JP2010077076A - Detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition satisfying both rich foaming and creamy foam quality, protecting skin from friction in cleaning, and obtaining a moisturizing feeling after the cleaning. <P>SOLUTION: The detergent composition contains (a) a polyalkylene glycol derivative expressed by formula (1): R<SP>1</SP>O-(CH<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>CH<SB>2</SB>O)<SB>n</SB>-R<SP>2</SP>(1) [wherein, R<SP>1</SP>, R<SP>2</SP>are each same or different H or 12-20C fatty acid residues; the ratio of the 12-20C fatty acid residue in the R<SP>1</SP>, R<SP>2</SP>is 0.55 to 0.90; and (n) is a number of 3 to 24 which is the average mole number of added oxytetramethylene group] and (b) an ionic surfactant having sulfuric acid group or sulfonic acid group. The component (a) is contained by 0.1 to 10 mass%, and the component (b) is contained by 1 to 30 mass%, and further, the ratio of the component (a) to the component (b), (a/b) is (1/40) to (1/1). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a detergent composition such as hair shampoo, facial cleanser, body soap, hand soap and the like.

  In recent years, it has become difficult to maintain healthy skin and hair, such as increased cleaning frequency due to lifestyle changes, increased ultraviolet light due to ozone depletion, and contact of harmful substances due to air pollution to the human body. An increasing number of people are complaining of skin and hair damage against the background of increasing factors. As such people's needs, less irritating detergents are required.

  In general, anionic surfactants having sulfate groups or sulfonic acid groups are widely used as main cleaning components of cleaning agents because of their high foaming power and cleaning power. However, an anionic surfactant having a sulfuric acid group or a sulfonic acid group has a strong degreasing power when used alone, and a moist feeling cannot be obtained on the hair and skin after washing, and the foam quality is rough. There was a problem that hair and skin may be damaged by friction during washing.

  Therefore, as an attempt to give a moist feeling after washing, by adding a moisturizing agent such as glycerin to give moist feeling to the skin and hair after washing, by blending oil such as lanolin, petrolatum, olive oil, A method for imparting moisture to the skin after washing has been performed so far.

  However, since the humectant is water-soluble, it is washed away at the time of rinsing, so that the contribution to the moist feeling of the skin after washing is insufficient. It was.

  In addition, as an attempt to reduce the friction between skin and skin or skin and hair by generating rich and creamy foam, a method of adding a thickening / foaming agent such as lauric acid diethanolamide has been used so far. However, the moist feeling after washing was insufficient.

Recently, an oil agent, which is a condensation product of an ester of diglycerin and a branched C 16-18 monocarboxylic acid with a C 6-10 dicarboxylic acid, is added to the cleaning agent. There has been proposed a cleaning composition that can improve the feeling of firmness and firmness of the skin later, and can provide an excellent moist feeling and emollient effect (Patent Document 1). However, the above detergent composition has insufficient foam creaminess and is insufficient in protecting hair and skin from friction during washing.
JP-A-9-125090

  As described above, in the above prior art, there has been a demand for a cleaning composition that achieves both rich foaming and creamy foam quality, protects hair and skin from friction during cleaning, and provides a moist feeling after cleaning. .

  Accordingly, an object of the present invention is to provide a cleaning composition that achieves both rich foaming and creamy foam quality, protects hair and skin from friction during cleaning, and provides a moist feeling after cleaning.

The cleaning composition of the present invention that achieves the above object comprises (a) a polyalkylene glycol derivative represented by the formula (1),
R ¹ O— (CH ₂ CH ₂ CH ₂ CH ₂ O) _n —R ² (1)
[In Formula (1), R < ¹ > and R < ² > show the hydrogen atom which may be the same or different, or a C12-C20 fatty acid residue. The ratio of the fatty acid residue having 12 to 20 carbon atoms in R ¹ and R ² is 0.55 to 0.90. n is the average addition mole number of an oxytetramethylene group, and is 3-24. ]
(B) A cleaning composition containing an ionic surfactant having a sulfate group or a sulfonic acid group, wherein the cleaning composition contains 0.1 to 10% by mass of the component (a), The component (b) is contained in an amount of 1 to 30% by mass, and the mass ratio (a / b) of the component (a) to the component (b) is in the range of 1/40 to 1/1.

