JPH01318099A - Liquid detergent composition - Google Patents

Abstract

PURPOSE: To provide a stabilized isotropic aqueous liquid detergent, by blending a surfactant, which includes soap, propylene glycol and calcium without including a specified amine.

CONSTITUTION: This detergent composition includes (i) a surfactant, which includes soap at 5wt.% or more in relation to the whole of the composition, at 20wt.% or more, (ii) propylene glycol at 5wt.% or more, (ii) calcium at 5mmol/l or less, and does not includes di-calkanol amine, which can form the compound with soap, or trialkanol amine. In the case where oxygen is used at 0.1-2wt.%, for example, in relation to the composition, boric acid, borax, namely, ortho and meta sodium borate or sodium pyroborate is desirably contained in the described composition at 0.25-15wt.%. Weight ratio of propylene glycol and boron is desirably set at 5:1 or more.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to soap-containing isotropic aqueous liquid detergent compositions.

An isotropic liquid detergent is a liquid detergent that does not have a lamellar structure. Detergents of this type are mostly free of builders, i.e. they do not contain substances that reduce water hardness due to calcium ions, or they contain soluble builders, such as suitable organic carboxylic acid derivatives, salts of polymeric carboxylic acid derivatives,
Contains only builders such as soap or mixtures of these substances.

The present invention relates to an isotropic detergent solution containing 5% by weight or more of soap.

It is already known to incorporate alkanolamines, in particular monoalkanolamines, dialkanolamines and trialkanolamines, into isotropic liquid detergents, as described for example in British Patent Specification GB 1590445.

These alkanolamines can also be used in unstructured (unsLruc
It has also been used in liquids (tured). These alkanolamines are known to play multiple roles in products. In addition to acting as a buffer, a hydrotrope (a substance that ensures the dissolution of the material and prevents the formation of surfactant structures that lead to salting out of the ingredients and undesirable high viscosities), boric acid and water-soluble borates may function as an enzyme stabilizer, even when present.

Recently, there has been a growing trend to legally limit or prohibit the use of detergent composition ingredients that are believed to be environmentally damaging. Also included are certain alkanolamines. Therefore, there is a need to find alternative materials that can perform all of the same functions as these alkanolamines, yet can be used in products in practical and economical amounts. One particularly important challenge is to find alternative materials that meet these criteria in compositions containing high levels of soaps and other surfactants.

BG2128242 (Colgate-Palmoli
ve) discloses a method for producing liquid detergent compositions containing anionic and nonionic synthetic detergent agents together with soap, propylene glycol and a relatively large amount of calcium. EP 151678 (Procter and
Similar compositions are also disclosed in Gan+ble. However, these known compositions are not always completely stable, especially when stored at low temperatures.

Now, surprisingly, if the calcium content of the composition is maintained below a certain critical level, stable isotropic compounds containing substantial amounts of soap and propylene glycol and free of dialkanolamines and trialkanolamines can be obtained. It has now been found that it is possible to produce detergent compositions with a sterilizing effect.

Therefore, the present invention provides (i) 20% by weight or more of a surfactant containing 5% by weight or more of soap based on the entire composition, (ii) 5% by weight or more of propylene glycol, and (iii) 5% by weight or more of propylene glycol.
Provided is an isotropic aqueous liquid detergent composition containing ol/1 or less of calcium. The composition is substantially free of dialkanolamines or trialkanolamines that can form complexes with soaps. Preferably, the composition is also substantially free of other amine or amide sources.

The calcium content of the composition of the invention is preferably 5 mmo
l/f or less, more preferably 3 tnol/1 or less, particularly preferably IIIIIIO1/1 or less. The compositions of the present invention are most preferably substantially free of calcium, i.e., no calcium is added to the composition, and calcium is derived from impurities in the materials used (i.e., calcium impurities in tap water). only exist.

Calcium content is calculated based on total calcium ions and calcium salts.

The compositions of the present invention are substantially free of dialkanolamines or trialkanolamines, and therefore the content of these components is usually at most 0.5% by weight of the composition, more preferably at most 0.1% by weight, particularly preferably at most 0.1% by weight of the composition. is 0.02% by weight or less. Most preferably, the compositions of the present invention are completely free of these dialkanolamines or trialkanolamines.

