JP6882144B6 - Compositions and cosmetic compositions - Google Patents

Description

The present invention relates to the fields of cosmetics, pharmaceuticals and foods, and to compositions and preparations having a cooling effect on the skin or mucous membranes containing menthol or menthol compounds with selected amides.

Menthol has been known as a cooling substance for decades and is still essential for many applications today, but it has many drawbacks: it is volatile, has a strong odor and has a bitter taste. It has the drawback of being there. Menthol no longer gives a refreshing sensation at high concentrations, but gives a stinging or burning sensation. Ultimately, menthol can interact with other chemical components and cannot be formulated as desired. This has led to the development of a wide variety of menthol compounds, many of which have excellent flavor properties.

WO 2012/061698 (Senomyx) discloses a complex amide that can be used as a TRPM8 modulator (transient receptor potential channel melastin member 8). This publication refers to substances that can bring hot or cold sensations to the skin and mucous membranes. These substances are especially recommended for use in food and body care products.

Despite recent advances and the development of increasingly effective coolants with terpene structures, they exhibit excellent sensory properties in both the cosmetics and food industries, are easily formulated and from an applied engineering point of view. A coolant or synergistic coolant mixture that has a beneficial effect on the final product and is as strong as the subjectively perceptible effect on the skin and mucous membranes despite particularly low applied concentrations. Is needed further.

Therefore, an object of the present invention is to provide a preparation of the above-mentioned type.

式中、Ｘは−ＯＹまたは−ＣＯＺを示し、かつＹは以下の基を示し：
（ｉ）１〜６個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基またはアリル基；
（ｉｉ）ヒドロキシまたは１〜６個の炭素原子を有するジヒドロキシアルキル基；
（ｉｉｉ）−ＯＣＲ^１基；
（ｉｖ）−ＯＣＯ（Ｍ）ＯＨ基；
（ｖ）−ＯＣＯ−Ｓ基；
（ｖｉ）−ＯＣ（ＣＨ_２）ｎＣＯＲ^２基；
式中、
Ｍは１〜１０個、好ましくは１〜４個の炭素原子を有する直鎖または分岐のアルキルおよび／またはアルケニル基を示し；
Ｓは５〜１２個の炭素原子を有する炭水化物基、好ましくはフルクトース、グルコース、またはスクロース基を示し；
ｎは０または１〜６、好ましくは２〜３の数を示し；
Ｒ^１は１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基、またはアリル基を示し；
Ｒ^２はヒドロキシル基または−ＮＲ^３Ｒ^４基を示し；
Ｒ^３およびＲ^４は、互いに独立して、水素または１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基を示し、
一方、Ｚは以下の基を示す：
（ｖｉｉ）ＮＲ^５Ｒ^６基または
（ｖｉｉｉ）ＮＨＲ^７基、
式中、
Ｒ^５およびＲ^６は、互いに独立して、水素または１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基、またはフェニル基またはアルコキシ基中に１〜６個、好ましくは１〜２個の炭素原子を有するアルコキシフェニル基を示し；
Ｒ^７は−（ＣＨ_２）_ｎＣＯＯＲ^８基を示し；
Ｒ^８は１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基を示し、かつ
ｎは０または１〜１０、好ましくは１〜４の数を示し、または
（ｂ２）芳香物質
を含む。
さらに、前記調製物は
（ａ）式（Ｉ）のアミド
Ａ^１−［Ｂ］−ＣＯ−ＮＲ^ａ−（ＣＨ_２）_ｐＡ^２ （Ｉ）
式中、
Ａ^１は任意に置換されたアリール、ヘテロアリールまたはシクロアルキル基を示し、
ＢはＯＣＲ^ｂＲ^ｂ、ＣＨＲ^ｃ−ＣＨＲ^ｄ、ＣＲ^ｅ＝ＣＲ^ｆまたはシクロアルキル基を示し、
ｐは１〜３の数を示し、
Ｒ^ａは任意に置換された１〜２０個の炭素原子を有するアルキル、ヘテロアルキル、アルケニル、ヘテロアルケニル、アリール、アラルキル、ヘテロアリールシクロまたはヘテロシクロアルキル基を示し、
Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ、Ｒ^ｅおよびＲ^ｆは独立して水素または１〜４個の炭素原子を有するアルキル基を示し、かつ
Ａ^２は窒素、酸素および硫黄から成る群からの1つ以上のヘテロ原子を有する任意に置換された５員または６員のヘテロアリール基を示し、
またはその塩、ならびに
（ｂ）メントールおよび/または式（ＩＩ）、（ＩＩＩ）および／または（ＩＶ）の前記メントール化合物
式中、Ｘは−ＯＹまたは−ＣＯＺを示し、かつＹは以下の基を示し：
（ｉ）１〜６個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基；
（ｉｉ）−ＣＲ^１基；
（ｉｉｉ）−ＣＯ（Ｍ）ＯＨ基；
（ｉｖ）−ＣＯ−Ｓ基；
式中、
Ｍは１〜１０個、好ましくは１〜４個の炭素原子を有する直鎖または分岐のアルキルおよび／またはアルケニル基を示し；
Ｓは５〜１２個の炭素原子を有する炭水化物基、好ましくはフルクトース、グルコース、またはスクロース基を示し；
Ｒ^１は１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基を示し；
一方、Ｚは以下の基を示す：
（ｖ）ＮＲ^５Ｒ^６基または
（ｖｉ）ＮＨＲ^７基、
式中、
Ｒ^５およびＲ^６は、互いに独立して、水素または１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル基、またはアルコキシ基中に１〜６個、好ましくは１〜２個の炭素原子を有するアルコキシフェニル基を示し；
Ｒ^７は−（ＣＨ_２）_ｎＣＯＯＲ^８基を示し、
Ｒ^８は１〜６個、好ましくは１〜２個の炭素原子を有する直鎖または分岐のアルキルまたはヒドロキシアルキル残を示し、かつ
ｎは０または１〜１０、好ましくは１〜４の数を示す、
を含む。 A first object of the present invention relates to a preparation having a cooling effect, wherein the preparation is an amide of the formula (a) (I) A ^1- [B] -CO-NR ^a- (CH ₂ ) _p A. ² (I)
During the ceremony
A ¹ represents an optionally substituted aryl, heteroaryl or cycloalkyl group,
B represents OCR ^b R ^b , CHR ^{c- CHR d} , CR ^e = CR ^f or cycloalkyl group.
p indicates a number from 1 to 3 and
^Ra represents an alkyl, heteroalkyl, alkenyl, heteroalkenyl, aryl, aralkyl, heteroarylcyclo or heterocycloalkyl group having 1 to 20 optionally substituted carbon atoms.
R ^b , R ^c , R ^d , ^Re and R ^f independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and A ² is one from the group consisting of nitrogen, oxygen and sulfur. Representing an arbitrarily substituted 5- or 6-membered heteroaryl group having the above heteroatoms,
Or salts thereof, and (b1) menthol and / or menthol compounds of formulas (II), (III) and / or (IV).

In the formula, X represents -OY or -COZ, and Y represents the following groups:
(I) A linear or branched alkyl or hydroxyalkyl group or allyl group having 1 to 6 carbon atoms;
(Ii) Hydroxy or dihydroxyalkyl group having 1 to 6 carbon atoms;
(Iii) -OCR ¹ groups;
(Iv) -OCO (M) OH group;
(V) -OCO-S group;
(Vi) -OC (CH ₂ ) nCOR ² units;
During the ceremony
M represents a linear or branched alkyl and / or alkenyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms;
S represents a carbohydrate group having 5-12 carbon atoms, preferably a fructose, glucose, or sucrose group;
n represents a number of 0 or 1-6, preferably 2-3;
R ¹ represents a linear or branched alkyl or hydroxyalkyl group having 1 to 6, preferably 1 to 2 carbon atoms, or an allyl group;
R ² indicates a hydroxyl group or -NR ³ R ⁴ groups;
R ³ and R ⁴ independently represent hydrogen or a linear or branched alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, preferably 1 to 2 carbon atoms.
On the other hand, Z indicates the following groups:
(Vii) NR ⁵ R ⁶ units or (vii) NHR ⁷ units,
During the ceremony
R ⁵ and R ⁶ are independent of each other and have one in a linear or branched alkyl or hydroxyalkyl group with hydrogen or 1-6, preferably 1-2 carbon atoms, or in a phenyl or alkoxy group. Shows an alkoxyphenyl group having ~ 6, preferably 1-2 carbon atoms;
R ⁷ indicates ⁸ − (CH ₂ ) _n COORs;
R ⁸ represents a linear or branched alkyl or hydroxyalkyl group having 1 to 6, preferably 1 to 2 carbon atoms, and n represents a number of 0 or 1 to 10, preferably 1 to 4. , Or (b2) contains an aromatic substance.
Further, the preparation is an amide of the formula (a) (I) A ^1- [B] -CO-NR ^a- (CH ₂ ) _p A ² (I).
During the ceremony
A ¹ represents an optionally substituted aryl, heteroaryl or cycloalkyl group,
B represents OCR ^b R ^b , CHR ^{c- CHR d} , CR ^e = CR ^f or cycloalkyl group.
p indicates a number from 1 to 3 and
^Ra represents an alkyl, heteroalkyl, alkenyl, heteroalkenyl, aryl, aralkyl, heteroarylcyclo or heterocycloalkyl group having 1 to 20 optionally substituted carbon atoms.
R ^b , R ^c , R ^d , ^Re and R ^f independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and A ² is one from the group consisting of nitrogen, oxygen and sulfur. Representing an arbitrarily substituted 5- or 6-membered heteroaryl group having the above heteroatoms,
Or a salt thereof, and (b) menthol and / or the menthol compound of formulas (II), (III) and / or (IV), where X represents -OY or -COZ and Y represents the following group: Show:
(I) A linear or branched alkyl or hydroxyalkyl group having 1 to 6 carbon atoms;
(Ii) -CR ¹ unit;
(Iii) -CO (M) OH group;
(Iv) -CO-S group;
During the ceremony
M represents a linear or branched alkyl and / or alkenyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms;
S represents a carbohydrate group having 5-12 carbon atoms, preferably a fructose, glucose, or sucrose group;
R ¹ represents a linear or branched alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, preferably 1 to 2 carbon atoms;
On the other hand, Z indicates the following groups:
(V) NR ⁵ R ⁶ units or (vi) NHR ⁷ units,
During the ceremony
R ⁵ and R ⁶ are independent of each other and have 1 to 6 hydrogen or 1 to 6 in a linear or branched alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, preferably 1 to 2 carbon atoms, or an alkoxy group. , Preferably exhibiting an alkoxyphenyl group having 1-2 carbon atoms;
R ⁷ indicates ⁸ − (CH ₂ ) _n COORs,
R ⁸ represents a linear or branched alkyl or hydroxyalkyl residue having 1 to 6, preferably 1 to 2 carbon atoms, and n represents a number of 0 or 1 to 10, preferably 1 to 4. ,
including.

Surprisingly, a mixture of the above type of menthol or menthol compound with an amide already known from WO 2012/061698 not only has the effect of synergistically enhancing the cooling effect, but also has a flavor. We also know that consumers will recognize that it will improve. The same applies to the majority of aromatic combinations.

Examining the sensory properties of oral and dental care products, it is even more noteworthy that a mixture of certain amides with menthol or menthol compounds synergistically reduces the solubility of hydroxyapatite and suppresses crystal growth. These properties also reduce enamel desalting and prevent tartar formation.

The amides that form the amide group (a) are known substances that can be produced by the relevant methods of organic chemistry. Regarding the manufacture thereof, the present inventors refer to all the contents of International Publication No. 2012/061698, and the contents disclosed therein are incorporated herein by reference.

In this regard, the two aryl or heteroaryl groups A ¹ and A ² in formula (I) are preferably independent of each other and optionally substituted phenyl, pyrrolyl, furanyl, thienyl, pyrazolyl, thiazolyl. , Isooxazolyl, isothiazoyl, pyridyl, pyrinidinyl or triazinyl groups. These groups may be substituted once or twice with alkyl, heteroalkyl, alkenyl, alkoxy, hydroxyl, amino, N-dialkylamino, halogen, nitro, cyano, acyl, carbonyl, carboxyl ester or amide groups. The two substituents may optionally form an aromatic ring having a heteroatom of an aliphatic ring or an aryl group, which may give rise to a bicyclic compound.

Group [B] preferably contains -OCH _2- , -OCH (CH ₃ )-, -OCH (CH ₂ CH ₂ ) _3- , -CH ₂ CH _2- or -CH = CH- group or cyclopropane. , Cyclobutane or cyclopentane.

In another preferred embodiment, ^Ra is an optionally substituted alkyl group having 1 to 6 carbon atoms or optionally substituted phenyl, pyrrolyl, furanyl, thienyl, pyrazolyl, thiazolyl, isooxazolyl, isothiazoyl, pyridyl, It shows a pyrinidinyl or triazinyl group and the substitution pattern can correspond to ^{the substitution pattern of A 1} and A ^2.

