JP2002167437A - Guanidine-modified silicone, method for producing the same, hair cosmetic, and fiber-treating agent using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a guanidine-modified silicone capable of giving an excellent gloss and a smooth feeling. SOLUTION: The guanidine-modified silicone is characterized by having a structure represented by general formula (1), wherein R is a 1-20C alkyl group, a 6-20C aryl group or hydroxyl group; (m) and (n) are each specified as 10<=m<=10,000 and 0<=n<=100; X, Y and Z are each a guanidino-terminated group-containing group represented by general formula (2), hydrogen atom, phenyl group, a 1-10C alkyl group, a 1-5C alkoxy group or hydroxyl group and each of the molecules has at least one guanidino-terminated group-containing group represented by general formula (2). The general formula (2) is represented by: -Q-(NH-Q')p-NHC(=NH)NH2, wherein Q and Q' are each a 1-20C alkylene group, a 6-20C aryl residue or a 1-5C alkoxy residue; (p) is 0, 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a guanidine-modified silicone which imparts excellent gloss and smooth feel, a method for producing the same, and a method for producing hair, fibers and the like which is smooth and moist by containing the guanidine-modified silicone. The present invention relates to a hair cosmetic and a fiber treatment agent that give a feeling.

[0002]

2. Description of the Related Art Conventionally, silicone-based compounds have been used in hair cosmetics such as shampoos, rinses and treatments, and fiber treatment agents such as softeners for clothing for the purpose of giving gloss and smooth feel to hair and fibers. Is used.

[0003] Among these silicone compounds, amino-modified silicones have an amino group in the molecule, so that they have good adsorptivity to various surfaces and are excellent in imparting flexibility to hair and fibers. As a result,
Japanese Patent Application Laid-Open No. 9-110653 discloses a technique applied as a hair cleaner, and Japanese Patent Application Laid-Open No. 05-044169 discloses a technique applied as a softening agent for fibers.

[0004] However, the amino-modified silicone is not at a satisfactory level in terms of its adsorbing power and durability to hair and fibers, and when incorporated into products such as hair cosmetics and fiber treatment agents, its effect is not sufficient. There was a problem that it could not be demonstrated. In addition, the texture of amino-modified silicone is becoming less preferred, and there is a problem. In recent years, with the development of technology, furthermore, it has excellent adsorption power and sustainability,
There is a strong demand for the development of compounds that can provide a glossy and smooth feel.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a guanidine-modified silicone that imparts excellent gloss and a smooth feel, a method for efficiently producing the same, and the hair, fibers, and the like having smoothness and a moist feeling by containing the guanidine-modified silicone. An object of the present invention is to provide a hair cosmetic and a fiber treatment agent that can be effectively and continuously applied.

[0006]

Means for solving the above problems are as follows. That is, <1> a guanidine-modified silicone represented by the following general formula (1).

The general formula (1)

Embedded image In the general formula (1), R represents an alkyl group having 1 to 20 carbon atoms;
It is any of an aryl group having 6 to 20 carbon atoms and a hydroxyl group. Each R may be the same type or different types. m and n are 10 ≦ m ≦ 10,000, 0 ≦ n ≦ 1
Satisfy 00. X, Y and Z are groups represented by the following general formula (2) having a guanidino group at a terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and Any of hydroxyl groups, and at least one group represented by the following general formula (2) having a guanidino group at a terminal in the same molecule.

Formula (2) -Q- (NH-Q ') _p-
NHC (= NH) NH _{2 In the} general formula (2), Q and Q ′ are an alkylene group having 1 to 20 carbon atoms and an aryl residue having 6 to 20 carbon atoms (in the present invention, “residue” A group having a structure in which one hydrogen atom has been removed from a predetermined group. The same applies to the following.)
It is any one of an alkoxy residue having 1 to 5 carbon atoms. Q and Q ′ may be the same type or different types. p
Is any of 0, 1 and 2.

