JPH0699709B2 - Liquid detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a liquid detergent composition, and more particularly to a skin cleansing agent, which is remarkably relieved of irritation and damage to the hair and has excellent usability. The present invention relates to a liquid detergent composition which has no residual aroma, excellent foaming power, and does not cause turbidity or fields in a wide temperature range from low temperature to high temperature.

[Problems to be Solved by Prior Art and Invention]

Alkyl glycosides, which are sugar derivative surfactants, not only produce stable foams themselves, despite being mild surfactants, but also act as foam stabilizers against other anionic surfactants. It is known to work, and has been attracting attention in recent years. For example, JP-A-58-104625 discloses a foaming surfactant composition containing an alkyl glycoside and an anionic surfactant, and JP-A-62-74999 discloses.
A liquid dishwashing detergent composition containing an alkylglycoside, an anionic surfactant and a fatty acid alkanolamide and having low irritation and excellent foaming power and detergency is described. However, all of these detergent compositions have a problem in that the residual aroma to the skin becomes a problem when a fragrance component for enhancing the palatability of the detergent composition is contained in a more practical viewpoint, or When the liquid detergent composition is exposed to a low temperature or a high temperature, it has a problem that turbidity or separation occurs.

On the other hand, terpene hydrocarbons are often used in various liquid detergent compositions to increase added value because they have a refreshing aroma, but when coexisting with ester hydrocarbons,
These hydrocarbons may not be sufficiently solubilized by the surfactant, resulting in turbidity or separation. Especially in a liquid detergent composition containing an alkyl glycoside, this tendency is strong, and when transparency is required, the commercial value is significantly impaired. In addition, when a composition which is turbid or separated is used, a large amount of aroma components adheres to the skin and hair, and even if it is rinsed well, the residual aroma is strong and uncomfortable.

Therefore, a liquid detergent composition that does not impair the residual aroma and temperature stability on the skin without impairing the hypoallergenicity, which is the characteristic of alkyl glycosides, and the formation of stable foams, even if it contains an aroma component, is desired. It was rare.

[Means for Solving the Problems]

In such an actual situation, the inventors of the present invention have conducted extensive studies to maximize the properties of the alkyl glycoside,
If a terpene-based hydrocarbon selected from monoterpenes and sesquiterpenes is used as an aroma component for enhancing the palatability of the detergent composition, and further a specific ester and a specific alcohol are blended at a specific ratio, an alkylglycoside can be obtained. A rich liquid foaming composition, low irritation, and a refreshing feeling of use are not impaired, the residual odor on the skin is improved, and a liquid detergent composition that does not cause turbidity or separation at low or high temperatures is obtained. Therefore, the present invention has been completed.

That is, the present invention provides the following components (a), (b), (c) and (d) (a) an alkyl glycoside 1 to 50% by weight (b) a terpene-based hydrocarbon selected from monoterpenes and sesquiterpenes ( c) R-COO-R '(wherein R is a hydrocarbon group which may contain a keto group, R'is a hydrocarbon group, and R and R'
Has a total carbon number of 2 to 15) (d) Alcohols represented by R "-OH (wherein R" represents a hydrocarbon group having 3 to 12 carbon atoms) Content of (d) / (c) is in the range of 0.2 to 5 by weight, and (c) / [(b) + (c) + (d)] is in weight ratio.
It is in the range of 0.001 to 0.2, and (b) + (c) + (d)
Which is 0.02 to 1.0% by weight of the liquid detergent composition.

In the present invention, the alkyl glycoside of the component (a) is
It is used as a main surfactant and has the following general formula (I) R ₁ (OR ₂ ) xGy (I) (wherein R ₁ is a linear or branched alkyl or alkenyl having 8 to 18 carbon atoms). Or an alkylphenyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, and x has an average value of 0.
To G, G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, and y is a residue having an average value of 1.0 to 3.0).

