention (1) The dimer acid di (octyldodecyl alcohol / phytosterol) ester compound in which R = octyldodecyl alcohol ester group and R ′ = phytosterol ester group in the above [Chemical Formula 1] was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 4.93, a hydroxyl value of 15.02, a saponification value of 82.31, and an HLB value of 1.29.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid di (octyldodecyl alcohol / phytosterol) ester compound has characteristic absorption at wavelengths of 1737.94 cm ⁻¹ (ester) and 1171.81 cm ⁻¹ (ether). It was.

Example 6: Synthesis of dimer acid (diglycerin / isostearyl alcohol / phytosterol) ester compound;
Dimer acid “Pripol 1009” (manufactured by Croda Japan) 652.6 g, diglycerin “diglycerin 801” (manufactured by Sakamoto Yakuhin Kogyo) 96.2 g, isostearyl alcohol “Lisonol 18SP” (manufactured by Higher Alcohol Industry) 312 g, phytosterol “phytosterol” SP ”(manufactured by Tama Seikagaku) was charged in each case, and esterification was performed at a reaction temperature of 250 ° C. for 2 hours and 30 minutes while flowing in nitrogen, and 1226 g of the nonionic surfactant (1) of the present invention (yield) 94.3%), that is, in the above [Chemical Formula 1], a dimer acid (diglycerin / isostearyl alcohol / phytosterol) ester compound in which R, R ′ = diglycerin ester group, isostearyl alcohol ester group, phytosterol ester group is used. Obtained.

  As a result of analysis of this product, it was a compound having an acid value of 7.47, a hydroxyl value of 76, a saponification value of 102.54, and an HLB value of 2.4.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid (diglycerin / isostearyl alcohol / phytosterol) ester compound has a wavelength of 3417.04 cm ⁻¹ (hydroxyl), wavelengths of 1738.90 cm ⁻¹ (ester) and 1172. Characteristic absorption was observed at 77 cm ⁻¹ (ether).

Example 7: Synthesis of dimer acid diPOE (3 mol) oleyl alcohol ester compound;
2 mol (760.5 g) of POE (3 mol) oleyl alcohol “EMALEX 503” (manufactured by Japan Emulsion) to 1 mol (539.5 g) of the dimer acid “Pripol 1009” (manufactured by Croda Japan) Then, the esterification reaction was carried out at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while flowing nitrogen, and 1242 g (yield 95.5%) of the nonionic surfactant (1) of the present invention, that is, the above [ Dimer acid diPOE (3 mol) oleyl alcohol ester compound in which R = POE (3 mol) oleyl alcohol ester group and R ′ = POE (3 mol) oleyl alcohol ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 6.72, a hydroxyl value of 8.85, a saponification value of 87.46, and an HLB value of 2.82.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid diPOE (3) oleyl alcohol ester compound showed characteristic absorption at wavelengths of 1739.87 cm ⁻¹ (ester) and 1120.69 cm ⁻¹ (ether). It was.

Example 8: Synthesis of dimer acid diPOE (3 mol) isostearate compound;
2 mol (520 g) of POE (3 mol) isostearic acid “EMALEX PEIS-3EX” (manufactured by Japan Emulsion) to 1 mol (780 g) of the dimer acid “Pripol 1009” (manufactured by Croda Japan) The non-ionic surfactant (1) of the present invention (1) 1240 g (yield 95.4%), that is, the above-mentioned [Chemical Formula 1] was prepared. In the above, a dimer acid diPOE (3 mol) isostearic acid ester in which R = POE (3 mol) isostearic acid ester group and R ′ = POE (3 mol) isostearic acid ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 9.15, a hydroxyl value of 14.28, a saponification value of 165.97, and an HLB value of 3.31.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid diPOE (3) isostearate ester compound showed characteristic absorption at wavelengths of 1738.90 cm ⁻¹ (ester) and 1173.73 cm ⁻¹ (ether). It was.

Example 9: Synthesis of dimer acid diPOE (10 mol) isostearate compound;
2 mol (364 g) of POE (10 mol) isostearic acid “EMALEX PEIS-10EX” (manufactured by Japan Emulsion) to 1 mol (936 g) of the dimer acid “Pripol 1009” (manufactured by Croda Japan) The non-ionic surfactant (1) of the present invention (1) 1257 g (yield 96.7%), that is, the above-mentioned [Chemical Formula 1] was obtained. ], Dimer acid diPOE (10 mol) isostearate compound in which R = POE (10 mol) isostearate group and R ′ = POE (10 mol) isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 9.6, a hydroxyl value of 11.74, a saponification value of 113.2, and an HLB value of 7.21.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid diPOE (10) isostearate compound has characteristic absorption at wavelengths of 1737.94 cm ⁻¹ (ester) and 1115.87 cm ⁻¹ (ether). It was.

Example 10: Synthesis of dimer acid diPOE (20 mol) isostearate compound;
2 mol (1046.5 g) of POE (20 mol) isostearic acid “EMALEX PEIS-20EX” (manufactured by Nihon Emulsion Co., Ltd.) with respect to 1 mol (253.5 g) of dimer acid “Pripol 1009” (manufactured by Croda Japan) Each was charged to a ratio, and the esterification reaction was performed for 6 hours and 30 minutes at a reaction temperature of 250 ° C. while flowing nitrogen, and 1265 g of nonionic surfactant (1) of the present invention (yield 97.3%), that is, In the above [Chemical Formula 1], dimer acid diPOE (20 mol) isostearate compound in which R = POE (20 mol) isostearate group and R ′ = POE (20 mol) isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 6.19, a hydroxyl value of 11.2, a saponification value of 78.52, and an HLB value of 10.26.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid diPOE (20) isostearate compound has characteristic absorption at wavelengths of 1736.97 cm ⁻¹ (ester) and 1112.97 cm ⁻¹ (ether). It was.

Example 11: Synthesis of dimer acid di (POE (6 mol) isostearic acid / phytosterol) ester compound;
1 mol (456.3 g) of POE (6 mol) isostearic acid “EMALEX PEIS-6EX” (manufactured by Japan Emulsion) with respect to 1 mol (486.2 g) of dimer acid “Pripol 1009” (manufactured by Croda Japan) Phytosterol “Phytosterol SP” (manufactured by Tama Seikagaku Co., Ltd.) was charged to a ratio of 1 mol (357.5 g), and esterification was performed at a reaction temperature of 250 ° C. for 5 hours and 30 minutes while flowing nitrogen. Nonionic surfactant (1) 1226 g (yield 94.3%), that is, in the above [Chemical Formula 1], R = POE (6 mol) isostearate group, R ′ = phytosterol ester group A (POE (6 mol) isostearic acid / phytosterol) ester compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 10.6, a hydroxyl value of 11.85, a saponification value of 109.32, and an HLB value of 3.49.

The compound per, results of infrared absorption spectrometry, the dimer of di (POE (6 moles) isostearic acid / phytosterol) ester compound, the wavelength 1737.94cm ^-1 (ester) and 1118.76cm ^-1 (ether) Characteristic absorption was observed.