  Furthermore, when the said cleaning composition contains the high molecular compound which has a cationic group, the foamability at the time of washing | cleaning and the creaminess of foam can be improved synergistically.

  According to the cleaning composition of the above invention, rich foaming and creamy foam quality are compatible, hair and skin are protected from friction during washing, and a moist feeling can be obtained after washing.

  Embodiments of the present invention will be described below.

In the polyalkylene glycol derivative (a) represented by the formula (1) according to the cleaning composition of the present invention, R ¹ and R ² may be the same or different from each other, a hydrogen atom or a fatty acid residue having 12 to 20 carbon atoms. It is. The fatty acid residue having 12 to 20 carbon atoms which is R ¹ and R ² is an acyl group derived from fatty acid. As the fatty acid, for example, a saturated fatty acid, an unsaturated fatty acid, a branched fatty acid, and a hydroxyl group-substituted fatty acid may be used, but a saturated fatty acid is more preferable in that rich foaming and creamy foam quality can be obtained.

  As fatty acids, lauric acid, tridecanoic acid, isotridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, nonadecanoic acid, arachidic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, palmitooleic acid Oleic acid, vaccenic acid, linoleic acid, linolenic acid, arachidonic acid, hydroxystearic acid and the like. Preferred are fatty acids having 14 to 18 carbon atoms such as myristic acid, palmitic acid, stearic acid, isostearic acid, and more preferred is palmitic acid.

That is, when the carbon number of the fatty acid residue of R ¹ and R ² is less than 12, the foam creaminess and the moist feeling after washing are insufficient, the feeling of friction during washing increases, and R ¹ and R ^{When the} number of carbon atoms of the fatty acid residue ² exceeds 20, the foaming property is deteriorated. Therefore, the fatty acid residues of R ¹ and R ² are preferably those having 12 to 20 carbon atoms. R ¹ and R ² may be the same or different, and may be one or more.

The proportion of the fatty acid residue having 12 to 20 carbon atoms in R ¹ and R ² is 0.55 to 0.90, more preferably 0.60 to 0.85, still more preferably 0.70. 0.80.

That is, when the ratio of the fatty acid residue having 12 to 20 carbon atoms in R ¹ and R ² is less than 0.55, the creaminess of foam and the moist feeling after washing are insufficient, and the feeling of friction during washing is insufficient. growing. On the other hand, when the ratio of the fatty acid residue having 12 to 20 carbon atoms in R ¹ and R ² exceeds 0.90, the foaming property is deteriorated.

  The oxytetramethylene group is an essential component to reduce the feeling of friction during washing and to give a moist feeling to the skin and hair after washing, and n is an average added mole number of the oxytetramethylene group of 3 to 24 Preferably, it is 5-20, More preferably, it is 7-15.

  This is because if n is less than 3, the foaming property is poor, the foam creaminess and the moist feeling after washing are insufficient, and the feeling of friction during washing increases. In addition, polytetramethylene glycol with n exceeding 24 has poor foamability.

  The polyalkylene glycol derivative (a) represented by the formula (1) of the present invention can be produced by a known method. For example, it can be obtained by an esterification reaction between polytetramethylene glycol and a fatty acid or a transesterification reaction with a fatty acid ester.

  Examples of the ionic surfactant (b) having a sulfate group and a sulfonate group used in the cleaning composition of the present invention include an alkyl ether sulfate ester salt, an alkyl sulfate ester salt, an alkylbenzene sulfonate salt, and an acylmethyl taurine. Examples thereof include salts, α-olefin sulfonates, acyl isethionates, acyl sulfosuccinates, and alkyl sulfobetaine salts.

  Among these ionic surfactants having a sulfate group and a sulfonate group, acylmethyl taurate, acyl isethionate, acyl sulfosuccinate, alkyl ether sulfate are superior in terms of foaming properties and excellent moisture feeling after washing. Ester salts are preferred. Moreover, as carbon number of an acyl group and an alkyl group, when foaming property and irritation | stimulation to skin are considered, C10-C14 is preferable.

