JPH0726115B2 - Detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid detergent compositions particularly suitable for, but not limited to, textile laundry, shampoo and, above all, applications for manual dishwashing in hard and soft water.

As used herein, the term "tableware" refers to cooking or eating where trace amounts of food or other leftover food, fat, protein, starch, gums, colorants, oils and organic burns are required to be washed away. Means kitchen utensils.

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

It has been found that the use of conventional dishwashing solutions based on alkylbenzene sulphonate / alkyl ether sulphate or based on alkyl sulphate ester / alkyl ether sulphate can be rough to the user. The mildness of the dishwashing liquid is therefore considered to be a desirable quality, and many specially formulated commercial products claim this quality.

Deterioration of proteins by surfactants is considered to be one of the major causes of surfactant-induced skin irritation and rough skin (G Imokawa et al., JOACS 52 , 484-489, December 1975).
The degree of protein denaturation by a surfactant depends on the type and concentration of the surfactant.

Currently marketed dishwashing compositions that have little interaction with proteins and are therefore considered to be relatively mild are:
Based on a combination of ether sulfates and amine oxides. For example, US-A-3 928 249 (Procter &
See Gamble). Betaine can also be used instead of amine oxide. See, for example, US 4 554 098 (Colgate). However, compositions of this type (especially when using amine oxides) not only benefit from the high cost of the active ingredient, but also of xylene sulfonate and / or ethanol to produce liquids that are stable and have an acceptable viscosity. It is expensive because it requires a large amount of such expensive hydrotropic agent.

EP 0232153 (Unilever) discloses a detergent composition based on a mixture of anionic and nonionic surfactants containing a suds booster, wherein at least some of the anionic surfactants are alkyl ether sulphates. Has been done.

It is preferable to include a large amount of nonionic surfactant in order to produce a mild system. This is because such surfactants are inactive against skin proteins and nonionic surfactant containing compositions require lesser amounts of expensive hydrotropes.

It has also been shown that nonionic surfactants have the ability to adequately remove greasy soil, which is often found especially in dishes. However, the nonionic surfactant has a low foaming property and unstablely foams.

GB 2 165 855 (Colgate) discloses a non-ionic surfactant-based mild liquid wash that has non-ionic ingredients in excess of 50% by weight of the total detergent content. However, for the reasons mentioned above, such nonionic surfactant-rich compositions may have a foaming drawback.

The above-mentioned US 4 554 098 (Colgate) has an average of 5 to 1 in the molecule.
Disclosed is a hypoallergenic dishwashing composition based on an alkyl ether sulphate containing 2 moles of ethylene oxide. However, this type of ether sulfate is not easily available as a commercial product. Further, it is considered that the amount of dioxane in the raw material ether sulfate increases as the EO content in the ether sulfate increases. Therefore, the use of widely used and commonly available ether sulfates containing less than 5 EO is preferred.

Therefore, there is a need to develop a cost-effective hypoallergenic dishwashing composition that is based on relatively inexpensive detergent raw materials and requires only a small proportion of expensive hydrotropes. .

The present invention provides for the careful selection of the active ingredients, in particular the limitation of the main anionic detergent active materials present, and the preparation with specific amounts of alkyl ether sulphates, foam boosters and nonionic detergent active materials. It is based on the recognition that a cost-effective and hypoallergenic liquid dishwashing composition with satisfactory performance can be obtained.

First, the present invention provides a liquid or gel stable detergent composition containing 10 to 80% by weight of an active detergent mixture and also containing water, wherein the active detergent mixture comprises (a) an alkyl ether sulfate. Anionic detergent active materials other than; (b) Alkyl ether sulphate having an ethoxylation average value of 1 to 5 (weight ratio of components (a) and (b) is 2: 1)
˜1: 10, preferably 2: 1 or 1.5: 1 to 1: 3, more preferably 2: 1 to 1: 2); (c) betaine and / or amine oxide (component (a)).
The molar ratio of (c) is 3: 1 to 1: 3, more preferably 2: 1 to 1: 2.
And (d) greater than 35% and less than 50% by weight of the active detergent mixture of a water-soluble nonionic detergent active material.