Preferably, when p indicates 2, R ^b , R ^c , R ^d , ^Re and R ^f all indicate hydrogen. To avoid ambiguity, specify that the individual preferred structural elements may all be preferred separately or, optionally combined with each other, to form a particularly preferred embodiment. Hereinafter, particularly preferable embodiments will be described in more detail using structural formulas A1 to A214.

The following substances are particularly preferred.
N- (1H-pyrazole-5-yl) -N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
N-Ethyl-N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
2- (P-trilloxy) acetyl chloride;
-N- (thiophen-2-ylmethyl) ethaneamine;
2- (2,3-dihydro-1H-indene-5-yloxy) -N- (1H-pyrazole-3-yl) -N- (thiophene-2-ylmethyl) acetamide;
2- (2,3-dihydro-1H-indene-5-yloxy) -N- (4-methyl-1H-pyrazole-3-yl) -N- (thiophene-2-ylmethyl) acetamide;
2- (2,3-dihydro-1H-indene-5-yloxy) -N- (3,5-dimethyl-1H-pyrazole-4-yl) -N- (thiophene-2-ylmethyl) acetamide;
N- (3-Methyl-1H-pyrazole-4-yl) -N- (thiophene-2-ylmethyl) -2- (P-tolyloxy) acetamide;
4- (N- (thiophen-2-ylmethyl) -2- (p-tolyloxy) acetamide) -1H-pyrazole-2-ium chloride;
N- (isoxazole-3-yl) -N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
2- (Benzo [d] [1,3] dioxol-5-yloxy) -N- (3-methyl-1H-pyrazole-4-yl) -N- (thiophene-2-ylmethyl) acetamide;
2- (Benzo [d] [1,3] dioxol-5-yloxy) -N- (1H-pyrazole-4-yl) -N- (thiophene-2-ylmethyl) acetamide;
N-Cyclopropyl-N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
N-allyl-N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
N-propyl-N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
2- (3-Methoxyphenoxy) -N- (1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) acetamide;
N- (bicyclo [2.2.1] heptane-2-ylmethyl) -N- (1H-pyrazole-3-yl) -2- (p-tolyloxy) acetamide;
N- (bicyclo [2.2.1] heptane-2-ylmethyl) -N- (1H-pyrazole-3-yl) -2- (p-tolyloxy) acetamide;
N- (bicyclo [2.2.1] heptane-2-ylmethyl) -3-phenyl-N- (1H-pyrazole-3-yl) propanamide;
N-Ethyl-N-((5-methylthiophen-2-yl) methyl) -2- (p-tolyloxy) acetamide;
N2- (4-ethylphenoxy) -N- (pyridin-3-yl) -N- (thiophen-2-ylmethyl) acetamide;
N- (1-Methyl-1H-pyrazole-5-yl) -N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
N- (bicyclo [2.2.1] heptane-2-ylmethyl) -2-phenoxy-N- (1H-pyrazole-3-yl) acetamide;
N-sec-Butyl-N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
N-Methyl-N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
2- (3-Methoxyphenoxy) -N- (pyridin-2-yl) -N- (thiophen-2-ylmethyl) acetamide;
2- (2-Isopropyl-5-methylphenoxy) -N- (1H-pyrazole-3-yl) -N- (thiophen-2-ylmethyl) acetamide;
N- (pyridin-2-yl) -N- (thiophene-2-ylmethyl) -2- (m-tolyloxy) acetamide;
2- (4-Ethylphenoxy) -N- (pyridin-2-yl) -N- (thiophen-2-ylmethyl) acetamide;
N-Ethyl-N- (thiazole-5-ylmethyl) -2- (p-tolyloxy) acetamide;
((R) -N- (1-Hydroxy-3-methylbutano-2-yl) -N-isopropyl-2- (m-tolyloxy) acetamide;
3,5-Dimethyl-N- (pyridin-2-yl) -N- (thiophene-2-ylmethyl) benzofuran-2-carboxamide;
N- (pyrazine-2-yl) -N- (thiophene-2-ylmethyl) -2- (p-tolyloxy) acetamide;
N-Benzyl-N-ethyl-2- (p-tolyloxy) acetamide;
2- (2-Isopropyl-5-methylcyclohexyloxy) -N- (2- (pyridin-4-yl) ethyl) acetamide;
N- (Fran-2-ylmethyl) -N- (pyridin-2-yl) -2- (p-tolyloxy) acetamide;
N-Ethyl-N- (thiazole-2-ylmethyl) -2- (p-tolyloxy) acetamide;
3,5,6-trimethyl-N- (pyridin-2-yl) -N- (thiophen-2-ylmethyl) benzofuran-2-carboxamide;
N-((5-ethylthiophen-2-yl) methyl) -N-phenyl-2- (p-tolyloxy) acetamide;
2-Phenoxy-N- (pyridin-3-yl) -N- (thiophen-2-ylmethyl) acetamide;
2- (3-Chlorophenoxy) -N- (pyridin-2-yl) -N- (thiophen-2-ylmethyl) acetamide;
N-((3-Methylthiophen-2-yl) methyl) -N-phenyl-2- (p-tolyloxy) acetamide;
(E) -N- (S-methyl-1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) -3-p-tolylacrylamide;
(E) -N- (1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) -3-p-tolylacrylamide;
・ (E) -3-p-trillacryloyl chloride;
(E) -3- (benzo [d] [1,3] dioxol-5-yl) -N- (1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) acrylamide;
(E) -N- (3,5-dimethyl-1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) -3-p-tolylacrylamide;
(E) -3- (benzo [d] [1,3] dioxol-5-yl) -N-ethyl-N- (thiophen-2-ylmethyl) acrylamide;
(E) -3- (4-Methoxyphenyl) -N- (1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) acrylamide;
N- (3,5-dimethyl-1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) cinnamamide;
N- (1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) cinnamamide;
(E) -3- (2,3-dihydro-1H-indene-5-yl) -N- (3,5-dimethyl-1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) Acrylamide;
・ (+/-)
(E) -2-Phenyl-N- (1H-pyrazole-4-yl) -N- (thiophen-2-ylmethyl) cyclopropanecarboxamide;
(E) -3- (2,3-dihydro-1H-indene-5-yl) -N- (1H-pyrazole-5-yl) -N- (thiophene-2-ylmethyl) acrylamide;
N-Ethyl-N- (thiophene-2-ylmethyl) cinnamamide;
2- (2,3-dihydro-1H-indene-5-yloxy) -N-ethyl-N- (thiazole-5-ylmethyl) acetamide;
2- (2,3-dihydro-1H-indene-5-yloxy) -N-ethyl-N- (thiazole-5-ylmethyl) acetamide;
(+/-) (E) -N-ethyl-2-phenyl-N- (thiophene-2-ylmethyl) cyclopropanecarboxamide;
N- (bicyclo [2.2.1] heptane-2-yl) -2- (2,3-dihydro-1H-indene-5-yloxy) -N- (1H-pyrazole-5-yl) acetamide;
N- (bicyclo [2.2.1] heptane-2-yl) -2- (cyclohexyloxy) -N- (1H-pyrazole-5-yl) acetamide;
2- (2,3-dihydro-1H-indene-5-yloxy) -N-ethyl-N-((5-methylthiophen-2-yl) methyl) acetamide;
(E) -N-Phenyl-N- (thiophene-2-ylmethyl) -3-p-tolylacrylamide;
(+/-) (E) -N, 2-diphenyl-N- (thiophene-2-ylmethyl) cyclopropanecarboxamide;
3,5-Dimethyl-N- (pyridin-2-yl) -N- (thiophene-2-ylmethyl) benzofuran-2-carboxamide;
(E) -N-allyl-3- (7-chlorobenzo [d] [1,3] dioxol-5-yl) -N- (thiophen-2-ylmethyl) acrylamide;
(E) -N-Ethyl-3- (4- (imidazole [1,2-a] pyridin-2-ylmethoxy) phenyl) -N- (thiophene-2-ylmethyl) acrylamide;
N- (cyclohexylmethyl) -N-ethyl-2- (p-tolyloxy) acetamide;

Menthol and menthol compounds The menthol compounds that can be used in the sense of the present invention and constitute group (b) are-in addition to the basic substance menthol itself-for example, menthol methyl ether, mentholicryl acetal (FEMA GRAS1 3807), menthol. Glyceryl ketal (FEMA GRAS 3808), menthol lactate (FEMA GRAS 3748), menthol ethylene glycol carbonate (FEMA GRAS 3805), menthol propylene glycol carbonate (FEMA GRAS 3806), menthol-N-ethyloxamate, monomethylsuccinate (FEMA GRAS) 3810), monomenthol glutamate (FEMA GRAS 4006), menthol-1,2-propanediol (FEMA GRAS 3784), menthol-2-methyl-1,2-propanediol (FEMA GRAS 3849), mentan carboxylic acid ester and It can be selected from the group consisting of amides WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30, and mixtures thereof.

The first important representative example of the substance constituting component (b) is monomentyl succinate (FEMA GRAS 3810), which is described in Brown & Williamson Tobacco Corp. Already obtained a patent as a substance in 1963 (US Pat. No. 3,111,127), and as a coolant, US Pat. No. 5,725,865 and US Pat. No. 5,843,466 (V. Mane). It is the target of Films). Both succinate and the analog monomentyl glutarate (FEMA GRAS 4006) constitute important representative examples of di- and polycarboxylic acid-based monomentyl esters.

Application examples of these materials can be found, for example, in the literature of International Publication No. 2003/043431 (Unilever) or European Patent Publication No. 1332772 (IFF).

^１ＦＥＭＡは「風味とエキス工業会（Ｆｌａｖｏｒ ａｎｄ Ｅｘｔｒａｃｔｓ Ｍａｎｕｆａｃｔｕｒｅｒｓ Ａｓｓｏｃｉａｔｉｏｎ）」の略で、ＧＲＡＳは「一般的に安全とみなされている（Ｇｅｎｅｒａｌｌｙ Ｒｅｇａｒｄｅｄ Ａｓ Ｓａｆｅ）」と定義される。ＦＥＭＡ ＧＲＡＳ評価はそのように示された物質は標準的な方法に従って試験され、毒性学的に安全とみなされていることを意味する。 Next to the preferred menthol compounds of the invention are carbonate esters of menthol with polyols such as glycols, glycerol or carbohydrates, such as menthol ethylene glycol carbonate (FEMA GRAS 3805 = Frescolat® MGC). , Menthol Propylene Glycol Carbonate (FEMA GRAS 3784 = Frescolat® MPC), Menthol 2-Methyl-1,2-Propanediol Carbonate (FEMA GRAS 3849), or the corresponding sugar derivatives.

¹ FEMA is an abbreviation for "Flavor and Extracts Manufacturers Association", and GRAS is defined as "Generally Regarded As Safe". A FEMA GRAS assessment means that the substances so indicated are tested according to standard methods and are considered toxicologically safe.

The use of such substances as coolants for tobacco is, for example, the subject of literature from 1968, US Pat. No. 3,419,543 (Mold et al.), And its use as a physiological coolant is It is disclosed in the claims of German Patent Application Publication No. 4226043 (H & R).

According to the present invention, preferred menthol compounds are marketed under menthol lactate (FEMA GRAS 3748 = Frescolat® ML), particularly preferably mentunglyceryl acetal (FEMA GRAS 3807) or trade name Frescolat® MGA. Menthone lyceryl ketal (FEMA GRAS 3808).

The former structure is obtained by esterification of menthol and lactic acid, and the later structure is obtained by acetalization of glycerol and menthone (see German Patent Application Publication No. 2608226, H & R). Another member of the compound in this group is 3- (1-Mentoxy) -1,2-, also known as Coolant 10 (FEMA GRAS 3784, US Pat. No. 6,328,982, see TIC). Propanediol, and 3- (1-mentoxy) -2-methyl-1,2, propanediol (FEMA GRAS 3849) with an additional methyl group.

3- (1-Mentoxy) -1,2,propanediol is produced starting from menthol, eg, according to the figure below (see US Pat. No. 4,459,425, Takagaso).

Another route for reacting menthol with epichlorohydrin in the first step is described in US Pat. No. 6,407,293 and US Pat. No. 6,515,188 (Takagasso). An overview of preferred menthol compounds characterized by CO bonds is given below.

Among these substances, mentholicryl acetal / ketal, menthol lactate and menthol ethylene glycol carbonate or menthol propylene glycol carbonate are described by Applicants as Frescolt® MGA, Frescolat® ML, Frescolat®. It is sold under the trade names MGC and Frescolat® MPC and has been shown to be particularly advantageous.

In the last century, menthol compounds having a CC bond at the 3-position were first developed in the 1970s, and the majority of representative examples of such compounds can also be used in accordance with the present invention. These substances are commonly referred to as WS type. The basic substance is a menthol derivative in which the hydroxyl group is substituted with a carboxyl group (WS-1). All other WS types are derived from this structure and are also preferred species of the present invention, eg, WS-3, WS-4, WS-5, WS-12, WS-14 and WS-30. The synthetic route is shown in the following two figures.

For example, esters derived from WS-1 are described in US Pat. No. 4,157,384 and the corresponding N-substituted amides are J.I. Soc. Cosmet. Chem. S. 185-200 (1978).

