JP4850774B2 - Cleaning composition - Google Patents

Description

  The present invention relates to a detergent composition that is less irritating to the skin and the like, is excellent in stability and foaming property, has a foamy quality, has a good feeling in use, and has excellent stability.

  Phosphate-based surfactants are less irritating to skin and hair than soaps, alkyl ether sulfates, alkyl sulfates, and the like, and are widely applied as components of skin cleansing agents. Further, due to its characteristics, it is applied to a wide range of mixed systems with other anionic surfactants and nonionic surfactants.

By the way, in general, a phosphate ester-based surfactant is obtained as a mixture of monoester and diester, and the alkyl phosphate ester is mixed with dialkyl phosphate having poor water solubility and poor foaming ability. When this is used alone as the main component of the cleaning agent, there are generally problems in foaming power and foam quality, and therefore several methods for further adding an auxiliary agent have been proposed. Among them, a method of adding a higher fatty acid salt as an auxiliary (Patent Document 1) is a method excellent in enhancing foaming power, but this method has a high weight ratio of alkyl phosphate ester and a low ratio of higher fatty acid salt. However, compared with only the higher fatty acid salt (soap), both foaming power and foam quality were still not satisfactory. Further, the method of adding a higher fatty acid salt to polyoxyethylene alkyl ether phosphate ester (Patent Document 2) is still not satisfactory in terms of foaming power and stability. On the other hand, the method using a glyceryl ether having an alkyl group or alkenyl group having 6 to 12 carbon atoms as an auxiliary agent (Patent Document 3) is somewhat effective in improving foaming power in the case of a monoalkyl phosphate ester salt. Although effective, if the ratio of monoalkyl phosphate salt / dialkyl phosphate ester salt is less than 95/5, both foaming power and foam quality can be achieved as compared with the case of using only higher fatty acid salts. It is difficult to be satisfied. In addition, the use of higher fatty acid salts alone has excellent foam performance such as foaming power and foam quality as described above, but there are problems in terms of skin irritation such as a squeaky feeling during rinsing and a feeling of squeezing after washing. It was. Furthermore, Patent Document 4 discloses a combination of a phosphoric acid monoester, a higher fatty acid salt, and an alkyl glyceryl ether, but these combinations having a high ratio of the phosphoric acid ester and a low ratio of the higher fatty acid salt are, I was still not satisfied with the foaming power and foam quality.
JP-A-57-49698 JP-A-1-316309 Japanese Patent Laid-Open No. 2001-107079 JP 2005-206804 A

  Therefore, the present invention provides a cleansing composition that is less irritating to the skin, etc., has excellent foaming properties, has a foamy quality, has a good feeling on use (rinse and feel after washing), and has excellent stability. The purpose is to do.

  The inventors of the present invention use a higher composition of fatty acid or salt thereof and a phosphate ester surfactant in a specific ratio and a glyceryl ether in combination for a detergent composition using a phosphate ester surfactant. Thus, it has been found that a detergent composition with less irritation to the skin and the like, excellent stability and foaming property, creamy quality and good usability can be obtained. Moreover, since it is such a composition, manufacture at the time of a mixing | blending was easy.

That is, the present invention provides a cleaning composition containing the following components (A), (B) and (C):
(A) (a ₁ ) A mixture of a phosphoric acid monoester surfactant represented by the general formula (1) and (a ₂ ) a phosphoric diester surfactant represented by the general formula (2). The phosphoric acid ester surfactant whose content ratio is (a ₁ ) / (a ₂ ) = 90 / 10-50 / 50 by weight ratio:

(Wherein R ¹ , R ² and R ³ each represent a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and X ¹ , X ² and Y represent a hydrogen atom, an alkali metal atom, an alkali, respectively. An earth metal atom, an alkanolamine or ammonium, and the average number of added moles k, m and n are each 0 to 10);
(B) General formula (3)
R ⁴ -COOM (3)
(Wherein R ⁴ represents a saturated or unsaturated aliphatic hydrocarbon group having 7 to 17 carbon atoms, and M represents a hydrogen atom, an alkali metal atom, an alkanolamine or ammonium)
A higher fatty acid represented by the formula:
(C) one or more glyceryl ethers having a linear or branched alkyl group or alkenyl group having 6 to 12 carbon atoms, and the content ratio of component (A) to component (B) is a component by weight (B) / component (A) = more than 1.5 and less than 10

  The cleaning composition of the present invention has little irritation to the skin, etc., excellent foaming properties, foam quality is creamy, and has a good feeling during use (rinse and feel after washing) and is excellent in stability. .

