JPH0333197A - Detergent compound - Google Patents

Abstract

PURPOSE: To obtain a detergent composition useful, for example, in washing textiles, shampooing, and washing tableware manually by incorporating a specified active detergent composition and water to form a stable composition in the form of a liquid or a gel.

CONSTITUTION: This stable composition in the form of a liquid or gel is composed of an active detergent mixture in an amount of 10 to 80 wt.% and water, the active detergent mixture being made up of (A) an anionic detergent active material, with preferably at least major part thereof being selected from among secondary alkanesulfonates, aliphatic acyl ester sulfonates, sulfosuccinic acid dialkyl esters, α-olefinsulfonates, primary alkylsulfonates, and alkylbenzenesulfonates, and mixtures thereof excepting alkyl ether sulfates, (B) an alkyl ether sulfate having an ethoxylation average value of 1 to 5, (C) a betaine and/or amine oxide, and (D) a water-soluble nonionic detergent active material in an amount of 35 to 50 wt.% of the total of the active detergent mixture with the weight ratio of A to B being 2:1 to 1:10 and the molar ratio of A to C being 3:1 to 1:3.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid detergent compositions which are particularly suitable for, but not limited to, textile washing, shampooing and manual dishwashing applications, especially in hard and soft water.

As used herein, the term "tableware" refers to food preparation or eating that requires cleaning to remove trace amounts of food or other uneaten food, fats, proteins, starches, gums, colorants, oils, and organic matter. means kitchen utensils that are

Light duty liquid detergent compositions suitable for use in dishwashing are well known. Many of the compositions currently on the market are based on sulfonate-type anionic detergents, especially alkylbenzene sulfonates, in combination with alkyl polyethoxy sulfates (alkyl ether sulfates). Sulfonate type anionic detergents are generally mainstream.

It has been found that the use of conventional dishwashing liquids based on alkylbenzene sulfonates/alkyl ether sulfates or based on alkyl sulfates/alkyl ether sulfates irritates the hands of the user. Hypoallergenicity in dishwashing liquids is therefore considered a desirable quality, and many specially formulated commercial products claim this quality.

Denaturation of proteins by surfactants is considered to be one of the main causes of skin irritation and skin roughness induced by surfactants (G 1mohv*, etc., JOAC351484-48).
9, December 1975). The degree of denaturation of proteins by surfactants depends on the type of surfactant and its concentration.

Currently available dishwashing compositions that have little interaction with proteins and are therefore considered to be relatively non-irritating are:
Based on a combination of ether sulfate and amine oxide. For example, US-A-3928249 (Pr.
See (Ocler & Gamble). Betaine can also be used instead of amine oxide. For example, U.S.
See No. 4554098 (colgtle).

However, compositions of this type (particularly when amine oxides are used) are not only expensive due to the high cost of the active ingredient, but also require the use of xylene sulfonate and/or ethanol to produce a stable and acceptable viscosity liquid. It is expensive because it requires large quantities of expensive hydrotropic agents.

EP No. 0232153 (Unilevet) Tel.
Detergent compositions are disclosed that are based on a mixture of anionic and nonionic surfactants, including a suds promoter, wherein at least some of the anionic surfactants are alkyl ether sulfates.

It is preferred to include a large amount of nonionic surfactant to produce a hypoallergenic system. This is because such surfactants are inert to skin proteins and compositions containing nonionic surfactants require less expensive hydrotropic agents.

It has also been shown that nonionic surfactants have the ability to effectively remove greasy stains, especially those often found on tableware. However, nonionic surfactants have low foaming properties and generate foam only unstablely.

GB 2165855 (colBle) discloses a mild, light liquid detergent based on nonionic surfactants, in which the nonionic components account for more than 50% by weight of the total detergent content. However, for the reasons mentioned above, such nonionic surfactant-rich compositions may suffer from foaming problems.

The above-mentioned US Pat. No. 4,554,098 discloses low-irritation dishwashing compositions based on alkyl ether sulfates containing an average of 5 to 12 moles of ethylene oxide in the molecule. Ether sulfate is not easily available commercially. Also, the amount of dioxane in the raw material ether sulfate is thought to increase as the EO content in the ether sulfate increases. Preference is given to using ether sulfates containing EO.

There is therefore a need to develop more cost-effective, hypoallergenic dishwashing compositions based on relatively inexpensive detergent raw materials and requiring relatively small amounts of expensive hydrotropes. .

The present invention is prepared by carefully selecting the active ingredients, in particular limiting the presence of the main anionic detergent actives, and containing specific amounts of alkyl ether sulfates, suds promoters and non-ionic detergent actives. It is based on the recognition that it is possible to obtain a cost-effective, hypoallergenic liquid dishwashing composition with satisfactory performance.