The composition of the invention preferably contains propylene glycol
, 5% by weight or more, most preferably 10% by weight or more. A typical dosage is about 15% by weight.

This propylene glycol is typically 20% by weight of the composition.
Use in an amount not to exceed.

We have found that the use of propylene glycol in the above content range not only provides similar functionality to the alkanolamines, but also has the advantage of facilitating the removal of stains that can normally be removed by bleaching. did.

When the enzyme is used in an amount of, for example, 0.1 to 2% by weight of the composition, boric acid, boron oxide, borax or sodium ortho-, meta- or pyroborate may also be present in the composition of the invention. .25-15% by weight, preferably 0.5-1
It is preferred to include 0% by weight, most preferably 0.5-3% by weight. This amount is calculated as boric acid containing an equivalent amount of boron.

The weight ratio of propylene glycol to boron is preferably 5:1 or more. A particularly suitable weight ratio is between 5:1 and 20:1, preferably about 10:1.

When such boron-containing compounds are present, glycerol is also preferably incorporated, although the amount required is usually somewhat less than that required in the absence of propylene glycol. The glycerol content in the composition of the present invention is usually 1 to 10% by weight, more preferably 1 to 10% by weight.
5% by weight, typically about 2.5% by weight.

Particularly suitable is the use of propylene glycol, boron compound and glycerol in combination in a weight ratio of 5 to 20:1:1 to 5, more preferably 7 to 15:1:2 to 4. It has been found that the stability of the enzyme is surprisingly high in liquid compositions containing this combination of propylene glycol, glycerol and boron compounds.

As used herein, the term "soap" refers to alkali metal soaps of long monocarboxylic or dicarboxylic acids, such as those containing from 12 to 18 carbon atoms. Typical of said acids are oleic acid, ricinoleic acid, dodecenylsuccinic acid, fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palm kernel oil or mixtures thereof. In the present invention, sodium soaps, potassium soaps of these acids or mixtures of these two soaps may be used.

The compositions of the present invention contain at least 5% by weight of soap, but there is no upper limit to the soap content. Thus, amounts up to 50% by weight may be used, for example. Typical amounts are 20-45% by weight, such as about 30%.

In addition to the soap, the compositions of the invention preferably also contain one or more synthetic surfactants. Preferably, the surfactant is selected from anionic, nonionic, zwitterionic and amphoteric.

Many suitable cleansing compounds are commercially available and are described, for example, in 5Chu+artz, Perry and Berch, "
5surface＾active Agents an
d Detergents”, Volume I and I
It is detailed in the literature such as T.

Preferred synthetic surfactants that can be used in the present invention are synthetic anionic compounds. These compounds are typically water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl groups of about 8 to about 22 carbon atoms. The term alkyl in this case also includes the alkyl portion of higher acyl groups. Examples of suitable synthetic anionic compounds include sodium and potassium primary or secondary alkyl sulfates, especially those obtained by the sulfation of higher (C9-C2o) alcohols produced by reducing the glycerides of tallow or coconut oil. Sodium and potassium alkyl (C9-C2o)benzenesulfonates, especially linear secondary alkyl (C+.-C2,)benzenesulfonates: sodium alkyl glyceryl ether sulfates,
Ethers of higher alcohols derived especially from tallow or coconut oil and synthetic alcohols derived from petroleum; coconut oil fatty acid monoglycerides sodium sulfate and sodium sulfonate; sulfuric esters of higher (C9-Cl8) fatty alcohols with alkylene oxides, especially ethylene oxide. Sodium and potassium salts of reaction products; reaction products of fatty acids, such as coconut oil fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide; primary or secondary monosulfur, phonic alkanes, e.g. -Olefin (C, ~C
2o) by reacting with sodium bisulfite; and those derived by reacting paraffins with S02 and CI2 and then hydrolyzing with base to obtain random sulfonate salts; and sulfonic acid olefins. . By olefin sulfonate is meant a material prepared by reacting an alpha-olefin with SOI, then neutralizing and hydrolyzing the reaction product.

It is usually preferred to use the sodium salt of anionic surfactants for economic reasons, but sometimes the potassium salt is also used, especially in compositions containing high contents of other sodium salts, such as sodium tripolyphosphate. can be used effectively. Mixtures of potassium and sodium salts may also be used. However, the composition of the present invention preferably does not substantially contain phosphate; among the anionic surfactants, alkali metal alkyl (C
6-C25) Benzene sulfates are particularly preferred because they are inexpensive, readily available, and also exhibit advantageous solubility.