<2> The average degree of polymerization is from 20 to 10,000
The guanidine-modified silicone according to <1>, wherein <3> The method for producing a guanidine-modified silicone according to <1> or <2>, wherein the amino-modified silicone represented by the following general formula (3) is reacted with a guanidination reagent. Is a method for producing a guanidine-modified silicone. General formula (3)

[0010]

Embedded image

In the general formula (3), R is any one of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxyl group. Each R may be the same type or different types. m and n are 10 ≦ m ≦ 10,00
0, 0 ≦ n ≦ 100. A, B and C are groups represented by the following general formula (4) having an amino group at the terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and Any one of hydroxyl groups, and at least one group in the same molecule includes a group represented by the following general formula (4) and having an amino group at a terminal. 'During _p -NH ₂ formula (4), Q and Q general formula (4) -Q- (NH-Q )' represents an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, And any one of alkoxy residues having 1 to 5 carbon atoms. Q and Q ′ may be the same type or different types. p is 0, 1, or 2;

<4> A hair cosmetic comprising the guanidine-modified silicone according to <1> or <2>.

<5> A fiber treating agent containing the guanidine-modified silicone according to <1> or <2>.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The guanidine-modified silicone of the present invention is represented by the following general formula (1). General formula (1)

[0015]

Embedded image

In the general formula (1), R is any one of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxyl group. Each R may be the same type or different types. m and n are 10 ≦ m ≦ 10,00
0, 0 ≦ n ≦ 100. X, Y and Z are groups represented by the following general formula (2) having a guanidino group at a terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and Any of hydroxyl groups, and at least one group represented by the following general formula (2) having a guanidino group at a terminal in the same molecule.

Formula (2) -Q- (NH-Q ') _p-
NHC (= NH) NH _{2 In the} general formula (2), Q and Q ′ are an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, and 1 to 1 carbon atoms.
Any one of the 5 alkoxy residues. Q and Q ′ may be the same type or different types. p is 0, 1 and 2
Is one of

In the general formula (1), R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
And any of hydroxyl groups. When R is an alkyl group having more than 20 carbon atoms, the guanidine-modified silicone has poor smoothness and gloss. Further, when R is an aryl group having less than 6 carbon atoms, the adsorbability and persistence of the effect of the guanidine-modified silicone is low, and when the R group is an aryl group having more than 20 carbon atoms, the smoothness of the guanidine-modified silicone is reduced. Not good.

Among the alkyl groups having 1 to 20 carbon atoms represented by R, an alkyl group having 1 to 10 carbon atoms is preferable from the viewpoints of adsorbability, persistence of the effect and smoothness. ~ 6 alkyl groups are more preferred. Among the aryl groups having 6 to 20 carbon atoms represented by R, an aryl group having 6 to 14 carbon atoms is preferable in terms of adsorptivity, persistence of effect, smoothness, and gloss, and 6 to 10 carbon atoms. Are more preferred.

In the general formula (1), m is 10 ≦ m
≤ 10,000 and 20 ≤ m ≤ 200
0 is preferable, and 30 ≦ m ≦ 1000 is more preferable. m
However, if it is less than 10, the smoothness and gloss are not good, while if it exceeds 10,000, the adsorbability and the persistence of the effect are low.

In the general formula (1), n is 0 ≦ n ≦
100 must be satisfied, and preferably 0 ≦ n ≦ 50,
0 ≦ n ≦ 20 is more preferable. If n exceeds 100, the adsorbability and the persistence of the effect are low.

In the general formula (1), X, Y and Z
Is a group represented by the general formula (2) and having a guanidino group at a terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group. At least one in the same molecule must contain a group represented by the general formula (2) and having a guanidino group at a terminal.

In the general formula (1), if at least one group represented by the general formula (2) having a guanidino group at a terminal is contained in the same molecule, excellent adsorptivity and long-lasting effect are obtained. And a compound having excellent smoothness and gloss.