Aroma substance
The aromatic substances constituting the component (b2) are anetol, acetanisol, acetaldehyde, acetylmethylcarbinol, 2-acetylpyrazine, 2-acetylpyridine, 2-acetylthiazolin, 2-acetylthiazole, allyl caproate, and alpha-amyl. Cinnamaldehyde, p-anisaldehyde, anis alcohol, dimethylisopropyldithiazine, benzaldehyde, benzylacetate, L-borneol, butyric acid, butyl acetate, 3-butylidenephthalide, caproic acid, carbachlor, L-carboxylic, d-carboxylic, Carbomenton, cis-carbyl acetate, cariophyllene, 1,8-cineole, 1,4-cineole, cinnamyl acetate, citral, citroneral, citronellol, citronellyl acetate, cuminaldehyde, cyclopentadecanolide, alpha-damascon, beta- Damascon, Alpha-Damasenone, Beta-Damasenone, Delta-Decalactone, Gamma-Decalactone, Dehydromentofluorolactone, Dihydromentofluorolactone, 2,3-diethylpyrazine, Dihydroannetor, Dihydrocarboxylic, Dihydrocoumarin, Beta-dihydroionone, Dimethylanthranilate, dimethylsulfide, dimethylpyrazine, sotron, diphenyloxide, divanillin, 2,4-decadienal, delta-dodecalactone, gamma-dodecalactone, acetic acid, ethyl acetate, ethyl butyrate, ethyl 2-methylbutyrate, caproic acid Ethyl, ethyl caprylate, ethyl cinnate, ethyl isobutyrate, ethyl vanillin, ethyl lactate, ethyl maltor, ethyl methylthiopropionate, 4-ethylphenol, ethyl isovalerate, eugenol, fencol, flaneol, filbertone, flavinone, Franbinone Methyl Ether, Flufurylthiol, Undecatorien, Geraniol, Geranyl Acetic Acid, Geranyl Isobutyrate, Guayacol, Heliotropin, 2-Heptanone, Z-4-Heptenal, Gamma-Hexalactone, Gamma-Heptalactone, Z -3-Hexenol, E-2-hexenol, hexanol, hexyl acetate, Z-3-hexenyl acetate, hexenyl E-2-hexyl acetate, alpha-hexyl cinnamaldehyde, hexenyl Z-3-caproate, phototrienol, indole, alpha- Iron, alpha-ionone, beta-ionone, isoa acetate Mill, isoamyl butyrate, isoamyl isovalerate, isobutyl acetate, isobutylthiazole, isobutylaldehyde, isobarrelaldehyde, isooigenol, isomentone, isopropylmethoxypyrazine, isobutylmethoxypyrazine, 2,4-isopropylmethylpyrazine, isopregol, jasmine lactone, cis -Jasmon, cerebrum, ketoisophorone, cresol, d-lymonen, L-linalol, D-linalol, linaryl acetate, linalol oxide, maltor, methylcyclopentenolone, L-mentone, D-mentone, L-menthol, D-menthol , Neomentol, L-menthyl acetate, D-menthyl acetate, massoia lactone, melonal, 1,8-mententhiol, 1,8-epithiomentan, 8,3-thiomentanone, mentoflolactone, menthadienyl acetate, 2,3- Methylpyrazine methoxymethylpyrazine, methyl anthranilate, methyl salicylate, timol, methyl butyrate, 2-methylbutyl acetate, methyl cinnate, 2,3-methylfuranthiol, 2,3-methyltetrathiol, methyl jasmonate, methyl dihydrojasmonate, Methyl thiobutyrate, 1,3-methylthiohexyl acetate, 1,3-methylthiohexanol, methionale, myrutenal, naringin, neral, nerol, neryl acetate, gamma-nonalactone, delta-nonalactone, E-2-nonenal, Z-6- Nonenal, Z-6-nonenol, notecaton, dihydronotecatone, 1,3-octenol, gamma-octalactone, delta-octalactone, peritrine, 1,3-pentenone, pentyl acetate, phenylacetaldehyde, phenylethyl alcohol, phenyl acetate Ethyl, piperitanate, prenylthiol, prenylthioacetate, rose oxide, rubenamine, rubescenamin, sabinene hydrate, scator, styrolyl acetate, terpineol, 4-terpinenol, 1,3-thiohexanol, 1, 3-thiohexyl acetate, 4,4,2-thiopentanone, trimethylpyrazine, gamma and delta-undecadylene, 2,4-decadienal, 2,4-nonazienal, 2,6-nonazienal, 2,4-undecadier Nar, vanillin, vinyl guayacol, whiskey lactone, Shinnam Ardehi Consists of de, cinnamon alcohol, diallyl disulfide, allyl isothiocyanate, hexanal, E-2-hexenal, octanal, decanal, tridecatenal, 12-methyltridecaneal, alpha-pinene, beta-pinene and piperiten, and mixtures thereof. Selected from the group.

In another preferred embodiment of the invention, the preparation contains, as component (c), a surfactant, an oil component, an emulsifier, a pearlescent wax, a thickener, a thickener, a hyperfat agent, a stabilizer, a polymer, Silicone compounds, fats, waxes, lecithin, phospholipids, UV protection factors, wetting agents, biogenic agents, antioxidants, deodorants, antiperspirants, anti-fluffing agents, film forming agents, swelling agents, insect repellents, self It may include cosmetic additives selected from the group consisting of tanning agents, tyrosine inhibitors (bleaching agents), hydrotropes, solubilizers, preservatives, perfume oils and colorants, and mixtures thereof. Such preparations are characterized by an improved shelf life, especially in the form of emulsions.

The preparation of the present invention contains components (a) and (b) of 0.1: 99 to 99.9: 1, preferably 10: 90 to 90:10, more preferably 25: 75 to 75:25, and particularly preferably. Can be included in a weight ratio of 40:60 to 40:60. Ingredients (a + b) and (c) are 0.01: 99.9 to 2:98, preferably 0.5: 99.5 to 1.5: 98.5, particularly preferably in a weight ratio of about 1:99. Can be included.

Industrial Applicability Cosmetic Preparations and / or Pharmaceutical Preparations A further object of the present invention relates to cosmetic preparations, which are:
(A) Amide of formula (I),
Includes (b) menthol and / or menthol compounds of formula (II), (III) and / or (IV), and (c) carriers approved for cosmetic use.

Cosmetic products would preferably be skin care products, hair care products, body care products, sunscreen products, as well as oral and dental care products. Particularly preferred are cosmetic preparations in the form of emulsions, microemulsions or PIT emulsions.

A further object of the present invention relates to a pharmaceutical preparation, which is an amide of formula (a) (I).
Includes (b) menthol and / or menthol compounds of formulas (II), (III) and / or (IV), and (c) carriers approved for pharmaceutical use, for the treatment of colds, characterized by the present invention. It is to be used for therapeutic purposes.

Pharmaceutical products would preferably be lozenges, candy-form cold remedies, cold syrups, cold ointments and cold sprays.

In this case, the cosmetic or pharmaceutical carrier preferably comprises a group consisting of water, an alcohol having 2 to 6 carbon atoms, a polyol having 1 to 10 carbon atoms and 2 to 4 hydroxyl groups, and an oil component. Will be selected. In addition to water, particularly preferred carriers are ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, and linear or branched esters, 6-22, preferably 8-18. Saturated and especially unsaturated fatty acids with carbon atoms, and alcohols with 1 to 6 carbon atoms.

Cosmetic preparations and / or pharmaceutical preparations according to the present invention have components (a) and (b) of 0.1: 99-99.9: 1, preferably 10: 90-90: 10, more preferably. It can be included in a weight ratio of 25:75 to 75:25, particularly preferably 40:60 to 60:40. Ingredients (a + b) and (c) weigh 0.01: 99.9 to 2:98, preferably 0.5: 99.5 to 1.5: 98.5, particularly preferably about 1:99. Can be included in ratio. The total content of the component (a + b) in the final product can be between 1-5,000 ppm, preferably 10-4,000 ppm, particularly preferably 100-1,000 ppm.

The cosmetic and / or pharmaceutical preparations are common auxiliaries and additives such as mild surfactants, oil components, emulsifiers, pearl luster waxes, thickeners, thickeners, hyperfat agents, etc. Stabilizers, polymers, silicone compounds, fats, waxes, lecithin, phospholipids, UV protection factors, wetting agents, biogenic agents, antioxidants, deodorants, antiperspirants, anti-fluff agents, film-forming agents, swelling agents , Insect repellents, self-tanning agents, tyrosine inhibitors (bleaching agents), hydrotropes, solubilizers, preservatives, perfume oils, colorants and the like.

Surfactants The composition may include surfactants such as anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants, the content of which is usually about 1 on average. ~ 70% by weight, preferably 5-50% by weight, particularly preferably 10-30% by weight. Typical examples of anionic surfactants are soap, alkylbenzene sulfonate, alkane sulfonate, olefin sulfonate, alkyl ether sulfonate, glycerol ether sulfonate, α-methyl ester sulfonate, sulfo fatty acid, alkyl sulphate, alkyl ether sulphate, glycerol. Ether sulphate, fatty acid ether sulphate, hydroxy-blended ether sulphate, monoglyceride (ether) sulphate, fatty acid amide (ether) sulphate, mono- and dialkyl sulfosuccinate, mono- and dialkyl sulfosuccinate, sulfotriglyceride, amide soap , Ethercarboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid tauride, N-acylamino acids such as acyllactylate, acyltaltalate, acylglutamate, and acylaspartate, alkyloligoglucoside sulfates, proteins. Fatty acid condensates (particularly wheat-based plant products) and alkyl (ether) phosphates. If the anionic surfactant comprises a polyglycol ether chain, they may exhibit conventional forms, but preferably exhibit a narrow homologous distribution. Typical examples of nonionic surfactants are aliphatic alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, aliphatic amine polyglycol ethers, alkoxylated triglycerides, hybrid ethers or hybrid formal. , Arbitrarily partially oxidized alkyl (alkenyl) oligoglycosides or glucuronic acid derivatives, fatty acid N-alkyl glucamides, protein hydrolysates (particularly wheat-based plant products), polyol fatty acid esters, sugar esters, sorbitan Ethers, polysolvates, and amine oxides. If the nonionic surfactant comprises a polyglycol ether chain, they may exhibit conventional forms, but preferably exhibit a narrow homologous distribution. Representative examples of cationic surfactants are quaternary ammonium compounds such as dimethyl distearyl ammonium chloride and esterified quaternary ammonium compounds, especially quaternary fatty acid trialkanoamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkyl betaine, alkylamide betaine, aminopropionate, aminoglycinate, imidazolium betaine and sulfobetaine. All of the aforementioned surfactants are known compounds. Typical examples of particularly suitable palliative, i.e., particularly skin-friendly surfactants are aliphatic alcohol polyglycol ether sulphates, monoglyceride sulphates, mono- and / or dialkyl sulfosuccinates, fatty acid esethionates, fatty acids. Sarcosinate, fatty acid tauride, fatty acid glutamate, α-olefin sulfonate, ether carboxylic acid, alkyloligoglucoside, fatty acid glucamide, alkylamide betaine, amphoteric acetal and / or protein fatty acid condensate, the latter is preferably a protein fatty acid condensate based on wheat protein. Is.

Oil components Suitable examples of oil components include gelve alcohols based on aliphatic alcohols with 6-18, preferably 8-10 carbon atoms, linear or branched C _6- C ₂₂ aliphatic alcohols. Straight-chain C _6- C ₂₂ fatty acid esters, or straight-chain or branched C _6- C ₂₂ branched C _6- C ₁₃ carboxylic acid esters, such as myristyl myristate, Myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl oleate, myristyl docosenoate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl oleate, docosenoic acid Cetyl, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl docosenoate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, Isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleate oleate, oleyl behenate, oleyl docosenoate, behenyl myristate, behenyl palmitate , Behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl dococenate, elsyl myristate, elsyl palmitate, elsyl stearate, elsyl isostearate, elsyl oleate, elsyl docosene, etc. Is included. Other suitable materials, branched alcohols, especially 2-ethyl esters of fatty acids C ₆ -C ₂₂ linear and hexanol, fatty alcohols, in particular maleic acid C ₆ -C ₂₂ linear or branched _{Esters of alkylhydroxycarboxylic acids C 18-} C ₃₈ with dioctyl, esters of linear and / or branched fatty acids with polyhydric alcohols (eg, propylene glycol, dimerdiol or trimertriol, etc.) and / or gelve alcohol, Triglycerides based on C _6- C ₁₀ fatty acids, liquid mono- / di- / triglyceride mixtures based on _{C 6-} C _{18 fatty acids, aromatic carboxylic acids, especially C 6-} C ₂₂ aliphatic alcohols with benzoic acid and / or esters of Guerbet alcohols, straight or branched 1 to 22 amino dicarboxylic of _C 2 _{-C 12} of a polyol having an alcoholic or 2-10 carbon atoms and 2 to 6 hydroxyl groups with carbon atoms Esters of acids, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C _6- C ₂₂ aliphatic alcohol carbonates, such as dicaprylyl carbonate (Ceteil® CC), 6-18. Esters of benzoic acid with gelve carbonates based on aliphatic alcohols having 8 to 10 C atoms, linear and / or branched C _{6 to} C ₂₂ alcohols (eg, Finsolv® TN). ), Straight or branched, symmetric or asymmetric dialkyl ethers with 6 to 22 carbon atoms per alkyl group, eg epoxidized with polyols such as dicapryryl ethers (Cetiol® OE). Includes ring-opening products of fatty acid esters, silicone oils (cyclomethicone, silicone methicone products, etc.) and / or aliphatic or naphthenic hydrocarbons such as squalane, squalane or dialkylcyclohexane.