If desired, nonionic synthetic surfactants can be used as the sole detersive compound or preferably in a mixture with anionic detergent compounds, especially alkylbenzene sulfonates. Specific examples include reaction products of alkylene oxide, usually ethylene oxide, with alkyl (C6-C22) phenols, usually containing 5 to 25 EO, i.e. 5 to 25 units per molecule, of ethylene oxide;
Mention may be made of condensation products of aliphatic (08-C,.) primary or secondary alcohols with ethylene oxide, usually from 2 to 30 EO, for example from 6 to 20 EO. Other examples of suitable nonionic surfactants include organic hydroxyl-containing groups, such as aliphatic primary or secondary (C8-Cl8
) Those obtained by first ethoxylating an alcohol and then propoxylating it. Other so-called nonionic surfactants include long chain tertiary phosphines and dialkyl sulfoxides.

Mixtures of synthetic surfactants, such as mixtures of anionic surfactants or mixtures of anionic surfactants and nonionic surfactants, may be used in particular to reduce the foaming properties of detergent compositions, or It may be used in detergent compositions to enhance detergency. The use of these mixtures is particularly useful in compositions for use in automatic washing machines that are sensitive to foaming.

Although suitable amounts of amphoteric or zwitterionic synthetic surfactants may be used in the liquid detergent compositions of the present invention, it is generally preferable not to use these substances due to their relative cost. When using amphoteric or zwitterionic synthetic surfactants,
They are usually used in small amounts in compositions based on anionic and/or nonionic surfactants, which are far more common than these substances.

If a synthetic surfactant is used, the amount usually ranges from about 2.0% to about 20%, preferably about 5% by weight of the composition.
% to about 15% by weight. The amount is selected depending on the desired properties and taking into account that the total amount of soap and synthetic surfactant exceeds 20% by weight. Most preferred are mixtures of anionic/nonionic synthetic surfactants,
Preferred is a mixture containing 2 to 7.5%, typically about 5%, by weight of anionic systems and about 5 to 15%, typically about 10%, by weight of nonionic systems.

The liquid detergent compositions of the present invention may also contain any of the common additives in the amounts normally used in liquid detergent compositions for textiles. Examples of these additives include defoamers such as alkyl phosphates, silicones; alkali salts such as sodium carboxymethyl cellulose, sodium silicate, alkali metal carbonates such as potassium carbonate, or alkali metal hydroxides. Anti-redeposition agents such as;
In addition to textile softeners, mention may be made of fluorescent agents, which are usually used in very small amounts, fragrances, enzymes such as proteases and amylases, and fungicides and colorants.

The compositions of the invention optionally further include a bleaching agent, preferably a peroxide bleaching agent. Examples of suitable peroxide compounds include hydrogen peroxide, alkali metal peroxides, perborates,
persulfates, peroxydisulfates, perphosphates, crystalline peroxyhydrates formed by reacting hydrogen peroxide with urea, i.e., urea peroxide, or alkali metal carbonates, i.e., alkali metal percarbonates. . Encapsulated bleaches may be used; preferred peroxide bleaches are sodium perborate tetrahydrate and -hydrate, and sodium percarbonate. Preferably, the bleaching agent is only partially dissolved in the system; the bleaching component is preferably present in an amount corresponding to 0.1 to 15% by weight of active oxygen, more preferably 0.5 to 10% by weight, typically 1 .0~5.
It is added in an amount corresponding to 0% by weight of active oxygen. When the bleaching agent is hydrogen peroxide, 1.5-7.5% by weight of the composition
of active oxygen, preferably about 100 to 150 mg/l, is released into the washing liquor.

Although the bleaching ingredients may be present in the system in solubilized form, it is also possible to have only a portion of the peroxygen bleach solubilized and the remaining portion present as solid particles suspended in the system.

Such solid particles may be added to the composition in the form of solid particles, but are preferably formed by in situ crystallization. In the case of perborate bleach particles, e.g.
294904 (Procter and Gambl
Preferably, the perborate quaternary hydrate is formed by crystallization in situ, as described under e). Other methods for the presence of bleaching agents in solid form are described in EP 293040 (Pr.
Octer and Gamble). These methods consist of adding one or more water-miscible solvents.