Example 12: Synthesis of dimer acid (isostearic acid POE (5 mol) hydrogenated castor oil / isostearyl alcohol / phytosterol) ester compound;
653.6 g of dimer acid “Pripol 1009” (manufactured by Croda Japan), 52 parts of isostearic acid POE (5 mol) hydrogenated castor oil “EMALEX RWIS-105EX” (manufactured by Japan Emulsion), isostearyl alcohol “Risonol 18SP” (high grade) 200.2 g of Alcohol Industry) and 153.4 g of phytosterol “Phytosterol SP” (manufactured by Tama Seikagaku Co., Ltd.) were respectively charged, and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 5 hours while flowing in nitrogen. Activator (1) 1232 g (yield 94.8%), that is, in the above [Chemical Formula 1], R, R ′ = isostearic acid POE (5 mol) hydrogenated castor oil ester group, isostearyl alcohol ester group, phytosterol ester Dimer acid (isostearate) Amino acid POE (5 mol) hydrogenated castor oil / isostearyl alcohol / phytosterol) ester compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 12.98, a hydroxyl value of 24.63, a saponification value of 123.94, and an HLB value of 2.0.

As a result of measuring the infrared absorption spectrum of the above compound, dimer acid (isostearic acid POE (5) hydrogenated castor oil / isostearyl alcohol / phytosterol) ester compound has a wavelength of 3456.59 cm ⁻¹ (hydroxyl group), 1736.97 cm. ^-1 (ester) and 1174.70 cm ⁻¹ (ether) showed characteristic absorption.

Example 13: Synthesis of dimer acid di (POE (10 mol) diglyceryl diisostearate / isostearyl alcohol) ester compound;
1 mol (729.3 g) of POE (10 mol) glyceryl diisostearate “EMALEX GWIS-210EX” (manufactured by Nihon Emulsion) to 1 mol (386.1 g) of dimer acid “Pripol 1009” (manufactured by Croda Japan) , Isostearyl alcohol “Lisonol 18SP” (manufactured by Higher Alcohol Industry) was charged to a ratio of 1 mole (184.6 g), and the esterification reaction was performed at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while flowing nitrogen. , 1238 g of nonionic surfactant (1) of the present invention (yield 95.2%), that is, in the above [Chemical Formula 1], R = POE (10 mol) glyceryl ester of diisostearic acid, R ′ = isostearyl alcohol ester Dimer acid (POE (10 mol) diisostearic acid) It was obtained Riseriru / isostearyl alcohol) ester compound.

  As a result of analysis of this product, it was a compound having an acid value of 5.82, a hydroxyl value of 6.28, a saponification value of 119.56, and an HLB value of 3.73.

As a result of measuring the infrared absorption spectrum of the above compound, dimer acid di (POE (10 mol) diglyceryl diisostearate / isostearyl alcohol) ester compound has wavelengths of 1737.94 cm ^-1 (ester) and 111.83 cm ^-1 ( The characteristic absorption was observed in ether).

Example 14: Synthesis of dimer acid dimer diol ester compound;
The dimer diol “Pripol 2033” (manufactured by Croda Japan) is charged to 1 mole (633.1 g) with respect to 1 mole (666.9 g) of the dimer acid “Pripol 1009” (manufactured by Croda Japan). The esterification reaction was carried out at a reaction temperature of 250 ° C. for 5 hours and 30 minutes while flowing in nitrogen to obtain 1234 g (yield 94.9%) of an oligomer compound.

  As a result of analysis of this product, it was a compound having an acid value of 5.5, a hydroxyl value of 19.1, a saponification value of 72.8, and an HLB value of 3.73.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer acid dimer diol ester compound showed characteristic absorption at wavelengths of 1738.90 cm ⁻¹ (ester) and 1171.81 cm ⁻¹ (ether).

Example 15: Synthesis of dimer diol monoisostearate compound;
To 1 mol (585.9 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan), isostearic acid “prisoline 3505” (manufactured by Unikema BV) is charged at a ratio of 1 mol (314.1 g). The esterification reaction was carried out at a reaction temperature of 250 ° C. for 4 hours and 30 minutes while flowing nitrogen, and 839.2 g (yield: 93.2%) of the nonionic surfactant (2) of the present invention, that is, The dimer diol monoisostearate compound in which R = H and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 2.48, a hydroxyl value of 74.1, a saponification value of 69.89, and an HLB value of 1.59.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol monoisostearate ester compound has wavelengths of 3350.50 cm ⁻¹ (hydroxyl group), 1738.90 cm ⁻¹ (ester), and 1171.81 cm ⁻¹ (ether). Characteristic absorption was observed.

Example 16: Synthesis of dimer diol diisostearate compound;
To 1 mol (583.2 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan), isostearic acid “prisoline 3505” (manufactured by Unikema BV) is charged in a ratio of 2 mol (616.8 g). The esterification reaction was performed for 6 hours and 30 minutes at a reaction temperature of 250 ° C. while flowing nitrogen, and 1134 g (yield 94.5%) of the nonionic surfactant (2) of the present invention, that is, in the above [Chemical Formula 2], A dimer diol diisostearate compound in which R = isostearate group and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 5.39, a hydroxyl value of 8.66, a saponification value of 104.8, and an HLB value of 0.94.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol diisostearic acid compound was found to have characteristic absorption at wavelengths of 1739.87 cm ⁻¹ (ester) and 1170.84 cm ⁻¹ (ether).

Example 17: Synthesis of dimer diol monostearate compound;
1 mol (590.4 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan) to 1 mol (309.6 g) of stearic acid “NAA-173K” (manufactured by NOF) The esterification reaction was carried out for 3 hours and 10 minutes at a reaction temperature of 250 ° C. while introducing nitrogen, and 832 g (yield 92.4%) of the nonionic surfactant (2) of the present invention, that is, in the above [Chemical Formula 2] Dimerdiol monostearate compound in which R = H and R ′ = stearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 1.73, a hydroxyl value of 71.24, a saponification value of 70.08, and an HLB value of 1.57.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol monostearate ester compound has wavelengths of 3359.18 cm ⁻¹ (hydroxyl group), 1739.87 cm ⁻¹ (ester), and 1171.81 cm ⁻¹ (ether). Characteristic absorption was observed.

Example 18: Synthesis of dimer diol distearate compound;
Stirric acid “NAA-173K; made by NOF” is charged in a proportion of 2 mol (459.9 g) with respect to 1 mol (440.1 g) of dimer diol “Pripol 2033; The esterification reaction was carried out for 7 hours at a reaction temperature of 250 ° C. while introducing nitrogen, and 835.8 g (yield 92.9%) of the nonionic surfactant (2) of the present invention, that is, = Dimerdiol distearate compound in which R = = stearic acid ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 4.31, a hydroxyl value of 3.17, a saponification value of 104.81, and an HLB value of 0.93.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol distearate compound was found to have characteristic absorption at wavelengths of 1739.87 cm ⁻¹ (ester) and 1170.84 cm ⁻¹ (ether).