In the general formula (2), as the alkylene group having 1 to 20 carbon atoms represented by Q and Q ', an alkylene group having 1 to 6 carbon atoms is preferable from the viewpoints of adsorbability and durability of the effect. Preferably, Q (Q ′) is a propylene group (3 carbon atoms),
Most preferably, Q ′ (Q) is an ethylene group (having 2 carbon atoms). As the aryl residue having 6 to 20 carbon atoms represented by Q and Q ′, the same description as the aryl group having 6 to 20 carbon atoms described in the description of R in the general formula (1) applies. The alkoxy residue having 1 to 5 carbon atoms represented by Q and Q ′ has 1 carbon atom in terms of adsorptivity and durability of the effect.
To 3 alkoxy residues are preferable, and an alkoxy residue having 1 to 2 carbon atoms is more preferable. p is most preferably 1.

In the general formula (1), X, Y and Z
The alkyl group having 1 to 10 carbon atoms represented by is preferably an alkyl group having 1 to 6 carbon atoms. Moreover, as a C1-C5 alkoxy group, a C1-C3 alkoxy group is preferable.

The average degree of polymerization of the guanidine-modified silicone of the present invention represented by the general formula (1) is from 20 to 1
About 0000 is preferable, and 50 to 3000 is more preferable. The properties of the guanidine-modified silicone are as follows:
° C) to viscous liquid to soft rubbery.

Specific examples of the guanidine-modified silicone of the present invention represented by the general formula (1) include a side chain in the polysiloxane represented by the following general formulas (5) to (8). "Side chain modification (general formula (5))" having a guanidino group bonded thereto, "both terminal modification (general formula (7)) and one terminal modification (general formula (7)) having a guanidino group bonded to a terminal in polysiloxane. 6) and the general formula (8)), "both terminal side chain modification" in which a guanidino group is bonded to both side chains and terminals in polysiloxane. Among these, the side chain guanidine-modified silicone represented by the general formula (5) is preferable from the viewpoint of persistence of the effect.

[0028]

Embedded image

[0029]

Embedded image

R in the general formulas (5) to (8) is R in the general formula (1), and X, Y and Z in the general formulas (5) to (8) are X in the general formula (1). , Y and Z, and m and n in the general formulas (5) to (8) are the same as m and n in the general formula (1), respectively.
Q and Q ′ in the general formulas (5) to (8) are Q and Q ′ in the general formula (2), p in the general formulas (5) to (8) is p and p in the general formula (2). Each is the same.

In the guanidine-modified silicone represented by the general formula (5), a guanidine-modified silicone in which Q is a propylene group, Q 'is an ethylene group, and p is 1 is particularly preferable in terms of adsorptivity.

The guanidine-modified silicone of the present invention described above is suitably produced by the following method for producing a guanidine-modified silicone of the present invention, and has excellent gloss and smooth feel.

[Method for producing guanidine-modified silicone]
In the method for producing a guanidine-modified silicone of the present invention, an amino-modified silicone represented by the following general formula (3) is reacted with a guanidination reaction reagent.

-Amino-modified silicone- The amino-modified silicone is represented by the following general formula (3). General formula (3)

[0035]

Embedded image

In the general formula (3), R is any one of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydroxyl group. Each R may be the same type or different types. m and n are 10 ≦ m ≦ 10,000,
0 ≦ n ≦ 100 is satisfied. A, B and C represent a group having an amino group at a terminal represented by the following general formula (4), a hydrogen atom,
Phenyl group, alkyl group having 1 to 10 carbon atoms, 1 to 1 carbon atom
5 is an alkoxy group or a hydroxyl group, and in the same molecule, at least one is represented by the following general formula (4)
And a group having an amino group at the terminal.