  Preferred surfactants satisfying the above conditions include, for example, caproyl methyl taurine sodium, lauroyl methyl taurine sodium, cocoyl methyl taurine sodium, sodium lauroiylisethionate, sodium cocoyl isethionate, sodium lauroyl sulfosuccinate, sodium cocoyl sulfosuccinate. And sodium lauryl ether sulfate.

  The component (a) is contained in the cleaning composition in an amount of 0.1 to 10% by mass, preferably 0.5 to 8% by mass, and more preferably 1 to 5% by mass.

  When the proportion of the component (a) in the cleaning composition is less than 0.1% by mass, the creaminess of the foam and the moist feeling after cleaning are insufficient, and the feeling of friction during cleaning is large. When the proportion of the component (a) in the cleaning composition exceeds 10% by mass, the foamability is deteriorated. In addition, (a) component may be used independently and may use 2 or more types together.

  The component (b) is contained in the cleaning composition in an amount of 1 to 30% by mass, preferably 2 to 25% by mass, more preferably 3 to 20% by mass.

  When the proportion of the component (b) in the cleaning composition is less than 1% by mass, the foaming property is poor, the foamy creamy feeling is insufficient, and the feeling of friction during cleaning is large. When the proportion of the component (b) in the cleaning composition exceeds 30% by mass, a moist feeling after cleaning cannot be obtained. (B) A component may be used independently and may use 2 or more types together.

  The mass ratio a / b of the component (a) and the component (b) of the present invention is 1/40 to 1/1, preferably 1/30 to 1/2, more preferably 1/25 to 1. / 3. When a / b is less than 1/40, the creaminess of the foam and the moist feeling after washing are insufficient, and the feeling of friction during washing is large. Moreover, when a / b exceeds 1/1, foaming property worsens.

  In the cleaning composition according to the present invention, a polymer compound having a cationic group can be used as necessary. The polymer compound having a cationic group is a polymer compound having a cationic group or a group that can be ionized to a cationic group, and includes an amphoteric polymer compound. By adding a polymer compound having a cationic group, foamability and foam creaminess can be synergistically enhanced.

  Examples of the polymer compound having a cationic group include cationized cellulose, diallyldimethylammonium chloride / acrylamide copolymer, acrylic acid / diallyldimethylammonium chloride copolymer, acrylic acid / diallyldimethylammonium chloride / acrylamide copolymer, acrylic resin. Acid / cationized methacrylic acid ester copolymer, acrylic acid / cationized methacrylic acid amide copolymer, acrylic acid / methyl acrylate / methacrylamidopropyltrimethylammonium chloride copolymer, 2-methacryloyloxyethyl phosphorylcholine And cationized polysaccharides such as cationized oligosaccharides, cationized dextran, and guar hydroxypropyltrimonium chloride. It is.

  Among these polymer compounds having cationic properties, copolymers with cationized cellulose, diallyldimethylammonium chloride / acrylamide copolymer, 2-methacryloyloxyethyl phosphorylcholine polymer, butyl methacrylate copolymer, etc. It is preferable to use, and it is more preferable to use a copolymer of 2-methacryloyloxyethyl phosphorylcholine and a copolymer with butyl methacrylate copolymer or the like.

  When adding the high molecular compound which has cationic property, as the addition amount, it is 0.001-5 mass% normally of a cleaning composition, Preferably it is 0.01-3 mass%, More preferably, it is 0.05. ˜1% by mass.

  Moreover, the cleaning composition of this invention contains another additive and a solvent as needed.

  As an additive, various components generally used in cosmetics, quasi-drugs, and pharmaceuticals can be blended as long as the effects of the present invention are not impaired. For example, hydrocarbons, higher alcohols, higher fatty acids and their triglycerides, ester oils, animal and vegetable oils, vitamins, UV absorbers, antioxidants, sequestering agents, ethanol, thickeners, preservatives, dyes, pigments And fragrances.

  As the solvent, water, 1,3-butylene glycol, dipropylene glycol, propylene glycol, glycerin, or the like can be used as necessary.

  The form of the cleaning composition according to the present invention is not particularly limited, and can be used in various forms such as a hair shampoo, a facial cleanser, a body soap, and a hand soap. In particular, use in hair shampoos, facial cleansers and the like is preferable.

  The present invention will be specifically described with reference to examples.