In the phosphoric acid ester represented by the general formulas (1) and (2) of the component (A) which is a hypoallergenic base used in the present invention, R ¹ , R ² and R ³ have 10 to 16 carbon atoms. In particular, 12 to 14 alkyl groups are preferred, and X ¹ , X ² and Y are preferably alkali metal atoms such as potassium or sodium and triethanolamine, and potassium is particularly preferred from the viewpoint of solubility in water. The average number of moles k, m and n of ethylene oxide added is preferably 0 to 4 moles, more preferably 0 to 2, and particularly preferably 0 to 1 mole from the viewpoint of foaming power.

The content ratio of the alkyl phosphate monoester (a ₁ ) and the alkyl phosphate diester (a ₂ ) in the component (A) is weight ratio (a ₁ ) / (a ₂ ) = from the viewpoint of ease of blending. 90/10 to 50/50, preferably 85/15 to 60/40, and more preferably 80/20 to 70/30. When the weight ratio (a ₁ ) / (a ₂ ) is less than 50/50, the foaming property is poor, and when the weight ratio (a ₁ ) / (a ₂ ) exceeds 90/10, the melting point of the alkyl phosphate ester mixture becomes high. Mixing becomes difficult.

  The content of the phosphoric ester surfactant as the component (A) is preferably 1 to 15% by weight of the cleaning composition of the present invention from the viewpoint of foaming, detergency and ease of blending, and 3 to 10% by weight. % Is more preferable.

Component (A) includes, for example, ethoxylate added with ethylene oxide to the corresponding aliphatic alcohol or the corresponding aliphatic alcohol to have an average addition mole number of more than 0 to 10, phosphoric anhydride, orthophosphoric acid, polyphosphoric acid or oxy Phosphate ester obtained by reacting with a phosphorylating agent such as chlorophosphoric acid, or phosphate ester obtained by partially or completely neutralizing the phosphate ester with an alkali such as sodium hydroxide or potassium hydroxide Salt. (a ₁ ) / (a ₂ ) can be controlled by the ratio between the aliphatic alcohol and the water contained in the phosphorylating agent.
As a method of obtaining (a ₁ ) / (a ₂ ) = 90/10 to 50/50, for example, by using orthophosphoric acid containing phosphoric anhydride and water during the reaction, the ratio of the raw alcohol to water is directly adjusted. to (a ₁₎ / a method for controlling the ratio of (a _2), and _{(a 1) / (a 2} ) = 100 / 0~95 / 5 phosphoric acid _{ester, (a 1) / (a} 2) There is a method of mixing = 50/50 phosphate ester at an appropriate ratio.

In the higher fatty acid represented by the general formula (3) of the component (B) or a salt thereof, R ⁴ is preferably an alkyl group having 7 to 17 carbon atoms, M is preferably an alkali metal atom, an alkanolamine or ammonium, Particularly preferred is an alkali metal atom such as potassium or sodium.

  The higher fatty acid salt may be prepared by neutralizing a higher fatty acid and a base in a compounding tank for producing a cleaning composition. Further, even if a part of the higher fatty acid salt undergoes salt exchange with the counter ion of the phosphate ester salt, the effect of the present invention is not hindered.

  Component (B) provides a foam quality improving effect not found in component (C), that is, a creamy foam quality, and also improves foamability.

  The higher fatty acid of component (B) or a salt thereof can be used alone or as a mixture of two or more. The content of the component (B) is preferably from 5 to 35% by weight, more preferably from 5 to 30% by weight, and more preferably from 10 to 25% by weight from the viewpoint of giving the cleaning property and foaming property of the cleaning composition of the present invention. Is particularly preferred.