Example 19: Synthesis of dimer diol monohydroxystearate compound;
1 mole (896 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan) with respect to 1 mole (504 g) of hydroxystearic acid “12-hydroacid HP” (manufactured by Ogura Gosei Kogyo) The esterification reaction was carried out for 4 hours and 30 minutes at a reaction temperature of 250 ° C. while introducing nitrogen, and the nonionic surfactant (2) of the present invention (2) (1283 g, yield 91.6%), that is, in the above [Chemical Formula 2] Dimerdiol monohydroxystearate compound in which R = H and R ′ = hydroxystearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 1.58, a hydroxyl value of 130.57, a saponification value of 65.96, and an HLB value of 2.5.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol monohydroxy stearate ester compound has wavelengths of 3359.18 cm ⁻¹ (hydroxyl group) 1738.90 cm ⁻¹ (ester) and 1174.70 cm ⁻¹ (ether). Characteristic absorption was observed.

Example 20: Synthesis of dimer diol mono (lauroyl sarcosine / N-myristoyl-N-methyl-β-alanine) ester compound;
Lauroyl sarcosine “Soipon SLA” (manufactured by Kawaken Fine Chemical Co., Ltd.), 0.5 mol (391.2 g), N-myristoyl-to 1 mol (1562.4 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan) N-methyl-β-alanine “Alanone AMA” (manufactured by Kawaken Fine Chemical Co., Ltd.) was charged to a ratio of 0.5 mol (446.4 g), and nitrogen was introduced at a reaction temperature of 130 ° C. for 6 hours and 40 minutes. An esterification reaction was performed, and 2076.3 g (yield: 86.5%) of the nonionic surfactant (2) of the present invention, that is, in the above [Chemical Formula 2], R = lauroyl sarcosine ester group or H, R ′ = N A dimerdiol mono (lauroylsarcosine / N-) which is myristoyl-N-methyl-β-alanine ester group or H To obtain a list yl -N- methyl -β- alanine) ester compound.

  As a result of analysis of this product, it was a compound having an acid value of 2.68, a hydroxyl value of 64.13, a saponification value of 72.94, and an HLB value of 3.52.

As a result of measuring the infrared absorption spectrum of the above compound, dimerdiol mono (lauroylsarcosine / N-myristoyl-N-methyl-β-alanine) ester compound has a wavelength of 3449.84 cm ⁻¹ (hydroxyl group), 1738.96 cm ^−. characteristic absorption was observed in ¹ (ester) and 1193.99Cm ^-1 (ether).

Example 21: Synthesis of dimer diol di (N-myristoyl-N-methyl-β-alanine / isostearic acid) ester compound;
1 mol (208 g) of N-myristoyl-N-methyl-β-alanine “Alanon AMA” (manufactured by Kawaken Fine Chemicals) with respect to 1 mol (400 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan), isostearin The acid “isostearic acid EX” (manufactured by Higher Alcohol Industry) was charged to a ratio of 1 mole (192 g), and the esterification reaction was performed at a reaction temperature of 130 ° C. for 9 hours and 30 minutes while flowing nitrogen. 748 g of nonionic surfactant (2) (yield 93.5%), that is, in the above [Chemical Formula 2], R = N-myristoyl-N-methyl-β-alanine ester group, R ′ = isostearic acid ester group Dimerdiol di (N-myristoyl-N-methyl-β-alanine / isostearic acid) ester compound It was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 2.40, a hydroxyl value of 7.0, a saponification value of 99.44, and an HLB value of 2.38.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol di (N-myristoyl-N-methyl-β-alanine / isostearic acid) ester compound has a wavelength of 3455.62 cm ⁻¹ (hydroxyl group), 1737.94 cm ^−. Characteristic absorption was observed in ¹ (ester) and 1172.77 cm ⁻¹ (ether).

Example 22: Synthesis of dimer diol dipyroglutamate compound;
Pyroglutamic acid “AJIDEW A-100” (Ajinomoto Co., Inc.) was charged in a ratio of 2 mol (464 g) to 1 mol (1136 g) of dimer diol “Pripol 2033” (manufactured by Croda Japan), respectively. The esterification reaction was performed for 12 hours and 30 minutes at a reaction temperature of 130 ° C. while flowing in, and 1478 g (yield 92.4%) of the nonionic surfactant (2) of the present invention, that is, in the above [Chemical Formula 2], R = pyrrole A dimer diol dipyroglutamate compound having a glutamic acid ester group and R ′ = pyroglutamic acid ester group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 9.7, a hydroxyl value of 46.59, a saponification value of 144.14, and an HLB value of 5.98.

As a result of measuring the infrared absorption spectrum of the above compound, the dimer diol dipyroglutamic acid ester compound was found to have characteristic absorption at wavelengths of 1741.80 cm ⁻¹ (ester) and 1198.81 cm ⁻¹ (ether). In addition, the hydroxyl value of the pyroglutamate group was 1707.08 cm ⁻¹ .

Example 23: Synthesis of POE (2 mol) dimer acid compound;
1300 g of dimer acid “Pripol 1009” (manufactured by Croda Japan) 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. to start addition of ethylene oxide, and the reaction is conducted at a reaction temperature of 160 to 165 ° C. When 208 g of ethylene oxide was added in 3 hours and 10 minutes of reaction time, it was cooled with water, 43 g of “KYOWARD 700SL” (manufactured by Kyowa Chemical Industry Co., Ltd.) at 90 to 100 ° C., and 20 ml of ion-exchanged water were dehydrated at 100 to 110 ° C. To do. -0.1 MPa for 30 minutes, and after filtration, 1458 g of EO adduct (yield 96.7%) in the above [Chemical Formula 3], AO = ethylene oxide, n + n ′ = 2, R = H, R ′ = H Of POE (2 mol) dimer acid compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 1.79, a hydroxyl value of 140.17, a saponification value of 172.91, and an HLB value of 4.2.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (2 mol) dimer acid compound was found to have a wavelength of 3419.94 cm ⁻¹ (hydroxyl group), 1741.80 cm ⁻¹ (ester) and 1170.80 cm ⁻¹ (ether). The characteristic absorption was observed.

Example 24: Synthesis of POE (2 mol) dimer acid diisostearate compound;
Then, 1 mol (648 g) of the POE (2 mol) dimer acid obtained in Example 23 is 2 mol (552 g) of isostearic acid “prisoline 3505” (manufactured by Unikema BV), respectively. The esterification reaction was carried out for 7 hours and 30 minutes at a reaction temperature of 250 ° C. while introducing nitrogen, and 1146 g (yield 95.5%) of the nonionic surfactant (3) of the present invention, that is, in the above [Chemical Formula 3] POE (2 mol) dimer acid diisostearate compound in which R = isostearate group and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 20.07, a hydroxyl value of 40.72, a saponification value of 190.05, and an HLB value of 1.67.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (2 mol) dimer acid distearate compound has characteristic absorption at wavelengths of 1743.72 cm ⁻¹ (ester) and 1161.20 cm ⁻¹ (ether). It was.