In the general formula (4), —Q— (NH—Q ′) _p —NH ₂ , wherein Q and Q ′ are an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, and It is any one of an alkoxy residue having 1 to 5 carbon atoms. Q and Q ′ may be the same type or different types. p is 0, 1, or 2;

In the general formula (3), R, m and n
Are R, m and n in the general formula (1), respectively.
Is the same as

In the general formula (3), A, B and C
Is a group represented by the general formula (4) having an amino group at a terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a hydroxyl group. In addition, it is necessary that at least one group represented by the general formula (4) and having an amino group at a terminal is included in the same molecule.

In the general formula (3), if at least one group represented by the general formula (4) and having an amino group at a terminal is contained in the same molecule, the guanidine modified compound of the present invention is preferably used. Silicone can be obtained. In the general formula (3), the hydrogen atom represented by A, B and C, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a hydroxyl group include It is the same as a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a hydroxyl group represented by X, Y and Z in the general formula (1).

In the general formula (4), Q, Q 'and p are respectively Q and Q in the general formula (2).
The same as Q ′ and p.

The amino-modified silicone is not particularly limited, and any desired one can be used depending on the application.
Specific examples include compounds represented by the following general formulas (9) to (19).

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

-Guanidination reaction reagent- Examples of the guanidination reaction reagent include cyanamide, S-methylisothiourea, S-ethylisothiourea, O-methylisourea, and O-ethylisourea. Cyanamide and the like are particularly preferred in terms of reactivity and handling.

-Reaction- In the above reaction, the above-mentioned amino-modified silicone is diluted with a small amount of a solvent such as an alcohol-based or ether-based solvent, and the reaction temperature is controlled to suppress a side reaction. In the presence, cyanamide, guanidination with a normal guanidination reaction reagent such as S-methylisothiourea,
A guanidine-modified silicone is obtained.

The reaction conditions depend on the physical properties of the reaction reagents and the like, and cannot be unconditionally determined. For example, the reaction conditions when cyanamide is used as the guanidination reaction reagent are shown below.

After the amino-modified silicone is neutralized with an inorganic acid such as hydrochloric acid or an organic acid such as acetic acid, cyanamide is added. As a method of adding the cyanamide, cyanamide may be added as powder, or may be added at a temperature higher than the melting point and added all at once or dropwise. After dissolving in a solvent or an ether-based solvent such as tetrahydrofuran, it may be added all at once or dropwise. When the cyanamide is added dropwise, the dropping time is not particularly limited,
From the viewpoint of production efficiency, a range of 0.1 to 3 hours is preferable.

The temperature at the time of the reaction is from 60 ° C. to 1
20 ° C is preferable, and 80 ° C to 100 ° C is more preferable.
If the temperature is lower than 60 ° C., the reaction rate may be low. If the temperature is higher than 120 ° C., undesired side reactions may occur in the polymerization reaction of cyanamide and the like. In addition, when cyanamide is added without a solvent, an exothermic reaction occurs, and therefore, care must be taken in controlling the reaction temperature. It is preferable to carry out the reaction in the presence of a solvent such as an alcohol or an ether, because the reaction temperature can be easily controlled.

According to the method for producing a guanidine-modified silicone of the present invention described above, it is possible to efficiently produce a guanidine-modified silicone which gives excellent gloss and a smooth feel. Hereinafter, the structure of the guanidine-modified silicone of the present invention obtained by the method for producing the guanidine-modified silicone of the present invention will be described with an infrared absorption spectrum (I
This will be described using the measurement results of R) and nuclear magnetic resonance spectrum (NMR). In addition, amino-modified silicone as a raw material (in the general formula (3), R, A and C are methyl groups, B
But, in the general formula (4), Q is -CH ₂ CH ₂ CH
_2- , a group in which Q ′ is —CH ₂ CH ₂ —, p = 1, m: 1
50, n: 2, average degree of polymerization: 150) and a guanidination reaction reagent (cyanamide) (after heating to 80 ° C., neutralize the amino-modified silicone with hydrochloric acid, add cyanamide and ripen for 6 hours) ) To form a guanidine-modified silicone (wherein R, Y and Z are methyl groups, X
But, in the general formula (2), Q is -CH ₂ CH ₂ CH
_2- , Q ′ is —CH ₂ CH ₂ —, a group in which p = 1, m: 2
00, n: 2, average degree of polymerization: 200), and the amino-modified silicone as the raw material and the obtained guanidine-modified silicone were measured.