The proportion of fatty acid residues having 12 to 20 carbon atoms in R ¹ and R ² (hereinafter referred to as “the proportion of fatty acid residues”) is the ester value (EV) of the esterified product and the hydroxyl value (OHV) of the esterified product. Was determined by measurement and calculated by the following method.

Fatty acid residue ratio = EV of esterified product / (EV of esterified product + OHV of esterified product)
EV of esterified product = saponification number of esterified product (SV) -acid value of esterified product (AV)
The hydroxyl value (OHV) of the esterified product, the saponification value (SV) of the esterified product, and the acid value (AV) of the esterified product were measured according to the method described in Japanese Industrial Standard (JIS).
OHV: JIS K-1557 6.4
SV: JIS K-0070 3.1
AV: JIS K-0070 4.1
<Synthesis method>
Below, the synthesis | combining method of the polyalkylene glycol derivative (compounds 1-3) which concerns on this invention and the polyalkylene glycol derivative (compounds 4-9) which concerns on a comparative example is demonstrated.

<Synthesis Method of Compound 1>
Palmitic acid ester of polytetramethylene glycol (8.6 mol) [Ratio of fatty acid residues = 0.75]
Polytetramethylene glycol (n = 8.6, hydroxyl value = 180.3, raw material name: PTG650, manufactured by Hodogaya Chemical Co., Ltd.) 622 g and palmitic acid (NAA-160 manufactured by Nippon Oil & Fats Co., Ltd.) 385 g at 200 ° C. For 10 hours to obtain 958 g of polytetramethylene glycol palmitate (Table 1: Compound 1). Since EV was 85.2 and OHV was 28.4, the ratio of fatty acid residues was 0.75.

[Calculation example of fatty acid residue ratio]
Since the ester compound has an SV of 85.3 and AV of 0.1, the EV is 85.2 (EV = SV-AV). And since OHV is 28.4, the ratio of fatty acid residues is 85.2 / (85.2 + 28.4) = 0.75.

<Synthesis Method of Compounds 2 and 3>
According to the synthesis method of Compound 1, Compounds 2 and 3 (polyalkylene glycol derivatives of the present invention) shown in Table 1 were synthesized.

<Synthesis of Compounds 4-7>
According to the synthesis method of Compound 1, compounds 4 to 7 (comparative substances) shown in Table 1 were synthesized.

<Synthesis Method of Compound 8>
Palmitic acid ester of polypropylene glycol (20 mol) [Ratio of fatty acid residues = 0.75]
1200 g of polypropylene glycol (n = 20, hydroxyl value = 47.2, raw material name: Uniol D-1200, NOF Corporation) and 390 g of palmitic acid (NAA-160 manufactured by NOF Corporation) at 200 ° C. Reaction was performed for 1 hour to obtain 1550 g of a palmitic acid ester of polypropylene glycol (Table 1: Compound 8). Since EV was 52.9 and OHV was 17.6, the ratio of fatty acid residues was 0.75.

<Method for Synthesizing Compound 9>
Palmitic acid ester of polyoxytetramethylene (8.6 mol) / polyoxyethylene (4.0 mol) block copolymer [fatty acid residue ratio = 0.75]
650 g of polytetramethylene glycol (n = 8.6, hydroxyl value = 180.3, raw material name: PTG650, manufactured by Hodogaya Chemical Co., Ltd.) and 0.83 g of potassium hydroxide as a catalyst were charged into the autoclave, and the air in the autoclave The catalyst was completely dissolved at 150 ° C. with stirring. Next, 178 g of ethylene oxide was dropped with a dropping device and stirred for 1 hour. Thereafter, the reaction composition was taken out from the autoclave, neutralized with phosphoric acid to pH 6 to 7, and treated at 100 ° C. for 1 hour under reduced pressure (30 mmHg or less) in order to remove the contained water. Furthermore, filtration was performed to remove the salt produced after the treatment, and 826 g of a polyoxytetramethylene (8.6 mol) / polyoxyethylene (4.0 mol) copolymer was obtained.