Emulsifiers Examples of suitable emulsifiers include nonionic surfactants derived from at least one of the following groups:
A linear aliphatic alcohol having 8 to 22 C atoms, a fatty acid having 12 to 22 C atoms, an alkylphenol having 8 to 15 C atoms in an alkyl group, and 8 to 22 in an alkyl group. Addition of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to an alkylamine with C atoms;
Alkyl and / or alkenyl oligoglycosides having 8 to 22 carbon atoms in an alkyl (alkenyl) group and their ethoxylated analogs;
-Addition of 1 to 15 moles of ethylene oxide to castor oil and / or hardened castor oil;
Addition of 15-60 mol of ethylene oxide to castor oil and / or hardened castor oil;
Partial esters of glycerol and / or sorbitan with unsaturated, linear or saturated fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms. And their adduct with 1-30 mol of ethylene oxide;
Polyglycerol (2-8 average) with saturated and / or unsaturated, linear or branched fatty acids with 12-22 carbon atoms and / or hydroxycarboxylic acids with 3-18 carbon atoms. Self-condensation), polyethylene glycol (molecular weight 400-5000), trimethylolpropane, pentaerythritol, sugar alcohols (eg, sorbitol), alkyl glucosides (eg, methyl glucoside, butyl glucoside, lauryl glucoside), and polyglucosides (eg, lauryl glucoside). Partial esters of (cellulose), as well as their adjuncts with 1-30 mol of ethylene oxide;
• A mixed ester of pentaerythritol, fatty acids, citric acid and fatty alcohols and / or a mixed ester of fatty acids, methylglucose and polyols, preferably glycerol or polyglycerols having 6-22 carbon atoms.
Mono-, di- and trialkyl phosphates, and mono-, di- and / or triPEG-alkyl phosphates and salts thereof;
・ Lanolin alcohol;
Polysiloxane-polyalkyl-polyether copolymers and corresponding derivatives;
Block copolymers, such as polyethylene glycol-30 dipolyhydroxystearate;
Polymer emulsifiers, such as Goodrich Pemulen types (TR-1, TR-2) or Cognis Cosmedia®. SP;
-Polyalkylene glycol, and-glycerol carbonate.

Hereinafter, particularly suitable emulsifiers will be described in more detail.
(A) Alkylene oxide Addition products of ethylene oxide and / or propylene oxide to aliphatic alcohols, fatty acids, alkylphenols or castor oil are known and constitute commercially available products. These are homologous mixtures and their average degree of alkoxylation corresponds to the ratio between the amount of ethylene oxide and / or the amount of propylene oxide to which the addition reaction takes place. _{The C 12/18} fatty acid mono- and diesters, which are the addition products of ethylene oxide to glycerol, are known as greasing agents for cosmetic preparations.

(A) Alkyl and / or alkenyl oligoglycosides Alkyl and / or alkenyl oligoglycosides, their production and their applications are known from the art. In particular, their production is carried out by reacting primary alcohols with 8-18 carbon atoms with glucose or oligosaccharides. As for glycoside groups, both monoglycosides in which the cyclic sugar group is glycosidic bonded to an aliphatic alcohol, and preferably oligomeric glycosides having an oligomerization degree of up to about 8 are suitable. As used herein, the degree of oligomerization is a statistical average value based on the general homologous distribution for such technical products.

(B) Partial glycerides Typical examples of suitable partial glycerides are hydroxystearic monoglyceride, hydroxystearic diglyceride, isostearic monoglyceride, isostearic diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinolic acid monoglyceride, ricinolic acid diglyceride, Linolic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride, and their industries. Mixtures for use, which may also contain small amounts of triglycerides secondary to the production process. Also suitable is an addition product of 1-30 mol, preferably 5-10 mol of ethylene oxide to the partial glyceride.

(C) Sorbitan ester Examples of suitable sorbitan esters include sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan diolate, sorbitan triolate, Sorbitan monoercaate, sorbitan sesquiercate, sorbitan diercaate, sorbitan triercaate, sorbitan monolithinolate, sorbitan sesquilithinolate, sorbitan diricinolate, sorbitan trilithinolate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, dihydroxy Sorbitan stearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesqui-tartrate, sorbitan di-tartrate, sorbitan tri-tartrate, sorbitan monocitrate, sorbitan sesquicitate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sesquimaleic acid Includes sorbitan, sorbitan dimaleate, sorbitan trimareate, and industrial mixtures thereof. Also suitable is an addition product of 1-30 mol, preferably 5-10 mol of ethylene oxide to the sorbitan ester.

(D) Polyglycerol Esters Typical examples of suitable polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform®). TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose di Stearate (TegoCare® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caplate (polyglycerol caprate T2010 / 90), polyglyceryl-3 cetyl ether (Chimexane® NL) ), Polyglyceryl-3 distearate (Cremophor® GS 32) and polyglyceryl polylithinolate (Admul® WOL 1403), polyglyceryl dimerate isostearate, and mixtures thereof. Examples of more suitable polyol esters are optionally 1-30 mol of ethylene oxide of trimethylolpropane or pentaerythritol with lauric acid, coconut oil fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like. Reacted mono, di and triester.

(E) Anionic Emulsifiers Typical anionic emulsifiers are aliphatic fatty acids having 12 to 22 carbon atoms, such as palmitic acid, steaic acid or bechenic acid, and dicarboxylic acids having 12 to 22 carbon atoms. Acids such as azelaic acid or sebacic acid.

(F) Amphoteric and cationic emulsifiers Zwitterionic surfactants can also be used as emulsifiers. The term zwitterionic surfactant refers to a surface active compound having one or more quaternary ammonium groups and one or more carboxylates and one sulfonate group in the molecule. A particularly suitable biionic surfactant is a biionic surfactant called betaine, specifically N-alkyl-N, N-dimethylammonium glycinate, for example, cocoalkyldimethylammonium glycinate. , N-acylaminopropyl-N, N-dimethylammonium glycinate, eg, cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-3, each having 8-18 C atoms in the alkyl or acyl group. Carboxymethyl-3-hydroxyethyl imidazoline, as well as cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate and the like. Particularly preferred are fatty acid amide derivatives known by the CTFA name cocamidopropyl betaine. Similarly, amphoteric surfactants are also suitable emulsifiers. The term amphoteric surfactant comprises one or more free amino groups and one or more -COOH or -S0 3 _H groups in addition to alkyl or acyl group in the molecule of the C _8/18, inner salt It is understood to refer to these surface active compounds capable of forming. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamide propylglycine, N-alkyl. Taurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each having about 8-18 C atoms in the alkyl group. Particularly preferred amphoteric tensides are N-cocoalkylaminopropionate, _{cocoacylaminoethylaminopropionate} , and C 12/18 acylsarcosine. Finally, a cationic surfactant is also suitable as an emulsifier, and in addition, an ester quat type is preferable, and a difatty acid triethanolamine ester salt having a quaternized methyl group is particularly preferable.

Fats and waxes Typical examples of fats are glycerides, i.e. solid or liquid plant or animal products consisting essentially of mixed glycerol esters of higher fatty acids, suitable waxes are specifically natural waxes. , For example, candelilla wax, carnauba wax, Japanese wax, espart wax, cork wax, guarma wax, rice germ oil wax, sugar cane wax, auricury wax, montan wax, beeswax, celac wax, whale wax, lanolin (wool wax) ), Cerecin, ozokelite (ground wax), vaseline, paraffin wax, microwax, etc .; chemically modified wax (hard wax), such as montan ester wax, sasol wax, etc. Johova waxes, specifically synthetic waxes such as polyalkylene waxes and polyethylene glycol waxes, are included. In addition to fat, fatty substances are also suitable as additives, such as lecithin and phospholipids. The term lecithin is understood by those skilled in the art as glycerophospholipids formed by esterification from fatty acids, glycerol, phosphates and choline. Therefore, lecithin is often referred to by experts as phosphatidylcholine (PC). Examples of natural lecithin, also called phosphatidic acid, include kephalin, which is a derivative of 1,2-diacyl-sn-glycerol-3-phosphate. On the other hand, it is usually understood to mean a mono- and preferably a diester of phosphoric acid with glycerol (glycerol phosphate), which is generally classified as fat. In addition, sphingosine or sphingolipids are also suitable.

Shiny pearl wax Examples of bright pearl wax are alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coconut fatty acid diethanolamides; partial glycerides, especially stearic acid monoglycerides; polyvalent, optionally hydroxy-substituted carboxylics. Esters of acids with aliphatic alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartrate; fatty substances such as aliphatic alcohols, aliphatic ketones, aliphatic aldehydes, aliphatic ethers and aliphatic carbonates. 12-22 of fatty acids, such as stearic acid, hydroxystearic acid or behenic acid, olefin epoxides having 12-22 carbon atoms, especially lauron and distearyl ethers (having a total of 24 or more carbon atoms). Ring-opening products with aliphatic alcohols having 1 carbon atom and / or polyols having 2-10 hydroxyl groups with 2 to 15 carbon atoms; and mixtures thereof.

Thickeners and Thickeners The first suitable thickeners are aliphatic alcohols or hydroxyaliphatic alcohols with 12 to 22, preferably 16 to 18 carbon atoms, such as partial glycerides, fatty acids or Hydroxy fatty acids are also suitable. Combinations of these substances with alkyloligoglucosides and / or fatty acids N-methylglucamide and / or polyglycerol poly-12-hydroxystearate of the same chain length are preferred. Suitable thickeners include, for example, Aerosil (hydrophilic silicic acid), polysaccharides, especially xanthan gum, guar guar, agar, alginate and tyrose, carboxymethyl cellulose and hydroxyethyl and hydroxypropyl cellulose, and higher molecular weight polyethylene of fatty acids. Glycol mono- and diesters, polysaccharides (eg, Goodrich Carboxole® and Pemulen product line; Sigma Synthalene®; Kelco Keltrol product line; Seppic Sepigel product line; Allid Colloids Calcare product line), polyacrylamides, polymers, polyvinyl alcohols and polyvinylpyrrolidones. Bentonite, such as Bentone® Gel VS-5PC (Rheox), which is a mixture of cyclopentasiloxane, disteardimonium hectorite and propylene carbonate, has also been found to be particularly effective. Also, surfactants such as ethoxylated fatty acid glycerides, polyols, eg esters of fatty acids with pentaerythritol or trimethylolpropane, aliphatic alcohol ethoxylates or alkyloligoglucosides with a narrow homologous distribution, and electrolytes such as electrolytes, eg. , Sodium chloride and ammonium chloride are also suitable.

Hyperfat Agents Suitable hyperfat agents for use include substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides, and fatty acid alkanolamides, where fatty acid alkanolamides are foam. It also functions as a stabilizer.

Stabilizer As the stabilizer, metal salts of fatty acids such as magnesium stearate, magnesium ricinoleate, aluminum stearate, aluminum ricinoleate, zinc stearate and / or zinc ricinoleate can be used.

Polymers Suitable cationic polymers include specifically cationic cellulose derivatives such as quaternized hydroxyethyl cellulose, cationic starch, diallyl ammonium salts available from Amerchol under the trade name of JR 400®. Condensation products of polyglycols and amines, such as copolymers of acrylamide, quaternized vinylpyrrolidone / vinylimidazole polymers, such as Luviquat® (BASF), quaternized collagen polypeptides, such as lauryldimonium hydroxy. Quarterized wheat polypeptides such as propyl hydrolyzed collagen (Lamequat® L / Gruenau), polyethylene imines, cationic silicone polymers such as amodimethicone, and copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartarenene). (Registered Trademarks) / Sandoz), Copolymers of Acrylic Acid with Dimethyldiallyl Ammonium Chloride (Merquat® 550 / Chemviron), Polyamino Polyamides and Crosslinked Water Soluble Polymers thereof, Cationic Chitin Derivatives, For example, Quadrified Chitosan Condensation products with dihalogen alkylenes, such as dibromobutane bis-dialkylamines (eg, bis-dimethylamino-1,3-propane), such as (optionally microcrystal-dispersed form), cationic guar gum, eg. , Celanese's Jaguar® CBS, Jaguar® C-17 or Jaguar® C-16, and other quaternary ammonium salt polymers, such as Miranol's Mirapol® A-. 15, Polymer (registered trademark) AD-1, Mirapol (registered trademark) AZ-1 and the like.