FIG. 1 shows a chart of an infrared absorption spectrum (IR) of the amino-modified silicone (raw material). FIG. 2 shows a chart of an infrared absorption spectrum (IR) of the guanidine-modified silicone. In FIG. 2, compared to FIG. 1, around 1678 cm ⁻¹ ,
Peak specific to guanidino group (peak representing C = N stretching)
Is observed.

FIG. 3 shows a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of the amino-modified silicone (raw material).
FIG. FIG. 4 shows a nuclear magnetic resonance spectrum ( ^13C -NMR) of the guanidine-modified silicone.
FIG. In FIG. 4, a signal (δ158.8 ppm) unique to the guanidino group is observed as compared with FIG.

[Hair Cosmetics, Fiber Treatment Agent] The guanidine-modified silicone of the present invention can be widely used for applications requiring the properties of general silicone compounds. Such applications include, for example, hair cosmetics, surface modifying agent compositions such as known shampoos, rinses, treatments, setting agents, permanent wave liquids, softeners, and wrinkle removers as polymers for fiber treatment agents. Can be used as The content of the guanidine-modified silicone in the composition is generally 0.1 to 0.1.
A ratio of about 10% by weight is preferred. Product forms used include liquids, creams, emulsions, gels, etc.
It may be in any form, and may be used in combination with a conventionally used known natural polymer, natural modified polymer, synthetic polymer or the like.

The hair cosmetic and fiber treating agent of the present invention described above contain the guanidine-modified silicone of the present invention to effectively and continuously impart smoothness and moist feeling to hair and fibers. Can be given.

[0056]

The present invention will be further described with reference to examples and comparative examples below, but the present invention is not limited to the following examples. In the following examples, "%" represents "% by weight" unless otherwise specified.

Example 1 A four-necked flask equipped with a reflux condenser, a dropping funnel, a thermometer, and a stirrer was prepared as follows:
250 g of the amino-modified silicone represented by the general formula (9) (m: 200, n: 1, average degree of polymerization: 200 in the general formula (9)) and 500 g of 2-propanol were added and the temperature was raised. After reaching 70 ° C., hydrochloric acid having a chemical equivalent of 0.95 times the chemical equivalent of the amino group was added, and then 10 g of cyanamide dissolved in 50 g of 2-propanol was added dropwise, and the reaction temperature was maintained at 70 ° C. After dropping, aged for 6 hours,
A guanidine-modified silicone represented by the following general formula (20) (m: 200, n: 1, average degree of polymerization: 200 in the general formula (20)) was obtained. From the results of IR / NMR measurement of the obtained guanidine-modified silicone, peaks and signals specific to guanidino groups were observed. General formula (20)

[0058]

Embedded image

(Example 2) In Example 1, the amino-modified silicone represented by the general formula (9) was replaced with the amino-modified silicone represented by the general formula (11)
In 1), m: 500, n: 3, average polymerization degree: 50
Guanidine-modified silicone represented by the following general formula (21) (m: 500, n: 3, average degree of polymerization: : 500). From the results of IR / NMR measurement of the obtained guanidine-modified silicone, peaks and signals specific to guanidino groups were observed.