First, the present invention provides a stable detergent composition in liquid or gel form containing 10 to 80% by weight of an active detergent mixture and also water, the active detergent mixture comprising (a) an alkyl ether sulfate; anionic detergent active materials other than; (b) alkyl ether sulfates with an average ethoxylation value of 1 to 5 (the weight ratio of components (a) and (b) is 2);
:1~1 :10. Preferably 2:1 or 1.5:1
~1:3, more preferably 2:1 to 1:2); (c) betaine and/or amine oxide (component (a)
The molar ratio of and (c) is 3:1 to 1:3, more preferably 2
:1 to 1:2; and (d) 35% of the active detergent mixture.
more than 50% by weight and less than 50% by weight of a water-soluble non-ionic detergent active material.

For reasons of cost efficiency and material availability, the component (-
at least a majority of 11, a secondary alkanesulfonate;
Selected from alkylbenzene sulfonate, primary alkyl sulfate, fatty acid ester sulfonate, sulfosuccinic acid dialkyl ester salt, and 2-α-olefin sulfonate.

The compositions of the present invention can show similar good performance in detergency tests as conventional compositions containing alkylbenzene sulfonates, but are significantly less irritating.

By replacing most of the nonionic detergent with an ether sulfate containing less than 5 EO, the hypoallergenicity of the composition based on the nonionic detergent base can be completely maintained, while the foaming performance can be significantly improved. A mixture of asymmetric sulfosuccinic acid dialkyl ester salts is included.

Suitable α-olefin sulfonates are generally 12-16
carbon atoms.

An example of such a material is Lipotsn 44G.
nCorporsion, a C14α-olefin sulfonate made in Japan.

A suitable fatty acid ester sulfonate has the formula:

R1-CH-co2 R2 SO,X (wherein RI is linear or branched C8-CI6 alkyl,
R2 is linear or branched C3-C4 alkyl, X is a solubilizing cation, and RI is preferably CIO""
'CI2 and R2 is preferably butyl) Component (a) of the active detergent mixture is used in the liquid composition.
Other detergent active materials on the side may also be included, such as alkyl glyceryl ether sulfonates or alkyl sarcosinate salts. The amount is preferably less than half the amount of component (a), more preferably one-fourth or less.

The second essential component (b) of the active detergent mixture is an alkyl ether sulfate (sometimes called alcohol ether sulfate or alkyl polyethoxy sulfate) having at least one ethylene oxide residue per molecule. Usually, the general formula % formula % (wherein R1 is a primary, -class or secondary C10'' CI8 alkyl group, X is a solubilizing cation, and the average degree of ethoxylation n is 1 to 5, preferably An alkyl ether sulfate which is a mixture of materials with R of 3 to 4 is incorporated into the composition. Particularly preferred values of R are 3 and 4.
3 is preferably a CIO-CI6 alkyl group. Since for a given alkyl ether sulfate there are materials with different degrees of ethoxylation and some non-ethoxylated materials, the value of n represents the average. Non-ethoxylated materials are, of course, alkyl sulphate salts, which correspond to component (a).

The amount of alkyl sulfate salt in the alkyl ether sulfate depends on the average degree of ethoxylation n. n is 3
, the alkyl sulfate salt typically constitutes 15 to 20% of the mixture, and less than the above range when n is on four sides. If the proportion of the alkyl sulfate salt is low, the presence of the alkyl sulfate salt can be ignored1, but the alkyl sulfate salt is involved in component (1).

When the average degree of ethoxylation is 2, the alkyl sulfate salt typically constitutes 30% of the mixture provided as "alkyl ether sulfate". Such mixtures can provide both component (b) and component (a), in which case component (a) consists entirely of the alkyl sulfate salt.

It has been found that alkyl ether sulfates with an average degree of ethoxylation of less than 1.5 cannot be used. Unless the alkyl sulfate salt in the alkyl ether sulfate accounts for most or all of component (a), the alkyl ether sulfate is a material having an average of at least 2 to 2.5 ethylene oxide residues per molecule. It is preferable that

Alkyl ether sulfates contain molecules with a different number of ethylene oxide residues in a statistical distribution. For alkyl ether sulfates with an average degree of ethoxylation of 1.5 sides, the proportion of molecules with only one ethylene oxide residue is also greater than the proportion with two ethylene oxide residues ( 2) having ethylene oxide residues is not substantially large. This feature is therefore an important property of component (b). If the average degree of ethoxylation is on two sides, as is the preferred case, the proportion of molecules with one ethylene oxide residue is equal to the proportion with two ethylene oxide residues and the proportion with ethylene oxide residues on that side. will be smaller than the proportion.