Example 25: Synthesis of POE (4 mol) dimer acid diisostearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mol (660 g) of POE (4 mol) dimer acid obtained in the same manner as in Example 23 was used with isostearic acid “prisoline 3505” ( The non-ionic surfactant (3) of the present invention was prepared by charging 2 moles (made by Unikema BV) to a ratio of 2 moles (540 g) and carrying out an esterification reaction at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while flowing nitrogen. 1146 g (95.5% yield), that is, in the above [Chemical Formula 3], a POE (4 mol) dimer acid diisostearate compound in which R = isostearate group and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 16.29, a hydroxyl value of 30.78, a saponification value of 174.9, and an HLB value of 2.53.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (4 mol) dimer acid diisostearate ester compound has characteristic absorption at wavelengths of 1740.83 cm ⁻¹ (ester) and 1171.81 cm ⁻¹ (ether). It was.

Example 26: Synthesis of POE (4 mol) unsaturated dimer acid diisostearate compound;
Next, isostearic acid is used with respect to 1 mol (550 g) of POE (4 mol) unsaturated dimer acid obtained by changing the dimer acid of Example 25 to unsaturated dimer acid “Pripol 1098” (manufactured by Claude Japan). “Prisorin 3505” (manufactured by Unikema BV) was charged to a ratio of 2 moles (450 g), respectively, and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 7 hours while introducing nitrogen, and the nonionic surfactant of the present invention (3) POE (4 mol) unsaturated dimer acid diisostearate compound in which R = isostearate group and R ′ = isostearate group in the above [Chemical Formula 3], 952 g (yield 95.2%) Got.

  As a result of analysis of this product, it was a compound having an acid value of 19.96, a hydroxyl value of 38.61, a saponification value of 177.26, and an HLB value of 2.54.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (4 mol) unsaturated dimer acid diisostearate ester compound has characteristic absorption at wavelengths of 1740.83 cm ⁻¹ (ester) and 1172.77 cm ⁻¹ (ether). Admitted.

Example 27: Synthesis of POE (20 mol) dimer acid diisostearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mole (1042.5 g) of POE (20 moles) dimer acid obtained in the same manner as in Example 23 was used with isostearic acid “prisoline 3505. (Produced by Unikema BV) at a rate of 2 moles (457.5 g), and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while flowing in nitrogen. Agent (3) 1451.9 g (yield 96.8%), that is, in the above [Chemical Formula 3], R = isostearic acid ester group, R ′ = isostearic acid ester group POE (20 mol) dimer acid diisostearic acid ester A compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 8.72, a hydroxyl value of 10.41, a saponification value of 114.97, and an HLB value of 7.2.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (20 mol) dimer acid diisostearate compound has characteristic absorption at wavelengths of 1737.94 cm ⁻¹ (ester) and 1115.87 cm ⁻¹ (ether). It was.

Example 28: Synthesis of POE (40 mol) dimer acid monoisostearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mole (1670 g) of POE (40 moles) dimer acid obtained in the same manner as in Example 23 was used with isostearic acid “prisoline 3505” ( Unikema BV) was added in an amount of 1 mol (330 g), and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 7 hours while flowing nitrogen, and the nonionic surfactant (3) 1955 of the present invention. 3 g (yield 97.8%), that is, in the above [Chemical Formula 3], POE (40 mol) dimer acid monoisostearate compound in which R = H and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 5.38, a hydroxyl value of 23.03, a saponification value of 72.81, and an HLB value of 11.8.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (40 mol) dimer acid monoisostearate compound was found to have wavelengths of 3489.38 cm ⁻¹ (hydroxyl group), 1736.97 cm ⁻¹ (ester) and 111.94 cm ^−. Characteristic absorption was observed in ¹ (ether).

Example 29: Synthesis of POE (5 mol) dimer acid mono (lauroyl sarcosine / N-myristoyl-N-methyl-β-alanine) ester compound;
With respect to 1 mol (947.7 g) of POE (5 mol) dimer acid obtained by controlling the number of moles of addition of ethylene oxide and the addition reaction time, the same procedure as in Example 23, lauroyl sarcosine “Soipon SLA” ”(Manufactured by Kawaken Fine Chemical) and 0.5 mol (188.5 g) of N-myristoyl-N-methyl-β-alanine“ Alanone AMA ”(manufactured by Kawaken Fine Chemical). Each was charged to a ratio, and the esterification reaction was carried out at a reaction temperature of 130 ° C. for 11 hours while flowing nitrogen, and 1178 g (yield 90.6%) of the nonionic surfactant (3) of the present invention, that is, the above [ Embedded image wherein R = lauroylsarcosine ester group or H, R ′ = N-myristoyl-N-methyl-β-alanine ester group or PO (5 moles) of dimer acid mono (lauroyl sarcosine / N- myristoyl -N- methyl -β- alanine) to give the ester compound.

  As a result of analysis of this product, it was a compound having an acid value of 4.06, a hydroxyl value of 28.77, a saponification value of 163.39, and an HLB value of 7.13.

As a result of infrared absorption spectrum measurement for the above compound, POE (5 mol) dimer acid mono (lauroyl sarcosine / N-myristoyl-N-methyl-β-alanine) ester compound has a wavelength of 3456.59 cm ⁻¹ (hydroxyl group). Characteristic absorption was observed at 1738.90 cm ⁻¹ (ester) and 1178.55 cm ⁻¹ (ether).

Example 30: Synthesis of POP (10 mol) POE (10 mol) dimer acid;
Charge 400 g of dimer acid “Pripol 1009” (manufactured by Croda Japan), stir and raise the temperature while flowing nitrogen. When the temperature is raised to 100 ° C., 3.2 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C. to start addition of propylene oxide, and the reaction is conducted at a reaction temperature of 160 to 165 ° C. and a reaction pressure of 0.06 to 0.1 MPa. When 412 g of propylene oxide is added in 1 hour, the reaction is started at the start of addition of ethylene oxide, reaction temperature of 160 to 165 ° C., and reaction pressure of 0.06 to 0.1 MPa. After adding 312 g of ethylene oxide in 1 hour of reaction time, it is cooled with water, 32 g of “KYOWARD 700SL” (manufactured by Kyowa Chemical Industry Co., Ltd.) and 11 ml of ion-exchanged water are added at 90 to 100 ° C. and dehydrated under reduced pressure at 100 to 110 ° C. 30 minutes passed at −0.1 MPa, and after filtration, 1068 g of PO + EO adduct (yield 95%) in the above [Chemical Formula 3], AO = propylene oxide + ethylene oxide, n + n ′ = 10 (PO) +10 (EO), POP (10 mol) POE (10 mol) dimer acid with R = H and R ′ = H was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 1.39, a hydroxyl value of 85.18, a saponification value of 70.17, and an HLB value of 6.6.