Examples of suitable anionic, biionic, amphoteric and nonionic polymers include vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, Methylvinyl ether / maleic anhydride copolymer and their esters, crosslinked polyacrylic acid with uncrosslinked polyacrylic acid and polyol, acrylamidepropyltrimethylammonium chloride / acrylate copolymer, octylacrylamide / methylmethacrylate / tert-butylaminoethylmethacrylate / 2 -Hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinylacetate copolymers, vinylpyrrolidone / dimethylaminoethylmethacrylate / vinylcaprolactamter polymers, and optionally derivatized cellulose ethers and silicones.

Silicone Compounds Suitable silicone compounds are, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicones, and amino, fatty-acids, alcohols, polys, which may be either liquid or resinous at room temperature. Ether, epoxy, fluorine, glycoside and / or alkyl modified silicone compounds. Also suitable is simethicone, which is a mixture of dimethicone having an average chain length of 200-300 dimethylsiloxane units and hydrogenated silicates.

UV Protective Factors The term UV Protective Factor refers to organic substances that are liquid or crystalline at room temperature, such as energy that can absorb UV light and then absorb in the form of radiation of longer wavelengths, such as heat (light protection filter). Is understood. Generally, the UV protection factor is contained in an amount of 0.1 to 5% by weight, preferably 0.2 to 1% by weight. The UVB filter may be oil-soluble or water-soluble. As an example of the oil-soluble substance, for example, it can be specifically shown as follows.
3-Benzylidene kanfa or 3-benzylidene norkanfa and derivatives thereof, such as 3- (4-methylbenzylidene) kanfa;
4-Aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic acid-2-ethylhexyl ester, 4- (dimethylamino) benzoic acid-2-octyl ester, and 4- (dimethylamino) benzoic acid amyl ester;
Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, and 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl. Ester (Octocrylen);
-Esters of salicylic acid, preferably salicylic acid-2-ethylhexyl ester, salicylic acid-4-isopropylbenzyl ester, and salicylic acid homomentyl ester;
Benzophenone derivatives, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone;
-Ester of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di-2-ethylhexyl ester;
Triazine derivatives such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octylriazone or dioctylbutamidotriazone (Uvasorb) (Registered trademark) HEB) etc .;
Propane-1,3-dione, for example 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;
-Ketotricyclo (5.2.1.0) decane derivative.

Suitable water-soluble substances include:
2-Phenylbenzimidazole-5-sulfonic acid and its alkalis, alkaline earths, ammonium, alkali ammonium, alkanolammonium, and glucoammonium salts;
· 1H-benzimidazole-4,6-disulfonic acid, 2,2 '- (1,4-phenylene) bis - disodium salt (Neo Heliopan ^(R) AP)
-Sulfonic acid derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts thereof;
-Sulfonic acid derivatives of 3-benzylidene campha, for example 4- (2-oxo-3-bornylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and theirs. Salt etc.

Of the typical UV-A filters, particularly suitable are derivatives of benzoylmethane, specifically 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-. 1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789), 2- (4-diethylamino-2-hydroxybenzoyl) -benzoic acid hexyl ester (Uvinul®) ) A Plus), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione, and enamin compounds. UV-A and UV-B filters can of course be used in mixtures. Particularly preferred combinations are derivatives of benzoylmethane, such as 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789) and -2-ethyl-hexyl 2-cyano-3,3-phenylsilicate. It consists of a combination of an ester (octocrylene) with an ester of cinnamic acid, preferably a 4-methoxy cinnamic acid-2-ethylhexyl ester and / or a 4-methoxy cinnamic acid propyl ester and / or a 4-methoxy cinnamic acid isoamyl ester. Advantageously, these combinations are combined with water soluble filters such as 2-phenylbenzimidazole-5-sulfonic acid and its alkalis, alkali metals, ammonium, alkylammonium, alkanolammonium and glucoammonium salts.

In addition to the soluble substances mentioned above, insoluble photoprotective pigments, i.e. finely dispersed metal oxides or salts thereof, are also suitable for this purpose. Examples of particularly suitable metal oxides include zinc oxide and titanium dioxide, and oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. Silicates (talc), barium sulphate or zinc stearate can be used as salts. Oxides and salts are used in the form of skin care and skin protective emulsions in the form of skin care and in the form of pigments for cosmetological cosmetics. In this case, the particles have an average particle size of less than 100 nm, preferably between 5 and 50 nm, particularly preferably between 15 and 30 nm. These particles can have a spherical morphology, but particles that deviate from the spherical morphology in an elliptical or any other manner can also be used. The pigment may be surface treated, i.e. hydrophilized or hydrophobized. Typical examples are coated titanium dioxide, such as titanium dioxide T805 (Degussa) or Eusolex® T2000, Eusolex® T, Eusolex® T-ECO, Eusolex®. TS, Eusolex® T-Aqua, Eusolex® T-45D (all Merck), Uvinul Ti02 (BASF) and the like. As the hydrophobic coating material, silicone is preferable, and trialkoxyoctylsilane or simethicone is particularly preferable. In sunscreens, substances called micro or nano pigments are preferably used. Finely divided zinc oxide, such as Z-COTE® or Z-COTE HP1®, is most preferably used.

Wetting agents Wetting agents are used to further optimize the sensory properties of the composition and are used to regulate skin moisture. At the same time, the cooling stability of the preparation according to the invention is increased, especially in the case of emulsions. The wetting agent is usually contained in an amount of 0.1 to 15% by weight, preferably 1 to 10% by weight, particularly preferably 5 to 10% by weight.

Examples of suitable substances according to the invention are amino acids, pyrrolidone carboxylic acids, lactic acid and salts thereof, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, collagen degradation products, chitosan or chitosan salts / derivatives, and especially polyols and polyols. Derivatives (eg glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycol, eg PEG-4, PEG-6, PEG-7, PEG -8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20, etc.), sugars and sugar derivatives (fluctose, glucose, maltose, maltol, mannitol, inositol, etc.) , Sorbitol, sorbitol silanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid, and salts thereof), sorbitol ethoxylated (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), honey and Hydrogenated honey, hydrogenated starch hydrolyzate, and a mixture of hydrogenated wheat protein and PEG-20 acetate copolymer. Preferred wetting agents according to the present invention are glycerol, diglycerols, triglycerols and butylene glycols.

Biogenic agents and antioxidants Biogenic agents include, for example, tocopherols, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy) ribonucleic acid and its fragmented products, β-glucan, retinol, bisabolol, allantin, fi. It is understood to mean tantriol, pantenol, AHA acid, amino acids, ceramides, pseudoceramides, essential oils, plant extracts such as cherry and bambar nut extracts, as well as vitamin complexes.

Antioxidants disrupt the photochemical reaction chain that occurs when UV radiation penetrates the skin. Typical examples of these substances are amino acids (eg, glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazole (eg, urocanic acid) and derivatives thereof, peptides such as D, L-carnosine, D. -Carnosine, L-carnosine and their derivatives (eg anserine), carotinoids, carotines (eg α-caronosine, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg) , Dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg, thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl) , Oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, Nucleosides and salts), as well as sulfoxyimine compounds at very low tolerable doses (eg, pmol-μmol / kg) (eg, butionine sulfoxyimine, homocysteine sulfoxyimine, butionine sulfone, penta-, hexa-, Heptationin sulfoxyimine), as well as (metal) chelating agents (eg, α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acid (eg, citric acid, lactic acid, malic acid), fumic acid, bile Acids, bile extracts, birylbin, biliberzine, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg, γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and them. Derivatives of, vitamin C and derivatives (eg, ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and coniferyl derived from benzoin. Benzoart, rutinic acid and its derivatives, α-glycosylrutin, ferulic acid, furfrilidene glucitol, carnosine, butylhydroxytoluene, buty Le hydroxyanisole, nordihydrocapsaicin guaiac resin acid, nordihydroguaiaretic acid, trihydroxy butyronitrile phenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase, zinc and derivatives thereof _(e.g., ZnO, ZnS0 4), selenium And derivatives thereof (eg, stilbene methionine), stilbene and its derivatives (eg, stilbene oxide, trans-stilbene oxide) and suitable derivatives of the active ingredient according to the present invention (salts, esters, ethers, sugars, nucleotides, etc.) Nucleosides, peptides and lipids).

Deodorants and antibacterial agents Cosmetic deodorants (deodorants) neutralize, mask or remove body odor. Body odor is caused by the action of skin bacteria on apocrine sweating, which is caused by the formation of decomposition products of unpleasant odors. Thus, deodorants include active ingredients that act as bacterial growth inhibitors, enzyme inhibitors, odor absorbers or odor masking agents.
(A) Bacterial growth inhibitor Suitable bacterial growth inhibitor is basically all substances active against gram-positive bacteria, such as 4-hydroxybenzoic acid and salts and esters thereof, N- (4-chlorophenyl). ) -N'-(3,4-dichlorophenyl) urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene -Bis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methylethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1,2-propane Diole, 3-iodo-2-propynylbutylcarbamate, chlorohexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrance, timol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, Phenoxyethanol, glycerol monocaprine, glycerol monocaprelate, glycerol monolaurate (GML), diglycerol monocaprine (DMC), and salicylic acid-N-alkylamides such as salicylic acid-n-octylamide or salicylic acid-n- Such as decylamide.

(B) Enzyme inhibitor For example, an esterase inhibitor is a suitable enzyme inhibitor. These are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate and tributyl citrate, and particularly preferably triethyl citrate (Hydagen® CAT). These substances inhibit enzyme activity and thus reduce the formation of odors. Other suitable substances as esterase inhibitors are dicarboxylic acids and esters thereof such as sterol sulphate or phosphate, such as lanosterol, cholesterol, campesterol, stigmasterol, and cytosterol sulphate or phosphate, such as glutaric acid, Glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, etc. Glutaric acid or diethyl ester of glutaric acid, as well as zinc glycinate.

(C) Odor Absorber A suitable odor absorber is a substance that can absorb odor-forming compounds and retain most of them. They reduce the partial pressure of the individual components and also reduce their diffusion rate. In this case, it is important that the perfume remains unaffected. Odor absorbers have no effect on bacteria. Odor absorbers include, for example, a complex zinc salt of ricinoleic acid as the main component or a specific, most odor-neutralizing air freshener known to those skilled in the art as a "fixing agent", such as Labdanum or Styrax. Includes extracts of the genus or derivatives of certain abietic acids. The odor masking agent functions as a fragrance or a perfume oil, and in addition to those functions, provides a deodorizing effect together with each scent as an odor masking agent. Examples of sesame oils include, for example, mixtures of natural and synthetic fragrances. Natural flavors are flowers, stems and leaves, fruits, fruit peels, roots, trees, herbs and grasses, needles and branches, and extracts of resins and balsams. Further suitable natural flavors are animal ingredients such as civets and castorium. Typical synthetic fragrance compounds are esters, ethers, aldehydes, ketones, alcohols and products of the hydrocarbon type. Ester-type fragrance compounds are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzylhomet, allylcyclohexylpropionate, styralyl propionate and benzyl salicylate. .. Examples of ethers include benzyl ethyl ether, examples of aldehydes include linear alkanals, citrals, citronerals, citronellyl oxyacetaldehydes, cyclamenaldehydes, hydroxycitrones with 8-18 carbon atoms. Examples of ketones are ionone and methylsedrill ketones, examples of alcohols are anetol, citralol, eugenol, isoeugenol, geraniol, linalol, phenylethyl alcohol and terpineol, of hydrocarbons, including lar, lilial and burgeonal. Examples are mainly terpenes and balsams. However, it is preferable to use a mixture of different fragrances, which together produce a pleasant scent. Low volatile essential oils commonly used as aromatic components are perfume oils such as sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, oliverham oil. Suitable as galvanum oil, radanum oil and lavandin oil. Preferably, bergamot oil, dihydromilsenol, linalool, lylar, citronellol, phenylethyl alcohol, α-hexyl cinnamon aldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, boisambrene forte, ambroxane, indol, Hezion, sandelice, lemon oil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal, lavandine oil, onisalvia oil, β-damascon, geranium oil bourbon, cyclohexyl salicylate, bergamot orange, iso -E-Super, Fixolide NP, Ebernil, iraldane gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat, Use individually or as a mixture.

(D) Antiperspirants Antiperspirants (antiperspirants) reduce the production of sweat by affecting the activity of the eccrine sweat glands, thereby reducing axillary moisture and body odor. Typically, an aqueous or anhydrous formulation of an antiperspirant contains the following ingredients:
・ Astringent,
・ Oil component,
・ Nonionic emulsifier,
・ Auxiliary emulsifier,
・ Thickener,
Excipients, such as thickeners or complexing agents, and / or
• Non-aqueous solvents such as ethanol, propylene glycol and / or glycerol.

As astringent antiperspirants, salts of aluminum, zirconium or zinc are mainly suitable. Such suitable anti-hydration activators are, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds, for example, propylene glycol-1,2-aluminum hydroxyalantoy. Nate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zircon tetrachlorohydrate, complex compounds with aluminum zircon pentachlorohydrate, and their complex compounds, specifically amino acids such as glycine. It is a complex compound. In addition, antiperspirants may also contain small amounts of common oil-soluble and water-soluble aids. Examples of such oil-soluble auxiliaries may include the following substances:
· Anti-inflammatory, skin-protective, or aromatic essential oils,
-Synthetic skin protectant and / or-Oil-soluble sesame oil.