In the formula (I), R ₁ is a linear or branched alkyl, alkenyl or alkylphenyl group having 8 to 18 carbon atoms, but having 9 to 9 carbon atoms from the viewpoint of solubility, foaming property and detergency. 14
Are preferred. In addition, R ₂ is an alkylene group having 2 to 4 carbon atoms, and preferably ₂ to 3 carbon atoms because of its water solubility. The average value of x is 0 to 5, and this value adjusts the water solubility and crystallinity of the component (a). That is, x
The larger the value of, the higher the water solubility and the lower the crystallinity. Therefore, the preferable value of x is 0 to 2. The structure of G in the formula (I) is determined by a monosaccharide or a raw material of two or more sugars. The raw materials of G include glucose, galactose, xylose, mannose, lyxose, arabinose and the like. When the mixture or the like is a disaccharide or more, maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose and the like, and mixtures thereof can be mentioned. Of these, particularly preferable monosaccharide raw materials are glucose or fructose in view of their availability and low cost, and maltose or sucrose for two or more sugars. y is greater than 1 when
That is, when two or more saccharides are used as hydrophilic groups, the sugar chain bonding mode is 1-2, 1-3, 1-4, 1-6 bond, and α
-, Β-pyranoside, or a furanoside bond and any mixture thereof having a mixed bonding mode (the measurement method of y in the present invention is based on the proton NMR method) . The average value of y is 1 to 3.
However, a particularly preferable average value is about 1 to 1.4.

The component (a) is compounded in the entire composition in an amount of 1 to 50% by weight (hereinafter, simply indicated by%), preferably 5 to 30%.

Examples of the component (b) of the present invention include monoterpene hydrocarbons or sesquiterpene hydrocarbons contained in plant aromatic oils. Examples of monoterpene hydrocarbons include D- or L-limonene contained in orange oil, lemon oil, etc.,
Α-Pinene contained in terpine oil and the like, α-terpionene contained in pine oil and the like can be exemplified, and as sesquiterpene hydrocarbons, fern oil, clover oil, caryophyllene often contained in cananga oil,
Cedren and the like can be exemplified. Each of the terpene hydrocarbons selected from monoterpenes and sesquiterpenes can be used alone as the component (b) of the present invention, and can be used as a mixture of two or more thereof. It is also possible to blend terpine oil and pine oil as they are in the composition of the present invention.

Examples of the ester as the component (c) of the present invention include geranyl acetate, neryl acetate, linalyl acetate, terpinyl acetate,
Dihydroterpinyl acetate, miltenyl acetate, dihydromyrenyl acetate, benzinl acetate, p-cresyl acetate, phenylethyl acetate, geranyl formate, benzyl formate, ethyl caproate, isoamyl caproate, ethyl enanthate, octyl enanthate, caprylic acid Preferred examples include isoamyl, octyl caprylate, methyl dihydrojasmonate, and methyl jasmonate. These can be used alone or in combination of two or more.

Examples of the alcohol as the component (d) of the present invention include butyldiglycol, geraniol, nerol, citronellol, linalool, myrcenol, terpineol, tetrahydrolinalool, tetrahydromyrcenol, mugol, dihydroterpineol, benzyl alcohol, phenylethyl. Alcohol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol etc. have 3 to 12 carbon atoms, monovalent, divalent,
One or more trivalent alcohol hydrocarbons are preferred examples.

In the components (b), (c) and (d), the weight ratio of (d) / (c) is in the range of 0.2 to 5, and (c) / [(b) +
(C) + (d)] is in the range of 0.001 to 0.2 by weight ratio,
(B) + (c) + (d) is from 0.02 of the cleaning composition of the present invention.
It must be 1.0% by weight. If it deviates from this range, the composition may become turbid or may separate, and the residual aroma to the skin or the like may be a problem, which is not preferable.