As a result of measuring the infrared absorption spectrum of the above compound, the POP (10 mol) POE (10 mol) dimer acid compound had a wavelength of 3473.95 cm ⁻¹ (hydroxyl group), 1736.97 cm ⁻¹ (ester), and 111.94 cm. Characteristic absorption was observed in ^-1 (ether).

Example 31: Synthesis of POP (10 mol) + POE (10 mol) dimer acid diisostearate compound;
Next, 2 moles (247. 247.) of isostearic acid “prisoline 3505” (manufactured by Unikema BV) with respect to 1 mole (652.5 g) of POP (10 moles) + POE (10 moles) dimer acid obtained in Example 30. 5 g), and an esterification reaction was performed at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while introducing nitrogen, and 856 g of the nonionic surfactant (3) of the present invention (yield 95.1%). ), That is, in the above [Chemical Formula 3], AO = propylene oxide + ethylene oxide, n + n ′ = 10 (PO) +10 (EO), R = isostearic acid ester group, R ′ = isostearic acid ester group POP (10 mol) + POE (10 mol) dimer acid diisostearate compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 7.06, a hydroxyl value of 13.99, a saponification value of 102.27, and an HLB value of 4.34.

As a result of measuring the infrared absorption spectrum of the above compound, the POP (10 mol) + POE (10 mol) dimer acid diisostearate compound has wavelengths of 1737.94 cm ⁻¹ (ester) and 111.94 cm ⁻¹ (ether). Characteristic absorption was observed.

Example 32: Synthesis of POB (2 mol) POE (4 mol) dimer acid compound;
1000 g of dimer acid “Pripol 1009” (manufactured by Croda Japan) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 100 ° C., 8 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C. to start addition of butylene oxide, and the reaction is conducted at a reaction temperature of 160 to 165 ° C. and a reaction pressure of 0.06 to 0.1 MPa. When 255 g of butylene oxide is added in a reaction time of 1 hour and 10 minutes, the reaction is started at the start of addition of ethylene oxide, reaction temperature of 160 to 165 ° C., and reaction pressure of 0.06 to 0.1 MPa. After 312 g of ethylene oxide has been added over a reaction time of 2 hours, the mixture is cooled with water, 32 g of “KYOWARD 700SL” (manufactured by Kyowa Chemical Industry Co., Ltd.) and 11 ml of ion-exchanged water are added at 90 to 100 ° C. and dehydrated under reduced pressure at 100 to 110 ° C. 30 minutes passed at −0.1 MPa, and after filtration, 1550 g of BO + EO adduct (yield 98.9%) in the above [Chemical Formula 3], AO = butylene oxide + ethylene oxide, n + n ′ = 2 (BO) +4 (EO) ), R = H, R ′ = H POB (2 mol) POE (4 mol) dimer acid compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 1.79, a hydroxyl value of 140.17, a saponification value of 172.91, and an HLB value of 5.0.

As a result of measuring the infrared absorption spectrum of the above compound, the POB (2 mol) POE (4 mol) dimer acid compound had wavelengths of 3457.55 cm ⁻¹ (hydroxyl group), 1737.94 cm ⁻¹ (ester) and 1122.62 cm. Characteristic absorption was observed in ^-1 (ether).

Example 33: Synthesis of POB (2 mol) + POE (4 mol) dimer acid diisostearate compound;
Next, 2 moles (508.) of isostearic acid “prisoline 3505” (manufactured by Unikema BV) with respect to 1 mole (791.7 g) of the POB (2 moles) + POE (4 moles) dimer acid obtained in Example 32. 3 g), and the esterification reaction was performed for 6 hours and 30 minutes at a reaction temperature of 250 ° C. while flowing nitrogen, and 1243 g of the nonionic surfactant (3) of the present invention (yield 95.6%). ), That is, in the above [Chemical Formula 3], AO = butylene oxide + ethylene oxide, n + n ′ = 2 (BO) +4 (EO), R = isostearic acid ester group, R ′ = isostearic acid ester group POB (2 mol) + POE (4 mol) dimer acid diisostearate ester compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 16.8, a hydroxyl value of 28.9, a saponification value of 154.37, and an HLB value of 2.56.

As a result of measuring the infrared absorption spectrum of the above compound, the POB (2 mol) + POE (4 mol) dimer acid diisostearate compound has characteristics at wavelengths of 1738.90 cm ⁻¹ (ester) and 111.87 cm ⁻¹ (ether). Absorption was observed.

Example 34: Synthesis of POE (2 mol) dimer diol compound;
1800 g of dimer acid “Pripol 2033” (manufactured by Croda Japan) 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. to start addition of ethylene oxide, and the reaction is conducted at a reaction temperature of 160 to 165 ° C. After adding 288 g of ethylene oxide in 1 hour and 10 minutes of reaction time, cool with water, add 50 g of “KYOWARD 700SL” (manufactured by Kyowa Chemical Industry) at 90-100 ° C., and 15 ml of ion-exchanged water, and dehydrate under reduced pressure at 100-110 ° C. To do. -0.1 MPa for 30 minutes, and after filtration, 2055 g of EO adduct (yield 98.4%) in the above [Chemical Formula 4], AO = ethylene oxide, n + n ′ = 2, R = H, R ′ = H Of POE (2 mol) dimer diol compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 0.08, a hydroxyl value of 79.98, and an HLB value of 3.2.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (2 mol) dimer diol compound was found to have characteristic absorption at wavelengths of 3399.68 cm ⁻¹ (hydroxyl group) and 1123.58 cm ⁻¹ (ether).

Example 35: Synthesis of POE (2 mol) dimer diol diisostearate compound;
Then, 1 mol (832 g) of the POE (2 mol) dimer diol obtained in Example 34 is 2 mol (768 g) of isostearic acid “prisoline 3505” (manufactured by Unikema BV), respectively. The esterification reaction was carried out for 7 hours and 30 minutes at a reaction temperature of 250 ° C. while charging and introducing nitrogen, and the nonionic surfactant (4) of the present invention (4) (1529.6 g, yield 95.6%), ], A POE (2 mol) dimer diol diisostearate compound in which R = isostearate group and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 5.14, a hydroxyl value of 9.4, a saponification value of 95.56, and an HLB value of 1.13.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (2 mol) dimer diol diisostearate ester compound has characteristic absorption at wavelengths of 1739.87 cm ⁻¹ (ester) and 1120.69 cm ⁻¹ (ether). It was.

Example 36: Synthesis of POE (4 mol) dimer diol diisostearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mol (999 g) of POE (4 mol) dimer diol obtained by the same operation as in Example 34 was used with isostearic acid “prisoline 3505” ( The non-ionic surfactant (4) of the present invention was prepared by charging 2 mol (801g) of Unikema BV) at a reaction temperature of 250 ° C for 7 hours and 30 minutes while flowing nitrogen. 1722 g (yield 95.7%), that is, in the above [Chemical Formula 4], a POE (4 mol) dimer diol diisostearate compound in which R = isostearate group and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 4.93, a hydroxyl value of 10.62, a saponification value of 88.02, and an HLB value of 2.03.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (4 mol) dimer diol diisostearate ester compound has characteristic absorption at wavelengths of 1739.87 cm ⁻¹ (ester) and 1119.73 cm ⁻¹ (ether). It was.