For reasons of cost efficiency and availability of materials, at least most of the component (a) is a secondary alkane sulfonate, an alkylbenzene sulfonate, a primary alkyl sulfate ester salt, a fatty acid ester sulfonate, a sulfonate. It is selected from succinic acid dialkyl ester salts and 2-α-olefin sulfonates.

The compositions according to the invention can show in the detergency test as good performance as conventional compositions containing alkylbenzene sulphonates, but are considerably less irritating.

By replacing most of the non-ionic detergents with ether sulfates containing less than 5 EO, the mildness of non-ionic detergent-based compositions can be completely retained and the foaming performance is significantly improved. However, it is particularly surprising to improve the cost efficiency.

In principle, the concentration of the active detergent mixture may be in the range from 10 to 80%, provided that a stable liquid or gel-like product can be obtained, preferably from 5 to 60% by weight.
Of particular interest are aqueous liquid compositions containing from about 40% by weight of the active detergent mixture.

Six detergent active materials have been mentioned above as being usable as component (a). The secondary alkane sulfonates used as component (a) are generally free radical reactions, ie paraffin sulfochlorination reactions (Reed reaction) RH + SO ₂ + Cl ₂ → RSO ₂ Cl + HCl followed by hydrolysis and neutralization or by sulfoxides. Chemical reaction RH + SO ₂ + 1 / 2O ₂ → RSO ₃ H followed by neutralization.

Secondary alkane sulfonates are usually of the general formula R ₁ R ₂ CHSO ₃ X, where R ₁ and R ₂ may be the same or different and each has a straight chain or branched chain having at least one carbon atom. An alkyl group of a chain, the length of the alkyl chain (ie the total number of carbon atoms of R ₁ and R ₂ + 1) is preferably 13 to 18, X
Are solubilizing cations) and have different alkyl chain lengths. An example of such a material is Hoec manufactured by the sulfoxidation method.
SAS60 (SAS is a trademark) manufactured by hst.

A suitable secondary alkane sulfonate prepared by the sulfochlorination process is Mersolat ™ from Bayer.

The alkylbenzene sulfonate used as component (a) is preferably a primary or secondary C ₈ -C ₁₆ alkyl group,
In particular it derived from alkylbenzenes having a C ₈ -C ₁₃ alkyl group. A suitable alkylbenzene sulfonate is Sh
Dobs 102 from ell and Marlon A from Huls.

The primary alkyl sulfate ester salt (primary alcohol sulfate ester salt) is preferably used as the component (a) and has the general formula ROSO ₃ X (wherein R is a C _{8 to} C ₁₈ primary alkyl group). , X are solubilizing cations). Suitable is
Dobanol 23A from Shell, the R of which is mainly C ₁₂ and C ₁₃ . As described in more detail below, the alkyl sulfate ester salt is also a constituent of the alkyl ether sulfate of component (b).

Suitable detergent active sulfosuccinic acid dialkyl ester salts have the general formula (Wherein R ₁ and R _2, which may be the same or different, are each 3
Represents a straight or branched chain alkyl group having .about.12 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms, and X represents a solubilizing cation. ) Compound.

The alkyl radicals R ₁ and R ₂ are preferably straight-chain or (in a mixture) predominantly straight-chain.

Among the sulfosuccinic acid dialkyl ester salts that may be advantageously used in the compositions of the present invention are GB2 105 325 (Unileve
r) C ₆ / C ₈ asymmetric materials, GB 2 104 913 (Unilever) disulfotyl succinate / dihexyl ester salt mixtures, GB210852
Included are mixtures of symmetrical and asymmetrical dialkyl sulfosuccinate salts described in Unilever.