In the liquid detergent composition of the present invention, in addition to the above essential components,
If necessary, known detergency (e) anionic surfactant, (f) amphoteric surfactant and / or (g) nonionic surfactant other than alkyl glycoside improve the detergency and foaming power. It can be appropriately added for the purpose.

Examples of such anionic surfactant (e) include polyoxyethylene (= 0 to 6) monoalkyl ether sulfate having an alkyl group having 8 to 14 carbon atoms and 8 carbon atoms.
~ 14 straight chain alkyl benzene sulfonate, 8 ~ 14 carbon atoms
Α-olefin sulfonate, a secondary alkane sulfonate having 8 to 18 carbon atoms, an α-sulfo fatty acid ester salt having 8 to 14 carbon atoms, and a polyoxyethylene having an alkyl group having 7 to 15 carbon atoms (= 0. To 6) alkyl ether carboxylate, polyoxyethylene (= 0 to 6) monoalkyl ether phosphate having an alkyl group having 8 to 14 carbon atoms,
N-acylmethyl taurate having 8 to 16 carbon atoms, 8 carbon atoms
To 14 polyoxyethylene (= 0 to 10) alkyl ether and sulfosuccinic acid monoester salt and 8 carbon atoms
One or more anionic surfactants selected from N to 16 N-acylglutamates are particularly preferred.

As the amphoteric surfactant (f), those selected from a carbobetaine type and a sulfobetaine type, and particularly the following or are preferable.

The following general formula (II) [In the formula, R ₃ represents a linear or branched alkyl group having 8 to 18 carbon atoms, R ₄ represents an alkylene group having 2 to 3 carbon atoms, and a
Represents a number of 0 to 30, b represents a number of 0 or 1, R ₅ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ₆ and
R ₇ is the same or different, an alkyl group having 1 to 3 carbon atoms, an alkanol group having 1 to 3 carbon atoms, and a group selected from the group consisting of — (C ₂ H ₄ O) _{1 to 6} H group and a mixture thereof. And R ₆ represents an alkylene group containing or not containing an OH group having 1 to 5 carbon atoms].

The following general formula (III) [In the formula, R ₃ represents a linear or branched alkyl group having 8 to 18 carbon atoms or an alkylamide group, R ₁₀ represents an alkylene group having 2 to 3 carbon atoms, and c represents a number of 0 to 30. , D is 0
Or the number of 1, R ₁₁ represents a single bond or an alkylene group having 1 to 5 carbon atoms, R ₁₂ and R ₁₃ are the same or different alkyl groups having 1 to 3 carbon atoms, an alkanol of 1 to 3 carbon atoms groups and - (C ₂ H ₄ O) indicates _{1 to 6 H} groups and a group selected from the group consisting of mixtures, R ₁₄ is 1 to 5 carbon atoms O
Which represents an alkylene group with or without an H group].

These anionic surfactants and / or amphoteric surfactants are preferably incorporated in the composition of the present invention in an amount of 0.1 to 20%, particularly 1 to 15%.

Further, as the nonionic surfactant (g) other than the alkyl glycoside, polyoxyethylene (= 3 to 20) alkyl ether having an alkyl group having 8 to 18 carbon atoms and the following amides and tertiary amine oxides Are preferred.

The following general formula (IV) [In the formula, R ₁₅ represents a linear or branched alkyl group having 8 to 18 carbon atoms, R ₁₆ and R ₁₇ are the same or different and each represents hydrogen, an alkyl group having 1 to 3 carbon atoms, or 1 to 1 carbon atoms. 3 alkanol groups and _{- (C 2 H 4 O)} 1~10 H groups and amide represented by a group] is selected from the group consisting of mixtures.