Common water-soluble additives include, for example, preservatives, water-soluble fragrances, pH regulators, such as buffering mixtures, water-soluble thickeners, specifically water-soluble natural and synthetic polymers, such as xanthan gum. , Hydroxyethyl cellulose, polyvinylpyrrolidone or high molecular weight polyethylene oxide and the like.

Film-forming agents Common film-forming agents include, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer, acrylic acid-based polymers, quaternary cellulose derivatives, collagen, hyaluronic acid. Or their salts, as well as similar compounds.

Anti-dandruff agents Suitable anti-dandruff agents include pyrocton olamine (1-hydroxy-4-methyl-6- (2,4,4-trimethylpentyl) -2- (1H) -pyridinone monoethanolamine salt). , Baypival® (clinbazole), Ketoconazole®, (4-acetyl-1- {-4- [2- (2,4-dichlorophenyl) r-2- (1H-imidazole-1-ylmethyl)) -1,3-dioxylan-c-4-ylmethoxyphenyl} piperazine, ketoconazole, erviol, selenium disulfide, colloidal sulfur, sulfapolyethylene glycol sorbitan monooleate, sulfaridinol polyethoxylate, sulfatar distillate, salicylic acid Includes (or in combination with hexachlorophene), na salt of undecylenoic acid monoethanolamide sulfosuccinate, Lamepon® UD (protein undecylenoic acid condensate), zincpyrithione, aluminumpyrithione and magnesiumpyrithione / dipyrithione magnesium sulfate.

Swelling Agent The swelling agent for the aqueous phase may be montmorillonite, clay minerals, pemulene, and alkyl-modified Goodrich. Other suitable polymers or swelling agents are Cosm. Tool. 108, 95 (1993) R.M. You can find it in the overview of Lochhead.

Insect repellent Suitable insect repellent is N, N-diethyl-m-toluamide, 1,2-pentanediol or ethylbutylacetylaminopropionate. Dihydroxyacetone is suitable as the self-tanning agent. Examples of suitable tyrosine inhibitors that prevent the production of melanin and are used as depigmenting agents include arbutin, ferulic acid, kojic acid, coumaric acid, ascorbic acid (vitamin C).

Ingredients for Oral Care and Dental Care Products Arbutin Toothpaste or Dental Cream is for water, thickeners, wetting agents, glossy or abrasive particles, surfactants, sweeteners, air fresheners, deodorants and oral or dental disorders It is generally understood to refer to a gel-like or paste-like preparation of a drug. In the toothpaste of the present invention, all conventional abrasive particles such as choke, dicalcium phosphate, insoluble sodium metaphosphate, aluminum silicate, calcium pyrophosphate, fine particle artificial resin, silicic acid, aluminum oxide and aluminum oxide trihydration. Things can be used.

Preferred abrasive particles suitable for toothpaste of the present invention are mainly fine particle xerogel silica, silica hydrogel, precipitated silica, aluminum oxide trihydrate, fine particle α-aluminum oxide or a mixture of these abrasive particles. It is contained in an amount of 15 to 40% by weight of. It is suitable that the wetting agent mainly contains a mixture of low molecular weight polyethylene glycol, glycerol, sorbitol or a product thereof in an amount of up to 50% by weight. Among the known thickeners, thickeners, fine particle silica gel and hydrophilic colloids such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl guar, hydroxyethyl starch, polyvinylpyrrolidone, high molecular weight polyethylene glycol and other vegetable rubbers such as tragant, agar. , Carrageenan moss, Arabic gum, xanthan gum and carboxyvinyl polymers (eg, Carbopol® products) are suitable. In addition to mixtures of mentholan and menthol compounds, oral and dental care products are particularly surfactants, preferably anionic and nonionic hyperfoaming surfactants such as, for example, the substances mentioned above, however, in particular, in particular. It may contain alkyl ether sulfates, alkyl polyglucosides, and mixtures thereof.

Other common toothpaste additives are:
Preservative and antibacterial substances such as methyl p-hydroxybenzoate, ethyl or propyl ester, sodium sorbate, sodium benzoate, bromochlorophene, phenylsalicylic acid ester, timol, etc .;
-Anti-tartar agents, specifically organic phosphates, such as 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid, and other, eg, Known anti-tartar agents known from US Patent Nos. 3,488,419, German Patent Application Publication No. 22244430 and German Patent Application Publication No. 2343196;
-Other caries preventatives such as sodium fluoride, sodium monofluorophosphate, stannous fluoride, etc .;
Sweeteners such as sodium saccharin, sodium cyclamate, sucrose, lactose, maltose, fructose or Aspartame® (L-aspartame-L-phenylalanine-methyl ester), stevia extracts, or their sweetening ingredients, in particular, Lebaugioside, etc .;
• Additional air fresheners such as eucalyptus oil, anise oil, fennel oil, caraway oil, methyl acetate, cinnamaldehyde, anethole, vanillin, timol, and mixtures of these with other natural and synthetic air fresheners;
-Pigments such as titanium dioxide;
・ Coloring agent;
• Buffering agents such as first, second or third alkali metal phosphates or citric acid / sodium citrate;
-Wound healing and anti-inflammatory substances such as allantoin, urea, azulene, chamomile active ingredient and acetylsalicylic acid derivatives.

In a preferred embodiment of the cosmetic preparation, the toothpaste is in the form of a water-soluble, pasty dispersion, with an amount of 0.5-2% by weight of a mixture of menthol and menthol compounds, as well as an abrasive, a wetting agent, a viscosity modifier. Contains agents and optionally other conventional constituents.

In mouthwash, aqueous alcohol solutions containing various concentrations of essential oils, emulsifiers, astringents and tonic drug extracts, anti-tartar agents, antibacterial additives and flavor modifiers are well combined. A more preferred embodiment of the present invention is a mouthwash in the form of an aqueous solution or an aqueous alcohol solution containing a mixture of menthol and menthol compounds in an amount of 0.5-2% by weight. In mouthwash diluted before use, a satisfactory effect can be obtained at higher concentrations, depending on the dilution ratio of interest.

Hydrotropes In addition, hydrotropes, such as ethanol, isopropyl alcohol, or polyols, may be used to improve fluidity; these substances generally correspond to the carriers described first. Suitable polyols for this purpose will preferably have 2 to 15 carbon atoms and 2 or more hydroxyl groups. Also, the polyol may contain other functional groups, in particular an amino group, or may be modified with nitrogen. A typical example is shown below:
・ Glycerol;
-Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycol with an average molecular weight of 100-1,000 daltons;
An industrial oligoglycerol mixture with a self-condensation degree of 1.5-10, such as an industrial diglyceride mixture with a diglycerol content of 40-50% by weight;
• Methylol compounds, such as trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
-Lower alkyl glucosides, especially those having 1 to 8 carbons in the alkyl group, such as methyl and butyl glucosides;
Sugar alcohols with 5-12 carbon atoms, such as sorbitol or mannitol;
• Sugars with 5-12 carbon atoms, such as glucose or sucrose;
-Amino sugars, such as glucamine;
• Dialcohol amines such as diethanolamine or 2-amino-1,3-propanediol.

Preservatives Examples of suitable preservatives include, for example, phenoxyethanol, formaldehyde solutions, parabens, pentandiol or sorbic acid, and silver complexes and cosmetics regulations sold under the trade name Surfacine®, Appendix 6. Other compound classes described in sections A and B are included.

Perfume oils and aroma agents Examples of perfume oils include mixtures of natural and synthetic perfumes. Natural fragrances include flowers (lily, lavender, rose, jasmine, neroli, Iran-Iran), stems and leaves (geranium, pachori, petitgrain), fruits (anis, coriander, caraway seeds, juniper berries), fruit peels ( Bergamot (lemon, orange), roots (mace, angelica, ceroli, cardamon, costus, iris, shove), trees (pine, sandals, guayak, cedar, rosewood), herbs and grass (tarragon, lemongrass, sage, thyme) ), Needles and branches (tarragon, fir, pine, mountain pine), resins and extracts of balsam (galvanum, elemi, benzoin, mira, frankincense, opopanax). In addition, animal raw materials such as musk and castorium are suitable. Typical synthetic fragrance compounds are esters, ethers, aldehydes, ketones, alcohols and hydrocarbon-type products. Ester-type fragrance compounds include, for example, benzylacetate, phenoxyethylisobutyrate, p-tert-butylcyclohexylacetate, linaryl acetate, dimethylbenzylcarbinate acetate, phenylethylacetate, linarylbenzoate, benzylformiate, ethylmethylphenyl. Glycinate, allylcyclohexylpropionate, styralylpropionate and benzyl salicylate. Examples of ethers are, for example, benzyl ethyl ethers, and examples of aldehydes are, for example, linear alkanols, citrals, citronerals, citronellyloxyacetaldehydes, cyclamenaldehydes, hydroxycitrones with 8-18 carbon atoms. Examples of ketones are lard, lyrial and burgeonal, examples of ketones are, for example, ionone, α-isomethylionone and methylsedrill ketone, examples of alcohols are, for example, anetol, citronellol, eugenol, isooygenol, geraniol, linalol. , Phenylethyl alcohols and terpineols, and examples of hydrocarbons are mainly terpenes and balsams. However, it is preferable to use a mixture of different fragrances, which together produce a pleasant scent. Low volatile essential oils, which are mainly used as aroma components, are also suitable as perfume oils, for example, sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil. , Vetibelle oil, Olivernam oil, Galvanum oil, Laboranum oil and Labandin oil. Preferably, bergamot oil, dihydromilsenol, lilial, lylar, citronellol, phenylethyl alcohol, α-hexyl cinnamonaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisambrene forte, ambroxane, indol, gedion. (Gedione), sandelice, lemon oil, mandarin oil, orange oil, allyl amylglycolate, cyclovertal, lavandine oil, onisalvia oil, β-damascon, geranium oil bourbon, cyclohexyl salicylate, bergamot orange , Iso-E-super, Fixolide NP, Ebernil, iraldane gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, irotyl and floramat. , Used individually or as a mixture.

Suitable fragrances include peppermint oil, sparemint oil, anis oil, star anis oil, caraway seed oil, eucalyptus oil, uikyo oil, lemon oil, winter green oil, clove oil, menthol and the like.

Colorants Approved substances suitable for cosmetic purposes are, for example, the publications "Cosmetic Days", Verlag Chemie, Weinheim, The Dye Communication of the German Research Association of the German Academic Association. .. For example, the substances listed in 81-106 can be used. Examples include cochineal red A (Cl. 16255), patent blue V (C. l. 42051), indanthrone (C. l. 73015), chlorophyllin (C. l. 75810), and quinoline yellow (C. l. 75810). 47005), Titanium Dioxide (Cl. 77891), Indanthrone Blue RS (C. l. 69800) and Akane (C. l. 58000). Luminol may also be included as a luminescent colorant. These colorants are usually used in concentrations of 0.001 to 0.1% by weight based on the total mixture.

The total amount of auxiliaries and additives can be 1-50% by weight, preferably 5-40% by weight, based on the drug of interest. The preparation can be produced by a standard cold method or a hot method, and the phase inversion temperature method is preferably used.

Food Preparations Another object of the present invention relates to food preparations, including:
(A) Amide of formula (I),
(B) Menthol and / or menthol compounds of formula (II), (III) and / or (IV), and (c) carriers approved for food purposes.
The carrier is selected from the group consisting of water, ethanol and glycerol.
The food preparation will preferably be beverages, dairy products, baked goods, especially chewing gum and candies.

The preparations of the present invention contain components (a) and (b) at 0.1: 99-99.9: 1, preferably 10: 90-90: 10, more preferably 25: 75-75: 25, in particular. Preferably, it may be contained in a weight ratio of 40:60 to 60:40. The components (a + b) and (c) have a weight ratio of 0.01: 99.9 to 2:98, preferably 0.5: 99.5 to 1.5: 98.5, particularly preferably about 1:99. Can be included in. The total content of the component (a + b) in the final product can be in the range of 1-5,000 ppm, preferably 10-4,000 ppm, particularly preferably 100-1,000 ppm.

Chewing gum A preferred food preparation comprising the amide and menthol or a mixture of the menthol compound as a flavoring agent is chewing gum. These products typically contain water-insoluble and water-soluble components.

Water-insoluble substrates Water-insoluble substrates, also referred to as "gum substrates," generally include natural or synthetic elastomers, resins, fats and oils, softeners, fillers, colorants, and optionally waxes. The amount of the base material with respect to the entire composition is usually 5 to 95% by weight, preferably 10 to 50% by weight, particularly preferably 20 to 35% by weight. In a typical embodiment of the invention, the substrate consists of 20-60% by weight synthetic elastomer, 0-30% by weight natural elastomer, 5-555% by weight softener, 4-35% by weight filler. It consists of and contains additives such as colorants, antioxidants, etc. in incremental amounts (although they dissolve in small amounts in water, if applicable).