Example 37: Synthesis of POE (5 mol) dimer diol monoisostearate compound;
With respect to 1 mol (786.5 g) of POE (5 mol) dimer diol obtained by controlling the number of moles of addition of ethylene oxide and the addition reaction time and the same operation as in Example 34, the isostearic acid “prisoline 3505 (Produced by Unikema BV) at a rate of 1 mole (313.5 g), and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 6 hours and 30 minutes while introducing nitrogen. Agent (4) 1062 g (yield 96.5%), that is, in the above [Chemical Formula 4], POE (5 mol) dimer diol monoisostearate compound in which R = isostearate group and R ′ = H was obtained. .

  As a result of analysis of this product, it was a compound having an acid value of 2.6, a hydroxyl value of 53.21, a saponification value of 56.97, and an HLB value of 3.43.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (4 mol) dimer diol diisostearate compound was found to have wavelengths of 3483.59 cm ⁻¹ (hydroxyl group) 1739.87 cm ⁻¹ (ester) and 1120.69 cm ⁻¹ ( The characteristic absorption was observed in ether).

Example 38: Synthesis of POE (5 mol) dimer diol diisostearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mol (855 g) of POE (5 mol) dimer diol obtained by the same operation as in Example 34 was used with isostearic acid “prisoline 3505” ( The non-ionic surfactant (4) of the present invention was prepared by charging 2 mol (645 g) of Unikema BV) at a reaction temperature of 250 ° C. for 6 hours and 30 minutes while flowing nitrogen. 1437 g (yield 95.8%), that is, in the above [Chemical Formula 4], POE (5 mol) dimer diol diisostearate compound in which R = isostearate group and R ′ = isostearate group was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 6.56, a hydroxyl value of 10.42, a saponification value of 86.4, and an HLB value of 2.44.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (5 mol) dimer diol diisostearate ester compound showed characteristic absorption at wavelengths of 1739.87 cm ⁻¹ (ester) and 1111.86 cm ⁻¹ (ether). It was.

Example 39: Synthesis of POE (10 mol) dimer diol diisostearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mole (687.5 g) of POE (10 mole) dimer diol obtained by the same operation as in Example 34 was used with isostearic acid “prisoline 3505. (Produced by Unikema BV) at a rate of 2 moles (412.5 g), and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while introducing nitrogen, and the nonionic surface activity of the present invention Agent (4) 1050 g (yield 95.5%), that is, in the above [Chemical Formula 4], POE (10 mol) dimer diol diisostearate compound in which R = isostearic acid ester group and R ′ = isostearic acid ester group Obtained.

  As a result of analysis of this product, it was a compound having an acid value of 8.09, a hydroxyl value of 11.7, a saponification value of 72.45, and an HLB value of 4.18.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (10 mol) dimer diol diisostearate ester compound has characteristic absorption at wavelengths of 1738.90 cm ⁻¹ (ester) and 111.76 cm ⁻¹ (ether). It was.

Example 40: Synthesis of POE (5 mol) dimer diol dihydroxy stearate compound;
The number of moles of addition of ethylene oxide and the addition reaction time were controlled, and 1 mole (657.6 g) of POE (5 moles) dimer diol obtained by the same procedure as in Example 34 was used. -Hydroacid HP "(manufactured by Ogura Gosei Kogyo Co., Ltd.) was charged to a ratio of 2 moles (542.4 g), and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 6 hours and 30 minutes while flowing nitrogen. Nonionic surfactant (4) 1153 g (yield 96.1%), that is, in the above [Chemical Formula 4], R = hydroxystearic acid ester group, R ′ = hydroxystearic acid ester group POE (5 mol) A dimer diol dihydroxy stearate compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 4.96, a hydroxyl value of 84.66, a saponification value of 82.24, and an HLB value of 3.63.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (5 mol) dimer diol dihydroxy stearate ester compound was found to have wavelengths of 3462.37 cm ⁻¹ (hydroxyl group) 1736.97 cm ⁻¹ (ester) and 1119.73 cm ^−1. Absorption of properties was observed in (ether).

Example 41 Synthesis of POE (4 mol) Dimer Diol Monopolyhydroxystearate Compound;
Polyhydroxystearic acid “K—” was added to 1 mol (354 g) of POE (4 mol) dimer diol obtained by controlling the number of moles of addition of ethylene oxide and the addition reaction time and in the same manner as in Example 34. PON306 "(manufactured by Ogura Gosei Kogyo Co., Ltd.) was charged to a ratio of 1 mole (846 g), and the esterification reaction was carried out at a reaction temperature of 250 ° C. for 5 hours and 30 minutes while flowing in nitrogen. Agent (4) 1180 g (yield 98.3%), that is, in the above [Chemical Formula 4], R = polyhydroxystearic acid ester group, R ′ = H, POE (4 mol) dimer diol monopolyhydroxystearic acid ester compound Got.

  As a result of analysis of this product, it was a compound having an acid value of 9.32, a hydroxyl value of 27.29, a saponification value of 135.19, and an HLB value of 2.5.

As a result of measuring the infrared absorption spectrum of the above compound, the POE (4 mol) dimer diol monopolyhydroxystearic acid ester compound has a wavelength of 3456.59 cm ⁻¹ (hydroxyl group) 1734.08 cm ⁻¹ (ester) and 1176.63 cm ^−. Characteristic absorption was observed in ¹ (ether).

Example 42: Synthesis of POP (10 mol) POE (10 mol) dimer diol compound;
550 g of dimer diol “Pripol 2033” (manufactured by Croda Japan) is charged and stirred, and the temperature is raised while introducing nitrogen. When the temperature is raised to 100 ° C., 4.4 g of potassium hydroxide is added. Further, the temperature is raised to 130 ° C. to start addition of propylene oxide, and the reaction is conducted at a reaction temperature of 160 to 165 ° C. and a reaction pressure of 0.06 to 0.1 MPa. After adding 594 g of propylene oxide in 2 hours, the reaction is started at the start of addition of ethylene oxide, reaction temperature of 160 to 165 ° C., and reaction pressure of 0.06 to 0.1 MPa. When 451 g of ethylene oxide is added in 1 hour of reaction time, it is cooled with water, and 44 g of “KYOWARD 700SL” (manufactured by Kyowa Chemical Industry Co., Ltd.) and 16 ml of ion-exchanged water are added at 90 to 100 ° C. and dehydrated under reduced pressure at 100 to 110 ° C. 30 minutes passed at −0.1 MPa, and after filtration, 1515 g of PO + EO adduct (yield 95%) in the above [Chemical Formula 4], AO = propylene oxide + ethylene oxide, n + n ′ = 10 (PO) +10 (EO), A POP (10 mol) POE (10 mol) dimer diol compound with R = H and R ′ = H was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 0.11, a hydroxyl value of 77.89, and an HLB value of 6.1.