  In the cleaning composition of the present invention, the preferable content of the component (A) and the component (B) is as described above, but the content ratio of the component (A) and the component (B) is further expressed by the weight ratio of the component (B). / Component (A) = More than 1.5 and less than 10 is important from the viewpoints of detergency, foaming power, foam quality, foam feel and skin irritation. The weight ratio of component (B) / component (A) is preferably 2-9, particularly preferably 2-5.

The glyceryl ether of component (C) has a linear or branched alkyl group or alkenyl group having 6 to 12 carbon atoms, such as an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, Those having an alkyl group having 6 to 12 carbon atoms such as 2-ethylhexyl group, n-nonyl group, n-decyl group and n-lauryl group are preferred, and further 6 to 11 carbon atoms, particularly 6 to 10 carbon atoms, especially It is preferable to have one or two, particularly one, alkyl group having 8 carbon atoms. One or more glyceryl ethers of component (C) can be used.
Component (C) has the effect of maintaining stability and improving foaming power.
The blending amount of component (C) is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2 to 1% by weight in the cleaning composition of the present invention.
Component (C) can be obtained, for example, by hydrolyzing the corresponding glycidyl ether and water at 100 to 230 ° C.

  By using components (A) and (B) in a weight ratio of component (B) / component (A) = more than 1.5 and less than 10 and further using component (C), higher fatty acid salts The foaming property, which is a drawback of phosphate ester surfactants, is improved to the same level as higher fatty acids. The foam quality is creamy and preferable. In addition, although the ratio of higher fatty acid salts is high, it is recognized that the skin is not tight, which is a feeling of use peculiar to phosphate ester surfactants, and the feeling of use is good. Furthermore, derived from the present invention, blending during production is easy without an increase in viscosity.

  The cleaning composition of the present invention is a cleaning composition useful as a body cleaning agent such as a skin cleaning agent such as a facial cleanser, a shampoo, a body shampoo, or a hair cleaner, and in particular, a facial cleanser, a body shampoo, etc. It is preferably used as a skin cleanser. In these detergent compositions, optional components can be blended depending on the purpose. Here, examples of the optional component include other anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, and conditioning components that are usually blended in these detergents.

  Other anionic surfactants include alkyl sulfates, polyoxyalkylene alkyl ether sulfates, sulfosuccinic acid surfactants, sulfosuccinamate surfactants, polyoxyalkylene alkyl amide ether sulfates, monoglyceride sulfates, Examples include olefin sulfonates, alkane sulfonates, acylated isethionates, acylated amino acid salts, polyoxyalkylene alkyl ether phosphates other than the component (A), and the like. Examples include glucoside, sucrose fatty acid ester, polyglycerin fatty acid ester, polyoxyalkylene alkyl ether, fatty acid alkanolamide, alkylamine oxide, fatty acid polyhydric alcohol ester and the like. Examples of cationic surfactants include linear or branched mono- or di-long alkyl quaternary ammonium salts, mono- or di-long alkyl tertiary amines, etc .; amphoteric surfactants include amide amino acids Examples thereof include a system active agent, a carbobetaine activator, a sulfobetaine activator, an amide sulfobetaine activator, an imidazolinium betaine activator, an amino acid betaine activator, and a phosphobetaine activator.

  Conditioning ingredients include higher alcohols, silicones and silicone derivatives, lanolin, squalene, hydrocarbons, protein derivatives, oils such as fatty acid esters of polyethylene glycol, cationized cellulose, cationized guar gum and Marquat 550 (Nalco), soft care Examples thereof include cationic polymers such as KG-301W [manufactured by Kao Corporation].