General formula (21)

Embedded image

Example 3 In Example 1, the amino-modified silicone represented by the general formula (9) was replaced with the amino-modified silicone represented by the general formula (10)
0), m: 100, n: 1, average degree of polymerization: 10
Guanidine-modified silicone represented by the following general formula (22) (m: 100, n: 1, average degree of polymerization: : 100). From the results of IR / NMR measurement of the obtained guanidine-modified silicone, peaks and signals specific to guanidino groups were observed.

General formula (22)

Embedded image

Example 4 In Example 1, the amino-modified silicone represented by the general formula (9) was replaced with the amino-modified silicone represented by the general formula (14) (general formula (1)
In 4), m: 250, n: 2, average degree of polymerization: 25
Guanidine-modified silicone represented by the following general formula (23) (in the general formula (23), m: 250, n: 2, average degree of polymerization, except that 0) was used. : 250). From the results of IR / NMR measurement of the obtained guanidine-modified silicone, peaks and signals specific to guanidino groups were observed.

Formula (23)

Embedded image

Example 5 Preparation of Hair Cosmetic (Shampoo Composition) A hair cosmetic (shampoo composition) having the following composition was prepared. -Composition of hair cosmetic (shampoo composition)-Sodium lauryl polyoxyethylene sulfate: 15.0% Lauroyl diethanolamide: 3.0% Guanidine-modified silicone obtained in Example 3: 1.
0% ・ Polyethylene glycol 1.0% ・ Fragrance 0.5% ・ Purified water: appropriate amount Total: 100.0%

<Evaluation> Using the obtained hair cosmetic (shampoo composition), sensory evaluation of 10 subjects showed that “smoothness upon rinsing”, “good finger passing”, "Smoothness" was evaluated according to the following evaluation criteria. Table 1 shows the results.

-Evaluation Criteria- -Smoothness at the time of rinsing--: Good smoothness at the time of rinsing.・ △: Smoothness during rinsing is normal. X: The smoothness during rinsing is poor.

--- Goodness of finger passing --- ○: Good finger passing.・ △: Good finger passing is normal. *: Finger passing is poor.

--- Smooth feeling ---: Good smooth feeling.・ △: Smoothness is normal ・ ×: Smoothness is poor.

Comparative Example 1 Preparation of Hair Cosmetic (Shampoo Composition) In the “composition of hair cosmetic (shampoo composition)” of “Example 5,” the guanidine-modified silicone obtained in Example 3 was used. , An amino-modified silicone represented by the general formula (10) (in the general formula (10), m: 10
0, n: 1, average degree of polymerization: 100) A hair cosmetic (shampoo composition) was prepared in the same manner as in Example 5, except that the average polymerization degree was changed to 100, and evaluated in the same manner. Table 1 shows the results.

[0071]

[Table 1]

Example 6 Hair Cosmetic (Rinse Composition)
Preparation) Hair cosmetic (rinse composition) having the following composition
Was prepared. -Composition of hair cosmetic (rinse composition)--Behenyl trimethyl ammonium chloride: 1.0%-Stearyl trimethyl ammonium chloride: 1.0%-Stearyl alcohol: 1.0%-Guanidine modified obtained in Example 1 Silicone: 1.
0% ・ Propylene glycol: 10.0% ・ Fragrance: 0.5% ・ Purified water: appropriate amount Total: 100.0%

<Evaluation> The obtained hair cosmetic (rinse composition) was subjected to sensory evaluation by 10 subjects to determine “no stickiness”, “smoothness at finish” when applied to hair, "Moist feeling at the time of finishing" and "comb passing property" were evaluated according to the following evaluation criteria. Table 2 shows the results
Shown in

-Evaluation Criteria- -No Stickiness ---- O: Good without stickiness.・ △: Stickiness is normal. X: There is a sticky feeling.

--- Smoothness at the time of finishing --- .largecircle .: Good smoothness at the time of finishing.・ △: Smoothness at the finish is normal. ×: Poor smoothness at the time of finishing.

--- Moist feeling at the time of finishing --- O: Good moist feeling at the time of finishing.・ △: Moist feeling when finished is normal. X: Moist feeling at the time of finish is inferior.