The following general formula (V) [In the formula, R ₁₈ represents a linear or branched alkyl group having 8 to 18 carbon atoms or an alkylamide group, and R ₁₉ represents 2 to 3 carbon atoms.
Is an alkylene group of, e is a number from 0 to 30, and f is a number from 0 or 1. R ₂₀ represents an alkylene group having 0 to 5 carbon atoms, and R ₂₁ and R ₂₂ are the same or different and have 1 to 1 carbon atoms.
An alkyl group having 3 carbon atoms, an alkanol group having 1 to 3 carbon atoms, and-
(C ₂ H ₄ O) _{1 to 6} H group and a group selected from the group consisting of a mixture thereof].

These nonionic surfactants are added to the composition of the present invention in an amount of 0.1
It is preferable that the content is -10%, especially 1-8%.

The pH range of the undiluted solution of the liquid detergent composition of the present invention is preferably 4 to 10, and particularly preferably 5 to 8.

Further, other optional components can be added to the liquid detergent composition of the present invention as long as the separation stability, cleaning performance and foaming performance of the composition are not impaired. For example, lower aliphatic alcohols such as ethyl alcohol; solubilizing agents such as sodium or potassium salts of toluenesulfonic acid or xylenesulfonic acid and urea; viscosity modifiers such as clay minerals and water-soluble polymer substances; calcite, silica stones. , Water-insoluble abrasives such as calcium phosphate, zeolite, polyethylene, nylon and polystyrene; moisturizers such as glycerin and sorbitol;
A texture-improving agent such as cationized cellulose; other enzymes, perfumes, dyes, antiseptic / antifungal agents and the like can be added.

〔The invention's effect〕

The liquid detergent composition of the present invention has excellent foaming power, irritation to the skin and hair, damage to the hair is remarkably alleviated, and also has excellent feeling in use, has no residual aroma on the skin, and has a low to high temperature. It is a liquid detergent composition that does not cause turbidity or separation in a wide temperature range.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Test method and evaluation method> (1) Foaming power test The foaming power is measured when 0.1% of commercially available butter as a stain component is added to a detergent solution having a detergent concentration of 0.5%. The measurement method is a detergent solution in which butter is added to a glass cylinder with a diameter of 5 cm.
Add 0 ml, stir for 10 minutes, and measure the foam height immediately after stopping.

(2) Hand feel after use Prepare two kinds of detergents A and B, and place each in 2 beakers.
Prepare a 10% detergent solution at 40 ° C. The wrists are separately immersed in the aqueous solutions of detergents A and B for 1 minute to the wrist. Then, after thoroughly rinsing, the feel of the hand after wiping the hand with a dry towel is scored based on the detergent A at the following evaluation points.

The above test is conducted on 10 test subjects, and the feeling of use of detergent B is evaluated by the sum of the scores obtained for each item.

(3) Residual fragrance property Immediately after the above-mentioned hand feel test, the same test subject smells the odor remaining in the hand, and the residual odor property is scored based on detergent A at the following evaluation points.

(4) Stability test The liquid detergent composition is put in a 50 ml glass bottle and stored in a thermostat at -5 ° C for 1 month, and then the state of the liquid (turbidity or separation phenomenon) is observed. The evaluation criteria at this time are as follows.

A: There is almost no change.

B: Some changes are observed.

C: There is considerable change.

D: Significant change is observed.

Example 1 A liquid detergent composition containing various alkyl glycosides, terpene-based hydrocarbons, ester-based hydrocarbons and alcohol-based hydrocarbons shown in Table 1 was prepared, and foaming power, hand feel, residual odor, The stability was evaluated. The results are shown in Table 1.

In addition, the comparative detergent Detergent A used for the test of the feel of the hand and the residual odor is 15 in Table 1, and this and detergent B (1 to 14 in Table 1).
A comparative test was conducted.

Example 2 A liquid detergent composition containing various alkylglycosides, terpene-based hydrocarbons, ester-based hydrocarbons, alcohol-based hydrocarbons and surfactants shown in Table 2 was prepared. The residual aroma and stability were evaluated. The results are shown in Table 2.