In addition, other components usually used in the detergent composition, for example, water-soluble polymers such as polysaccharides such as methylcellulose, hydroxyethylcellulose, carboxyvinyl polymer, xanthan gum; polyoxyalkylene sorbitan ester, polyoxyethylene glycol di Viscosity modifiers such as stearate and ethanol; Chelating agents such as ethylenediaminetetraacetic acid (EDTA) and phosphonates; Preservatives such as methylparaben and butylparaben; Active ingredients such as vitamins and their precursors; Animals and plants such as lecithin and gelatin Extracts or derivatives thereof; fine polymer powders such as nylon and polyethylene; anti-inflammatory agents such as dipotassium glycyrrhizinate; bactericides and anti-dandruff agents such as triclosan, trichlorocarban, octopirox, zinc pyrithione; Antioxidants such emissions; pearling agents, ultraviolet absorbers, pH adjusting agents, dyes, perfumes, water can be optionally added within the range not damaging the effects of the present invention.
The cleaning composition of the present invention preferably has a pH of 7-11.
The cleaning composition of the present invention is preferably used together with water having a hardness of 1 to 30 ° DH. The water used here preferably has a pH of 4 to 9.

  The cleaning composition of the present invention can be produced according to a conventional method. There is no restriction | limiting in particular about the dosage form of the cleaning composition of this invention, It can be set as various conventionally well-known dosage forms, for example, a liquid body shampoo, creamy face wash, etc. The cleaning composition of the present invention is particularly suitable as a cleaning agent for body such as skin and hair.

Production Example 1
In a 500 mL reaction vessel, 187.3 g (1.0 mol) of raw alcohol (lauryl alcohol) was added under a nitrogen atmosphere, and 31.9 g of 85% by weight orthophosphoric acid [P ₂ O ₅ · nH ₂ O expressed as P ₂ O ₅ 19.6 g (0.14 mol) H ₂ O 12.3 g (0.68 mol)] was added, and the mixture was stirred and mixed at 35 ° C. Further, 62.1 g (0.43 mol) of phosphorus pentoxide (effective content 98.5% by weight) was gradually added over 60 minutes with stirring. The temperature rose to 65 ° C, the temperature was further raised, and the reaction was carried out at 80 ° C for 12 hours. Further, 10.0 g of water was added and hydrolysis was carried out at 80 ° C. for 3 hours to neutralize the phosphate ester with potassium hydroxide, and the lauryl phosphate K salt shown in Table 1 (monolauryl / dilauryl = 80 / 20) was obtained.

Production Example 2
In the same manner as in Production Example 1, the amount of water relative to lauryl alcohol was adjusted and reacted so that monolauryl / dilauryl = 60/40, and lauryl phosphate K salt (monolauryl / dilauryl) shown in Table 1 was reacted. Body = 60/40).

Production Example 3
In the same manner as in Production Example 1, the amount of water relative to lauryl alcohol was adjusted and reacted so that monolauryl / dilauryl = 70/30, and the resulting phosphate ester was neutralized with triethanolamine. The lauryl phosphate triethanolamine salt (monolauryl body / dilauryl body = 70/30) shown in Table 1 was obtained.

Production Example 4
In a 500 mL reaction vessel, 230.4 g (1.0 mol) of raw alcohol (lauryl alcohol, EO = average 1 mol addition product) was added under a nitrogen atmosphere, and 31.9 g of 85 wt% orthophosphoric acid [P ₂ O _5. When expressed as nH ₂ O, 19.6 g (0.14 mol) of P ₂ O ₅ (12.3 g (0.68 mol)) of H ₂ O was added and stirred and mixed at 35 ° C. Further, 62.1 g (0.43 mol) of phosphorus pentoxide (effective content 98.5% by weight) was gradually added over 60 minutes with stirring. The temperature rose to 65 ° C, the temperature was further raised, and the reaction was carried out at 80 ° C for 12 hours. Further, 10.0 g of water was added and hydrolysis was carried out at 80 ° C. for 3 hours to neutralize the phosphate ester with potassium hydroxide, and the polyoxyethylene (1) lauryl ether phosphate K salt (monolauryl) shown in Table 1 was obtained. Body / dilauryl body = 80/20).

Production Example 5
In the same manner as in Production Example 1, lauryl alcohol, EO = average 1 mol addition product is changed to myristyl alcohol, EO = average 1 mol addition product, and myristyl alcohol / dimyristyl product = 85/15. The amount of water with respect to EO = average 1 mol addition product was adjusted and reacted to obtain polyoxyethylene (1) myristyl ether phosphate K salt (monomyristyl / dimyristyl = 85/15) shown in Table 1.