With the exception of alkyl sulfate salts, the preferred alkyl ether sulfates of component (b) are mixtures of compounds of the formula %, where n is a positive integer, with the proviso that the average EO value is less than 5. It is.

Examples of preferred alkyl ether sulfates for use in the present invention have a degree of ethoxylation (n) of 3.
D+b1nol (trademark) 23-3 manufactured by Ell and an equivalent material having a degree of ethoxylation of 4. These materials are based on CI2-Cl5 (50% each) primary alcohols (approximately 75% linear, 25% 2-methyl branched). Another preferred material is Cbia+ict A
Battle! Litl™ 123 is a branched primary alcohol with a degree of ethoxylation of 3 to 4 and an alkyl chain length distribution similar to D++btncl 23. Empi, manufactured by Brightj SND Wilson and based on intermediate coconut alkyl groups, with a degree of ethoxylation of 4
c.

MD (trademark) is also preferred.

A suitable example of a secondary alcohol ether sulfate is U
aioa Cgtbide Tergilol 15/
Alcohol-derived materials such as S/3™ (this material is not currently commercially available). In the general manufacturing method of secondary alkyl ether sulfate,
Very small amounts of alkyl sulfate salts will be present in the product.

It is desirable that component (b) constitutes at least 12% of the active detergent mixture, preferably at least 20 or 30%. Preferably it constitutes no more than 40% of the active detergent mixture. However, if component (b) is substantially or completely associated with component (a), component (bl) may account for up to 50% of the mixture.

The solubilizing cation of the anionic detergent active material of components (a) and (b), designated as X in the above formula, may be any that provides the desired solubility of the anionic material. Monovalent cations such as alkali metal ions, ammonium and substituted ammonium ions are typical, although divalent ions can also be used which provide satisfactory solubility. In particular, magnesium ions can be present to improve water softening performance and can be incorporated as anionic active material magnesium salts or inorganic magnesium salts or in hydrotropic systems.

Component (c) is betaine, amine oxide or a mixture thereof. For economy and therefore cost efficiency, these
In particular, it is preferable to avoid using large amounts of amine oxide. In that case the amount of amine oxide is 10% of the active detergent mixture.
It is preferably less than % by weight. Preferably the amount of betaine is less than 30% by weight of the mixture. Preferably the total amount of amine oxide and betaine is less than 30% by weight of the active detergent mixture, more preferably less than 15% or 1% by weight of the active detergent mixture.
It is 0% by weight or less. Preferably, betaine is used alone.

A suitable betaine has the formula: R6 RN　”　　　C) 12　　CO27 Simple betaine and formula: %formula% Contains amidobetaine.

In both formulas, R is a straight chain or branched chain C8-CI1! It is an alkyl group. lauryl group or middle coconut
caIcoconut) can be an alkyl group.

R6 or R2 is each C0~C, alkyl or C1~
C, hydroxyalkyl. Examples of sulfobetaines are -CH,2CO2- (cHz) i 803 or H -CH2-CH2R3So.

The above formula is replaced by .

A suitable simple betaine is Albright & Wils
It is Empigen BB made by on. That is, in the above formula, R is CI2 to CI4 alkyl derived from coconut, and R6 and R7 are both methyl.

Gold+m1dl with complete coconut alkyl group
TeHo L7 manufactured by TeHo L7 is also preferred.

Suitable amine oxides have the formula %, where R is a straight or branched C8-C18 alkyl group, and R6 and R2 are each C1-C, alkyl, or C,-C,hydroxyalkyl. ). A suitable amine oxide is lb+light & Wilsoa
The product is E+apigen 08. In this case R is intermediate coconut alkyl and R6 and R7 are both methyl.

Component (d) is a water-soluble non-ionic detergent active material on one side;
For example, materials commonly used in detergent compositions. Component (e
The betaine and amine oxide of ) do not form part of the component (dl).

Component (d) is preferably a polyalkoxylated material, especially an ethoxylated nonionic detergent active material on one side. In this case, the material is 12.0 to 16,0
It is desirable to have an HLB value of .

Component (d) may be a polyethoxylated aliphatic alcohol with an alkyl chain length of C5 to C18, preferably Ca-Cl6, and an average degree of ethoxylation of 4 to 14. Suitable nonionic detergents have the general formula %, where R is an alkyl group, preferably 8 to 8 carbon atoms.
18 pieces, more preferably 8 to 16 pieces, even more preferably 9 pieces
A straight-chain alkyl group having ~12 carbon atoms, with an average degree of ethoxylation m of 5 to 14, more preferably 6 to 1
2) highly foaming ethoxylated short chain alcohols. Particularly preferred non-ionic detergents are those in which R is C5-C
11 (mainly straight chain) and m is 8 Do made by 5hell
br++ol 91-8 or Lirlet C,-
It is 10EO.

