KR101061618B1 - Amide derivative compounds and methods for their preparation, and emulsifiers and hair conditioning compositions comprising the same - Google Patents

Abstract

The present invention relates to amide derivative compounds and methods for their preparation and emulsifiers and hair conditioning compositions comprising the same. Amide derivative compounds of the present invention have a structure of formula (1) or (2).

[Formula 1] [Formula 2]

The amide derivative compound of the present invention is an amide bond of the carboxyl groups of amino acids and dicarboxylic acids to increase the solubility in water. Thus, when used in hair conditioning compositions, no warming process is required, and can be used as an emulsifier in parallel with tertiary amido amines.

Amide Derivative Compounds, Amino Acids, Dicarboxylic Acids, Emulsification

Description

Amide derivatives and preparing method, and emulsifying agent and hair conditioning composition containing thereof

The present invention relates to an amide derivative compound, a method for preparing the same, and an emulsifier and hair conditioning composition including the same. Specifically, the present invention relates to a new structure having improved solubility in water and an emulsifier prepared by amide bonding an amine group and a carboxyl group of an amino acid. An amide derivative compound of the present invention, and a preparation method thereof, and an emulsifier and hair conditioning composition comprising the same.

Conditioning products, such as rinse, are used to make hair thin and acidic when rinsing hair, to give flexibility, and to give dehydrated hair a conditioning effect with appropriate oil to make hair soft and shiny. In order to achieve the above object, such a conditioning product uses an oil, such as oil, waxes, silicones, etc., and when applied to the hair, the oil must be well dispersed to facilitate delivery, and thus undergoes an emulsification process. Therefore, the process of emulsification is very important in conditioning products such as rinse.

Hair conditioning compositions using traditional emulsification methods are prepared by emulsifying higher fatty acid alcohols with nonionic surfactants or quaternary cationic surfactants (ammonium salts), followed by mixing oils, waxes, silicones, etc. In this case, problems such as the feeling of massage of the hair and the feeling of softening when rinsing are pointed out. In order to solve the above problem, USP-6365142 discloses a new emulsification method using a tertiary amine and an organic acid having a small molecular size. The method does not have to use quaternary ammonium salts, which are irritating to the scalp and hair, and has an advantage over the conventional emulsification method in terms of use. In addition, the patent uses a commercially available small-molecular organic acid, including L- glutamic acid and L-aspartic acid, which are acidic amino acids, of which glutamic acid has the best effect. However, glutamic acid, which is actually applied as a representative organic acid, is an acidic amino acid, and the acidic amino acid contains two basic amino acids and an acidic carboxyl group in one molecule, and one of the carboxyl groups has a pKa value of 4.2 due to the influence of the amine group. To about 4.5. Since the value of pKa is larger than the pH value of the carboxyl group, the carboxyl group does not dissociate and the solubility in water is lowered. Therefore, there is a disadvantage that a heating process of 20 minutes or more must be added.

KAO developed a new emulsification method using organic acids in the same way, and additionally developed and applied a new material without stimulation by increasing the alkyl group length of the existing amidoamine (JP-2000-304798, JP-2005-343861). ). Korean Patent 2005-0092821 also discloses the application of this new emulsification method using amidoamine and L-aspartic acid, which is an organic acid. However, all of the above patents have a disadvantage of low solubility in water because they use the organic acid mentioned in the preceding patent.

In Korean Patent 2003-0066869, EDTA is used as an organic acid, but EDTA has a disadvantage in that it is inferior in usability and stability because of difficulty in effective emulsification as compared to conventional organic acids.

In order to solve the above problems, an object of the present invention is to enable emulsification using tertiary amines in parallel and to have excellent solubility in water so that no heating process is required, and an amide derivative compound having a new structure and an emulsifier comprising the same And hair conditioning compositions.

The present invention to achieve the above object,

It provides an amide derivative compound represented by the formula (1) or (2):

[Formula 1]

(In Chemical Formula 1,

R ₁ represents the side chain structure of all amino acids, natural or unnatural,

R ₂ is hydrogen or an alkyl group of C ₁ to C ₃ ,

m is an integer of 1 to 8).

[Formula 2]

(In Chemical Formula 2,

R ₁ and R ₂ are the same as defined in the formula (1).)

The present invention to achieve another object of the present invention,

It provides an emulsifier comprising the amide derivative compound.

The present invention to achieve another object of the present invention,

A method of preparing an amide derivative compound comprising reacting an amino acid with a dicarboxylic acid derivative or anhydride thereof in an organic solvent, water or a mixture thereof.

The amino acid may be represented by the following Chemical Formula 3:

(3)

(In Chemical Formula 3,

R ₁ and R ₂ are the same as defined in the formula (1).)