The comparative detergent used for the test of hand feel and residual odor was detergent A (15 in Table 1) and detergent B (16 to 2 in Table 2).
A comparative test was conducted on 7).

Claims (9)

[Claims] 1. The following components (a), (b), (c) and (d) (a) Alkyl glycoside 1 to 50% by weight (b) One or more kinds selected from monoterpenes and sesquiterpenes Terpene hydrocarbon (c) R-COO-R '(wherein R is a hydrocarbon group which may contain a keto group, R'is a hydrocarbon group, and R and R'
Has a total carbon number of 2 to 15) (d) Alcohols represented by R "-OH (wherein R" represents a hydrocarbon group having 3 to 12 carbon atoms) Content of (d) / (c) is in the range of 0.2 to 5 by weight, and (c) / [(b) + (c) + (d)] is in weight ratio.
It is in the range of 0.001 to 0.2, and (b) + (c) + (d)
Is 0.02 to 1.0% by weight of the liquid detergent composition. 2. An alkyl glucoside is represented by the following general formula (I) R ₁ (OR ₂ ) xGy (I) (wherein R ₁ is a linear or branched alkyl, alkenyl or alkyl group having 8 to 18 carbon atoms). Represents a phenyl group, R ₂ represents an alkylene group having 2 to 4 carbon atoms, and x has an average value of 0.
To G, G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, and y is a number having an average value of 1.0 to 3.0). The liquid detergent composition according to 1. 3. The liquid detergent composition according to claim 2, wherein in the alkyl glycoside of the general formula (I), R is an alkyl group having 8 to 14 carbon atoms, x is 0 and y has an average value of 1 to 1.4. . 4. The following components (e), (f) and (g) (e) Anionic surfactant 0.1 to 20% by weight (f) Amphoteric surfactant 0.1 to 20% by weight (g) ( Nonionic surfactant other than component a) 0.1 to 10
The liquid detergent composition according to claim 1, which contains one or more selected from wt.%. 5. The liquid detergent composition according to claim 4, wherein the anionic surfactant is one or a mixture of two or more selected from sulfates, sulfonates, phosphates and carboxylates. 6. The liquid detergent composition according to claim 4, wherein the amphoteric surfactant is one kind or a mixture of two or more kinds selected from carbobetaine type and sulfobetaine type. 7. A nonionic surfactant other than the component (a),
The liquid detergent composition according to claim 4, which is one kind or a mixture of two or more kinds selected from polyalkylene addition type, amine oxide type, mono- and diethanolamide type. 8. An anionic surfactant, polyoxyethylene (= 0 to 6) alkyl ether sulfate having an alkyl group having 8 to 14 carbon atoms, linear alkylbenzene sulfonate having 8 to 14 carbon atoms, carbon Α-Olefin sulfonate having 8 to 14 carbon atoms, secondary alkane sulfonate having 8 to 18 carbon atoms, α-sulfo fatty acid ester salt having 8 to 14 carbon atoms, and polyoxy having an alkyl group having 7 to 15 carbon atoms ethylene(
= 0-6) Alkyl ether carboxylate, C8-
Polyoxyethylene having 14 alkyl groups (= 0 to
6) Monoalkyl ether phosphate, N having 8 to 16 carbon atoms
One or two selected from acylmethyl taurate, a monoester salt of polyoxyethylene (= 0 to 10) alkyl ether having 8 to 14 carbon atoms and sulfosuccinic acid, and an N-acyl glutamate salt having 8 to 16 carbon atoms; 6. The liquid detergent composition according to claim 4, which comprises one or more kinds. 9. The nonionic surfactant is a polyoxyethylene (= 3-20) alkyl ether having an alkyl group having 8 to 14 carbon atoms, mono- or ethanolamide of a fatty acid having 8 to 14 carbon atoms, and 8 carbon atoms. The liquid detergent composition according to claim 4 or 7, which is one or more selected from tertiary amine oxides having 14 to 14 alkyl groups.