The remaining component of the compositions of the invention is water, usually in an amount of about 40% to about 75%, preferably about 45% by weight.
~65% by weight.

To obtain effective cleaning power, liquid detergent compositions must be alkaline, preferably from about 8.5 to about 12, preferably from about 9 to about 11 when the composition is used as an aqueous solution at the recommended concentration. to obtain a pH of . To meet this requirement, the undiluted liquid composition preferably has a pH of 7 to 12.5, e.g.
H. A pH that is too high 1 For example, a pH above about 13 is not very desirable from a safety point of view 0 When a bleaching agent such as hydrogen peroxide is present in the liquid composition of the present invention, it has a high cleaning power and a large physical and In order to obtain chemical stability at the same time, the pn is usually 7,
5-10.5, preferably 8-10, especially 8.5-10
Make it. Of course, the components of such highly alkaline detergent compositions must necessarily be selected with alkaline stability in mind, especially in the case of pH-sensitive substances such as enzymes, especially suitable proteolytic enzymes.

The viscosity of the liquid detergent composition of the invention is preferably below 1000 mPas, more preferably below 500 mPas at 25°C, measured at 21 s-'. A particularly suitable viscosity is 80-480-4O0.

In addition to propylene glycol, the compositions of the invention contain further alkaline buffers, such as potassium carbonate, so that the pH is maintained above 8.5, especially when used in hard water or at low concentrations. It may contain alkali metal carbonates such as.

Compositions of the invention may be manufactured by any suitable method. However, preferably, the alkali is dissolved in water at room temperature and the anionic surfactant and fatty acid are neutralized on the spot).
, optional acidic anionic surfactant and propylene glycol, and the mixture is heated to 55° C. with stirring, followed by optional nonionic surfactant and fatty acids, and foam enhancement if desired. A method is used which consists of dissolving a premix which also contains the agent into said mixture at a temperature above the melting point of these components. Builder and buffer salts are preferably added as final ingredients, and if a bleaching agent such as hydrogen peroxide is used, this is also added last.

The liquid detergent compositions of the invention are usually diluted with water and used in the form of an aqueous laundry liquor, for example for cleaning textiles in a washing machine. Preferably, the washing liquid contains 0.1 to 10% by weight, preferably 5 to 15 g, of a liquid detergent composition.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Dog m Dodecylbenzenesulfone [Na salt 4.8CI3
~C,, (7EO) alcohol nonionic surfactant
9.6 Top Coconut Oil Fatty Acid
12.3 Oleic acid
17.8KOH3,5 NaOfi2.
5 Glycerol 2.5 Propylene glycol 14.0 Ethanol
3.5 boric acid
1.0 enzyme
0.5 trace acid content
0.9 water
The rest of this composition is prepared by dissolving KOFI and NaOH in water at room temperature, adding dodecylbenzenesulfonic acid Na salt, boric acid, and diol, heating the mixture with stirring,
Thereafter, a premixture of co-C,,(7EO)alcohol nonionic surfactant, coconut oil fatty acid, and oleic acid was prepared by dissolving into the mixture at a temperature above the melting point of these components. The remaining ingredients were added last.

The viscosity of the final product at 25°C is 240, measured at 21s-
mPa5, and pH was 9.4.

This product was used in a N1ele H785 at a temperature of 40° C. and a concentration of 10 g/ffi. When compared to a triethanolamine-containing liquid detergent (Sunil), the product of this example was superior in its ability to remove bleachable stains such as tea, blackberry and red wine.

3 while varying the glycerol content of the composition of Example 1.
Enzyme stability at 7°C was measured. Table 1 shows the enzyme 5avi
nase 16. Stability at 37° C. after 9 weeks of OL grade is shown (pH=9.6).

2.5 48 Results expressed in % residual activity.

E111E1 Dissolve NaOH and KOH in water at room temperature, add anionic surfactant, boric acid, propylene, and rangelicol,
The following composition is prepared by heating this mixture with stirring, then dissolving into the mixture a premix of ethoxylates and fatty acids having a temperature above the melting point of the ingredients, and finally adding the remaining ingredients. did.