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

An example of such a material is Liporan 440, Lion Corporation,
It is a C ₁₄ α-olefin sulfonate made in Japan.

Suitable fatty acid ester sulfonates have the formula:

(Wherein R ₁ is linear or branched C ₈ -C ₁₆ alkyl, R ₂ is linear or branched C ₁ -C ₄ alkyl, X is a solubilizing cation, and R _{1 is} Is preferably C _{10 to} C ₁₂ and R ₂ is preferably butyl) Component (a) of the active detergent mixture is used in liquid compositions 1
It may also contain one or more other detergent active ingredients such as alkyl glyceryl ether sulfonates, or alkyl sarcosinate salts. The amount thereof is preferably less than half of the component (a), more preferably 1/4 or less thereof.

The second essential component (b) of the active detergent mixture is an alkyl ether sulphate having at least one ethylene oxide residue per molecule (sometimes referred to as alcohol ether sulphate or alkyl polyethoxy sulphate). Normally, the general formula _{R 3 - (OCH 2 CH 2} ) nOSO 3 X ( wherein R ₃ is C ₁₀ -C ₁₈ alkyl group of the primary or secondary, X is a solubilizing cation, average Ethoxylation degree n
Is 1 to 5, preferably 3 to 4), and the alkyl ether sulfate, which is a mixture of materials, is added to the composition. Particularly preferred values of n are 3 and 4. R ₃ is preferably a C ₁₀ -C ₁₆ alkyl group. The value of n represents an average, since there are materials with different degrees of ethoxylation and some non-ethoxylated materials in a given alkyl ether sulfate. The non-ethoxylated material is, of course, an alkyl sulphate ester salt, which corresponds to component (a).

The amount of alkyl sulphate salt in the alkyl ether sulphate depends on the average degree of ethoxylation n. n is 3
In the case of, the alkyl sulfate salt is typically a mixture of
It constitutes 15 to 20%, and when n is 4 or more, it is less than the above range. When the proportion of the alkyl sulfate ester salt is low, the presence of the alkyl sulfate ester salt can be ignored, but the alkyl sulfate ester salt is involved in the component (a).

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

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

Alkyl ether sulphates contain molecules with different numbers of ethylene oxide residues in a statistical distribution. In alkyl ether sulphates with an average degree of ethoxylation of 1.5 or more, the proportion of molecules with only one ethylene oxide residue is higher than that with two ethylene oxide residues (greater than 2). ) It is not substantially larger than the proportion having ethylene oxide residues. This feature is therefore an important property of component (b). If the average degree of ethoxylation is 2 or more as in the preferred case, the proportion of molecules having one ethylene oxide residue is greater than the proportion having 2 ethylene oxide residues and the proportion having more ethylene oxide residues. Will also be smaller.

Except for the alkyl sulfate component (b) of the preferred alkyl ether sulfates wherein the formula _{R 3 - (OCH 2 CH 2} ) Although the n-OSO ₃ X (wherein n is a positive integer, provided that the average EO The value is less than 5).

Examples of preferred alkyl ether sulphates for use in the present invention are Shells with a degree of ethoxylation (n) of 3.
Dobanol (TM) 23-3 manufactured by and a material having an ethoxylation degree of 4 equivalent thereto. These materials C ₁₂ ~C
₁₃ (50% each) Primary alcohol (straight chain about 75%, 2
-Methyl branch 25%). Another preferred material is a Chimica Augusta Lial (TM) 123 based alkyl ether sulphate, which is a branched primary with an ethoxylation degree of 3-4 and an alkyl chain length distribution similar to Dobancl 23. It is alcohol. Ethoxylation degree 4
, Albright based on the intermediate coconut alkyl group
Wilson's Empicol MD ™ is also preferred.