Other suitable materials have R of 8 to 18, preferably 11 to 1.
secondary alkyl having 5 carbon atoms, m is 5
-14, preferably 6-12.

For example, TeBNol manufactured by Union Cxtbide
15/S/12 (Currently not commercially available) or 5o
It is a material of the llznol A series (manufactured by Nippon Shokubai).

It is preferred to strip the polyethoxylated alcohol mixture to reduce odor in the composition.

Component (d) is a compound of the general formula (wherein R is a straight-chain or branched alkyl having 7 to 18 carbon atoms, R8 is an ethyleneoxy or propyleneoxy group, Y is hydrogen or -R, (cH ,C)!2(a)H.

Ethoxylated alkanolamides in which p is on one side, q is on one side or 0, and R can be lauryl or coconut alkyl) may also be used. Examples of ethoxylated alkanolamides are 5lcpsn Chemictl Co.
A+aidox L5 and ^m1doxC made by ap*B
It is 5.

As component (a) it is also possible to use ethoxylated alkylphenols as well as ethoxylated fatty acids, ie polyethylene glycol esters of fatty acids.

Component (d) constitutes at least 35%, but less than 50% by weight of the active detergent mixture.

Components optionally present in the active detergent mixture of the compositions of the invention include mono- or dialkanolamides on one side, preferably C8 to C,8, more preferably CIG"'
CI8 carboxylic acid mono or di(a)2-C1) alkanolamide.

These have the general formulas R4-Co-NHR and R2
OON (Rs)' 2, in which R4 is C7-C
I? It is an aliphatic group, preferably linear and saturated, and Rs is a hydroxyethyl or hydroxypropyl group. R5 is preferably a 2-hydroxyethyl group.

This type of material is generally manufactured from fatty acids of natural origin,
It contains molecules with R4 groups of various chain lengths; for example, coconut ethanolamide contains primarily CI2 and C,
Consists of 4 materials, arbitrary amounts of C,, CI. , CI6, C
Also includes I8 material. Preferred are ethanolamides derived from so-called intermediate coconut fatty acids, most preferably from lauric acid.

Mono- and di-ethanolamides from 5% of the detergent mixture
It can account for 20%.

In addition to the active detergent mixture and water, the liquid detergent compositions of the present invention will generally need to contain on one side a hydrodovey agent. The hydrodovey agent is a material that is present in the composition to adjust solubility, viscosity, clarity, and stability, but does not itself effectively contribute to the performance of the product. Examples of hydrotropic agents include lower aliphatic alcohols, especially ethanol;
Urea: Includes toluene and lower alkylbenzene sulfonates such as sodium xylene sulfonate and mixtures thereof. Preferred are alcohols, neureas and xylene sulfonates. Since hydrotropes are expensive and occupy a part of the composition without contributing to the performance of the composition,
It is desirable to use as little as possible.

For example, the use of the amine oxides described above requires large amounts of alcohol as a hydrotrope. For this reason and because of their high cost, the use of significant amounts of tertiary amine oxides is preferably avoided in the present invention.

In a preferred form of the invention, the weight of the hydrotropic agent in the composition is less than 12% by weight of the active detergent mixture.

The compositions of the invention may also contain conventional minor ingredients such as perfumes, dyes, preservatives and fungicides.

The stable liquid detergent compositions of the invention can be used in all conventional detergent fields, especially those where foaming is advantageous, such as textile laundry products, general household and industrial cleaning compositions, carpet shampoos, car wash products, general laundry supplies, shampoo,
It can be used in foaming bath products, especially when washing dishes by hand.

The invention is further illustrated by the following non-limiting examples.

Examples Examples 1-4 The foaming performance and hypoallergenicity of various aqueous compositions were compared. Composition of the invention! and ■ were compared with a comparative composition (A) containing more than 50% by weight of non-ionic detergent active material.

Foaming performance is Fe1ls l1nd 5eilc+
Modification 5c based on the principle described in 1951.53° 207
Evaluated by blscbt@r-Dierkes test. Concentration f in water of 24 H (French hardness) at 45℃
Aqueous solution 1 of each test material containing 1.64% active detergent
00ml was rapidly vibrated inside a graduated cylinder using a vertically vibrating perforated disk. After the initial occurrence of bubbles,
Dirt (11.2 g each of 9.5 parts of commercial cooking fat, 0.25 parts of oleic acid, 0.25 parts of stearic acid, and 1 part of wheat starch in 120 parts of water at 15 second intervals until foaming disappears) (10 seconds of gentle agitation and 5 seconds of rest). Results were recorded as number of stain increments (NSI score). Spotting of 6 or less is generally considered insignificant. Shown as average.