Examples of suitable synthetic elastomers are polyisobutylene, isobutylene-isoprene copolymers (“butyl elastomers”), styrene-butadiene with an average molecular weight (according to GPC) of 10,000 to 100,000, preferably 50,000 to 80,000. Copolymers (styrene: butadiene ratios such as 1: 3 to 3: 1), average molecular weight (depending on GPC) of 2,000 to 90,000, preferably 10,000 to 65,000 of polyvinyl acetate, polyisoprene, polyethylene, Includes vinyl acetate-vinyl laurate copolymers, and mixtures thereof. Examples of suitable natural elastomers are rubbers such as smoked or liquid latex or guayule rubber, and natural rubbers such as gelton, lechi caspi, perilo, solver, massaland babalata, massaland ba chocolate. , Nispero, Rosinba, Chicle, Guttahankan, etc., as well as mixtures thereof. The choice of synthetic and natural elastomers and their mixing ratios essentially depends on whether or not chewing gum can be used to make balloons (“bubble gum”). Preferably, an elastomer mixture containing gelton, chicle, solver, and massalanda is used.

In many cases, elastomers are found to be too hard or poorly malleable during processing, so it has been found advantageous to include special softeners, but of course the softening. The agent must also meet all specific conditions for approval as a food additive. In this respect, the softening agent is mainly an ester of a resin acid, for example, an ester of a completely or partially hydrogenated monomer or oligomeric resin acid and a lower fatty alcohol or polyol. In particular, methyl, glycero or pentaerythritol esters, and mixtures thereof, are used for this purpose. Alternatively, terpene resins that can be derived from alpha-pinene, beta-pinene, delta-limonene or mixtures thereof are also suitable.

As fillers or tempers, magnesium or calcium carbonate, pomegranate powder, silicates, especially magnesium silicates or aluminum silicates, clay, aluminum oxide, talc, titanium dioxide, mono-, di- and calcium triphosphate, and cellulose polymers Suitable.

Suitable emulsifiers are tallow, hardened tallow, hardened or partially hardened vegetable oils, cocoa butter, partially glycerides, lecithin, triacetin and saturated or unsaturated fatty acids with 6-22, preferably 12-18 carbon atoms, and them. Is a mixture of.

For example, suitable colorants and bleaches are FD and C types, plant and fruit extracts approved for use as food colorants, and titanium dioxide.

The substrate composition may or may not contain a wax, and examples of wax-free compositions can be found, among others, in US Pat. No. 5,286,500. The contents of the specification are referenced and incorporated herein by reference.

Water-soluble ingredients In addition to the water-insoluble gum substrate, chewing gum preparations are usually prepared, for example, with softeners, sweeteners, fillers, flavoring substances, flavor enhancers, emulsifiers, colorants, acidifiers, antioxidants. It contains a water-soluble component consisting of the above, but in this case, the component exhibits at least sufficient water solubility. Thus, depending on the water solubility of the particular component, the individual components may be present in either the water-insoluble phase or the water-soluble phase. However, for example, a combination of water-soluble and water-insoluble emulsifiers may be used, in which case the individual components are in different phases. The water-insoluble moiety usually comprises 5-95% by weight, preferably 20-80% by weight of the composition.

A water-soluble softener or plasticizer is added to the chewing gum composition to improve chewing properties and chewing sensations, typically present in the mixture in an amount of 0.5-15% by weight. Typical examples are glycerol, lecithin, and aqueous sorbitol, hydrogenated starch hydrolysates or corn syrup.

As the sweetener, both sugar-containing compounds and sugar-free compounds are suitable, which are 5 to 95% by weight, preferably 20 to 80% by weight, particularly preferably 30 to 60% by weight, based on the chewing gum composition. Use in the amount of. Typical sugar sweeteners are sucrose, dextrose, maltose, dextrin, dried invert sugar, fructose, fructose, galactose, corn syrup and mixtures thereof. Suitable alternative sugars are sorbitol, mannitol, xylitol, hydrogenated starch hydrolysate, maltitol and mixtures thereof. In addition, as additives, so-called HIAS (“high-sweetness artificial sweeteners”) sweeteners, such as sucralose, aspartame, acesulfame salts, alitame, saccharin and saccharin salts, individually or in admixture. Saccharin acid and its salts, glycyrrhizin, dihydrochalcone, thaumatin, monellin and the like are suitable. Hydrophobic HIAS, which is the subject of WO 2002/091849 (Wrigleys), and Stevia extract and its active ingredients, in particular rebaugioside A, are particularly effective. The amount of these substances used depends primarily on their sweetness and is usually in the range of 0.02-8% by weight.

Particularly suitable for the production of low-calorie chewing gum are fillers such as polydextrose, raftilose, raftilin, fructooligosaccharide (NtraFlora), palatinose oligosaccharide, guar gum hydrolyzate (Sun Fiber) and dextrin. And so on.

The choice of additional flavoring material is not substantially limited and is not critical to the essence of the invention. Generally, the total amount of total flavoring material is 0.1 to 15% by weight, preferably 0.2 to 5% by weight, based on the chewing gum composition. Examples of other suitable flavoring substances include essential oils, synthetic flavoring substances, such as those used in oral care products and dental care products, such as anis oil, star anis oil, caraway seed oil, eucalyptus oil. , Eucalyptus oil, lemon oil, winter green oil, clove oil, etc. are included.

In addition, chewing gum may include, for example, auxiliaries and additives suitable for dental care, especially in combating plaque and gingival inflammation, such as chlorhexidine, CPC or triclosan. Acidity regulators (eg, buffers or urea), anti-cavity agents (eg, phosphates or fluorides) and biogenic agents (antibodies, enzymes, caffeine, plant extracts) may also be included, but these substances. Is approved for food use and is subject to no inconvenient interaction with each other.

Capsules The preparations of a particular amide and menthol or menthol compound can be prepared in capsule form in cosmetic, pharmaceutical and food preparations, individually or completed and manufactured. In addition to the usual gelatin-based macrocapsules, types called microcapsules or nanocapsules are suitable. These are spherical aggregates having a diameter in the range of about 0.0001 to about 5 mm, preferably 0.005 to 0.5 mm, containing at least one solid or liquid nucleus enclosed in at least one continuous shell. Will be understood by those skilled in the art. More precisely, they are finely dispersed liquid or solid phases surrounded by film-forming polymers, which are deposited on the enclosing material during its production, after emulsification and droplet formation or interfacial polymerization. According to another method, the molten wax can be absorbed into a matrix (“microsponge”) and further enclosed in the film-forming polymer as microparticles. According to the third method, the particles are alternately coated with a polymer electrolyte having a variable charge (layer-by-layer method). Microscopically small capsules can be dried as powder. In addition to single-core microcapsules, multi-core aggregates, also called microspheres, are known and contain two or more nuclei dispersed within a continuous shell material. Single-core or multi-core microcapsules may also be additionally surrounded by a second, third, or other outer shell. The outer shell may consist of natural, semi-synthetic or synthetic material. Examples of natural shell materials are arabic gum, agar, agarose, maltodextrin, alginic acid or salts thereof, such as sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shelac. , Polysaccharides, eg, polypeptides such as starch or dextran, protein hydrolysates, sucrose and wax. Semi-synthetic shell materials include chemically modified celluloses, especially cellulose esters and ethers, such as cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, and starch derivatives, especially starch ethers and esters. included. The synthetic outer shell material is specifically a polymer such as polyacrylate, polyamide, polyvinyl alcohol or polyvinylpyrrolidone. Examples of known microcapsules are the following commercial products (each shell material is shown in parentheses): Hypromellose Microcapsules (gelatin, arabic gum), Colletica Thermospheres (marine collagen), Lipotec Microcapseln (alginic acid, agar). , Induchem Unispheres (lactoose, microcrystalline cellulose, hydroxypropylmethylcellulose); Gelatin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar) and Kuhs Properties. Nanosperse (phospholipids), and Primaspheres and Primasponges (chitosan, alginate) and Primacys (phospholipids). Of particular interest for encapsulation of preparations for cosmetic applications are cationic polymers, especially chitosan coacervates, with anionic polymers, especially alginates. Corresponding manufacturing methods are described, for example, in the following documents, International Publication No. 2001/001926, International Publication No. 2001/001927, International Publication No. 2001/001928 and International Publication No. 2001/0019929 (Cognis). There is.

Gel-forming agents Microcapsules are agents that are often dissolved or dispersed in the gel phase. A preferred gel-forming agent is a substance that exhibits the property of forming a gel in an aqueous solution at a temperature higher than 40 ° C. Typical examples of these gel-forming agents are heteropolysaccharides and proteins. The preferred heat-gelled heteropolysaccharide is agarose, which can be present with up to 30% by weight of non-gelled agaropectin in the form of agar obtained from red algae. The main components of agarose are the linear polysaccharides of D-galactose and 3,6-anhydro-L-galactose, which are linked alternately at β-1,3 and β-1,4. The heteropolysaccharide preferably has a molecular weight in the range of 110,000 to 160,000 and is tasteless and odorless. Suitable alternatives are pectin, xanthan (including xanthan gum) and mixtures thereof. Further, a preferred type is one that forms a gel even with a 1% by weight aqueous solution, does not dissolve below 80 ° C, and does not re-coagulate at a temperature higher than 40 ° C. Examples of the group of thermogelled proteins are various types of gelatin.

Cationic Polymers Suitable cationic polymers include cationic starches, diallylammonium salts and acrylamides, such as cationic cellulose derivatives, for example, quaternized hydroxyethyl cellulose available from Amerchol under the trade name Polymer JR 400®. Copolymers with, quaternized vinylpyrrolidone / vinylimidazole polymers, eg, condensation products of polyglycols with amines, such as Luviquat® (BASF), quaternized collagen polypeptides, eg lauryldimonium. Copolymers of adipic acid with dimethylaminohydroxypropyldiethylenetriamine, such as quaternized wheat polypeptides such as hydroxypropyl hydrolyzed collagen (Lamequat® L / Gruenau), polyethyleneimine, cationic silicone polymers such as amodimethicone. (Cartarene® / Sandoz), copolymer of acrylic acid with dimethyldialylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamide, and crosslinked water-soluble polymers thereof, cationic chitin derivatives, eg, optionally. Condensation products with dihalogen alkylenes such as quaternized chitosan in microcrystal dispersion form, such as bisdialkylamines such as dibromobutane, such as bis-dimethylamino-1,3-propane, cationic guar gum, eg. , Celanese's Jaguar® CBS, Jaguar® C-17, Jaguar® C-16, etc., and quaternized ammonium salt polymers such as Miranol's Mirapol® A. -15, Polymer® AD-1, Polymer® AZ-1, and the like are included. Preferably, chitosan is used as the encapsulating material. Chitosan constitutes a biopolymer and belongs to the group of hydrophilic colloids. Chemically, these chitosans are partially deacetylated chitins of different molecular weights containing the following ideal monomer units:

In contrast to many hydrophilic colloids, which are negatively charged in the range of biological pH values, chitosan is a cationic biopolymer under these conditions. Positively charged chitosan can interact with opposing charged surfaces and is therefore used in cosmetic hair and body care products and pharmaceutical preparations. The starting material for chitosan production is chitin, preferably chitin derived from the remaining crustacean shells, which is available in large quantities as an inexpensive raw material. In this case, in the method first disclosed by Hackmann et al., Usually, chitin is first added with a base to deproteinize, then mineral acid is added to dechloride, and finally a strong base is added to deacylate. The molecular weight can be widespread. The type used is preferably an average molecular weight of 10,000 to 500,000 daltons or 800,000 to 1,200,000 daltons and / or Brookfield viscosity of less than 5,000 mPas (glycolic acid in 1% by weight), 80. It will have a degree of deacetylation of ~ 88% and an ash content of less than 0.3% by weight. Usually, to improve water solubility, chitosan is used in its salt form, preferably in the form of glycolate.

Anionic Polymers Anionic polymers are used to form membranes with cationic polymers. Alginic acid salts are particularly suitable for this application. Alginic acid is a mixture of carboxyl group-containing polysaccharides having the following ideal monomer units:

The average molecular weight of alginic acid or alginate is in the range of 150,000 to 250,000. In this case, alginic acid salts are understood both as their complete and partially neutralized products, especially as alkaline salts, of which sodium alginate (“algin”), as well as ammonium and alkaline earth salts, are preferred. Is. Particularly preferred are mixed alginates, such as sodium alginate / magnesium or sodium alginate / calcium. However, in another embodiment of the invention, anionic chitosan derivatives, such as carboxylation products, especially succinylation products, are also suitable for this application. Alternatively, poly (meth) acrylates having an average molecular weight in the range of 5,000 to 50,000 daltons, and various carboxymethyl celluloses are also suitable. Instead of the anionic polymer, anionic surfactants or low molecular weight inorganic salts such as pyrophosphates may be used to form the outer shell membrane.

