GB2226045A

GB2226045A - Liquid detergent compositions

Info

Publication number: GB2226045A
Application number: GB8928095A
Authority: GB
Inventors: Yasushi Maruyama
Original assignee: Lion Corp
Current assignee: Lion Corp
Priority date: 1988-12-19
Filing date: 1989-12-12
Publication date: 1990-06-20
Anticipated expiration: 2009-12-12
Also published as: GB2226045B; GB8928095D0; JPH02166196A

Abstract

A liquid detergent composition comprising (1) an anionic surface-active agent and (2) an amide-betaine type ampholytic surface-active agent can be adjusted to an appropriate viscosity by blending (3) a branched diol with 4 to 12 carbon atoms or a mono- or diol with 4 to 12 carbon atoms having at least one ether bond in its molecule. The composition has an improved foaming ability of creating smooth creamy foams. When used as shampoo, the composition is easy to dispense from the container and to spread over the hair and renders the hair smooth and tangling-free.

Description

Liquid Detergent Compositions This invention relates to a liquid detergent composition, and particularly to one having an increased ability of creating smooth creamy foams.

Current liquid detergent compositions such as shampoo compositions are required to be mild and create creamy smooth foams. Ampholytic surface-active agents are used to this end. Among the ampholytic surface-active agents, amide-betaine type ampnolytic surface-active agents are often used in shampoo compositions because of their less st mulation to the skin, good foaming ability, biodegrad- ability, and high conditioning effect to the cin and hair.

The amide-betaine type surface-active agents, however, are more expensive than anionic surface-active agents and are often blended with the iatter to form a cost-efficient shampoo composton. Since combination of an amidebetaine type surface-active agent with an anionic surfaceactive agent forms a gel, the resuiting shampoo composition becomes so viscous that it is somewhat difficult to dispense from a container upon use or to spread over the hair.

To eliminate these problems of shampoos on use, it was proposed to add a lower alcohol such as ethanol to the shampoo composition. This approach undesirably deteriorates the foaming ability and shelf stability of the shampoo composition.

There is a need for a liquid detergent composition having a good foaming ability and a pleasant feel on use.

According to the present invention, there is provided a liquid detergent composition comprising (1) an anionic surface-active agent, (2) an amide-betaine type ampholytic surface-active agent, and (3) at least one compound selected from branched diols with 4 to 12 carbon atoms and mono- and diols with 4 to 12 carbon atoms having at least one ether bond in their molecule.

A preferred embodiment of the invention may provide a novel and improved liquid detergent composition having an improved foaming ability of creating smooth creamy foams which when used as shampoo, renders hairs smooth to prevent tangling during hair washing and/ or may provide such a liquid detergent composition having a moderate viscosity and presenting a pleasant feel on use.

Blending a branched aliphatic diOl with 4 to 2 carbon atoms or a mono- or diol with 4 to 12 carbon atoms having at least one ether bond in its molecule to a liquid detergent composition comprising an anionic surface-active agent and an amide-betaine type ampholytic surface-active agent, we have discovered that the mono- or diolmay te effectve'n breaking the gel formed by coflining the anionic surface- active agent with the amide-betaine type ampholytic surfaceactive agent, reducing the viscosity of the composItIon to an adequate level of 5,000 centipoise or lower at 2500. The composition thus has an improved foaming ability of creating smooth creamy foams so that when used as shampoo, the composition renders the individual hairs smooth to prevent tangling during hair washing. At the same time, the composition is smooth to spread over the hair and easy to dispense from the container, presenting an overall pleasant feel on use.

DETAILED BESCRIPTION OF T'W. INVENTION The first component of the liquid detergent composition of the invention is an anionic surface-active agent. It may be selected from commonly used numerous anionic surfaceactive agents, preferably from anionic surface-active agents (A) to (D) shown below with better results.

(A) Sulfates of the formula: R-(OR)m-OSO3M ..... (1) In formula (1), R1 is selected from the class consisting of alkyl groups having 8 to 18 carbon atoms and alkyl phenyl groups substituted with an alkyl group having 5 to 15 carbon atoms; R2 is an alkyl group having 2 to 3 carbon atoms; M1 is selected from the class consisting of alkali metals, alkaline earth metals, and alkyl- or hydroxyalkylsubstituted amines and ammoniums wherein the alkyl piety has t, to 8 carbon atoms; and letter m has an average value of 0 to 6.