As a result of measuring the infrared absorption spectrum of the above compound, the POP (10 mol) POE (10 mol) dimer diol compound has characteristic absorption at wavelengths of 3478.77 cm ⁻¹ (hydroxyl group) and 1112.97 cm ⁻¹ (ether). Admitted.

Example 43: Synthesis of POP (10 mol) + POE (10 mol) dimer diol diisostearate compound;
Next, a ratio of 2 mol (252 g) of isostearic acid “prisoline 3505” (manufactured by Unikema BV) to 1 mol (648 g) of the POP (10 mol) + POE (10 mol) dimer diol obtained in Example 42 The non-ionic surfactant (4) 859.5 g (yield 95.5%) of the present invention was subjected to an esterification reaction at a reaction temperature of 250 ° C. for 7 hours and 30 minutes while flowing nitrogen. That is, in the above [Chemical Formula 4], AO = propylene oxide + ethylene oxide, n + n ′ = 10 (PO) +10 (EO), R = isostearic acid ester group, R ′ = isostearic acid ester group POP (10 mol) + POE ( 10 mol) Dimer acid diisostearate compound was obtained.

  As a result of analysis of this product, it was a compound having an acid value of 8.77, a hydroxyl value of 14.39, a saponification value of 54.71, and an HLB value of 4.0.

As a result of measuring the infrared absorption spectrum of the above compound, the POP (10 mol) + POE (10 mol) dimer acid diisostearate compound has a wavelength of 3476.84 cm ⁻¹ (hydroxyl group), 1737.94 cm ⁻¹ (ester) and Characteristic absorption was observed at 1113.90 cm ⁻¹ (ether).

  Hereinafter, the dimer acid ester compound, the dimer diol ester compound and the polyoxyalkylene dimer acid ester compound, the polyoxyalkylene dimer diol ester compound of the present invention, or a nonionic surfactant composition containing one or more of these as active ingredients depending on the formulation examples. The result of having evaluated the effect of a thing is shown concretely.

Evaluation Example 1: Skin Care Cream A skin care cream having the composition shown in Table 1 was prepared using the nonionic surfactant of the present invention obtained in Examples 1 to 43. In this skin care cream preparation method, Component 1 and Component 2 were each heated to 70 ° C., Component 2 was added gradually to Component 1 and emulsified with a homomixer.

Evaluation item:
1. Good spread (lightness)
2. 2. Emollient effect 3. Persistence of emollient effect Product viscosity Diameter stability

(Evaluation method 1)
About the sensory evaluation of the said evaluation items 1-4, it was made to actually apply | coat to the paneler and the practical evaluation was performed. The criteria for sensory evaluation were ◎ for very good, ◯ for good, △ for normal, and x for poor.

(Evaluation method 2)
The diameter stability of the evaluation item 5 was evaluated by the following method. That is, each skin care cream after adjustment was left in a temperature-controlled room where the atmosphere was repeated at −5 to 40 ° C., and the state of the skin care cream was observed one month after this cycle test. The evaluation criteria for the time stability were ○ if it was stable for one month in a cycle test at −5 ° C. and 40 ° C., and × if it was separated in one month (repeating condition was [−5 ° C. × 48 hours ] → [40 ° C. × 120 hours] for one month with one cycle).

  The skin care creams of the present invention products 1 to 4 showed excellent quality in all the items of good spreadability (lightness) at the time of application, emollient effect, sustained emollient effect, product viscosity and time stability. On the other hand, the comparative product 1 in which the polyoxyalkylene-modified organopolysiloxane is blended in place of the nonionic surfactant of the present invention is superior in spreading at the time of coating than the present invention 1 to 4, but the emollient effect and its sustainability are improved. It was inferior. And the comparative product 2 which mix | blended dipolyhydroxystearic acid PEG-30 instead of the nonionic surfactant of this invention was inferior to the spread at the time of application | coating, and a product viscosity (it described with the mass%). .

Example 44: W / O-emulsion UV base cake;
A W / O-emulsion UV base cake having the composition shown in Table 2 below was prepared as follows. That is, component 1 was heated to 85 ° C., component 2 was heated to 75 ° C., and component 2 was gradually added while stirring component 1. Component 3 was then added and filled before solidifying. This W / O-emulsion UV base cake showed excellent sensory properties with good stability, glossiness and elongation equivalent to or better than products using silicone surfactants.

Example 45: W / O-emollient cream (silicone free);
The W / O-emollient cream shown in Table 3 below was prepared as follows. That is, component 1 and component 2 were each uniformly dissolved at 70 ° C., and component 2 was mixed while stirring component 1. The W / O-emollient cream prepared in this way is characterized in that it does not contain any silicone in the formulation, and is compatible with both a functional and moist feeling similar to a product using a silicone surfactant. It was a good cream.

Example 46: W / O-emulsion cake foundation;
The W / O-emulsion cake foundation having the composition shown in Table 4 below was prepared as follows. That is, component 1 was heated to 85 ° C. and component 2 was heated to 70 ° C., and component 2 was gradually added while heating and stirring component 1. Component 3 was then added and filled before solidifying. This W / O-emulsion cake foundation exhibited excellent sensory properties with good stability, glossiness and elongation equivalent to or better than products using silicone surfactants.

Example 47: W / O-emulsion cake foundation (silicone free);
A W / O-emulsion cake foundation having the composition shown in Table 5 below was prepared as follows. That is, component 1 was heated to 85 ° C. and component 2 was heated to 70 ° C., and component 2 was gradually added while heating and stirring component 1. Component 3 was then added and filled before solidifying. This W / O-emulsion cake foundation was characterized by not including any silicone in the formulation, and exhibited a functionality close to that of a product using a silicone surfactant.

Example 48: W / O-night cream;
A W / O-night cream having the composition shown in Table 6 below was prepared as follows. That is, component 1 and component 2 were each uniformly dissolved at 70 ° C., and component 2 was mixed while stirring component 1. This W / O-night cream showed excellent sensory properties with good stability, glossiness and elongation equal to or better than products using silicone surfactants.

Example 49: W / O-emollient essence;
A W / O-night cream having the composition shown in Table 7 below was prepared as follows. That is, component 1 and component 2 were uniformly dissolved at 80 ° C., and component 2 was mixed while stirring component 1. This W / O-emollient essence was excellent in temperature stability and exhibited an excellent sensory feeling with good gloss and elongation.

Example 50: a cleansing gel;
A cleansing gel having the composition shown in Table 8 below was prepared as follows. That is, component 1 and component 2 are each heated to 70 ° C. and dissolved uniformly. Next, component 1 was added while stirring component 2. This cleansing gel was transparent and very viscous, difficult to sag during use, and was excellent in pigment dispersibility, so it was well suited to foundations, makeup, etc., and exhibited an excellent sensation in cleansing performance.