--- Comb passability --- .largecircle .: Comb passability is good.・ △: The combability is normal. X: Poor combability.

Comparative Example 2 Hair Cosmetic (Rinse Composition)
Preparation) “Hair cosmetics (rinse composition)” in “Example 6”
Of the guanidine-modified silicone obtained in Example 1 with the amino-modified silicone represented by the general formula (9) (in the general formula (9), m: 200, n: 1,
A hair cosmetic (rinse composition) was prepared and evaluated in the same manner as in Example 6, except that the average polymerization degree was changed to 200). Table 2 shows the results.

[0079]

[Table 2]

(Example 7-Spray type fiber treating agent)-Preparation of spray type fiber treating agent-The guanidine-modified silicone obtained in Example 1 was dispersed in an appropriate amount of water to prepare a stock solution. The undiluted solution was charged into a can together with dimethyl ether (propellant) at a ratio of undiluted solution / propellant = 60/40 (volume ratio) to prepare a spray type fiber treatment agent (aerosol can). At this time, the concentration of the guanidine-modified silicone was adjusted to be 2 g per 100 ml of the total volume of the stock solution and the propellant.

<Evaluation> Using the obtained spray-type fiber treatment agent, the stock solution in the aerosol can was spray-coated uniformly on the surface of the test cloth for 4 seconds, and then the temperature was 25 ° C. and the relative humidity was 60.
% For 6 hours and dried. After that, according to the sensory evaluation of 10 subjects, "rigidity"
"Iron sliding" and "texture" were evaluated according to the following evaluation criteria. Table 3 shows the results.

-Evaluation Criteria- -Bendiosity--: ：: Hardness comparable to glue. ○: Hardness comparable to soft glue.・ △: Somewhat hard feeling. X: The same state as unprocessed.

--- Iron sliding ---: ：: Very smooth ○: Smooth △: Slightly smooth ×: Same as untreated.

--- Hand feeling-- O: Flexible and resilient.・ △: Some flexibility and resilience. X: The same state as unprocessed.

(Example 8-Spray type fiber treatment agent) In "Production of spray type fiber treatment agent" of "Example 7",
Except that the guanidine-modified silicone obtained in Example 1 was replaced with the guanidine-modified silicone obtained in Example 2, a spray type fiber treatment agent (aerosol can) was prepared in the same manner as in Example 7, and the same procedure was repeated. Was evaluated. Table 3 shows the results
Shown in

(Example 9-Spray type fiber treatment agent) In "Production of spray type fiber treatment agent" of "Example 7",
Except that the guanidine-modified silicone obtained in Example 1 was replaced with the guanidine-modified silicone obtained in Example 3, a spray-type fiber treatment agent (aerosol can) was produced in the same manner as in Example 7, and the same procedure was followed. Was evaluated. Table 3 shows the results
Shown in

(Example 10-Spray type fiber treatment agent)
In “Production of spray type fiber treatment agent” of “Example 7,” the guanidine-modified silicone obtained in Example 1 was replaced with
A spray fiber treatment agent (aerosol can) was prepared in the same manner as in Example 7 except that the guanidine-modified silicone obtained in Example 4 was used, and evaluated in the same manner. Table 3 shows the results.

(Comparative Example 3-Spray type fiber treatment agent) In "Production of spray type fiber treatment agent" of "Example 7",
A spray fiber treatment agent (aerosol can) was prepared in the same manner as in Example 7, except that the guanidine-modified silicone obtained in Example 1 was replaced with a vinyl acetate emulsion.
It evaluated similarly. Table 3 shows the results.

(Comparative Example 4-Spray type fiber treatment agent) In "Production of spray type fiber treatment agent" of "Example 7",
A spray fiber treatment agent (aerosol can) was prepared in the same manner as in Example 7, except that the guanidine-modified silicone obtained in Example 1 was replaced with polydimethylsiloxane.
It evaluated similarly. Table 3 shows the results.