  826 g of the obtained polyoxytetramethylene (8.6 mol) / polyoxyethylene (4.0 mol) copolymer and 386 g of palmitic acid (NAA-160, NOF Corporation) were reacted at 200 ° C. for 10 hours. As a result, 1182 g of palmitic acid ester of polyoxytetramethylene (8.6 mol) / polyoxyethylene (4.0 mol) block copolymer was obtained (Table 2: Compound 9). Since EV was 71.0 and OHV was 23.7, the ratio of fatty acid residues was 0.74.

  Tables 1 and 2 show chemical structures and constituent elements of the compounds synthesized by the synthesis method described above.

<< Examples 1-4 and Comparative Examples 1-12 >>
As shown in Table 4, the compounds 1 to 3 according to the present invention are used as the component (a), the compounds 4 to 9, the diglyceryl isopalmitic acid ester sebacic acid condensate and the petrolatum are used as the component (a ′). The components shown in Table 3 were selected as components, and hair shampoos (cleaning compositions) of Examples 1 to 4 and Comparative Examples 1 to 12 were prepared by the following preparation methods.

<< Preparation Methods of Examples 1-4 and Comparative Examples 1-12 >>
A predetermined amount of ion-exchanged water was charged into a 1000 L beaker, and a polymer (hydroxyethyl cellulose (including cationized cellulose in Examples 4 and 10)) as one of common components was dispersed while stirring with a propeller. After heating this to 80 degreeC and confirming that the polymer melt | dissolved, the remaining component was added in random order, and it mixed and stirred at 80 degreeC for 1 hour. After confirming that all the components were dissolved (emulsified depending on the formulation), the components were cooled to 40 ° C. or lower by air cooling, and hair shampoos of Examples 1 to 4 and Comparative Examples 1 to 12 were obtained.

"Evaluation methods"
A. About “Foamability” A 5% by mass aqueous solution of a hair shampoo was stirred for 5 seconds with a Milcer tester (manufactured by Iwatani Co., Ltd., IFM-100), and the height of the foam after standing for 1 minute was measured. Judgment was made based on the following criteria, and A and B were considered acceptable.
(Score): (Evaluation)
A: Foam height of 60 mm or more B: Foam height of 50 mm to less than 60 mm C: Foam height of 40 mm to less than 50 mm D: Foam height of less than 40 mm “Creaminess of foam” A 5% by mass aqueous solution of a hair shampoo was stirred for 5 seconds with a Milcer tester (Iwatani Co., Ltd., IFM-100), and the density of the foam immediately after stirring was measured. Judgment was made based on the following criteria, and A and B were considered acceptable.
(Score): (Evaluation)
A: Density of foam 0.04 g / cm ³ or more B: Density of foam 0.03 g / cm ³ or more ~0.04g / cm ³ less than C: density of foam 0.02 g / cm ³ or more to 0. 03G / cm ³ less than D: density of the foam 0.02 g / cm ³ less than C. “Friction feeling at the time of washing” Twenty women were allowed to wash their hair using 10 g of hair shampoo, and each panelist rated the feeling of friction at the time of washing according to the following absolute evaluation. And the score of all the panelists was totaled for every sample, and 30 or more points were set as the pass. However, if 3 or more panelists gave a score of 0, they were rejected.

<Absolute evaluation criteria>
(Score): (Evaluation)
3: The friction between the hair and the finger is small, and the slipperiness is sufficient for the foam. 2: The friction between the hair and the finger is slightly small, and the foam is easy to slip. 1: The friction between the hair and the finger is slightly large. Did not feel very slippery on the foam 0: The friction between the hair and the fingers is large, and the foam does not feel slippery. About “moisture feeling after washing” Each panelist asked about 20 women to wash their hair with 10g of hair shampoo, wiped moisture with a towel, and then air-dried for 20 minutes. The following absolute rating was given a score of 4 levels. And the score of all the panelists was totaled for every sample, and 30 or more points were set as the pass. However, if 3 or more panelists gave a score of 0, they were rejected.

<Absolute evaluation criteria>
(Score): (Evaluation)
3: Feeling sufficient moisture in the hair 2: Feeling slightly moistened in the hair 1: Not feeling too moisturized in the hair 0: Feeling no moist feeling in the hair <Evaluation result of the cleaning composition>
Table 4 shows the evaluation results of the cleaning composition evaluated by the above evaluation method.