Example 51 Cleansing Cream;
A cleansing cream having the composition shown in Table 9 below was prepared as follows. That is, component 1 and component 2 are each heated to 75 ° C. and dissolved uniformly. Next, component 1 was added while stirring component 2. Since this cleansing cream was excellent in pigment dispersibility, it was familiar with foundations, makeup, and the like, and exhibited a sensuality excellent in cleansing performance.

Example 52: cleansing oil;
Cleansing oils having the compositions shown in Table 10 below were prepared as follows. That is, component 1 and component 2 are each heated to 60 ° C. and dissolved uniformly. Next, component 2 was added while component 1 was being stirred. This cleansing oil can be used even with wet hands, and since it has excellent pigment dispersibility, it is well-familiar with foundations, makeup, and the like, and exhibits an excellent sensuality in cleansing performance.

Example 53: cleansing balm;
A cleansing balm having the composition shown in Table 11 below was prepared. That is, component 1 was heated to 80 ° C. to dissolve uniformly, and filled into a container at 70 ° C. before solidifying. This cleansing balm is a dosage form with excellent usability, and because of its excellent pigment dispersibility, it was well-familiar with foundations, makeup, etc., and exhibited an excellent sensation in cleansing performance.

Example 54: eye cream;
Eye creams having the compositions shown in Table 12 below were prepared. That is, component 1 is heated to 75 ° C. and component 2 is heated to 70 ° C. to dissolve uniformly. Next, component 1 was added while stirring component 2. This eye cream showed good sensation with good stretch and a feeling of tightening with the eyes.

Example 55: Hair wax;
A hair wax having the composition shown in Table 13 below was prepared as follows. That is, component 1 is heated to 85 ° C. and component 2 is heated to 70 ° C. to dissolve uniformly. Next, component 2 was added while stirring component 1. This hair wax was excellent in fiber feeling and exhibited an excellent sensation for maintaining styling.

Example 56: Hair shampoo;
A hair shampoo having the composition shown in Table 14 below was prepared as follows. That is, component 1 is heated to 70 ° C. and component 2 is heated to 75 ° C. to dissolve uniformly. Next, component 1 was gradually added while stirring component 2. Thereafter, 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 57: Hair conditioner;
A hair conditioner having the composition shown in Table 15 below was prepared as follows. That is, component 1 is heated to 75 ° C. and component 2 is heated to 80 ° C., and dissolved uniformly. Next, component 1 was gradually added while stirring component 2. Thereafter, component 3 was added and cooled to 30 ° C. This hair conditioner kept the moisture of the hair, gave gloss and moist feeling, and showed excellent sensuality as a smooth finger.

Example 58: Lipstick;
Lipsticks having the compositions shown in Table 16 below were prepared as follows. That is, component 1 was heated and dissolved, and component 2 was added thereto, kneaded with a roll mill and uniformly dispersed, de-processed, poured into a mold, rapidly cooled, and formed into a stick shape. This lipstick had a good sensation with a good fit with the skin and good spreadability.

Example 59 Sunscreen lotion;
A sunscreen lotion having the composition shown in Table 17 below was prepared as follows. That is, component 1, component 2 and component 3 are dissolved at room temperature. Next, component 2 and component 3 were gradually added while stirring component 1. This sunscreen lotion suppressed breakage due to sweat and the like, and was excellent in pigment dispersibility.

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

Claims (4)

A nonionic surfactant composition obtained by esterifying a carboxylic acid group at both ends of a dimer acid with an alcohol, an alkylene oxide adduct thereof, and an alkylene oxide adduct of a fatty acid, wherein the dimer acid has the following structure A nonionic surfactant composition containing at least one selected from the group consisting of ester derivatives.

(However, in the formula, R and R ′ are hydrogen or a compound residue used in the esterification reaction. However, when either R or R ′ is hydrogen, the other is the residue of the compound used in the esterification reaction. A, b, c, d are integers of 1 or more and a + b + c + d = 12 to 40. RO and R′O are monoester compounds, sesquiester compounds, diester compounds depending on the degree of esterification. Become.) The hydroxyl groups at both ends of dimer diol, polyoxyalkylene dimer acid, and polyoxyalkylene dimer diol (alkylene carbon number C2 to C4) are selected from the group consisting of fatty acid and esterification and / or fatty acid and acylamino acid and pyroglutamic acid. A nonionic surfactant composition obtained by esterification reaction with an amino acid comprising a dimer diol ester derivative, a polyoxyalkylene dimer acid ester derivative and a polyoxyalkylene dimer diol ester derivative having the structure shown below: A nonionic surfactant composition containing at least one selected.

(However, in the formula, R and R ′ are hydrogen or the fatty acid and amino acid residue used for esterification, but when either R or R ′ is hydrogen, the other is the fatty acid used for esterification. E, f, g, and h are integers of 1 or more and in the range of e + f + g + h = 12 to 40. In addition, RO and R′O are monoester compounds, sesquiester compounds, It becomes a diester compound.)

(However, in the formula, R and R ′ are hydrogen or the fatty acid and amino acid residue used for esterification, but when either R or R ′ is hydrogen, the other is the fatty acid used for esterification. I, j, k, l is an integer of 1 or more and i + j + k + 1 = 12-40, and (AO), (AO) ′ is a single alkylene of C2, C3 or C4 (AO), (AO) ′ is a C2-C4 alkylene oxide block or random addition polymer, n + n ′ represents the average number of moles of alkylene oxide added, It is an integer of 40. Also, the emulsification characteristics vary depending on the type of alkylene oxide and the number of moles added.RO and R'O are monoester compounds, sesquiester compounds, diester compounds depending on the degree of esterification. It becomes.)

(However, in the formula, R and R ′ are hydrogen or the fatty acid and amino acid residue used for esterification, but when either R or R ′ is hydrogen, the other is the fatty acid used for esterification. M, o, p, q are integers of 1 or more and m + o + p + q = 12 to 40. Also, (AO), (AO) ′ is a single alkylene of C2, C3 or C4 (AO), (AO) ′ is a C2-C4 alkylene oxide block or random addition polymer, n + n ′ represents the average number of moles of alkylene oxide added, It is an integer of 40. Also, the emulsification characteristics vary depending on the type of alkylene oxide and the number of moles added.RO and R'O are monoester compounds, sesquiester compounds, diester compounds depending on the degree of esterification. It becomes.)   A nonionic interface comprising at least one selected from the group consisting of a dimer acid ester derivative, a dimer diol ester derivative, a polyoxyalkylene dimer acid derivative, and a polyoxyalkylene dimer diol derivative having the structure according to claim 1 or 2. Cosmetics containing an active agent composition.   A nonionic interface comprising at least one selected from the group consisting of a dimer acid ester derivative, a dimer diol ester derivative, a polyoxyalkylene dimer acid derivative, and a polyoxyalkylene dimer diol derivative having the structure according to claim 1 or 2. An external preparation containing an activator composition.