Production Example 6
In the same manner as in Production Example 1, lauryl alcohol, EO = average 1 mol addition product is changed to lauryl alcohol, EO = average 2 mol addition product, so that monolauryl / dilauryl product = 75/25, lauryl alcohol, The amount of water with respect to EO = average 2 mol addition product was adjusted and reacted to obtain polyoxyethylene (2) lauryl ether phosphate K salt (monolauryl / dilauryl = 75/25) shown in Table 1.

Production Example 7
208 g of 2-ethylhexyl glycidyl ether, 104.8 g of water, 5.82 g of lauric acid and 18.5 g of potassium hydroxide were placed in an autoclave and stirred at 140 ° C. for 5 hours. After dehydration at 100 ° C. under reduced pressure (6.67 kPa), 9.7 g of lauric acid and 2.72 g of potassium hydroxide were added, reacted at 160 ° C. for 15 hours, and then distilled under reduced pressure (53 to 67 Pa, 120 to 123 ° C.). To give 2-ethylhexyl glyceryl ether shown in Table 1.

Production Example 8
In the same manner as in Production Example 7, 2-ethylhexyl glycidyl ether was changed to n-octyl glycidyl ether to obtain n-octyl glyceryl ether shown in Table 1.

Examples 1-8 and Comparative Examples 1-7
A cleaning composition having the composition shown in Table 1 was prepared by mixing each component at 70 ° C. (pH adjusted to 9), and foaming properties, foam quality, rinsing properties, feel after washing, low irritation and stability Sex was evaluated. The results are shown in Table 1.
(1) Foaming property, foam quality, rinsing property, feel of washing and low irritation Foaming property when washing hand and arm are washed by applying 1g of cleaning agent to palm. The 10 panelists evaluated the foam quality, rinsing properties, feel of washing and low irritation according to the following evaluation criteria.
(Foaming)
4: The amount of foam is very large.
3: The amount of foam is large.
2: A little foam amount.
1: The amount of foam is small.
(Foam quality)
4: Fine, very creamy and good foam quality.
3: Creamy and good foam quality 2: Slightly creamy foam quality 1: Light and rough foam quality.
(Rinse)
4: Not squeaky and good rinsing properties.
3: Almost squeezed, slightly rinsable 2: Slightly squeezed, slightly rinsable 1: Scratch, poorly rinsed (feel of washing up)
4: Good feeling of use with no feeling of being washed up.
3: There is almost no feeling of picking up after washing, and the feeling of use is slightly good 2: Feeling of picking up after washing is somewhat good: Feeling of use is slightly bad 1: Feeling of picking up after washing is bad Rank A: Average score is 3.5 or more B: Average score of 2.5 or more and less than 3.5 C: Average score of 1.5 or more and less than 2.5 D: Average score of less than 1.5 (hypoallergenic)
A: All people did not feel irritation.
B: 1 or more and 2 or less people felt irritation, but it was an acceptable weak irritation.
C: 1 to 2 people felt irritation, but it was an unacceptably strong irritation.
D: Three or more people felt irritation.

(2) Stability The cleaning composition was placed in a glass bottle and stored at 20 ° C. for 1 month, and then the appearance was visually evaluated according to the following criteria.
A: Transparent.
○: Slightly cloudy.
Δ: Slightly cloudy.
X: A precipitate is formed and separated.

Examples 9-11
A face wash and a whole body cleanser were prepared according to the following formulation. Both are mild and have good foaming properties in all regions where the pH of the water used is 4 to 9 and in all regions where the hardness of the water used is 1 to 30 ° DH. The foam quality was creamy, the rinsing property, the feel of washing was good and the stability was good.

Example 9 (face wash)
(Component) (wt%)
Lauryl phosphate K salt 2.0
(Monolauryl / Dilauryl = 75/25)
Polyoxyethylene (1) lauryl ether phosphate K salt a) 6.0
(Monolauryl / Dilauryl = 75/25)
Lauric acid K salt 10.0
Myristic acid K salt 7.0
Palmitic acid K salt 7.0
Dipropylene glycol 10.0
2-Ethylhexyl glyceryl ether 0.5
Sorbit solution 10.0
Sodium chloride 0.5
Ethylene glycol distearate 2.0
Methylparaben 0.2
Propylparaben 0.1
BHT 0.2
Fragrance 0.05
Purified water balance
Total 100.00
a) Compounds in () indicate the average number of moles of ethylene oxide added, and in the general formulas (1) and (2), k = m = n = 1.