  According to the evaluation of Examples 1 to 4 shown in Table 4, the shampoo containing the alkylene glycol derivative according to the example of the present invention and the ionic surfactant having a sulfate group and a sulfonate group has a foaming property, The slipperiness (friction feeling at the time of washing) of the foam was good, the foam was creamy, and the hair after washing and drying had a moist feeling.

  On the other hand, in Comparative Examples 1-12, sufficient effect is not acquired. Hereinafter, Comparative Examples 1 to 12 will be specifically described.

  In Comparative Example 1, since the type of fatty acid in the polyalkylene glycol derivative is behenic acid having more than 20 carbon atoms, the foamability was insufficient.

  In Comparative Example 2, since the type of fatty acid in the polyalkylene glycol derivative was acetic acid having less than 12 carbon atoms, the creaminess of foam, the slipperiness of foam, and the moisture feeling of the hair after washing were insufficient.

  In Comparative Example 3, since the average addition mole number n of the oxytetramethylene group in the polyalkylene glycol derivative is less than 3, the foaming property, foam creaminess, foam slipperiness, and moisture feeling after washing It was insufficient.

  In Comparative Example 4, since the ratio of the fatty acid residue in the polyalkylene glycol derivative exceeds 0.90, the foamability was insufficient.

  In Comparative Example 5, since the polyalkylene glycol derivative has a polyoxypropylene group instead of a polyoxytetramethylene group, it is insufficient in foam creaminess, foam slipperiness, and moisture feeling after washing. Met.

  In Comparative Example 6, since the polyalkylene glycol derivative is composed of a block copolymer of polyoxytetramethylene and polyoxyethylene, the creaminess of foam, the slipperiness of foam, and the moisture feeling of the hair after washing were insufficient. It was.

  Since Comparative Example 7 uses a diglyceryl isopalmitate sebacic acid condensate that is an oil agent other than the polyalkylene glycol derivative according to the present invention, the foam creaminess and foam slipperiness were insufficient. .

  Since Comparative Example 8 uses petroleum jelly, which is an oil agent other than the polyalkylene glycol derivative according to the present invention, foaming properties, foam creaminess, and foam slipping properties were insufficient.

  In Comparative Example 9, the blending amount of the component (b), that is, the ionic surfactant exceeds 30% by mass, and the mass ratio a / b of the component (a), that is, the polyalkylene glycol derivative to the component (b) is 1. Since it is less than / 40, the creaminess of the foam, the slipperiness of the foam, and the moist feeling after washing were insufficient.

  In Comparative Example 10, the blending amount of the component (a) exceeds 10% by mass, and the mass ratio a / b of the component (a) to the component (b) exceeds 1/1. It was enough.

  In Comparative Examples 11 and 12, since an anionic surfactant having a carboxylic acid group was blended in place of the component (b), all of them were insufficient in foam creaminess, foam slipperiness, and moist feeling after washing. Met.

  As described above, the detergent composition containing the polyalkylene glycol derivative according to the present invention has good foaming properties and foam creaminess, and also has a good feeling of friction during washing and a feeling of moisture after washing. is there.

  Furthermore, as shown in Example 4, by adding a polymer compound having a cationic group, better foaming properties and foam creaminess can be obtained.

Claims (2)

(A) Polyalkylene glycol derivative represented by formula (1) R ¹ O— (CH ₂ CH ₂ CH ₂ CH ₂ O) _n —R ² (1)
[In Formula (1), R < ¹ > and R < ² > show the hydrogen atom which may be the same or different, or a C12-C20 fatty acid residue. The ratio of the fatty acid residue having 12 to 20 carbon atoms in R ¹ and R ² is 0.55 to 0.90. n is the average addition mole number of an oxytetramethylene group, and is 3-24. ]
(B) a detergent composition containing an ionic surfactant having a sulfuric acid group or a sulfonic acid group,
In the cleaning composition,
(A) 0.1-10 mass% component is contained,
(B) 1-30 mass% of components are contained,
A cleaning composition, wherein the mass ratio (a / b) of component (a) to component (b) is in the range of 1/40 to 1/1. Furthermore, the cleaning composition of Claim 1 containing the high molecular compound which has a cationic group.