Illustrative examples of the sulfates of formula (1) include natural lauryl alcohol polyoxyethylene (m=:) sulfate ester, oxo-sythesized C11-C15 aliphatic alcohol polyoxy- ethylene (m=3) sulfate esters, oxo-sytthesized C12-Ci3 aliphatic alcohol oxyethylene sulfate esters, C12-C13 aliphatic alcohol sulfate esters, and derivatives thereof in which the sulfate ester moiety is converted to sodium, potassium or alkanol amine salts of sulfuric acid. Most preferred among them is polyoxyethylene (m=3) lauryl ether sodium sulfate.

(B) Sulfonates of the formula: R3 S03M2 (2) In formula (2), R3 is selected from the class consisting of a-olefins having 12 to 16 carbon atoms, vinylidene type olefins having 12 to 16 carbon atoms, inner olefines having 12 to 16 carbon atoms, hydroxyalkyl groups having i2 to 16 carbon atoms, and linear and branched paraffins having 10 to 18 carbon atoms; and M2 is selected from the class consisting of alkali metals and alkyl- or hydroxyalkyl-substituted amines and ammoniums wherein the alkyl moiety has l to 8 carbon atoms.

Illustrative examples of the sulfonates of formula (2) include α-olefin sulfonates known as AOS salts. The AOS salts are generally obtained by preparing a-olefins having 12 to 16 carbon atoms on average by a wax cracking process or an ethylene polymerization process using a Ziegler catalyst. The a-olefins are then sulfonated with a gaseous anhydrous sulfuric acid in an inert gas diluent while spreading the olefins as a thin film, and neutralized with an alkali metal or alkaline earth metal hydroxide such as sodium hydroxide, followed by hydrolysis.The resulting product is a mixture containing in % by weight, 10 to 45% of hydroxyalkane sulfonates (HOS) (more particularly, 0.5 to 8%, often 1 to 5% of 2HOS, and 5 to 44.5% of 3 or higher HOS), 55 to 80% of alkenyl sulfonates (ANS), and 3 to 15% of aisulfonates (DS).

C, N-acylglutamic acids and salts of the formula:

-ormula (3), R4 is a non-aromatic hydrocarbon group having 9 to 17 carbon atoms; and M3 and M4 are independently selected from the class consisting of an ammonium ion, a C1-8 8 alkanol amine ion, a C1 8 alkyl amine ion, a basic amino acid cation, sodium, potassium, an alkaline earth metal, and hydrogen.

Illustrative examples of the N-acyiglutamic acids and derivatives of formula (3) include N-lauroylglutamic acid, N-myristoylglutamic acid, N-palmitoylglutamic acid, N-acyl.

glutamic acids synthesized from a fat liquid which is obtained by stripping off lower and higher carbon number fractions from coconut oil fatty acids or hardened beef tallow fatty acids, and a mixture of such N-acylglutamic acids, as well as monoethanol amine salts, diethanol amine salts. triethanol amine salts, sodium salts and potassium salts of such N-acylglutamic acids. They may be used in an optically active form or racemic modification.

(D) N-acyl-N-alkylamino acids and salts of the formula:

In formula (4), R5 is a non-aromatic hydrocarbon group having 9 to 17 carbon atoms; R6 is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; M5 is selected from the class consisting of an ammonium ion, a C1.8 alkanol amine ion, a C1.8 alkyl amine ion, a basic amino acid cation, sodium, potassium, an alkaline earth metal, and hydrogen; and letter p is equal to 1 or 2.

Illustrative examples of the N-acyl-N-alkylamino acids and salts of formula (4) include N-lauroyl-N-ethylglycine, N-lauroyl-N-isopropylglycine, N-lauroylsarcosine, N myristoylsarcosine, N-palmityolsarcosine, N-lauroyl-N methyi-p-alanine, N-lauroyl-N-ethyl-ss-alanine, N-myrlstoyl ss-alanine, N-palmitoyl-ss-alani..e, and a mixture thereof as well as monoethanol amine salts, diethanol amine salts, triethanol amine salts, sodium salts and potassium salts thereof.