A suitable example of a secondary alcohol ether sulfate is Un
Materials derived from alcohols such as Tergitol 15 / S / 3 ™ from ion Carbide (this material is not currently marketed). A common method for making secondary alkyl ether sulphates results in the presence of very small amounts of alkyl sulfate ester salts in the product.

It is desired that component (b) comprises at least 12%, preferably at least 20 or 30% of the active detergent mixture. It preferably constitutes up to 40% of the active detergent mixture. However, if component (b) is substantially or completely related to component (a), component (b) may comprise 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 one that provides the anionic material with the desired solubility. Monovalent anions such as alkali metal ions, ammonium and substituted ammonium ions are typical, but divalent ions which provide satisfactory solubility can also be used. In particular magnesium ions may be present to improve soft water performance and can be incorporated as magnesium or inorganic magnesium salts of the anionically active material or in the hydrotropic system.

Component (c) is betaine, an amine oxide or a mixture thereof. For economy, and thus cost efficiency, these
In particular, it is preferable to avoid using a large amount of amine oxide. The amount of amine oxide is then 10% of the active detergent mixture.
It is preferably not more than weight%. Preferably the amount of betaine is less than 30% by weight of this mixture. The total amount of amine oxide and betaine is preferably 30 in the active detergent mixture.
% By weight or less, more preferably 15% by weight or less or 10% by weight
It is the following. It is preferred to use betaine alone.

The formula for proper betaine is: Simple betaines and expressions for: Amide betaine of.

Ryoshikichu R is C ₈ -C ₁₈ alkyl group linear or branched. Lauryl group or middle cut coconu
t) It may be an alkyl group. R ₆ or R ₇ are each C _{1 to} C ₃
Alkyl or C ₁ -C ₃ hydroxylalkyl. Examples of sulfobetaine -CH ₂ CO ₂ ^- and _{- (CH 2) 3 SO 3} - or It has the above formula replaced by.

A suitable simple betaine is Empigen BB from Albright & Wilson
Is. That is, in the above formula, R is C ₁₂ -C ₁₄ alkyl derived from coconut, and R ₆ and R ₇ are both methyl. Gold with a perfect coconut alkyl group
Tego L7 from smidt is also preferred.

Suitable amine oxides are of the formula RR ₆ R ₇ N—O where R is a straight or branched chain C ₈ -C ₁₈ alkyl group and R ₆ and R ₇ are each C ₁ -C ₃ alkyl, or C ₁ -C ₃ hydroxyalkyl). A suitable amine oxide is Empigen OB from Albright & Wilson. In this case, R is intermediate coconut alkyl and R ₆ and R ₇ are both methyl.

Component (d) is one or more water-soluble nonionic detergent active materials,
For example, the materials commonly used in detergent compositions. Betaine and amine oxide of component (c) do not form part of component (d).

Component (d) is preferably a polyalkoxylated material, especially one or more ethoxylated nonionic detergent active materials. In this case it is desirable that such a material has an HLB value of 12.0-16.0.

Component (d) are C ₈ -C _18, preferably may be a polyethoxylated aliphatic alcohol having an average degree of ethoxylation of the alkyl chain lengths and 4-14 of C ₈ -C _16. Suitable nonionic detergents of the general formula _{R- (OCH 2 CH 2) m} -OH ( wherein R is an alkyl group, preferably 8 to carbon atoms
18 pieces, more preferably 8 to 16 pieces, further preferably 9 to 12 pieces
A straight chain alkyl group having 8 carbon atoms and an average degree of ethoxylation m of 5-14, more preferably 6-12).
High foaming ethoxylated short chain alcohols of Particularly preferred nonionic detergents are Shell Dobanol 91-8, where R is C _{9 to} C ₁₁ (mainly linear) and m is 8, or Lia.
is let C ₁₁ -10EO.

Other suitable materials are secondary alkyls having 8 to 18, preferably 11 to 15 carbon atoms, and m of 5 to 14,
Preferably, the material is 6-12. For example, Union Ca
It is a material of Tergitol 15 / S / 12 manufactured by rbide (currently not commercially available) or Softanol A series (manufactured by Nippon Shokubai).