Several in vitro and in vivo methods have been reported to assess the protein denaturing efficacy of surfactants and mixtures thereof (Miyr!ov* et al., Ill' J Cot Sci.
6°33-46.1984 and references cited therein) One method of this type involves the use of skin-derived (
ProlleF et al., Int J Cot Sci 6
．． 263-273.1984) or wheat malt-derived (T
1st prize to Illll, Anll Bioche+a 66
489-498.1975) and the detergent.

The in vivo irritating properties of the composition are determined by Flex (I I e
x) Can be evaluated using a wash test. In this test, a clean product was rubbed on the panelist's forearm and then rinsed. This method was repeated four times a day for five days, and the degree of erythema that occurred was evaluated by an experienced assessor.

A comparison of the results of the Wheat Germ Acid Phosphatase (WGAP) test and the Flex Wash test revealed that under the test conditions
Compositions that produce less than 40% enzyme inhibition are substantially hypoallergenic; the difference in hypoallergenicity between products that produce less than 40% inhibition was shown to be no detectable difference in the flex wash test. . Enzyme tests are so sensitive that in real life situations there is a threshold for protein denaturation, below which it is impossible to distinguish between all active ingredients and the irritant nature of the product. The results of the WGAP test are expressed as percent inhibition (i.e. 10
0% - percentage of residual activity). Water caused no inhibition, ie 100% residual activity.

Lirle+ 123-3S' Li11el 123-48' DobInol 23- A' Lhlel 123- S' Lixlel C, 1OEO' Empigen BB' Empilra LME' Plunger test (a), 04% effective detergent) 24 cloves H 5 cloves H W.G.A.P. % Inhibition Monoalkyl Ether Sulfate Monoprimary Alkyl Sulfate Salt - Nonionic Detergent 4-Betaine 5-Ethanolamide The Examples show that Compositions I and 1 produce greater foaming performance than A. As mentioned above, although the WGAP inhibition percentage of A is smaller than that of A and A, there is no difference in hypoallergenicity. Therefore, the composition of the present invention combines hypoallergenicity and performance.

Hirohito singer Unilever Namrose ・Pen Note Sharp

Claims (8)

[Claims] (1) A liquid or gel stable detergent composition containing from 10 to 80% by weight of an active detergent mixture and also containing water, wherein the active detergent mixture is (a) an anionic detergent other than an alkyl ether sulfate; an active material; (b) an alkyl ether sulfate with an ethoxylation average value of 1 to 5; (c) a betaine and/or an amine oxide; and (d)
consisting of water-soluble non-ionic detergent active materials in an amount of greater than 35% and less than 50% by weight of the active detergent mixture;
A detergent composition characterized in that the weight ratio of a) and (b) is 2:1 to 1:10, and the molar ratio of components (a) and (c) is 3:1 to 1:3. (2) At least the majority of the component (a) is a secondary alkanesulfonate, fatty acyl ester sulfonate, sulfosuccinic acid dialkyl ester salt, α-olefin sulfonate, or primary alkyl sulfate ester salt. 2. Composition according to claim 1, characterized in that it is selected from: (3) The composition according to claim 1 or 2, characterized in that the weight ratio of components (a) and (b) is 2:1 to 1:2. 4. Composition according to claim 1, characterized in that the total amount of amine oxide and betaine is not more than 20% by weight of the active detergent mixture. (5) The composition according to any one of claims 1 to 4, wherein component (c) is substantially free of amine oxide. (6) Alkyl ether sulfate (b) has the general formula:
R-(OCH_2CH_2)_n-OSO_3X (wherein R is a C_1_0 to C_1_8 alkyl group, x is a solubilizing cation, and the average degree of ethoxylation n is 2 to 12
Composition according to any one of claims 1 to 5, characterized in that it is provided by a mixture of materials. (7) The alkyl ether sulfate (b) is a group in which the alkyl group R is present in less than 20% of the material on the alkyl chain length C_1_4 side, and the average degree of ethoxylation n is 3.
Composition according to any one of claims 1 to 6, characterized in that it is provided by a primary alkyl ether sulfate of ~8. (8) Composition according to any one of claims 1 to 7, characterized in that the nonionic detergent active material (d) is a material with a chain length of less than C_1_2.