The dicarboxylic acid derivative may be represented by the following formula (4) or (5):

[Formula 4]

(In Formula 4,

m is an integer from 1 to 8,

X and Y are each a hydroxy group or a halogen.)

[Chemical Formula 5]

(In Chemical Formula 5,

X and Y are each a hydroxy group or a halogen.)

The reaction temperature of the reaction may be 25 to 120 ℃.

The organic solvent may be alone or a mixture thereof selected from the group consisting of alcohols, glycols, monoalkylglycols, dialkylglycols, ketones, acetonitrile, 1,4-dioxane, acetone, methylethylketone and acetonitrile.

The present invention to achieve another object of the present invention,

Amide derivative compounds of the present invention; And a tertiary amido amine.

The organic acid may be included in an amount of 0.1 to 2 parts by weight based on the total composition.

The amide derivative compound of the present invention can be used as an emulsifier. When used as an emulsifier, the amide derivative compound of the present invention does not need to go through a warming process because it has excellent solubility while improving emulsifying power. Thus, the process is simplified and the cost is saved.

The hair conditioning composition comprising the amide derivative compound of the present invention is emulsifiable without using a quaternary ammonium compound, so there is no irritation to the scalp and hair.

The hair conditioning composition comprising the amide derivative of the present invention is well dispersed in the conditioning components, so the conditioning effect is increased.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily implement the present invention.

The present invention provides an amide derivative compound represented by the following general formula (1) or (2):

[Formula 1]

(In Chemical Formula 1,

R ₁ represents the side chain structure of all amino acids, natural or unnatural,

R ₂ is hydrogen or an alkyl group of C ₁ to C ₃ ,

m is an integer of 1 to 8).

[Formula 2]

(In Chemical Formula 2,

R ₁ and R ₂ are the same as defined in the formula (1).)

The amide derivative compound of the present invention having the above structure amide-bonds the amine group and the carboxyl group of an amino acid so that the influence on the carboxyl group of the amine group is lost. Therefore, the values of pKa and pH of the carboxyl group become similar, so that the solubility of the amide derivative compound in water increases. Therefore, in the case of using the amide derivative compound of the present invention having the above structure, a heating process for increasing the solubility is unnecessary, so that the process is simple and the cost is reduced. In addition, since -NH remaining after the amide bond, the donor of the hydrogen atom, the carboxyl group serves as an acceptor of the hydrogen atom to form a stable structure is excellent in emulsifying power.

In Formula 1, R ₁ represents all the side chain structures of natural or unnatural amino acids. Amino acids are the basic structural units of proteins that make up the body of an organism. The amino group combines amino groups, carboxyl groups and substituents (R, side chains). Amino acids are classified into four types of acidic, basic, hydrophilic, and hydrophobic according to the side chain properties. The type and characteristics of amino acids are determined by hydrogen and 20 kinds of R groups. R ₁ in Formula 3 means all R groups of these amino acids.

The carboxyl group bonded to the benzene ring in Formula 2 may be substituted at any carbon position of benzene, but is preferably substituted at 2, 3 or 4 carbon positions.

The present invention provides an emulsifier comprising an amide derivative compound represented by the following formula (1) or (2). As described above, the amide derivative compound may be used as an emulsifier because it has excellent solubility and emulsifying power.

The emulsifier may further include an emulsifier component commonly used in the art in addition to the amide derivative compound, and those skilled in the art may appropriately adjust the content thereof.

The method for preparing the amide derivative compound of the present invention includes the step of reacting an amino acid with dicarboxylic acid or anhydride thereof.

The amino acid may be represented by the following Chemical Formula 3:

(3)

(In Chemical Formula 3,

R ₁ and R ₂ are the same as defined in Formula 1)

Specific examples of the amino acids include alanine, cysteine, aspartic acid, glutamic acid, phenylalanine, glycine, histidine, isoleucine, lysine, leucine, methionine, asparagine, proline, glutamine, arginine, proline, glutamine, arginine, serine, threonine, seleno Cysteine, valine, tryptophan, tyrosine, and the like, but are not limited thereto.

The dicarboxylic acid may be represented by the following Chemical Formula 4 or the following Chemical Formula 5:

[Formula 4]

(In Formula 4,

m is an integer from 1 to 8,

X and Y are each a hydroxy group or a halogen.)

[Chemical Formula 5]

(In Chemical Formula 5,

X and Y are each a hydroxy group or a halogen.)

Specific examples of the dicarboxylic acid of Chemical Formula 4 include succinic acid, tartaric acid, glutamic acid, adipic acid, and the like, but are not limited thereto. Specific examples of Chemical Formula 5 include phthalic acid, a hydroxy group of phthalic acid substituted with halogen, and the like.