The ccmpcsition of the invention may contain one or more of the above-mentioned anionic surface-acvive agents The amount of the anionic surface-active agent blended is not particularly limited although it is preferably at least 5% by weight, more preferably at least 10% by weight of the entire composition. A composition containing less than 5% by weight of the anionic surface-active agent would be less foaming. The upper limit is preferably 30% by weight, especially 20% by weight from the standpoint of economy.

The second component of the liquid detergent composition of the invention is an amide-betaine type ampholytic surface-active agent. Preferably it has the general formula:

In formula (I), R is an alkyl or alkenyl group having 9 to 17 carbon atoms, preferably 11 to 13 carbon atoms, for example, a coconut oil fatty acid residue, a palm oil fatty acid residue, and a lauric acid residue. Substituent R may have either a branched or a linear chain, with the linear chain being preferred. Letter x is an integer of 2 to 4, preferably equal to 3; y and z are independently 0 or integers of 1 to 3, preferably both y and z are equal to 0.

The preferred amide-betaine type ampholytic surfaceactive agents have the general formula:

therein R' is an alkyl. or alkenyl group having 11 to 13 car on atoms. Most preferred is coconut oil fatty acid amide propyl betaine.

The amide-betaine type ampholytic surface-act ve agent may be readily synthesized, for example, by a process involving the following scheme wherein R and x are as defined above.

The composition of the invention may contain one or more of the above-mentioned amide-betaine type ampholytic surface-active agents. The amount of the amide-betaine type ampholytic surface-active agent blended is not particularly imited although it is preferably 1 to 15% by weight, more preferably 3 to 10% by weight of the entire composition. A composition containing less than 1% by weight of the amidebetaine type ampholytic surface-active agent would have a too low foaming ability to render hairs smooth and tanglingfree during shampooing. The upper limit of 15% by weight largely depends on economy.

The third component of the liquid detergent composition of the invention is a mono- or diol. It is selected from the group consisting of branched aliphatic diols having 4 to 12 carbon atoms, preferably 5 to 8 carbon atoms and aliphatic mono- and diols having 4 to 12 carbon atoms, preferably 5 to 8 carbon atoms and containing at least one ether bond in their molecule. Illustrative examples of the branched diols include 3-methylbutane-1,3-diol, 2-methylpentane-2,4-diol, 2,2-dimethylpropane-1,3-diol, 2,5dimethylhexane-2,5-diol, 2-ethylhexane-1,3-diol, and 2,2,4trimethylpentane-1,3-diol. Illustrative examples of the mono- and diols having an ether bond include dipropylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and diethylene glycol monoethyl ether.

These mcno- and diols may be used alone or in admixture of two or more. The amount of the mono- or diol blended is not partcularly limited and is generally suc an effective amount that the composition may have an appropriate viscosity for the intended application. The amount of the mono- or diol blended is preferably 0.1 to 10% by weight, more preferably 1 to 7% by weight of the entire composition.

The liquid detergent composition of the invention is preferably adjusted to a viscosity of up to 5,000 centipoise at 250C for practical reasons including ease of dispensing from a container on use and ease of spreading over the hair.

The liquid detergent compositions of the invention may find application as shampoo compositions, dish washing detergents, liquid skin cleansers and the like. Most often, the liquìd-detergent compositions of the invention contain, in addition to the essential components1 any suitable additives depending on their intended purpose and applica tion. For example, there may be additionally blended various cationic surface-active agents, nonionic surfaceactive agents, and ampholytic surface-active agents other than the amide-betaine type defined herein, as well as thickeners, UV absorbers, antiseptic agents, emulsifiers, antidandruff agents, antioxidants, tonic agents, perfumes, and other additives commonly used in conventional products.

These additives, each alone or in admixture, may be blended in effective amounts. Purified water is typically used as the solvent for making a liquid composition.

The liquid detergent composition of the present invention has an improved foaming ability of creating smooth creamy foams so that when used as shampoo, the composition renders individual hairs smooth and tangling-free during flair washing. At the same time, the composition has an appropriate viscosity so that it is smooth to spread over te hair and easy to dispense from the container, presenting an overall pleasant feel on use.

EXAMPLE Examples of the present invention are given below by wa of illustration and not by way of limitation. All percents are by weight unless otherwise statea.

First, it is described how to evaluate shampoo co-..positions.

E:affi:uation (1) Shampoo performance (foaming ability) (1-1) Foaming A panel consisting of 10 women and 10 men washed their hair with a shampoo composition, carrying out an organoleptic evaluation on foamability according to the following ratings.