The polyethoxylated alcohol mixture is preferably stripped to reduce the odor associated with the composition.

As the component (d), a general formula (In the formula, R is a linear or branched alkyl having 7 to 18 carbon atoms, R ₈ is an ethyleneoxy or propyleneoxy group, Y is hydrogen or —R ₈ (CH ₂ CH ₂ O) qH. , P is 1 or more and q is 0 or 1 or more, and R may be lauryl or coconut alkyl), and an ethoxylated alkanolamide may also be used. Examples of ethoxylated alkanolamides are Stepan Chemical Compan
Amidox L5 and Amidox C5 manufactured by y.

Ethoxylated alkylphenols as well as ethoxylated fatty acids, ie polyethylene glycol esters of fatty acids, can be used as component (d).

Component (d) is at least 35% by weight of the active detergent mixture, provided that
Make up less than 50% by weight.

Component to be present in any in the active detergent mixture of the composition of the present invention, one or more mono- or di-alkanolamides, preferably C ₈ -C _18, more preferably C ₁₀ -C ₁₈ carboxylic acid mono- or di (C ₂ ~C ₃₎ alkanolamides. Each of these general formulas R ₄ -CO-NHR ₅ and R ₄ -CO-
N (R ₅ ) ₂ where R ₄ is a C _{7 to} C ₁₇ aliphatic group, preferably linear and saturated, and R ₅ is a hydroxyethyl or hydroxypropyl group. R ₅ is preferably a 2-hydroxyethyl group.

Materials of this type are generally made from fatty acids of natural origin,
Including molecules with R ₄ groups of various chain lengths, eg
Coconut ethanolamide mainly consists C ₁₂ and C ₁₄ material, also including _{C 8, C 10, C 16} , C 18 material any amount.
Preferred are ethanolamides derived from so-called intermediate coconut fatty acids, most preferably lauric acid.

Mono- and di-ethanolamide are 5% of the detergent mixture
Can account for 20%.

Liquid detergent compositions of the present invention will generally need to include, in addition to the active detergent mixture and water, one or more hydrotropic agents. Hydrotopic agents are materials that are present in the composition to control solubility, viscosity, clarity and stability, but do not themselves effectively contribute to product performance. Examples of hydrotropic agents include lower aliphatic alcohols, especially ethanol; urea; toluene and lower alkylbenzene sulfonates such as sodium xylene sulfonate and mixtures thereof. Preferred are alcohols, urea and xylene sulfonates. Since hydrotropic agents are expensive and do not contribute to the performance of the composition and occupy a portion 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 hydrotropic agent. For this reason and cost, it is preferred in the present invention to avoid the use of substantial amounts of tertiary amine oxides.

In a preferred form of the invention, the weight of hydrotropic agent in the composition is not more than 12% by weight of the active detergent mixture.

The compositions of the present invention may also contain conventional minor ingredients such as fragrances, pigments, preservatives and bactericides.

The stable liquid detergent composition of the present invention can be used in all conventional detergent fields, especially in areas where foaming is advantageous, such as textile laundry products, general household and industrial cleaning compositions, carpet shampoos, car wash products, etc. Laundry products, shampoo,
It can be used for foaming bath products, especially for hand-washing dishes.

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

Examples Examples 1-4 The foaming performance and mildness of various aqueous compositions were compared. Compositions I and II of the invention were compared with a comparative composition (A) containing more than 50% by weight of nonionic detergent active material.