The anhydride of the dicarboxylic acid may be an anhydride of the dicarboxylic acid represented by the formula (4) or (5). The anhydride of the dicarboxylic acid of Formula 4 or 5 is a cyclic anhydride formed by dehydration of two -COOH, which can be reacted with the amino acid of Formula 3 to produce an amide derivative compound of Formula 1.

The reaction of the amino acid of Formula 3 and the dicarboxylic acid of Formula 4 or 5 is shown in Schemes 1 and 2.

Scheme 1

Scheme 2

The reaction can be carried out in an organic solvent, water or a mixture thereof. Since the amino acids are water soluble and the dicarboxylic acid or anhydride thereof is mainly solubilized in an organic solvent, the reaction may be carried out in a mixture of water and an organic solvent or the amino acid may be allowed to proceed in a dispersed state in an organic solvent. The organic solvent may be used alone or a mixture thereof selected from the group consisting of alcohols, glycols, monoalkyl glycols, dialkyl glycols, ketones, 1,4-dioxane, acetone and methyl ethyl ketone.

The reaction may proceed at 25 to 120 ° C, preferably at 60 to 100 ° C. If it is less than 25 ℃ reaction rate is slow and the reaction yield is low, and if it exceeds 120 ℃ cost is expensive and the yield improvement of the reaction is inefficient because it is inefficient.

The hair conditioning composition of the present invention is an amide derivative compound of the present invention; And tertiary amido amines. Since the hair conditioning composition of the present invention does not use quaternary ammonium salts that are irritating to hair and scalp, it has little irritation to the scalp, and has excellent emulsification ability, including the amide derivative compound and the tertiary amido amine, so that the emulsion is well dispersed. . In addition, since the amide derivative compound has excellent solubility in water, a heating process is not necessary in preparing the hair conditioning composition.

The amide derivative compound of the present invention may be included in 0.1 to 2 parts by weight based on 100 parts by weight of the total composition. When included in less than 0.1 parts by weight it may have a bad effect on the emulsification state, the dispersion of the emulsion may not occur well, and when included in excess of 2 parts by weight may lower the pH may cause irritation of the scalp.

The tertiary amido amine acts as an emulsifier together with the amide derivative compound. The tertiary amido amine may be used without limitation, those known in the art, specifically, stearamidopropyldimethylamine, cocamidopropyldimethylamine, beheniramidopropyldimethylamine, etc. It is not limited to this.

The hair conditioning composition includes components commonly used in hair conditioning compositions such as surfactants, fatty substances, wetting agents, silicones, oils, perfumes, preservatives, vitamins, proteins, etc., in addition to the amide derivative compounds and tertiary amido amines of the present invention. This may be included, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are only for the description of the present invention, and thus the scope of the present invention is not limited.

Example 1 Preparation of Amide Derivative Compound Using Glycine and Succinic Anhydride

To a four-necked flask equipped with a mechanical stirrer, a cooler, a thermometer, and a distillation apparatus, 38 g of glycine and 55 g of succinic anhydride are added, 400 ml of 1,4-Dioxane is added, and the temperature is raised to 85 ° C. while stirring. The mixture is stirred for 8 hours while maintaining the temperature, and the reaction is terminated while the reactant is almost dissolved. At least 90% of the solvent is evaporated using a reduced pressure evaporator, and then 300 ml of acetonitrile is added to give 79 g of a fine white powdery precipitate. This white powder was confirmed to have a succinic acid amide structure of glycine with 98% purity by NMR analysis. NMR results are shown in FIG. (1H-NMR (D 2 O) δ = 3.9 (s, 2H), 2.7-2.5 (2m, 4H))

<Examples 2 to 7>

An amide derivative compound was prepared in the same manner as in Example 1, except that another amino acid was used instead of the glycine of Example 1. The results are shown in Table 1 below.

division amino acid Reaction temperature Amide derivative compound properties NMR purity Example 1 Glycine 85 ℃ White powder 98% Example 2 Alanine 90 ℃ White powder 99% Example 3 Balin 90 ℃ White powder 97% Example 4 Leucine 100 ℃ Yellow slime 92% Example 5 Iroleucine 100 ℃ Yellow slime 93% Example 6 Serine 100 ℃ Yellow slime 85% Example 7 Sacosin 90 ℃ White powder 97%

Example 8 Preparation of Amide Derivative Compound Using Alanine and Glutaric Anhydride

30g of alanine and 45g of glutaric anhydride are added to a four-necked flask equipped with a mechanical stirrer, a cooler, a thermometer, and a distillation apparatus, and 400ml of 1,4-Dioxane is added. The temperature is increased to 100 ° C while stirring. The mixture is stirred for 12 hours while maintaining the temperature, and the reaction is completed while the reactant is almost dissolved. At least 90% of the solvent is evaporated using a reduced pressure evaporator, and then 300 ml of acetonitrile is added to give 63 g of a fine white powdery precipitate. This white powder confirmed that the glutaric acid amide structure of alanine was 97% pure by NMR analysis.