Evaluation ratings O: full foaming, easy shampooing # : moderate foaming, less easy shampooing X: poor foaming, difficult shampooing (1-2) Smoothness and non-tangling during shampooing The same panel as above washed their hair with a shampoo composition, carrying out an organoleptic evaluation how the hair was smooth and tangling-free during washing according to the following ratings.

Evaluation ratings 0: smooth, tangling-free A: some tangling X: not smooth, tangling (2) Use (2-1) Spread to the hair The same panel as above washed their hair with a shampoo composition, carrying out an organoletic evaluation how easily the composition could be spread over the hair during washing according to the following ratings.

Evaluation ratings 0: easy spreading A: less easy spreading X: difficult spreading (2-2) Container outflow A commercial liquid shampoo bottle was filled with a shampoo composition. The same panel as above carried out an organoleptic evaluation how easily the composition could be dispensed from the bottle according to the following ratings. At the same time, the shampoo composition was measured for viscosity (Brookfield viscosity in centipoisej at 250C.

Evaluation ratings 0: easy dispensing viscosity: up to 5,000 cp at 250C A: less easy dispensing viscosity: 5,000-10,000 cp at 250C X: difficult dispensing viscosity: more than 10,000 cp at 250C Examples 1-6 and Comparative Examples 1-2 Shampoo compositions having formulations shown in Table 1 were prepared and evaluated by the above-described procedures.

The results are shown in Table 1.

Table 1 Examples Composition (% by weight) CE1 CE2 E1 E2 E3 E4 E5 E6 Polyoxyethylene lauryl ether sodium sulfate (average E.O. 3 mol) 15 15 15 15 15 15 8 Sodium α-olefin (C14) sulfonate - - - - - - 6 12 Coconut fatty acid amide propyl betaine 5 5 5 5 5 5 5 2-methylpentane-2,4-diol 4 - - - 3.5 3.5 3-methylbutane-1,3-diol - - 4 - - - Ethylene glycol monoethyl ether - - 4 - - Dipropylene glycol - - - - 4 - Purified water balance Total Evaluation 100 100 100 100 100 100 100 Foaming O O O O O O O Smoothness & non-tangling X O O O O O O Spread O X O O O O O Dispensing O X O O O O O As is evident from Table 1, the shampoo composition having only the anionic surface-active agent blended (Comparative Example 1) was insufficient to render the hair smooth and tangling-free during washing.The shampoo composition having both the anionic surface-active agent and amide-betaine type ampholytic surface-active agent blended (Comparative Example 2) was effective in rendering the hair smooth and tangling-free during washing, but too viscous to spread over the hair or to dispense from the container.

In contrast, the shampoo compositions having the anionic surface-active agent, amide-betaine type ampholytic surtace-active agent, and mono- or diol blended (Examples 16) were well foamable to create smooth creamy foams, effective to render the hair smooth and tangling-free during washing, and easy to spread over the hair and to dispense from the container, presenting an overall pleasant feel on se.

Equivalent results were obtained when the anionic surface-active agent was replaced by any of the previously enw-.erated agents, or example, polyoxyethylene lauryl ether ethanol amine salt, sodium salt of N-laurylglutamic acids an sodium N-lauroylsarcosine and when the mono- or diol was replaced by any of the previously enumerated mono- ana tic s, for example, 2,2-dimethylpropane-1,3-diol, 2-ethylhexyl-1,3-diol, ethylene glycol monomethyl ether, and aiethylene glycol monoethyl ether.

Examples 7-8 Shampoo compositions having formulations shown in Table 2 were prepared and evaluated by the above-described procedures.

The results are shown in Table 2.

Table 2 examples Composition (% bv weiaht) Polyoxyethylene lauryl ether sodium sulfate (average E.O. 3 mol) 15 Sodium a-olefin sulfonate - 6 Coconut fatty acid amide propyl betaine 5 4 2-methylpentane-2,4-diol 4 3 Cononut fatty acid diethanol amide 3 4 Ethylene glycol distearate Anhydrous sodium sulfate 1 1 Citric acid C.2 0.3 Methyl p-hydroxybenzoate 0.2 Cationic cellulose : :.0 - Perfume 3.4 0.4 Dye 0.0003 0.001 Purified water bal. bal Total 100 100 Evaluation Foaming Smoothness & mon-tangling 0 0 ^ Spread C Dispensing O 0 As is evident from Table 2, the shampoo compositions of the present invention maintained a high foaming ability and a pleasant feel on use when various additives including ethylene glycol distearate, anhydrous sodium sulfate, and citric acid were blended with the essential components.