Ex3Ex4Ex5 Na salt 5.0 −
-Second alkylsulfonic acid Na salt 5,0
-Cl3~C,, (7EO) alcohol nonionic surfactant 10.0 - -coconut oil (IOEO) alcohol nonionic surfactant -10,010,0 top coconut oil fatty acid 11.011.011.
0 Oleic acid 16.0 16.0
16.0NaOH1,62,42,4 KOJ1 4.4 3.4
3.4 Glycerol 3.5 2.5
-Propylene glycol 12.0 15.
015.0 Ethanol 3.5 2
．． 5 2.5 Boric acid 1.0
1.0 1.0 Enzyme 0.5
0.5 0.5 Trace components 0.
9--Water...
...Remaining...Ex6Ex7Ex8 Na salt 2.5 4.8
8.9CI3~C+5 (7EO) Alcohol nonionic surfactant 7.0 9.612.
0 coconut oil fatty acids 8.1 11.01
4.1 Oleic acid 16.7 16
．． 0 3.4NaOH2,21,4- KOH3,04,25,6 Glycerol 3.5 3.0 3.
5 Propylene glycol 8.0 12.0
9.0 Ethanol 4.5 3.5
2.5 Boric acid 1.0 1
．． 0 1.5 Sodium carbonate
1.5 2.5 Enzyme 0.
5 0.5 0.6 Trace components 0
．． 9 0.9 0.9 water
...Remaining...9 to 10 The following compositions were manufactured by the methods of Examples 3 to 8.

H2O...Remaining... KOH2,572,57 NaOH1,911,91 Boric acid t,oo t,o
.

Fluorescent agent (Tinopal CBS-X)
0.06 0.06 propylene glycol
s,oo s,o.

Glycerol 3.34 3.34
CI2-C14 alkylbenzene sulfonate 7.69 7.6
9 Ethoxylated CI) ~ CIS alcohol 7E0
19.00 19.00 Polydimethylsiloxane 0.03 0.03 Fatty acid mixture (60/40 oleic acid/coconut oil fatty acid) 15.0OL5.00 Protease (Savinase 16.OL) 0.26 0
．． 34 fragrance 0.35
0.35 Opacifying agent 3.00
3.00 dye solution o, i
o o,t.

Amylase 0.10
Dequest 2066
2.77 Dog Name" ↓ The following compositions were manufactured by the methods of Examples 3 to 8.

Weight jL2LH20 remaining Sodium citrate 1.20 Sodium formate 0.9ONaO111
,89 Fluorescent agent 0.13 Propylene glycol to, o.

Glycerol 3.5001□～
CI4^BS (M^RLON AS3) 1
1.50PAS 3.
00 Ethoxylated C11-CI'i Alcohol 7E01
3.00 Dodecenylsuccinic acid 10.
62 fat a (Priolene 6902)
3.5410 Savinase 16
．． OL) 0.65 amylase
0.25 aminosilane
0.05 Opacifying agent -〇・30 Dye solution (1%) 0.10De
quest 2066 0.87
Unilever Namrose Ben Note Sharp

Claims (9)

[Claims] (1) (i) 2 containing soap in an amount of 5% or more by weight of the entire composition
0% by weight or more of a surfactant; (ii) 5% by weight or more of propylene glycol; (iii) 5mmol/l or less of calcium;
An isotropic aqueous liquid detergent composition substantially free of dialkanolamines or trialkanolamines that can form complexes with soaps. 2. The composition of claim 1, comprising an enzyme and boric acid or a salt thereof capable of stabilizing the enzyme in the composition in the presence of propylene glycol. (3) The composition according to claim 1 or 2, also comprising 1 to 5% by weight of glycerol. (4) Claims 1 to 3 wherein the ratio of propylene glycol to boron compound to glycerol is 5 to 20:1:1 to 5.
The composition according to any one of. (5) Measured at 21s^-^1, the viscosity at 25℃ is 1
5. The composition according to any one of claims 1 to 4, which has a thermal resistance of 000 mPas or less. (6) The composition according to any one of claims 1 to 5, having a pH of 7 to 12.5. (7) The composition according to any one of claims 1 to 6, containing 2.0 to 20% by weight of a synthetic surfactant. (8) A method for treating textile products, which comprises bringing textile products into contact with an aqueous liquid containing the detergent composition according to claim 1. (9) A method according to claim 8, characterized in that the aqueous liquid contains from 5 to 15 g/l of detergent composition.