To produce encapsulated microcapsules, an aqueous solution of a gel-forming agent, preferably 1-10% by weight, preferably 2-5% by weight of agar, is usually selected and heated under reflux. The solution is boiled, preferably at 80-100 ° C., with 0.1 to 2% by weight, preferably 0.25 to 0.5% by weight of cationic polymer, preferably chitosan and 0.1 to 25%. A second aqueous solution containing an amount of active ingredient in an amount of% by weight, preferably 0.25 to 10% by weight is added; this mixture is referred to as a matrix. The active substance loading of the microcapsules may be 0.1 to 25% by weight based on the weight of the capsules. If desired, a water-insoluble component, such as an inorganic pigment, may be added at this stage to adjust the viscosity, usually in the form of an aqueous or aqueous / alcoholic dispersion. In addition, it may be advantageous to add emulsifiers and / or solubilizers to the matrix to emulsify or disperse the active substance. After the matrisk is made from the gel-forming agent, the cationic polymer and the active ingredient, the matrix can optionally be very finely dispersed in the oil phase by heavy shearing to produce the smallest particles in the subsequent encapsulation step. .. In this case, it has been found to be particularly advantageous to heat the matrix to a temperature in the range of 40-60 ° C, while cooling the oil phase to 10-20 ° C. In the essential, final step, the actual encapsulation, ie the formation of the outer shell membrane, is carried out by contacting the cationic polymer in the matrix with the anionic polymer. To this end, the matrix optionally dispersed in the oil phase is anion of about 1-50% by weight, preferably 10-15% by weight, at a temperature in the range of 40-100 ° C, preferably 50-60 ° C. It is recommended to treat with an aqueous solution of the sex polymer and remove the oil phase at the same time or later, if necessary, in this step. Generally, the aqueous preparation obtained from this step exhibits a microcapsule content in the range of 1-10% by weight. In many cases it may be advantageous if the polymer solution contains other components such as emulsifiers or preservatives. After filtration, microcapsules preferably having an average diameter in the range of about 0.01-1 mm are obtained. It is recommended to sift the capsules to ensure that the particle size distribution is as uniform as possible. The microcapsules obtained by such a method may exhibit any desired form within the limits of production, but are preferably substantially spherical. Alternatively, the anionic polymer may be used in the production of the matrix and the encapsulation may be carried out with a cationic polymer, especially chitosan.

Alternatively, encapsulation may be performed using only cationic polymers, in which case the properties of these polymers that solidify at pH values above the pKs value are utilized.

In a second separate step for producing the microcapsules of the present invention, an O / W emulsion containing an effective amount of emulsifier in addition to the oil component, water and active component is first produced. To make a matrix, the composition is mixed with a corresponding amount of anionic polymer aqueous solution with vigorous stirring. Film formation is performed by the addition of a chitosan solution. The entire step is preferably carried out in a weakly acidic range of pH = 3-4. If necessary, the pH can be adjusted by adding a mineral acid. After film formation, the pH value is raised to 5-6, for example by adding triethanolamine or other bases. This causes an increase in viscosity, which is due to additional thickeners such as polysaccharides, especially xanthan gum, guar guar, agar, alginate and tyrose, carboxymethyl cellulose and hydroxyethyl cellulose, high molecular weight polyethylene glycol mono- and fatty acids. Further supplementation can be made by adding diesters, polyacrylates, polyacrylamides and the like. Finally, the microcapsules are separated from the aqueous phase, for example by decantation, filtration or centrifugation.

In a third separate step, the formation of microcapsules is preferably carried out using nuclei surrounded by solid, eg, crystalline nuclei, layer-by-layer with a backcharged polymeric electrolyte. In this regard, European Patent No. 1064088 (Max-Planck Gesellschaft) is referenced.

Application of Preparations Finally, the present invention also relates to the application of mixtures for the production of cosmetic preparations, pharmaceutical preparations, and food preparations, wherein the mixture is an amide of formula (a), and ( b) Contains menthol and / or menthol compounds of formulas (II), (III) and / or (IV).
The total content of the component (a + b) in the final product is preferably 1 to 5,000 ppm, more preferably 10 to 4,000 ppm, and particularly preferably 100 to 1,000 ppm.

Examples 1 to 7, Comparative Examples V1 to V4
20% by weight polyisobutylene (MW60,000), 51% by weight sorbitol, 5% by weight mannitol, 8% by weight glycerol, 8.2% by weight Lycasin and glycerol 1: 1 mixture, 0 A chewing gum composition consisting of .2% by weight glycerin (99.5% by weight water added) was prepared and mixed with 0.5% by weight of each of the various coolants. The chewing gum composition was then sensory evaluated on a scale of 1 (almost unnoticed) to 10 (prominent) by a panel of 5 trained individuals. The composition of the coolant is summarized in Table 1 with individual taste and aroma rating ratings (the average of the ratings in each case is shown). Examples 1-7 follow the invention and Examples V1-V4 are shown together for comparison.

In the sensory evaluation, all the preparations of the present invention showed clearly superior results to the comparative products, in particular, the preparations felt sweeter than bitterness, the tar flavor was almost completely masked, and it was unpleasant and spicy. The pungent odor was clearly reduced.

Examples 8-14, Comparative Examples V5 to V8
Various clear O / W sunscreen emulsions were prepared according to the PIT method by mixing the ingredients listed in Table 2.

Sunscreen lotions differ only in terms of coolant, and in some cases independently with various menthyl compounds 2- (2-isopropyl-5-methylphenoxy) -N- (1H-pyrazole-3-yl) -N- (thiophene). It was a (1: 1) mixture with -2-yl) -methylacetamide (structure A86).

After preparation, the lotion was placed in a transparent PET bottle and stored at 30 ° C. The lotion was then evaluated for appearance after 12, 24 and 48 hours. In this example, (+) = no change, (#) = formation of small droplets, (-) = precipitation of oil droplets on the surface with a slight yellowish discoloration. The results are summarized in Table 3. Examples 8-14 follow the present invention, and Examples V5-V8 are shown together again for comparison. The preparations of the present invention show clearly improved stability.

The table below shows a number of preparation examples for cosmetic preparations, pharmaceutical preparations and food preparations.

（１−４）ヘアリンス、（５−６）ヘアトリートメント剤、（７−８）シャワー入浴剤、（９）シャワーゲル、（１０）洗浄ローション

(1-4) Hair rinse, (5-6) Hair treatment agent, (7-8) Shower bath salt, (9) Shower gel, (10) Cleaning lotion

（１１−１４）シャワー浴「２イン１」、（１５−２０）シャンプー

(11-14) Shower bath "2 in 1", (15-20) Shampoo

（２１−２５）フォーム浴、（２６）柔軟クリーム、（２７、２８）保湿乳液、（２９、３０）ナイトクリーム

(21-25) Foam bath, (26) Soft cream, (27, 28) Moisturizing emulsion, (29, 30) Night cream

（３１）Ｗ／Ｏ日焼け止めクリーム、（３２−３４）Ｗ／Ｏ日焼け止めローション、（３５、３８、４０）Ｏ／Ｗ日焼け止めローション、（３６、３７、３９）Ｏ／Ｗ日焼け止めクリーム

(31) W / O sunscreen cream, (32-34) W / O sunscreen lotion, (35, 38, 40) O / W sunscreen lotion, (36, 37, 39) O / W sunscreen cream

Examples 15-19, Comparative Examples V9-V11
A blinded study was first conducted to determine the reduction in apatite stability. For this purpose, the temperature of the reaction vessel containing 300 ml of desalted water was controlled to 37 ° C., and 0.5 g of hydroxyapatite powder (standard surface area 60 m ² / g, Merck) was suspended in the vessel. The pH value of the suspension was maintained at a constant value of 5 using an automatic burette used to add lactic acid. The amount of 0.1 mol of lactic acid consumed to stabilize the pH was recorded using a recorder. The consumption of lactic acid recorded after 2 hours was comparable to _{the solubility (Lu) of the untreated hydroxyapatite powder.}

The test was then continued with the addition of 50 mg or 150 mg of the active ingredient mixture to be tested. The consumption of lactic acid recorded after 2 hours was comparable to _{the solubility (L b) of the treated hydroxyapatite powder.} The decrease in apatite solubility (ALR in%) caused by the active ingredient was calculated as follows.

ALR (%) = ( _Lu- L _b ) ^* 100 / _Lu (%)
The results of the measurements are summarized in Table 8.

A further blinded study was first conducted to elucidate the suppression of crystal growth by hydroxyapatite (KWI in%). To this it was prepared 0.0008 moles of _KH 2 P0 ₄ solution and reaction vessel containing the 0.012 mol of CaCl ₂ solution 45ml of 400 ml. The pH was adjusted to 7.4 by titrating this solution with 0.05 mol KOH solution. After maintaining a stable pH value for 30 minutes or more, 100 mg of hydroxyapatite powder (standard surface area 60 m ² / g, Merck) was added. The pH value of the suspension was maintained at a constant value of 7.4 using an automatic burette that could be used to add 0.05 mol of KOH solution. The amount of 0.05 mol KOH solution consumed to stabilize the pH was recorded using a recorder. The consumption of KOH solution ( _Ku ) recorded after 2 hours was comparable to the formation of hydroxyapatite (growth of crystals in suspension).

The test was then continued with the addition of 6 mg or 30 mg of the active ingredient to be tested. _{The consumption (KB} ) of 0.05 mol of KOH solution recorded after 2 hours was equivalent to the formation of hydroxyapatite (growth of crystals in suspension) under the influence of the active ingredient. The suppression of crystal growth by the active ingredient was calculated as follows.

^{_{KWI (%) = (K u}} -K b) * 100 / K u (%)
The results of the measurements are summarized in Table 8.

Examples 15-19 clearly show that the preparations according to the invention showed higher apatite solubility and stronger apatite crystal growth inhibition compared to the individual components. Oral care products and toothpastes containing such mixtures are characterized by their excellent effectiveness in tartar formation.

構造Ａ１２４：Ｎ−フェニル−Ｎ−（チオフェン−２−イルメチル）−２−（ｍ−トリルオキシ）アセトアミド Tables 9 and 10 below show a number of examples of formulations for toothpaste and mouthwash.

Structure A124: N-Phenyl-N- (thiophene-2-ylmethyl) -2- (m-tolyloxy) acetamide

Finally, Table 11 summarizes a number of exemplary formulations of dentifrice compositions.

構造Ａ１５７：Ｎ−（ピリジン−２−イル）−Ｎ−（チオフェン−２−イルメチル）−３−ｐ−トリルプロパンアミド

Structure A157: N- (pyridin-2-yl) -N- (thiophen-2-ylmethyl) -3-p-tolylpropanamide

Claims (12)

A component (a) selected from the group consisting of compounds having the following formulas:

In addition, a component selected from the group consisting of menthone lyceryl acetal, menthone lyceryl ketal and menthyl lactate (b).
Composition containing. Component (a) selected from the group consisting of the following:
2- (2-Isopropyl-5-methylphenoxy) -N- (1H-pyrazole-3-yl) -N- (thiophen-2-yl) -methylacetamide having the following formula

And N- (1H-pyrazole-5-yl) -N- (thiophen-2-ylmethyl) -2- (p-tolyloxy) acetamide having the following formula

In addition, a component selected from the group consisting of menthol lyceryl acetal, menthol glyceryl acetal, menthol lactate, menthol methyl ether, menthol ethylene glycol carbonate and menthol succinate (b).
Composition containing. Surfactants, oils, emulsifiers, pearl luster waxes, thickeners, thickeners, superfat agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UV protection factors, wetting agents, organisms Origin agents, antioxidants, deodorants, antiperspirants, anti-fake agents, film-forming agents, swelling agents, insect repellents, self-tanning agents, tyrosine inhibitors, hydrotropes, solubilizers, preservatives, perfume oils and The composition according to claim 1, further comprising a colorant and an additive (component c) selected from the group consisting of a mixture thereof. The composition according to claim 3, wherein the components (a + b) and (c) are contained in a weight ratio of 0.01: 99.9 to 2:98. (1) The component (a) of claim 1,
(2) A cosmetic composition comprising the component (b) of claim 1 and (3) a carrier acceptable for the cosmetic preparation. The carrier is selected from the group consisting of water, alcohols having 2 to 6 carbon atoms, polyols having 1 to 10 carbon atoms and 2 to 4 hydroxyl groups, and oils. The cosmetic composition according to claim 5. The cosmetic composition according to claim 5, which comprises a product selected from the group consisting of skin care products, hair care products, body care products, and sunscreen products. Surfactants, oils, emulsifiers, pearl luster waxes, thickeners, thickeners, superfat agents, stabilizers, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, UV protection factors, wetting agents, organisms Origin agents, antioxidants, deodorants, antiperspirants, anti-fake agents, film-forming agents, swelling agents, insect repellents, self-tanning agents, tyrosine inhibitors, hydrotropes, solubilizers, preservatives, perfume oils and The composition according to claim 2, further comprising a colorant and an additive (component c) selected from the group consisting of a mixture thereof. The composition according to claim 8, wherein the components (a + b) and (c) are contained in a weight ratio of 0.01: 99.9 to 2:98. (1) The component (a) of claim 2,
(2) A cosmetic composition comprising the component (b) of claim 2 and (3) a carrier for a cosmetic preparation. The carrier is selected from the group consisting of water, alcohols having 2 to 6 carbon atoms, polyols having 1 to 10 carbon atoms and 2 to 4 hydroxyl groups, and oils. The cosmetic composition according to claim 10. The cosmetic composition according to claim 10, comprising a product selected from the group consisting of skin care products, hair care products, body care products, and sunscreen products.