Although some preferred embodiments have been described, many modifications and variations may be made thereto in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention =nay be practiced otherwise than as specifically described.

Claims

CLAIMS:

1. A liquid detergent composition comprising an anionic surface-active agent, an amide-betaine type ampholytic surface-active agent, and at least one compound selected from branched aliphatic diols with 4 to 12 carbon atoms and mono- and diols with 4 to 12 carbon atoms having at least one ether bond in their molecule.

2. The composition of claim 1 comprising at least 5% by weight of the anionic surface-active agent.

3. The composition of claim 1 or 2 comprising ; to 15% by weight of the amide-betaine type ampholytic surface-active agent.

4. The composition of claim :, 2 or 3 comprising 0.1 to 10% by weight of the mono- or diol compound.

5. The composition of any preceding claim wherein said anlonic surface-active agent is selected from (A) sulfates of the formua: R-(OR)m-OSO3M ..... (1) wherein R1 is selected from alkyl groups having 8 to 18 carbon atoms and alkyl phenyl groups substituted with an alkyl group having 5 to 15 carbon atoms; R2 is an alkyl group having 2 to 3 carbon atoms;M1 is selected from the class consisting of alkali metals, alkaline earth metals, and alkyl- or hydroxyalkylsubstituted amines and ammoniums wherein the alkyl moiety has 1 to 8 carbon atoms; and letter m has an average value of 0 to 6 ; (B) sulfonates of the formula: R3SO3M2 (2) wherein R is selected from α- olefins having 12 to 16 carbon atoms, vinylidene type olefins having 12 to 16 carbon atoms, inner olefines having i2 to 16 carbon atoms, hydroxyalkyl groups having 12 to 16 carbon atoms, and linear and branched paraffins having 10 to 18 carbon atoms; and M2 is selected from alkali metals and alkyl- or hydroxyalkyl-substituted amines and ammoniums wherein the alkyl moiety has 1 to 8 carbon atoms ; (C) N-acylglutamlc acids and salts of the formula: M COC-CH2-CH2-CH-COOM4 ...... (3) R4CO-NH wherein R4 is a non-aromatic hydrocarbon group waving 9 to @ carbon atoms; and M3 and M4 are independent y selected an an ammonium ion, a Cl-s alkanol amine ion, a C1-8 alkyl amine ion, a basic amino acid oaticn, sodium, potassium, an alkaline earth metal, and rcgen; and (D) N-acyl-N-alkylamino acids and salts of the formula : R6 R5-CO-N-(CH2)p-COCM5 ...... (4) wherein R5 is a non-aromatic hydrocarbon group having 9 to 7 carbon atoms; R6 is a hydrogen atom or a linear or ranched alkyl group having 1 to 4 carbon atoms : M5 is selected from an ammonium ion, a C1-8 alkanol amine ion, a C1-8 alkyl amine ion, a basic amino acid cation, sodium, potassium, an alkaline earth metal, and hydrogen; and letter p is equal to 1 or 2.

6. The composition of any preceding claim wherein said amide-hetaine type ampholytic surface-active agent has the general

wherein R is an alkyl or alkenyl group having 9 to 17 carbon atoms, letter x is an integer of 2 to 4, and y and z are independently 0 or integers of 1 to 3.

7. The composition of any of claims 1 - 5 wherein said amide-betaine type ampholytic surface-active agent has the general formula:

wherein R' is an alkyl or alkenyi group having carbon atoms.

8. he composition of any preceding claim wherein said branched diol with 4 to 12 carbon atoms is selected from 3-methylbutane-1,3-diol, 2-methylpentane-2,4diol, 2,2-dimethylpropane-1,3-diol, 2,5-dimethylhexane-2,5diol, 2-ethylhexane-1,3-diol, and 2,2,4-trimethylpentane- 1,3-diol.

9. The composition of any preceding claim wherein said mone- or diol with 4 to 12 carbon atoms having at east one ether bond is selected from dipropylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and diethylene glycol monoethyl ether.