Example 10 (body shampoo)
(Component) (wt%)
Lauryl phosphate K salt 1.3
(Monolauryl / Dilauryl = 75/25)
Polyoxyethylene (1) lauryl ether phosphate K salt a) 3.8
(Monolauryl / Dilauryl = 75/25)
Lauric acid K salt 6.0
Myristic acid K salt 4.5
Palmitic acid K salt 4.5
Dipropylene glycol 0.7
2-Ethylhexyl glyceryl ether 0.3
Lauroyl hydroxysulfobetaine 10.0
Polyoxyethylene sorbitan triisostearate (160EO) 2.0
Glycerin 5.0
N, N-dimethylaminoethyl diethyl methacrylate sulfate / N, N-
4% by weight aqueous solution of dimethylacrylamide / polyethylene glycol dimethacrylate copolymer b) 2.5
Ethylene glycol distearate 2.0
Methylparaben 0.1
Propylparaben 0.2
BHT 0.2
Fragrance 0.05
Purified water balance
Total 100.00
a) () shows the average number of moles of ethylene oxide added, and in the general formulas (1) and (2), k = m = n = 1.
b) Sofcare KG-301W; manufactured by Kao Corporation

Example 11 (body shampoo)
(Component) (wt%)
Lauryl phosphate triethanolamine salt 1.3
(Monolauryl / Dilauryl = 75/25)
Polyoxyethylene (1) lauryl ether phosphate triethanol amine salt a) 3.8
(Monolauryl / Dilauryl = 75/25)
Lauric acid triethanolamine salt 6.0
Myristic acid triethanolamine salt 4.5
Palmitic acid triethanolamine salt 4.5
Dipropylene glycol 0.7
n-octyl glyceryl ether 0.3
Lauroyl hydroxysulfobetaine 10.0
Polyoxyethylene sorbitan triisostearate (160EO) 2.0
Glycerin 5.0
N, N-dimethylaminoethyl diethyl methacrylate sulfate / N, N-
4% by weight aqueous solution of dimethylacrylamide / polyethylene glycol dimethacrylate copolymer b) 2.5
Ethylene glycol distearate 2.0
Methylparaben 0.1
Propylparaben 0.2
BHT 0.2
Fragrance 0.05
Purified water balance
Total 100.00
a) () shows the average number of moles of ethylene oxide added, and in the general formulas (1) and (2), k = m = n = 1.
b) Sofcare KG-301W; manufactured by Kao Corporation

Claims (3)

The following components (A), (B) and (C)
(A) (a ₁ ) a phosphate monoester surfactant represented by the general formula (1)
(A ₂ ) A mixture with the phosphoric acid diester surfactant represented by the general formula (2), the content ratio of which is (a ₁ ) / (a ₂ ) = 90 / 10-50 / 50 phosphate ester surfactant:

(Wherein R ¹ , R ² and R ³ each represent a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, and X ¹ , X ² and Y represent a hydrogen atom, an alkali metal atom , Lucanolamine or ammonium is represented, and the average number of moles added, k, m and n are each 0 to 10);
(B) General formula (3)
R ⁴ -COOM (3)
(Wherein R ⁴ represents a saturated or unsaturated aliphatic hydrocarbon group having 7 to 17 carbon atoms, and M represents a hydrogen atom, an alkali metal atom, an alkanolamine or ammonium)
A higher fatty acid represented by the formula:
(C) one or more glyceryl ethers having a linear or branched alkyl group or alkenyl group having 6 to 12 carbon atoms, and the content ratio of component (A) to component (B) is a component by weight (B) / component (A) = more than 1.5 and less than 10 cleaning composition.   The cleaning composition according to claim 1, comprising 1 to 15% by weight of component (A).   The cleaning composition of Claim 1 or 2 which contains 5-35weight% of a component (B).