Foaming performance was evaluated by a modified Schlachter-Dierkes test based on the principle described in Fette und Seifen 1951, 53 , 207. Concentration 0.04 in 24 ° FH (French hardness) water at 45 ° C
100 ml of an aqueous solution of each test material containing 10% of active detergent was rapidly shaken inside a graduated cylinder using a vertically oscillating disc. After the first appearance of bubbles, stains (water 120
9.5 parts of commercially available cooking fat, 0.25 part of oleic acid, 0.25 part of stearic acid, and 10 parts of wheat starch) were added in 0.2 g increments at 15-second intervals (10 seconds for gentle stirring and 5 seconds for stillness) until foaming disappeared. . Results were recorded as the number of soil increases (NSI score).
Point differences of 6 or less are generally considered insignificant. The results are typically shown as an average of 3 to 4 times.

Several in vitro and in vivo methods for assessing the protein denaturing efficacy of detergents and mixtures thereof have been reported (Miyazowa et al., Int J Cos Sci 6, 33-46, 1984, and references cited therein). reference). In this type of one way, the skin-derived (Prottey like, Int J Cos Sci 6, 263~27
3,1984) or derived from wheat malt (Tanaka et al., Anal Biochem 6
6 , 489-498, 1975) to investigate the interaction of detergents with acid phosphatase enzymes.

The in vivo irritation of the composition can be evaluated using the flex wash test. In this test, clean products were rinsed after rubbing with the panelists' forearms. This method was repeated 4 times a day for 5 days, and the degree of erythema developed was evaluated by a skilled assessor.

By comparing the results of the Wheat Malt Acid Phosphatase (WGAP) test and the Flex Laundry test, compositions that produce less than 50% enzyme inhibition under the test conditions are substantially hypoallergenic; produce less than 40% inhibition. It showed that the mildness difference between the products was not detectable in the flex wash test. Enzyme tests are so sensitive that they have a threshold for protein denaturation in real-life situations, below which it is not possible to distinguish between the irritants of all active materials and products.
The results of the WGAP test are expressed as percentage inhibition (ie 100% -percentage residual activity). Water does not cause any inhibition, ie 10
It resulted in 0% residual life.

The examples show that compositions I and II give greater foaming performance than A. As mentioned above, although the% WGAP inhibition of A is smaller than that of I and II, there is no difference in terms of mildness. Therefore, the composition of the present invention has both mildness and performance.

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Claims (7)

[Claims] 1. A liquid or gel stable detergent composition containing 10 to 80% by weight of an active detergent mixture and also water, said active detergent mixture comprising: (a) a primary alkyl sulfate ester. (B) an alkyl ether sulfate having an ethoxylation average value of 1 to 5; (c) betaine and / or amine oxide; and (d) an amount of more than 35% and less than 50% by weight of the active detergent mixture. It consists of a water-soluble nonionic detergent active material, the weight ratio of components (a) and (b) is 2: 1 to 1: 3, and the molar ratio of components (a) and (c) is 3: 1 to 1: 3. 3. A detergent composition which is 3. 2. Composition according to claim 1, characterized in that the weight ratio of components (a) and (b) is from 2: 1 to 1: 2. 3. The total amount of amine oxide and betaine is not more than 20% by weight of the active detergent mixture,
The composition according to claim 1 or 2. 4. The composition according to claim 1, wherein the component (c) is substantially free of amine oxide. 5. The alkyl ether sulfate (b) has the general formula: R- (OCH ₂ CH ₂ ) n-OSO ₃ X (wherein R is a C ₁₀ -C ₁₈ alkyl group, and X is a solubilizing cation). The composition according to any one of claims 1 to 4, characterized in that it is provided by a mixture of materials of which the average degree of ethoxylation n is 2 to 12). 6. The alkyl ether sulfate (b) is
The alkyl group R is a group in which less than 20% of materials having an alkyl chain length of C ₁₄ or more are present, and the average degree of ethoxylation n is 3 to
8. A primary alkyl ether sulphate which is 8 provided by any one of claims 1-5.
The composition according to the item. 7. A composition according to any one of claims 1 to 6, characterized in that the nonionic detergent active material (d) is a material with a chain length of less than C ₁₂ .