[0090]

[Table 3]

[0091]

According to the present invention, a guanidine-modified silicone imparting excellent gloss and a smooth feel, a method for efficiently producing the same, and the guanidine-modified silicone containing the guanidine-modified silicone provide smoothness to hair and fibers. It is possible to provide a hair cosmetic and a fiber treatment agent that can provide moist feeling effectively and continuously.

[Brief description of the drawings]

FIG. 1 is a diagram showing a chart of an infrared absorption spectrum (IR) of an amino-modified silicone (raw material).

FIG. 2 is a chart showing a chart of an infrared absorption spectrum (IR) of guanidine-modified silicone.

FIG. 3 is a diagram showing a chart of a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of an amino-modified silicone (raw material).

FIG. 4 is a diagram showing a chart of a nuclear magnetic resonance spectrum ( ¹³ C-NMR) of guanidine-modified silicone.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshio Yajima 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Fumio Wakui 1-3-7, Honjo, Sumida-ku, Tokyo Within Lion Corporation (72) Inventor Takashi Koyama 1-3-7 Honjo, Sumida-ku, Tokyo F-term within Lion Corporation (reference) 4C083 AC072 AC122 AC642 AC692 AC792 AD112 AD161 AD162 EE06 EE07 4J035 BA02 BA04 CA022 CA052 CA062 CA19M CA191 FB01 LB14 4L033 AA01 AA04 AB01 AB04 AC02 AC03 AC09 CA64

Claims (5)

[Claims] 1. A guanidine-modified silicone represented by the following general formula (1). General formula (1) In the general formula (1), R represents an alkyl group having 1 to 20 carbon atoms;
It is any of an aryl group having 6 to 20 carbon atoms and a hydroxyl group. Each R may be the same type or different types. m and n are 10 ≦ m ≦ 10,000, 0 ≦ n ≦ 1
Satisfy 00. X, Y and Z are groups represented by the following general formula (2) having a guanidino group at a terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and Any one of hydroxyl groups, and at least one group represented by the following general formula (2) having a guanidino group at a terminal in the same molecule. General formula (2) -Q- (NH-Q ') _p -NHC (= N
H) NH _{2 In the} general formula (2), Q and Q ′ are any of an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, and an alkoxy residue having 1 to 5 carbon atoms. It is. Q and Q ′ may be the same type or different types. p
Is any of 0, 1 and 2. 2. The guanidine-modified silicone according to claim 1, wherein the average degree of polymerization is from 20 to 10,000. 3. The method for producing a guanidine-modified silicone according to claim 1, wherein the amino-modified silicone represented by the following general formula (3) is reacted with a guanidination reagent. A method for producing a guanidine-modified silicone. General formula (3) In the general formula (3), R represents an alkyl group having 1 to 20 carbon atoms;
It is any of an aryl group having 6 to 20 carbon atoms and a hydroxyl group. Each R may be the same type or different types. m and n are 10 ≦ m ≦ 10,000, 0 ≦ n ≦ 1
Satisfy 00. A, B and C are groups represented by the following general formula (4) having an amino group at the terminal, a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and Any one of hydroxyl groups, and at least one group in the same molecule includes a group represented by the following general formula (4) and having an amino group at a terminal. 'During _p -NH ₂ formula (4), Q and Q general formula (4) -Q- (NH-Q )' represents an alkylene group having 1 to 20 carbon atoms, an aryl residue having 6 to 20 carbon atoms, And any one of alkoxy residues having 1 to 5 carbon atoms. Q and Q ′ may be the same type or different types. p is 0, 1, or 2; 4. A hair cosmetic comprising the guanidine-modified silicone according to claim 1 or 2. 5. A fiber treatment agent comprising the guanidine-modified silicone according to claim 1 or 2.