Example 9 Preparation of Amide Derivative Compound Using Glycine and Paraphthalic Anhydride

To a four-necked flask equipped with a mechanical stirrer, a cooler, a thermometer, and a distillation apparatus, 25 g of glycine and 56 g of paraphthalic anhydride are added, 400 ml of methyl ethyl ketone is added, and the temperature is raised to 85 ° C. while stirring. Stir for 8 hours while maintaining the temperature and when the reaction is completed to obtain 59g of fine white powdery precipitate. This white powder confirmed the paraphthalic acid amide structure of glycine with 98% purity by NMR analysis.

Examples 10 to 15 Preparation of Hair Rinses Containing Amide Derivative Compounds

Hair rinse was prepared using the amide derivative compound prepared in Example. Amide derivative compounds used in the preparation of the hair rinse are shown in Table 2 below.

division Amide Derivative Compound Example 1
A

Example 2
B

Example 3
C

Example 4
D

Example 7
E

Example 9
F

Using the amide derivative compounds of the A to F to prepare a hair rinse in the composition shown in Table 3 in the following manner. After dissolving the prepared amide derivative compound in purified water, a solid solution material such as cetyl alcohol, stearyl alcohol and stearamidopropyl dimethylamine is dissolved and added to 70 ° C. The mixture thus obtained is cooled to 50 ° C. or lower and the remaining constituents are added with stirring and cooled to room temperature. The units in the table below are parts by weight.

Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Stearamidopropyl Dimethylamine 2.0 2.0 2.0 2.0 2.0 2.0 Amide Derivative Compound 0.7 (A) 0.7 (B) 0.7 (C) 1.0 (D) 1.0 (E) 1.2 (F) Cetyl alcohol 2.0 2.0 2.0 2.0 2.0 2.0 Stearyl alcohol 4.0 4.0 4.0 4.0 4.0 4.0 Cyclodimethicone 2.0 2.0 2.0 2.0 2.0 2.0 incense A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount A reasonable amount Purified water Balance Balance Balance Balance Balance Balance system 100 100 100 100 100 100

In the preparation of the hair rinse, the amide derivative compound was well dissolved in purified water without a separate heating process.

Experimental Example 1 Confirmation of Emulsifying Power

The emulsified state of the hair rinse prepared in Examples 10 to 15 was confirmed under a microscope and the results are shown in Table 4 below.

division result Example 10

Example 11

Example 12

Example 13

Example 14

Example 15

According to Table 4, the rinse of Examples 10 to 15 containing the amide derivative compound of the present invention was well dispersed in water.

Experimental Example 2 Physical Properties of Hair Rinse

The viscosity and pH of the hair rinse prepared in Examples 10 to 15 were measured and the results are shown in Table 5 below.

Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Viscosity (cP) 21,200 18,400 19,000 22,000 21,200 20,400 pH 5.64 5.32 5.50 5.70 5.66 5.53

Since water exhibited a viscosity and pH similar to that of a conventional hair rinse, it can be confirmed that the water can be emulsified using the amide derivative compound of the present invention without compromising the physical properties of the conventional rinse.

As described above, the amide derivative compound of the new structure of the present invention can be used in combination with a tertiary amine in addition to an amine to emulsify the hair conditioning composition. The cost is reduced.

1 is an NMR result of an amide derivative compound prepared according to an embodiment of the present invention.

Claims (9)

delete An emulsifier comprising an amide derivative compound represented by the following formula (1) or (2). [Formula 1]

(In Chemical Formula 1, R ₁ represents a side chain structure of a naturally occurring or synthetic amino acid, R ₂ is hydrogen or an alkyl group of C ₁ to C ₃ , m is an integer of 1 to 8). [Formula 2]

(In Chemical Formula 2, R ₁ and R ₂ are the same as defined in the formula (1).) delete delete delete delete delete Amide derivative compounds represented by the following formula (1) or (2); And tertiary amido amines. [Formula 1]

(In Chemical Formula 1, R ₁ represents a side chain structure of a naturally occurring or synthetic amino acid, R ₂ is hydrogen or an alkyl group of C ₁ to C ₃ , m is an integer of 1 to 8). [Formula 2]

(In Chemical Formula 2, R ₁ and R ₂ are the same as defined in the formula (1).) The method of claim 8, The amide derivative compound is a hair conditioning composition, characterized in that contained in 0.1 to 2 parts by weight based on the total composition.

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